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the apparatus diagrammatically illustrated in fig1 has a conveyor line 2 for bottles 3 . gas samples are taken from the bottles 3a , 3b , 3c and 3d in a testing section of the conveyor line 2 . this is done by lowering sampling probes 4 , 5 , 6 and 7 into the bottles through the bottle neck , without touching the bottle , so as to prevent any possible contamination . gas is withdrawn from each bottle by means of the probe and is conducted via a conduit 8 , 10 , 12 and 14 respectively to a distributor unit with switch valves 16 , 17 , 18 and 19 . in one position of the switch valves , the gas withdrawn from the individual bottle is fed via outlet conduits 22 , 23 , 24 and 25 respectively from the switch valves to a collector conduit 21 . this collector conduit is connected to a suction pump 26 which pumps the gas from the individual bottle and discharges it to atmosphere via conduit 27 . while bottles 3a to 3d are present in the test line , gas is continuously extracted from the bottles by the pump 26 and supplied to the switch valves . by means of a control unit 30 , which may be linked with a higher - ranking control 35 , one of the valves 16 to 19 is then switched via the electrical control lines 31 - 34 for a predetermined period , so that the gas from the individual bottle concerned , which is flowing through the valve , passes to a second collector conduit 20 which is connected to the inlet to the testing unit 1 , which may for example be a pid unit , but is preferably a mass spectrometer . intake of gas through the conduit 20 to the mass spectrometer 1 is effected by the transfer pump incorporated in it . after the intake of gas from one of the bottles under test , e . g . from bottle 3a , by the mass spectrometer , the valve 16 is switched again so that the flow of gas from the bottle 3a is again switched through to the outlet conduit 22 . as soon as the mass spectrometer 1 is ready for the next analysis i . e . for analysis of the gas flow from the bottle 3b , the valve 17 is switched so that the gas flow from the bottle 3b passes briefly to the collector conduit 20 and thence to the mass spectrometer 1 . in the same way , valves 18 and 19 are then switched briefly in succession so that gas samples from the bottles 3c and 3d can be separately analysed in succession . the probes 4 to 7 are then lifted from the bottles 3a to 3d , and another four bottles are moved up on the conveyor line 2 . the probes are lowered into this new set of bottles , and gas samples are again taken . the previously tested bottles 3a to 3d are conveyed further along the conveyor line , and those bottles of this group for which an unacceptable contamination has been detected by the mass spectrometer 1 are removed from the conveyor line by a rejector device . the tested bottles which are uncontaminated then proceed , after passing through at least one washing machine , to a bottling machine where they are filled again with a drink product . thus , with an apparatus and / or with the process as described with reference to fig1 a plurality of bottles can be tested by a single testing unit or mass spectrometer . to allow this to happen with the conveyor line 2 running at high capacity , the process is preferably performed , as described with reference to fig1 if so that a gas flow is continuously supplied from each bottle to a distributor unit 16 to 19 . the transfer time for the gas samples from the probes 4 to 7 through the conduits 8 to 14 is then of no consequence so far as the measurement is concerned . for the mass spectrometer 1 , the individual gas sample is available at the outlet of the distributor device , or switch valves 16 to 19 , that is to say , only the transfer distance through the conduit 20 to the mass spectrometer counts towards the measuring time . a large number of bottles e . g . 16 bottles with rapid transfer on the conveyor line 2 , can be analysed in this way using a single mass spectrometer 1 . further measures can be taken to assist high - speed analysis . for example , in a preferred apparatus , air is blown into the bottles during sampling in order to increase the concentration of the contaminants contained in the samples . this can preferably be accomplished by constructing the conduits 8 , 10 , 12 and 14 as twin conduits with sample gas extracted through one conduit as described and with air blown into the bottles through the other conduit ( by means of a pump not shown in the drawing ) through additional outlets in the probes 4 to 7 . in addition it has proved advantageous to heat at least the sample gas conduits of the pipes 8 , 10 , 12 and 14 in order to prevent condensation of the sample gas on the conduit concerned . the feed conduit 20 to the mass spectrometer 1 can also be heated . one function of the control unit 30 is to control the switching of the valves 16 to 19 . in addition the control unit 30 can also control the lowering and raising of the probes 4 to 7 into and out of the individual bottles . however , this can also be effected by a higher - ranking control 35 controlling the bottle handling system as a whole , which will be explained in more detail with reference to fig3 . alternatively , the controls 30 and 35 may be constructed as a combined unit . alternatively , the lowering and raising of the probes can be performed by purely mechanical means using cam - operated lifters . fig2 shows , again in highly diagrammatic form , another embodiment of an apparatus for carrying out the process . two testing units , or , preferably , mass spectrometers , 1 and 1a are provided . one mass spectrometer 1 is for testing bottles 3a , 3b and 3c ; the other mass spectrometer 1a is for testing the bottles 3d , 3e and 3f . thus , in this embodiment also , each individual mass spectrometer caters for several bottles tested together . the individual bottles are tested in a similar manner to that described for fig1 . first , e . g . bottles 3a and 3d are tested by their respective mass spectrometers 1 and 1a , as the switch valves 16 and 16a briefly switch the gas flow to the conduits 20 and 20a so that the gas sample from bottle 3a can be analysed by the mass spectrometer 1 and the gas sample from bottle 3d can be analysed by the mass spectrometer 1a . the valves are then switched back to the collector conduits 21 and 21a respectively and thence to the suction pump 26 . testing of gas samples from the bottles 3b and 3e then proceeds in a similar manner . fig3 shows a plan view in diagrammatic form of a bottle testing apparatus 40 operating in accordance with the process . returned bottles are randomly fed to the device on a conveyor line 41 . the bottles are fed to the device in the upright position and are normally open , i . e . uncapped , and are not yet washed . by means of a conveyor and resulting backup pressure , bottles 3 are supplied to a star wheel 42 which also forms the line stop , and are also released into a worm conveyor 43 which feeds the bottles at regular intervals and in an upright position . a number of testing devices can be provided along this conveyor section 43 . these will be described in detail with reference to fig5 . in particular , the bottles can be checked for correct height , and for the presence of a cap or other stopper and of residual liquid . unsuitable bottles can be rejected from the worm conveyor by one of the rejectors 51 or 52 . the bottles s passing these preliminary checks pass from the worm conveyor 43 on to a feed carousel 45 . from this feed carousel 45 the bottles are fed to a main carousel 47 . testing , e . g . in the form of a mass spectrometric analysis , is performed while the bottles are in the main carousel 47 . only four bottles 3a to 3d are shown diagrammatically in fig3 . in reality the main carousel is capable of receiving a larger number of bottles to be tested , e . g . 16 bottles , which are tested by a mass spectrometer located above the main carousel . after testing , the bottles pass via a discharge carousel 48 to a discharge worm conveyor 49 . a further rejector 53 is located at this discharge worm conveyor to reject those bottles which have been identified by the mass spectrometer as contaminated . rejection may be performed in various known ways , e . g . by means of a jet of compressed air , or by an electromechanically operated pushrod - type rejector . however , the preferred method is to use a &# 34 ; soft &# 34 ; diversion system whereby those bottles which are to be removed are guided in an upright position on to another conveyor line . in this way , overturning of bottles containing possibly harmful liquids can be avoided . these bottles are conveyed , in an upright position , to a disposal point . downstream of the worm conveyor 49 , the uncontaminated bottles are discharged to a conveyor line 50 which conveys them to a washing station and then onwards to a filling station . a control box 54 is arranged on a boom . the controls for the apparatus as a whole can be separately accommodated . fig4 shows , partly in section , a view of part of the main carousel 47 of fig3 . it shows a bottle 3b which is held by holding devices 62 and 63 on the carousel . the other bottles and their holding devices on the carousel are not shown in the drawing . inserted into the bottle shown in the drawing is the probe 5 for taking the gas sample . the probe 5 is mounted on a movable carriage 61 which can be raised along a carriage guide 60 from the lower position shown in the drawing to the upper position shown in chain - dotted outline only . at the point where the bottles enter the carousel , the individual carriage 61 belonging to the holding device 63 is in the upper position . after a bottle has entered the holding device , the carriage 61 is lowered along the carriage guide 60 , causing the corresponding probe to enter the bottle through the bottle neck without touching it . a hose 10 is connected to the probe 5 . the connection is omitted from the drawing for the sake of clarity . when the carriage 61 is in the lower position , the line of the hose is as represented by the hose designated with the reference number 10 . when the carriage 61 is in its upper position , the line of the hose is as represented by the short section 8 of the hose behind the hose 10 . the hose 10 is led to the centre of the carousel . it has a conduit 11 through which the gas sample is withdrawn from the bottle . the conduit 11 is connected by a coupling 80 to the top of the carousel . from the coupling a passageway 81 in the top of the carousel leads to the switch valve 17 . one outlet of the switch valve is connected by a pipe 23 to a central pipe 21 of the carousel which leads to the suction pump 26 ( fig1 ) ( not shown in fig4 ). the other outlet of the switch valve 17 leads via the passageway 20 in the top of the carousel to a coupling 82 . the carousel parts which have been mentioned so far revolve with the bottle at the same rate as the carousel . the fixed mass spectrometer 1 , which is represented in merely diagrammatic form in fig4 by a corresponding block , is arranged above the coupling 82 . through this coupling 82 the fixed mass spectrometer is connected to the revolving carousel i . e . to its passageways 20 . the electrical control leads to the switch valves are not shown in fig4 . these run from the control unit via sliding contacts to the valves revolving with the carousel . the carousel shown in fig4 carries e . g . 16 receiver positions ( holders ) for bottles under test , and an equal number of carriages , probes , hoses , couplings , electrical switch valves and passageways 20 to the single coupling 82 . in the interests of clarity , only two switch valves , the valve 17 and the valve 36 , are shown in fig4 . the remaining elements are likewise only partly depicted , e . g . hoses 8 , 10 and 28 . through a central pipe 71 , passageways 73 , couplings 70 , pipes 72 and the corresponding hoses , clean air can be blown into all bottles under test to raise the concentration of contaminants in the gas sample obtained . the flexible hoses 10 are also heated to prevent condensation of the sampled gas inside the hose . fig5 shows diagrammatically the steps in the testing process in the apparatus according to fig3 . the incoming bottles on the conveyor line arrive at the star wheel 42 , where non - upright bottles cause a line stop . in the feed worm - conveyor , the height of each individual bottle is then checked by means of two photoelectric barriers . oversize or undersize bottles are eliminated . the next check is performed by means of an ultrasonic sensor which detects whether the cap has been removed from each bottle . bottles with caps or other stoppers are eliminated . a weight sensor is then used to check whether a relatively large quantity of residual liquid is present in the bottle . if so , the bottle is eliminated . from the entry module the bottles pass via the feed carousel to the main carousel . on the main carousel , the sample gas is removed from the bottles and fed to the mass spectrometer or pid testing unit for analysis . the time during which a bottle remains on the carousel is much longer than the measuring time available per bottle ( for comparison : the measuring time per bottle is about 240 ms whereas the time on the carousel ( assuming 300 bottles per minute ) is about 2 sec .). to make full use of the relatively long period during which the bottles are on the carousel , the removal of the sample gas is performed in several stages : ______________________________________stage 0 as soon as the bottle is on the main carousel , a probe dips into the bottle to withdraw the gas sample . stage 1 from all 16 gas sampling hoses on the mainremoval of gas carousel are permanently drawing air intosample to the valve block . as soon as a samplingvalve block . hose is lowered into a bottle , a sample of the gas in the bottle is pumped via the hose to the valve block . through a valve in the valve block , it is either pumped directly back to atmosphere by the air pump , or diverted to the mass spectrometer by a switching operation of the valve . at any given time one of the 16 valves on the valve block is switched through to the mass spectrometer , and the others are closed and their sample gas is being discharged to atmosphere . in addition to the withdrawal of sample gas , clean air is blown into the bottles . this is in order to obtain a higher concentration of the sampling gas . lastly , all gas sampling hoses are heated to prevent condensation of the gas inside the hose . stage 2 from as already stated , one of the 16 valvesvalve block is switched through at any one time . to mass this allows the sample gas to pass fromspectrometer the corresponding sampling hose and its related bottle to the mass spectrometer where it can be analysed . by suitable cycled switching of the valves , every individual bottle on the carousel can be analysed in turn . this 2nd stage is sequential , that is to say only one bottle can be &# 34 ; handled &# 34 ; at any given time , unlike the 1st stage in which 15 stations are &# 34 ; handled &# 34 ; in parallel , i . e . simultaneously . ______________________________________ analysis of the sample gas in the mass spectrograph finally determines whether a bottle is contaminated or not . instead of the electrically controlled distributor unit which has been described , a distributor unit which is entirely mechanically controlled by the rotation of the carousel can also be provided for the sample gas flows . instead of the carousel which has been described , testing can also be performed along one or more parallel or serial linear sections of a conveyor path , as illustrated in principle in fig1 and 2 . fig6 shows a mechanical distributor unit which is mounted on the carousel 47 shown in fig4 in place of the electrically switched distributor unit in fig4 ( in fig6 the carousel 47 has been omitted ). the mechanical distributor unit has a lower rotating part 100 which is connected to the rotational axis of the carousel 47 . this part 100 rotates with the carousel and with the bottles . the rotating part 100 carries a plurality of connections 180 for the pipes 11 ( shown in fig4 but not fig6 ). through these connections , the gas samples pass into the interior of the distributor unit . a stationary part 110 with rotation preventer 111 is arranged axially above the rotating part 100 . from this stationary part 110 a connection 121 leads to the suction pump 26 ( shown in fig1 but not fig6 ), which continuously sucks air ( gas samples ) from the bottles . from the stationary part , another connection 182 leads to the stationary mass spectrometer 1 ( not shown in fig6 ). if a second mass spectrometer 1a is provided , a corresponding connection 182a is provided . the rotating part 100 and the stationary part 110 slide on one another on sealing faces 104 and 105 respectively . the distributor chambers are provided in one or both of the sealing faces 104 , 105 . a first distributor chamber 106 in the sealing face 105 serves as extraction chamber and is in permanent communication with the suction pump via the connection 121 . a second distributor chamber 107 serves as linking chamber for the gas sample to be supplied to the testing unit 1 and is in permanent communication with the connection 182 . the extraction chamber 106 is in the form of a circular arc ( fig7 ) and communicates via through - bores with all connections 180 and their respective pipes 11 and bottles , except for a single connection 180 , shown in the left half of the drawing in fig6 which is in communication with the linking chamber 107 . through this connection 180 , the gas sample withdrawn from the corresponding bottle via the pipe 11 is dispensed through the chamber 107 and the connection 182 to the mass spectrometer . the gas samples from all other bottles pass via the chamber 106 and the connection 121 to the suction pump and out to atmosphere . the rotation of the carousel , and with it the lower part of the distributor unit , brings each connection 180 in succession into communication with the chamber 107 and thus with the mass spectrometer , while the other connections 180 stay in communication with the chamber 106 . if two mass spectrometers 1 and 1a are used , a second chamber arrangement 106a , 107a can be provided , as indicated in chain - dotted outline in fig8 . the extraction chambers 106 and 106a may communicate i . e . be connected to the same pump connection 121 . the chambers 107 , 107a , on the other hand , are separate , each being connected to its respective mass spectrometer 1 or 1a . a doubled processing capacity is thus obtained . the sealing faces 104 , 105 are fabricated and finished as minimum - wear dry - bearing mating faces , e . g . as hard metal sliding faces on both sides , or as copper sliding faces on both sides , or as a hard metal sliding face on one side mating with a ceramic sliding face . in the illustrated embodiment the sliding faces can easily be replaced . to obtain a good seal between the sealing faces 104 , 105 the two parts 100 , 110 of the distributor unit are axially loaded by means of a ball - mounted spring 108 . a central fastening allows rapid assembly or dismantling of the distributor unit . for the individual gas sample fed to the mass spectrometer , the illustrated arrangement provides a short , straight path , reducing the memory effect . to supply the air for injection into the bottles , the illustrated example is provided with a central duct 171 which opens into connections 170 to which the pipes for the heated flexible hoses 10 are connected .
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the present invention is directed to instable machinery vibration detection apparatus which includes not only a transducer which may be used to measure machine vibration , but also contains integral electronics which may be used to determine if a fault condition has occurred , thereby creating a &# 34 ; smart &# 34 ; accelerometer package . an accelerometer package , designated by the numeral 12 , according to a preferred embodiment of the present invention is shown in fig2 . an external housing 28 holds electronics circuit 18 including circuit board 31 and mounted electronic components 27 in close proximity to transducer 20 . external housing 28 provides shielding from electromagnetic fields which may be in the general vicinity of the package due to radio transmitters , etc . ( not shown ). by enclosing all necessary components within external housing 28 , the signals from transducer 20 contain less noise and have a relatively greater signal to noise ratio . this allows for a reduction in filtering and amplification circuity . six pin connector 22 provides a ready method for electrically connecting the accelerometer package 12 to thruster control circuitry 24 ( see fig1 ). fig1 shows accelerometer package 12 mounted on rocket thruster 10 adjacent oxidizer valve 14 . related rocket thruster components including fuel valve 16 and electrical junction box 34 are also indicated in fig1 . thruster control and warning circuitry 24 uses the fault signal from accelerometer package 12 to change operating modes of thruster 24 and / or to shut down thruster 10 in an orderly manner before failure . also thruster control and warning circuitry 24 may activate an indication of failure , such as a warning light or bell ( not shown ). thruster control and warning circuity 24 may include actual electronic circuitry or a software controlled computer . it is highly desirable to avoid any false or spurious indications of machine or thruster failure which may result from noise and ground loops . a ground loop , or voltage difference , may exist between ground 17 and ground 15 due to a variety of reasons , some of which may be unknown and difficult to detect during operation . these ground loops may cause a spurious indication of thruster failure and may be difficult to detect during operation of rocket thruster 10 . a combination of transducer 20 and electronics circuit 18 into the same housing 28 greatly reduces the possibility of spurious signals due to ground loops and other noise which otherwise could detrimentally affect transducer 20 and related circuitry 18 . additional means for preventing spurious signals due to typically transient differences in voltage between grounds 17 and 15 are discussed subsequently . fig3 provides a preferred embodiment of circuit 18 contained within accelerometer package 12 . a single power source ( not shown ) is connected at connector 22 , pin 1 , with a common ground shown at pin 2 . this source voltage is filtered by capacitor 21 and is used by regulator 40 to provide 5 volts at output pin o . the regulated 5 volt output is filtered by capacitor 25 . field effect diode 23 regulates current flow to transducer 20 . transducer 20 changes resistance in response to &# 34 ; g &# 34 ; forces , thus creating an electrical transducer signal which corresponds in magnitude and frequency to machine or thruster vibrations . &# 34 ; g &# 34 ; forces are generally understood to be the forces which act on a mass described by using the force of gravity as a unit force acting on a mass , e . g ., two &# 34 ; g &# 34 ; s would be a force acting on a mass twice that which would occur due to gravity . frequency adjust 38 is set for a desired center frequency selected to be equal to the expected unstable vibration frequency of the machinery or thruster to be monitored and may be calibrated by reading with a frequency counter ( not shown ) at pin 6 of decoder 32 . a frequency band around the desired center frequency may be set using switch 28 which selects either wide bandwidth capacitor 26 for an approximately 300 hertz bandwidth or narrow bandwidth capacitor 29 for a bandwidth of approximately 75 hertz . with narrow band width capacitor 29 connected to switch 28 , approximately 50 incoming cycle signals of a requisite magnitude within the frequency band are required before a fault condition is indicated at pin 8 of decoder 32 . with wide bandwidth capacitor 26 connected to switch 28 , approximately 10 to 15 cycles are required to generate a fault signal . these values are calculated assuming a center frequency of 1000 hz , and will typically vary with a change in center frequency . the pulse counting feature which is inherent to preferred embodiment lm567 decoder circuit 32 prevents transient pulses within the window from generating a fault signal . by taking advantage of this inherent feature of the lm567 decoder circuit 32 which might in other circumstances be a disadvantageous characteristic , it is possible to obtain an effective delay in the circuitry without adding extra delay circuitry . the lm567 decoder circuit 32 includes a loop filter connection at pin 2 so that capacitor 26 or 29 is used to complete this loop filter . the lm567 decoder circuit 32 may also use external resistive components ( not shown ). a general description of the lm567 decoder is disclosed on pages 5 - 51 through 5 - 55 of the publication entitled &# 34 ; semiconductor master selection guide 1989 &# 34 ; by national semiconductor and is incorporated herein by reference . in operation , alternating current from transducer 20 , that corresponds in magnitude and frequency to machine vibration &# 34 ; g &# 34 ; forces , passes through signal capacitor 27 to signal threshold adjust 30 which determines the desired amplitude trip level based on accelerometer calibration data . for example , if a basic accelerometer produces 1 volt per &# 34 ; g &# 34 ; force and the amplitude threshold desired is 1 . 5 &# 34 ; g &# 39 ; s &# 34 ;, a simulated signal at the desired frequency and at 1 . 5 volts ( typically applied with a signal generator ) is fed into circuit 18 , and signal threshold adjust 30 is used to set a trip level which produces an output at pin 8 of decoder 32 or pins 3 and 4 of connector 22 . all adjustments described above might be set during accelerometer manufacture / calibration , and the entire package permanently encapsulated with a sealing material to minimize or eliminate effects of vibration during use . alternatively , these calibration sequences may be determined by the user if field adjustments are desired . a machinery fault condition results in the impedance seen at pin 8 of decoder 32 changing from a high impedance to a low impedance due to the sinking of an open collector integral to decoder 32 . as a result , current flows through light emitting diode 35 between pins 1 and 2 of optical isolator 38 . a resulting output then occurs at pins 3 and of optical isolator 38 , which is also available at pins 3 and 4 of connector 22 . a separate power supply , load , and ground connection to pins 3 and 4 of connector 22 is made through indicated wires 46 , 47 , and 48 which results in a circuit independent of the common circuit ground wire or land 42 connected to pin 2 of connector 22 . therefore , if return wire 46 is analogous to ground 15 of fig1 if ground 42 of fig3 is analogous to ground 17 of fig1 ., and if grounds 15 and 17 of fig1 are at different voltages with respect to each other , the output signal received from accelerometer package 12 by thruster control 24 will be unaffected by this voltage difference . the accelerometer package 12 and thruster control 24 circuits are thus electrically isolated from each other via optical coupling . the optical isolator 38 precludes unwarranted or inadvertent shutdown caused by electrical ground loop conditions of which an end user of accelerometer package 12 may not be aware , since the output of optical isolator 38 is independent of the ground at pin 2 of connector 22 . for backup and corroboration purposes , the output of transducer 20 is also made available at pin 5 of connector 22 through direct current blocking capacitor 33 . the foregoing description of the invention has been directed in primary part to a particular , preferred embodiment in accordance with the requirements of the patent statutes and for the purposes of illustration . it will be apparent , however , to those skilled in the art that many modifications and changes in the specifically described accelerometer package 12 may be made without departing from the scope and spirit of the invention . for example , although developed for accelerometers , the teachings of this invention could be used with various types of transducers generating dynamic signals of user interest , i . e ., pressure transducers , acoustic sensors , flowmeters , etc . micro - circuitry and surface mount technology may allow control circuitry or parallel decoders operable at different frequencies to be included within accelerometer package 12 . other means for isolating the output of the package may also be used . for example , it may be possible in some situations to use differential transmission of the fault signal from accelerometer package in accordance with rs - 422 or rs - 485 as defined by the electronics industry association ( eia ) so that the effects of ground shifts and noise signals will appear as common mode voltages on the transmission line and thereby be nullified . if it is desired to have a latched output condition upon fault detection rather than a pulse , an optical silicon controlled rectifier ( scr ) may be used , and could be reset by an external reset switch or by dropping the load . it may be desirable for some applications to have an output pulse of a fixed time duration so that circuitry may be added to produce a pulse having a fixed time duration in response to a variable width fault pulse signal . therefore , the invention is not restricted to the preferred embodiment illustrated , but covers all modifications which may fall within the scope of the spirit of the invention .
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various embodiments of the present invention will be described in detail with reference to the tables and figures , wherein like reference numerals represent like parts throughout the several views . reference to various embodiments does not limit the scope of the invention , which is limited only by the scope of the claims attached hereto . additionally , any examples set forth in this specification are not intended to be limiting and merely set forth some of the many possible embodiments for the claimed invention . the program environment in which a present embodiment of the invention is executed illustratively incorporates a general - purpose computer or a special purpose device such as a hand - held computer . details of such devices ( e . g ., processor , memory , data storage , display ) may be omitted for the sake of clarity . it is also understood that the techniques of the present invention may be implemented using a variety of technologies . for example , the methods described herein may be implemented in software executing on a computer system , or implemented in hardware utilizing either a combination of microprocessors or other specially designed application specific integrated circuits , programmable logic devices , or various combinations thereof . in particular , the methods described herein may be implemented by a series of computer - executable instructions residing on a suitable computer - readable medium . suitable computer - readable media may include volatile ( e . g ., ram ) and / or non - volatile ( e . g ., rom , disk ) memory , carrier waves and transmission media ( e . g ., copper wire , coaxial cable , fiber optic media ). exemplary carrier waves may take the form of electrical , electromagnetic or optical signals conveying digital data streams along a local network , a publicly accessible network such as the internet or some other communication link . accordingly , in one aspect , the present invention provides a computer implemented method for creating a utility bill from a dynamic tariff , said method comprising the steps of : inputting at least one tariff component into the dynamic tariff ; identifying dependencies in each of the at least one tariff component ; iterating through an evaluation process until each of the at least one tariff components are evaluated to solve the dynamic tariff ; and creating a first utility bill from the solved dynamic tariff , wherein said dynamic tariff comprises at least one tariff component ; wherein said at least one tariff component corresponds to at least one component of said first utility bill ; and wherein said dynamic tariff corresponds to at least one utility tariff . the evaluation process may comprise determining an order to evaluate each of said at least one tariff component ; and evaluating each of said at least one tariff component in the determined order . the method may further comprise the steps of : inputting data from a data source into the at least one tariff component ; comparing said first utility bill to a second utility bill ; and validating the second utility bill based on the comparison , wherein said data source is the second utility bill . the method may further comprise the steps of : inputting data from a data source into the at least one tariff component ; and predicting a second utility bill based on the at least one utility tariff . the data source may be selected from the group consisting of estimated values , measured values from at least one utility meter , at least one historical utility bill , at least one historical interval meter reading , at least one historical non - interval meter reading , and a statistical baseline model . the method may further comprise the steps of : inputting data from a data source into the at least one tariff component ; predicting a set of utility bills based on the at least one utility tariff ; and predicting an annual utility budget based on the set of utility bills . the method may further comprise the steps of : inputting data from a data source into the at least one tariff component ; predicting a first set of utility bills based on a first utility tariff ; predicting a second set of utility bills based on a second utility tariff ; predicting a first annual utility budget from the first set of utility bills ; predicting a second annual utility budget from the second set of utility bills ; comparing said first and second annual utility budgets ; and selecting from the first and second utility tariff corresponding to a lowest utility budget selected from the group consisting of the first annual utility budget and the second annual utility budget . the tariff component may comprise meter data , or an expression . the expression may contain a reference to an internal system function or a reference to an external system function . the utility tariff may comprise a time - of - use tariff , or a market - based pricing tariff . in another aspect , the present invention provides a computer system for recreating a utility tariff comprising : a processor ; an input means ; a display ; a data source ; a dynamic tariff comprising at least one tariff component ; and at least one utility tariff , wherein said dynamic tariff corresponds to the least one utility tariff . the system may further comprise an order of dependencies identified in each of the at least one tariff component . the system may further comprise : data from said data source ; a first utility bill created from solving the dynamic tariff ; and a second utility bill , wherein the data from said data source is input into the at least one tariff component , wherein said data source is the second utility bill , and wherein the first utility bill is compared to the second utility bill to validate at least one component of the second utility bill . the system may further comprise : data from said data source ; and a first utility bill , wherein the data from said data source is input into the at least one tariff component ; and wherein the first utility bill is predicted from the at least one utility tariff . the data source may be selected from the group consisting of estimated values , measured values from at least one utility meter , at least one historical utility bill , at least one historical interval meter reading , at least one historical non - interval meter reading , and a statistical baseline model . the system may further comprise : data from said data source ; a set of utility bills predicted from the at least one utility tariff ; and an annual utility budget predicted from the set of utility bills , wherein the data from said data source is input into the at least one tariff component . the system may further comprise : data from said data source ; a first utility tariff ; a second utility tariff ; a first set of utility bills predicted from the first utility tariff ; a second set of utility bills predicted from the second utility tariff ; a first annual utility budget predicted from the first set of utility bills ; and a second annual utility budget predicted from the second set of utility bills , wherein the data from said data source is input into the at least one tariff component , and wherein a comparison of the first and second annual utility budgets allows a selection of a lowest utility budget from the group consisting of the first and second utility tariffs . the tariff component may comprise meter data , or at least one expression . the utility tariff may comprise a time - of - use tariff , or a market - based pricing tariff . in yet another aspect , the present invention provides a computer implemented method for recreating at least one utility tariff , said method comprising the steps of : inputting at least one tariff component into a dynamic tariff ; identifying dependencies in each of the at least one tariff component ; determining an order to evaluate said at least one tariff component ; evaluating said at least one tariff component in the determined order in an evaluation process ; and iterating through an evaluation process until each of the at least one tariff components are evaluated to solve the dynamic tariff , wherein said dynamic tariff comprises at least one tariff component , and wherein said dynamic tariff corresponds to at least one utility tariff . the evaluation process may comprise : determining an order to evaluate each of said at least one tariff component ; and evaluating each of said at least one tariff component in the determined order . in another aspect , the present invention provides a computer readable memory having recorded thereon statements and instructions for execution by a computer to carry out the methods set out above . tariff . a schedule of rates , fees or prices for any utility bill . dynamic tariff . a representation , according to a preferred embodiment of the present invention , of a tariff , which comprises at least one tariff component . the dynamic tariff is preferably represented in software in a computerized system , and is evaluated by the utility tariff engine . there is no restriction on the number of tariff components , or the type of tariff component that may be represented within a dynamic tariff . tariff component or dynamic tariff component . a field that may represent at least one element found in a tariff , such as a unique identifier , a database expression , a mathematical function or calculation , a storage location , an assigned value , or a meter reading . the tariff component may also represent an element not found in the tariff itself and / or not provided on utility bills ( e . g . a reference to an external piece of data ). meter component . a subset of tariff components that represent values measured by a utility meter , and optionally the type and nature of the measurement . non - meter component or user - defined component . a subset of tariff components that represent constant values , calculations , and / or data references and optionally the type and nature of the tariff component . tariff component expression . any expression , mathematical , logical or otherwise , that is contained within a tariff component . utility tariff engine . a combination of novel software constructs that form a system with capabilities to represent and evaluative utility tariffs . in a preferred embodiment , the utility tariff engine evaluates the dynamic tariff . tariff solver . in a preferred embodiment , a run - time interpreter that parses and executes the expressions contained within the tariff components . time - of - use (“ tou ”) tariff or interval tariff . also known as time of day ( tod ) or seasonal time of day ( stod ). a tariff that takes into account when a utility was consumed . it involves dividing the day , month and year into tariff slots and with higher rates at peak load periods and low tariff rates at off - peak load periods . market - based pricing . commodity prices of electric power or other forms of energy determined in an open wholesale market system of supply and demand under which prices are set solely by agreement as to what buyers will pay and sellers will accept . such prices could recover less or more than full costs , depending upon what the buyers and sellers see as their relevant opportunities and risks . for the consumer , trading activity in the wholesale market is reflected as continuously - changing commodity energy rates , typically adjusted hourly . a market - based pricing tariff is calculated , at least in part , on the wholesale market rate , meaning that commodity unit costs are not known in advance . meter data source or meter component data . refers to data that is measured , sampled , aggregated or otherwise indirectly or directly derived from the meter . the data may also represent any measurable or sampled property of utility use / demand or meter operation . utility bill data source . refers to all data from a utility bill to be verified . interval meter . refers to an advanced utility meter that measures consumption or demand at a higher frequency than a conventional meter ( typically at 5 minute , 15 minute , or 1 hour intervals ); and optionally , but generally , communicates that information via some network back to the local utility for monitoring and billing purposes . this is contrasted against a traditional meter which is used to produce much less frequent readings , typically one per month . api or application programming interface . an interface designed to enable interaction between software programs or systems . in the context of an electric utility or electricity retailer , a tariff is a published schedule of prices or terms of how electricity is sold . this would typically list the prices ( or rates ) for various services or components of the service such as : service charges , fees levied by the regulator , energy consumption ( e . g . kwh ) unit costs , time of day ranges for various unit cost levels , tiers defining volume - based discounts or increases and , peak demand ( e . g . kw ) charges . the tariff can also contain rules for usage and descriptions of the services provided . it is understood that reference to an electric utility is by way of example only , and that the present invention is operable for all utilities , such as natural gas , fuel oil , water , cable tv , telecommunications , transport of goods , etc . the dynamic tariff , as referred to in the context of the utility tariff engine of the present invention , is an operator - defined collection of one or more tariff components , examples of which are represented graphically in fig2 . all tariff components contain at least one of a number of common elements such as , for example , a unique identifier ( e . g ., a name ), an optional expression which can be interpreted and evaluated , a storage location for the result obtained through evaluating the expression , an optional assigned value and an optional unit . a special class of tariff components called meter components are those which represent values measured by the meter . meter components include additional properties that indicate the utility type and nature of the underlying measurement ( e . g ., consumption , demand , etc ), and optionally measurement unit ( e . g . kilowatt - hours , therms , cubic meters ). the dynamic tariff comprises one or more meter components and , optionally , one or more non - meter components . in its most basic form the dynamic tariff when representing a consumable utility will contain at least two components , a meter component representing consumption and a non - meter component representing a calculation to derive the final total . in defining tariff components the operator can recreate the logic of the rate tariff used by the utility provider or create a custom tariff of their own for the purpose of generating their own utility bills . referring to fig2 , in its most basic form , the tariff component 200 consists of a unique identifier 201 , an optional assigned value 202 , an optional expression 203 , a computed value 204 , an optional unit of measure 205 and an optional utility and measurement type 206 . when a utility and measurement type 206 has been specified the result is a special type of tariff component 200 called a meter component 106 ( see fig1 ). meter components represent those tariff components which represent metered values such as consumption of natural gas or peak demand or electricity . during the processing of the utility tariff , the result of evaluation of the tariff component expression 203 is stored 250 as the computed value 204 . in a preferred embodiment , the operator defines one tariff component for each line item on a utility bill . the number of components defined by the operator depends on how much information the operator wishes to capture and the validation goals . however , to enable accurate bill validation , preferably all components which contribute to the final total are represented in the dynamic tariff . for example , a simple dynamic tariff might include the tariff components shown in table 1 . advantageously , a user may define additional components beyond those necessary for computation . for example , components may be included to compute intermediate values for analysis purposes , or to use as a place holder for business - or accounting - related processes ( e . g . an accounting department tracking number ). surprisingly , by not limiting the type of element represented by the tariff component , the dynamic tariff allows unforeseen benefits such as automated categorizing , analysis , optimization , etc . in other business processes beyond the utility bills themselves . one example of this would be a tariff component to identify the data source for the bill generated by the utility . bills can be read visually by a person , read remotely via a data feed , read visually by the building owner , or simply estimated ( i . e . not read at all ). a similar bill is generated in all cases , and a “ reading source ” field could be used to deal with source data uncertainties when reporting conclusions . similarly , a tariff component could be used to indicate the means of data transfer to the database . data transfer can be fully automated from the utility company &# 39 ; s system or can have various levels of human involvement up to and included reading and transcribing data from low quality photocopy . in the case of manual entry , an experienced clerk will be much more reliable than a junior clerk . a “ data transfer method ” field that identified the data entry mechanism and the individual doing the entry would inform system users of the level of uncertainty at the data entry stage when interpreting outputs . fig1 shows the utility tariff engine 101 and the various data sources . the meter data source provides data that is measured , sampled , aggregated or otherwise directly derived from the meter . this data is also referred to as meter component data and may represent any measurable or sampled property of utility use / demand or meter operation , including the relative and / or absolute time the measurement or sample was taken , the duration over which the measurement or sample was obtained , or the temporal relationship between measurements or samples , or other related temporal , scalar , or sequential characteristics . the utility bill data source provides all data from a utility bill to be verified . this includes but is not limited to the billing period , account number and / or other identifying properties , all measured values and units including consumption and demand , marginal rates , delivery charges , taxes , subtotal , and final total , in addition to historical bills . these data sources are accessible within the utility tariff engine using the respective identifiers within the tariff component expressions . referring to fig1 , the utility tariff engine 101 enables the operator to process utility tariffs 104 and thus validate and / or generate utility bill ( s ) 107 . the processing of the utility tariff 104 is performed by the utility tariff solver 102 which contains an expression evaluator 103 capable of evaluating expressions contained within the tariff components 105 , 106 . these expressions may contain references to api 140 and remote service 150 functionality via proxy objects 108 - 116 loaded into the script engine 120 . api proxy objects 108 - 115 leverage functionality inherent in the host software api 140 and access data 171 - 176 within the local data storage 170 or from remote services 150 ( i . e . web services ). in addition , remote service proxies 116 enable integration with other remote services 150 outside the scope of the host software and identified by the operator which conform to a predefined specification for exchanging structured information . the use of remote service proxies allows for , but is not limited to , the integration remote data storage 180 such as meter readings 181 , real time market rates 182 , and weather data 183 . a tariff component may contain an expression which can be evaluated by the utility tariff solver . these expressions can be simple static values , complex formulae incorporating mathematical statements or even references to other tariff components as can be seen in table 1 . in some situations even the types of expressions shown in table 1 can be insufficient to fully and accurately describe the tariff . in a preferred embodiment , the present invention supports added functionality for querying one or more related objects or data sources ( e . g . meter , baseline model , facility , commodity price feed , etc .) within the expressions . an example where this is particularly useful is in the case of time - of - use tariffs . a time - of - use tariff is a special type of tariff which takes into account when the utility use occurs . these types of tariffs commonly segment the day into periods identified as ‘ on ’ or ‘ off ’ peak . prior to the present invention , this diversity in tariff structures usually required some special processing within the software . advantageously , since the tariff component expressions may contain references to objects within the system , these complexities can be addressed within the dynamic tariff directly , resulting in a consistent approach to simulating tariffs regardless of their specific structure . specifically , all types of tariffs , such as interval or non - interval , may be simulated using the same underlying constructs and processes , and hence the same utility tariff engine . previously , accounting for interval tariffs and non - interval tariffs would require two different systems ( i . e ., different engines ). in one aspect of the present invention , the functional differences between interval tariffs and non - interval tariffs can be handled within the tariff component expressions . for example , when dealing with a time - of - use tariff , a tariff component expression can query a utility meter for a consumption value within one or more on - peak period ( s ). for those tariffs incorporating continually - changing market - based pricing , a tariff component expression can query an external commodity price database or data feed . thus all tariffs , regardless of type , can be simulated in a similar manner , while unique aspects can be addressed by the functionality provided within the tariff component expressions . the preferred method employed by the tariff solver is represented graphically in fig3 . the role of the tariff solver is to solve the tariff by evaluating each tariff component . the order in which tariff components are evaluated is determined by dependencies identified within the expression . more specifically , tariff components are solved as values for referenced items become available . in practice this is accomplished through an iterative approach wherein the solver attempts to evaluate each tariff component 106 , 105 , 200 . the process begins at step 301 , where all tariff components are initially unprocessed . at the start of the iterative solving process ( step 302 ), for each unprocessed tariff component the solver attempts to read an input value from the input value data source and to store it in the tariff component ( steps 302 to 305 ) as the optional assigned value 202 ( see fig2 ). if the tariff component has an expression 203 , the solver determines if the expression can be solved based on the state of the items referenced in the expression ( steps 307 , 308 ). if values for all dependents are available , the evaluation proceeds to step 309 , the result is stored as the computed value 204 , and the tariff component is flagged as processed ( step 311 ). if evaluation cannot proceed , the next tariff component is processed ( step 312 ). if , at the end of an iteration , the solver is unable to evaluate at least one tariff component , the solving process terminates ( steps 312 , 313 ). this type of termination may be due to expression error , missing values or circular references . circular references are permitted only where an input value has been assigned to the tariff component referenced in a circular manor prior to solving . references to dependents are replaced with each dependent &# 39 ; s value prior to evaluation . when resolving references , the utility tariff solver will use a tariff component &# 39 ; s assigned value if it has been set , otherwise the computed value will be used . the preferred method to evaluate tariff component expressions is represented graphically in fig4 . in a preferred embodiment , the expressions given to tariff components are evaluated using a scripting engine such as microsoft vbscript , python or any other dynamic language . the first step in this process is to load relevant api objects into the scripting engine ( steps 401 to 403 ). each object is given a unique name so that reference to these objects may be resolved at evaluation time . in addition , processed tariff components are added to the scripting engine so that tariff component expressions can reference other tariff components ( step 404 ). prior to evaluating the tariff component expressions , all references are resolved and converted from a ‘ user friendly ’ syntax to a syntax more suitable for evaluation by the scripting engine ( step 405 ). for example the reference to the tariff component representing consumption might be written by the operator as ‘[ consumption ]’. once resolved , this reference would appear as an api call to obtain the referenced component , for example , tariff . getcomponent (“ consumption ”)&# 39 ;. once all references have been resolved the expression is evaluated by the scripting engine ( step 406 ). if an error occurs ( step 407 ), an exception is thrown and is then processed by the tariff solver ( step 408 ). otherwise , the result of the evaluation is returned to the tariff solver ( steps 409 , 410 ). the simple tariff shown in table 2 illustrates the solving process . in this example , the tariff component identified by the name “ consumption ” is given an expression which will query the underlying baseline model for a value . the solving process iterates through each component and if the expression does not contain any unresolved / unsolved references , it is evaluated . in the first iteration , the expressions for “ consumption ”, “ marginal rate ”, and “ tax rate ” can be evaluated . as previously described , the expression for “ consumption ” queries the baseline model for a predicted value . this prediction will generally be a function of the variables affecting utility use , such as time , weather , and other operator - defined variables . if the baseline model predicts the consumption during the billing period to be 1 , 000 , then the state of the tariff after iteration 1 is shown in table 3 . table 3 shows two remaining components yet to be solved . the component “ sub total ” is the only one which does not contain unsolved references . hence after iteration 2 “ sub total ” has been calculated as indicated in table 4 . only one component , the “ final total ” remains unsolved . all other tariff components have been evaluated and thus the expression for “ final total ” no longer contains unsolved references . after the third and final iteration the tariff has been completely solved as can be seen in table 5 . in example 1 , all tariff components were assigned an expression , which illustrates how the utility tariff engine can also be used as a forecasting tool , allowing for the accurate prediction of each line item of a utility bill before it has been received . when the associated meter does not provide frequent interval readings , the underlying prediction is obtained through the use of a baseline model . the accuracy of this prediction is maximized by the use of an industry standard methodology ( ashrae guideline 14 ) in computing baseline models . if interval readings are available they are used to compute the predicted value . the present invention also allows use of the utility tariff engine to predict an annual utility budget under a specific utility tariff . unlike utility bill prediction , which predicts the cost during a specific billing period , annual utility budget prediction determines anticipated cost over a typical year . preferably , a baseline model may be used to provide predictions by way of meter component expressions , such as those shown in example 1 . however , when the focus is a typical or average year , the inputs to the model may represent conditions which would be expected in a typical year . in terms of weather , this means using composite data simulating the typical meteorological year for a range of weather stations , specifically the industry standard ashrae wyec2 “ weather year for energy calculations 2 ”, or the most current version of that data set . similarly , any operator - defined variables ( site - specific variables such as industrial output , meals served , beds occupied that influence energy use ) will use values expected for the year being budgeted . using the baseline models to generate predictions for the various meter components makes it possible to compute each line item on the utility bill for each month in the budget year . traditionally , utilities were monopolies within geographic areas and building owners have had no choice among utility providers or tariffs . this has changed in recent years , and continues to change as competition is introduced into utilities industries . one aspect of the present invention provides the user with a scientifically valid way to compare competing utility tariffs , to inform procurement decisions . when an annual budgeting process is applied to the same utility meter using more than one possible utility tariff , the budget outputs provide a means for the user to quickly compare expected annual costs for each tariff and thus select the most cost effective tariff option . the baseline model predictions are based on the user &# 39 ; s best available predictions of future operating conditions , and incorporate industry standard “ typical year ” weather data , so the result is the most computationally reliable comparison possible . this is an improvement over previous methods which predicted costs based on previous years , or used simplified models which often reflect outcome bias of the party presenting the comparison . in another aspect of the present invention , the utility tariff engine may be used to verify the accuracy of utility bills issued by utility providers , by duplicating the calculations published by the utility providers . this process is used to capture instances of incorrect billing , a situation that is surprisingly common , but which is usually missed without a rigorous validation process . referring to fig6 , utility bills 603 within a utility bill data source 605 are imported into the system using a utility bill import process 604 . the utility bill data source includes but is not limited to spreadsheets , flat files , local or remote data storage , and erp systems . each imported utility bill is then processed one at a time 602 . using the account information from the bill , the relevant tariff is retrieved 606 from the collection of utility tariffs defined in the system 607 . the values present on the bill are then used to populate 608 the assigned value 202 ( see fig2 ) on each relevant tariff component . this is accomplished using an operator - defined utility bill import mapping profile 609 which establishes links between components in the incoming bill record and tariff components . once the input values have been mapped , the dynamic tariff is solved 610 using the process illustrated in fig3 . if an error occurs 613 during the solving process , the error message is stored for review by the operator and the utility bill 611 is flagged 614 as failing critically . if the solving process was successful , a number of validation checks are performed 616 based on a series of validation settings 617 chosen by the operator . these checks may include , but are not limited to , overlapping billing dates , date gaps from previous bill , variance checks between input and calculated values , previous bill variance , and previous year variance . if a check fails , an error message is stored and it is then determined if the failure was critical 618 , 619 . if so , the bill is flagged as failing critically 620 and no further checks are performed . otherwise the bill is flagged as failing non - critically 622 and any remaining checks are executed 621 . in example 1 , none of the tariff components was assigned a value , however , it is possible to do so , which allows for the validation of received utility bills . validation of utility bill values is performed through a comparison between the assigned and calculated values . for meter components , this results in a direct comparison between either the baseline model prediction or interval readings for traditional meters and interval meters , respectively , and that which is indicated on the bill . this can be demonstrated by expanding on example 1 . assume that the utility bill contains the information shown in table 6 . in comparing the assigned and calculated values it is easy for the operator to identify any source of divergence . in this example 2 , the variance in the final total can be traced back to the marginal rate , and it would appear that the utility provider has adjusted this value since the time when the tariff was created . while this is a simple example the procedure outlined can be applied to validate very complicated tariff structures . in a preferred embodiment , the tariff engine supports interval readings and tariffs based on interval readings . the system stores the interval readings as they are received and performs automatic rollups at varying intervals ( day , week , month , etc ). tariffs defined for interval meters may contain expressions which when evaluated by the tariff solver query this data through a number of exposed api objects / functions to accurately resolve the tariff component values . thus the expressions can reference objects which manage the collection of interval data . a list of expressions which operate on interval data are shown in table 8 . in these examples the meter component identified by the name “ consumption ” represents the consumption component of an interval meter . by leveraging the functionality provided by these expressions it is possible to define dynamic tariffs that use the interval meter readings as the source for the computed values as illustrated in table 9 . in another preferred embodiment , the tariff engine supports tariffs based on tou rates . in the context of the tariff engine , the meter components in a tou tariff have the capability to represents collections of meter readings occurring within defined time and / or date ranges , as opposed to single reading values . this capability can make use of interval readings if they are required for calculation by the particular tou tariff and supported by an interval meter installation . the tariff solver evaluates tou tariffs using the same procedure as non - tou tariffs . the only difference between the tou tariff and the non - tou tariff is the use of dynamic references within the tou tariff component expressions . specifically , the tou expressions can reference objects which manage the collection of tou data . examples of such expressions are shown in table 10 . a sample tou tariff which exhibits two rates , one for on - peak and another for off - peak , is shown in table 10 . validation of utility bills based on tou tariffs is performed using the same procedure as non - tou tariffs . in this case the on and off peak consumption values read from the utility bill will be compared to the values predicted by the respective baseline models . in yet another preferred embodiment of the present invention , the utility tariff engine can be used to accept continually - changing market - based pricing data provided by the electrical system operator , combine it with interval readings , and accurately reproduce the retail charges for a billing period . this is accomplished by exposing a data feed of current and historic rates through an api object accessible via the tariff component expression . in the example shown in table 11 , the expression defined for the tariff component “ consumption marginal rate ” retrieves the per unit charge for consumption for the period of interest by querying the utility provider object . in yet another aspect of the present invention , the utility tariff engine can be used not only to perform bill validation but also to perform bill generation as illustrated in fig7 . in this application , the process starts 701 with the operator defining the billing period ( start and end date ) 703 which is then used to populate the relevant tariff components 702 . each utility meter associated with the account is retrieved and used to populate the relevant meter components ( 704 to 707 ) with consideration of the operator - supplied billing period 703 . this can either be actual meter readings ( values ) or proxy objects which enable querying of the meter for specific information via the tariff component expression 203 ( see fig2 ). this includes but is not limited to consumption , min / max demand , real demand , apparent demand , power factor , etc . the dynamic tariff is then solved using the process illustrated in fig3 . if an error occurs 709 during the solving process it is displayed for operator review 710 . otherwise the bill is created 711 and the computed value for each tariff component is rendered on the bill as line items 712 . the utility bill is then issued 713 using any chosen medium ( e . g ., email , fax , print , etc .) before processing the next account . advantageously , this embodiment of the invention can be used in a landlord / tenant situation , in which the landlord bills the tenant for actual utility use . it can also be used by facility owners to allocate utility costs among profit or cost centres .
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a method and apparatus for analysis of optimized program files is herein described . specific details are set forth to provide a thorough understanding of the present invention . it will be apparent , however , that the present invention may be practiced without these details . in other instances , well - known structures and devices are depicted in block diagram format to avoid unnecessarily obscuring the present invention . a generic representation of core files and executables , or gcore as it is henceforth referenced , contains information about core files and executables . according to an embodiment , gcore includes a superset of binary formats used within unix . examples include : the executable and linking format ( elf ), the common object file format ( coff ), the programmable instruction set computers format ( prisc ), and the mobilization stationing , planning , and execution system format ( mspes ). this superset of binary formats can be extended to support a multitude of binary formats . since gcore captures different segments across a multitude of binary formats , gcore overcomes the debugging requirement of having a compiled binary for each platform . the code base for gcore is generic therefore analysis can be performed on any platform . according to an embodiment , analysis of the gcore can be done according to the techniques described herein . in the analysis of a core file , it is often difficult to ascertain what caused an executable to fail . most data required for meaningful analysis of the core file exist in the core file &# 39 ; s data sections . this data exists in raw binary format . interpreting this data as such is not possible because symbol information is not available . in optimized executables , symbol information is stripped and therefore is not available . debugging core dumps produced by executables on many operating systems involves determining the state of a process at the time of core dump . the state of a process at the time of a core dump comprises information such as the following : the function call stack and parameters of the called function . the values of local and global variables in the executable . contents of registers signal state at point of failure of the above , in optimized executables , it is often not possible to get the parameters of the function calls and the values of the variables , whether local or global . this necessitates recompiling the code unoptimized and reproducing the problem to produce a core dump . however , in the real world , this can cause few problems : unoptimized executables do not always behave exactly like optimized ones . the problem may be difficult to reproduce consistently . for larger executables , it may be difficult to isolate errors because it may not be feasible to recompile large portions of code as unoptimized according to an embodiment , analyzing the core dump of an optimized executable file is accomplished by reconstructing the information about symbol types found in the executable . type information describes the entire declaration of a symbol . for example , for a declaration like “ int * a [ 10 ]”, “* a ”, “* a [ 5 ]” or just “ a ” itself can all produce meaningful data . reconstruction of this information is possible by parsing declarations in the original source code . after parsing , symbols extracted from the core are matched with their corresponding type details . for each symbol , an entry is added to a types table . the type information is combined with the starting address for each symbol in the core and the type &# 39 ; s size to extract the values of program variables when the execution of the program was halted . according to an embodiment , an analyzer examines the declaration of the structure and the type information , referring to the header file where the structure defined . based on this information , type information may be determined by the size of intrinsic data types , for example , the number of bytes for integer , and for character . after an executable has been compiled and optimized , symbol type information is stripped from the executable . an entry in an optimized executable has an address which points to a data segment within the core file . from just the operating system core file and the optimized executable , it is impossible to gather enough information to reconstruct what caused the failure . after compilation , some information exists about global symbols , such as the symbol name , the address of the data , and its value . however , no information about symbol type and size exist . according to an embodiment , analyzing the core dump of an optimized executable is done by reconstructing information about the types of the symbols found in the optimized executable . fig1 is a block diagram that depicts a high level overview of a system for analysis of optimized executables . according to an embodiment , a system for analysis of a generic representation of an optimized executable core file , such as a gcore file , is provided . to create a generic core file for analysis , a converter component 110 is employed to convert data from optimized executable 102 and operating system core file 104 . the converter component 110 reads both input files from the executable 102 and operating system core file 104 , combines them into a generic format , and establishes initial linkages between these two input files within the gcore 106 . symbol information 118 and type information 120 extracted from source files 130 is added to gcore 106 . the gcore 106 is processed by an offline analyzer 200 , which provides access to program structures and values that existed at the point of failure . the program structures and values are used in analysis and debugging of this failure . according to an embodiment , fig2 . depicts details of offline analyzer 200 . a parser and analyzer 202 processes information from executable 102 , such as global , local , and structure / union members , and information about function parameters . the parser and analyzer 202 processes information from the operating system core file 104 , such as virtual addresses and offsets . the parser and analyzer 202 also processes user commands 208 , which contain user - defined type definitions which share namespace with global symbols extracted by parsing code declarations for various types and functions . from the processed information , parser and analyzer 202 interprets the processed information and generates an external reconstructed symbol table 204 and a types table 206 . the reconstructed symbol and type information can now be made available to third party applications such as a debugger or some other tool 212 . according to an embodiment , reconstruction of symbol and type information is performed by parsing declarations in source code . symbols obtained from the operating system core file have corresponding type details . therefore , for each type there exists an entry in a types table . a starting address for each symbol is available in the basic symbol table available in the executable . from this information , type and size information can be gleaned as well . as depicted in fig2 , symbol table 204 and types table 206 are generated by the parser and analyzer 112 with entries corresponding to each symbol in the executable 102 . fig3 depicts details of symbol table 204 and types table 206 according to an embodiment of the present invention . according to an embodiment , reconstruction of symbol and type information is depicted through four closely interlinked lists 300 . the four closely interlinked lists 300 represent value and parameter details for reconstructing symbol and type information . according to an embodiment , symbol table 204 is represented by two distinct lists , symbol list 310 and symbol info list 308 . each entry in symbol list 310 points to an entry in symbol info list 308 , which lists symbol type details . entries in symbol info list 308 each have a pointer which corresponds to an entry in type table 206 . the type table 206 is represented by two distinct lists , types list 306 and type offset list 314 . there is an entry in type list 306 corresponding to every type in the executable 102 . complex types , such as structures and functions have an additional pointer to a types offset list 314 that lists related elements or parameters . symbol table 204 has an entry for each type listed in the type offset list 314 . entries in this type offset list 314 refer to an entry in the symbol table 204 that identifies its parent . an identifier , such as a flag , may be used to distinguish a parent symbol from a child symbol . the four closely interlinked lists 300 represent details for reconstructed symbol and type tables as depicted in 204 and 206 respectively . external creation of the symbol and types information can be an effective solution to the problems that arise because of the optimization of executables after compilation of program source code , such as c programs . the invention eliminates the need for recompiling optimized executables , as it reduces overhead ( due to recompilation time ) and enables analysts to determine causes of core dumps . issues , for example , such as those related to memory corruption , disappear once executables are recompiled with debug option . the invention is therefore applicable to any executable . to ensure that the released code performs well , executables are built with the maximum optimization level . therefore , the invention simplifies analysis of errors encountered in any optimized executable . the approach for analysis of optimized executables described herein may be implemented in a variety of ways and the invention is not limited to any particular implementation . the approach may be implemented as a stand - alone mechanism . furthermore , the approach may be implemented in computer software , hardware , or a combination thereof . fig4 is a block diagram that depicts a computer system 400 upon which an embodiment of the invention may be implemented . computer system 400 includes a bus 402 or other communication mechanism for communicating information , and a processor 404 coupled with bus 402 for processing information . computer system 400 also includes a main memory 406 , such as a random access memory ( ram ) or other dynamic storage device , coupled to bus 402 for storing information and instructions to be executed by processor 404 . main memory 406 also may be used for storing temporary variables or other intermediate information during execution of instructions to be executed by processor 404 . computer system 400 further includes a read only memory ( rom ) 408 or other static storage device coupled to bus 402 for storing static information and instructions for processor 404 . a storage device 410 , such as a magnetic disk or optical disk , is provided and coupled to bus 402 for storing information and instructions . computer system 400 may be coupled via bus 402 to a display 412 , such as a cathode ray tube ( crt ), for displaying information to a computer user . an input device 414 , including alphanumeric and other keys , is coupled to bus 402 for communicating information and command selections to processor 404 . another type of user input device is cursor control 416 , such as a mouse , a trackball , or cursor direction keys for communicating direction information and command selections to processor 404 and for controlling cursor movement on display 412 . this input device typically has two degrees of freedom in two axes , a first axis ( e . g ., x ) and a second axis ( e . g ., y ), that allows the device to specify positions in a plane . the invention is related to the use of computer system 400 for implementing the techniques described herein . according to one embodiment of the invention , those techniques are performed by computer system 400 in response to processor 404 executing one or more sequences of one or more instructions contained in main memory 406 . such instructions may be read into main memory 406 from another computer - readable medium , such as storage device 410 . execution of the sequences of instructions contained in main memory 406 causes processor 404 to perform the process steps described herein . in alternative embodiments , hard - wired circuitry may be used in place of or in combination with software instructions to implement the invention . thus , embodiments of the invention are not limited to any specific combination of hardware circuitry and software . the term “ computer - readable medium ” as used herein refers to any medium that participates in providing instructions to processor 404 for execution . such a medium may take many forms , including but not limited to , non - volatile media , volatile media , and transmission media . non - volatile media includes , for example , optical or magnetic disks , such as storage device 410 . volatile media includes dynamic memory , such as main memory 406 . transmission media includes coaxial cables , copper wire and fiber optics , including the wires that comprise bus 402 . transmission media can also take the form of acoustic or light waves , such as those generated during radio wave and infrared data communications . common forms of computer - readable media include , for example , a floppy disk , a flexible disk , hard disk , magnetic tape , or any other magnetic medium , a cd - rom , any other optical medium , punch cards , paper tape , any other physical medium with patterns of holes , a ram , a prom , and eprom , a flash - eprom , any other memory chip or cartridge , a carrier wave as described hereinafter , or any other medium from which a computer can read . various forms of computer readable media may be involved in carrying one or more sequences of one or more instructions to processor 404 for execution . for example , the instructions may initially be carried on a magnetic disk of a remote computer . the remote computer can load the instructions into its dynamic memory and send the instructions over a telephone line using a modem . a modem local to computer system 400 can receive the data on the telephone line and use an infrared transmitter to convert the data to an infrared signal . an infrared detector can receive the data carried in the infrared signal and appropriate circuitry can place the data on bus 402 . bus 402 carries the data to main memory 406 , from which processor 404 retrieves and executes the instructions . the instructions received by main memory 406 may optionally be stored on storage device 410 either before or after execution by processor 404 . computer system 400 also includes a communication interface 418 coupled to bus 402 . communication interface 418 provides a two - way data communication coupling to a network link 420 that is connected to a local network 422 . for example , communication interface 418 may be an integrated services digital network ( isdn ) card or a modem to provide a data communication connection to a corresponding type of telephone line . as another example , communication interface 418 may be a local area network ( lan ) card to provide a data communication connection to a compatible lan . wireless links may also be implemented . in any such implementation , communication interface 418 sends and receives electrical , electromagnetic or optical signals that carry digital data streams representing various types of information . network link 420 typically provides data communication through one or more networks to other data devices . for example , network link 420 may provide a connection through local network 422 to a host computer 424 or to data equipment operated by an internet service provider ( isp ) 426 . isp 426 in turn provides data communication services through the worldwide packet data communication network now commonly referred to as the “ internet ” 428 . local network 422 and internet 428 both use electrical , electromagnetic or optical signals that carry digital data streams . the signals through the various networks and the signals on network link 420 and through communication interface 418 , which carry the digital data to and from computer system 400 , are exemplary forms of carrier waves transporting the information . computer system 400 can send messages and receive data , including program code , through the network ( s ), network link 420 and communication interface 418 . in the internet example , a server 430 might transmit a requested code for an application program through internet 428 , isp 426 , local network 422 and communication interface 418 . processor 404 may execute the received code as it is received , and / or stored in storage device 410 , or other non - volatile storage for later execution . in this manner , computer system 400 may obtain application code in the form of a carrier wave . in the foregoing specification , the invention has been described with reference to specific embodiments thereof . it will , however , be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention . thus , the specification and drawings are , accordingly , to be regarded in an illustrative rather than a restrictive sense . the invention includes other contexts and applications in which the mechanisms and processes described herein are available to other mechanisms , methods , programs , and processes . in addition , in this disclosure , certain process steps are set forth in a particular order , and alphabetic and alphanumeric labels are used to identify certain steps . unless specifically stated in the disclosure , embodiments of the invention are not limited to any particular order of carrying out such steps . in particular , the labels are used merely for convenient identification of steps , and are not intended to imply , specify or require a particular order of carrying out such steps . furthermore , other embodiments may use more or fewer steps than those discussed herein .
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referring now to the drawings in which like reference numerals designate like parts , a blow - molding machine generally indicated by reference numeral 1 is shown in fig1 and 3 . the blow molding machine 1 includes an in - mold label dispenser 2 which utilizes a label transfer apparatus 3 having a label transfer carrier 4 in accordance with the present invention as is hereinafter described . the blow molding machine 1 also includes a mold 5 formed by a pair of mold halves 5a , 5b . the mold halves can be open as is shown in fig1 to remove a molded part . while the mold 5 is open , labels 6 can be appropriately positioned therein , as is shown in fig2 . with the mold 5 closed , plastic may be injected into the mold cavity 7 and blown or expanded to make a part , as is shown in fig3 . the mold cavity 7 is formed by cavity portions 7a , 7b in the respective mold halves 5a , 5b . usually the mold cavity walls are not planar or flat ; rather they typically have a curvature and often are stepped , e . g ., at the top where a spout of molded bottle part joins the body portion of such bottle . molded parts of different sizes and shapes usually require labels of correspondingly different sizes and shapes . the label transfer carrier 4 of the invention is of a size and shape which preferably correspond to those of the label 6 . additionally , the label transfer carrier 4 has a substantially planar label support surface , as is described further below , to hold and to support a label 6 securely and without distortion . the label transfer carrier 4 further is flexible to deform generally to a shape which tends to match that of the respective mold cavity wall 8b , for example , as the label transfer carrier is brought into engagement with the mold cavity wall to deposit a label 6 thereon . controlled vacuums from a vacuum source 9 are used to hold a label 6 on a label transfer carrier 4 and subsequently to hold a label on a mold cavity wall 8b , for example , on which the label has been positioned . schematic vacuum line connections are depicted at 9a , 9b , 9c . a supply 10 of labels 6 is provided on the label transfer apparatus 3 , as is seen in fig1 - 3 . the supply 10 includes a pair of cassettes 11a , 11b or other storage containers as supports for a plurality of labels . the cassette 11a may hold labels for one surface of the molded part and the cassette 11b may hold labels for a different surface . the label transfer apparatus 3 also includes a robot arm assembly 12 which supports the respective label transfer carriers 4 and moves them to respective cassettes to pick labels there and then to respective mold halves 5a , 5b to deposit the labels there . fig1 shows the first step of an in - mold labeling process . the mold halves 5a , 5b are open , and a plastic injection device 15 is disposed above mold halves 5a , 5b ready to inject the parison ( plastic intended to be molded ) after the labels 6 have been deposited on respective walls of the mold cavities 7a , 7b . a conventional control 16 , such as a conventional computer control , controls automatic operation of the blow molding machine 1 , label transfer apparatus 3 , and various other parts described herein . mold halves 5a , 5b are in an open position , ready to receive the labels 6 . the robot arm assembly 12 of the label transfer apparatus 3 has disposed on each end a label transfer carrier 4 of the present invention . if a label is to be positioned on only one surface of the molded part , then the robot arm assembly 12 may have only one arm or , alternatively , no label is picked up by one of the arms thereof . in operation of the blow molding machine 1 under control of the computer control 16 , the mold 5 is opened , as is shown in fig1 and the label transfer apparatus 3 is moving labels into the mold cavity 7 . the control 16 causes the label transfer apparatus 3 to place labels into engagement with respective mold cavity walls 8a , 8b . as is seen in fig2 the respective label transfer carriers 4 deform and press the labels 6 into engagement with the mold cavity walls 8a , 8b . the control 16 causes vacuum to be applied , e . g ., via lines 9a , 9b , to respective mold halves 5a , 5b to retain the labels 6 in position and causes the vacuum in line 9c to be terminated so that the labels 6 are released from the label transfer carriers 4 . the label transfer apparatus 3 then is moved to pick up more labels 6 , as is shown in fig3 and the mold 5 is closed to mold the part in conventional fashion . subsequently , the mold 5 is opened and the molded part including integral labels is discharged , and the operation is repeated to make more parts . as is shown in fig1 the label transfer apparatus 3 has picked up labels 6 from cassettes 11a , 11b . the labels 6 are held in a substantially flat position against the respective label transfer carrier 4 by the controlled vacuum source 9 . the robot arm assembly 12 moves the label transfer carriers 4 with the labels 6 from the respective cassettes 11a , 11b to the respective mold halves 5a , 5b . the robot arm assembly 12 pushes the label transfer carriers 4 against the respective mold cavity walls 8a , 8b as is shown in fig2 . the label transfer carriers 4 deform so as to conform to or to match the surface of the mold cavity walls 8a , 8b in order to ensure accurate placement of labels 6 . the controlled vacuum from vacuum source 9 via vacuum line 9c holding labels 6 against label transfer carriers 4 is cut off when the label transfer carriers 4 are pressed against the mold cavity walls 8a , 8b . vacuum from vacuum source 9 is applied via vacuum lines 9a , 9b through holes in the mold cavity walls 8a , 8b to remove labels 6 from their respective label transfer carrier 4 and affix the labels 6 to the respective mold cavity walls 8a , 8b . the robot arm assembly 12 is then removed from the mold 5 and returns to cassettes 11a , 11b to pick up labels 6 again , the first step in the next in - mold labeling process . the mold halves 5a , 5b are closed , as is shown in fig3 and the plastic injection device 15 is lowered into the mold 5 . a parison is blown into the mold 5 . the labels 6 bond to the parison as a result of heat and pressure . as such , molding and labeling occur simultaneously . the label transfer carrier 4 is shown in detail in fig4 - 8 . the face 20 of the label transfer carrier 4 is configured in a shape and size which matches that of the label 6 to be transferred . the face 20 has channels 21 which radiate vertically and horizontally such that the face 20 is divided into surface area quadrants or sections 22 . the channels 21 provide vacuum to a substantial portion of label 6 . if desired , the channels 21 may be arranged diagonally , circularly , curved , or in some arrangement other than that shown in the drawings . preferably the arrangement of channels 21 and surface area sections 22 provide sufficient vacuum to hold a label 6 securely without movement of the label ; to avoid distortion of the label by being drawn into a channel ; and / or to avoid damage to the label by a free unsupported edge of the label stock engaging another surface . preferably one or more channels 21 a generally circumscribe the perimeter of the face 20 inwardly spaced from an edge portion 22a of the face . such channels 21a and edge portion 22a of the face tend to cooperate with the label 6 to seal or otherwise to hold the label fully extended , in planar flat engagement with other portions of the face 20 . such sealing function enhances accurate positioning of the label 6 on the label transfer carrier 4 and on a mold cavity wall 8a , or 8b . controlled vacuum is supplied to the channels 21 , and hence to label 6 , via a central passageway 23 and portholes 24 . the central passageway 23 is located adjacent to the face 20 and runs the entire length of label transfer carrier 4 . the portholes 24 are spaced equidistant along the central axis of the central passageway 23 , thereby linking the channels 21 on the face 20 to the central passageway 23 . a controlled vacuum is applied to the central passageway 23 . as such , vacuum flows in the central passageway 23 , through the portholes 24 and along the channels 21 so as to hold a label 6 to the face 20 of the label transfer carrier 4 . preferably the label 6 is held against and , thus , is supported by the surface area sections 22 and does not distort while being so held . also , preferably the width of the channels 21 is sufficiently small as not to distort the label 6 by pulling the label 6 into a channel due to vacuum . further , preferably there is a suitable frictional force provided by the face 20 of the label transfer carrier 4 to the label 6 to help resist movement of the label 6 relative to the face as the vacuum is applied via channels 21 , as the label 6 is carried , by the label transfer apparatus 3 and as the label 6 is applied against a wall of the mold cavity 7 . thus , the material of the label transfer carrier 4 , especially at face 20 , preferably is not especially slippery and , more preferably has a sufficiently high coefficient of friction for the expressed purpose . the shape of the label transfer carrier 4 preferably is the same or substantially the same as the shape of the label 6 . additionally , preferably the channels 21 extend along and about the entire or substantially the entire perimeter of the face 20 so that the label 6 is held securely not only at the approximate center of the label 6 but also about the entire perimeter of the label 6 . using multiple channels 21 which extend from the central passageway 23 and spine 30 and providing broad area of support of the label 6 by the support sections 22 help to obtain uniform distribution of vacuum over substantially the entire label 6 . the label 6 , therefore , is held accurately and securely and such accuracy and security are maintained as the label transfer carrier 4 is urged into deforming abutment with a mold cavity wall , 8a for example , thereby to obtain relatively accurate and clean ( no folds , bends , tears , misalignments , etc .) positioning of the label 6 in the mold cavity 7 . in fig8 the back view of the label transfer carrier 4 is seen . a spine 30 is centered on the vertical axis of the label transfer carrier 4 for flexible support thereof . the spine 30 is rectangular , but of non - uniform height , possessing a u - shape cutaway 31 running along a portion of the spine 30 to facilitate secure mounting to the robot arm assembly 12 . the spine 30 also has a raised connection portion 32 , which contains an aperture 33 running transversely therethrough . a pin - pivot arrangement is used to connect the label transfer carrier 4 to the robot arm assembly 12 . the aperture 33 is designed to receive a pin ( not shown ) for connecting the label transfer carrier 4 to the robot arm assembly 12 . the connection portion 32 may be reinforced to support the weight and operation of the label transfer carrier 4 and to avoid wear . for the accuracy of positioning on the mentioned pin and to facilitate manual manipulations of the label transfer carrier 4 , the connection portion 32 may have a generally rectangular cross - section or shape , which also may improve strength and avoid wear , as was mentioned above . the spine 30 has a central passageway 23 cut through substantially its entire length . the central passageway 23 is attached to a source of suction or vacuum 9 , and serves as the central flow path for said vacuum or suction . also shown in fig8 are ribs 34 , which run perpendicular to the central axis of the spine 30 . the ribs 34 are tapered . the ribs 34 are thickest where they meet the spine 30 , and become gradually thinner as they approach the edge of the label transfer carrier 4 . although tapered in this embodiment , the ribs 34 could also be of uniform height . furthermore , the ribs 34 could run parallel to the spine 30 , or at some angle between parallel and the perpendicular configuration shown . the tapered ribs 34 preferably are located in the label transfer carrier 4 on the back side 35 thereof opposite a respective channel 21 . the ribs 34 , therefore , provide reinforcement for the label transfer carrier 4 to prevent the channels from changing cross - sectional shape , i . e ., width , as vacuum is applied and as the label transfer carrier is pressed against a mold cavity wall , such as wall 8b . therefore , the applied vacuum will be substantially uniform over the entire length of the channels 21 and face 20 of the label transfer carrier 4 . due to the tapered shape of the ribs 34 , such ribs are relatively more stiff adjacent the spine 30 and are less stiff and more flexible radially away or in any event a distance away from the spine 30 . by increasing flexibility of the ribs 34 remotely of the spine 30 , the face 20 is more easily deformed to follow the shape and contour of the mold cavity wall , such as wall 8b . therefore , the label transfer carrier 4 is able to provide substantially full support of the label 6 as the label 6 is picked from a cassette 11a , 11b , is moved into the mold 5 , and is placed securely into engagement with the mold cavity wall 8a , 8b . accordingly , such placement is made accurately and ordinarily without damaging the label 6 . fig4 is a side view of label transfer carrier 4 . the spine 30 has raised connection portion 32 in order to accommodate the aperture 33 which will be used for connecting the label transfer carrier 4 to the robot arm assembly 12 . the u - shaped cutaway 31 is more clearly shown in this view . the cutaway 31 provides the space necessary for attachment of the label transfer carrier 4 to the robot arm assembly 12 via the aperture 33 . the central passageway 23 may be plugged at one end , such as the same end of the label transfer carrier 4 as the u - shaped cutaway 31 is located . the vacuum source 9 is coupled to the other end of the central passageway 23 . portholes 24 , used to connect the central passageway 23 to the face 20 of the label transfer carrier 4 , are more clearly shown . the portholes 24 provide a path for the vacuum from central passageway 23 to the face 20 of the label transfer carrier 4 . fig7 is a top view of the label transfer carrier 4 . this figure more clearly illustrates how the ribs 34 taper , being thickest where they meet the spine 30 and gradually becoming thinner as they approach the edge of label transfer carrier 4 . moreover , fig7 illustrates that central passageway 23 has a u - shape , with the opening of the u adjacent the back side of face 20 . the shape of central passageway 23 is only exemplary . the central passageway 23 could be circular or any other shape suitable for passage of vacuum or suction . fig6 is a sectional view of label transfer carrier 4 . this figure illustrates that all portions of the label transfer carrier 4 may be made from the same material . the label transfer carrier 4 preferably has a unibody construction . the entire label transfer carrier 4 is made out of the same material , such material being flexible in nature . this facilitates manufacturing . an example of a good material for construction of this transfer apparatus would be silicone . silicone serves as a useful material for constructing the label transfer carrier 4 in that it is flexible so as to provide a relatively flat surface that will conform to the mold cavity walls 8a , 8b that the label 6 is being deposited on . in addition , silicone provides a non - stick surface which prevents the label 6 from sticking and thereby becoming attached to the label transfer carrier 4 . however , the silicone material has suitable coefficient of friction characteristics to help avoid slippage of the label 6 relative to the label transfer carrier 4 . silicone , however , is not the only material that can be utilized for this label transfer carrier 4 . other materials could be flexible plastics , flexible metals , rubber , or any other suitable materials which are flexible and have a non - stick surface . in another embodiment of this invention , illustrated in fig9 and 10 , a plurality of holes 40 are contained on the face 41 of the label transfer carrier 4 . the holes 40 are connected to the central passageway 42 via channels 43 contained within the ribs 44 . as in the previous embodiment , the central passageway 42 is connected to a source of vacuum or suction . the holes 40 replace the channels previously described , and illustrated in fig5 . the holes 40 would be relatively small , generally considered pinholes , so as to avoid the label 6 being drawn into the holes 40 , thereby distorting the label 6 and resulting in misplaced or misaligned labels . the device according to the present invention offers numerous advantages over known devices . since the apparatus is made of a flexible material , it has the capability of conforming to mold cavity walls 8a , 8b while depositing the label 6 . in addition , this flexibility prevents any unnecessary scoring of mold cavity walls 8a and 8b , which may result in imperfections in the final molded product . additionally , by providing a face 20 which conforms to the size and shape of the label 6 to be deposited , the label carrier 4 reduces the number of deformities occurring in the label 6 , therefore minimizing inconsistencies in positioning of the label 6 on mold cavity walls 8a and 8b .
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fig1 shows , in a first illustrative embodiment , a cannula assembly consisting of an injection cannula 1 , a cannula guide 10 for the injection cannula 1 , and a pressure force distributor 6 . the cannula assembly serves for subcutaneous administration of a liquid product , e . g . a medicament , for example insulin . the injection cannula 1 has a penetrating portion 3 with a length dimensioned for the subcutaneous administration and with a free cannula tip 2 at its distal end . the proximal end of the penetrating portion 3 is adjoined by a securing portion 4 which is at an angle , in the illustrative embodiment at a right angle , to the penetrating portion 3 . the penetrating portion 3 and the securing portion 4 are made in one piece from a plastic material . the securing portion 4 is connected to a catheter for delivery of the product , in the present illustrative embodiment a liquid medicament . the securing portion 4 lies on a top face of the pressure force distributor 6 and , at the area of the angle , is guided through a central passage of the pressure force distributor 6 so that the penetrating portion 3 protrudes freely from the underside of the pressure force distributor 6 and at right angles to said underside . if the injection cannula is inclined relative to a tissue surface for the purpose of oblique insertion through the skin , the angle would be obtuse , for example 120 °. the pressure force distributor 6 has a planar configuration , in the form of a round plate in the illustrative embodiment . the injection cannula 1 and the pressure force distributor 6 are separately produced parts . the injection cannula 1 is held with frictional engagement in the central passage of the pressure force distributor 6 and is secured lying flat on the top face of the pressure force distributor 6 . in a modified design , the injection cannula 1 and the pressure force distributor 6 can also be formed in one piece , or the injection cannula 1 can be embedded with its securing portion 4 in the pressure force distributor 6 and cohesively connected to the pressure force distributor 6 . the cannula guide 10 is an air - filled balloon with a flexible balloon wall 11 , so that a cannula guide is obtained which has a flexible axial portion 15 between an underside 13 and a top face 14 . the balloon 10 is annular and encloses the penetrating portion 3 of the injection cannula 1 . the cannula tip 2 is set back a short distance behind an underside 13 of the balloon 10 . the pressure force distributor 6 is secured lying on the top face 14 of the balloon 10 . the balloon 10 bears with its internal pressure uniformly over the entire penetrating portion 3 . the internal pressure of the balloon 10 is at least as great as the atmospheric pressure , and an overpressure prevails inside the balloon wall 11 . arranged in the balloon 10 there is a support structure 12 , approximately at the axial center of the penetrating portion 3 . the support structure 12 , as the name is intended to suggest , is planar and flat in the axial direction , i . e . in the longitudinal direction of the injection cannula 1 . in the illustrative embodiment , the support structure is a thin support plate , e . g ., a support membrane , which can be deformed into a flat shell . the support structure 12 extends , transversely with respect to the injection cannula 1 , across the entire radial width of the balloon 10 , from its annular outside wall to its annular inside wall , and thus forms , in addition to the annular inside wall of the balloon 10 running along the length of the penetrating portion 3 , a local support for the injection cannula 1 . the underside 13 of the balloon 10 is provided , for example coated , with an adhesive , so that an outer adhesive surface is obtained which ensures an adhesive connection of the cannula assembly 10 to the surface of the body tissue , generally the surface of the skin . the coating may be in the form of a layer or a portion of the wall of the balloon may be formed to have adhesive properties . the balloon wall 11 is likewise provided with an adhesive across its entire inner surface . similarly , the support structure 12 is also provided with an adhesive on its underside directed toward the underside 13 and on its top face directed toward the top face 14 . in this way , inner adhesive surfaces 16 are obtained which adhere to one another in a collapsed state of the balloon 10 . it would in principle also suffice to provide an adhesive only on the underside and top face of the planar support structure 12 and / or only on the inner surfaces of the balloon wall 11 on the underside 13 and top face 14 of the balloon 10 . fig2 , 3 and 4 show the cannula assembly of the first illustrative embodiment in use . in fig2 , the cannula assembly is placed on the surface of the body tissue 9 and fixed adhesively by means of its underside 13 formed as an outer adhesive surface . no external force is applied to the cannula assembly , or at most a light pressure force which is directed axially in the direction of the surface of the body tissue 9 and which is sufficient to establish the adhesive connection . the cannula tip 2 is located a short distance above the surface of the body tissue 9 , i . e . there is still no contact with the body tissue 9 . fig3 shows the cannula assembly of the first illustrative embodiment in the initial phase of insertion of the injection cannula 1 into the skin . by means of a pressure force f exerted on the pressure force distributor 6 in axial continuation of the penetrating portion 3 and directed axially in the direction of the body tissue 9 , the pressure force distributor 6 presses against the balloon 10 via the top face 14 of said balloon 10 , and the latter accordingly deforms under the pressure force f . because of the pressure force f , the injection cannula 1 moves axially in the direction toward the surface of the body tissue 9 , comes into contact with the surface and initially just presses against the surface , until the surface has reached a critical tension at which the cannula tip 2 pierces the surface and penetrates into the body tissue 9 . fig3 shows the cannula assembly directly before it pierces the surface of the body tissue 9 . during the movement toward the surface of the body tissue 9 , during the piercing of the surface and during the penetration into the body tissue 9 , the penetrating portion 3 of the injection cannula 1 slides along the inside wall of the balloon 10 surrounding it . the support structure 12 stabilizes and guides the injection cannula 1 in the first instance . the balloon 10 , in which the support structure 12 is accommodated , additionally supports and guides the penetrating portion 3 of the injection cannula 1 throughout the entire injection procedure . the support structure 12 and the balloon 10 thus stabilize the penetrating portion 3 against bending or even buckling . the cannula portion protruding freely from the underside of the pressure force distributor 6 , the penetrating portion 3 , can therefore have less flexural rigidity , namely a lower modulus of elasticity and / or a lower geometrical moment of inertia , than conventional injection cannulas which are not laterally supported during the piercing of the tissue surface and their onward penetration into the tissue . the injection cannula 1 is accordingly less “ bulky ” when it is sitting in the body tissue 9 during the administration of product . the balloon 10 is constructed such that it bursts when its internal pressure exceeds a predetermined limit value . this limit value is provided for through a suitable dimensioning of the balloon wall 11 , i . e . through the use of a suitable wall material and through the wall thickness . the balloon wall 11 is configured such that , when the pressure limit value is exceeded , it tears and the balloon 10 suddenly collapses . the design of the balloon 10 is advantageously such that the balloon 10 bursts after the cannula tip 2 is already pressing against the body tissue 9 but when the cannula tip 2 has not yet penetrated the body tissue 9 . the penetration , i . e . piercing of the tissue surface , takes place directly together with the collapse of the balloon 10 . the balloon 10 , and the cannula guide according to the present invention in general , is also advantageously configured in such a way that , by means of the manual pressure on the top face 14 , i . e . the application of the pressure force f , the surface of the body tissue 9 is tensioned at the injection site and , in this way , the pressure force required for penetration of the surface is reduced . fig4 shows the cannula assembly in the implanted state . the injection cannula 1 protrudes with its penetrating portion 3 into the body tissue 9 . the balloon 10 has completely or substantially completely collapsed and forms a flat plaster adhering to the surface of the body tissue 9 , since the outer adhesive surface on the underside 13 of the previous balloon 10 adheres to the body tissue 9 and the inner surfaces 16 adhere to one another . in this state , the product is administered through the injection cannula 1 over the course of several days . fig5 shows a second illustrative embodiment of a cannula assembly consisting of an injection cannula 1 , a pressure force distributor 6 and a cannula guide 17 . the injection cannula 1 and the pressure force distributor 6 are designed as in the first illustrative embodiment . the cannula guide 17 also forms a flexible axial portion 15 which , as in the first illustrative embodiment , extends from the underside 13 to the top face 14 of the cannula guide 17 . the cannula guide 17 of the second illustrative embodiment is designed as a bellows with pairs of support webs 18 pointing at an angle to one another and to the penetrating portion 3 , and folding joints 19 a and 19 b which are in each case formed between two adjacent support webs 18 . the inner folding joints 19 a are not only joints , but at the same time also form a supporting and guiding position for the penetrating portion 3 . the support webs 18 are of different lengths , with the length increasing from the underside 13 to the top face 14 . two support webs 18 of identical length are in each case connected to one another in a foldable manner at the outer folding joints 19 b . when the assembly is placed in position on the surface of the body tissue 9 , the most distal support web 18 points obliquely and radially outward from the most distal inner folding joint 19 a , such that an open funnel is obtained on the underside 13 . therefore , as in the first illustrative embodiment , when a pressure force f is exerted , the tissue surface is tensioned at the injection site and , this way , penetration of the tissue surface is made easier . the bellows structure forming the cannula guide 17 elastically yields in the axial direction when an axial pressure force f is exerted , up to the point where a limit value is reached for the axial pressure force f , but abruptly collapses when the limit value is exceeded . the cannula guide 17 is designed like the cannula guide 10 of the first illustrative embodiment in terms of its deformation properties , as far as the initial elastic resiliency and abrupt collapse are concerned . fig6 shows the cannula assembly of the second illustrative embodiment in the implanted state of the injection cannula 1 , in which the latter &# 39 ; s penetrating portion 3 has penetrated into the body tissue 9 . in this state , the cannula guide 17 of the second illustrative embodiment likewise forms a flat plaster , because the support webs 18 are folded in pairs on top of one another . to stabilize the cannula guide 17 in the folded state , the support webs 18 are also provided with inner adhesive surfaces 16 . moreover , those support webs 18 with undersides pointing toward the body tissue 9 are provided with outer adhesive surfaces 13 a on these undersides , such that the support webs 18 on the one hand adhere to one another via their outer surfaces and , because the support web lengths increase from distal to proximal , they also adhere directly on the surface of the body tissue . fig7 shows a cannula assembly of a third illustrative embodiment . the cannula assembly differs from the cannula assemblies of the other illustrative embodiments in terms of its cannula guide 20 , which in the third illustrative embodiment is designed as an umbrella structure , i . e ., as a structure which can be opened , expanded or spread open in the manner of an umbrella and can be shorted in the length direction of the injection cannula 1 . fig8 shows the cannula assembly of the third illustrative embodiment in a state in which it is placed on the body tissue 9 before insertion of the injection cannula 1 into the skin . as can be seen from fig8 , the cannula guide 20 comprises several spreadable struts 21 which are each attached in an articulated manner to an underside of the force distributor 6 directed toward the body tissue 9 . the articulated attachment is such that the inherently axially stiff spreadable struts 21 can be pivoted toward the underside of the force distributor 6 at their respective articulation . in relation to the injection cannula 1 , the spreadable struts 21 point radially outward from their articulations . they are arranged in uniform distribution around the injection cannula 1 . the spreadable struts 21 are each supported on the injection cannula 1 via several support struts 22 . the support struts 22 are each attached in an articulated manner to the spreadable struts 21 and form an axial slide guide for the injection cannula 1 , which axial guide laterally supports the injection cannula 1 and axially guides it in a linear movement . the articulated attachments of the support struts 22 to the spreadable struts 21 are designated by 23 , and the slide guides at the respective other end of the support struts 22 are designated by 24 . along the spreadable struts 21 , the articulated attachments 23 are each at a distance from the articulated attachments of the spreadable struts 21 on the force distributor 6 which corresponds to the length of the respective support strut 22 . thus , for example , the support struts 22 which have the greatest distance a from the articulated attachments of the spreadable struts 21 on the force distributor 6 each have a length a corresponding to the distance . the support struts 22 arranged closer to the force distributor 6 each have lengths corresponding to their distances measured along the spreadable struts 21 . with uniform distribution , as shown in the illustrative embodiment , lengths 2 / 3 a and 1 / 3 a are obtained for the further support struts 22 . fig9 shows the cannula assembly of the third illustrative embodiment with the injection cannula 1 inserted into the body tissue 9 . the spreadable struts 21 are pivoted , about their articulated attachments on the force distributor 6 , toward the force distributor 6 and are thus spread open . the support struts 22 are pivoted about their articulated attachments 23 toward their respective spreadable strut 21 and come to lie one on the other , so that overall a flat structure is obtained in the spread or compressed state , which flat structure at the same time also serves as a plaster for attachment to the tissue surface . as is indicated in fig7 and can be seen from fig9 , the cannula assembly of the third illustrative embodiment comprises a plaster 25 which , in accordance with the spreading mechanism , can be designated as an umbrella - type plaster . the plaster is similar to the cover of an umbrella . it is secured on or carried by the spreadable struts 21 . in the non - inserted state , i . e . before being spread open , it hangs loosely like the cover of an umbrella between the spreadable struts 21 , whereas in the inserted state it is stretched out and adheres with its underside on the tissue surface . fig1 shows another illustrative embodiment of a cannula assembly in accordance with the present invention . the cannula assembly again consists of the injection cannula 1 with the pressure force distributor 6 and a cannula guide 26 . the injection cannula 1 and the pressure force distributor 6 are formed as in the other illustrative embodiments . like the cannula guide 10 of the first illustrative embodiment and in principle also the cannula guide 17 of the second illustrative embodiment , the cannula guide 26 is designed as a hollow chamber structure . however , the hollow chamber structure 26 of fig1 is divided into a large number of hollow cells or hollow chambers . the hollow chamber structure 25 is anisotropic in the sense that it offers less resistance to deformation in the longitudinal direction of the penetrating portion 3 than it does to a deformation in the transverse direction . in one embodiment , the hollow chamber structure 26 is a honeycomb structure with walls which between them enclose the cavities of the honeycomb structure and are arranged uniformly . the injection cannula extends through the honeycomb structure and is laterally supported and axially guided by the walls of the honeycomb structure . fig1 shows the cannula assembly of the embodiment of fig1 with the injection cannula 1 inserted into the body tissue 9 . the hollow chamber structure 26 has collapsed axially . the hollow chamber structure 26 is also provided on its underside with an adhesive surface for securing it on the body tissue 9 . fig1 shows another illustrative embodiment of a cannula assembly , which is a modification of the embodiment of fig1 . a porous material forms the cannula guide 27 as a porous structure , which is likewise to be designated as a hollow chamber structure . the porosity of the material is a closed porosity , for example of the kind that sponge structures have . in fig1 , the hollow chamber structure 27 is shown with a coarser porosity on one side of the injection cannula 1 than on the other . however , actual cannula assemblies do not have this kind of difference in porosity , and instead they have a porosity comprising pores of randomly distributed pore size , although this porosity is uniformly present in the hollow chamber 27 seen as a whole . embodiments of the present invention , including preferred embodiments , have been presented for the purpose of illustration and description . they are not intended to be exhaustive or to limit the invention to the precise forms and steps disclosed . obvious modifications or variations are possible in light of the above teachings . the embodiments were chosen and described to provide the best illustration of the principles of the invention and the practical application thereof , and to enable one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated . all such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth they are fairly , legally , and equitably entitled .
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the invention can perhaps be better understood by referring to the drawings . fig1 is an oblique , perspective view of a sensor 2 , an embodiment of the invention . sensor 2 preferably has an outer coating of biocompatible silicone . fig2 is a top , partial cross - section of a schematic representation of sensor 2 where a wire spiral inductor coil 4 is positioned in planar fashion in a substrate 6 . optionally sensor 2 may have recesses 8 , each with a hole 10 , to receive a tether wire ( not shown here ) for delivery of the device into a human patient , as described below . in the embodiment of the invention shown in fig3 , a wire 12 connects coil 4 to a capacitor plate 14 positioned within coil 4 . fig4 is a slightly oblique cross - section across its width of the embodiment of the invention shown in fig2 , where it can be seen that sensor 2 is comprised of a lower substrate 20 and an upper substrate 22 . lower substrate 20 and upper substrate 22 are constructed from a suitable material , such as glass , fused silica , sapphire , quartz , or silicon . fused silica is the preferred material of construction . lower substrate 20 has on its upper surface 24 an induction coil 26 , and upper substrate 22 has a recess 28 with a surface 30 having an induction coil 32 thereon . the top surface of upper substrate 22 forms a membrane 34 capable of mechanically responding to changes in a patient &# 39 ; s physical property , such as pressure . the end 36 of sensor 2 has a notch or recess 38 . in similar fashion , fig5 is a slightly oblique cross - section across its width of the embodiment of the invention shown in fig3 . the primary difference between fig4 and 5 is the presence of upper capacitor plate 42 and lower capacitor plate 44 on surfaces 24 and 30 , respectively . in the embodiment of fig4 , the spiral coil 4 itself acts as the capacitive element of the lc circuit that describes the operation of the sensor . fig6 is a variation of fig5 where the outline of upper substrate 22 is shown but the details of lower substrate 20 can be seen more clearly , including individual coils of inductor coil 26 . a wire 46 connects lower capacitor plate 44 to induction coil 26 . the size of the sensors of the invention will vary according to factors such as the intended application , the delivery system , etc . the oval sensors are intended to be from about 0 . 5 in . to about 1 in . in length and from about 0 . 1 in . to about 0 . 5 in . in width , with a thickness of from about 0 . 05 in . to about 0 . 30 in . as shown in fig4 and 5 , upper substrate 22 can be significantly thinner than lower substrate 20 . by way of example , upper substrate 22 may be from about 100 to about 300 microns thick , whereas lower substrate 20 may be from about 500 to about 1500 microns thick . in an alternate embodiment of the invention , both substrates may be of the same thickness ranging from about 100 to about 1000 microns . in the embodiment of the invention shown in fig7 , a sensor 50 is attached to a hollow tube 52 that has a flexible tip 54 . fig8 shows the sensor 50 and specific features of the tethering system , namely proximal holes 56 and distal holes 58 disposed in a hollow tube 52 . fig9 shows a tether wire 60 that is attached to sensor 50 at sensor holes 62 and hollow tube holes 56 and 58 , and a tether wire 60 is positioned slidably within a hollow tube 52 . a better appreciation of certain aspects of the invention , especially of a delivery system , can be obtained from fig1 which shows a vessel introducer 66 and the delivery system 68 . further details of the delivery system are shown in fig1 . a double lumen tube 70 has one channel that accepts a guidewire 72 and a second channel that accepts the sensor tether wire . the guidewire 72 can be advanced through hub 74 . a rigid delivery capsule 78 is disposed at the far end of the delivery catheter and flexible tip 80 is connected to the catheter via a hollow tube 81 extending through the delivery capsule 78 . a sensor 82 is positioned inside a slot in the delivery capsule 78 proximal to flexible tip 80 . fig1 shows a lateral , cross - sectional view of this arrangement where the sensor 82 is inside the slot of delivery capsule 78 and the flexible tip 84 of the tether wire is disposed between the end of delivery capsule 78 and flexible tip 80 . fig1 shows delivery catheter 68 loaded into the previously placed vessel introducer 66 prior to introduction of the sensor into the body . fig1 shows that the sensor 82 on tether tube 52 has been advanced out of delivery capsule 78 and the delivery catheter has been removed . in fig1 , the tether wire has been retracted into the hollow tether tube , releasing the sensor . the tether wire , tether tube and vessel introducer 66 are then all removed . the pressure sensor of the invention can be manufactured using micro - machining techniques that were developed for the integrated circuit industry . an example of this type of sensor features an inductive - capacitive ( lc ) resonant circuit with a variable capacitor , as is described in allen et al ., u . s . pat . nos . 6 , 111 , 520 and 6 , 278 , 379 , all of which are incorporated herein by reference . the sensor contains two types of passive electrical components , namely , an inductor and a capacitor . the sensor is constructed so that the fluid pressure at the sensor &# 39 ; s surface changes the distance between the capacitor &# 39 ; s substantially parallel plates and causes a variation of the sensor &# 39 ; s capacitance . in a preferred embodiment the sensor of the invention is constructed through a series of steps that use standard mems manufacturing techniques . fig1 shows the first step of this process in which a thin layer of metal ( protective mask ) 90 is deposited onto the top and bottom surface of a fused silica substrate 92 ( alternative materials would be glass , quartz , silicon or ceramic ). substrate diameters can range from about 3 to about 6 in . substrate thickness can range from about 100 to about 1500 microns . a pattern mask is then created on one side of the substrate to define the location of cavities that need to be etched into the surface . fig1 shows trenches or cavities 94 are etched into one surface of the substrate 92 to depths ranging from about 20 to about 200 microns . this etching is accomplished using any combination of standard wet and dry etching techniques ( acid etch , plasma etch , reactive ion etching ) that are well known in the mems industry . the protective metal mask is removed using standard metal etching techniques in fig1 , a thin metal seed layer 96 ( typically chromium ) is deposited on the etched side of the substrate using standard metal deposition techniques such as sputtering , plating or metal evaporation . in fig1 a layer of photo - resistive material 98 is applied to the etched surface of the substrate using standard spin coating procedures . fig2 shows that a mask aligner and uv light 102 is used in a photolithographic processes to transfer a pattern from a mask 104 to the photoresist coating on the substrate . in fig2 , the non - masked portions of the photoresist are removed chemically creating a mold 106 of the desired coil pattern . fig2 shows copper 108 electroplated into the mold to the desired height , typically from about 5 to about 35 microns . in fig2 , the photoresist 110 and seed layer 112 are etched away leaving the plated copper coils 114 . in fig2 , the two processed substrates 118 and 120 are aligned such that the cavities 122 and 124 with plated coils are precisely orientated in over one another and temporarily bonded to each other . fig2 and 26 show that by using a beam 125 from a co2 laser 126 ( or other appropriate laser type ), the individual sensors 130 are cut from the glass substrate . fig2 shows an early stage in the cutting process where the laser beam 125 has only just begun heating up the surrounding material . fig2 shows a later stage in the process where one side has already been completely cut and sealed , and the laser beam is in the process of cutting and sealing the other side . the laser cutting process results in a permanent , hermetic seal between the two glass substrates . the laser energy is confined to a precise heat effect zone 128 in which the hermetic seal is created . fig2 represents an embodiment of the invention wherein a sensor 132 attached to a delivery catheter 134 has a stabilizer or basket 136 . the stabilizer can be any appropriate device or structure that can be fixedly attached to a sensor of the invention to assist the sensor in maintaining position , location , and / or orientation after the sensor is delivered to an intended site . the stabilizer can comprise any appropriate physiologically acceptable rigid or slightly flexible material , such as stainless steel , nitinol , or a radiopaque metal or alloy . this sensor design provides many important benefits to sensor performance . the hermetic seal created during the laser cutting process , coupled with the design feature that the conductor lines of the sensor are sealed within the hermetic cavity , allows the sensor to remain stable and drift free during long time exposures to body fluids . in the past , this has been a significant issue to the development of sensors designed for use in the human body . the manufacturing methodology described above allows many variations of sensor geometry and electrical properties . by varying the width of the coils , the number of turns and the gap between the upper and lower coils the resonant frequency that the device operates at and the pressure sensitivity ( i . e ., the change in frequency as a result of membrane deflection ) can be optimized for different applications . in general , the design allows for a very small gap between the coils ( typically between about 3 and about 35 microns ) that in turn provides a high degree of sensitivity while requiring only a minute movement of the coils to sense pressure changes . this is important for long term durability , where large membrane deflection could result in mechanical fatigue of the pressure sensing element . the thickness of the sensor used can also be varied to alter mechanical properties . thicker substrates are more durable for manufacturing . thinner substrates allow for creating of thin pressure sensitive membranes for added sensitivity . in order to optimize both properties the sensors may be manufactured using substrates of different thicknesses . for example , one side of the sensor may be constructed from a substrate of approximate thickness of 200 microns . this substrate is manufactured using the steps outlined above . following etching , the thickness of the pressure sensitive membrane ( i . e ., the bottom of the etched trench ) is in the range of from about 85 to about 120 microns . the matching substrate is from about 500 to about 1000 microns thick . in this substrate , the trench etching step is eliminated and the coils are plated directly onto the flat surface of the substrate extending above the substrate surface a height of from about 20 to about 40 microns . when aligned and bonded , the appropriate gap between the top and bottom coils is created to allow operation preferably in a frequency range of from 30 to 45 mhz and have sensitivity preferably in the range of from 5 to 15 khz per millimeter of mercury . due to the presence of the from about 500 to about 1000 micron thick substrate , this sensor will have added durability for endovascular delivery and for use within the human body . the sensor exhibits the electrical characteristics associated with a standard lc circuit . an lc circuit can be described as a closed loop with two major elements , a capacitor and an inductor . if a current is induced in the lc loop , the energy in the circuit is shared back and forth between the inductor and capacitor . the result is an energy oscillation that will vary at a specific frequency . this is termed the resonant frequency of the circuit and it can be easily calculated as its value is dependent on the circuit &# 39 ; s inductance and capacitance . therefore , a change in capacitance will cause the frequency to shift higher or lower depending upon the change in the value of capacitance . as noted above , the capacitor in the assembled pressure sensor consists of the two circular conductive segments separated by an air gap . if a pressure force is exerted on these segments it will act to move the two conductive segments closer together . this will have the effect of reducing the air gap between them which will consequently change the capacitance of the circuit . the result will be a shift in the circuit &# 39 ; s resonant frequency that will be in direct proportion to the force applied to the sensor &# 39 ; s surface . because of the presence of the inductor , it is possible to electromagnetically couple to the sensor and induce a current in the circuit . this allows for wireless communication with the sensor and the ability to operate it without the need for an internal source of energy such as a battery . thus , if the sensor is located within the sac of an aortic aneurysm , it will be possible to determine the pressure within the sac in a simple , non - invasive procedure by remotely interrogating the sensor , recording the resonant frequency and converting this value to a pressure measurement . the readout device generates electromagnetic energy that penetrates through the body &# 39 ; s tissues to the sensor &# 39 ; s implanted location . the sensor &# 39 ; s electrical components absorb a fraction of the electromagnetic energy that is generated by the readout device via inductive coupling . this coupling induces a current in the sensor &# 39 ; s circuit that oscillates at the same frequency as the applied electromagnetic energy . due to the nature of the sensor &# 39 ; s electro - mechanical system there exists a frequency of alternating current at which the absorption of energy from the readout device is at a maximum . this frequency is a function of the capacitance of the device . therefore , if the sensor &# 39 ; s capacitance changes , so will the optimal frequency at which it absorbs energy from the readout device . since the sensor &# 39 ; s capacitance is mechanically linked to the fluid pressure at the sensor &# 39 ; s surface , a measurement of this frequency by the readout device gives a relative measurement of the fluid pressure . if calibration of the device is performed , then an absolute measurement of pressure can be made . see , for example , the extensive discussion in the allen et al . patent , again incorporated herein by reference , as well as gershenfeld et al ., u . s . pat . no . 6 , 025 , 725 , incorporated herein by reference . alternative readout schemes , such as phase - correlation approaches to detect the resonant frequency of the sensor , may also be employed . the pressure sensor is made of completely passive components having no active circuitry or power sources such as batteries . the pressure sensor is completely self - contained having no leads to connect to an external circuit or power source . furthermore , these same manufacturing techniques can be used to add additional sensing capabilities , such as the ability to measure temperature by the addition of a resistor to the basic lc circuit or by utilizing changes in the back pressure of gas intentionally sealed within the hermetic pressure reference to change the diaphragm position and therefore the capacitance of the lc circuit . it is within the scope of the invention that the frequency response to the sensor will be in the range of from about 1 to about 200 mhz , preferably from about 1 to about 100 mhz , and more preferably from about 2 to about 90 mhz , and even more preferably from about 30 to about 45 mhz , with a q factor of from about 5 to about 150 , optimally from about 5 to about 80 , preferably from about 40 to about 100 , more preferably from about 50 to about 90 . in a further embodiment of the invention there is no direct conductor - based electrical connection between the two sides of the lc circuit . referring again to the sensor described in the allen et al . patents , the device is constructed using multiple layers upon lie the necessary circuit elements . disposed on the top and bottom layer are metal patterns constructed using micro - machining techniques which define a top and bottom conductor and a spiral inductor coil . to provide for an electrical contact between the top and bottom layers small vias or holes are cut through the middle layers . when the layers are assembled , a metal paste is forced into the small vias to create direct electrical connections or conduits . however , experimentation has shown that due to additional capacitance that is created between the top and bottom inductor coils , a vialess operational lc circuit can be created . this absence of via holes represents a significant improvement to the sensor in that it simplifies the manufacturing process and , more importantly , significantly increases the durability of the sensor making it more appropriate for use inside the human body . further , the invention is not limited to the implantation of a single sensor . multiple pressure sensors may be introduced into the aneurysm space , each being positioned at different locations . in this situation , each sensor may be designed with a unique signature ( obtained by changing the resonant frequency of the sensor ), so that the pressure measurement derived from one sensor can be localized to its specific position within the aneurysm . a significant design factor that relates to the performance of the sensor and the operation of the system is the quality factor ( q ) associated with the sensor . the value of q is one of the key determinates as to how far from the sensor the external read - out electronics can be located while still maintaining effective communication . q is defined as a measure of the energy stored by the circuit divided by the energy dissipated by the circuit . thus , the lower the loss of energy , the higher the q . additional increases in q can be achieved by removing the central capacitive plate and using capacitive coupling between the copper coils to act as the capacitor element . in operation , energy transmitted from the external read - out electronics will be stored in the lc circuit of the sensor . this stored energy will induce a current in the lc loop which will cause the energy to be shared back and forth between the inductor and capacitor . the result is an oscillation that will vary at the resonant frequency of the lc circuit . a portion of this oscillating energy is then coupled back to the receiving antenna of the read - out electronics . in high q sensors , most of the stored energy is available for transmission back to the electronics , which allows the distance between the sensor and the receiving antenna to be increased . since the transmitted energy will decay exponentially as it travels away from the sensor , the lower the energy available to be transmitted , the faster it will decay below a signal strength that can be detected by the receiving antenna and the closer the sensor needs to be situated relative to the receiving electronics . in general then , the lower the q , the greater the energy loss and the shorter the distance between sensor and receiving antenna required for sensor detection . the q of the sensor will be dependent on multiple factors such as the shape , size , diameter , number of turns , spacing between turns and cross - sectional area of the inductor component . in addition , q will be greatly affected by the materials used to construct the sensors . specifically , materials with low loss tangents will provide the sensor with higher q factors . the implantable sensor ascending to the invention is preferably constructed of various glasses or ceramics including but not limited to fused silica , quartz , pyrex and sintered zirconia , that provide the required biocompatibility , hermeticity and processing capabilities . preferably the materials result in a high q factor . these materials are considered dielectrics , that is , they are poor conductors of electricity , but are efficient supporters of electrostatic or electroquasiatatic fields . an important property of dielectric materials is their ability to support such fields while dissipating minimal energy . the lower the dielectric loss ( the proportion of energy lost ), the more effective the dielectric material in maintaining high q . for a lossy dielectric material , the loss is described by the property termed “ loss tangent .” a large loss tangent reflects a high degree of dielectric loss . with regard to operation within the human body , there is a second important issue related to q , namely , that blood and body fluids are conductive mediums and are thus particularly lossy . the consequence of this fact is that when a sensor is immersed in a conductive fluid , energy from the sensor will dissipate , substantially lowering the q and reducing the sensor - to - electronics distance . for example , the sensors described above were immersed in saline ( 0 . 9 % salt solution ), and the measured q decreased to approximately 10 . it has been found that such loss can be minimized by further separation of the sensor from the conductive liquid . this can be accomplished , for example , by encapsulating the sensor in a suitable low - loss - tangent dielectric material . however , potential encapsulation material must have the flexibility and biocompatibility characteristics of the sensor material and also be sufficiently compliant to allow transmission of fluid pressure to the pressure sensitive diaphragm . a preferred material for this application is polydimethylsiloxane ( silicone ). as an example , a thin ( i . e ., 200 micron ) coating of silicone was applied to the sensor detailed above . this coating provided sufficient insulation to maintain the q at 50 in a conductive medium . equally important , despite the presence of the silicone , adequate sensitivity to pressure changes was maintained and the sensor retained sufficient flexibility to be folded for endovascular delivery . one additional benefit of the silicone encapsulation material is that it can be optionally loaded with a low percentage ( i . e ., 10 - 20 %) of radio - opaque material ( e . g ., barium sulfate ) to provide visibility when examined using fluoroscopic x - ray equipment . this added barium sulfate will not affect the mechanical and electrical properties of the silicone . as described above , it is desirable to increase the q factor of a sensor , and the q factor can be increased by suitable selection of sensor materials or a coating , or both . preferably both are used , because the resulting high q factor of a sensor prepared in this fashion is especially suitable for the applications described . when introduced into the sac of an abdominal aorta , the pressure sensor can provide pressure related data by use of an external measuring device . as disclosed in the allen et al . patents , several different excitation systems can be used . the readout device generates electromagnetic energy that can penetrate through the body &# 39 ; s tissues to the sensor &# 39 ; s implanted location . the sensor &# 39 ; s electrical components can absorb a fraction of the electromagnetic energy that is generated by the readout device via inductive coupling . this coupling will induce a current in the sensor &# 39 ; s circuit that will oscillate at the same frequency as the applied electromagnetic energy . due to the nature of the sensor &# 39 ; s electromechanical system there will exist a frequency of alternating current at which the absorption of energy from the readout device is at a minimum . this frequency is a function of the capacitance of the device . therefore , if the sensor &# 39 ; s capacitance changes so will the frequency at which it minimally absorbs energy from the readout device . since the sensor &# 39 ; s capacitance is mechanically linked to the fluid pressure at the sensor &# 39 ; s surface , a measurement of this frequency by the readout device can give a relative measurement of the fluid pressure . if calibration of the device is performed then an absolute measurement of pressure can be made . the circuitry used to measure and display pressure is contained within a simple to operate , portable electronic unit 400 , as shown in fig2 . this unit 400 also contains the antenna 402 needed to perform the electromagnetic coupling to the sensor . the antenna 402 may be integrated into the housing for the electronics or it may be detachable from the unit 400 so that it can be positioned on the surface of the body 404 in proximity to the implanted sensor and easily moved to optimize the coupling between antenna and sensor . the antenna 402 itself may consist of a simple standard coil configuration or may incorporate ferrous elements to maximize the coupling efficiency . the electronic device 400 would feature an lcd or led display 406 designed to clearly display the recorded pressure in physiologically relevant units such as mm hg . in an alternative embodiment , the display 406 may be created by integrating a commercially available hand - held computing device such as a palm ® or micro - pc into the electronic circuitry and using this device &# 39 ; s display unit as the visual interface between the equipment and its operator . a further advantage of this approach is that the hand - held computer could be detached from the read - out unit and linked to a standard desktop computer . the information from the device could thus be downloaded into any of several commercially available data acquisition software programs for more detailed analysis or for electronic transfer via hard media or the internet to a remote location . accordingly , the present invention provides for an impedance system and method of determining the resonant frequency and bandwidth of a resonant circuit within a particular sensor . the system includes a loop antenna , which is coupled to an impedance analyzer . the impedance analyzer applies a constant voltage signal to the loop antenna scanning the frequency across a predetermined spectrum . the current passing through the transmitting antenna experiences a peak at the resonant frequency of the sensor . the resonant frequency and bandwidth are thus determined from this peak in the current . the method of determining the resonant frequency and bandwidth using an impedance approach may include the steps of transmitting an excitation signal using a transmitting antenna and electromagnetically coupling a sensor having a resonant circuit to the transmitting antenna thereby modifying the impedance of the transmitting antenna . next , the step of measuring the change in impedance of the transmitting antenna is performed , and finally , the resonant frequency and bandwidth of the sensor circuit are determined . in addition , the present invention provides for a transmit and receive system and method for determining the resonant frequency and bandwidth of a resonant circuit within a particular sensor . according to this method , an excitation signal of white noise or predetermined multiple frequencies is transmitted from a transmitting antenna , the sensor being electromagnetically coupled to the transmitting antenna . a current is induced in the resonant circuit of the sensor as it absorbs energy from the transmitted excitation signal , the current oscillating at the resonant frequency of the resonant circuit . a receiving antenna , also electromagnetically coupled to the transmitting antenna , receives the excitation signal minus the energy which was absorbed by the sensor . thus , the power of the received signal experiences a dip or notch at the resonant frequency of the sensor . the resonant frequency and bandwidth are determined from this notch in the power . the transmit and receive method of determining the resonant frequency and bandwidth of a sensor circuit includes the steps of transmitting a multiple frequency signal from transmitting antenna , and , electromagnetically coupling a resonant circuit on a sensor to the transmitting antenna thereby inducing a current in the sensor circuit . next , the step of receiving a modified transmitted signal due to the induction of current in the sensor circuit is performed . finally , the step of determining the resonant frequency and bandwidth from the received signal is executed . yet another system and method for determining the resonant frequency and bandwidth of a resonant circuit within a particular sensor includes a chirp interrogation system . this system provides for a transmitting antenna which is electromagnetically coupled to the resonant circuit of the sensor . an excitation signal of white noise or predetermined multiple frequencies , or a time - gated single frequency is applied to the transmitting antenna for a predetermined period of time , thereby inducing a current in the resonant circuit of the sensor at the resonant frequency . the system then listens for a return signal which is coupled back from the sensor . the resonant frequency and bandwidth of the resonant circuit are determined from the return signal . the chirp interrogation method for determining the resonant frequency and bandwidth of a resonant circuit within a particular sensor includes the steps of transmitting a multi - frequency signal pulse from a transmitting antenna , electromagnetically coupling a resonant circuit on a sensor to the transmitting antenna thereby inducing a current in the sensor circuit , listening for and receiving a return signal radiated from the sensor circuit , and determining the resonant frequency and bandwidth from the return signal . the present invention also provides an analog system and method for determining the resonant frequency of a resonant circuit within a particular sensor . the analog system comprises a transmitting antenna coupled as part of a tank circuit which in turn is coupled to an oscillator . a signal is generated which oscillates at a frequency determined by the electrical characteristics of the tank circuit . the frequency of this signal is further modified by the electromagnetic coupling of the resonant circuit of a sensor . this signal is applied to a frequency discriminator which in turn provides a signal from which the resonant frequency of the sensor circuit is determined . the analog method for determining the resonant frequency and bandwidth of a resonant circuit within a particular sensor includes the steps of generating a transmission signal using a tank circuit which includes a transmitting antenna , modifying the frequency of the transmission signal by electromagnetically coupling the resonant circuit of a sensor to the transmitting antenna , and converting the modified transmission signal into a standard signal for further application . the invention further includes an alternative method of measuring pressure in which a non - linear element such as a diode or polyvinylidenedifluoride piezo - electric polymer is added to the lc circuit . a diode with a low turn - on voltage such as a schottky diode can be fabricated using micro - machining techniques . the presence of this non - linear element in various configurations within the lc circuit can be used to modulate the incoming signal from the receiving device and produce different harmonics of the original signal . the read - out circuitry can be tuned to receive the particular harmonic frequency that is produced and use this signal to reconstruct the fundamental frequency of the sensor . the advantage of this approach is two - fold ; the incoming signal can be transmitted continuously and since the return signal will be at different signals , the return signal can also be received continuously . the above methods lend themselves to the creation of small and simple to manufacture hand - held electronic devices that can be used without complication . the preceding specific embodiments are illustrative of the practice of the invention . it is to be understood , however , that other expedients known to those skilled in the art or disclosed herein , may be employed without departing from the spirit of the invention of the scope of the appended claims .
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fig2 illustrates one example in which the present invention is embodied in a single - lens - reflex camera . after , the ray of light for taking a photograph having passed through taking lens 1 is reflected by quick - return - mirror 2 , of which the central portion is provided with a semi - transparent mirror , an image is made on a focussing glass . at the same time a luminous flux is transmitted through the semi - transparent mirror to form an image a ccd 4 , which is provided at the position corresponding to the focal point by interposing auxiliary mirror 3 . thus , the focal point is detected . if the luminance of a subject is low , as is obvious from fig1 it takes a long time before the charge transfer is started . to cope therewith , in the case that a transfer is not started within a certain period of time from the start of storing quantity of light in ccd , a warning to the operator to check for camera shakiness caused by a shaking hand , is to be given . generally , the time for utilizing the image made on ccd to detect focus should be less than 200 msec , assuming that the focal length of the taking lens is 50 mm , lest inaccurate focus detection should occur because of camera shakiness caused by hand . the circuit , which is used in the invention and exhibited diagrammatically , is shown in fig3 . a concrete example of the warning signal generating circuit is shown in fig4 and the operational conditions thereof are shown in fig5 . in fig3 ccd control circuit receives clock - pulses from an oscillator osc . ccd module 4 starts the storing upon receipt of reset signal φr . on the other hand , an automatic gain control ( agc ) signal is given in the form of an analog voltage and said voltage is reduced in proportion to the quantity of light from the time when the ccd starts the storing and , at the point of time when said voltage reached a certain value ( e . g . 0 ), a transfer start signal φt is given . in fig4 r - s flip - flop ( ff ) is set by receiving reset signal φr and is reset by receiving transfer start signal φt . transistor tr is switched on and off by output q from r - s ff . when transistor tr is switched off by receiving reset signal φr , the charging of capacitor c1 is started by a constant - current source . this charging voltage is compared , as described hereunder , with reference voltage v ref that is variable according to the lenses , etc . which may be used , by means of comparator c . when a subject has a sufficient luminance , transistor tr is switched on by receiving transfer start signal φt before the charging voltage for capacitor c1 reaches reference voltage v ref . when a subject has a low luminance , the charging voltage for capacitor c1 rises above reference voltage v ref because of the delayed issuance of transfer start signal φt that makes charging of capacitor c1 stop . this fact means that storage time in ccd is being delayed and there is the possibility that the hand holding the camera will begin shaking . thus , a warning device d , such as a led or buzzer , is actuated by the output from comparator c and an alarm is given . shutter times required to compensate for the shakiness caused by hand holding of the camera vary depending on the focal distances of the taking lenses used . when a lens with long focal length is used , a short shutter time should applied lest inaccurate focus detection should be occur because of camera shakiness by hand . accordingly , if a bleeder resistance r is built - in a lens , or if focal length information is sent to variable resistor r by means of a pin provided to a lens and the reference voltage v ref is varied according to the interchangeable lenses , it is possible to adjust suitably the warning time limit . as described above , in the present invention it is possible to indicate that a subject luminance is below a certain limit , by utilizing the storage time in ccd that is a focus detecting element . accordingly , it is possible to warn not only that there is a possibility of causing a shakiness by hand because of the long time exposure on taking a photograph in aperture priority mode but also that there is a possibility of lowering the focal point detection accuracy because of a prolonged storage time in ccd and because of a shakiness by hand . moreover , the present invention can be applied effectively not only to automatically focussing type cameras , but also to cameras having a rangefinder utilizing a focussing system in which a focal point is detected electrically .
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example embodiments will now be described more fully with reference to the accompanying drawings . example embodiments are provided so that this disclosure will be thorough , and will fully convey the scope to those who are skilled in the art . numerous specific details are set forth such as examples of specific components , devices , and methods , to provide a thorough understanding of embodiments of the present disclosure . it will be apparent to those skilled in the art that specific details need not be employed , that example embodiments may be embodied in many different forms and that neither should be construed to limit the scope of the disclosure . in some example embodiments , well - known processes , well - known device structures , and well - known technologies are not described in detail . the terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting . as used herein , the singular forms “ a ,” “ an ,” and “ the ” may be intended to include the plural forms as well , unless the context clearly indicates otherwise . the terms “ comprises ,” “ comprising ,” “ including ,” and “ having ,” are inclusive and therefore specify the presence of stated features , integers , steps , operations , elements , and / or components , but do not preclude the presence or addition of one or more other features , integers , steps , operations , elements , components , and / or groups thereof . the method steps , processes , and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated , unless specifically identified as an order of performance . it is also to be understood that additional or alternative steps may be employed . when an element or layer is referred to as being “ on ,” “ engaged to ,” “ connected to ,” or “ coupled to ” another element or layer , it may be directly on , engaged , connected or coupled to the other element or layer , or intervening elements or layers may be present . in contrast , when an element is referred to as being “ directly on ,” “ directly engaged to ,” “ directly connected to ,” or “ directly coupled to ” another element or layer , there may be no intervening elements or layers present . other words used to describe the relationship between elements should be interpreted in a like fashion ( e . g ., “ between ” versus “ directly between ,” “ adjacent ” versus “ directly adjacent ,” etc .). as used herein , the term “ and / or ” includes any and all combinations of one or more of the associated listed items . according to the present teachings , as illustrated in fig1 a - 1d , a fan - folded design as the structure of an energy harvester 10 . in some embodiments , energy harvester 10 can comprise a plurality of horizontal bimorph beams 12 a - 12 n and vertical rigid beams 14 . the bimorph beams 12 are connected to each other by the vertical rigid links 14 . the bimorph beams 12 can comprise a spring brass layer 16 as the substrate and two piezoelectric patches 18 attached on the brass layer 16 . brass is chosen for the substrate due to its large density and relatively large young &# 39 ; s modulus . however , it should be understood that alternative materials may be used . when the beams 12 are deflected , electrical energy is generated by the piezoelectric layers 18 . one end 20 of the design is clamped to a base structure 22 as the other end 24 is free to move . a tip mass 26 may be placed at the free end 24 of the energy harvester 10 . one major advantage of using this design is the decrease in the natural frequencies of the structure without significant increase in the size of the energy harvester 10 . adding tip mass 26 and link mass 14 to the system decreases the natural frequency even more . in some embodiments , the source of the vibration of the system is heartbeat acceleration and a natural frequency under 200 hz is a desired natural frequency for the energy harvester 10 . energy harvester 10 consists of several uniform composite beams 12 and each beam is modeled with the euler - bernoulli beam theory . the structure vibrates due to base excitation . each beam 12 a can bend and deflect which changes the start position of the next beam 12 b . the deflection of the beam w i is a function of the length x , and time t . the index i is the beam number ( from 1 to n ). the coupled mechanical equation of a beam with tip mass is : where ρa is the total mass per unit length of the beam , which is a function of b ( width of the beam ), density of the piezoelectric and substrate ( ρ p , ρ s ), and their thickness ( t p , t s ): w rel ( x , t ) is the deflection along the z - axis ( fig1 a ), yi is the equivalent bending stiffness of the composite beam . m l is the link mass and x * is 0 ( if i is an odd number ) or length of the beam , l , ( if i is an even number ). index k is from 2 to n . m t is the tip mass and δ ( x ) is the dirac delta function that satisfies : we solve the undamped , uncoupled equation to find the free vibration mode shapes . in order to find the free vibration modes , we set the left hand side of eq . ( 1 ) to zero : the solution for the free vibration can be shown as a linear combination of all natural motions of the beam ( section 11 ): where , ji is the jth natural mode shape of the ith beam , and t j is the time dependent function . substituting eq . ( 6 ) in eq . ( 5 ): where a i1 , a i2 , a i3 , a i4 and β j are calculated using the boundary , continuity and equilibrium conditions , and c is : by using the above equations and considering boundary and continuity conditions , the mode shapes and natural frequencies of a fan - folded structure are derived in the next section . in order to find the coefficients in eq . ( 8 ) we use two boundary conditions at each end , zero deflection and slope at the clamped end , zero moment and force at the free end . for a fan - folded structure ( fig1 ) we have : x * is zero or l ( length of the beam ), depending on the configuration of the fan - folded structure . the plus sign in the last equation is associated with x free *= 0 and the minus sign is associated with x free *= l . ω nj is the natural of the jth mode : there are four unknown coefficients for each beam . to find these coefficients , more equations are needed . by writing the continuity and equilibrium condition at the joints where beams are connected we have four more equations for every connection : again here , the x end is zero or ‘ l ’ depending on the connection place . in the last equation if x end = 0 the sign of the terms associated with the link mass ( m l ) is positive and if x end = l the sign is negative . due to the small size of the structure we do not consider the effect of the moment of the link mass in the third equation . if the size increases we need to add that term to the equation . these set of equations can be written in matrix form : in order to have a nontrivial solution for eq . ( 18 ) the condition det ( n )= 0 must be satisfied . the values of ω nj which makes this determinant zero are the natural frequencies of the structure . for finding the coefficients of the mode shapes we solve eq . ( 18 ) for a given value of a 11 . after finding the coefficients of the first beam the other beam &# 39 ; s modes are calculated as : to verify the method , two known cases of a cantilevered beam and a two member structure were compared to the results using this method . the main advantage of this method is reducing the matrix size which decreases the numerical calculation significantly . when the number of the beams increases the decrease in overall time of the calculations is considerable . another advantage of this formulation is avoiding extremely large values of determinant which might cause numerical errors . in the configuration that we have the beams are connected electrically in parallel . since the deflection of the beams is opposite of each other in some mode shapes , we use a switch to keep or to reverse the polarity of the generated voltage . these switches decide if the current going to each member should be added to or subtracted from the current in other members . considering the switches and using eq . ( 6 ) and eq . ( 1 ), we have : where p i is the switch for the ith member and it is either 1 or − 1 . the sign of the switches for each mode is decided based on : the arrangement of these switches might be different for each mode , but for building energy harvester 10 one cannot change the switches during the vibration . so the states of the switches are assigned based on the dominant vibration mode . we then multiply eq . ( 21 ) by ji and we integrate from zero to l ( length of the beam ). due to orthogonality condition : the mode shapes used in here are the mass normalized mode shape that satisfies : using eq . ( 7 ) and considering mass normalized mode shapes , we have : { umlaut over ( t )} j = ωnj 2 t j =− χ j v ( t )− γ j { umlaut over ( w )} b ( 25 ) by taking the fourier transform of eq . ( 25 ), we have the frequency domain equation : ( ω nj 2 − ω 2 ) η j ( ω )=− χ j v ( ω )− γ j a b ( ω ) ( 27 ) in which , η j ( ω ), v ( ω ), and a b ( ω ) are the fourier transforms of t j , v ( t ), and { umlaut over ( w )} b . one equation is known so far , meaning another equation is needed to solve for the two unknowns , t j and v ( t ). the equations which relate the strain and electric displacement to the stress and the electric field are the piezoelectric constitutive equations : d 3 =− d 31 y p s 1 − ε 33 s e 3 t 1 = y p ( s 1 − d 31 e 3 ) ( 28 ) in the above equations , t 1 is the normal stress along the x - axis , s 1 is the normal strain in x - axis , d 31 is the piezoelectric coupling coefficient , y p the young &# 39 ; s modulus of the piezoelectric layer , e 3 the electric field across the thickness of the piezo layer , ε 33 s the permittivity at constant stress , and d 3 the electric displacement along the thickness . using the above equation and the kirchhoff laws for parallel connection , we have : where i i ( t ) is the current in each member and c p is the internal capacitance for the piezo layer : to have the total current , we sum the current over all the members and if we model the damping as the modal damping ( 2ξω n jω ) the transfer function for parallel connection resulting from eq . ( 25 ) and eq . ( 31 ) is : using eq . ( 32 ) the expression for the multi - mode power frequency response function is : using the expression in eq . ( 32 ) for voltage and replacing it in eq . ( 25 ) the tip deflection of the structure is calculated as : accordingly , in some embodiments , energy harvester 10 can comprise seven bimorph piezoelectric beams 12 connected to each other by rigid beams 14 making a zig - zag shape . the first beam 12 a is clamped to a wall 22 and the last beam 12 e is free at one end 24 ( fig1 a and 1b ). we find the free vibration modes of the configuration . here we have the first four modes of the design . in our calculation we just consider the first natural frequency of energy harvester 10 . the higher modes are not considered in our calculations due to their high natural frequency and their little effect on the final results . fig2 a - 2d exhibit the first four modes of a seven beam structure . after finding the mode shapes , the frequency response function plots for a seven beam structure are generated . the structure consists of seven bimorph beams with 1 cm length and 1 cm width . psi — 5a4e piezo sheets from piezo systems , inc . can be used as the piezoelectric element . the thickness of the brass layer and the piezoelectric layer are 0 . 02 and 0 . 01 inch . each beam is connected to the next beam by a brass rigid beam . the length of the rigid part is 0 . 14 cm . the tip mass is 30 times the weight of one beam ( in some embodiments , tip mass is 20 times or more the weight of one beam ). a minimum safety factor of 20 is considered for energy harvester 10 to avoid fracture at where the beams are connected and where the first beam is clamped . the frequency response function of the voltage is plotted for the parallel connection of the piezoelectric layers . the voltage is proportional to the base acceleration , therefore in order to have the normalized voltage we plot the voltage per base acceleration in fig3 . the natural frequencies are the points where we have the maximum voltage ( peaks of the plot ). to maximize the output power we choose the load resistance as where ω 1 is the first natural frequency of energy harvester 10 . the normalized power output with respect to the square of base acceleration for a bimorph clamped free beam is illustrated in fig4 . as it is seen that natural frequency of energy harvester 10 are decreased significantly when they are compared to the case without tip and link masses . the first natural frequency has higher amplitude comparing to the next natural frequencies . fig5 a and 5b show the tip relative acceleration and displacement to the base acceleration , respectively . the peaks in these frequency response functions are the natural frequencies of the energy harvester . we then consider the heartbeat acceleration as the base acceleration of the system . to estimate the vibrations in the vicinity of the heart due to the heartbeat we use the ultrasonic velocity measurements performed by kanai . fig6 a and 6b show the heartbeat acceleration in time domain and frequency domain , respectively . considering this base acceleration and using eq . ( 32 ) and eq . ( 33 ), we calculate the voltage and power generated by energy harvester 10 . the time of the excitation is 9 seconds . we only consider the first natural frequency in our calculation . the next natural frequencies generated power is much less than the generated power from the first natural frequencies . the instantaneous power across a 87 kω purely resistive load is plotted in fig7 . the value of the resistive load matches the resistance having the maximum power in the first natural frequencies of energy harvester 10 . the average power for generated electricity in fig7 is 2 . 18 μw . as it mentioned the power needed for a pacemaker is less than 1 μw which shows that the generated power is sufficient for a pacemaker . in this article , the main goal is to reduce the size of the energy harvester while generating enough energy to power a pacemaker . as a result , the case presented is just a case to show that we can generate the needed power for the pacemaker while keeping the size limitations . the heartbeat spectrum in the frequency domain shows that the high amplitudes are at low frequencies ( less than 50 hz ) and we can have the maximum power at 39 hz . author believes that by changing the tip mass and changing the beam numbers and the thickness of the beams we can reduce the first natural frequency even more and it is expected that the generated power will be increased significantly . in this disclosure , generation of electricity from fan - folded or serpentine - shaped , bimorph piezoelectric beams with the tip mass was studied . the method for finding the mode shapes and natural frequencies of the system was explained . the boundary conditions and equilibrium and continuity conditions were discussed . for a case study , the mode shapes and natural frequencies of the configuration were calculated . the frequency response function for the voltage and power of the energy harvester were calculated and plotted . the relative tip acceleration and displacement were calculated in the frequency domain . the electro - mechanical equations were solved for this configuration and the energy generated from 9 seconds of heartbeats was calculated . it was shown that the energy harvester generates enough energy to power a pacemaker . the fan - folded geometry and the tip mass makes it possible to have the energy harvester in small size ( 1 cm by 1 cm by 1 cm ). adding the tip mass reduced the natural frequency significantly . energy harvester 10 can be implemented inside the body to generate the electricity needed for pacemakers and makes it possible to have an autonomous pacemaker without the need of a battery . the input vibrations to the energy harvester are caused by heartbeats . the present teachings provide energy harvesting from heartbeat vibrations using fan - folded piezoelectric beams . the generated energy from the heartbeat can be used to power a leadless pacemaker . a leadless pacemaker is implanted in the heart to control abnormal heart rhythms . unlike traditional pacemakers , leadless pacemakers do not have leads and do not need an open surgery for implantation . the required power for a pacemaker is about 1 μw . the main obstacle for development of leadless pacemakers is the power issue . the battery takes about 60 % of the size of a conventional pacemaker . the size of the conventional pacemaker batteries is too large for leadless pacemakers . the battery size issue hindered the development of leadless pacemakers for 20 years . recently novel batteries have been developed that make leadless pacemakers realizable . still , the battery life is the same as traditional pacemakers and typically lasts about 6 to 7 years . extraction of leadless pacemakers is very difficult so when the battery is depleted , a new pacemaker has to be implanted . it has been demonstrated that the principles of the present teachings generates an order of magnitude more power than the nominal power needed for a leadless pacemaker . the small size of the energy harvester and sufficient output power of energy harvester 10 are but a few of the advantages of the present invention . by way of non - limiting example , in some embodiments , the present device can be sized to about 2 cm × 1 cm × 0 . 5 cm . ( 1 cc in volume ). in order to utilize the 3 - dimensional space available to the energy harvester , in some embodiments energy harvester 10 comprises a fan - folded design . energy harvester 10 of the present teachings can comprise several piezoelectric beams stacked on top of each other ( fig1 ). each beam is a bimorph piezoelectric beam , with one brass layer as the substrate and two piezoelectric layers attached on each side . the bimorph beams are connected to each other by rigid links made from platinum , for example . in some embodiments , platinum is chosen for the links due to its high density . one end of the structure is clamped as the other end is free to move . high natural frequency is one major problem in small energy harvesters . in order to generate sufficient power for a pacemaker , the first natural frequency of the energy harvester should be less than about 50 hz . the fan - fold geometry is an effective design to reduce the natural frequency . the mass of the tip and the link can be adjusted to reduce the natural frequency . this fanfolded design makes it possible to generate more than 20 μw ( more than the 1 μw required for pacemaker operations ). energy harvester 10 of the present teachings does not incorporate magnets and is thus magnetic resonance imaging ( mri ) compatible . although our device is a linear energy harvester , it is shown that energy harvester 10 is relatively insensitive to the heartrate ( fig2 . a ). as seen in fig3 , the natural frequencies and the mode shapes of energy harvester 10 are calculated . the method is verified by experimental investigations ( fig2 b ). the developed analytical model is verified through comparison of theoretical and experimental voltage and tip displacement transfer functions . the foregoing description of the embodiments has been provided for purposes of illustration and description . it is not intended to be exhaustive or to limit the disclosure . individual elements or features of a particular embodiment are generally not limited to that particular embodiment , but , where applicable , are interchangeable and can be used in a selected embodiment , even if not specifically shown or described . the same may also be varied in many ways . such variations are not to be regarded as a departure from the disclosure , and all such modifications are intended to be included within the scope of the disclosure .
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for purposes of the present invention , a “ buy - side trader ” is to be understood as a trader who executes orders ( buy , sell , sell short ) for the mutual funds and / or hedge funds of an asset management company . now with reference to prior art methods concerning buy - side traders interaction with several ats &# 39 ; s , fig1 generally depicts how this was accomplished . in the example of fig1 , buy - side trader 10 is permitted to trade with two ats &# 39 ; s , ( e . g ., ats 20 and 30 ). accordingly , for buy - side trader 10 to use both of these ats &# 39 ; s ( e . g ., ats &# 39 ; s 20 and 30 ), buy - side trader 10 had to independently contact each terminal system ( e . g ., computer terminals 22 , 32 ) associated with each respective ats ( e . g ., ats 20 and 30 ). thus , buy - side trader 10 had to be enabled to use at least two differing protocols to conduct business with each respective ats ( e . g ., ats 20 and 30 ). the buy - side trader 10 communicates with ats 20 through computer trading terminal 22 , and with ats 30 through computer trading terminal 32 . as is conventional , for enabling trades , trading terminal 22 of ats 20 is connected to its ats database and processor system 24 and trading terminal 32 of ats 30 is connected to its database and processor system 34 . it is of course to be appreciated that each aforesaid ats 20 , 30 may also simultaneously be coupled to other third party buy - side traders . for instance , with respect to ats 30 , its trading terminal is shown coupled to third party buy - side traders 60 and 70 . it is shown in fig1 that buy - side trader 10 is not a subscriber of ats 40 consisting of trading terminal 42 and database and processor system 44 . and like ats 40 , buy - side trader 10 is also not a member of ats 50 consisting of trading terminal 52 and database and processor system 54 . thus buy - side trader 10 does not have access to either of ats &# 39 ; s 40 and 50 as there can be no interaction between their respective trading terminals 42 and 52 , and database and processor system &# 39 ; s 44 and 54 . therefore as can be seen from fig1 , in the prior art system , buy side trader 10 must use separate trading terminals ( 22 , 32 ) associated with each respective ats ( 20 , 30 ). thus the buy - side trader 10 must be able to use multiple applications on one or more terminals to compare and share prices and to make his / her bids / offers . further , the buy - side trader 10 may split a large order into bids or offers between two or more terminals or applications . the trading terminals 22 and 32 typically use different protocols to access market data , place bids and offers and execute transactions . in some real sense , this destroys the ability to trade in real - time due to the natural delays associated with collecting information from a number of trading terminals , using a number of different protocols and responding on one or more on such trading terminals . such separate systems and terminals not only make it difficult to obtain optimal data it makes it difficult to perform analytics against the data to aid in trading decisions . as seen in fig2 , the present invention eliminates the need for a buy - side trader 100 to be individually coupled to each trading terminal ( 112 , 122 , 132 , 142 , 152 , 162 ) for each respective ats ( 110 , 120 , 130 , 140 , 150 , 160 ). this is achieved through the use of an aggregating computer system ( acs ) 105 . preferably , acs 105 comprises a computer processor coupled to one or more databases and having the necessary algorithms and software programs for enabling the below described functionality . what is shown in fig2 is the acs 105 electronically coupled to a plurality ats &# 39 ; s 110 - 160 via their respective trading terminals 112 - 162 . it is to be appreciated that the acs 105 is only applicable for use with buy - side traders and is not intended for any sell - side traders in furtherance of maintaining the anonymity of the buy - side trader . in the preferred embodiment of the present invention , acs 105 is preferably coupled to the trading terminals of ats &# 39 ; s for : itg posit 110 ; liquidnet 120 ; harborside 130 ; instinet cross 140 ; pipeline 150 ; and nyfix millennium 160 . it is of course to be appreciated that in accordance with the present invention , acs 105 is coupled and interoperable with as many different ats &# 39 ; s as desired , thus the present invention is not to be understood to be limited only to the ats &# 39 ; s shown in fig2 . the acs 105 performs a number of interrelated functions that may be carried out on one computer or a network of computers . acs 105 is configured to provide the buy - side trader 100 complete access and functionality to each aforesaid coupled ats ( 110 , 120 , 130 , 140 , 150 , 160 ) on a single computer platform . as will be explained below , the buy - side trader 100 , through implementation of acs 105 , will become immediately aware if any volume in trades of stock become available from any of the ats &# 39 ; s ( 110 , 120 , 130 , 140 , 150 , 160 ) to which buy - side trader 100 previously submitted an order to . further , the acs 105 is configured to be fully interoperable with each aforesaid ats 110 - 160 such that acs 105 is programmed with the individual communication protocols associated with each platform associated with each ats 110 - 160 necessary to enable bilateral trading communication between the acs 105 and each ats 110 - 160 . it is to be appreciated that while the underlying principle and goal of crossing networks is the same , each ats operates slightly differently and maintains different membership criteria . the platform will give full access to the information maintained on each crossing network as well as complete functionality of each ats . protocols included will be basic communication to enter buy / sell orders that interact with each ats , the ability to include / exclude any of the ats &# 39 ; s , the ability to negotiate with participants on each system , the ability to change parameters during the life of the order - order size , price limits , percentage to be executed over the course of the day given the opportunity , ability to expand upon the order if original order is completed , ability to receive and negotiate a program ( a program is a computer file of numerous orders that need to be executed over a specific time period , given specific parameters such as price or other strategies . an example of a program trade would be a file consisting of 250 buys / 250 sells that need to be executed if able to do so in the inside quote . the system needs to be able to handle that type of order flow as well since it is a large percentage of trading volume on a daily basis . furthermore , there are no existing platforms to send small cap programs to and this platform is ideal for such a program given the illiquid nature of small cap stocks .) therefore , as depicted in fig2 , rather than a buy - side trader 100 being individually coupled to each individual ats , as is required by the prior art system of fig1 , the acs 105 of the present invention is configured to enable instantaneous communication with each aforesaid ats so to submit and collect order information from each individual ats . it is to be appreciated that acs 105 communicates anonymously with each ats 110 - 160 whereby the identity of the buy - side trader 100 is concealed to each ats 110 - 160 and the buy - side trader accesses all pools of liquidity on each ats quickly and efficiently without adversely affecting the stock price . in other words , the buy - side traders 100 are never displayed to any other third party since the acs 105 functions as an anonymous intermediary between the buy - side trader 100 and each aforesaid ats . it is to be appreciated that acs 105 may be configured in numerous configurations , including , but not limited to as a software system on a pc associated with a buy - side trader , as a broker - dealer type of platform , or as a hybrid solution that allows the buy - side trader to interoperate with both aforesaid buy - side traders pc and broker - dealer type of platform . through preferably the software implemented in acs 105 , a buy - side trader preferably controls the various known parameters of their order through the use of price limits , inclusion / exclusion of any of the ats &# 39 ; s 110 - 160 , percentage of the overall order to send each ats , and access to a smart router . in regards to the present invention , a smart router is to be understood as preferably be enabled to transmit orders to the most advantageous ats based on historical trading data . for example , if the buy - side trader wanted to send an order in xyz to the platform , the smart router would determine from historical data , which of the ats &# 39 ; s traded the most overall volume in xyz in the past month . the smart router could be set up using different parameters depending on the buy - side trader &# 39 ; s strategy . some trading styles are more price sensitive ( in which case price data could be obtained — which ats provided liquidity with minimum price impact in the past month ? some traders care more about volume — which ats traded the most volume in the past month in stock , xyz ? some traders are more concerned with market cap — which ats traded the largest percentage of small cap stocks in the past month ?) in summation , the smart router equips the buy - side trader with the ability to send his / her order in real time to the optimum destination based on historical performance . as will also be explained below , once there has been a “ hit ” by one of the ats &# 39 ; s 110 - 160 regarding an order submitted by acs 105 , the acs 105 is configured to automatically terminate the orders submitted to the remaining ats &# 39 ; s 110 - 160 . thus , this is advantageous because the buy - side trader 100 is enabled to reevaluate the outstanding order strategy so as to not mislead the market that there are actually several other orders on the same side of one security via the remaining ats &# 39 ; s 110 - 160 . preferably , all reports that are transmitted back to the buy - side trader 100 from the various ats &# 39 ; s 110 - 160 are transmitted to the buy - side trader via fix . it is noted fix stands for financial information exchange technology and it is a network which connects the buy - side to the sell - side and connects both the buy - side and the sell - side to ats &# 39 ; s and connects the sell - side to the trading floors — such as nyse , amex . this electronic network enables order flow to be sent and executed in real time and eliminates a great deal of human error since all parameters of the order are transmitted electronically instead of being verbalized . while fix does not eliminate the need for human interaction , it sends the basic order information and then the traders can discuss the real detail of the order and the corresponding execution reports . with the acs 105 and its interoperability with the ats &# 39 ; s 110 - 160 being described above , its method of operation will now be described with reference to fig3 and with continuing reference to fig2 . starting at step 300 , a buy - side trader 100 contacts acs 105 to place a buy order for a prescribe commodity ( e . g ., stock in xyz corp .). the buy - side trader 100 prescribes at least the necessary parameters for such an order , step 305 . for instance , such parameters of an order may include : order size or number of shares , price limits , percentage of the order to be worked over the course of the day or percentage of the order to be sent to each ats if it should not be divided equally among the 6 ats &# 39 ; s , the ability to reload if the first part of the order is executed , strategies in line ( to pay inside the quote ) or scale ( to bring the stock in if you &# 39 ; re a buyer or scale it up if you &# 39 ; re a seller ) momentum — to continue to pay up as a buyer or to continue to sell at lower prices . for purposes of more fully understanding the method depicted in fig2 , a trading scenario will be described whereby a buy - side trader 100 desires to buy 60 , 000 shares of xyz corp . at a price no higher than $ 43 . 00 per share . after the acs 105 receives the buy - side trader &# 39 ; s 100 order , it then formats the order for submission to each ats 110 - 160 it is preferably coupled to , step 310 . as mentioned above , each individual submission of an order to each ats 110 - 160 shall meet the protocol requirement prescribed by each aforesaid individual ats 110 - 160 . additionally , acs 105 preferably divides the buy - side trader &# 39 ; s 100 order request ( e . g ., 60 , 000 ) equally for each ats 110 - 160 an order is to be submitted thereto , step 315 . for example , if the acs 105 is to submit an order to each ats 110 - 160 , then each submission to each ats 110 - 160 shall be for 10 , 000 shares of xyz corp . thus in step 320 , an order for 10 , 000 shares of xyz corp . at a price no higher than $ 43 . 00 per share is electronically submitted from acs 105 to each of ats &# 39 ; s 110 , 120 , 130 , 140 , 150 and 160 . after submission , acs 105 awaits reports from each ats 110 - 160 indicating whether an individual order ( e . g ., 10 , 000 shares of xyz corp .) on a respective ats was executed or not , step 325 . at step 330 a determination is made as to whether any of the ats &# 39 ; s 110 - 160 to which an order was submitted actually executed an aforesaid order submission ( e . g ., 10 , 000 shares of xyz corp .). if no , then a determination is made as to whether a report has been issued from one of the ats &# 39 ; s 110 - 160 to which an order was submitted indicating a decline for execution of the order , step 335 . if yes ( an order submission was declined by ats 130 ), then the acs 105 cancels the order submission to that declining ats ( e . g ., ats 130 ) with the remaining individual orders ( e . g ., 10 , 000 shares of xyz corp .) for each of the remaining ats &# 39 ; s ( e . g ., ats &# 39 ; s 110 , 120 , 140 , 150 and 160 ) being in an active state , step 340 . and if at step 335 , a determination is made that no reports were issued from any ats &# 39 ; s declining execution of an order , then the process returns to step 330 for a determination as to whether any of the remaining ats &# 39 ; s executed an aforesaid order submission ( e . g ., 10 , 000 shares of xyz corp .). if at step 330 reports were issued from one or more ats &# 39 ; s indicating that the bid was at least partially executed ( e . g ., ats 110 executed the order for the entire 10 , 000 shares of xyz corp . and ats 160 executed the order for 5 , 000 shares ) then the outstanding order submissions to the remaining ats &# 39 ; s ( e . g ., ats &# 39 ; s 120 , 140 and 150 ) are immediately canceled , step 345 . preferably acs 105 then determines the remaining balance of the shares for the buy - side trader &# 39 ; s original order ( step 305 ) that is still outstanding ( e . g ., 45 , 000 shares of xyz corp . ), step 350 . next , acs 105 determines which ats should the outstanding balance of the order ( e . g ., 45 , 000 shares of xyz corp .) be submitted to for execution thereof , step 355 . if at step 330 only one ats ( e . g ., ats 110 ) executed an order , then acs 105 would preferably determine to send the outstanding balance of the order ( e . g ., 45 , 000 shares of xyz corp .) to that ats ( e . g ., ats 110 ). if however more than one ats executed an order submission from acs 105 ( e . g ., ats 110 executed the order for the entire 10 , 000 shares of xyz corp . and ats 160 executed the order for 5 , 000 shares ), then acs 105 preferably determines from which ats that previously executed an order ( ats 110 and 160 ) should receive the submission for the outstanding order balance ( e . g ., 45 , 000 shares of xyz corp .). it is to be appreciated that acs 105 may use various parameters to make this determination including bid price , share availability , number of participants on the other side of the trade , trading style of the buy side trader who is the user of the system — passive — more price sensitive / aggressive — more concerned with accumulating volume , the user &# 39 ; s entire picture ( if filled on 15 , 000 shares and the remaining order is for 45 , 000 shares , the determination on whether or not to send the entire 45 , 000 shares is largely based on what the buy - side trader &# 39 ; s entire order is for .) even though the user sent 60 , 000 shares to the platform , he / she may have an additional 1 million shares behind it . for purposes of this description , acs 105 determines that ats 110 will receive the outstanding balance of the order ( e . g ., 45 , 000 shares of xyz corp .) since ats 110 originally executed the order for more shares ( e . g ., 10 , 000 ) than that of ats 160 ( e . g ., 5 , 000 shares ). thus , at step 360 acs 105 submits a bid for the balance ( e . g ., 45 , 000 shares of xyz corp .) of the original buy - side traders order ( e . g ., 60 , 000 shares ) to the ats as determined in step 355 ( e . g ., ats 110 ). it is to appreciated that in the event the ats determined in step 355 ( e . g ., ats 110 ) is unable to execute on the entire balance remaining ( e . g ., 45 , 000 shares ) then the acs 105 may be configured to recalculate the balance remaining after execution by the ats determined in step 355 ( e . g ., ats 110 ) and submit that balance for execution to another ats involved in the determination of step 355 ( e . g ., ats 160 ). therefore a clear advantage of the present invention is that acs 105 is enabled to simultaneously place bids / offers to a plurality of ats &# 39 ; s , with each bids / offers only being a portion of the buy - side traders entire order ( step 305 ) so as to acquire the desired commodity at a most efficient price since no one ats is initially aware of the entire buy - side trader &# 39 ; s order . otherwise , if an ats was originally aware of the entire buy - side trader &# 39 ; s order , that ats could cause unfavorable changes in the price of the aforesaid desired commodity . a further advantage of the present invention is that when one or more ats &# 39 ; s report execution of an order , the acs 105 automatically cancels the outstanding orders with all other ats &# 39 ; s . this is advantageous because it does not leave any footprints . in other words , it does not leave the impression that there are 6 individual orders on one side for that one security . in an alternative embodiment of the present invention , at step 355 , instead of the acs 105 determining which ats shall receive the submission for the balance of the buy - side trader &# 39 ; s order , a user of acs 105 contacts the buy side - trader 100 to strategize as to which ats shall receive the balance of the order . this is advantageous because at this point , the buy - side trader is given information regarding the order flow across 6 ats &# 39 ; s at the same time . this enables the buy - side trader to rethink strategy and change parameters of the order if necessary . this gives the buy - side trader options — to change order , to stick with original parameters to reload or add to the order , to strategize based upon information received and to have a trained professional deliver and interpret the information — to aid in the negotiation process with the ats &# 39 ; s . in summary , a system and method for aggregating and strategically accessing multiple ats &# 39 ; s across multiple platforms for maximizing the value of a buy - side trader &# 39 ; s order has been described . although the present invention has been described with emphasis on particular embodiments , it should be understood that the figures are for illustration of the exemplary embodiment of the invention and should not be taken as limitations or thought to be the only means of carrying out the invention . further , it is contemplated that many changes and modifications may be made to the invention without departing from the scope and spirit of the invention as disclosed .
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referring now to fig1 there is shown a side view of an assembled nuclear reactor stud hole plug according to this invention . the plug comprises a cylindrical body 10 having threads 11 along at least a portion of the cylindrical wall thereof . in a typical reactor , the stud holes have a diameter of about seven inches and the stud hole plugs necessarily have about the same diameter . typically , the plugs would have an axial length of about six inches . it should be understood that the size of the stud hole plugs depends upon the configuration of the reactor and the precise dimensions form no part of this invention . the plug is shown in sectioned portions of the reaction vessel flange 12 and head flange 13 . spaced from one end of the plug ( the top in fig1 ) is a metal reaction plate 14 which holds a beveled resilient grommet 15 against the plug body 10 . referring now to fig1 and 2 , a plurality of bolts 16a , 16b , 16c , 16d hold the reaction plate 14 against the beveled resilient seal 15 . in the reaction plate is an opening 7 that permits a tool to be inserted in a socket provided in the plug so that the plug can be turned into or out of the stud hole . in a typical refueling procedure , the metal studs holding the reaction head flange 13 against the reaction vessel flange 12 are removed . the stud hole plugs are threaded into the stud holes and tightened down until the resilient seal engages the inside of the stud hole , the flange surface adjacent the stud hole and the rim therebetween to thus provide a three way seal . because of this three way seal , the plug and flange can sustain substantial damage before a seal will not be effected . typically , the next step of the refueling is removal of the reactor head and flooding of the space above the reactor with borated water ( boric acid ). the seal provided by the stud hole plug prevents the corrosive liquid from entering and corroding the internal threads in the stud hole . after refueling , the borated water is pumped away and the head is replaced prior to removal of the plugs and insertion of the studs . referring to fig3 and 4 , the plug 10 is made from a polymer such as high density nylon . typically , the cylindrical plug body has undersized threads 11 to accommodate thermal expansion . at one axial end and centered thereon there is a raised portion 18 of lesser diameter . in the case of a stud hole plug having a diameter of about seven inches , the raised portion may , for example , have a diameter of about 3 . 5 inches and an axial depth of about one inch . the axial end of the raised centered portion 18 has a socket 19 therein . the socket is sized to receive a tool for applying torque to the plug for turning it into and out of the stud hole . preferably , the socket in the center portion has a butterfly configuration as shown in fig4 . this socket configuration will cooperate with the driving tool to be described with reference to fig8 and 9 . a plurality of circumferentially spaced stud holes are provided on the axial shoulder 20 between the raised portion and the cylindrical wall of the plug for receiving fasteners 16 to hold the reaction plate 14 in place . referring now to fig5 the reaction plate has a circular shape with a diameter somewhat greater than the stud holes in the reactor vessel flange and somewhat smaller than the through holes in the reactor head flange . the diameter of the reaction plate is the largest diameter of the stud hole plug and therefore , the plug can be turned into the stud holes without removing the head and thereafter the head can be removed with the plugs in place . the diameter of the reaction plate is at least about 0 . 25 inch greater than the diameter of the stud hole . the reaction plate has an opening 7 therein for permitting a torquing tool to pass through and engage the socket in the raised center portion of the plug body . the particular hole depicted has a circular center portion and two opposite radially extending portions to permit a tool with shaft 30 and two wing extensions 31 and 32 ( see fig8 and 9 ) to pass therethrough and engage the socket walls . preferably , the reaction plate is stainless steel . referring now to fig6 and 7 , the grommet 15 is shown to have an annular configuration with a central opening 22 so that it can surround the raised center portion 18 of the plug body and rest between the reaction plate 14 on the shoulder 20 surrounding the raised center portion . preferably , the grommet is comprised of a weak acid resistant material such as neoprene , polyorganosiloxane , polyisoprene resins , butadiene polymers , styrene / butadiene polymers , polysulfide dihalide resins , polychloroprene compositions , polyisobutylene compositions , and polyvinylchloride resins . the grommet is at least about one inch thick . the grommet has an exterior conical surface 23 tapering from a diameter equal to the diameter of the circular reaction plate to a diameter equal to the diameter of the edge of the shoulder of the body . the grommet , while deformable , is impervious to liquids . circumferentially spaced through holes 24a , 25b , 24c , and 24d are provided to receive the fasteners 16 securing the reaction plate to the plug body . the grommet is about 0 . 03 inches thicker than the raised portion of the plug body . thus , when the reaction plate is tightened against the raised portion , it slightly squeezes the grommet . the axial distance between the shoulder of the body and the reaction plate is fixed by the height of the raised portion of the plug and thus the grommet can only be squeezed the desired distance . referring to fig8 and 9 , a torquing tool especially for use with the reaction plug thus far described has an elongate shaft 30 with wing portions 31 and 32 at one axial end sized to pass through the opening in the reaction plate and then into the socket . the depth of the wings is such to permit the rotation of the tool after it has been inserted through the hole in the reaction plate to thus engage the sides of the socket . an annular capture plate 33 is positioned for axial movement away from the wing portions 31 and 32 . the capture plate is biased by spring 34 anchored by guide plate 35 fixed to the shaft . thus , when the tool is inserted in the socket , the capture plate engages the surface of the reaction plate of the plug and the spring is compressed . after the tool is rotated to engage the sides of the socket , the reaction plate is captured between the wings and the capture plate . this enables the tool to be used to raise and lower a stud hole plug into place . the grommet plays no structural role in the raising , lowering or torquing of the stud hole plug into place because the body of the stud hole plug is directly engaged by the tool . referring now to fig1 and 11 , there is shown an alternate embodiment of a reaction plate for a plug according to this invention . the reaction plate 14 has a handle 40 rather than an opening . no socket is provided in the raised portion of the plug body with which this reaction plate is used . the handle has extensions 41 and 42 that extend through the plate so that they can be inserted in bores provided in the raised portion of the plug body . lifting or turning the handle applies a lifting force or turning torque directly upon the plug body . referring to fig1 and 13 , there is shown a tool for manipulating the stud hole plug according to the embodiment of fig1 and 11 . the tool has an elongate shaft 45 with an end piece sized to slide between the handle 40 and the reaction plate 14 . having thus described my invention with the detail and particularity required by the patent laws what is desired to be protected by letters pat . is set forth in the following claims :
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referring to fig1 a , 1 b and 2 , the reference numeral 10 generally designates a partially assembled dual - level load limiting seat belt retractor for a motor vehicle according to the present invention . the illustrated assembly includes a metal frame 12 that is mounted in a vehicle door pillar , a spool 14 on which the seat belt ( not shown ) is wound , and a spool support assembly 16 that couples the spool 14 to the frame 12 . the spool support assembly 16 includes a spool connector 18 , a locking base 20 , first and second torsion bars 22 and 24 , a bridge bolt 26 , and a switching mechanism 28 . the first and second torsion bars 22 and 24 are arranged coaxial with the locking base 20 . the spool 14 and outboard end 22 a of the first torsion bar 22 are rotationally fixed to the spool connector 18 . the bridge bolt 26 is internally splined , and rotationally fixes the inboard end 22 b of the first torsion bar 22 to the inboard end 24 a of the second torsion bar 24 . the outboard end 24 b of the second torsion bar 24 is rotationally fixed to the locking base 20 . the locking base 20 has an end portion 20 a that passes through a sidewall 12 a of frame 12 , and an annulus 20 b disposed within the frame 12 . the bridge bolt 26 is disposed within the annulus 20 b of locking base 20 , and is provided with exterior threads that meshingly engage complementary threads formed on the inner periphery of annulus 20 b . the switching mechanism 28 is disposed between the spool 14 and frame 12 , and ordinarily prevents lateral displacement of the bridge bolt 26 toward the end portion 20 a of locking base 20 due to relative rotation between it and the locking base 20 . a take - up spring ( not shown ) coupled to the spool connector 18 rotationally biases the spool support assembly 16 in a direction to retract the seat belt . apart from this spring bias , the components of spool support assembly 16 are free to rotate with respect to the frame 12 during normal usage . in the event of an actual or anticipated crash event , however , a locking mechanism 30 ( shown in outline in fig1 ) responsive to vehicle deceleration and / or rapid payout of the seat belt mechanically engages the locking base 20 to the frame 12 . although the locking mechanism 30 prevents further rotation of the locking base 20 , the torsion bars 22 and 24 provide a load limiting function when the force applied to the seat belt reaches a predetermined level by absorbing mechanical energy while allowing a limited amount of additional seat belt payout . the torsion bars 22 and 24 have different energy absorption characteristics due to differences in their geometry , and two different levels of load limiting are achieved depending on which torsion bar is absorbing energy . the default energy absorption level is determined by the first torsion bar 22 , which begins absorbing energy at a relatively high load level due to its relatively large size ( compared to torsion bar 24 ). a lower energy absorption level determined by the second torsion bar 24 can be selectively activated in the course of an actual or anticipated crash event to allow limited seat belt payout at a lower load level . this may be appropriate , for example , if the occupant is relatively small and / or the crash severity is relatively low . selective activation of the lower energy absorption level is achieved with the switching mechanism 28 , which includes a set of detent wedges 32 , a retainer band 34 , and a pyrotechnically deployed cutting mechanism 36 . the detent wedges 32 are received in a set of openings 38 formed in the annulus 20 b of locking base 20 between the spool 14 and retractor frame 12 . the retainer band 34 circumscribes the detent wedges 32 , and retains them within the respective openings 38 . the inboard face 32 a of each detent wedge 32 is cammed , and when the detent wedges 32 are retained in the openings 38 , their cammed faces 32 a engage a complementary cammed surface 26 b formed on the end of bridge bolt 26 . as indicated above , this prevents lateral displacement of the bridge bolt 26 toward the end portion 20 a of locking base 20 due to relative rotation between it and the locking base 20 . as explained below , activating cutting mechanism 36 severs the retaining band 34 , establishing a period of low energy absorption as the bridge bolt 26 rotates with respect to the locking base 20 and thereby moves laterally toward the end portion 20 a of locking base 20 . the cutting mechanism 36 includes a generally cylindrical housing 40 captured in a mounting flange 12 b of retractor frame 12 , a piston 42 , a squib 44 , and an electrical connector 46 . the piston 42 is disposed within an axial bore 48 of housing 40 and includes an integral chisel - point pintle 50 that extends out of bore 48 toward the retaining band 34 . electrical activation of the squib 44 charges the housing bore 48 with pressurized gas , thereby displacing piston 42 outward and causing the chisel - point 50 a of pintle 50 to strike and sever the retaining band 34 . the operation of the retractor 10 is now described with respect to fig3 a - 3c , 4 a - 4 c and 5 a - 5 c . it is assumed for purposes of the description that an actual or anticipated crash event is in progress , and the locking mechanism 30 has mechanically engaged locking base 20 to the retractor frame 12 . fig3 a , 4 a and 5 a depict an initial or default condition in which the cutting mechanism 36 is not activated , and the retaining band 34 retains the detent wedges 32 in the openings 38 of locking base 20 . in this condition , the bridge bolt 26 is rotationally fixed to the locking base 20 . the force ( load ) applied to the seat belt rises rapidly once the locking base 20 engages the frame 12 and the occupant moves forward . the corresponding torque applied to the spool 14 is transferred to the outboard end 22 a of the first torsion bar 22 through the spool connector 18 . the inboard end 22 b of the first torsion bar 22 attempts to rotate the bridge bolt 26 , but cannot since the bridge bolt 26 is rotationally fixed to the locking base 20 as mentioned above . in other words , the bridge bolt 26 reinforces the torsion bar 24 when rotationally locked , so that the second torsion bar 24 is effectively bypassed . when the load reaches a predetermined limit l 1 , the first torsion bar 22 twists to absorb energy while permitting limited additional seat belt payout as depicted in fig5 a . if the high level load limit condition is deemed to be appropriate given the occupant size and crash severity , the cutting mechanism 36 is not activated , and the load limiting continues at the level l 1 until the occupant energy is expended . if it is determined that a lower level load limit is desired , the cutting mechanism 36 is activated as depicted in fig4 b . this severs the retaining band 34 and allows the bridge bolt 26 to drive the detent wedges 32 radially outward by camming action as depicted in fig4 c . with the detent wedges 32 shifted out of the way , the bridge bolt 26 rotates within the annulus 20 b of locking base 20 and moves laterally rightward as depicted in fig3 b . the inboard ends 22 b and 24 a of the first and second torsion bars 22 and 24 rotate with the bridge bolt 26 , placing the second torsion bar 24 in series with the first torsion bar 22 . since the second torsion bar 24 has a lower energy absorption characteristic than the first torsion bar 22 , the seat belt load drops to a lower level l 2 as the seat belt continues its load - limited payout ; see fig5 b . this condition prevails until rightward lateral movement of the bridge bolt 26 is prevented due to its engagement with the end portion 20 a of locking base 20 as depicted in fig3 c . during this low - level interval of load limiting , the seat belt may payout an additional 400 mm or so , as indicated in fig5 b . when the cammed end of bridge bolt 26 engages the end portion 20 a of locking base 20 , the bridge bolt 26 is once again rotationally fixed to the locking base 20 , and the bridge bolt 26 effectively by - passes the second torsion bar 24 . at such point , the first torsion bar 22 is the only energy - absorbing element in the load path , and load limiting can only continue at the upper load limit l 1 as depicted in fig5 c . as best seen in fig1 a and 2 , the retractor 10 of the present invention achieves a dual - level load limiting functionality without significantly increasing its size . unlike prior dual - level load limiting retractors , the switching mechanism 28 is disposed within the retractor frame 12 , and the increased functionality is achieved without significantly increasing the retractor width . as a result , the packaging drawbacks associated with prior dual - level load limiting retractors are avoided . at the same time , the additional manufacturing cost required to achieve the increased functionality is relatively low , as the individual components are relatively inexpensive to manufacture and easy to assemble . in summary , the retractor 10 of the present invention presents a compact and low - cost alternative to other dual - level load limiting retractors . while described with respect to the illustrated embodiment , it is recognized that numerous modifications and variations in addition to those mentioned herein will occur to those skilled in the art . for example , the first and second torsion bars 22 and 24 can be formed as a single element instead of two separate elements , and so on . accordingly , it is intended that the invention not be limited to the disclosed embodiment , but that it have the full scope permitted by the language of the following claims .
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the ice transport system of the present invention is seen in fig1 and 3 and is generally referred to by the numeral 10 . transport system 10 includes an ice dispenser 12 having an ice retaining and dispensing bin 14 as defined by a bin liner 14 ′. ice dispenser 12 , as will be understood by those of skill , is an adapted combination ice / beverage dispenser of the type well known in the art . such dispensers typically include a cold plate underlying bin 14 for receiving ice thereon through a hole in liner 14 . a portion of the stored ice that falls through such hole cools the cold plate and hence liquid beverage components flowing there through to beverage dispensing valves . dispenser 12 is different from such ice / beverage dispensers in that it lacks such cold plate and valves , hence a beverage dispensing capacity . however , it does include the insulated ice retaining bin 14 and , as is also well known , a dispensing wheel 15 having ice lifting paddles 15 ′ around the perimeter thereof and ice stirring arms 15 ″. also , without the need for the valves and a cold plate the ice bin can be designed to provide for increased ice capacity . as is understood , rotation of wheel 15 , by a motor 16 , lifts ice to chute opening 17 so that the ice then flows down chute 18 . chute 18 is connected to a tube 20 which is , in turn , connected to a suction or ice receiving inlet 22 of a venturi 24 . as is known in the art wheel 15 can be turned at different rates by , for example , rheostatic control of motor 16 . a blower 26 includes an air filter 27 on an inlet 28 thereof and an air outlet 29 connected to a water assisted air to air heat exchanger 30 . blower 26 is , for example , of the regenerative type as manufactured by gast manufacturing corporation , benton harbor , mich ., denoted a regenair ® model and providing an air flow of 215 cubic feet per minute with a pressure of 95 inches of water . as seen by also referring to fig4 - 6 , heat exchanger 30 includes a fluted or spiraled coiled tube 32 within an insulated housing 34 thereof . tube 32 is connected to blower outlet 29 and on its opposite end to air inlet 35 of venturi 24 . tube 32 is made of aluminum and is of the type manufactured , for example , by delta - t limited , of tulsa , okla . a fan 36 provides for the blowing of air through a housing opening 34 ′ and over tube 32 to exit through a housing air outlet 34 ″. a drain 37 extending from the bottom of bin liner 14 is connected to a tube 38 . tube 38 is connected to a further heat exchange tube 40 that extends around tube 32 in close contact there with and following the spiraled grooves thereof . as seen specifically in fig6 tube 40 can also be placed within tube 32 , as indicated by the phantom lined tube marked as 40 ′. tube 32 can also be a conventional non spiraled cylindrically surfaced tube , and tubes 40 or 40 ′ can simply extend in a coaxial fashion along the length thereof against the interior or exterior surfaces respectively . in fact , interior tube 40 ′ could extend along a central axis of tube 32 and not in contact with the interior surfaces thereof . tube 32 extends in a coiled fashion within housing 34 and exits therefrom connecting with an air inlet 42 of venturi 24 . an ice transport tube 44 extends from an outlet 46 of venturi 24 to a remote ice storage location 48 . storage location 48 can be for example an ice storage bin , or an ice storage bin as part of an automatic ice dispenser or a combination beverage and ice dispenser . a further detailed view of venturi 24 is seen by referring to fig7 and 8 . as can be understood , venturi 24 consists of a common and inexpensive y - junction made of polyvinyl chloride ( pvc ), as is commonly known and used in the plumbing industry . such junction is modified herein to include an air flow concentrating disk 49 . a disk 49 is received in air inlet end 35 and includes a central conical hole 49 ′ for providing an enhanced venturi effect for providing suction along to tube 20 as is indicated by the air direction flow arrows of fig7 . an ice maker 50 is preferably positioned atop dispenser 12 and provides for making ice to fill bin 14 . as is well understood in the art , ice maker 50 includes an ice forming evaporator e , a water pump p fluidly connected to a water reservoir tray t , which tray t is fluidly connected by a fluid level maintaining valve , not shown , to a potable source of water along a line l . a refrigeration system includes a condenser c and a compressor cp . in operation during an ice making mode , water from tray t continually flows over evaporator e by the operation of pump p . at the same time , evaporator e is cooled by the operation the refrigeration system . ice is therefore built up on evaporator e and harvested when of sufficient thickness . the harvested ice then falls directly into bin 14 . an ice bin level sensor 52 is located in bin 14 and connected to a control 54 . control 54 is also operatively connected to the control system of ice maker 50 that regulates the ice making and ice harvesting thereof . a bin level sensor system 56 is located in remote storage location 48 and also connected to control 54 . in operation , it will be understood by those of skill that sensor system 56 can actually consist of high and low level sensors . thus , when the low level sensor indicates low ice , control 54 can operate the transport system 10 of the present invention to deliver ice to location 48 and stop such delivery upon the high level sensor indicating the presence of ice , i . e . that location 48 is full . with respect to such ice transport , it can be understood that control 54 operates motor 16 resulting in the dispensing of ice from bin 14 down chute 18 into tube 20 . at the same time control 54 operates blower 26 and fan 36 to provide for flows of air through and over tube 32 respectively . ice falling down tube 20 will approach venturi 24 and then be sucked by the action thereof into tube 44 and propelled there along by the air flow produced by blower 26 to be delivered to remote location 48 . it will be appreciated by those of skill that a major advantage of the present invention is its ability to continuously transport ice . thus , ice will be transported to remote location 48 as long as wheel 15 is operated and there is sufficient ice in primary storage bin 14 . in that regard , ice bin level sensor 52 and control 54 provide for the operating of ice maker 50 to insure a full reserve of ice in bin 14 . heat exchanger 30 operates to cool the air produced by blower 26 . those of skill will understand that blower 26 will produce air that is heated typically above that of ambient , particularly where ambient is an air conditioned interior space . thus , heat exchanger 30 , by the operation of fan 34 , serves to cool that air before it reaches the ice so as to limit any melting thereof as it is transported . the spiraled tube provides for better heat transfer by presenting greater exterior surface area to the air flow produced by fan 36 and as the air flowing therein has a more turbulent flow , as opposed to a traditional cylindrical tube . tubes 40 or 40 ′ provide for further cooling of the transport air flow through heat exchange with the cold melt water draining from bin 14 as the ice therein melts . thus , the present invention provides for use of cooled water that would be otherwise wasted and directly drained away . those of skill will understand that in certain application where large volumes of ice are not transported and / or transported relatively short distances , such as , less than 20 feet , air exchanger 30 may not be required . in such an installation , blower 26 would simply be directly connected to the inlet 35 of venturi 24 . it will also be understood by those skilled in the art that dispenser 12 can include a beverage dispensing capacity where such is desirable at the location thereof . thus , dispenser 12 can be of the combination ice / beverage type and only slightly modified with respect to connecting the ice chute thereof to venturi 24 . as seen in the further embodiment depicted in fig2 and generally referred to by the numeral 60 , there can be a plurality of remote ice storage / dispensing locations 64 and 66 . a diverter provides for directing flow from tube 44 to either one of a plurality of ice transport tubes , such as , tubes 70 and 72 for specific delivery of the ice to remote ice retaining locations 64 and 66 , respectively . for example , a diverter 68 is used to direct ice flow selectively thereto . as seen in fig9 diverter 68 , as with venturi 24 , can be made from a y - junction as used in venturi 24 . a pivoting rod 68 a extends there through and includes a flapper valve 69 secured thereto . flapper valve 69 is moveable by a drive means , not shown , such as a solenoid or linear actuator , from a normally closed position , represented by the solid line thereof , to be held in an open position , represented by the dashed line thereof . as can be understood by reference to fig2 when diverter 68 is in the open position ice will be diverted to remote location 64 and will be blocked from entering ice location 66 . conversely , when valve 69 of diverter 68 is in the closed position ice will be delivered exclusively to remote location 66 . those of skill will understand that more than two remote locations could be serviced with the use of additional diverters 68 . in such case , only one location would be filled at a time wherein such location would be the only one to have its diverter 68 in the open position , with the remainder in the closed position . naturally , the “ end ” location would not require a diverter as ice would be delivered thereto by default wherein all the diverters simply remain in their normally closed position . control 54 would then be operatively connected to diverter 68 for regulating which tube 70 or 72 ice is directed along as determined by ice level sensing systems 78 and 80 respectively . velocity reducers 81 can be used to slow the speed of the individual ice pieces as they flow downward through the tube portions 72 and 74 . reducers 81 consist essentially of an increased diameter tube portion having an exhaust air outlet , not shown . thus , some of the air pressure moving the ice is reduced as the flow thereof enters the increased diameter section and as that air is permitted to escape there from to ambient . in one embodiment of the present invention wherein a 215 cubic feet m per minute air flow is used , tubes 44 , 70 and 72 have an inside diameter of 2 inches and reducers 81 have an inside diameter of 4 inches and a length of 2 feet . tube portions 70 and 72 will typically have a length of between 4 to 8 feet reaching from the ceiling of the particular installation to the remote storage container . the remote storage containers are typically located between 40 to 90 feet from the primary storage bin 14 . those of skill will appreciate that variation can be made as to tube lengths , diameters thereof , air flow rate and the like to achieve desired results given the demands of a particular installation . thus , for example , longer or shorter ice transport distances can be provided for and / or the transport of greater amounts of ice per unit time . the present invention can also be connected to a source of cooled air such as an existing air conditioning system 82 . thus , a duct 84 thereof can be connected to the inlet 27 of blower 26 . also , in this case , outlet 29 of blower 26 could be directly connected to venturi 24 as any heat exchange with the ambient air would be rendered redundant and probably counter productive . in operation , it can be appreciated that cooled air provided by system 82 can significantly and positively reduce the temperature of the ice moving air within the various ice transport tubes . in this manner , any melting of ice as it is transported can be greatly reduced . as is seen in co - pending application no . 60 / 124 , 058 , now u . s . pat . no . 6 , 324 , 863 and incorporated herein by reference thereto , ozone can be generated to provide for retarding or reducing the growth of microorganisms in the context of beverage dispensers and ice makers . in the present invention an ozone generator 86 can be similarly connected to ice maker 50 , as is disclosed in the above referenced &# 39 ; 058 application . thus ozone can be absorbed directly into the water through a venturi , not shown , connected to a flow of water from pump p . in addition , thereto , or as an alternate method , ozone can simply flow along a tube 88 into bin 14 . additionally , or in the alternative , a further ozone generator 86 ′ can be located adjacent to the air conditioning system 82 and provide for introduction of ozone into duct 84 . use of an ozone generator will provide for increasing the sanitary state of the ice produced by ice maker 50 . in addition , that ice will provide some bactericidal and / or bacteriostatic effect with respect to the presence thereof in the various transport tubes as well as in a remote storage location . if ozone is allowed to simply flow by gravitational force down into bin 14 , it will likewise have a beneficial sanitizing effect as it settles therein and as a fraction thereof is then sucked into and pushed through the transport tubes to and in the remote ice storage locations . introduction of ozone into duct 84 can also serve as a strategy for the reduction of the growth of microorganisms in the tube 32 and the associated transports tubes and remote storage locations . as is seen in co - pending application no . 60 / 122 , 935 now u . s . pat . no . 6 , 324 , 863 and incorporated herein by reference thereto , chlorine can also be utilized to provide for a sanitizing effect in the context of beverage and ice equipment . thus , a chlorine generator 90 can be connected to water supply line l . in this manner , a level of active chlorine can be produced that can reduce or eliminate microorganism growth in the produced ice , and at the same time results in ice that is safe to consume . use of a chlorine generator 90 separately or in conjunction with ozone generator 86 can likewise provide for beneficial reduction and / or control of the growth of microorganisms in bin 14 , as well as the associated transport tubes and remote ice storage locations . thus , the presence of active chlorine in the ice can provide for a retardation of such growth in those components as it is moved there through , melts and leaves small residues of chlorine therein . tubes 20 and 46 , or 70 , 72 or 74 , venturi 24 , liner 14 ′, as well as the liners of the remote storage locations 48 or 62 , 64 and 66 , are comprised of plastic and come into contact with the ice as it is stored and transported . these components can be made of suitable plastic materials that include therein various chemicals that are known to kill or stop the growth of a variety of microorganisms on the surfaces thereof . examples thereof are seen generally in u . s . pat . nos . 5 , 906 , 825 ; 4 , 401 , 702 . a particular such compound is a wide spectrum antibiotic known as triclosan , specifically , 2 , 2 , 4 ′ trichloro 2 ′- hydroxy - diphenyl - ether . expertise in the application of triclosan in a variety of plastics is provided , for example , by microban products company , huntersville , n . c . use of triclosan or other such anti - microbial in the various plastic ice contact components of the present invention can serve as an additional way to reduce any growth of microorganisms thereon . such use can be exclusive of , or complementary with , the use of ozone and / or chlorine as described above .
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this invention relates in large part to polymeric metal chelates and polymeric chelating agents formed using romp . polymeric chelating agents are useful for binding to ( i . e ., chelating ) one or more metal ions and thus forming metal chelates . polymeric chelating agents of this invention are useful generally in any application in which art - known chelating agents are currently employed , such as in purification methods and in analytical methods . polymeric metal chelates have a variety of uses including , among others , applications in therapy , diagnostics , clinical research , biological research , and in analytical methods . metals that can be chelated by the chelating agents of this invention to form metal chelates generally include transition metals , actinide metals and lanthanide metals , and more specifically to gd ( iii ) and dy , fe , mn , pu , u , eu , cu and zn ( in various oxidation states ). polymeric metal chelates of gd ( iii ) are particularly useful as mri contrast enhancing agents . the invention further relates to certain new monomeric chelating agents and metal chelates , including metal chelates of gd ( iii ) useful as mri contrast agents . the polymeric chelating agents and metal chelates of this invention incorporate chelating groups into the backbone of a romp - derived polymer . the structures of various romp - derived polymer backbones are illustrated in formulas 1 , 2 , 2a , 2b , 3 , 3a and 3b . integration of the chelating group into the polymer backbone means that functional groups directly bonded to the polymer backbone are part of the chelating group . the chelating group is not simply tethered to the polymer backbone via a linker . scheme 1 illustrates several examples showing how the chelating group ( without chelated metal ion ) are integrated into different romp - derived backbones . variables in scheme 1 are as defined above . each individual polymeric chelating agent and metal chelate described and / or shown herein is intended to be incorporated to the extent that it can be specifically included or excluded in a claim , if necessary . the polymeric and monomeric metal chelates and mri contrast agents of this invention are generally water - soluble . mri contrast agents which exhibit significant water solubility provide benefit because the agents are typically administered in multigram dosages to the individual subject to the mri assay and more water soluble agents require generally lower administration volumes which provide for ease of administration . the mri contrast agents of this invention generally exhibit water - solubility that is significantly greater than that of currently - employed clinical mri contrast agents . relaxivity is a measure of the ability of an agent to enhance contrast in a magnetic resonance image . relaxivities were determined as the slope of the line generated by plotting the inverse of t 1 relaxation time versus concentration . relaxivity is measured in units of mm − 1 s − 1 . for polymers which carry more than one metal ion ( i . e ., gd ( iii )), it is useful to examine relaxivity / metal ion ( i . e ., per gd ( iii ) ion ). monomer contrast agents of this invention ( as exemplified by compound 11 , see the examples ) exhibit relaxivity of the order of 10 mm − 1 s − 1 . the relaxivities of exemplary shorter ( e . g ., dp = 8 ) and longer polymeric contrast agents of this invention can be compared . for example , a shorter polymeric contrast agent ( agent 10 a , see the examples ), which on average contains 2 gd ( iii )/ polymer , exhibits relaxivity of the order of 20 mm − 1 s − 1 — relaxivity that is approximately additive with gd ( iii ) ion . in contrast , a significant increase in per gd ( iii ) ion relaxivity ( i . e . better than additive ) is observed for longer polymeric contrast agents as exemplified by agent 10 b ( see the examples ), which has dp of 30 and on average carries 7 . 5 gd ( iii ) ions . thus , longer polymeric contrast agents of this invention are generally preferred as long as they remain water - soluble . in specific embodiments , linear polymeric chelating agents herein can have dp ranging from 8 - 100 , dp ranging from 10 to 50 , dp ranging from 20 to 40 , dp ranging from 25 to 35 and dp of 30 . dp is the degree of polymerization and is the number of monomer units in the polymer . the invention also relates to block polymers comprising one or more blocks that are romp - derived polymers that in turn contain one or more hydroxypyridonate ( hopo )- based chelating moieties integrated into the polymer backbone . these chelating moieties can bind metals as noted above . in specific embodiments , the invention provides block polymeric metal chelates of transition metals , actinide metals , or lanthanide metals , and more specifically provides block polymers that chelate one or more gd ( iii ) metal ions and which are useful as mri contrast agents . more specifically the invention relates to graft block polymers which are chelating agents and metal chelates . a graft polymer is a polymer comprising a main chain polymer block and one or preferably more than one graft side chain blocks . the side chain blocks are typically different in structure ( e . g ., polymer backbone , side - chain composition , length , etc .) and / or configuration compared to the main chain polymer block . specific graft block polymers that are chelating agents and metal chelates have main chains that are romp - derived polymer blocks carrying one or more hopo - based chelating moieties integrated into the polymer backbone . the graft polymer portion can be any polymer that can be grafted to the main chain romp - derived polymer . in specific embodiments , the graft side chains are also romp - derived polymer blocks which preferably differ form the main chain block . in preferred embodiments , the graft side chain romp - derived polymers do not contain metal chelating groups . in specific embodiments , the main chain romp - derived polymer contains at least one and preferably more than one side chain which is itself a monomer for romp . in this embodiment , the graft polymer block side groups can be formed by romp from the one or more romp monomer side groups of the main chain . the romp - derived main chain polymer can contain one or more chelating groups and metal - containing chelating groups r 3 as disclosed herein . the romp - derived main chain polymer can contain one or more r 4 groups as defined herein . in specific embodiments , the main chain generated by romp can contain r 4 groups that are spacer groups , solubilizing groups , targeting groups , labeling groups or groups that increase the rotational correlation time of the polymer . the main chain polymer generated by romp can have any of the structures as defined herein for romp - derived polymeric metal chelates and chelating agents , but , in addition , carries at least one and preferably more than one side chain which is a romp monomer to allow formation of the graft polymer side chains . in specific embodiments , the main chain block carries chelating side groups and one or more than one grafted side chain romp - derived polymer blocks . in specific embodiments , the graft block polymers herein carry one or more chelating groups ( with or without chelated metal ), one or more solubilizing groups , one or more targeting groups , and / or one or more labeling groups . the graft block polymers may also contain one or more r 4 groups which serve to increase the rotational correlation time of the polymer . the graft side chain romp - derived polymer can have any of the romp - derived backbone structures as described herein and can carry any of the spacer side groups as described herein . in specific embodiments , the graft side chain romp polymer carries side groups which are hydrophilic and which promote water - solubility of the block polymer . preferably the romp - derived main chain ranges in dp from about 10 - 40 and more preferably ranges in dp from about 10 - 20 . preferably , the graft side chain romp - derived polymers range in dp from about 5 to about 50 and more preferably range in dp form 10 to 30 . in specific embodiments , the main chain block has dp of 10 - 15 and the side chain block have dp of 15 to 30 . in specific embodiments there are 2 - 4 side chain blocks . in specific embodiments , the main chain block comprises on average 10 monomers carrying chelating groups ( r 3 ) and on average 4 monomers to which side chain grafts are formed . fig1 is a schematic illustration comparing a linear polymer 5 with a graft block polymer 10 which contains a main chain 11 and several graft block side chains 12 . the arrows indicate that the graft block polymer will tumble more slowly around the indicated axis than the linear polymer . this indicates the graft block polymer will exhibit an increased rotational correlation time compared to the linear polymer . polymers carrying chelated gd ( iii ) ions which have higher rotational correlation times will exhibit enhanced potency as mri contrast agents . schemes 2 and 3 illustrate exemplary graft block polymers in which the main chain romp - derived block polymer carries chelating groups . scheme 2 illustrates grafting of romp - derived polymer side chains onto a rom - derived main chain . in this scheme , a precursor main chain romp - derived polymer is reacted to graft a plurality of graft side chain romp - derived polymers to the main chain . the precursor romp - derived polymer main chain carries x side groups carrying reactive groups that can subsequently be functionalized to hopo - based chelating groups and carries y side groups that are romp monomers for forming grafts . the graft side chains are formed by reacting a romp monomer carrying a protected side group , which , when deprotected , will be a hydrophilic , charged group that promotes water - solubility of the polymer . in the illustrated scheme , z is the average number of monomer units in the graft side chain romp - derived polymer . in specific embodiments , x + y ranges from 10 - 20 and z ranges from 5 to 30 . in specific embodiments , the ratio of x / y ranges from 0 . 5 to 5 and in specific embodiments , x / y is 2 - 3 . in specific embodiments , z is 18 - 25 and in other embodiments z is 20 . scheme 3 illustrates the synthesis of a romp - derived polymer that is used as the main chain polymer in the graft block polymer . it will be appreciated that the romp - derived main chain block can be prepared having any of the polymer backbone structures illustrated herein and having any of the r 1 or r 2 groups or having any of the r 3 and / or r 4 groups as illustrated herein . it will be further appreciated that that the graft side chain romp - derived polymers can be prepared having any of the polymer backbone structures illustrated herein and to carry any side chain groups that are illustrated herein . it will be appreciated that the graft block polymer can be derivatized as illustrated in scheme 1 in view of examples provided herein with any of the hopo - based chelating groups illustrated herein . in specific embodiments , polymeric mri contrast agents of this invention carry on average 3 or more gd ( iii ) ions . in other embodiments , they carry on average 5 or more gd ( iii ) ions . in yet other embodiments , they carry on average 7 or more gd ( iii ) ions . in additional embodiments , they carry on average 10 or more gd ( iii ) ions . in specific embodiments , polymeric mri contrast agents of this invention exhibit relaxivity of about 10 mm − 1 s − 1 per gd ( iii ) ion . in specific embodiments , polymeric mri contrast agents of this invention exhibit relaxivity of greater than 10 mm − 1 s − 1 per gd ( iii ) ion . in specific embodiments , polymeric mri contrast agents of this invention exhibit relaxivity of greater than 12 mm − 1 s − 1 per gd ( iii ) ion . in specific embodiments , polymeric mri contrast agents of this invention exhibit relaxivity of greater than 14 mm − 1 s − 1 per gd ( iii ) ion . in specific embodiments , metal chelating polymeric compounds of the invention have one or more r3 groups . in specific embodiments , polymers having multiple chelating groups and one or more cell targeting or cytotoxic compounds are presented . specific embodiments of the invention are trimers or tetramers of only r3 are used as contrast agents for mri with improved signal over conventionally used chelate contrast agents . the ratio of chelating side group to spacer group is varied by adjusting the stoichiometry of conjugation of those groups with the polymer backbone . in the specific examples , 0 . 25 equivalents per monomer of the chelating side group are employed with 0 . 75 equivalents of the spacer group to give a ratio of spacer to chelating groups of 3 : 1 . the stoichiometry can be varied , as is known in the art , to obtain desired relative amounts of different polymer side chains . it is preferred for mri contrast agents to have a polymer that has the highest number of chelating groups per polymer that bind gd ( iii ), while minimizing interference between the chelating groups and preserving polymer solubility in water . exemplary polymers , in which all of the monomers carry chelating side groups and no spacers , exhibited very low relaxivity values , the observed low relaxivity is believed to be the result of chelating groups blocking water access to adjacent metal chelates . chelating agents of this invention can form high stability complexes with gd ( iii ) compatible with safe administration to individuals subjected to imaging assays . the term “ reactive functional group ” is used broadly herein to refer to a functional group which can react to form a bond to a chemical compound of interest , to a particle or the surface of a solid . reactive functional groups are used herein to form a bond between a metal chelating agent of this invention , e . g ., an mri contrast agent of this invention with a chemical compound of interest or a particle or solid surface such that the agent is attached or bonded to the chemical compound , particle or solid . the bond that is formed is typically a covalent bond , but need not be a covalent bond . a variety of reactive functional groups are known in the art that can be employed for this function . the reactive functional group is chosen based on the structure and chemical reactivity of the agent and the species ( compound , particle or surface ) to which it is intended to form a bond . compounds of interest include targeting groups ( see below ), macromolecules ( polysaccharides , proteins , peptides , nucleic acids , and small molecules ). particles and solids of interest include nanoparticles , beads and substrates made of resin , glass , plastics and similar materials , and labeling groups ( see below ). in specific examples , reactive groups are activated ester groups , which is a generic term used in the art to refer to ester groups that are activated to be more reactive , for example , by the presence of a good leaving group . in specific embodiments n - hydroxysuccinimide esters can be employed as reactive groups . the linking group that is formed between a chelating agent of this invention and a compound of interest , a particle or a solid can be selectively cleavable . the linking group can be selected such that it can be selectively cleaved by exposure to a reactive species or medium . for example , the bond can be cleavable by a change in ph , exposure to a reactive chemical or biological species ( i . e ., a reagent or enzyme ) or exposure to light of a selected wavelength . the term “ targeting group ” is used herein to refer to a chemical moiety that can be attached to a chelating or contrast agent of this invention and which exhibits an affinity for binding to , adsorption on , being absorbed by , or entering into a macromolecule ( particularly a biologically functional macromolecule ), or a target cell or tissue , such as a cancerous cell or tumor tissue , or a biological fluid , such as blood . a targeting group can be a small molecule , such as a peptide , nucleic acid , receptor ligand , sugar , antigen , or other small molecule exhibiting a binding affinity for a cell surface , receptor or for a macromolecule . a targeting group can be a peptide . the targeting group can also be a macromolecule , including without limit saccharides , polysaccharides , lectins , receptors , ligands for receptors , proteins , antibodies , poly ( ethers ), dendrimers , poly ( amino acids ) and nucleic acids . in specific embodiments , the targeting group can bind a component of blood , particularly a protein component of blood , such as serum albumin . a contrast agent comprising a targeting group that binds a blood component can enhance its blood pool residence time and rotational correlation time . in specific embodiments , targeting groups are linear and cyclic peptides , which may be naturally - occurring or synthetic peptides , such as peptides containing the arginine - glycine - aspartate ( rgd ) sequence motif . specific examples of rgd peptides include among others the cyclic peptide rgdfk ( targeting agent 1 ) and gggggrgdy ( targeting agent 2 ). as illustrated below , exemplary peptide targeting agents useful in this invention will contain a peptide sequence for targeting , such as the rgd sequence for targeting to integrins , as well as a functional group , such as an amine , that can be conjugated to the polymer backbone via a reactive group which reacts with amines . the targeting group , may itself contain a spacer group ( e . g ., for a peptide targeting group a glycine linker ) and may further contain a label that facilitates detection of the presence of the targeting group , such as a group that aids in 1 h - nmr characterization . any targeting group that contains a hydrazine or acylhydrazide ( or is derivatized to contain a hydrazine or acylhydrazide ), can be readily reacted with the ketone of r 2 to link the targeting groups to the metal chelate or chelating agent through the formation of a hydrazone or hydrazide linkage , respectively . additionally , amine derivates of targeting groups can be attached at r 2 , r s or r 5 as defined in the summary of the invention above , through an amide linker . various derivatives of targeting peptides can be attached to the polymers herein through various linkers , including among others , urea , thiourea , and squarate . in specific embodiments , amine - containing targeting groups ( and guanidinium - substituted amines ) can be reacted with the n - hydroxysuccinimide esters to connect them to the backbone . it will be appreciated in the art that a variety of linkers can be employed to couple or conjugate derivatized targeting groups to the polymers of this invention . the term “ labeling group ” is used herein to refer to any chemical species , particle or solid which exhibits or can be stimulated to exhibit a detectable signal . the label may be a radioactive label , a fluorescent label , a small molecule label ( e . g ., biotin ), a reactive label ( e . g ., a species whose reaction with a reagent or substrate can be detected , for example an enzyme ). in specific embodiments , the labeling group is a fluorophore . exemplary fluorophores are those that contain a hydrazine group which can be readily reacted with the chelating and mri contract agents of this invention . in specific embodiments , the labeling group is a radioactive label . any labeling groups , particularly a fluorophore , that contains a hydrazine or acylhydrazide can be readily reacted with the ketone at r 2 to link the labeling group ( e . g ., fluorophore ) to the metal chelator or chelating agents through the formation of a hydrazone or hydrazide linkage , respectively . additionally , amine derivatives of labeling groups can be attached at r 2 , r s or r 5 as defined in the summary of the invention above , through an amide linker . other linkers can be employed as well with derivatized labeling groups including among others , urea , thiourea , and squarate . in specific embodiments , amine - containing labeling groups ( and guanidinium - substituted amines ) can be reacted with the n - hydroxysuccinimide esters to connect them to the backbone . it will be appreciated in the art that a variety of linkers can be employed to couple or conjugate a labeling group to the polymers of this invention . in a specific embodiment , the attachment of one or more fluorescent labels to a mri contrast agent of this invention would enable both fluorescent microscopy and mr imaging — which can be useful , for example , in biological research applications , in developmental biology , or verification of mr images with histology . the attachment of one or more radioactive labels to a mri contrast agent of this invention would be useful for dual imaging with pet ( positron emission tomography ) or spect ( single photon emission computed tomography ). radioactive labels for pet include carbon - 11 , oxygen - 15 , fluorine - 18 , and bromine - 75 ; while radioactive labels for spect include chelates of xenon - 133 , technetium - 99 , or iodine - 123 . the radiolabels can , for example , be conjugated at r 2 through a hydrazone or acylhydrazide linker , similar to that mentioned for above . additionally , amine derivates of either fluorescent or radiolabels could be attached at r 2 , r s or r 5 through an amide linker . in specific embodiments , the chelating agents , metal chelates , and mri contrast agents of this invention can be bonded or attached to particles or solid surfaces . the attachment to particles , solids or surfaces can be formed through a selectively cleavable linker such that the agent can be selectively separated from the particle , solid or surface . in specific embodiments , the particles are nanoparticles ( see , for example , the description in brigger et al . nanoparticles in cancer therapy and diagnosis , advanced drug delivery reviews 54 ( 2002 ) 631 - 651 ) which are useful in cancer therapy and diagnosis . the mri contrast agents of this invention can be attached to nanoparticles loaded with anticancer drugs / targeted to cancer cells to provide combination diagnostic / therapeutic agents . chemical reactions similar to those discussed above for attachment of labeling groups and targeting groups can be employed to link chelating agents and metal chelates of this invention to particles , such as nanoparticles , and to solids . the polymeric and monomeric chelating agents and metal chelates of this invention can be prepared by methods described herein in the examples and or by routine adaptation of these methods by varying the type and relative amounts of starting monomers , by varying reagents and other reactants as is known in the art and by employing additional methods that are known in the art . in exemplary embodiments , polymers of this invention can be prepared as illustrated in the specific examples herein in which a precursor romp - derived polymer comprising monomers carrying reactive groups ( e . g ., activated esters ) is reacted with a mixture of components that are to be attached to the polymer . scheme 2 illustrates , for example , synthesis of polymeric metal chelates in which a portion of the monomers of the polymer carry chelating groups and a portion carry spacer / solubilizing groups . the various polymeric chelating agents and metal chelates of this invention can be prepared by methods analogous to those illustrated in the examples . the methods illustrated in the examples and scheme 3 can also be employed to prepare main chain romp - derived polymers of the graft block polymers of this invention . graft block polymers of this invention can be synthesized for example employing methods as illustrated in scheme 2 . in general the terms and phrases used herein have their broadest art - recognized meaning , which can be found by reference to standard texts , journal references and contexts known to those skilled in the art . any definitions provided are provided to clarify the specific use of these terms and phrases in the context of the invention . the term “ alkyl ” refers to a monoradical of a branched or unbranched ( straight - chain or linear ) saturated hydrocarbon and to cycloalkyl groups having one or more rings . unless otherwise indicated preferred alkyl groups have 1 to 30 carbon atoms and more preferred are those that contain 1 - 22 carbon atoms . short alkyl groups are those having 1 to 6 carbon atoms including methyl , ethyl , propyl , butyl , pentyl and hexyl groups , including all isomers thereof . long alkyl groups are those having 8 - 30 carbon atoms and preferably those having 12 - 22 carbon atoms as well as those having 12 - 20 and those having 16 - 18 carbon atoms . the term “ cycloalkyl ” refers to cyclic alkyl groups having preferably 3 to 30 carbon atoms having a single cyclic ring or multiple condensed rings . cycloalkyl groups include , by way of example , single ring structures such as cyclopropyl , cyclobutyl , cyclopentyl , cyclooctyl , and the like , or multiple ring structures such as adamantanyl , and the like . the term “ alkenyl ” refers to a monoradical of a branched or unbranched unsaturated hydrocarbon group and to cycloalkenyl groups having one or more rings wherein at least one ring contains a double bond . unless otherwise indicated preferred alkyl groups have 1 to 30 carbon atoms and more preferred are those that contain 1 - 22 carbon atoms . alkenyl groups may contain one or more double bonds ( c ═ c ) which may be conjugated or unconjugated . preferred alkenyl groups are those having 1 or 2 double bonds and include omega - alkenyl groups . short alkenyl groups are those having 2 to 6 carbon atoms including ethylene ( vinyl ), propylene , butylene , pentylene and hexylene groups , including all isomers thereof . long alkenyl groups are those having 8 - 30 carbon atoms and preferably those having 12 - 22 carbon atoms as well as those having 12 - 20 carbon atoms and those having 16 - 18 carbon atoms . the term “ cycloalkenyl ” refers to cyclic alkenyl groups of from 3 to 30 carbon atoms having a single cyclic ring or multiple condensed rings in which at least one ring contains a double bond ( c ═ c ). cycloalkenyl groups include , by way of example , single ring structures such as cyclopropenyl , cyclobutenyl , cyclopentenyl , cyclooctenyl , cylcooctadienyl and cyclooctatrienyl . the term “ alkynyl ” refers to a monoradical of an unsaturated hydrocarbon having one or more triple bonds ( c ≡ c ). unless otherwise indicated preferred alkyl groups have 1 to 30 carbon atoms and more preferred are those that contain 1 - 22 carbon atoms . alkynyl groups include ethynyl , propargyl , and the like . short alkynyl groups are those having 2 to 6 carbon atoms , including all isomers thereof . long alkynyl groups are those having 8 - 22 carbon atoms and preferably those having 12 - 22 carbon atoms as well as those having 12 - 20 carbon atoms and those having 16 - 18 carbon atoms . alkyl , alkenyl , alkynyl and aryl groups may be substituted or unsubstituted . alkyl , alkenyl , alkynyl and aryl groups may be optionally substituted as described herein and may contain non - hydrogen substituents dependent upon the number of carbon atoms in the group and the degree of unsaturation of the group . unless otherwise indicated substituted alkyl , alkenyl , alkynyl and aryl groups preferably contain 1 - 10 , and more preferably 1 - 6 , and more preferably 1 , 2 or 3 non - hydrogen substituents . preferred non - hydrogen substituents unless otherwise stated are halides , hydroxides , alkyl , and aryl groups ( e . g ., benzyl or phenyl groups ). the term alkoxy ( or alkoxide ) refers to a — o - alkyl group , where alkyl groups are as defined above . the term alkeneoxy ( alkenoxide ) refers to a — o - alkenyl group where alkenyl groups are as defined above and wherein a double bond is preferably not positioned at the carbon bonded to the oxygen . the term alkyneoxy ( alkynoxide ) refers to a — o - alkynyl group where alkynyl groups are as defined above and wherein a triple bond is not positioned at the carbon bonded to the oxygen . the term “ aryl ” refers to a group containing an unsaturated aromatic carbocyclic group of from 6 to 22 carbon atoms having a single ring ( e . g ., phenyl ), one or more rings ( e . g ., biphenyl ) or multiple condensed ( fused ) rings , wherein at least one ring is aromatic ( e . g ., naphthyl , dihydrophenanthrenyl , fluorenyl , or anthryl ). aryls include phenyl , naphthyl and the like . aryl groups may contain portions that are alkyl , alkenyl or alkynyl in addition to the unsaturated aromatic ring ( s ). the term “ alkaryl ” refers to the aryl groups containing alkyl portions , i . e ., - alkylene - aryl and - substituted alkylene - aryl ). such alkaryl groups are exemplified by benzyl , phenethyl and the like . the term “ thioalkoxyl ” refers to an alkyl group attached to the remainder of the molecule via a sulfur atom (— s - alkyl ). the term “ thioether ” refers to an ether group attached to the remainder of the molecule via a sulfur atom . the term “ ester ” refers to chemical entities containing a — coo — moiety , as understood in the art , and in particular can include groups of the form rco — o — or — co — or where r is optionally substituted alkyl , alkenyl , alkynyl or aryl . the term “ activated ester ” is understood in the art to refer to an ester group activated for reaction , for example , by the presence of a good leaving group . the term “ ether group ” also “ alkoxyalkyl ” refers to an alkyl group in which one or more — ch 2 — groups are replaced with — o —. unless otherwise specified preferred alkoxyalkyl groups have from 3 to 30 carbon atoms and more preferably have 6 to 22 carbon atoms . ether groups include groups of the formula : —[( ch 2 ) a — o —] b — ch 3 where a is 1 - 10 and b is 1 - 6 . more specifically , a can be 2 , 3 or 4 and b can be 1 , 2 or 3 . alkoxyalkyl groups can be branched by substitution of one or more carbons of the group with alkyl groups . the term “ thioether ” refers to refers to an alkyl group in which one or more — ch 2 — groups are replaced with — s —. unless otherwise specified preferred thioether groups have from 3 to 30 carbon atoms and more preferably have 6 to 22 carbon atoms . thioether groups include groups of the formula : —[( ch 2 ) a — s —] b — ch 3 where a is 1 - 10 and b is 1 - 6 . more specifically , a can be 2 , 3 or 4 and b can be 1 , 2 or 3 . thioether groups can be branched by substitution of one or more carbons of the group with alkyl groups . the term “ alkylene ” refers to a diradical of a branched or unbranched saturated hydrocarbon chain , which unless otherwise indicated can have 1 to 10 carbon atoms , or 1 - 6 carbon atoms , or 2 - 4 carbon atoms . this term is exemplified by groups such as methylene (— ch 2 —), ethylene (— ch 2 ch 2 —), more generally —( ch 2 ) n —, where n is 1 - 10 or more preferably 1 - 6 or n is 2 , 3 or 4 . alkylene groups may be branched , e . g ., by substitution with alkyl group substituents . alkylene groups may be optionally substituted as described herein . alkylene groups may have up to two non - hydrogen substituents per carbon atoms . preferred substituted alkylene groups have 1 , 2 , 3 or 4 non - hydrogen substituents . hydroxy - substituted alkylene groups are those substituted with one or more oh groups . the term “ alkoxyalkylene ” refers to a diradical of a branched or unbranched saturated hydrocarbon chain in which one or more — ch 2 — groups are replaced with — o —, which unless otherwise indicated can have 1 to 10 carbon atoms , or 1 - 6 carbon atoms , or 2 - 4 carbon atoms . this term is exemplified by groups such as — ch 2 och 2 —, — ch 2 ch 2 och 2 ch 2 —, — ch 2 ch 2 och 2 ch 2 och 2 ch 2 — and more generally —[( cr ″ 2 ) a — o —] b —( cr ″ 2 ) c , where r ″ is hydrogen or alkyl , a is 1 - 10 , b is 1 - 6 and c is 1 - 10 or more preferably a and c are 1 - 4 and b is 1 - 3 . alkoxyalkylene groups may be branched , e . g ., by substitution with alkyl group substituents . the term “ amino ” or “ amine group ” refers to the group — nh 2 or to the group — nrr where each r is independently selected from the group consisting of hydrogen , alkyl , substituted alkyl , cycloalkyl , substituted cycloalkyl , alkenyl , substituted alkenyl , cycloalkenyl , substituted cycloalkenyl , alkynyl , substituted alkynyl , aryl , heteroaryl and heterocyclic provided that both r &# 39 ; s are not hydrogen . specific amine groups are those in which each r can be hydrogen or an optionally substituted alkyl group , including hydroxide - substituted amines . the term “ amide ” refers to a group containing the — co — nr — moiety where r is selected from the group consisting of hydrogen , alkyl , substituted alkyl , cycloalkyl , substituted cycloalkyl , alkenyl , substituted alkenyl , cycloalkenyl , substituted cycloalkenyl , alkynyl , substituted alkynyl , aryl , heteroaryl and heterocyclic . specific amide groups are optionally substituted alkyl amides , including hydroxide - substituted amides . the term “ heterocycle ” or “ heterocyclic ” refers to a monoradical saturated or unsaturated group having a single ring or multiple condensed rings , from 2 - 22 carbon atoms and from 1 to 6 hetero atoms , preferably 1 to 4 heteroatoms , selected from nitrogen , sulfur , phosphorus , and / or oxygen within at least one ring . heterocyclic groups may be substituted . haloalkyl refers to alkyl as defined herein substituted by one or more halides ( e . g ., f —, cl —, i —, br —) as defined herein , which may be the same or different . a haloalkyl group may , for example , contain 1 - 10 halide substituents . representative haloalkyl groups include , by way of example , trifluoromethyl , 3 - fluorododecyl , 12 , 12 , 12 - trifluorododecyl , 2 - bromooctyl , 3 - bromo - 6 - chloroheptyl , and the like . haloalkyl groups include fluoroalkyl groups . in the definitions herein optional substitution includes substitution with one or more halogens , nitro groups ; cyano groups ; isocyano groups ; thiocyano groups (— s — c ≡ n ); isothiocyano groups (— n ═ c ═ s ); azide groups ; — so 2 groups ; — oso 3 h groups ; straight - chain , branched or cyclic alkyl , alkenyl or alkynyl groups ; halogenated alkyl groups ; hydroxyl groups ; alkoxy groups ; carboxylic acid and carboxylic ester groups ; amine groups ; carbamate groups , thiol groups , thioether and thioester groups ; sulfoxide groups , sulfone groups ; sulfide groups ; sulfate and sulfate ester groups ; sulfonate and sulfonate ester groups ; sulfonamide groups , sulfonate ester groups ; phosphine groups ; phosphate and phosphate ester groups ; phosphonate and phosphonate ester groups ; various silyl groups , including alkyl - substituted silyl groups . some particular ring substituents include : — br , — oh , — so 3 , isothiocyano , thiocyano , carboxylic acid and carboxylic acid derivatives , — nh 2 , amines and — no 2 and any salts thereof . compounds of the present invention , and salts or esters thereof , may exist in their tautomeric form , in which hydrogen atoms are transposed to other parts of the molecules and the chemical bonds between the atoms of the molecules are consequently rearranged . it should be understood that all tautomeric forms , insofar as they may exist , are included within the invention . additionally , the compounds may have trans and cis isomers and may contain one or more chiral centers , therefore existing in enantiomeric and diastereomeric forms . the invention can encompass all such isomers , individual enantiomers , as well as mixtures of cis and trans isomers , mixtures of diastereomers ; non - racemic and racemic mixtures of enantiomers ( optical isomers ); and the foregoing mixtures enriched for one or more forms ; except as stated otherwise herein . when no specific mention is made of the configuration ( cis , trans or r or s ) of a compound ( or of an asymmetric carbon ), then any one of the isomers or a mixture of more than one isomer is intended . the processes for preparation can use racemates , enantiomers , or diastereomers as starting materials . when enantiomeric or diastereomeric products are prepared , they can be separated by conventional methods , for example , by chromatographic or fractional crystallization . the inventive compounds may be in the free or hydrate form . as to any of the above groups which contain one or more substituents , it is understood , that such groups do not contain any substitution or substitution patterns which are sterically impractical and / or synthetically non - feasible . in addition , the compounds of this invention include all stereochemical isomers arising from the substitution of these compounds . the compounds of this invention may contain one or more chiral centers . accordingly , this invention is intended to include racemic mixtures , diasteromers , enantiomers and mixture enriched in one or more stereoisomer . the scope of the invention as described and claimed encompasses the racemic forms of the compounds as well as the individual enantiomers and non - racemic mixtures thereof . when a group of substituents is disclosed herein , it is understood that all individual members of that group and all subgroups , including any isomers , enantiomers , and diastereomers of the group members , are disclosed separately . when a markush group or other grouping is used herein , all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure . a number of specific groups of variable definitions have been described herein . it is intended that all combinations and subcombinations of the specific groups of variable definitions are individually included in this disclosure . specific names of compounds are intended to be exemplary , as it is known that one of ordinary skill in the art can name the same compounds differently . when a compound is described herein such that a particular isomer , enantiomer or diastereomer of the compound is not specified , for example , in a formula or in a chemical name , that description is intended to include each isomers and enantiomer of the compound described individually or in any combination . additionally , unless otherwise specified , all isotopic variants of compounds disclosed herein are intended to be encompassed by the disclosure . for example , it will be understood that any one or more hydrogens in a molecule disclosed can be replaced with deuterium or tritium . isotopic variants of a molecule are generally useful as standards in assays for the molecule and in chemical and biological research related to the molecule or its use . isotopic variants may also be useful in diagnostic assays and in therapeutics . methods for making such isotopic variants are known in the art . specific names of compounds are intended to be exemplary , as it is known that one of ordinary skill in the art can name the same compounds differently . many of the molecules disclosed herein contain one or more ionizable groups [ groups from which a proton can be removed ( e . g ., — cooh ) or added ( e . g ., amines ) or which can be quaternized ( e . g ., amines )]. all possible ionic forms of such molecules and salts thereof are intended to be included individually in the disclosure herein . with regard to salts of the compounds herein , one of ordinary skill in the art can select from among a wide variety of available counterions those that are appropriate for preparation of salts of this invention for a given application . in specific applications , the selection of a given anion or cation for preparation of a salt may result in increased or decreased solubility of that salt . every formulation or combination of components described or exemplified herein can be used to practice the invention , unless otherwise stated . whenever a range is given in the specification , for example , a temperature range , a time range , or a composition or concentration range , all intermediate ranges and subranges , as well as all individual values included in the ranges given are intended to be included in the disclosure . it will be understood that any subranges or individual values in a range or subrange that are included in the description herein can be excluded from the claims herein . all patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains . references cited herein are incorporated by reference herein in their entirety to indicate the state of the art as of their publication or filing date and it is intended that this information can be employed herein , if needed , to exclude specific embodiments that are in the prior art . for example , when composition of matter are claimed , it should be understood that compounds known and available in the art prior to applicant &# 39 ; s invention , including compounds for which an enabling disclosure is provided in the references cited herein , are not intended to be included in the composition of matter claims herein . as used herein , “ comprising ” is synonymous with “ including ,” “ containing ,” or “ characterized by ,” and is inclusive or open - ended and does not exclude additional , unrecited elements or method steps . as used herein , “ consisting of ” excludes any element , step , or ingredient not specified in the claim element . as used herein , “ consisting essentially of ” does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim . in each instance herein any of the terms “ comprising ”, “ consisting essentially of ” and “ consisting of ” may be replaced with either of the other two terms . the invention illustratively described herein suitably may be practiced in the absence of any element or elements , limitation or limitations which is not specifically disclosed herein . one of ordinary skill in the art will appreciate that starting materials , biological materials , reagents , synthetic methods , purification methods , analytical methods , assay methods , and biological methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation . all art - known functional equivalents , of any such materials and methods are intended to be included in this invention . the terms and expressions which have been employed are used as terms of description and not of limitation , and there is no intention that in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof , but it is recognized that various modifications are possible within the scope of the invention claimed . thus , it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features , modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art , and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims . all references cited herein are hereby incorporated by reference to the extent that there is no inconsistency with the disclosure of this specification . some references provided herein are incorporated by reference to provide details concerning additional assay methods , sources of starting materials and biological materials , additional starting materials , additional reagents , additional methods of synthesis , additional methods of analysis , additional biological materials and additional uses of the invention . commercial chemicals were of reagent grade or better and used without further purification unless otherwise noted . dichloromethane and diisopropylethylamine were distilled from calcium hydride ; tetrahydrofuran ( thf ) was distilled from sodium / benzophenone , and methanol was distilled from magnesium . flash chromatography was performed using silica gel 60 , 230 - 450 mesh ( sorbent technologies ). analytical thin - layer chromatography ( tlc ) was carried out on em science tlc plates precoated with silica gel 60 f 254 ( 250 - μm layer thickness ). tlc visualization was accomplished using a uv lamp and / or charring with potassium permanganate stain ( 3 g kmno 4 , 20 g k 2 co 3 , 5 ml 5 % ( w / v ) aqueous naoh , 300 ml h 2 o ). milliq water and pd - 10 columns ( amersham biosciences ) were used for polymer purification . 1 h nmr spectra were obtained using a bruker ac - 300 ( 300 mhz ) or varian unity - 500 ( 500 mhz ) spectrometer , and 13 c nmr spectra were obtained using a bruker ac - 300 ( 75 mhz ) spectrometer . chemical shifts are reported relative to residual solvent signals ( cdcl 3 : 1 h : δ 7 . 27 , 13 c : δ 77 . 23 ; cd 3 od : 1 h : δ 3 . 31 , 13 c : δ 49 . 15 ; dmso - d 6 : 1 h : δ 2 . 50 , 13 c : δ 39 . 51 ; d 2 o : 1 h : δ 4 . 79 , 13 c : δ 39 . 51 — internal dmso - d 6 standard ). 1 h nmr data are assumed to be first order with apparent doublets and triplets reported as d and t , respectively . multiplets are reported as m , and resonances that appear broad are designated as bs . high - resolution electrospray ionization mass spectra ( hresi - ms ) were obtained on a micromass lct . liquid chromatography and mass spectrometry ( lc - ms ) analysis was performed on a shimadzu lc - ms containing a c18 column ( supelco discovery , 2 . 1 × 150 mm ) equilibrated with 0 . 4 % ( v / v ) formic acid . polydispersity index ( pdi ) values were obtained using a beckman coulter high - performance liquid chromatography system , two polymer laboratories plgel 5 μm mixed - d 300 × 7 . 5 mm columns in series , polymer laboratories easical polystyrene standards ( ps - 1 ), and cirrus gpc offline gpc / sec software version 1 . 2 . elemental analyses and gd solution concentration determinations were performed at desert analytics laboratory , tucson , ariz . the longitudinal water proton relaxation rate at 60 mhz was measured by using a bruker mq60 nmr analyzer ( bruker canada , milton , ont . canada ) operating at 1 . 5 t , by means of the standard inversion - recovery technique ( 20 data points , 8 scans each ). a typical 90 °- pulse length was 6 . 16 μs , and the reproducibility of the t 1 data was ± 0 . 3 %. temperature was maintained at 22 ° c . with a haake g cooling circulator . 3 - hydroxy - 6 - methyl - 2 - oxo - 1 , 2 - dihydropyridine - 4 - carboxylic acid ethyl ester ( 4 ) ( doble , d . m . j . ; melchoir , m . ; o &# 39 ; sullivan , b . ; siering , c . ; xu , j . ; pierre , v . c . ; raymond , k . n . inorg . chem . 2003 , 42 , 4930 - 4937 ), 10 - methoxydec - 9 - en - 2 - one ( pontrello , j . k . ; allen , m . j . ; underbakke , e . s . ; kiessling , l . l . j . am . chem . soc . 2005 , 127 , 14536 - 14537 ), and ( h 2 imes )( 3 - br - py ) 2 ( cl ) 2 ru ═ chph ( love , j . a . ; morgan , j . p . trnka , t . m . ; grubbs , r . h . angew . chem ., int . ed . 2002 , 41 , 4035 - 4037 ) were synthesized following the previously described procedures . modifications to a previously described procedure were used ( holmes , t . j . ; vennerstrom , v . j . j . ; choi , k . e . j . org . chem . 1984 , 49 , 4736 - 4738 ). a suspension of 2 , 5 - dihydroxybenzoic acid ( 40 . 0 g , 0 . 263 mol ) and ammonium cerium ( iv ) sulfate ( 315 g , 0 . 528 mol ) in carbon tetrachloride ( 3 l ) was mechanically stirred rapidly in the dark for 45 min . the suspension was filtered , and freshly cracked cyclopentadiene ( 50 ml , 0 . 61 mmol ) was added to the filtrate , and the mixture was allowed to stir . the solution color immediately changed from dark to light yellow . after 10 min , the solvent was removed under reduced pressure . the resulting orange solid was washed with hexanes , dissolved in dichloromethane , and concentrated three times to yield 2 . 79 g ( 4 . 5 %) of 13 as an orange solid . formation of 13 only occurred with new bottles of carbon tetrachloride ; distilled carbon tetrachloride did not yield the desired product . 1 h nmr ( 300 mhz , cdcl 3 ): δ = 1 . 55 - 1 . 69 ( m , 2h , ch 2 ), 3 . 32 - 3 . 36 ( m , 1h , ( ch ) 2 — ch — ch 2 ), 3 . 53 - 3 . 57 ( m , 1h , ( ch ) 2 — ch — ch 2 ), 3 . 63 - 3 . 68 ( m , 2h , ( ch ) 2 — ch — c ( o )), 6 . 10 - 6 . 17 ( m , 2h , hc ═ ch , 14 . 19 ( bs , 1h , oh ), 15 . 12 ( bs , 1h , c ( o ) oh ; 13 c nmr ( 75 mhz , cdcl 3 ): δ = 47 . 0 (( ch ) 2 — ch — ch 2 ), 47 . 6 (( ch ) 2 — ch — ch 2 ), 49 . 5 ( ch 2 ), 49 . 6 (( ch ) 2 — ch — c ( o )), 50 . 1 (( ch ) 2 — ch — c ( o )), 107 . 3 (( c ( o )) 2 — c ═ c ), 135 . 5 ( hc ═ ch ), 135 . 9 ( hc ═ ch ), 173 . 4 , 175 . 5 , 193 . 2 , 199 . 2 ; esi - ms calcd for c 12 h 10 o 5 [ m − h ] − : 233 . 0450 . found 233 . 0457 . to a cooled ( 0 ° c . ), stirred mixture of aqueous 50 % koh ( 100 ml ) and diethyl ether ( 200 ml ) was added nitrosomethyl urea ( 17 . 6 g , 171 mmol ). when the ether layer turned yellow , it was decanted into an erlenmeyer flask containing koh pellets at 0 ° c . the ether layer was then decanted into an ether solution ( 200 ml ) of 13 ( 2 . 00 g , 8 . 54 mmol ) at 0 ° c . after 30 min , the reaction mixture was warmed to ambient temperature and stirred for 1 h . purification was performed using silica gel chromatography ( dichloromethane ) to yield 1 . 89 g ( 85 %) of 3 as a sticky yellow solid . 1 h nmr ( 300 mhz , cdcl 3 ): δ = 1 . 41 - 1 . 57 ( m , 2h , ch 2 ), 3 . 21 - 3 . 31 ( m , 2h , ( ch ) 2 — ch — ch 2 ), 3 . 51 - 3 . 54 ( m , 2h , ( ch ) 2 — ch — c ( o )), 3 . 83 ( s , 3h , co — ch 3 ), 3 . 96 ( s , 3h , c ( o ) o — ch 3 ), 6 . 07 - 6 . 18 ( m , 2h , hc ═ ch ); 13 c nmr ( 75 mhz , cdcl 3 ): δ = 48 . 8 (( ch ) 2 — ch — ch 2 ), 49 . 0 (( ch ) 2 — ch — ch 2 ), 49 . 0 ( ch 2 ), 49 . 2 (( ch ) 2 — ch — c ( o )), 49 . 4 (( ch ) 2 — ch — c ( o )), 52 . 9 ( co — ch 3 ), 59 . 8 ( c ( o ) o — ch 3 ), 135 . 0 ( hc ═ ch ), 136 . 1 ( hc ═ ch ), 158 . 9 , 164 . 7 , 194 . 8 , 195 . 4 ; esi - ms calcd for c 14 h 14 o 5 [ m + h ] + : 263 . 0919 . found 263 . 0929 . to a refluxing solution of 2 ( 2 . 50 g , 9 . 53 mmol ) in acetone ( 60 ml ) was added dimethyl sulfate ( 9 . 0 ml , 95 mmol ). a 10 % methanolic koh solution was added dropwise until the color of the solution stopped changing from purple to tan . the reaction mixture was heated at reflux for 1 h , at which point a 2 n hcl solution was added until the mixture turned clear . the reaction mixture was extracted four times with dichloromethane , dried over sodium sulfate , and concentrated . purification was performed using silica gel chromatography ( 1 : 4 ethyl acetate / hexanes ) to yield 1 . 86 g ( 67 %) of 14 as a yellow oil . 1 h nmr ( 300 mhz , cdcl 3 ): δ = 2 . 15 - 2 . 23 ( m , 2h , ch 2 ), 3 . 83 ( s , 3h , o — ch 3 ), 3 . 83 ( s , 3h , o — ch 3 ), 3 . 85 ( s , 3h , o — ch 3 ), 3 . 90 ( s , 3h , co 2 — ch 3 ), 4 . 16 - 4 . 18 ( m , 2h , ch — ch ( c )— ch 2 ), 6 . 76 - 6 . 82 ( m , 2h , hc ═ ch ); 13 c nmr ( 75 mhz , cdcl 3 ): δ = 47 . 6 ( ch — ch ( c )— ch 2 ), 48 . 0 ( ch — ch ( c )— ch 2 ), 52 . 5 ( co 2 — ch 3 ), 61 . 6 ( o — ch 3 ), 61 . 9 ( o — ch 3 ), 62 . 2 ( o — ch 3 ), 68 . 5 ( ch 2 ), 119 . 2 , 137 . 2 , 142 . 5 ( hc ═ ch ), 142 . 8 ( hc ═ ch ), 144 . 0 , 146 . 6 , 146 . 8 , 147 . 9 , 167 . 0 ; tlc : r f = 0 . 67 ( 2 : 1 ethyl acetate / hexanes ); esi - ms calcd for c 16 h 18 o 5 [ m + na ] + : 313 . 1052 . found 313 . 1037 . to a solution of 14 ( 0 . 591 g , 2 . 05 mmol ) in methanol ( 50 ml ) was added a 4 n naoh solution ( 50 ml ), and the resulting reaction mixture was heated at reflux for 5 h . methanol was removed under reduced pressure and a 3 n hcl solution was added to achieve ph 1 . the reaction mixture was extracted three times with ethyl acetate , dried over sodium sulfate , and concentrated under reduced pressure to yield 0 . 567 g of 15 as a brown oil in nearly quantitative yield . 1 h nmr ( 300 mhz , cdcl 3 ): δ = 2 . 18 - 2 . 27 ( m , 2h , ch 2 ), 3 . 86 ( s , 3h , o — ch 3 ), 3 . 89 ( s , 3h , o — ch 3 ), 3 . 92 ( s , 3h , o — ch 3 ), 4 . 19 - 4 . 22 ( m , 2h , ch — ch ( c )— ch 2 ), 6 . 78 - 6 . 86 ( m , 2h , hc ═ ch ); 13 c nmr ( 75 mhz , cdcl 3 ): δ = 47 . 6 ( ch — ch ( c )— ch 2 ), 47 . 9 ( ch — ch ( c )— ch 2 ), 61 . 6 ( ch 3 ), 62 . 1 ( ch 3 ), 62 . 5 ( ch 3 ), 68 . 5 ( ch 2 ), 117 . 9 , 137 . 8 , 142 . 4 ( hc ═ ch ), 142 . 9 ( hc ═ ch ), 144 . 2 , 147 . 2 , 147 . 6 , 148 . 6 , 170 . 6 ; esi - ms calcd for c 15 h 16 o 5 [ m − h ] − : 275 . 0920 . found 275 . 0910 . to a solution of 15 ( 0 . 972 g , 3 . 52 mmol ) in dichloromethane ( 80 ml ) was added n - hydroxysuccinimide ( 0 . 547 g , 4 . 75 mmol ) and 1 -[ 3 -( dimethylamino ) propyl ]- 3 - ethylcarbodiimide hydrochloride ( 0 . 890 g , 4 . 64 mmol ), and the resulting reaction mixture was stirred under dinitrogen for 15 h . the reaction mixture was diluted with dichloromethane ( 100 ml ), washed twice with a 0 . 01 n hcl solution ( 50 ml ), dried over sodium sulfate , and concentrated under reduced pressure . purification was performed using silica gel chromatography ( dichloromethane → 2 : 1 ethyl acetate / hexanes ) to yield 0 . 898 g ( 68 %) of 3 as a colorless sticky solid . 1 h nmr ( 300 mhz , cdcl 3 ): δ = 2 . 19 - 2 . 27 ( m , 2h , ch — ch 2 — ch ), 2 . 89 ( bs , 4h , ch 2 — ch 2 ), 3 . 86 ( s , 3h , o — ch 3 ), 3 . 92 ( s , 3h , o — ch 3 ), 3 . 95 ( s , 3h , o — ch 3 ), 4 . 19 - 4 . 23 ( m , 2h , ch — ch ( c )— ch 2 ), 6 . 78 - 6 . 85 ( m , 2h , hc ═ ch ); 13 c nmr ( 75 mhz , cdcl 3 ): δ = 25 . 9 ( ch 2 — ch 2 ), 47 . 7 ( ch — ch ( c )— ch 2 ), 47 . 9 ( ch — ch ( c )— ch 2 ), 61 . 7 ( o — ch 3 ), 62 . 3 ( o — ch 3 ), 62 . 6 ( o — ch 3 ), 68 . 6 ( ch — ch 2 — ch ), 137 . 7 , 142 . 4 ( ch ═ ch ), 143 . 0 ( ch ═ ch ), 144 . 2 , 147 . 9 , 149 . 6 , 149 . 9 , 161 . 4 , 169 . 1 ; tlc : r f = 0 . 42 ( 2 : 1 ethyl acetate / hexanes ); esi - ms calcd for c 19 h 19 no 7 [ m + na ] + : 396 . 1059 . found 396 . 1069 . to a solution of 4 ( 8 . 69 g , 44 . 1 mmol ) in dimethylformamide ( 440 ml ) was added potassium carbonate ( 12 . 7 g , 91 . 6 mmol ) and methyl iodide ( 27 . 5 ml , 441 mmol ), and the resulting reaction mixture was stirred for 15 h . the reaction was concentrated under reduced pressure and diluted with dichloromethane ( 200 ml ) and water ( 200 ml ). the layers were separated , and the aqueous layer was extracted with dichloromethane ( 50 ml ). the combined organic layers were dried over sodium sulfate and concentrated under reduced pressure . purification was performed using silica gel : chromatography ( 2 : 1 ethyl acetate / hexanes ) to yield 7 . 89 g ( 80 %) of 16 as a tan solid . 1 h nmr ( 300 mhz , cdcl 3 ): δ = 1 . 36 ( t , 3h , j = 7 . 1 hz , ch 2 — ch 3 ), 2 . 32 ( s , 3h , c — ch 3 ), 3 . 52 ( s , 3h , n — ch 3 ), 3 . 94 ( s , 3h , o — ch 3 ), 4 . 33 ( q , 2h , j = 7 . 1 hz , ch 2 ), 6 . 16 ( s , 1h , ch ); 13 c nmr ( 75 mhz , cdcl 3 ): δ = 14 . 3 ( ch 2 — ch 3 ), 20 . 7 ( c — ch 3 ), 31 . 9 ( n — ch 3 ), 60 . 4 ( o — ch 3 ), 61 . 7 ( ch 2 ), 103 . 8 ( ch ), 129 . 5 , 140 . 3 , 146 . 4 , 160 . 7 , 165 . 4 ; tlc : r f = 0 . 20 ( 2 : 1 ethyl acetate / hexanes ); esi - ms calcd for c 11 h 15 no 4 [ m + h ] + : 226 . 1079 . found 226 . 1072 . to a solution of 16 ( 7 . 51 g , 33 . 3 mmol ) in methanol ( 350 ml ) was added a 4 m sodium hydroxide solution ( 350 ml ). the resulting solution was heated at reflux , and after 2 h , methanol was removed under reduced pressure . an aqueous 3 n hcl solution was used to adjust the resulting solution to ph 1 . the solution was extracted with ethyl acetate ; the organic extracts were dried over sodium sulfate , and solvent was removed under reduced pressure to yield 6 . 44 g ( 98 %) of 5 as a tan solid . 1 h nmr ( 300 mhz , cd 3 od ): δ = 2 . 40 ( s , 3h , c — ch 3 ), 3 . 58 ( s , 3h , n — ch 3 ), 3 . 86 ( s , 3h , o — ch 3 ), 6 . 36 ( s , 1h , ch ); 13 c nmr ( 75 mhz , cd 3 od ): δ = 20 . 6 ( c — ch 3 ), 32 . 6 ( n — ch 3 ), 61 . 0 ( o — ch 3 ), 105 . 9 ( ch ), 132 . 8 , 143 . 4 , 146 . 6 , 162 . 6 , 168 . 2 ; esi - ms calcd for c 9 h 11 no 4 [ m − h ] − : 196 . 0610 . found 196 . 0615 . to a solution of 5 ( 5 . 36 g , 27 . 2 mmol ) in dichloromethane ( 500 ml ) was added n - hydroxysuccinimide ( 4 . 23 g , 36 . 7 mmol ) and 1 -[ 3 -( dimethylamino ) propyl ]- 3 - ethylcarbodiimide hydrochloride ( 6 . 89 g , 35 . 9 mmol ), and the resulting reaction mixture was stirred under dinitrogen for 15 h . the reaction mixture was washed twice with a 0 . 01 n hcl solution ( 150 ml ), dried over sodium sulfate , and concentrated under reduced pressure . purification was performed using silica gel chromatography ( 1 : 49 methanol / dichloromethane ) to yield 7 . 83 g ( 98 %) of 6 as a tan solid . 1 h nmr ( 300 mhz , cdcl 3 ): δ = 2 . 31 ( s , 3h , c — ch 3 ), 4 . 08 ( s , 4h , ch 2 ), 3 . 50 ( s , 3h , n — ch 3 ), 3 . 98 ( s , 3h , o — ch 3 ), 6 . 29 ( s , 1h , ch ); 13 c nmr ( 75 mhz , cdcl 3 ): δ = 20 . 6 ( c — ch 3 ), 25 . 8 ( ch 2 ), 32 . 0 ( n — ch 3 ), 60 . 8 ( o — ch 3 ), 103 . 0 ( ch ), 122 . 8 , 140 . 7 , 148 . 8 , 159 . 9 , 160 . 3 , 169 . 0 ; tlc : r f = 0 . 33 ( 1 : 19 methanol / dichloromethane ); esi - ms calcd for c 13 h 14 n 2 o 6 [ m + h ] + : 295 . 0930 . found 295 . 0931 . tritylchloride resin ( 2 . 0 g , 3 . 2 mmol ) was swelled in tetrahydrofuran ( 20 ml ) for 15 min at which point tris ( 2 - aminoethyl ) amine ( 4 . 98 ml , 32 . 0 mmol ) was added , and the resulting solution was mixed for 20 h . the resin was drained and washed four times with 20 ml of 17 : 2 : 1 dichloromethane / methanol / diisopropylethylamine , and three times with 20 ml of dichloromethane . to the washed resin was added dichloromethane ( 20 ml ), diisopropylethylamine ( 5 . 57 ml , 32 . 0 mmol ), and 6 ( 3 . 77 g , 12 . 8 mmol ), and the resulting solution was stirred for 20 h . the resin was drained and washed three times with 20 ml of dichloromethane and dried under reduced pressure . a solution of 38 : 1 : 1 trifluoroacetic acid / triisopropylsilane / water ( 24 ml ) was added to the resin ; after 2 h , the resin was filtered and rinsed with trifluoroacetic acid ( 5 ml ). the combined trifluoroacetic acid - containing filtrate was reduced in volume to 2 ml . this solution was added dropwise to diethyl ether ( 400 ml ) at 0 ° c ., and the resulting precipitate was collected . purification was performed using basic alumina chromatography ( 1 : 9 → 3 : 7 methanol / dichloromethane ) to yield 1 . 0 g ( 63 %) of 7 as a white solid . 1 h nmr ( 300 mhz , cd 3 od ): δ = 2 . 39 ( s , 6h , c — ch 3 ), 2 . 62 - 2 . 78 ( m , 8h , h 2 n — ch 2 and n —( ch 2 ) 3 ), 3 . 48 ( t , 4h , j = 6 . 2 hz , c ( o ) nh — ch 2 ), 3 . 56 ( s , 6h , n — ch 3 ), 3 . 88 ( s , 6h , o — ch 3 ), 6 . 40 ( s , 2h , ch ); 13 c nmr ( 75 mhz , cd 3 od ): δ = 20 . 7 ( c — ch 3 ), 32 . 6 ( n — ch 3 ), 39 . 1 ( c ( o ) nh — ch 2 ), 40 . 3 ( h 2 n — ch 2 ), 54 . 5 ( n —( ch 2 ) 3 ), 57 . 7 ( n —( ch 2 ) 3 ), 60 . 9 ( o — ch 3 ), 105 . 7 ( ch ), 133 . 3 , 143 . 3 , 145 . 5 , 161 . 9 , 166 . 4 ; tlc : r f = 0 . 21 ( 1 : 19 methanol / dichloromethane on basic alumina plates ); esi - ms calcd for c 24 h 36 n 6 o 6 [ m + h ] + : 505 . 2775 . found 505 . 2794 . polymerizations were carried out under an argon atmosphere in scintillation vials . solutions of ( h 2 imes )( 3 - br - py ) 2 ( cl ) 2 ru ═ chph ( 5 . 35 mm ) and 3 ( 0 . 134 m ) in degassed dichloromethane were cooled to − 20 ° c . the solutions were combined in the desired monomer to initiator ratio , and degassed dichloromethane was added to bring the final concentration of 3 to 38 . 3 mm . the reactions were allowed to warm slowly to ambient temperature . after consumption of 3 , as determined by tlc , 10 - methoxydec - 9 - en - 2 - one ( 20 μl , 0 . 10 mmol ) was added , and the reaction mixture was allowed to stir for 15 h . the reaction mixtures were added dropwise to a 30 - fold volume excess of diethyl ether . the resulting white solid was collected , and residual solvent was removed under reduced pressure . yield = 76 . 3 mg ( 71 %) black solid . 1 h nmr ( 500 mhz , dmso - d 6 ): δ = 1 . 53 ( bs ), 2 . 50 ( bs ), 2 . 86 ( bs , c (═ o )— ch 2 — ch 2 — c (═ o )), 3 . 73 ( bs , o — ch 3 ), 4 . 24 ( bs ), 5 . 52 ( bs , 18h , hc ═ ch ), 7 . 14 ( bs , 5h , c 6 h 5 ); pdi 1 . 58 ; calculated mw 3217 ; m w 2788 ; m n 1760 . yield = 165 mg ( 94 %) off - white solid . 1 h nmr ( 500 mhz , dmso - d 6 ): δ = 1 . 07 ( bs ), 2 . 84 ( bs , c (═ o )— ch 2 — ch 2 — c (═ o )), 3 . 64 ( bs , o — ch 3 ), 5 . 31 ( bs , 63h , hc ═ ch ), 7 . 00 ( bs , 5h , c 6 h 5 ); pdi 1 . 21 ; calculated mw 11431 ; m w 5004 ; m n 4122 . general procedure for conjugation of polymers with compounds 7 and 14 to a solution of polymer 8a or 8b ( 5 mg ) in dimethylsulfoxide ( 200 μl ) and diisopropylethylamine ( 10 equivalents per monomer unit ) was added 7 ( 0 . 25 equivalents per monomer unit ) and n -( 3 - aminopropyl ) guanidine bis - trifluoroacetic acid salt ( 0 . 75 equivalents per monomer unit ). after 15 h , the entire reaction mixture was passed through a pd - 10 column . fractions containing polymer were collected , and solvent was removed under reduced pressure . yield = 12 . 4 mg ( 70 %) brown solid . 1 h nmr ( 500 mhz , dmso - d 6 ): δ = 1 . 18 ( bs ), 1 . 68 ( bs ), 2 . 31 ( bs ), 2 . 65 ( bs ), 3 . 20 ( bs ), 3 . 43 ( bs ), 3 . 68 ( bs ), 4 . 12 ( bs ), 5 . 42 ( bs , 17h , hc ═ ch ), 6 . 22 ( bs , 2 . 9h , c — ch ═ c — ch 3 ), 7 . 20 ( bs ), 7 . 69 ( bs ), 8 . 31 ( bs ). yield = 8 . 37 mg ( 38 %) brown glass . 1 h nmr ( 500 mhz , dmso - d 6 ): δ = 1 . 18 ( bs ), 1 . 68 ( bs ), 2 . 31 ( bs ), 2 . 65 ( bs ), 3 . 20 ( bs ), 3 . 43 ( bs ), 3 . 68 ( bs ), 4 . 12 ( bs ), 5 . 42 ( bs , 62h , hc ═ ch ), 6 . 22 ( bs , 7 . 6h , c — ch ═ c — ch 3 ), 7 . 20 ( bs ), 7 . 69 ( bs ), 8 . 31 ( bs ). a solution of 7 ( 0 . 304 g , 0 . 603 mmol ), 3 ( 0 . 150 g , 0 . 402 mmol ), and diisopropylethylamine ( 0 . 350 ml , 2 . 01 mmol ) in dichloromethane ( 10 ml ) was stirred under dinitrogen for 4 h , at which point solvent was removed under reduced pressure . purification was performed using silica gel chromatography ( 1 : 19 methanol / dichloromethane ) to yield 0 . 202 g ( 66 %) of 12 as a white solid . 1 h nmr ( 300 mhz , cdcl 3 ): δ = 2 . 10 - 2 . 20 ( m , 2h , ch — ch 2 — ch ), 2 . 33 ( s , 6h , c — ch 3 ), 2 . 79 - 2 . 86 ( m , 6h , n —( ch 2 ) 3 ), 3 . 49 - 3 . 55 ( m , 12h , c ( o ) nh — ch 2 and n — ch 3 ), 3 . 80 ( s , 3h , o — ch 3 ), 3 . 81 ( s , 3h , o — ch 3 ), 3 . 82 ( s , 3h , o — ch 3 ), 3 . 94 ( s , 6h , o ═ c — c (═ c )— o — ch 3 ), 4 . 11 - 4 . 14 ( m , 2h , ch — ch ( c )— ch 2 ), 6 . 27 - 6 . 31 ( t , 1h , j = 5 . 6 hz , ( ch 3 — o — c ) 2 — c — c (═ o )— nh ), 6 . 55 ( s , 2h , ch 3 — c ═ ch — c ), 6 . 73 - 6 . 78 ( m , 2h , ch ═ ch ), 8 . 16 - 8 . 20 ( t , 2h , j = 5 . 2 hz , ch — c — c (═ o )— nh ); 13 c nmr ( 75 mhz , cdcl 3 ): δ = 20 . 8 ( c — ch 3 ), 31 . 9 ( n — ch 3 ), 38 . 2 ( c ( o ) nh — ch 2 ), 47 . 6 ( ch — ch ( c )— ch 2 ), 47 . 9 ( ch — ch ( c )— ch 2 ), 53 . 7 ( n —( ch 2 ) 3 ), 53 . 8 ( n —( ch 2 ) 3 ), 60 . 0 ( o ═ c — c (═ c )— o — ch 3 ), 61 . 6 ( o — ch 3 ), 62 . 1 ( o — ch 3 ), 62 . 4 ( o — ch 3 ), 68 . 4 ( ch — ch 2 — ch ), 104 . 5 ( ch 3 — c ═ ch — c ), 122 . 3 , 129 . 3 , 137 . 4 , 140 . 2 , 142 . 4 ( ch ═ ch ), 142 . 9 ( ch ═ ch ), 144 . 2 , 145 . 1 , 145 . 7 , 146 . 9 , 147 . 7 , 160 . 2 , 163 . 9 , 166 . 2 ; tlc : r f = 0 . 26 ( 2 : 23 methanol / dichloromethane ); esi - ms calcd for c 39 h 50 n 6 o 10 [ m + h ] + : 763 . 3667 . found 763 . 3648 . to a solution of methyl ether - protected chelate ( 1 eq . of 9a , 9b , or 12 ) in anhydrous dimethylsulfoxide ( dmso ) under argon was added a solution of sodium ethanethiolate ( 2 . 5 eq . per ome ) in anhydrous dmso to make a final solution of between 0 . 4 and 26 mm chelate and between 44 and 328 mm sodium ethanethiolate . the resulting solution was heated to 142 ° c . for 1 . 5 h at which point a four - fold volume excess of water was added to quench excess sodium ethanethiolate . the reaction mixture was concentrated to dryness under reduced pressure , and lc - ms of the product resulting from 12 showed one major product with a mass corresponding to four of five methyl ethers removed . to ensure that the remaining methoxy group was not in a position to interfere with metal chelation , a portion of the intermediate ( 0 . 80 mg , 1 . 2 μmol ) was dissolved in anhydrous dmso ( 11 . 4 μl ) under argon . to the resulting solution was added ch 2 i 2 ( 1 . 4 μmol , 0 . 11 μl ) and sodium carbonate ( 2 . 5 μmol , 0 . 27 mg ), and the reaction was heated to 55 ° c . for 8 h , as illustrated below . the mixture was cooled to ambient temperature , and 2 ml of water was added . lc / ms indicated that there was one major product with mass ([ m + h ] + = 721 . 4 ) corresponding to the formation of a methylene bridge between the two ortho hydroxyl groups . this result indicates that the remaining methoxy group was not in a position to interfere with metal chelation . additional support for the position of the remaining methoxy group is found in the work of feutrill and mirrington ( feutrill , g . i . ; mirrington , r . n . tetrahedron lett . 1970 , 16 , 1327 - 1328 ). they treated a series of anisole compounds with sodium ethanethiolate and found that ortho - methoxy groups underwent complete demethylation while para - methoxy groups yielded selective mono - demethylation . the intermediate was dissolved in water in a concentration between 0 . 1 and 6 . 5 mm , and five drops of dmso were added . one equivalent of gdcl 3 . 6h 2 o per chelating group was then added , and the ph of the resulting solution was adjusted to 7 using 0 . 1 n naoh and 0 . 1 n hcl solutions . the reaction mixture was heated to 80 ° c . for 1 h , at which point the ph was readjusted to 7 . the reaction mixture was allowed to sit at ambient temperate for 15 h . the ph was brought to 10 using a 0 . 1 n naoh solution to precipitate any unchelated gadolinium as gd ( oh ) 3 . gd ( oh ) 3 was removed by filtration through a 0 . 45 μm syringe filter . the ph of the filtered solution was brought to 7 using a 0 . 1 n hcl solution , and the resulting solution was directly used for t 1 acquisition . after measurement of t 1 , solutions were analyzed for gd concentration , and the t 1 and gd concentration data were used to calculate per gd relaxivity . per gd relaxivity was multiplied by the number of chelates per polymer ( as determined by nmr spectroscopy of polymers 9 ) to determine molecular relaxivity values . esi - ms calcd for c 35 h 42 n 6 o 10 [ m + h ] + : 707 . 3 . found 707 . 4 . esi - ms calcd for c 35 h 38 gdn 6 o 10 [ m − ch 3 + na + 2h ] + : gd isotope pattern centered at 870 . 2 , found gd isotope pattern centered at 870 . 1 . maximum gd concentrations ranged from 0 . 0054 % to 0 . 0176 %. relaxivity ( r 1 ): 10 . 5 ± 0 . 8 mm − 1 s − 1 ( error is given as the standard deviation ). χ r3 = 0 . 25 , χ r4 = 0 . 75 . maximum gd concentrations ranged from 0 . 0040 % to 0 . 0046 %. ionic relaxivity ( r 1 ): 10 . 1 ± 0 . 5 mm − 1 s − 1 ; molecular relaxivity ( r 1 ): 18 . 8 ± 0 . 9 mm − 1 s − 1 ( errors are given as standard deviations ). χ r3 = 0 . 25 , χ r4 = 0 . 75 . maximum gd concentrations ranged from 0 . 0005 % to 0 . 0048 %. ionic relaxivity ( r 1 ): 14 . 8 ± 0 . 2 mm − 1 s − 1 ; molecular relaxivity ( r 1 ): 111 . 0 ± 1 . 5 mm − 1 s − 1 ( errors are given as standard deviations ). n -( bis - boc - guanyl )- n - boc - 1 , 3 - diaminopropane ( 1 . 00 g , 2 . 40 mmol ) was dissolved in 20 ml of 95 % trifluoroacetic acid ( tfa ), 2 . 5 % water , and 2 . 5 % triisopropylsilane ( v / v / v ). after 14 h , the volume was reduced to a sticky residue under a stream of air . the residue was washed with diethyl ether , dissolved in water , and freeze dried to yield 0 . 568 g ( 69 %) of the desired salt as an extremely viscous , colorless oil . 1 h nmr ( 300 mhz , d 2 o ): δ = 1 . 96 - 2 . 06 ( m , 2h , ch 2 — ch 2 — ch 2 ), 3 . 11 ( t , 2h , j = 8 . 0 hz , n — ch 2 — ch 2 ), 3 . 35 ( t , 2h , j = 7 . 0 hz , n — ch 2 — ch 2 ); 13 c nmr ( 75 mhz , d 2 o ): δ = 27 . 6 ( ch 2 — ch 2 — ch 2 ), 38 . 3 ( n — ch 2 ), 39 . 7 ( n — ch 2 ), 158 . 3 ( c —( n ) 3 ); esi - ms calcd for c 4 h 12 n 4 [ 2m + h ] + : 233 . 3 . found 233 . 1 ; anal . calcd for c 8 h 14 f 6 n 4 o 4 : c , 27 . 91 ; h , 4 . 10 ; f , 33 . 12 ; n , 16 . 28 . found : c , 27 . 87 ; h , 4 . 24 ; f , 31 . 17 ; n , 15 . 55 . to a solution of n - boc - 1 , 3 - diaminopropane ( 5 . 00 ml , 28 . 6 mmol ) in dimethylformamide ( dmf ) ( 100 ml ) was added diisopropylethylamine ( diea ) ( 3 . 72 ml , 21 . 4 mmol ) and bis - boc - guanylpyrazole ( 3 . 31 g , 10 . 7 mmol ). the reaction mixture was stirred for 14 h , at which time dmf was removed under reduced pressure . water ( 20 ml ) was added , and the mixture was extracted with dichloromethane . the organic layer was dried over magnesium sulfate , and solvent was removed under reduced pressure . purification was performed using silica gel chromatography ( 5 : 1 → 2 : 1 hexanes / ethyl acetate ) to yield 3 . 07 g ( 69 %) of the desired product as a white solid . 1 h nmr ( 300 mhz , cdcl 3 ): δ = 1 . 43 ( s , 9h , ch 3 ), 1 . 49 ( s , 18h , ch 3 ), 1 . 64 - 1 . 72 ( m , 2h , ch 2 — ch 2 ch 2 ), 3 . 10 - 3 . 17 ( m , 2h , nh — ch 2 — ch 2 ), 3 . 44 - 3 . 50 ( m , 2h , nh — ch 2 — ch 2 ), 5 . 60 ( s , 1h , nh ), 8 . 34 ( t , 1h , j = 5 . 6 hz , nh ), 11 . 41 ( s , 1h , nh ); 13 c nmr ( 75 mhz , cdcl 3 ): δ = 28 . 3 ( ch 3 ), 28 . 5 ( ch 3 ), 28 . 7 ( ch 3 ), 30 . 4 ( ch 2 — ch 2 — ch 2 ), 37 . 3 ( nh — ch 2 — ch 2 ), 37 . 8 ( nh — ch 2 — ch 2 ), 79 . 0 ( c ( ch 3 ) 3 ), 79 . 4 ( c ( ch 3 ) 3 ), 83 . 4 ( c ( ch 3 ) 3 ), 153 . 4 , 156 . 4 , 156 . 9 , 163 . 5 ; tlc : r f = 0 . 36 ( 2 : 1 hexanes / ethyl acetate ); esi - ms calcd for c 19 h 36 n 4 o 6 [ m + h ] + : 417 . 2713 . found 417 . 2693 . values of the rotational correlation time ( τ r ) were estimated using the debye - stokes equation shown below and data acquired for other linear gd iii containing polymers ( toth , e . ; helm , l . ; kellar , k . e . ; merbach , a . e . chem . eur . j . 1999 , 5 , 1202 - 1211 ; the chemistry of contrast agents in medical magnetic resonance imaging ; merbach , a . e ., toth , e ., eds . ; john wiley & amp ; sons , ltd . : new york , 2001 ). assuming that the microviscosity and density of the polymers are the same , the ratio of molecular radii can be expressed by the ratio of the molecular weights . while the debye - stokes equation provides estimation for spherical molecules , the romp - derived polymers and polymers in the above references are both linear and the ratio of their molecular weights is used only as an approximation . debye - stokes equation ( η = microviscosity , r eff = molecular radius , k b = the boltzmann constant , t = temperature ) table 1 below shows average molecular weight ( mw ), τ r , and per gd relaxivity for two linear polymers from the literature ( τ g , global motion correlation time , was used to estimate τ r for comparison to romp - derived polymers 10a and 10b because of the rigid connection to the polymer backbone ). the τ r data for romp - derived polymers 10a and 10b were estimated by plotting τ r vs . mw for the published polymers , and using the resulting slope with the molecular weights of polymers 10a and 10b . the ratio of τ r to relaxivity was then examined , and the relaxivity values in parentheses for 10a and 10b would be expected for linear polymers with their molecular weights and estimated τ r values . these estimates match up very well with the actual measurements indicating that there is relaxivity increase due to increase in τ r . thus , the observed increase is proportional to what is seen in linear polymers of gd iii diethylenetriaminepentaacetic acid ( dtpa ). additional experimental details of the synthesis and analysis of polymers useful as contrast agents may be found in allen m . j ., raines , r . t . and kiessling , l . l . ( 2006 ) j . amer . chem . soc . 128 ( 20 ): 6534 - 6536 and supporting information thereof , each of which is incorporated by reference in its entirety herein .
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while this invention is susceptible of embodiments in many different forms , there is shown in the drawings and will herein be described in detail , preferred embodiments of the invention with the understanding the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the broad aspect of the invention to the embodiments illustrated . the present invention will have the following main components and techniques for operation of the device . fig1 shows a schematic representation of the process for making the multilayered sheet 10 . an extruder 110 generally extrudes a sheet 20 of polypropylene through a die 111 . the preferable die is about 72 ″ ( width ) by 9 . 5 ″ ( height ) by 11 ″ depth . the die lip opening is approximately 66 ″ wide , but it can be reduced or deckled so as to more closely match or align width - wise with the sheet it is being applied to or laid upon ( discussed below ). the extruded sheet &# 39 ; s thickness can be varied depending upon the application and desired results . thicknesses can range from 0 . 020 ″ and upwards . specific thicknesses that have proved sufficient and adequate are 0 . 25 ″, 0 . 30 ″, 0 . 35 ″ and 0 . 40 ″. widths range from about 40 ″ to about 58 ″. the lengths range from about 40 ″ and upwards . the extruded sheet 20 is passed through a series of nips 201 , 202 formed between a series of chill rollers 121 , 122 , 123 and passed over and partially around additional chill rollers 124 , 125 , 126 and idlers 131 , 132 . in the preferred embodiment , the nip 201 is produced by confronting rollers 121 , 122 . roller 121 has a diameter of about 32 ″ and is maintained at a temperature of about 150 ° f . to about 180 ° f . while roller 122 has a diameter of about 32 ″ and is maintained at a temperature of about 200 ° f . to about 230 ° f . a second nip 202 is produced by confronting rollers 122 , 123 . roller 123 also has a diameter of about 32 ″ and is maintained at a temperature of about 200 ° f . to about 230 ° f . the chill rollers 124 , 125 , 126 123 are preferably sized and maintained to bring the temperature down towards room / ambient temperature . a supply of non - woven , spunbond polypropylene 40 ( in sheet form ) is carried by a supply roller 140 . the spunbond polypropylene is available from many suppliers . the spunbond polypropylene can be any width meeting a customer &# 39 ; s demand or need , generally between about 40 ″ and 58 ″, and a thickness of various gauges . for example , a gauge spunbond of about 0 . 010 works well . the making of spunbond fabrics is well - known in the industry . such fabrics are used in many products today . the non - woven sheet 40 is passed around one or more idlers 133 , 134 and fed into the first nip 201 downstream of the die 111 wherein it is forced into abutment with the extruded sheet 20 . this specific area of the process is shown in further detail of fig2 . the feeding of the non - woven - sheet 40 with the extruded sheet 20 occurs within inches of the extruder &# 39 ; s die 111 and just before contacting the rollers 121 , 122 forming the nip . in this manner , it is believed , the extruded polypropylene 20 is bonded to the non - woven sheet 40 by a melding of fibers from the non - woven sheet 40 into the extruded sheet 20 . the first nip 201 has a clearance or opening sized to compress the multilayered sheet passing therethrough . the gauge or thickness depends on the end product desired . for example , for 0 . 025 ″ thick ( gauge ) multilayered sheets , the nip gap is set at about 0 . 030 ″; for 0 . 030 ″ thick sheets , the nip gap is set at about 0 . 035 ″, for sheets of 0 . 035 ″ and 0 . 040 ″ thick , the nip gap is set at about 0 . 040 ″ and 0 . 045 ″, respectively . the second nip gap 202 can be set similar to the first gap 201 . the above process and resulting product are very different from those in which the extrusion is extruded directly onto a substrate . here , there is an intentional space ( x in fig2 ) between the die nozzle or lip 111 and the mating of the non - woven sheet 40 to the extruded sheet 20 . that distance x has been found to be about 5 inches . the non - woven substrate 40 is carried by the bottom roller 121 to contact with the extruded sheet 20 and first nip 201 . the plastic exits the die &# 39 ; s nozzle / lip 111 at about 450 ° f . and immediately cools down to about 340 ° f . the melting point of polypropylene is roughly 340 ° f . the two sheets 20 , 40 come together at the first nip 201 to form the combined ( multilayered ) sheet 10 . the combined product goes through a controlled cool - down by passing around and over a series of chill rollers . specifically , the chiller rollers 121 , 122 , 123 , 124 , 125 , 126 , generally 32 ″ diameter , are positioned to bring the temperature of the multilayered sheet 10 down in temperature . as noted , in practice , it has been found that chill rollers with the following temperatures work well : roller 121 at approximately 150 ° f .- 180 ° f . ; roller 122 at approximately 200 ° f .- 230 ° f . ; roller 123 at approximately 200 ° f .- 230 ° f . ; and , rollers 124 - 126 at a moderate rate of cooling down towards room temperature ( approximately 100 ° f .- 150 ° f .). the resultant product can be gauged so as to have a thickness of any desired or preferred amount . for example , successful gauges have been produced having a gauge of 0 . 025 ″, 0 . 030 ″, 0 . 035 ″ and 0 . 040 ″. a test sample combining a non - woven polypropylene sheet ( 40 ) ( 2 . 0 - 3 . 0 oz / yd spunbond ) of 0 . 013 ″ with an extruded polypropylene sheet ( 20 ) gauged at 0 . 025 ″. the resultant multi - layered sheet was measured at 0 . 030 ″. it is believed multilayered products of 0 . 025 ″- 0 . 080 ″ would be typical . it is also believed that some melting occurs the in non - woven substrate 40 in the plane of intersection with the extruded sheet 20 ( fig3 ). the results of the above process were extremely surprising to those investigating setting - up , running , and analyzing the above process and sheets . the resulting product was an extremely well - bonded multilayered sheet having strength and integrity with a “ softer ” side . the sheet is easily recyclable because no adhesive is used with the two layers of polypropylene . and , significantly , as compared to prior products , the above described product is less expensive to produce and arguably easier to make since adhesive is neither purchased nor incorporated in the manufacturing process . in addition , there is an inseparable bond between the non - woven sheet 40 and the extruded sheet 20 . this resolves a common de - lamination problem associated with similar sheets bonded adhesively together . it should be noted that while the extruded sheet 20 is shown and depicted as being substantially solid , it can also be an extruded corrugated plastic . the extruding of corrugated plastic sheets is known in the industry and can include internal hollows or channels between the outer surfaces of the sheets . while the above process and resulting product were discussed broadly , it is recognized other variants can be made without deviating from the spirit of the invention . for example , other plastics , apart from polypropylene , can be used . the size , temperatures and number of the pressure rollers can be varied . in addition , other uses of the resultant product can be made .
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the term &# 34 ; sucrose fatty acid lower esters &# 34 ; as used herein refers to mono -, di -, and tri - esters of sucrose and mixtures thereof . the term &# 34 ; fatty acids &# 34 ; used in the specification and claims means organic fatty acids having at least two and as many as twenty - four carbon atoms , and may be saturated or unsaturated and may have straight or branched chains . examples of fatty acids that can be used in this invention are myristic , palmitic , stearic , oleic , linoleic and behenic acids . mixtures of fatty acids may also be used ; for example , fatty acids derived from natural triglycerides such as soybean , peanut , coconut , cottonseed , palm , palm kernel , corn , olive , safflower , or sunflower oils . the total amount of fatty acids present in the reaction mixture can be a maximum that theoretically will react to completely esterify all the free hydroxyls of the sucrose lower esters . in general then , the total amount of fatty acid will be one mole for each mole of free hydroxyl moieties available on the sucrose lower ester reactant . for example , six moles of fatty acid will be present in a reaction with one mole of sucrose diester . the term &# 34 ; sucrose fatty acid polyesters &# 34 ; as used herein refers to those having an average degree of substitution of 4 to 8 . the term &# 34 ; solvent &# 34 ; used in the description and claims means any material that is liquid at the synthesis reaction temperature and pressure and will dissolve , suspend or hold the fatty acids and sucrose lower esters in the reaction mixture in an amount effective to expedite contact of the reactants for the desired esterification to produce sucrose polyesters . examples of suitable solvents that can be used in this invention are anhydrous aprotic solvents such as tetrahydrofuran . other ethers ( diethyl ether , dioxane ), aromatic hydrocarbons , halogenated hydrocarbons , nitromethane , and pyridine may be used . in the practice of the present invention , the sucrose fatty acid lower esters and the fatty acids are coupled in the presence of a condensing agent such as dicyclohexylcarbodiimide . other carbodiimides , e . g ., diethylcarbodiimides , n , n &# 39 ;- carbonyl - di ( 2 - methylimidazole ), pentamethyleneketene - n - cyclohexylimine , diphenylketene - n - cyclohexylimine , alkoxyacetylenes , 1 - alkoxy - 1 - chloroethylenes , tetraalkyl phosphites , isopropyl polyphosphate , phosphorus oxychloride , phosphorus trichloride , thionyl chloride , oxalyl chloride , and triphenyl phosphines may also be used . theoretically , one mole of condensing agent reacts with one mole of fatty acid and one mole of free sucrose hydroxyl groups in the coupling reaction . however , best results are achieved by using a slight excess of condensing agent over the theoretical toichiometric amount required . typically , 1 to 1 . 2 moles of condensing agent , preferably 1 . 15 , are used . the esterification reaction is carried out in the presence of a catalyst , including hypernucleophilic agents , such as , for example , 4 - dimethylaminopyridine . other nucleophilic tertiary amines ( pyridine , 4 - dimethylaminopyridine , 4 - morpholino - pyridine , 4 - diethylaminopyridine , 4 - methoxy - pyridine , and tralkylamines ), tetraalkylammonium hydroxide , and inorganic bases ( sodium hydrogen carbonate , sodium carbonate , potassium carbonate , and barium carbonate ) may also be used . in the reaction mixture , an equimolar proportion of catalyst and sucrose lower ester is used preferentially . according to a preferred embodiment of the present invention , the sucrose lower fatty acid ester is dissolved in an effective amount of solvent with fatty acids and catalyst . to this solution is added a solution of the condensation agent dissolved in the same solvent . the reaction mixture may be warmed at reflux to speed and stir the reaction . the length of reaction time varies with the reaction conditions and may require several days . the sucrose polyester end product obtained in the condensation reaction can be separated from contaminants by solvent extraction and washing , as , for example , by concentrating the product in vacuuo , taking it up in ether or other suitable solvent and acid washing followed by drying and filtration , and removing the ether by evaporation . it may be further purified in a known manner , such as by way of chromatography conducted in a usual manner , for example , by using silica gel as adsorbent and hexane as a developer . the following example details one method for producing sucrose polyester in accordance with the present invention . it is to be understood that this example is merely illustrative and is not to be construed as being limitative . all percentages given are weight percentages , and are based on the weight at the particular stage of processing described . in this example , oleic acid is coupled to sucrose distearate to form predominantly hepta and octaesters . a 250 - ml flask equipped with a reflux condenser and a drying tube is charged with 7 . 2 grams ( 0 . 035 mole ) 1 , 3 - dicyclohexylcarbodiimide dissolved in 30 ml tetrahydrofuran . to this is added a solution of 4 . 6 grams ( 0 . 005 mole ) sucrose stearate ( ryoto spe - 570 , containing an average of two fatty acid residues per molecule sucrose ), 0 . 6 grams ( 0 . 005 mole ) 4 - dimethylaminopyridine , and 8 . 48 grams ( 0 . 03 mole ) oleic acid dissolved in 100 ml tetrahydrofuran . the mixture is warmed at reflux for four days and then concentrated in vacuuo . the residue obtained is dissolved in 200 ml diethyl ether , washed with 100 ml 5 % hcl , and dried over sodium sulfate . following filtration , the ether is evaporated and the residue is dissolved in hexane and subjected to flash chromatography on silica gel . evaporation of the hexane eluant affords a colorless , slightly opaque oil . elemental analysis for c 143 . 4 h 259 . 6 0 18 . 3 formula weight 2276 . 81 : calculated (%): c : 75 . 65 ; h : 11 . 49 ; 0 : 12 . 86 ; found (%): c : 75 . 47 ; h : 11 . 70 nmr spectrum in cdc1 3 : chemical shift in ppm ( multiplicity , intensity , assignment ): 5 . 34 ( multiplet , 11 . 6 h , hc ═ ch ); 3 . 88 and 3 . 68 ( broad apparent triplet and multiplet , respectively , 15 h , sucrose ch and oh ); 2 . 39 ( triplet , 14 h , ch 2 - co 2 ); 2 . 0 , 1 . 9 - 1 . 5 , and 1 . 28 ( multiplets , 278 h , ch 2 ); and 0 . 88 ( triplet , 21 . 8 h , ch 3 ). analysis of the nmr results supports a composition having a 7 . 3 : 1 ratio of fatty acids : sucrose . the above description is for the purpose of disclosing to a person skilled in the art how to practice the present invention . this description is not intended to detail all the obvious modifications and variations of the invention which will become apparent upon reading . however , applicants do intend to include all such obvious modifications and variations within the scope of their invention which is defined by the following claims .
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preferred embodiments provide real - time permutation generators for construction of interleavers in turbo coding schemes which can operate with a data block of variable size . because the block size can take on many different values ( e . g ., roughly 100 to 100 , 000 ), permutations for all these values cannot be constructed “ off - line ”; and the preferred embodiments provide a method for generating the permutation whenever it is required . preferred embodiment transmitters and receivers incorporate the preferred embodiment permutation generators for turbo coding . the main permutation generator features are : a . the method is applicable to data blocks of any practical size . b . no memory is required for storing the permutations in the transmitter and the receiver . c . the method for generating the permutations is very simple and thus does not impose a serious burden on the complexity of the encoder or the decoder . d . the permutation maps even indices to even indices . this feature is significant for some applications . the permutation generator relies on a modulo operation with a modulus selected according to block size . in particular , a table relates a parameter to block size , and the permutation is defined as multiplication by the parameter followed by modulo with respect to block size . [ 0028 ] fig1 a illustrates a preferred embodiment communications system encoder which sends data in packets whose length ( block size ) can vary in a very large range ; the interleaver uses the block - size - generated permutation . this extends the encoder of fig2 a . fig1 b shows a preferred embodiment communication system serial decoder ; this extends the decoder fig2 b , again by use of the block size to determine the interleaver permutation parameter . other preferred embodiments analogously extend parallel and mixed decoders to use the block size to determine the interleaver permutation parameter . denote the length of the packet , in terms of information symbols , by k packet . for a binary turbo coding scheme , the information symbols are bits while for a non - binary scheme , such as a turbo - tcm scheme , the information symbols are defined over a non - binary alphabet . a practical turbo coding system would usually have an upper bound on the size of the packet , k packet . this bound , k max , might be determined by a constraint on the maximal delay or by a constraint on some system resource , e . g ., storage memory . if k packet & gt ; k max , then the packet will be divided in the transmitter into n packet blocks of size k i so that k packet = σ i k i for 1 ≦ i ≦ n packet and k min ≦ k i ≦ k max the values of the sequence lengths k i should be about equal . the size of the longest and of the shortest sequence should be determined as follows : k min is the shortest sequence for which it is still worthwhile to apply turbo coding . this sequence can be several hundred symbols long . in the receiver , each of the n packet blocks will be decoded by applying an iterative decoding procedure and the data packet of size k packet will be reconstructed . because the performance of the turbo coding scheme improves with increasing the block size , it would be worthwhile to set k max to be as large as possible . note that large packets will have the best performance since for large packets it would be possible to divide the packet of size k packet so that all k i are close to k max . the shortest sequence of length k min will be used only when k packet = k min . for k packet & gt ; k max it would always be possible to divide the packet into sequences of length k i so that k i & gt ; k min , ( i = 1 , 2 , . . . , n packet ) provided that k max & gt ; 2k min . the rules for dividing the packet of length k packet into n packet sequences of length k i should be simple and known to both the transmitter and the receiver . the task of the permutation generator is to apply a deterministic memoryless procedure that can generate valid permutations that can be used for interleaving a data block of any given size k in the range k min ≦ k i ≦ k max . the permutation generator calculates for any integer index k the corresponding index π ( k ) in the permuted sequence for 0 ≦ k , π ( k )≦ k − 1 . for the permutation generator to be applicable in a turbo coding scheme , the following features are required : a . for every admissible value of the information sequence size k , the generator should provide a valid permutation ; i . e ., all indices should be properly mapped . b . no strict constraints should be imposed on the value of k . c . the number of parameters of the permutation generator should be small . d . the computational complexity of the permutation generator should be small . e . in order to provide good performance when employed in a turbo - coding scheme , the generated permutations for all admissible values of the information sequence k should resemble , as much as possible , a good pseudo - random permutation . the preferred embodiment permutation generators comply with the foregoing and use only one parameter that is read from a look - up table . the preferred embodiments have the further feature that π (.) maps even indices into even indices . the preferred embodiment permutation generators proceed with the following steps for a given block size k : ( a ) use the table of fig3 to pick the appropriate value of the parameter α k depending on the value of k . ( b ) if k is a multiple of α k , then replace k by k + 2 . ( c ) define the permutation π as : π ( k )= α k * k ( mod k ) for 0 ≦ k ≦ k − 1 . in every range of values of k in fig3 there a few values for which k is a multiple of α k in step b . for example , the values of k in the range 1526 ≦ k ≦ 1765 we have α k = 41 and thus obtain k as a multiple of α k for six k values : 1558 , 1599 , 1640 , 1681 , 1722 , and 1763 . in other ranges in fig3 the number of values for which k is a multiple of α k is likewise small . in many practical systems , there would be a constraint that k is an even integer or even that k is a multiple of 8 . in the above range , there are only three k values which are both even and a multiple of α k and only one ( k = 1640 ) which is both a multiple of 8 and a multiple of α k . alternative preferred embodiments follow foregoing steps ( a ) and ( c ) of the first preferred embodiments but substitute the following step ( b ′) for the foregoing step ( b ) which replaces k by k + 2 in the case k is a multiple of α k : ( b ′) if k is a multiple of α k , then use the α k from the preceding range of k values in the table of fig3 . for example , if k = 1640 , then step ( a ) gives α k = 41 and previous step ( b ) would have incremented k to 1642 . however , step ( b ′) just repicks α k = 37 and proceeds to step ( c ). lastly , for k in the range 144 ≦ k ≦ 229 , use α k = 11 . note that α k ≅{ square root } k and is prime and that the product of two successive α k s as used in steps ( a )-( b ′) is smaller than the k range endpoint of the second α k . thus step ( b ′) always provides a usable α k . indeed , the list of α k s of the table of fig3 is just a listing of the primes ( except for 89 ) from 13 to 257 , and the ranges for k are roughly just the ranges between corresponding products of two successive α k s . for example , α k = 41 corresponds to the range 1526 ≦ k ≦ 1765 where 1526 = 41 * 37 + 9 and 1765 = 43 * 41 + 2 . of course , another table can be generated using another sequence of pairwise - relatively prime α k s together with k range endpoints equal to products of two successive α k s + a small number . of course , the α k has to be relatively prime to its ks for the modulo permutation to be one - to - one . for the table of fig3 k min equals 144 and k max equals 2 16 (= 65 , 536 ). this very large range of block sizes should be sufficient for covering all practical applications of turbo coding . this spread of k values is divided into 50 ranges with each range having an α k value . in an actual implemented system only a portion of the table of fig3 ( determined by the actual values of k min and k max ) would be required so there is no need to store the entire table in the transmitter and in the receiver . furthermore , the size of the stored table can be further reduced in size by merging two adjacent k ranges into a single k range and using the larger of the two α k s as the α k for the merged k range . this merger should have a very small effect on performance , especially when the values of the α k s are close . note that the multiplication operation in step ( c ) is multiplication by a constant value of α k . a multiplication by a constant is simpler to implement than multiplication of two integer variables . the multiplication can be avoided by applying the following observation : in an implemented system , one usually computes permutations of successive values of k . thus , when π ( k ) is known , the value of π ( k + 1 ) can be obtained by using a recursion : π ( k + 1 ) = { π ( k ) + α k for π ( k ) + α k & lt ; k π ( k ) + α k - k for π ( k ) + α k ≥ k also the modulo operation in step ( c ) does not require a division operation . it can be easily implemented by a counter . the preferred embodiments can be modified in various ways while retaining the features of a parametric permutation generator for interleaving in turbo codes . for example , the number of recursive convolution codes used could be increased with a separate interleaver for each further code . the block size could be beyond those listed in fig3 . the ranges of block size could roughly track products of three successive primes and step ( b )′ of the preferred embodiment iterated to find a suitable parameter value . a subset of the primes could be used to generate the segments and parameters .
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reference will now be made to the drawings in which the various elements of the present invention will be given numerical designations and in which the invention will be discussed so as to enable one skilled in the art to make and use the invention . it is to be understood that the following description is only exemplary of the principles of the present invention , and should not be viewed as narrowing the claims which follow . in a first aspect of the invention , a novel approach is used to solve many of the joining problems mentioned above . a rotating friction stir riveting tool having a non - consumable shoulder combined with a detachable and at least partially consumable pin forms the basis of a friction stir riveting joining method of the present invention . the pin may be totally consumable or partially consumable . fig3 shows an example of how the tool can be constructed . fig3 shows a friction stir riveting tool 30 having a shoulder area 32 and a detachable and at least partially consumable pin 34 . in this particular embodiment , the detachable and at least partially consumable pin 34 includes a small gap 36 . the small gap 36 is formed by a much smaller pin diameter portion 42 of the pin 34 . this small pin diameter portion 42 of the pin 34 will be caused to break . the small gap 36 enables the detachable portion 38 of the pin 34 to remain embedded within the work pieces as a rivet . it is also noted that the non - detached portion 40 of the pin 34 might also be the top of another pin segment as will be explained . using fig4 as an illustration , to friction rivet steel or another metal using a tool of this first embodiment of the present invention , the tool 30 is rotated at a speed that allows the pin 34 of the tool to machine a first work piece material 50 away to form a hole 54 therein . features can be added to the end of the pin 34 to facilitate machining the desired hole . for example , a cutting feature 44 is shown in this first embodiment . it is preferred but not required that the depth 56 of the hole 54 extend completely through the first work piece material 50 and at least partially into the second work piece material 52 . it should be understood that depending upon the application , the hole 54 may only extend partially into the first work piece material 50 , completely through the first work piece material but not into the second work piece material 52 , completely through the first work piece material but only partially into the second work piece material , or substantially through both the first and the second work piece materials . one the initial hole 54 has been made , the tool 30 can then have the pin 34 make the desired level of penetration in accordance with understood principles of friction stir riveting . the pin 34 may extend completely through both the first and second work piece materials 50 , 52 , or it may extend completely through the first work piece material but only partially into the second work piece material . again , this depends upon the application of the user . in this first embodiment , once the depth 56 of the hole 54 has extended into the second work piece 52 as shown in fig4 , the rotational speed of the tool 30 is slowed down to generate heat between the pin 30 and the two first and second work pieces 50 , 52 that are being joined together . a spindle ( not shown ) that is holding and rotating the tool 30 can either be immediately stopped or slowed down until the torque required to rotate the tool exceeds the shear strength of the smaller pin diameter portion 42 . the smaller pin diameter portion 42 is designed to shear the detachable portion 38 of the pin 34 off of the tool 30 at a specified torque . in this first embodiment , once the detachable portion 38 of the pin 34 has been sheared off the tool 30 , the tool is retracted and a new pin 34 can be replaced . the detachable portion 38 of the pin 34 or rivet left behind in the first and second work piece materials 50 , 52 is friction welded into the work pieces . there is a bond not only under the tool shoulder between the first and second work pieces 50 , 52 but around the pin 34 or rivet . in an alternative embodiment of the present invention as shown in fig5 , a tool 60 has a hole 62 disposed through a central axis . the hole 62 allows a multi - segmented pin 64 ( shown here with three segments separated by a smaller diameter pin portion 72 ) to be inserted and pushed through the hole 62 as needed . the multi - segmented pin 64 includes a plurality of gaps 66 having a smaller diameter pin portion 72 . some type of plunger mechanism 68 would then be used to push the multi - segmented pin 64 through the tool 60 and out a working end 70 . as each segment of the multi - segmented pin 64 is broken off , the plunger mechanism 68 pushes the multi - segmented pin down through the hole 62 until enough of the pin 64 is exposed for the next friction stir riveting process . in this way , multiple rivets can be inserted into work pieces without having to stop and reload a multi - segmented pin 64 . the number of segments that can be used in a multi - segmented pin 64 should not be considered to be limited to three . fig5 is for illustration purposes only . more segments can be disposed on the multi - segmented pin 64 . the number of segments may also depend on the length of the tool 60 and the length of the plunger mechanism 68 . fig6 is provided to illustrate a multi - segment pin 64 that can be used for an automatic and rapid friction stir riveting process . the segments of the multi - segment pin 64 are co - axial so that they can be disposed in the hole through the central axis of the friction stir riveting tool 60 . the materials used to create a tool having a shoulder that can be used in the present invention can be found from tools created by some of the inventors that can be used to join high melting temperature materials such as steel and stainless steel together during the solid state joining processes of friction stir welding . this technology involves using a special friction stir welding tool . the shoulder can be created using materials such as polycrystalline cubic boron nitride ( pcbn ) and polycrystalline diamond ( pcd ). other materials that can be included are refractories such as tungsten , rhenium , iridium , titanium , molybdenum , etc . the work pieces that can be joined using the principles of the present invention include materials that have melting temperatures higher than bronze and aluminum . this class of materials includes , but is not limited to , metal matrix composites , ferrous alloys such as steel and stainless steel , non - ferrous materials , superalloys , titanium , cobalt alloys typically used for hard - facing , and air hardened or high speed steels . however , the present invention can also be used on materials that may be considered to be all other lower melting temperature materials that are not included within the definition of the higher melting temperatures described above . the shoulder 32 of the tool 30 can be made from polycrystalline cubic boron nitride or similarly described materials that can prevent adhesion of the shoulder to the first work piece 50 and provide superior thermal stability and wear resistance characteristics . several shoulder configurations can be used to form the shape of the rivet head or even cut away the rivet head after the pin 34 has been friction welded into the work pieces 50 , 52 . the materials used for the pin 34 are generally going to be those that can consumed during the friction stir riveting process . such materials will preferably enhance the bond between the first and second work piece materials , and are known to those skilled in the art of friction stir welding . alternative embodiments of the present invention include various aspects that should also be considered as important elements . first , a variety of cutting structures or profiles can be used on the end of the pin 34 that will be inserted as a rivet . a helically notched profile could be used as an alternate cutting structure instead of the feature shown in fig3 . in another alternative embodiment , inert gas such as argon or carbon dioxide can be caused to flow through the center of the tool 30 to prevent oxidation during friction stir riveting . in another alternative embodiment , more than two work pieces might be joined using the friction stir riveting process of the present invention . the length of the segments of the pin 34 would therefore be adjusted according . in another alternative embodiment , it should be noted that the work pieces that are being joined can be the same or different materials , depending upon the application . similarly , the material used in the pin might be a different material from the work pieces , the same material as at least one of the work pieces , or the same as the material on all the work pieces . pin profiles can be varied greatly . the pin profile can be a taper , hexagonal , or any desired shape that will perform a cutting process and friction stir riveting process . the shape will likely depend on various aspects , such as the desired bonding characteristics or the strength of the various materials being used . in another embodiment , the pin could also be hollow . the pin could be in rod or wire form and fed automatically through the center of the tool . when a square shape is used for the pin , this allows for torque from the tool to be transmitted to the pin or rivet . however , other torque transmitting profiles could be used . even a round shape could be used for the pin as long as a clamping force or clamping mechanism on the outside diameter of the pin material is sufficient to keep the pin from slipping within the tool when rotational forces are applied . the pin or rivet can have a variety of hardnesses or hardness profiles to facilitate work piece penetration . the tool can run to a specified position or load value at rpms ranging from 1 to 10 , 000 rpm . the tool could be run in the same configuration as fusion spot welding . for example , rather than using clamping with welding tips in a c clamp configuration , a small diameter rotating tool ( fig3 ) could be placed in a c clamp on the end of a robot . the c clamp configuration could also be used manually . the pin can have a fastener on the “ head ” so mechanical attachment can be used at that location . for example , the end of a friction rivet can have a threaded stub that is left to protrude above the work pieces after they have been joined . a nut could then be used to attach another component to the work pieces . some of the advantages of the friction stir riveting process include , but should not be considered limited to , a solid state joining process that is rapid , low energy input process requirements , low residual stresses because of the solid state process , no predrilled hole is necessary as in conventional riveting , there is reduced or eliminated distortion of the work pieces , no hole is left in the work pieces as in fssw , the process can be used in confined areas , z - axis forces are comparable to current forces required to resistance spot weld , the shoulder / pin ratio can be sized to generate a specific heat profile to optimize joint strength , corrosion resistant pin materials can be used , because the process is completed at an elevated temperature the formation of the pin or rivet has not yielded and will have greater energy absorption characteristics , the pin or rivet material can be overmatched to the work piece material for greater strength , and the rivet or pin can be used at the tip of a crack to prevent further crack propagation in a work piece . it is generally the case that the pin will be made using a material that is harder than the materials being joined . however , the pin might be softer , but pushed with sufficient force and quickly enough ; it can be used to join the harder work piece materials . another aspect of the invention is the option of removing the material being cut from the hole in the work pieces and being formed by the pin . one method of removing the material is to use a pecking motion . a pecking motion of the tool can also be combined with a fluid flow to remove the material . the fluid can be compressible or non - compressible , including gas , air , mist , and water . as previously mentioned . the present invention can be used to join different materials together , and is not limited to three body ( two work pieces and a pin ) configurations . multiple layers of materials can be joined simultaneously . any number of materials can be bonded so long as the materials are subjected to a temperature gradient that is less than the melting temperature of the materials being bonded . the range of surface travel speeds of the tool should be considered to be from 0 . 1 mm per minute to 10 meters per minute . the rotational speed of the tool can vary from 1 rpm to 100 , 000 rpm . coatings can be used on the tool , on the work pieces being joined , or on both the tool and the workpieces . the tool of the present invention can be a composite tool , such as a tool having a cbn shoulder , or different materials having a higher or lower modulus than the materials being bonded . the hardness of the materials being bonded should be considered to include all materials on the rockwell scales a , b and c . the cutting edge on the pin of the present invention can have any suitable cutting geometry . thus , any feature can be included on the pin that enables cutting , cutting and heating , and heating with the intent of causing a bond . the pin may also be threaded . thus , the pin does not have to have a cutting geometry . an alternative embodiment uses heating of the pin to enable creation of a hole or an aperture in or through other work piece materials . the present invention enables diffusion bonding on multiple planes , include axially and the sides of the hole that is created . it is to be understood that the above - described arrangements are only illustrative of the application of the principles of the present invention . numerous modifications and alternative arrangements may be devised by those skilled in the art without departing from the spirit and scope of the present invention . the appended claims are intended to cover such modifications and arrangements .
| 1 |
fig1 of the accompanying drawings shows part of a vacuum pump comprising a shaft 1 positioned within a pump body 2 which includes , as shown , three body portions 3 , 4 , 5 , all of which are sealingly fixed together . the shaft 1 is mounted for rotation in the body 2 by means of bearings 6 in the body portion 5 and bearings 7 in the body portion 3 . the vacuum pump is of the type having a second shaft ( not shown ) whose axis is parallel to the shaft 1 . the shafts have respective gears 8 , 9 , which engage each other . means ( not shown ) are provided to rotate the second shaft about its longitudinal axis with the interengaging gears 8 , 9 causing the shaft 1 to rotate also . the gears and the drive motor ( not shown ) generally require lubrication , and it is the oil employed for this purpose that contaminates an internal chamber 11 within which the shaft 1 rotates with a mist of oil suspended in the air or gas present in the chamber . the term &# 34 ; oil &# 34 ; is not limited to hydrocarbon oil or mineral oil but is defined to include any lubricating liquid . the shaft 1 is sealed within the body portion 3 by means of shaft seals in the form of a series of piston rings 12 contained in a piston ring carrier 10 secured to and rotatable with the shaft 1 . this ensures that the chamber 11 in which the lower parts ( as viewed in fig1 ) of the two shaft are contained is sealed from the pumping chambers of the vacuum pump which are positioned above the body portion 13 as viewed in fig1 . one of the piston rings 12 is positioned between passageways 13 , 14 in the body portion 3 so that a flow of gas , for example nitrogen , from a common source a can be passed to either side of the ring 12 so as to equalize pressure across it , thereby assisting sealing and causing a generally upward flow of gas ( as viewed in fig1 ) across the piston rings above the passageway 13 and hence into the pump outlet . the shaft 1 is adapted to carry an annular filter 15 in concentric fashion for rotation therewith . the filter comprises an annular coalescing filter element 16 supported at either end by annular end caps 17 , 18 of u - shaped cross section as shown and which are themselves sealingly fixed to the shaft 1 by means of o - rings 19 , 20 . for this purpose , the end caps 17 have cylindrical annular surfaces of sufficient axial extent to fit tightly onto o - rings 19 with clearances either side . the filter element 16 is further supported and constrained on its outer and inner surfaces by two annular expanded metal components conforming in shape to , and in contact with , the inner and outer surfaces of the filter element . there is a gas flow path from the chamber 11 through the outer annular expanded metal component in a generally radial direction through the coalescing filter element 16 and from the inner expanded metal component into a series of six equally spaced radially directed bores 21 in the shaft 1 ( two of which appear in fig1 ). the bores 21 , themselves , communicate with a further bore 22 directed axially along the shaft 1 . the bore 22 is sealed at the base ( as shown ) of the shaft and at its upper end communicates in the vicinity of the body portion 3 with a further set of six radially oriented bores 23 which extend through radial drillings in the piston ring carrier 10 to the outer surface of the carrier 10 . the piston ring carrier 10 has on the lowermost part of its outer curved surface a two start screw or scroll 24 whose turns afford communication between the bores 23 and the chamber 11 . in use of the vacuum pump , as the shaft 1 is rotated at high speed , the method of the invention allows air or gas present within the chamber 11 to be urged continuously towards the filter element 16 which it enters in a generally radial direction as shown by the heavier arrows in fig1 and thence to circulate through the filter element 16 into the bores 21 and then 22 and finally via the bores 23 where it is returned via the screw 24 back into the chamber 11 . the rotation of the screw or scroll 24 itself provides the driving force for recirculation of air or gas in the manner illustrated . in accordance with the method of this invention , oil droplets suspended in the air or gas which are drawn into the filter element 16 are retained therein by virtue of the physical properties of the coalescing filter . air or gas which has been cleaned of its oil content passes through the filter and is recirculated as described above . retained oil droplets tend to merge with other droplets retained by the filter to form droplets of increased size and , as they become more massive , the droplets are periodically ejected or flung from the filter in a generally radially outward direction as shown by the smaller arrows . there is a possibility for interaction between the inwardly directed oil - containing air / gas stream and the outwardly directed coalesced oil drops which is believed to enhance filtration efficiency . drops of the oil flung from the filter element 16 impact onto the side of the body portion 4 and fall to the base of the pump body in the vicinity of the body portion 5 . in this manner , the atmosphere within the chamber 11 is continuously recirculated through the filter 15 where the oil mist is coalesced into liquid and removed at each pass so that the concentration of oil mist within the chamber 11 is reduced to a low level . because of the lowered oil mist concentration , the ability for oil to pass the piston rings 12 and into the pumping chambers above the body portion 3 is reduced . it would be appreciated that it is important that the filter 15 should normally operate with a low pressure drop across it . in the construction shown , the scroll 24 creates an elevated pressure in chamber 11 which causes the flow of contaminated air through the filter . an excessive pressure drop causes a resistance to this flow , reducing the rate of filtration and permitting oil mist to build up in the chamber 11 . the filter element 15 is shown in greater detail in fig2 . the annular oil coalescing filter 16 may be fabricated or molded from a fibrous organic or inorganic material and preferably from a fibrous inorganic material such as glass microfibers . it should have a structure and pore size such that it will retain particles and droplets having a size from about 0 . 01 to about 10 microns and , in particular , particles of size less than about 1 . 5 microns which form a major component of oil suspended in air in a vacuum pump of the present kind . suitable media commonly have an efficiency of between 99 . 97 and 99 . 9999 % when subjected to a dioctyl phthalate test to astm d 1986 - 1971 ( military standard 282 ). the coalesing filter may be formed from layers of sheet wrapped one around the other , formed from pleated sheet or , as is preferred in the present case , it is made by molding or vacuum forming . it will during manufacture normally be impregnated with a resin binder which imparts a degree of mechanical strength and is compatible with the coalescing action . suitable media for the coalescing element are disclosed in patent specification numbers gb - a - 1014882 ( domnick hunter ) and gb - a - 1544822 and gb - a - 1603519 ( process scientific innovations ). in particular , it is preferred that the filter element 16 should be molded from borosilicate glass microfibers according to the process described in gb - a - 1603519 . the filter 15 which is typically of outside diameter 6 cm and length 3 cm is formed as a single component for convenience in fitting to or removal from the shaft 1 . during manufacture , the inner and outer expanded metal supports 27 , 28 , are offered to the outer and inner surfaces of the element 16 , after which the annular end caps 17 , 18 are adhered thereto . the expanded metal supports 27 , 28 are conveniently of expanded stainless steel mesh of thickness about 0 . 5 mm and open area 60 %. the element 16 may be of borosilicate glass microfiber impregnated with an epoxy resin , the end caps 17 , 18 may be machined from aluminum alloy , and they may be adhered to the filter element 16 and inner and outer supports 27 , 28 by means of an epoxy adhesive , grades of which exhibit good resistance to chemical attack and have service temperatures of , for example , about 130 ° c . as an alternative polyurethane or phenolic adhesive can be used , the chemical resistance of phenolic adhesives being especially good . in a variation shown in fig3 the end cap 17 , 18 may be made from a rigid plastics material , e . g . a 30 % glass - filled polybutylene terephthalate and , on the outer face of the outer expanded metal support 27 , there may be provided a drainage layer of large pore size organic woven , non - woven or foam material , e . g . of polyester needle felt , which drainage layer is treated with a fluorocarbon to reduce oil retention . such drainage layers are disclosed in u . s . pat . no . 5 , 129 , 923 . fig4 shows a further variant in which the coalescing filter has only a single expanded metal support member 27 on the outer surface and is sandwiched between end caps 31 , 32 which have axial extension 33 in which are formed retaining grooves 34 for o - ring seals . with this structure , the filter can be fitted onto a plain shaft and can be supplied complete with a fresh pair of o - ring scale which are held captive within the element and are replaced such time that the element is exchanged . in a further variant shown in fig5 and 6 , a splash guard fits over the outer cylindrical surface of the filter 15 covering a lower part of the outer surface for most of the axial extend of the exposed part . the splash guard 35 is an annulus of liquid - impermeable material formed with outwardly projecting louvers 37 which are formed with ports 39 at their trailing ends with reference to the direction of rotation as indicated by the arrow . it may conveniently be formed integrally with the lower end cap 35 , as shown , and be molded from a suitable plastics material , e . g . glass - filled polybutylene terephatlate . it has been found that , when the shaft 1 is rotating at low speeds particularly during starting and stopping of the vacuum pump , the filter element 15 is likely to be splashed with oil which at these low rotation speeds is retained by the coalescing element 16 and contributes to pressure drop . the splash guard 35 reduces the likelihood of the coalescing element becoming directly splashed with oil and hence enables the filter to operate with a lower pressure drop during starting or at low running speeds , but it does not significantly impede ingress of contaminated air or ejection of coalesced oil droplets . in fig7 there is shown a further variant of the filter in which the end faces of end caps 17 , 35 , the lower end cap 35 incorporating an integral splash guard as aforesaid , are provided with axially extending seals 40 , 41 . the filter fits in a recess between radially enlarged portions 42 , 43 of the rotating shaft , one of which is removable to permit the filter to be fitted and replaced . the use of axially extending face seals instead of the shaft seals in the previous embodiments permits a wider range of manufacturing tolerance for the axial spacing between end caps 17 , 35 of the filter . in the embodiment shown , the seals 40 , 41 are glued in place on the end caps 17 , 35 . in a variant , the end caps 17 , 35 could be formed on their end surfaces with an axial extension having a molded in o - ring receiving groove similar to the groove in fig4 . fig8 shows an alternative form of the invention for use with a rotary shaft which intrudes into a closed hydraulic chamber or tank . as shown , an upper tank wall 60 closes off the internal space 61 of the tank at an aperture 62 through which shaft 1 &# 39 ; extends . the shaft is rotatable by means of a fractional horsepower motor diagrammatically indicated at 63 . the shaft 1 &# 39 ; is formed with an axial bore 22 &# 39 ; and radial bores 21 &# 39 ;, 23 &# 39 ; as aforesaid . at its upper and lower ends are fitted an intake filter 45 and a coalescing filter 47 , each having the same structure as the filter shown in fig5 . the filters 45 , 47 are replaceably mounted on the shaft 1 by means of end caps 49 held in place by threaded studs 50 . the intake filter 45 rotates within a mesh guard 52 . as the level of liquid 54 within the space 61 falls , air is drawn into the space 61 through the inlet filter 45 where solid contaminants such as dust together with any liquid contaminants are filtered out . clean air enters the space 61 through the filter 47 . when the tank is refilled with hydraulic liquid 54 , the direction of flow is recovered , end mist droplets are coalesced and returned to the main body of oil 54 by the mechanism previously described . in a modification , it is desired to filter the gas in space 61 continuously through the filter 47 , the diameter of the inlet filter 45 is increased to a value greater than that of the coalescing filter 47 , in which case the preferential direction of gas flow is into the filter 47 and out from the filter 45 .
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fig1 - 3 illustrate a first embodiment of a device constructed in accordance with the present invention . a tube inserter 100 includes a cannula 110 having a threaded cutting portion 112 at its distal end and a conduit 114 ( shown in dashed line in fig1 ) running from its distal end along a portion of the length of the cannula 110 . holes 116 formed in the tip of cannula 110 and holes 118 formed in the side of cannula 110 create a fluid passageway from the holes 116 to the holes 118 along conduit 114 . a catheter 120 comprises an outer tube having an outer threaded portion 122 at the distal end and a lumen 124 running along its entire length , with the ends of the lumen 124 defining a distal opening 126 and a proximal opening 128 . in a preferred embodiment the catheter 120 includes graduated markings ( not shown ) on the outer surface to indicate distances , for example , the distance from each graduation to the cutting tip 112 . in addition , if desired , the graduated markings can be angled so that they provide the user of the device with an indication of the preferred insertion angle . at the proximal end of catheter 120 is a head assembly 130 , which includes a check valve 134 , a port 136 and an o - ring 138 . in the embodiment illustrated in fig1 - 3 , a threaded outer portion 132 is shown , to provide a compression fit between a chest tube inserted in the catheter and the head assembly , as discussed in more detail below . a control device , such as a leur cap , is affixed or otherwise associated with port 136 to enable control of the flow of fluid or other materials therethrough . the location of port 136 along the catheter 120 should coincide with the holes 118 when the cannula 110 is inserted into the catheter 120 as shown in fig3 . the o - ring ( or other sealing means ) is positioned within the lumen 124 such that , when the cannula 110 is inserted into the catheter 120 as shown in fig3 it allows fluid to travel from the distal end of the tube inserter 100 , through holes 116 , through conduit 114 , and out through holes 118 to port 136 , while preventing the flow of fluid towards the portion of the proximal end of the tube inserter 100 past port 136 . an adjustable flange 140 is positionable along the threaded portion 122 of catheter 120 . its position can be adjusted to be closer to or farther from the distal end of the tube inserter 100 . in a preferred embodiment the adjustable flange comprises a disk having a centrally - located opening formed therein , with the opening having internal threading to match the external threading of threaded portion 122 . so configured , the adjustable flange can be moved up or down the catheter 120 by rotation of the adjustable flange thereon . although not shown , if desired the adjustable flange 140 can be angled to the preferred insertion angle to act as a guide for the user . check valve 134 allows the cannula 110 to be inserted into the lumen 124 when desired ( shown inserted in fig3 ). when cannula 110 is removed from lumen 124 ( shown in fig2 ), the check valve 134 prevents the inflow or out flow of fluids ( or any material or composition ) through the proximal opening 128 . referring to fig4 - 7 , the method of using the present invention for insertion of a chest tube is now described . referring to fig4 the tube inserter 100 , fully assembled as shown in fig3 is placed tip first against the insertion location 400 on the skin 402 of a patient so that the threaded cutting portion 112 is in contact with the entrance location . the entire tube inserter 100 is then turned and advanced into the pleural space 404 . the screw design allows for a controlled insertion into the chest , with minimal pushing force , since progression relies on rotation of the pitched screw threads . the threaded cutting portion 112 eliminates the need for an initial incision , and the air / fluid passageway in the cannula 110 provides a method for the user of the device to determine whether the tip of the device is in the pleural space 404 and the nature of the injury ( e . g ., the presence of blood at port 136 indicates the presence of hemothorax ). as shown in fig5 the adjustable flange 140 limits the depth of the penetration by stopping the insertion at the skin 402 , and therefore minimizes the risk of injury to internal organs , such as to lung 504 . further , the ability to easily adjust the depth of penetration using adjustable flange 140 allows a non - physician to simply set the depth and be assured that a maximum depth is not exceeded . fig5 illustrates the tube inserter 100 fully inserted into the patient , such that the threaded cutting portion 112 has pierced the parietal pleura and entered the pleural space 404 . note that the cutting portion 112 has stopped short of contacting the visceral pleura 502 and the lung 504 . when insertion is complete and it has been determined that the device tip is in the pleural space 404 , as shown in fig6 the cannula 110 along with its threaded cutting portion 112 is removed , leaving the catheter 120 in place , with the check valve and leur cap closed . a chest tube 700 , which is connected to a heimlich valve or other type of one - way valve , can now be advanced into the pleural space 404 as shown in fig7 . preferably the chest tube 700 is locked or otherwise secured in place in the catheter 120 during use , to prevent it from accidentally being advanced into or retracted from the pleural cavity . for example , the chest tube 700 can be supplied with a mating device 702 having an internal threading which matches the outer threading 132 of catheter 120 ; the exact method and structure for maintaining the chest tube in place is not the focus of this invention and therefore any method and structure for maintaining a tight or “ compression fit ” is contemplated by the previous description . the excavation of pneumothorax and / or hemothorax is carried out in the usual manner using the chest tube and the appropriate removal methods and apparatus . the device can be inserted to the chest wall at various angles with minimal normal (“ push ”) and rotational forces , and with a high degree of control of insertion depth . while in this operative position , the chest tube and catheter 120 remain positionally stable within the chest wall . due to the threading along the outer surface of the catheter 120 , a high degree of force is required to pull the assembly out accidentally . further , once the pneumothorax or hemothorax has been resolved , the apparatus is easily removed from the chest by rotating the apparatus out along the threads . fig8 illustrates an alternative embodiment for the cannula of the present invention . as shown in fig8 a cannula 810 has a spline 811 running from the cutting tip 812 up to a location 818 . location 818 is selected so that it will be adjacent to port 136 ( fig2 ) when the cannula is inserted into catheter 120 . the spline provides a fluid passage ( i . e ., a conduit ) along the outer edge of the cannula ( between the cannula 110 and the inner wall of catheter 120 ) so that fluid may pass from the tip of the cannula to the port 136 , as described above with respect to fig1 - 3 . while there are many materials that can be used to fabricate the device of the present invention , in a preferred embodiment the cutting tip 112 is made of stainless steel or titanium in a generally conical shape , with threads , and converging at a sharpened tip at the distal end thereof . the remainder of the device , in a preferred embodiment , is made of injection molded clear plastic so that fluid traveling through the device may be viewed by the user . obviously other materials can be used without detracting from the novel aspects of the invention disclosed herein . the present invention enables prompt and inexpensive management of pneumo / hemothorax in humans and has broad - range application in areas such as combat casualty care , fire and rescue , and shock trauma centers . further , while the present invention is disclosed and described in a preferred embodiment pertaining to chest tubes , it is understood and contemplated that it can be applied to insertion devices of other types , such as abdominal drains and drains inserted into joints or other body cavities ; introduction of a port of entry into the body ( e . g ., pleural and peritoneal spaces , joints ) for diagnostic and therapeutic purposes ; introduction of a laproscope , and firm and stable fixation of other medical instrumentation to soft tissues ( e . g ., chest and abdominal wall ) using the screw concept disclosed herein . the foregoing is considered as illustrative only of the principles of the invention . further , since numerous modifications and changes will readily occur to those skilled in the art , it is not desired to limit the invention to the exact construction and applications shown and described . accordingly , all suitable modifications and equivalents may be resorted to , falling within the scope of the invention and the appended claims and their equivalents .
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with more particular reference to the drawings there is illustrated generally at 1 in fig1 , and 3 , a daughter board having mounted thereon a dielectric housing 2 . the board 1 includes a plurality of conducting circuit pads some of which are illustrated at 4 . electrical receptacles some of which are illustrated at 6 are provided within corresponding apertures 8 or cavities within the housing 2 . each of the receptacles 6 have electrically conducting tail portions 10 which project outwardly of the housing cavities and which are bent to project into corresponding apertures 12 of the board 1 . as shown more particularly in fig2 the tail portions 10 communicate with corresponding electrical paths 4 . to ensure electrical conductivity the tail portions 10 are soldered to the paths 4 . for convenience in routing of the paths 4 , the tail portions 10 project outwardly from the cavities 8 of the housing 2 in staggered fashion and are connected to the board in two separate rows . as shown the cavities 8 and 10 within the housing 2 are disposed in two separate rows parallel to the surface of the board 1 . each of the cavities 8 have a funnel entry or opening 14 through one end 16 of the housing 2 . the edge 18 of the board is overlied by a lip portion 20 of the housing 2 . as shown the lip portion 20 may be segmented . alternatively the lip portion may be continuous if desired . the sharp edges of the end surface 16 are chamfered as shown at 22 for a purpose to be described . the housing 2 is mounted to the edge margin adjacent the edge 18 by a pair of projecting plastic rivets 24 in registration within corresponding apertures 26 of the board 1 . the rivets 24 may be expanded with an enlarged head portion 28 as shown in fig3 in order to permanently mount the housing 2 to the edge margin of the board 1 . also shown in fig3 taken in conjunction with fig1 and 4 , a mother board 30 is provided with two rows of electrically conducting elongated posts or pins 32 which are mounted to the board 30 by press - fit connections within apertures of the board and which project interiorly of an enclosing dielectric housing 34 . as shown the housing 34 includes three rows of apertures 36 through an end wall 38 . the posts 32 occupy only two of the three rows of apertures 36 and therefore are arranged in rows offset within the interior of the housing 34 for complementary alignment with the funnel entry openings 14 of the housing 2 which are offset along the end surface 16 . the housing 34 has an open end 40 the interior edge surfaces of which are chamfered as shown at 42 in order to provide a funnel entry for receipt therein of the externally chamfered end 16 of the housing 2 . as shown in fig4 when the daughter board 1 and the housing 2 thereof are received within the confines of the housing 34 , the lip portion 20 engages against a sidewall of the housing as well as the end wall 38 of the housing 34 in order to maintain the housing 2 and the daughter board 1 in desired alignment within the housing 34 . the apertures 14 of the housing 2 are offset along the end wall 16 of the housing , in order to align the receptacles 6 over the corresponding offset rows of posts or pins 32 . the posts or pins are electrically received within the receptacles 6 when the daughter board 1 is correctly pluggably connected to the mother board 30 as shown in fig4 . as a further feature the housing 2 is provided with a slotted portion 46 extending through the housing to allow insertion of an extraction tool for deflecting the latch portion 48 of the receptacles 6 to allow their removal from the housing 2 . the slotted portion extends transversely through the housing 2 and intersects each of the projecting latch portions 48 of a first row of receptacles 6 . all of the latch portions can be deflected into the bodies of the receptacles by inserting an elongated tool through the slotted portion 46 . this will allow removal of the row of receptacles from the housing 2 . the other row of receptacles 6 include their latch portions 48 projecting into a recess 47 which communicates with each of the cavities 8 containing said other row of receptacles . an extraction tool can be inserted into the recess for deflecting a latch portion 48 of a selected receptacle of said other row into the body of the receptacle to permit removal of the receptacle from its corresponding cavity 8 . in addition the recess 46 communicates between the rows of cavities 8 to permit an extraction tool to enter the recess 47 , pass through a cavity 8 and into the recess 48 in order to deflect a latch portion of selected receptacle of the first row , permitting removal of the selected individual receptacle from the housing 2 . the first row of receptacles 6 are disposed closer to the end 16 of the housing than the other row of receptacles . this staggered row arrangement assures that the first row of receptacles will be received over a corresponding row of posts 32 before the other row of receptacles are received over the other corresponding row of posts 32 . such a feature divides the total insertion force required for mounting the receptacles collectively on the posts into smaller forces created sequentially and not in summation as the rows of receptacles are mounted over the corresponding rows of posts 32 . the mother board housing 34 is provided with pairs of slotted or notched openings 50 thereof to provide clearances for receipt of a tool which might be utilized to grip and remove the housing 2 from the mother board housing 34 if necessary . although a preferred embodiment of the present invention has been described in detail other embodiments and also modifications are intended to be covered by the spirit and scope of the apended claims .
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by way of example , the invention will be described with reference to the widely used 10 / 100 mbps ethernet local area networks ( lans ) typically found in workplace environments . such ethernet lans conform to the ieee 802 . 3 , 802 . 3u and 802 . 3x network standards which are incorporated herein by reference . referring first to the schematic representation of fig1 there is shown a network communications system 10 for connecting , for example , a plurality of portable computers 12 , 14 and 16 to each other and to an ethernet local area network 18 via an rj - 45 wall jack 20 . the specific embodiment of the system 10 shown in fig1 has eight ( 8 ) client or computer ports 22 for connecting as many computers . the computers 12 , 14 and 16 typically comprise notebook or handheld computers provided with network interface cards or adapters 24 . examples of such adapters 24 are the ethernet pc cards and ethernet / modem combo pc cards manufactured by xircom , inc ., thousand oaks , calif . a flat , category 5 compliant lan cable 26 terminated with an rj - 45 modular plug 28 connects - each of the computers 12 , 14 and 16 with the system 10 . the system 10 is a compact unit designed to be placed on a conference room table top 30 a portion of which is shown in fig1 . a default mode for the operation of the system 10 might be client - to - enterprise lan access . the network communications system 10 may also operate as a stand alone client concentrator facilitating networking among the users within a conference room with or without connection to a backbone network . the network communications system 10 is connectable to a standard electrical power wall outlet 32 and to the ethernet lan 18 by means of an adapter assembly 34 . the adapter assembly 34 includes a power cord 36 for connection to the wall outlet 32 ; an ethernet lan cable 38 terminated with an rj - 45 modular plug 40 for connection to the lan wall jack 20 , and a combined power / ethernet lan cable 42 described in greater detail below . in addition , in accordance with a preferred embodiment of the invention , the system 10 may be coupled to a second , cascaded network communications system 44 . up to three ( 3 ) 8 - port systems may be cascaded or daisy chained in this fashion thereby facilitating the networking of up to twenty - four ( 24 ) computers . such cascading is effected by means of combined power / ethernet lan daisy chain cables 46 and 48 , also described in greater detail below . with reference now also to fig2 - 5 , the system 10 comprises an outer housing 50 including a base 52 and a cover 54 , each preferably fabricated of molded plastic . the base 52 of the outer housing 50 includes a bottom wall 56 having inner and - outer surfaces 58 and 60 , and opposite side walls 62 and 64 defining the eight ( 8 ) client computer ports 22 from each of which a flat lan cable 26 may be pulled out by a user for connection to a computer . four rubber feet 66 attached to bottom wall 56 adjacent the comers thereof help resist any tendency for the system 10 to slide along the table top 30 when a cable is withdrawn from a client port 22 . the four client ports 22 along one side 62 of the base 52 are in transverse alignment with the four client ports 22 along the other side 64 of the base 52 , as best seen in fig5 . the cover 54 has a generally horizontal top wall 68 having an inner surface 70 and an outer surface 72 . the inner surface 58 of the bottom wall 56 of the base 52 defines eight ( 8 ) wells 80 each of which is positioned adjacent one of the client ports 22 . with reference now also to fig6 and 7 , removably mounted within each of the wells 80 is a generally cylindrical communications cable dispenser 82 . the dispensers 82 are identical ; each preferably takes the form of a take - up device containing a spring loaded reel carrying communications cable 84 . a cable dispenser or take - up device of the type that may be used with the present invention is generally disclosed in u . s . pat . nos . 5 , 797 , 558 and 5 , 655 , 726 , which patents are incorporated herein by reference . as already indicated , in the preferred embodiment under consideration , the communications cable 84 carried by the reel of each cable dispenser 82 is in the form of flat , category 5 twisted pair 10 / 100 mbps ethernet transceiver cable : each cable dispenser 82 has a casing 86 including two projections 88 and 90 on the outer surface thereof . the projection 88 has a transverse surface 92 - and the projection 90 has a transverse surface 94 . the cable 84 of each cable dispenser 82 has a first portion 96 that emerges from an aperture in the transverse surface 92 of the projection 88 . the first portion 96 of the cable 84 is fixed , that is , it is non - extendible relative to the cable dispenser 82 . the cable 84 includes as a second portion the cable length 26 that is extendible from an aperture in the transverse surface 94 of the projection 90 against a resilient bias provided , for example , by a flat coil spring within the dispenser 82 , and is thereby retractable into the dispenser . further , in the present invention , the cable dispenser preferably includes a mechanism for allowing the cable to be latched in an extended state to relieve strain on the cable during use . a mechanical switch 100 in the top surface 101 of the cable dispenser casing 86 allows a user to select latching or non - latching reel operation . the length of the second portion 26 of the cable 84 is compatible with typical conference room environments , for example , six to eight feet long , the first and second portions 96 and 26 of the cable 84 have ends 102 and 104 , respectively , carrying an rj - 45 modular plug 106 and the rj - 45 modular plug 28 . the plug 28 has a rear surface 110 provided with a slotted , resilient pad 112 that engages the transverse surface 94 of the projection 90 on the casing 86 to absorb shock in the event a user suddenly releases the extended cable portion 26 . mounted on the top surface 101 of the dispenser casing 86 and extending along a diameter thereof , is an upwardly projecting , flat grip or handle 114 facilitating the lifting of the cable dispenser 82 and the removal thereof from its associated well 80 . adjacent the inner end 116 of the handle 114 and disposed perpendicular thereto is a short , upstanding abutment 118 . the base 52 of the system 10 includes a molded plastic inner housing 130 extending the length of the base . the inner housing 130 has a horizontal upper wall 132 that defines eight ( 8 ) longitudinally spaced jack apertures 134 and four transverse channels 136 , each channel being in alignment with a pair of opposed client ports 22 . the inner housing 130 further includes a generally vertical wall 138 defining eight ( 8 ) arcuate recesses 140 for receiving the inner portions of the cable dispensers 82 . a portion of the vertical wall 138 in each arcuate recess 140 is slotted ( at 142 ) so as to define a generally u - shaped , resilient tab 144 hinged along the bottom thereof . the resilient tab 144 carries an outwardly projecting latch 146 that engages the top of the abutment 118 on the top of the associated cable dispenser 82 to lock the dispenser in place and prevent it from being lifted . to remove a cable dispenser 82 for replacement , the associated resilient tab 144 is pressed inwardly , that is , away from the dispenser , thereby causing the latch 146 to clear the associated abutment 118 thus allowing the dispenser to be lifted out of its well 80 by means of the handle 114 . projecting upwardly from the inner surface 58 of the bottom base wall 56 is a stop 148 that engages the transverse surface 94 on the dispenser projection 90 . the stop 148 thereby prevents the cable dispenser 82 from rotating counterclockwise within its well 80 when the second portion 26 of the cable 84 is withdrawn from the dispenser . [ 0035 ] fig8 is a top plan view of the base of the communications system with the inner housing 130 removed thereby exposing a printed circuit board ( pcb ) 150 extending substantially the length of the base 52 . fig9 is a perspective of the pcb 150 . mounted on one surface of the pcb 150 are first and second monolithic integrated circuits 152 and 154 comprising network interconnection circuitry preferably in the form of lan switches . mounted on the other surface of the pcb 150 opposite the lan switch ic &# 39 ; s 152 and 154 are heat sinks 156 and 158 , respectively , for transferring heat away from the switches . the pcb 150 also carries an inverted 10 - contact rj - 45 jack 160 at one end of the pcb 150 for connection to the combined power / ethemet lan cable 42 of the adapter assembly 34 , and an inverted 10 - contact rj - 45 jack 162 at the other end of the pcb 150 for connecting the system 10 to the second communications system 44 by means of the combined power / ethernet lan daisy chain cable 46 . the pcb 150 further carries eight ( 8 ) upright client port rj - 45 jacks 164 intermediate the ends of the pcb . the jacks 164 are arranged as two pairs 164 a , 164 b of individual jacks and a central jack complex 164 c integrating the remaining four rj - 45 jacks 164 in a single unit . with the inner housing 130 in place in the base 52 , the eight client port jacks 164 carried by the pcb line up with the jack apertures 134 in the upper wall 132 of the inner housing 130 . [ 0036 ] fig1 is a high - level block diagram of the electronics of the 8 - port network communications system 10 . as shown in fig1 , the first switch 152 may comprise , by way of example , a model bcm5308 single chip , 3 . 3 volt 10 / 100 base - t / tx 9 - port switch manufactured by broadcom corp . the second switch 154 may comprise a model bcm5304 single chip , 3 . 3 volt 10 / 100 base - t / tx 5 - port switch also manufactured by broadcom corp . the switches 152 and 154 are connected by an expansion bus 168 and are coupled to sram buffer memories 170 and 172 , respectively . six transmit / receive ports of the first switch 152 interface with the enterprise power / ethernet rj - 45 jack 160 and five of the client port rj - 45 jacks 164 which receive the mating rj - 45 plugs 106 on the ends 102 of the fixed cable portions 96 . three transmit / receive ports of the second switch 154 interface with the rj - 45 jacks 164 of the remaining three client ports . a fourth transmit / receive port of the second switch 154 interfaces with the cascade or daisy chain rj - 45 jack 162 . a pass - through 24vdc power bus 174 for supplying cascaded systems such as the system 44 is connected between the power / ethernet and daisy chain jacks 160 and 162 . connected to the 24vdc bus 174 is a regulator 176 for supplying 3 . 3vdc to the various ic &# 39 ; s carried by the pcb 150 . the use of multiport network interconnecting circuits such as the lan switches 152 and 154 and their connection to lan port jacks are well known in the art and need not be described in greater detail . it will also be obvious to those skilled in the art that instead of a lan switching arrangement , the system may be set up as a less expensive , conventional concentrator or repeater hub . the system 10 also includes means for providing a visual indication of the status of each of the client ports 22 . with reference to fig4 and 5 , with the inner housing 130 in place , four portions 178 of the pcb 150 are exposed by the transverse channels 136 defined by the inner housing . with reference also to fig8 and 12 , each of the exposed portions 178 of the pcb carry a set of three status indicating leds 180 - 182 on each side of the pcb , each set of leds being associated with one of the client ports 22 . the leds of each set are vertically aligned with the upper two leds 180 and 181 in close proximity to each other and the third led 182 being below and spaced apart from the upper pair . the upper pair of leds 180 , 181 of each led set indicates ( through 2 different colors ) link integrity , that is , whether a good 10 mbps or 100 mbps connection has been made , while the third led 182 of each set indicates lan send / receive activity . light from - the leds is transmitted to the exterior surface 72 of the cover 54 via light pipes of lexan or the like . specifically , as shown in fig1 and 12 , each client port has associated with it a pair of vertically aligned , upper and lower , l - shaped light pipes 184 and 186 carried by the inner surface 70 of the cover 54 . the light pipe 184 has an inner end 184 a and an outer end 184 b . likewise , the light pipe 186 has inner and outer ends 186 a and 186 b . with the outer housing cover 54 in place , the inner end 184 a of the upper light pipe 184 is positioned to receive light from one or the other of the leds 180 , 181 of the upper led pair ; similarly , the inner end 186 a of the lower light pipe 186 is positioned to receive light from the lower led 182 when the cover 54 is in place . the outer ends 184 b and 186 b of the light pipes 184 and 186 communicate with the outer surface 72 of the cover 54 and thus light transmitted by the light pipes from the leds is visible to the users of the system to indicate the status of each client port 22 . the use of leds to indicate the status of lan ports is well known in the art , being routinely used , by way of example , in connection with network interface cards or adapters such as those mentioned above . [ 0039 ] fig1 shows the details of the adapter assembly 34 for connecting the system 10 to the enterprise lan 18 and the source of electrical power 32 . the adapter assembly 34 comprises an enclosure 190 , the combined power / ethernet lan cable 42 extending from one end of the enclosure 190 , and the 120vac power cord 36 and category 5 compliant ethernet lan cable 38 extending from the other end of the enclosure 190 . with reference also to fig3 and 10 , the combined power / ethernet lan cable 42 has first and second ends 42 a and 42 b and is terminated at the end 42 b with a 10 - contact position rj - 45 modular plug 192 for connection to the internal jack 160 , while , as already indicated , the lan cable 38 is terminated with an eight contact rj - 45 modular plug 40 for connection to the wall lan jack 20 . the enclosure 190 contains a pcb 194 carrying a 120vac - to - 24vdc power supply 196 connected to the power cord 36 and conductors 198 providing a pass - through for the ethernet lan signals . by way of example , the overall length of the adapter assembly of fig1 may be 25 feet . as shown in the cross section of fig1 , the combined power / ethernet cable 42 includes a core group of category 5 compliant conductors comprising two twisted wire pairs 200 / 201 and 202 / 203 connected to the pass - through conductors 198 for transmitting network signals . the core group of conductors 200 - 203 is encased in insulative filler material ( for example , fibrillated polypropylene ) 204 in turn enveloped by a tubular , double sided aluminum foil / mylar emi / rfi shield 206 having a drain line 208 . the shielding 206 is surrounded by fibrillated polypropylene filler 210 which in turn is enveloped by a braided emi rfi shield 212 and an outer tubular . insulative jacket 214 of , for example , flexible pvc . embedded in the filler 210 is an outer group of conductors comprising two twisted wire pairs 216 / 217 and 218 / 219 connected to the power supply . 196 for supplying 24vdc electrical power to the system 10 . with reference to fig1 , the combined power / lan cable 46 for cascading the systems 10 and 44 is identical to the combined power / lan cable 42 of the adapter assembly 34 except that the cascading cable 46 is terminated at each of the first and second ends 46 a and 46 b with a 10 - contact rj - 45 modular plug 220 . with reference also to fig3 and 10 , to cascade the systems of the invention , one of the plugs 220 is inserted in the daisy chain rj - 45 jack 162 of the first system such as the system 10 while the other plug 220 is inserted in the enterprise rj - 45 jack 160 of the second system such as the system 44 . the overall length of the cable 46 may be 6 feet , for example . [ 0042 ] fig1 is a chart listing the pin or contact assignments of the mating 10 - contact rj - 45 modular plugs and jacks used in the system of the present invention . thus , the conductors 200 / 201 and 202 / 203 of the core or lan group of conductors are connected to contact nos . 1 - 4 while the conductors 216 / 217 and 218 / 219 of the outer or power group of conductors are connected to contact nos . 7 - 10 . middle contact positions nos . 5 and 6 are devoid of contacts so as to provide additional electrical isolation between the two groups of conductors . with reference again to fig3 - 5 and 8 , in the event heat dissipation from the lan switch ics 152 and 154 through the use of heat sinks 156 , 158 alone is insufficient , a cooling fan 230 housed within a slotted enclosure 232 at one end of the system 10 may be provided . cooling air discharge slots 234 formed in the bottom wall 56 of the base 52 at the other end of the system 10 vent cooling air flowing along the length of the pcb 150 . with reference to fig1 , there is shown an alternative embodiment of the invention comprising a system 240 having four client computer ports 242 two of which are visible in fig1 . it will be evident that the preceding detailed description applies equally to the four port version of the invention , except that typically only a single lan switching ic would be required . while the invention has been particularly shown and described with reference to preferred embodiments thereof , it will be understood by those skilled in the art that the foregoing and other changes in form and detail may , be made therein without departing from the scope of the invention as defined by the appended claims . for example , it will be appreciated by those skilled in the art that the invention is equally applicable to “ small office / home office ” ( soho ) environments .
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illustrated in fig1 is a golf training device 11 of the present invention . the golf training device 11 includes a platform 13 having a plurality of vertical support members 15 such as rectangular legs . the legs may include a plurality of holes 17 and may be attached to a side 19 of the platform 13 by means of screws or bolts 21 . the holes 17 and the screws 21 may be used to adjust the height of the platform 13 . although the means illustrated include the holes and screws , numerous other means of adjusting the vertical position of the platform 13 can be envisaged by a person having ordinary skill in the art . for example , telescoping legs may be secured by nuts , or pins . the platform 13 is preferably covered with a mat of synthetic grass material 23 . the golf training device also includes a golf club 25 having a shaft 27 which is shortened considerably . thus , the club 25 of the present invention is generally 27 inches long and will usually be a seven , eight or nine iron which has some substantial loft . the reason for selecting a club with considerable loft is that it is desirable to get the ball 29 airborne in order to determine how the student is progressing . typically , the platform 13 may be varied in height depending upon the height of the player and the length of the club . the standard platform 13 would generally be 18 &# 34 ; by 36 &# 34 ; by 9 &# 34 ; high and the golf club will have a 27 &# 34 ; shaft . it is desirable to provide additional weight to the golf club so that it feels like a standard golf club or perhaps somewhat heavier . this can be done by filling the shaft with lead shot . the principle behind the invention is that by achieving a reduction of the forces acting on the left wrist , the student can experience the feel of the correct position of the left wrist . the forces acting on the left wrist are a function of the length of the shaft because of the moment created by the head of the club . thus , by reducing the length of the shaft , the moment produced by the head of the club is reduced and thus the strength and skill that is required to maintain the proper trajectory of the head of the club is reduced . the invention also contemplates a method of teaching and practicing the proper golf swing . in the method of the invention a ball is placed on a horizontal platform disposed a predetermined vertical distance from the ground . a golf club having a shortened shaft is disposed in the hands of the student . the student is then instructed as to the proper stance , grip and shown the correct path of the club face . drills are then provided to make the student understand how the path of the club face is controlled with emphasis on the correct position of the left arm and hand ( assuming a right handed golfer ). advantageously , the golf club of the invention has the approximate weight of a full size club yet lacks the normal inertia permitting the student to concentrate on the feel and control of the swing . typically , the following drills are followed using the shortened shaft club as shown in the flow diagram of fig2 : 1 . short swing of the shortened shaft golf club with the left hand and forearm while feeling a straight to slightly convex position of the back of the left wrist ; 2 . short swing of the shortened shaft golf club with both arms while experiencing the feel of the controlling left hand and forearm from drill 1 ; 3 . short swing of the shortened shaft golf club with the right hand and forearm while feeling the natural pivoting action of the body on the right leg and hip in the backswing and downswing and the left leg and hip in the follow through ; 4 . short swing of the shortened shaft golf club with both arms while experiencing the feel of the natural pivoting action of the body on the right leg and hip in the backswing and downswing and the left leg and hip in the follow through ; 5 . full swing of the shortened shaft golf club with the right arm feeling the natural pivoting of the body on the right leg and hip in the backswing and downswing and the left leg and hip in the follow through ; and 6 . full swing with both arms while experiencing the feel of the natural pivoting of the body on the right leg and hip in the backswing and downswing and the left leg and hip in the follow through . it has been found that a basic problem in learning the necessary muscle control and developing the proper muscle memory is that the left and right arms often tend to work against each other . the correct swing can only occur when each hand and arm independently follows the right path and cooperate . the present teaching and practice method of the invention , by virtue of the above listed drills , permits learning of the movements of each arm and hand with the easily managed shortened club . the actual hitting of the ball from the raised platform provides the necessary feedback so that the golfer may determine when he achieves the correct movements . thus , the apparatus and method of the invention permits an instructor to easily teach a person a correct golf swing by permitting the swing to be broken into its basic elements , the feel of each element by each hand and arm learned and those elements integrated into a full swing without the distortion caused by any slight deviations magnified by the inertial effect of a full length club . when the student has mastered the &# 34 ; feel &# 34 ; evidenced by the proper flight of the ball , he may then move to the full size club and be able to sense inaccuracies in his swing .
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the development of virus specific monoclonal antibodies and the check of their cross reactivities are bases of virological researches ( bergter 1990 ). identification and purification of cell membrane bound viral proteins of peptides belong to the state of the art ( eckert and kartenbeck 197 ). likewise , the methods to prepare murine , humanized , or human monoclonal antibodies and the preparation of antigen binding mab fragments are known ( peters and baumgarten 1990 , lidell and weeks 1996 ). the identification and isolation of viral and virus induced antigens from the plasma membrane of effected cells and the generation of monoclonal antibody are depicted in example 1 . first , it will be clarified by immunocytological and electron microscopical basic examinations whether viral proteins are principally integrated into the cell membrane of infected cells , which are susceptible to a radio immunotherapy . for this purpose , the binding of virus specific antibodies to infected cells is detected by incubation with labeled murine monoclonal antibodies ( payne et al . 1990 , stirling 1990 , kaito et al . 1994 , sabri et al . 1997 ) by means of fluorescence or electron microscopy . if such antigens can be detected in the cytoplasm membrane it must be clarified in a second step , which antigens have been detected . therefore , virus infected cells are lysed and the membrane proteins separated by gel electrophoresis . blotted to nitrocellulose the membrane proteins will be subsequently analyzed with antiserum or murine monoclonal antibodies . for the immunization and generation of monoclonal antibodies purification of the viral or virus induced antigens integrated into the cell membrane that have been found is required . for this purpose , viruses are cultivated in suitable cell culture systems , for example , hiv in h9 - cells , mt - 4 cells , molt - 4 cells , hut - 78 cells etc . ( bergter 1990 ) and hcv in daudi - cells ( nakajima et al . 1996 ) and isolated from the cell culture supernatant . first , the cells and the cell debris are spun down , second the virus is sedimented from the purified supernatant by centrifugation with 27 . 000 × g . third the virus pellet is resuspended in sample buffer and separated by gel electrophoresis . finally , the antigen fraction corresponding to the antigen searched for on the plasma membrane is isolated . this antigen is used for the immunization of mice and for the preparation of monoclonal antibodies . the monoclonal antibodies thus produced are preferably checked for cross reactivities with different virus isolates , which check occurs by means of elisa , immunoblot , or ripa . the suitable monoclonal antibody ideally possesses a broad cross reactivity and thereby comprises the entire quasi - species of an infected patient . if no monoclonal antibody recognizing all virus isolates is isolated , isolate specific monoclonal antibodies are prepared which antibodies will subsequently be specifically employed for the therapy of the isolate detected from case to case . as has been described above as well , in the meantime cellular receptor molecules have been identified for quite a number of viruses , which receptor molecules mediate the adsorption of the viruses to the surface of the host cell . the methods to identify and generate such receptor molecules belong to the state of the art . the procedure will be described in example 2 . the receptor for hiv - 1 and hiv - 2 is the cd4 receptor , whereas hcv probably binds to the ldl receptor ( seipp et al . 1997 ). the respective virus ( e . g . hcv ) is separated by gel electrophoresis such that the ( hc ) viral antigens may be isolated . binding studies will be carried out on tissue samples ( from the liver ) and cell culture systems and the cellular receptor responsible for the adsorption of the virus that has been searched for is identified ( dorig et al . 1993 , treichel et al . 1997 ). this receptor is isolated with established methods ( suzuki et al . 1983 ) and the binding epitope analyzed in detail by analyzing the binding of the antigen to distinct cleavage products . the receptor molecule is finally cloned ( bergelson et al . 1998 ) and thus further processed on a large scale for the conjugation with the radioisotope and the therapeutic use according to the present invention . the monoclonal antibodies or host receptor molecules are conjugated with a radio nuclide ( alpha or beta emitter ). the conjugation of radio nuclides to proteins is sufficiently described and belongs to the prior art ( review in : eckert and kartenbeck 1996 ). the procedure will be depicted exemplarily in example 3 although different methods ( e . g . zalutzky et al . 1989 ) may be more or less suitable for distinct conjugate constructs such that the conjugation methods have to be individually adapted and optimized . suitable monoclonal antibodies or receptor molecules for therapeutic purposes are radioactively conjugated with the chloramine t method ( hunter and greenwood 1962 ) following the recipe of eckert and kartenbeck 1997 . a radioisotope is transiently oxidized by hypochlorite which is released by chloramine t ( n - chloro - p - toluene - 4 - sulfonamide , na salt ) in aqueous medium . then the strongly electrophilic radioisotope in this state preferably binds to the benzene rings of the aromatic amino acids contained in the protein . to treat the monoclonal antibodies and receptor molecules , respectively , gently the reaction is terminated after a short incubation by an excess of bisulfite , whereby both the residual chloramine t and oxidized but still unbound radioisotopes are reduced and thus deactivated . finally , the mab - radioisotope conjugate is isolated by gel electrophoresis and further processed with distinct auxiliaries for its use , preferably for its intravenous use . further methods are likewise available ( harrison and royle , 1984 ; zalutsky et al . 1989 ). according to any of these methods , for instance , the conjugates a7 ) may be prepared . in vitro investigations show whether and with which affinity the radio immunoconjugate bind via the antigen binding site of the monoclonal antibodies or host receptor molecules , to the corresponding epitopes of viral proteins integrated into the cell membrane of virus infected cells , and whether the cells are damaged by the radioisotope mediated radiation . these investigations are performed in suitable cell culture systems . in the following steps preclinical in vivo investigations relating to the effectiveness of the radioimmunotherapy may be performed on nude mice and other animal models before the clinical application is tested in infected patients . in case of the hcv treatment hcv infected chimpanzees ( tabor et al . 1978 , walker et al . 1997 ) are an example for a suitable test system . in different phase i studies ( dose escalation studies ) the maximally tolerable dose ( mtd ) in regard of side effects , pharmacokinetics and immunogenicity are to be determined . by the subsequent clinical investigations ( phase ii and iii studies ) the effect of distinct radioimmunopharmacons shall finally be checked with small groups of patients suffering from progressive disease and with randomized groups of patients ( fiebig 1995 ). the short half life of the radionuclide ( be they α - or β - emitters ) is responsible for the requirement that the radioimmunoconjugate is prepared in the vicinity of a center and its fast transport to the therapist , respectively . the short half life is relevant in so far as longer half - lives would expose the patient to a radiation dose too big and too long . prerequisite for the therapy of patients suffering from hiv , viral hepatitis and , optionally , other viral infections by means of radionuclides having short half lives is thus the installation of specialized interdisciplinary centers , in which not only the professional therapy of the infected patients but also an application in time of the radioimmunoconjugate under aspects of anti - radiation precautions is secured . prerequisite for a successful therapy may also be the pretherapeutic decrease of the virus load which can be accomplished by a previous treatment of the patient with antiviral or anti - retroviral agents . thereby , a higher dose of the radioimmunopharmacon is brought to the virus replicating cells , and this brings about an improved therapeutic effect . otherwise , it would be conceivable that the radioimmunopharmacon is caught by free virus particles and the cytotoxic effect is decreased . in case of an hcv infection a prior treatment with ifn - α or ribavirin may occur . this may be done as a mono - or a combination therapy . prior to the application of a preparation based on 131 i diagnostics and blockage of the thyroid gland following the well known specimen must additionally occur . for the radioimmunotherapy a stationary accommodation for several days is required in order to shield the patient from the surrounding until the radiation eases off . the radioimmunopharmacon is administered periphero - or centrovenously as bolus , short infusion , or permanent therapy for several days in a dosage of 25 - 300 mci , preferably 50 - 300 , more preferred 100 - 200 mci . the dosage is administered once or in cycles by repeating the administration in intervals of several weeks . optionally , in case of an existing hypersensitiveness against the monoclonal antibody or against the receptor molecule , a previous treatment with a glucocorticoid , with an anti - histamine and / or with an h 2 - antagonist is required immediately prior to the administration of the preparation ( lorenz 1994 ). a particularly preferred embodiment of the invention is the use of humanized and human monoclonal antibodies , whereby the immunogenicity of murine mab conjugates can be circumvented . such immunogenicity may proof to make sense , on the other hand , if it is desired to additionally sensibilize the immune system against the virus infection . a further preferred embodiment is directed to the use of fragments of monoclonal antibodies or cell receptors as immunologically effective component of the radioimmunoconjugates since the smaller molecule size may result in an improved capacity to pass through tissue and to pass the blood - brain - barrier . the radioimmunotherapy of viral infections have a tremendous preventive significance , in particular in cases in which a preventive elimination of virus is to avoid and to combat , respectively , oncological diseases as they are known , for example as a consequence of hiv , htlv - 1 , htlv - 2 , hhv8 , ebv , hcv and hbv infections . although beta and alpha emitters have entered into the radioimmunotherapy of malignant diseases , the above described therapy is , quite in contrast thereto , not only an entirely new indication or radioimmunopharmacons generally , but a basically different therapeutical approach and claim for highly specifically constructed antiviral preparations with very exactly defined areas of application . whereas monoclonal antibodies against tumor specific proteins of the cell are used in the radioimmunotherapy of malignant diseases , for the above described radioimmunoconjugates , monoclonal antibodies , their fragments , or other proteins and peptides with the therapeutical object specifically against viral ( i . e ., not of the cell ) and virus induced ( not cell type specific ) proteins . 1 . alter h j , purcell r h , holland p v et al . : transmissible agent in non - 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1914 .
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this invention is now described in detail for making an array of non - volatile memory cells , and more specifically for eprom circuits . the method involves forming non - volatile memory cells on rows of device areas that lie between columns of device areas that intersect the row device areas , and are essentially orthogonal to each other . the column device areas provide buried bit lines for the nvm formed from the fets . the nvm cells are formed from a single fet that incorporates a floating gate over the fet channel area . the floating gate also extends vertically upward on the sidewalls of the control gate , thereby increasing the capacitor area between the floating and control gates . a thin , high - dielectric - constant insulating layer composed of a silicon oxide / silicon nitride / silicon oxide ( ono ) layer is formed on the floating gate prior to forming the control gate and provides a reliable , pin - hole free , interlevel dielectric layer . although the invention is described for making non - volatile memory cells using n - channel fets on a p - doped silicon substrate , it should be well understood by those skilled in the art that the nvm cells can also be formed from p - channel fets . furthermore , by incorporating additional processing steps , these non - volatile memory cells can be formed on chips with p and n wells , thereby providing for complementary metal oxide / silicon ( cmos ) circuits using conventional fets having a single gate electrode , such as those required on the periphery of a memory chip for accessing and reading and writing information to and from the array of memory cells . referring initially to fig1 a schematic elevational view is shown of an eprom cell area . for practical reasons , only a single memory cell of the array of memory cells is depicted . the line through region 3a - 3a &# 39 ; indicates the cross - sectional area shown in fig2 a - 7a , and the line through region 3b - 3b &# 39 ; indicates the cross - sections shown in fig2 b - 7b . to better understand the invention , a brief overview of the non - volatile cell structure is provided , and then the detailed process descriptions are given with reference to fig2 a - 7a , and fig2 b - 7b . fig1 shows a portion of an array of non - volatile memory cell areas on a substrate 10 having an array of column device areas , one of the many columns labeled 2 is shown in the fig . also shown is one row device area labeled 4 for an array of device areas on the substrate . the row and column device areas are defined and electrically isolated from each other by forming planar field oxide regions 12 . also shown in fig1 are wells labeled 6 that are etched in an insulating layer 14 deposited over the substrate after forming the row and column device areas . each well is eventually used to form a single fet in each memory cell area over a row device area having an additional floating gate to provide for a non - volatile memory ( nvm ) cell . also shown in fig1 is a patterned portion of a first polysilicon layer 20 extending over the well areas 6 on a gate oxide ( now shown ) grown on the exposed device area . the patterned first polysilicon layer 20 completely covers the gate oxide in the wells and extends over the insulating layer 14 , as shown in fig1 . the patterned first polysilicon layer 20 on the gate oxide and extending upward on the well sidewalls of the wells 6 will eventually form the floating gate for the fets having increased surface area and thereby increased capacitive coupling . fig2 a - 7a and fig2 b - 7b show the cross - sectional view for one of the many cells formed concurrently by the method of this invention . referring now to fig2 a - 7a , the details of the new and improved memory cell structure and process for manufacturing an array of nvm cells are described . the process starts by providing a semiconductor substrate 10 . the preferred substrate is typically composed of a p - doped single crystal silicon having a & lt ; 100 & gt ; crystallographic orientation , doped for example with boron . the substrate or p - well for fabricating the n - channel fet is typically doped having a concentration between about 1 e 14 to 1 e 15 atoms / cm 3 . referring now to fig2 b , a planar field oxide 12 is formed in the substrate . the method for making the field oxide 12 involves using a photoresist mask and anisotropic etching to form trenches in the silicon substrate to a depth of between about 3000 and 10000 angstroms , the trenches having essentially vertical walls . the trenches can be etched , for example , using a chlorine based gas mixture and reactive ion etching ( rie ). after stripping the photoresist , a thermal oxide is grown in the trenches on the silicon substrate to provide a good quality interface . typically the thermal oxide is between about 100 and 500 angstroms thick . in addition , it is desirable to provide a p + implant in the bottom of the trenches to form a channel - stop layer to prevent surface inversion . still referring to fig2 b , a conformal first insulating layer 12 is deposited on the substrate sufficiently thick to fill the trenches . preferably the first insulating layer 12 is composed of a silicon oxide deposited by low pressure chemical vapor deposition ( lpcvd ) using , for example , tetraethosiloxane ( teos ) as the reactant gas . layer 12 is then planarized by plasma etching back the silicon oxide to the substrate surface using , if necessary , a planarizing layer such as photoresist or a polymer and a plasma etch having a 1 - to - 1 etch rate selectivity . alternatively , layer 12 can be polished back to the substrate surface using chemical / mechanical polishing ( cmp ). the remaining insulating layer 12 in the trenches forms the field oxide regions 12 between the intersecting row and column device areas 4 and 2 , respectively , as shown in fig1 and in cross sectional view in fig2 b . referring still to fig2 a and 2b , a second insulating layer 14 is deposited on the silicon substrate . preferably layer 14 is deposited by lpcvd using a reactant gas such as teos . the preferred thickness of layer 14 is between about 2500 and 5000 angstroms . conventional photolithographic techniques and anisotropic plasma etching are used to etch wells 6 having essentially vertical walls in the insulating layer 14 to the surface of the substrate 10 . as shown in fig1 the wells 6 are formed over the row device areas 4 and also extending over the field oxide region 12 . the fets having floating gates providing for the nvm cells are now formed in the wells 6 . as shown in fig2 a and 2b , the fet gate oxide 16 is formed by thermal oxidation of the exposed silicon surface within the well areas 6 . preferably the gate oxide is grown to a thickness of between about 40 and 200 angstroms , for example , by thermal oxidation in a dry oxygen ambient . referring next to fig3 a and 3b , the floating gate electrodes are formed from a first polysilicon layer 20 , which is conformally deposited on the second insulating layer 14 and in the wells 6 . layer 20 is preferably deposited by lpcvd using , for example , a reactant gas such as silane ( sih 4 ). the polysilicon is preferably in - situ doped during deposition by adding to the silane a dopant gas such as phosphine ( ph 3 ). the desired thickness of layer 20 is between about 300 and 1000 angstroms . the dopant concentration of layer 20 is preferably between about 1 . 0 e 20 and 1 . 0 e 21 atoms / cm 3 . the polysilicon layer 20 is patterned by conventional photolithographic techniques and anisotropic plasma etching to leave portions over the gate oxide 16 and on the sidewalls 5 in the well areas 6 , as shown in fig3 a , while removing most of the polysilicon layer 20 over the field oxide regions 12 and over the sidewalls 7 , as shown in fig3 b . this eventually provides a floating gate electrode having vertical extending portions on the sidewalls 5 that increase the capacitive coupling , as shown in fig3 a . next , a thin dielectric insulating layer 22 is formed on the patterned first polysilicon layer 20 , as shown in fig4 a and 4b . preferably , insulating layer 22 is composed of a silicon oxide / silicon nitride / silicon oxide ( ono ) having a thickness of between about 50 and 100 angstroms . layer 22 can be formed by thermally oxidizing the polysilicon layer 20 and depositing a silicon nitride layer using , for example , lpcvd by reacting dichlorosilane ( sicl 2 h 2 ) and ammonia ( nh 3 ) at a temperature between 700 ° and 800 ° c . the silicon nitride layer is then subjected to a thermal oxidation to oxidize the surface of the silicon nitride layer , to complete the ono . layer 22 serves as the interlevel dielectric insulating layer between floating gates formed from the first polysilicon 20 layer and a second polysilicon layer that is deposited later to form the control gate electrode for the fet . referring still to fig4 a , a conformal second polysilicon layer 24 is deposited over the dielectric insulating layer 22 thereby filling the wells 6 . layer 24 is used to form the control gates for the fets . polysilicon layer 24 can be deposited by lpcvd using , for example , silane , and is also conductively doped with an n + dopant such as phosphorus or arsenic by ion implantation or in - situ doped during the polysilicon deposition . layer 24 is deposited to a thickness sufficient to fill the trenches , which is preferably to a thickness greater than about 3000 angstroms . now referring to fig5 a and 5b , the second polysilicon layer 24 , the dielectric insulating layer 22 , and portions of the first polysilicon layer 20 are chemical / mechanically polished back to the surface of the second insulating layer 14 . the polishing back to layer 14 forms an array of electrically isolated fet gate electrodes having floating gate electrodes , such as the floating gate 20 that extends vertically upward along the sidewalls of the control gate 24 . the increase surface area of the floating gate on the sidewall significantly increases the capacitive coupling between the floating gate 20 and control gate 24 . via the thin interlevel dielectric insulating layer 22 , there - between . the high dielectric constant of the silicon nitride in layer 22 further increases the capacitive coupling . referring now to fig6 a and 6b , the second insulating layer 14 in which the wells 6 are formed is now selectively removed to the surface of the silicon substrate 10 , thereby exposing the device areas adjacent to the fet gate electrodes composed of layers 16 , 20 , 22 , and 24 , and also exposing the substrate surface in the column device areas . second insulating layer 14 is removed by selectively etching in a solution of hydrofluoric acid ( hf / h 2 o ). still referring to fig6 a and 6b , lightly doped source / drain ( ldd ) areas are formed adjacent to the fet gate electrode . preferably the lld areas are formed by ion implantation using , for example , arsenic ( as 75 ) or phosphorus ( p - ) ions . the ion implant dose is preferably between about 1 . 0 e 13 and 5 . 0 e 13 ions / cm 2 , and the ion implant energy is between about 20 and 70 kev . the ldd implant is also formed in the exposed column device areas ( labeled 2 in fig1 ) which will later serve as the bit lines for the array of nvm cells . the masking effect of the fet gate electrodes to the ion implantation results in the lightly doped source / drain areas being self - aligned to the gate electrodes . next as shown in fig6 a and 6b , a conformal third insulating layer 30 is deposited on the substrate and etched back to form sidewall spacers 30 on the sidewalls of the fet gate electrodes . the insulating layer 30 is preferably composed of silicon oxide ( sio 2 ) and is deposited in a lpcvd reactor using a reactant gas , such as teos . the preferred thickness of layer 30 is between about 1000 and 3000 angstroms , and etched back to form sidewall spacers 30 having a width about equal to the thickness of layer 30 . the heavily doped source / drain contact areas 28 are formed next by using ion implantation and also using arsenic ( as 75 ) or phosphorus ( p - ) ions as the implant source . the ion implant dose is preferably between about 1 . 0 e 15 and 7 . 0 e 15 ions / cm 2 and is implanted at an ion energy of between about 10 and 70 kev . this implant is carried in the exposed column device areas 2 in fig1 to form the buried bit lines for the array of fets in the nvm cells . referring now to fig7 a and 7b , a conformal fourth insulating layer 32 is deposited over the gate electrodes and elsewhere on the substrate to insulate the fet devices and the bit lines from the next level of interconnecting metallurgy . the preferred insulating layer 32 is also a plasma enhanced cvd - deposited silicon oxide ( sio 2 ) or atmospheric pressure cvd - deposited sio2 , using , for example teos . alternatively a borophosphosilicate glass ( bpsg ) can be used , for example , using a boron and phosphorus doped teos ( bpteos ). the preferred thickness of layer 32 is between about 500 and 3000 angstroms for undoped sio 2 , and between about 2000 and 10000 angstroms for bpsg . contact openings 8 are then etched in layer 32 to the control gate electrode 24 over the planar field oxide regions 12 , as shown in fig7 b . the contact openings 8 are preferably etched using conventional photolithographic techniques and anisotropic plasma etching . for example , this can be carried out in a reactive ion etching chamber using an etchant gas such as trifluoromethane ( chf 3 ) or alternatively carbon tetrafluoride ( cf 4 ) and helium ( he ). still referring to fig7 b , the eprom is now completed by depositing and patterning a third polysilicon layer 34 to form the word lines 34 that contact the gate electrodes through the contact openings 8 . the polysilicon layer 34 is preferably deposited using lpcvd and a reactant gas such as silane ( sih 4 ), and is deposited to a thickness of between about 2000 and 5000 angstroms . preferably the third polysilicon layer is conductively doped n + , using for example , phosphorus ( p ), either by ion implantation or by in - situ doping with phosphine ( ph 3 ) during the lpcvd of the polysilicon layer 34 . in addition , a silicide layer can be formed on the third polysilicon layer 34 prior to patterning to further enhance conductivity and improve device performance . layer 34 is then patterned using an anisotropic plasma etching that has a high etch rate selectivity to silicon oxide , such as using an etchant gas mixture containing chlorine . since the polysilicon layer 34 is patterned so as not to cover the gate electrodes , layer 34 is not shown in fig7 a . while the invention has been particularly shown and described with reference to the preferred embodiments thereof , it will be understood by those skilled in the art that various changes in form and details may be made without departing from the spirit and scope of the invention .
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the present inventors conducted an extensive research on methods for continuous decomposition of polyurethane resins for recovery of components and found the following . the polyurethane resin is dissolved in a polyamine compound and an insoluble precipitate is easily removed by filtration or the like . then the solution is continuously supplied to a water tank kept at a high temperature and a high pressure . on the other hand , the insoluble precipitate is heated , dissolved in a polyamine compound and continuously supplied in a liquid form to said water tank kept at a high temperature and a high pressure . in this way , the polyurethane resin can be completely decomposed in a short time even at a low added water ratio ( ratio of water / compound to be hydrolyzed ) into a polyol compound and a polyamine compound as an intermediate of a polyisocyanate compound , namely into the raw materials of the polyurethane resin . the polyurethane resin to be decomposed in the invention is a polymer which can be prepared by reacting a polyisocyanate compound with an active hydrogen compound . examples of the polyisocyanate compound are those having 2 to 3 isocyanate groups and isocyanate equivalence of 80 to 140 , such as toluene diisocyanate ( tdi ), diphenylmethane diisocyanate ( mdi ), polymeric mdi , hydrogenated mdi , modified mdi , isophorone diisocyanate ( ipdi ), hexamethylene diisocyanate ( hdi ), xylene diisocyanate ( xdi ), and hydrogenated xdi . among these preferable are tdi , mdi and polymeric mdi , and especially preferable is tdi . a polyol compound is typical of active hydrogen compound . examples of the polyol compound are polyether polyol having 2 to 8 functional groups and oh number of 20 to 500 mgkoh / g which is prepared from alkylene oxide such as ethylene oxide or propylene oxide , and an active hydrogen - containing initiator ; polyester polyol ; and acryl polyol . especially preferable is polyether polyol . the method of the present invention is feasible for decomposition of any polyurethane resins having bonds such as urethane bond , allophanate bond , urea bond , biuret bond and amide bond , irrespective of molecular structure , structural units and degree of polymerization . products of polyurethane resins to be decomposed in the present invention include defective articles and the cuttings made in molding or fabricating articles of flexible , semi - rigid or rigid polyurethane foams as cushion materials in beds , sofas , chairs and the like to be used in households or offices , or in automotive articles such as seats , head rests , sun - visors , internal panels , armrests and the like ; waste of such articles ; the cuttings made in manufacturing articles of polyurethane resin elastomers such as tires , tubes and shoe soles ; and waste of these articles . especially preferable are products of flexible polyurethane foam . when foam products are decomposed in the practice of the invention , it is preferred to shred the foam products by a shredder or the like , or in the case of elastomer products being decomposed , the products are desirably crushed by a crusher or the like . these products may contain minor quantities of fibers , leathers , synthetic leathers , metals and the like which are constituent materials of foam products . polyamine compounds for use herein as a solubilizer for polyurethane resins include not only amines generally useful as the raw material of polyurethane resins , typically toluenediamine , but also diaminodiphenylmethane , polymethyl polyphenyl polyamine , and mixtures thereof . especially preferable is toluenediamine . the amount of polyurethane resins relative to the polyamine compound is the same as or larger than the polyamine compound in terms of weight ratio , suitably about 2 to about 10 times , or preferably about 2 to about 3 times , the amount of the polyamine compound . that is , a far larger amount of polyurethane resins than polyamine compounds can be decomposed according to the present invention . if the polyurethane resin is decomposed in 0 . 5 times the amount of polyamine compound , the insolubles are not produced in the reaction and the whole solution is solidified at room temperature , raising an operational problem . however , when a polyurethane resin is dissolved in a small amount of a polyamine compound to the utmost extent and then decomposed at an elevated temperature , the polyamine compound is migrated as an urea to the solids , resulting in the decomposition product containing a light - colored liquid substantially consisting of a polyol . in this case , the amount of the polyurethane resin relative to the polyamine compound is about 3 to about 10 times , preferably about 3 to about 7 times the amount of the polyamine compound in terms of weight ratio although variable depending on the kinds of polyamine compound and polyurethane resin to be used . the polyurethane resin is decomposed with a polyamine compound at a temperature of 120 to 250 ° c ., preferably 150 to 200 ° c . if the temperature is lower than said range , it takes a longer period of time until completion of decomposition . on the other hand , if the temperature is higher than said range , the polyamine compound is caused to decompose or polymerize , resulting in a lower recovery ratio . when a polyurethane resin is used in about 2 to about 3 times the amount of a polyamine compound , the liquid of the decomposition product comprises a polyol and a urea soluble in the polyol and may further contain small amounts of undissolved , urethane bond - containing polyol and polyamine as the solubilizing agent . on the other hand , when a polyurethane resin is used in about 3 to about 10 times the amount of a polyamine compound , or in other words when a large amount of a polyurethane compound is dissolved in a small amount of a polyamine compound to achieve thermal decomposition , the liquid obtained as the decomposition product substantially consists of a light - colored polyol , and thus a re - usable polyol can be recovered without undergoing hydrolysis as an additional step at a high temperature and under a high pressure . the solids obtained by decomposition may contain a urea insoluble in the liquid , and contaminants contained in the polyurethane resin to be decomposed , such as fibers , organic fillers and the like . these solids can be easily separated from the polyol by filtration or like means . when required , the liquid obtained from the polyurethane resin is filtered to remove the insolubles and contaminants such as fibers and the like . then the residue is transported to a hydrolysis device . the insolubles are thermally dissolved again in a polyamine compound and the solution is transported to the hydrolysis device optionally after removal of insolubles and contaminants such as fibers . when the insolubles are dissolved in a polyamine compound , the temperature is in the range of 120 to 250 ° c ., preferably 150 to 200 ° c . if the temperature is lower than said range , it takes a longer period of time until completion of decomposition . on the other hand , if the temperature is higher than said range , the polyamine compound is caused to decompose or polymerize , resulting in a lower recovery ratio . the amount of the polyamine compound to be used can be any in which the insolubles have been confirmed to become dissolved in the polyamine compound . a preferred ratio by weight of the polyamine compound to the insolubles is 0 . 5 - 2 : 1 . if the ratio is less than 0 . 5 : 1 , a larger amount of the insolubles would remain , whereas if the ratio is more than 2 : 1 , an increased amount of polyamine compound would not contribute to the dissolution , leading to a significantly lowered efficiency . specific examples of the filter to be used herein are automatic filter press , rotary - disc filter devices , and centrifugation type filter devices which are provided with filter cloth made of teflon , polyphenylene sulfide or glass fibers , metal gauze formed from sus , a ceramic filter or the like . hydrolysis devices to be used herein are not structurally limited . preferred examples of useful hydrolysis devices include those so designed that the solution of polyurethane resin is mixed with heated water at a column bottom , the mixture is moved upwardly to a column body , and the hydrolyzate and the carbon dioxide gas generated are continuously discharged outwardly from the column via a pressure control valve arranged at a column top . in short , the structure of hydrolysis device should assure application of pressure for maintaining the temperature of heated water required for the hydrolysis and should assure a period of time for flow of liquid which is required for the hydrolysis . the hydrolysis proceeds at a temperature of 200 to 320 ° c ., preferably 240 to 300 ° c . if the temperature is lower than said range , the decomposition is retarded . on the other hand , if the temperature is higher than said range , there occur side reactions such as breakage of polyether chain and condensation of polyamine compound thus produced . although the pressure applied in this step does not directly affect the yield of the obtained product , it is preferred to control the pressure at a level which is sufficient to retain the heated water in the liquid form . the weight ratio of heated water to liquid to be hydrolyzed is 0 . 3 - 5 . 0 : 1 , preferably 0 . 5 - 3 . 0 : 1 although variable depending on the type of polyurethane resin to be decomposed . if the ratio is lower than said range , the polyurethane resin incompletely decomposes into a polyamine compound and a polyol compound , whereas in the case of the ratio being higher than the range , a larger - size device is required and greater energy loss is involved , leading to uneconomical operation . while the reaction can proceed in the absence of a catalyst , a small amount , for example about 0 . 001 to 0 . 1 wt . % based on the polyurethane resin of alkali metal hydroxide , ammonia or the like can be used as a catalyst . it takes about 5 minutes to about 2 hours , preferably about 10 minutes to about 1 hour to complete the hydrolysis . then the hydrolyzate is led to a dehydrating device . predominant amounts of water and carbon dioxide gas are vaporized due to reduction of pressure by a pressure control valve and are recovered as the gas . when required , the obtained gas may be dewatered by means such as distillation under reduced pressure or blowing dry nitrogen . the obtained hydrolyzate , which is practically a mixture of a polyamine compound and a polyol compound , can be separated into a polyamine compound and a polyol compound by conventional means such as distillation , centrifugation or extraction of solvent . a suitable separation procedure is selected according to the kind of polyurethane resin to be decomposed . treatment with propylene oxide or like alkylene oxide for conversion of amino terminal group to hydroxyl group enables utilization as a polyol compound without separation of polyamine compound from the hydrolyzate . the polyamine and polyol obtained by the method of the invention are the same compounds as the raw materials to be usually used in preparing a polyurethane , and can be used by themselves as the raw materials of a polyurethane resin because they are similar or superior to these raw materials in purity and quality . the urea - containing solids obtained as an insoluble in the invention can be used as a crosslinking agent for various resins or as a reactive filler . the present invention will be described in more detail with reference to the following examples to which , however , the present invention is not limited at all . a 150 g quantity of toluenediamine was charged into a 4 - necked , 1000 - ml flask equipped with a thermometer , a stirrer and a nitrogen inlet tube and was heated to 200 ° c . gradually added to the liquid were the cuttings of soft polyurethane foam having a density of 25 kg / m 3 which was . prepared by foaming polypropylene triol ( 3000 in molecular weight ) and toluene diisocyanate ( takenate 80 , product of takeda chemical industries , ltd .) to give a solution . with the addition of 150 g of polyurethane foam , a precipitate was formed and was increased with continuous addition of the foam . a total of 400 g of polyurethane foam was added and subjected to a reaction for 1 hour , and eventually for a total of 6 hours at 200 ° c . the reaction mixture was cooled to 25 ° c . and was filtered with 100 - mesh metal gauze to give 250 g of a solution and 270 g of the residue . the solution had a viscosity of 2500 mpa · s ( 25 ° c . ), and the acetyl equivalent was 150 mgkoh / g . the residue was found to contain a polyurea by gel permeation chromatography and nmr . the solution ( 40 g ) obtained in example 1 and 60 g of pure water were charged into a 200 - ml autoclave equipped with a thermometer and a pressure gage . the air in the autoclave was replaced with nitrogen gas and was heated to 270 ° c . at that time , the internal pressure was 6 . 7 mpa . the increase of pressure was not detected although the autoclave was left to stand at the same temperature for 20 minutes . the autoclave was cooled to room temperature . the contents of the autoclave were diluted with methanol and analyzed by gpc with the result that concerning the polyol portion , no polymer was detected except the peak corresponding to triol having a molecular weight of 3000 while in the amine region , only the peak corresponding to toluenediamine was detected . the nmr analysis confirmed that no urethane bond existed in the reaction product . these facts ascertained that the polyurethane foam was completely decomposed into toluenediamine and polypropylene glycol . a 200 g quantity of toluenediamine was added to 270 g of the residue obtained in example 1 and the mixture was heated to 200 ° c . to dissolve the residue in the diamine for recovery of 460 g of a solution . the solution was hydrolyzed in the same manner as in example 2 with water retained at a high temperature and a high pressure in the autoclave . the obtained hydrolyzate was found by nmr to be toluenediamine . with use of the same device as used in example 1 , 150 g of toluenediamine and 400 g of the cuttings of molded foam ( density of 50 kg / m 3 ) useful for automotive seats and prepared by foam molding of polyether triol ( with terminals activated with ethylene oxide ) and toluene diisocyanate were gradually added to undergo a reaction at 200 ° c . for 10 hours . the reaction mixture was cooled to 25 ° c . and filtered with 100 - mesh metal gauze , whereby 380 g of the solution and 110 g of the residue were obtained . the solution had a viscosity of 3400 mpa · s ( 25 ° c . ), and the acetyl equivalent was 190 mgkoh / g . the solution ( 30 g ) obtained in example 4 and 70 g of pure water were heated in the same manner as in example 2 in a 200 - ml autoclave equipped with a thermometer and a pressure gage . then , the mixture was left to stand at 290 ° c . for 30 minutes . at that time , the pressure was made constant at 4 . 9 mpa . the autoclave was cooled to room temperature . the contents of the autoclave were analyzed in the same manner as above with the result that no urethane bond existed in the reaction product . gpc analysis shows that the detected peak corresponded to toluenediamine and polyether polyol used as the raw material . toluenediamine ( 100 g ) was added to 110 g of the residue obtained in example 4 . then the mixture was heated to 200 ° c . to dissolve the residue in the toluenediamine for recovery of 150 g of the solution . the solution was hydrolyzed in the autoclave with water retained at a high . temperature and a high pressure in the same manner as in example 5 . nmr confirmed that the hydrolyzate was toluenediamine . a 100 g quantity of toluenediamine was charged into a 4 - necked , 1000 - ml flask equipped with a thermometer , a stirrer and a nitrogen inlet tube and was heated to 200 ° c . gradually added to the liquid were the cuttings of soft polyurethane foam having a density of 25 kg / m 3 which was prepared in the same manner as in example 1 to give a solution . with the addition of 150 g of polyurethane foam , a precipitate was formed and was increased with continuous addition of the foam . a total of 400 g of polyurethane foam was added and subjected to a reaction for 1 hour , and eventually for a total of 6 hours at 200 ° c . the reaction mixture was cooled to 100 ° c . and was filtered to give 240 g of a solution . the solution had a viscosity of 1200 mpa · s ( 25 ° c . ), and the acetyl equivalent was 94 mgkoh / g . from this , an amount of amine in polypropylenetriol was 2 wt . % calculated as toluenediamine . according to the invention , polyurethane resins can be completely decomposed in a short time into a polyol compound useful as the raw material of polyurethane resin and a polyamine compound , i . e . an intermediate of polyisocyanate . according to the invention , the polyurethane resin can be continuously decomposed because the decomposition product is provided as a liquid and the contaminants can be easily removed . the separation into a polyamine compound and a polyol compound can be done to some extent prior to hydrolysis using water retained at a high temperature and a high pressure . since the polyol compound assumes a liquid form at room temperature , the problem involved in supply of liquid can be substantially overcome . the sparingly polyol - soluble substance obtained in aminolysis can be eliminated prior to the hydrolysis using water retained at a high temperature and a high pressure , so that the polyol can be more , easily purified after hydrolysis . further the present invention has a great advantage that a large amount of polyurethane resin can be decomposed relative to the pollyamine compound .
| 2 |
fig1 shows an arrangement in which microwaves are produced in a hollow waveguide 1 having a rectangular cross section . the microwaves are output through a side opening 2 in the hollow waveguide 1 with the aid of at least one waveguide 3 in the form of a rod , and are introduced into a transmission chamber 4 . the transmission chamber 4 is essentially bounded by metallic walls 5 . a treatment chamber 6 projects into a recess located on one longitudinal side of the rectangular transmission chamber 4 and , with the exception of the wall 7 pointing towards the adjacent transmission chamber 4 , is bounded on all sides by metallic walls 8 . the treatment chamber 6 is designed as a vacuum chamber . the transmission wall 7 comprises a plate 9 which is permeable for microwaves , a large number of antenna elements 10 which extend at right angles to the permeable plate 9 into the transmission chamber 4 , as well as a metallic plate 11 which extends over the entire longitudinal side of the transmission chamber 4 . through - chambers 12 are formed in the metallic plate 11 , are open towards the permeable plate 9 , and are thus bounded by it . at the sides , the square through - chambers are bounded by thin walls 13 , designed in the form of grids , of the metallic plate 11 . located on the surface is a circular through - opening 14 of roughly the same thickness as the walls 13 , the through - openings 14 having a diameter d which is between 2 and 5 times as great as the diameter d of the antenna elements 10 , which are arranged centrally in the through - opening 14 and in the through - chamber 12 . the antenna elements 10 project to a certain extent over the metal plate 11 into the transmission chamber 4 , in which case it is possible to influence the amount of injected microwave energy by means of the length of the antenna elements . the antenna elements 10 are preferably kept available in different lengths and are used experimentally in different lengths in order to achieve an optimized configuration . changing to an antenna element 10 having a different length immediately and dramatically changes the resonance condition in the transmission chamber 4 . in order to allow adaptations to be carried out in each case here , the transmission chamber 4 is provided on the side opposite the hollow waveguide 1 with a movable metallic piston 15 , by means of which an optimum resonance condition can be set empirically once again in the transmission chamber 4 . fig2 shows the metallic plate 11 with its circular through - openings 14 on the surface . the antenna elements 10 , which are in the form of rods , are inserted centrally into the circular through - openings 14 . the view of the underneath of the metallic plate 11 according to fig3 shows that the through - chambers 12 have a square cross section and expand in stepped form underneath the through - opening 14 . the through - chambers 12 are bounded by the walls 13 designed in the form of grids . fig4 shows the schematic arrangement of the hollow waveguide 1 , transmission chamber 4 and treatment chamber 6 , which are all respectively designed to be cuboid . fig5 shows a modified exemplary embodiment , in which three waveguides 3 project into the hollow waveguide in arrangements that are parallel to one another and parallel to the transmission wall 7 , these waveguides 3 extending over the length of the transmission chamber 4 . fig5 shows that each waveguide 3 is allocated on each of its two sides a row of circular through - openings 14 with antenna elements 10 , the symmetrical arrangement on both sides of the waveguide 3 being a major feature . conductive intermediate walls 16 are used to form compartments for each waveguide 3 , and these compartments preclude any mutual influence between the antenna elements 10 through a plurality of waveguides 3 . a movable piston 15 is provided as an electrically effective end wall for each compartment 17 . fig6 shows a cascaded design of the transmission wall 7 &# 39 ;. a further metallic plate 18 is in this case placed on the metallic plate 11 and is provided with similar through - chambers 19 and circular through - openings 20 . a coupling antenna element 21 is inserted centrally into the through - chamber 19 and the through - opening 20 , projects out of the through - chamber 19 into the transmission chamber 4 , and naturally ends at a distance from the surface of the metallic plate 11 . as can be seen , a plurality of antenna elements 10 project into the through - chamber 19 , for example four antenna elements 10 in a symmetrical arrangement with respect to the central coupling antenna element 21 . the advantage of this arrangement is that it results in the microwave energy being transmitted uniformly through the numerous antenna elements 10 , but the adjustment tasks need be carried out only with the coupling antenna elements 21 ( in particular by means of their length ), while the antenna elements 10 can be designed to have the same length , that is to say they no longer need be adjusted ( fig6 a ). the adjustment of the considerably smaller number of coupling antenna elements 21 is , however , sufficient to take account of homogeneous transmissions from the transmission chamber 4 . fig7 shows the arrangement according to fig1 but with a coil arrangement 22 being provided around the treatment chamber 6 in order to form a magnetic field in the treatment chamber 6 . the magnetic field considerably increases the number of collisions between gas particles , so that plasma ignition can be achieved even in a hard vacuum . furthermore , the treatment chamber 6 is provided with a grid 23 , in the form of a screen , between the transmission wall 7 and a treatment table 24 . the grid 23 has a negative voltage applied to it , so that it traps electrons and allows only ions to pass through . in this way , the arrangement is used as an ion source for treatment of products that are placed on the treatment table 24 . in the case of the embodiment illustrated in fig8 an arrangement comprising numerous permanent magnets 25 , of alternately opposite polarity , is located underneath the treatment table . this achieves local compression of the plasma , which assists ignition of the plasma . in the case of the embodiment illustrated in fig9 the antenna elements 10 are designed with different lengths and all end at the plate 9 , which is permeable for microwaves , of the transmission wall 7 . the antenna elements project with different lengths out of the through - openings 14 . the injection of the microwave energy , which is introduced into the chamber 4 , into the antenna elements 10 can be regulated by means of the projecting length of the antenna elements . otherwise , the antenna elements 10 are located in through - chambers 12 , which are bounded by the walls 13 . in the case of the embodiment illustrated in fig1 , the antenna elements 10 project with different lengths out of the through - openings 14 in the direction of the chamber 4 , but run between the through - openings 14 and the microwave - permeable plate 9 of the transmission wall 7 in a common intermediate space 26 , which is produced by the fact that the intermediate walls 13 according to the exemplary embodiments illustrated in fig1 , 8 and 9 are omitted . fig1 shows an exemplary embodiment in which the antenna elements 10 have through - openings 14 and through - chambers 12 passing through them , a common intermediate space 27 being formed , however , between the through - chambers 12 and the plate 9 , which is permeable to microwaves , of the transmission wall 7 , into which intermediate space 27 the antenna elements 10 likewise project with different lengths according to this exemplary embodiment . this makes it possible to control not only the microwave energy injected into the antenna elements from the chamber 4 , but also the microwave energy emitted into the treatment chamber 6 . fig1 shows a schematic illustration for excitation of the plasma in the treatment chamber 6 by means of electromagnetic radio - frequency energy whose frequency is thus below microwave frequency . for this purpose , the adjacent chamber 4 is designed as a type of coaxial conductor having an inner conductor 28 which extends over the length of the chamber 4 and having a rectangular casing 29 which surrounds the inner conductor 28 at a distance from it and is composed of electrically conductive material . antenna elements 10 &# 39 ; likewise project at right angles to a transmission wall 7 &# 34 ; between the adjacent chamber 4 and the treatment chamber 6 . within the adjacent chamber 4 , the antenna elements 10 &# 39 ; have angled ends 30 , which run essentially parallel to the inner conductor 28 . the antenna elements 10 &# 39 ; have throughchambers 12 &# 39 ; passing through them , and these throughchambers 12 &# 39 ; are bounded by electrically conductive walls 13 &# 39 ;. located within the through - chambers 12 &# 39 ; are sealing pieces 31 which are composed of dielectric material and have no adverse effect on radio - frequency conduction . the sealing pieces 31 run essentially aligned with walls 32 which bound the treatment chamber 6 and are composed of electrically conductive material . the antenna elements 10 &# 39 ; have sealing pieces 31 passing through them , and their ends 33 project into the treatment chamber 6 . end pieces 34 are integrally formed at the ends 33 and run essentially parallel to a common opposing electrode 35 , which is at ground potential . in order to reduce the mutual influence between the antenna elements 10 &# 39 ;, compartment walls 36 are located both within the chamber 4 and within the treatment chamber 6 and shield the ends 30 and 34 of the antenna elements 10 &# 39 ; from one another . a plasma is produced by means of radio - frequency excitation in the treatment chamber 6 , which is sealed in a gas - tight manner by the walls 32 and the sealing pieces 31 , in which case it is possible to make the plasma uniform and to set a desired energy profile by virtue of the nature of the injection of radio - frequency energy into the antenna elements 10 &# 39 ; via the bent ends 30 .
| 7 |
hereinafter , a cathode structure of a magnetron in accordance with the present invention will be described in detail by way of embodiments . fig2 a and 2b are a plane view and longitudinal sectional view of a cathode structure of a magnetron according to the present invention . in fig2 a and 2b , the fitting of one of the two leads , that is , a side lead 25 into a spacer hole 28a is made to have relatively small looseness enough to strongly tighten the side lead 25 , and a metal fixing material 31 including a metal solder material , or a pasty metal powder and the like is poured into or spread on the fitting portion , and it is fixed or sintered . the other spacer hole 28b is made to have a large looseness l &# 39 ; with respect to a diameter of the other lead , that is , a center lead 26 , for example , by setting the looseness , l &# 39 ;= 0 . 3 - 1 . 0 mm or so , extraneous sounds are not produced . fig3 a and 3b are a plane view and longitudinal sectional view of a spacer portion of a second embodiment of the cathode structure of the magnetron according to the present invention . in fig3 a and 3b , a spacer hole 28c is formed in a polygon shape ( or polygon ), and a minimum inner diameter of the spacer hole 28c has small looseness l &# 39 ;, for example , l &# 39 ;= 0 . 05 - 0 . 15 mm or so with respect to a diameter of a side lead 25 . fig3 c and 3d show a spacer hole 28k formed in a rectangular shape . when such a spacer is assembled in the cathode structure shown in fig1 b , advantages are obtained including ; 1 ○ since the side lead 25 is fitted into the spacer 28 tightly , the inclination of the spacer 28 in the axial direction is small . in addition , since the center lead 26 is fitted into the spacer 28 very loosely , even when the center lead 26 and the spacer 28 move relative to each other under frictional resistance due to thermal expansion , a chance of producing extraneous sounds is very rare , and 2 ○ due to the tight fitting of the side lead 25 into the spacer 28 , a relative displacement of the two leads is suppressed , and the strength and a vibration - resistant property are increased . fig4 a and 4b are a plane view and longitudinal sectional view of a spacer of a third embodiment , and fig5 a and 5b are a plane view and longitudinal sectional view of a spacer of a cathode structure of magnetron of a fourth embodiment of the present invention . in fig4 a and 4b , a recess portion 28d is formed in a part of the spacer 28 adjacent to a spacer hole 28a in the lengthwise direction so that the recess portion 28d is connected to the spacer hole 28a at one end thereof . a width of the recess portion 28d is substantially equal to the diameter of the spacer hole 28a . in contrast in fig5 a and 5b , a recess portion 28e is formed in a part of the spacer 28 adjacent to a spacer hole 28a in a direction at right angles to the lengthwise direction so that the recess portion 28e is connected to a spacer hole 28a . also in this case , a width of the recess portion 28e is equal to the diameter of the space hole 28a . these recess portions 28d and 28e limit the coating area of a metal fixing material 31 , and easily prevent the electrical short - circuit between the leads . fig6 a and 6b are a plane view and longitudinal sectional view of a spacer portion of a fifth embodiment of the present invention , in which a recess portion 28f is formed in the upper surface of the spacer 28 so that one side of the recess portion 28f passes through the center of a spacer hole 28a in a direction at right angles to the lengthwise direction . in this case , as is the case in fig4 a and 4b , the flowing out of a metal fixing material 31 is prevented , and further , the short circuiting between a side lead 25 and a center lead 26 due to the metal fixing material 31 is prevented . fig7 is a sectional view of the cathode structure in which the spacer 28 having the recess portion 28d , 28e , or 28f in fig4 , and 6 is used . in fig7 a solder material such as a ru - mo material , a ru - mo - ni material , or a ni material is pasted and spread on the recess portion 28d , 28e , or 28f , and then the solder material is fused and fixed . alternatively , a pasted mo powder is spread on the recess portion and it is sintered . by pouring such a metal fixing material 31 on the outer surface of the side lead 25 at the position of the recess portion 28d , a gap between the spacer hole 28a and the side lead 25 is filled with the metal fixing material 31 , and it is possible to inhibit the relative movement between the spacer 28 and the side lead 25 . in this case , if the spacer holes 28c and 28k are in the polygon shape or rectangular shape as shown in fig3 a and 3b , and fig3 c and 3d , respectively , the rotation of the spacer 28 can be suppressed more firmly . the metal fixing material 31 may naturally be applied to the spacer 28 shown in fig3 a and 3b , however , if the recess portion is formed in the spacer as shown in fig4 a , 4b - 6a , 6b , the metal fixing material 31 can be poured more easily into an optimum portion , and thus , there is little fear of causing short - circuiting between both leads 25 and 26 due to excessive spreading of the metal fixing material 31 on an unrequired portion on the surface of the spacer 28 . further , the spacer hole 28a shown in fig4 a , 4b - 6a , 6b may be formed in the rectangular shape ( or polygon ), and the spreading of the metal fixing material 31 on the fitting portion of the side lead 25 with respect to the spacer 28 shown in fig7 and the sintering of the metal fixing material 31 may be carried out simultaneously with the assembling of a filament , etc ., or the spreading and sintering of the metal fixing material 31 may be carried out beforehand in relation to the side lead 25 and the spacer 28 . lastly , fig8 a , 8b , - 10a , 10b show various recess portions formed in the spacer 28 . in other words , fig8 a and 8b are a plane view and longitudinal sectional view of a spacer portion of a sixth embodiment of the present invention , a recess portion 28g is formed in the upper surface of the spacer 28 from one side thereof adjacent to a spacer hole 28a downwardly towards the center of a spacer hole 28a . that is , the bottom surface of the recess portion 28g is inclined from the one side of the spacer 28 towards the center of the spacer hole 28a . next , fig9 a and 9b are a plane view and longitudinal sectional view of a spacer portion of a seventh embodiment of the present invention , in which a recess portion 28h is formed in the upper surface of the spacer 28 circularly and coaxially with a spacer hole 8a . further , fig1 a and 10 are a plane view and longitudinal sectional view of a spacer portion of an eighth embodiment of present invention , in which a recess portion 28i is formed in the upper surface of a spacer 28 in a countersink shape coaxially with a spacer hole 28a , and in the longitudinal section of spacer , the recess portion 28i is in an arcuate shape . further , in the embodiments described in the foregoing , the description of the fixing is made only in relation to the spacer and the side lead . however , the present is not limited to this , and as shown in fig1 a and l1b , the center lead 26 may be fixed , and the side lead 25 may be fitted into a spacer hole 28a with looseness therebetween . as described in the foregoing , the present invention provides advantages in that since the engagement between one of the two leads and the spacer is tightened , the cathode structure is good in the vibration resistant property and the high - impact property . moreover , since the other lead and the spacer hole have large looseness therebetween , there is no portion causing the friction therebetween , the extraneous sounds are not produced , and even when the diameter of the leads is reduced , sufficient strength can be insured . thus , a magnetron which is inexpensive and which exhibits high performance can be obtained .
| 7 |
the following description and associated figures depict specific examples to teach those skilled in the art how to make and use the best mode of the invention . for the purpose of teaching inventive principles , some conventional aspects have been simplified or omitted . those skilled in the art will appreciate variations from these examples that fall within the scope of the invention . those skilled in the art will appreciate that the features described below can be combined in various ways to form multiple variations of the invention . as a result , the invention is not limited to the specific examples described below , but only by the claims and their equivalents . fig1 illustrates communication system 100 in an example of the invention . communication system 100 includes base stations 101 - 103 , internet interfaces 104 - 106 , and service node 107 . base station 101 establishes internet connectivity over communication link 114 to internet interface 104 . in some variations , internet interface 104 represents an internet service provider ( isp ), and base station 101 establishes the internet connectivity by logging - on to the isp over communication link 114 . internet interface 104 and service node 107 are configured to communicate over the internet . thus , base station 101 and service node 107 can communicate with one another over communication link 114 and the internet . in some variations , communication link 114 is asymmetrical to provide more bandwidth from service node 107 to base station 101 than from base station 101 to service node 107 . an asymmetric communication link is especially suitable for data applications , such as internet browsing or music downloads , where there is more traffic from service node 107 to base station 101 than from base station 101 to service node 107 . communication link 114 could be an asymmetrical digital subscriber line ( adsl ) link , docsis link , 802 . 11 link ( wi - fi ), 802 . 16 link ( wi - max ), broadband over power line ( bpl ) link , or some other form of internet access link . base station 101 registers with service node 107 over communication link 114 and the internet . during registration , service node 107 validates base station 101 . validation includes establishing that the entity attempting to register is who they say they are , and that that entity is entitled to register . in some variations , base station 101 and service node 107 are each be programmed with a secret user name and access code for base station 101 . service node 107 validates base station 101 by obtaining the user name and secret access code from base station 101 during registration , and then checking the user name and secret access code in a validation database to ensure that the user name and secret access code are associated with base station 101 , and that base station 101 is entitled to register . service node 107 will deny service to base station 101 if validation fails . base station 101 and service node 107 establish a communication tunnel between one another over communication link 114 and the internet . typically , the tunnel would be a secure internet protocol ( ip ) tunnel . the security could be provided through encryption or some other means . base station 101 and service node 107 could include conventional internet utilities , such as internet ports , firewalls , and internet access software . base station 101 includes an antenna and exchanges user communications in a wireless format with wireless communication devices over wireless links 111 . the wireless format could be code division multiple access ( cdma ), global system for mobile communications ( gsm ), ieee 802 . 11 ( wi - fi ), ieee 802 . 16 ( wi - max ), free - space laser , e - band , or some other wireless communication format . base station 101 exchanges the user communications with service node 107 over the tunnel . service node 107 processes the user communications to provide a communication service to the wireless communication devices . examples of communication services include telephony , instant messaging , push - to - talk , internet access , video downloads , and audio downloads , although there could be alternative communication services . in some variations , service node 107 comprises a mobile switching center . in some variations , base station 101 and service node 107 may not maintain permanent internet connectivity , registration , and / or tunneling . base station 101 and / or service node 107 could establish and de - establish the internet connectivity based on a predetermined schedule . for example , base station 101 could establish the internet connectivity on monday morning at 7 : 00 and de - establish the internet connectivity on friday evening at 6 : 00 . numerous and more complex schedules could be used . likewise , base station 101 and / or service node 107 could register and de - register base station 101 based on a predetermined schedule . base station 101 and / or service node 107 could establish and de - establish the tunnel based on a predetermined schedule . these predetermined schedules for internet connectivity , registration , and tunneling could the same or different . in some variations , base station 101 and / or service node 107 could establish the internet connectivity , register with the service node , and establish the tunnel based on a predetermined schedule , and then de - establish the internet connectivity , de - register with the service node , and de - establish the tunnel based on the predetermined schedule . thus , based on a predetermined schedule , base station 101 and service node 107 can transition between a disconnected state where they have no interaction with one another , and a connected state where they interact to deliver the communication service to the wireless communication devices . in some variations , base station 101 could establish and de - establish the internet connectivity based on end - user activity . for example , base station could establish the internet connectivity in response to a service request from one of the wireless communication devices and de - establish the internet connectivity after a time period elapses with a lack of other service requests from the wireless communication devices . numerous and more complex end - user activity - based control schemes could be used . likewise , base station 101 could register and de - register with service node 107 based on end - user activity , or base station 101 could establish and de - establish the tunnel based on end - user activity . these end - user activity - based control schemes for internet connectivity , registration , and tunneling could the same or different . in some variations , base station 101 could establish the internet connectivity , register with service node 107 , and establish the tunnel based on an end - user activity control scheme , and then de - establish the internet connectivity , de - register with service node 107 , and de - establish the tunnel based on the same end - user activity control scheme . thus , based on end - user activity , base station 101 and service node 107 can transition between a disconnected state where they have no interaction with one another , and a connected state where they interact to deliver the communication service to the wireless communication devices . other techniques to detect end - user activity could be used , such as motion detectors , human proximity detectors , or even a simple on - off switch that the end - users may control manually . a remote control system could transfer control messages to base station 101 and service node 107 to direct these systems to establish and de - establish internet connectivity , registration , and tunneling . the remote control could be based on a predetermined schedule , expected end - user activity , or some other factor . in some variations , base station 101 is relatively small , which allows for a relatively small bandwidth load on communication link 114 . base station 101 may be omni - directional meaning the base station has no sectors . base station 101 may have a maximum capacity of 20 simultaneous wireless communication devices . base station 101 may have a maximum of three radio frequency ( rf ) receive channels and three rf transmit channels . base stations 102 and 103 could be configured and operate as described for base station 101 . base station 102 could exchange user communications with wireless communication devices over wireless communication links 112 and exchange the user communications with service node 107 through a tunnel over communication link 115 and the internet . likewise , base station 103 could exchange user communications with wireless communication devices over wireless communication links 113 and exchange the user communications with service node 107 through a tunnel over communication link 116 and the internet . note that service node 107 is capable of interacting with multiple base stations as described above . service node can register , validate , and establish tunnels to multiple base stations . service node 107 may do so based on differing schedules , end - user activity , or remote control . thus , service node 107 can support a dynamically changing mix of base stations . fig2 illustrates communication system 200 in an example of the invention . communication system 200 includes base station 201 , adsl modem 202 , digital subscriber line access multiplexer ( dslam ) 203 , central office 204 , internet routers 205 - 206 , and mobile switching center ( msc ) 207 . base station 201 is coupled to adsl modem 202 by communication link 212 . adsl modem 202 is coupled to dslam 203 by adsl link 213 . dslam 203 is coupled to internet router 205 by ip link 214 and to central office 204 by time division multiplex ( tdm ) link 217 . internet router 205 is coupled to internet router 206 over ip link 215 . internet router 206 is coupled to msc 207 by ip link 216 . communication links 211 - 217 could be conventional . base station 201 establishes internet connectivity to msc 207 over a communication link ( comprised of links 212 - 213 , modem 202 , and dslam 216 ) and the internet ( comprised of internet routers 205 - 206 and links 214 - 216 ). in some variations , internet router 205 represents an isp , and base station 201 establishes the internet connectivity by logging - on to the isp . msc 207 and dslam 203 are configured to communicate over the internet . thus , base station 201 and msc 207 can communicate with one another over the above described communication link and the internet . base station 201 registers with msc 207 over the communication link and the internet . during registration , msc 207 validates base station 201 by establishing that base station 201 is actually the entity attempting to register , and that base station 201 is entitled to register . msc 207 will deny service to base station 201 if validation fails . base station 201 and msc 207 establish a communication tunnel between one another over the communication link and the internet . typically , the tunnel would be a secure ip tunnel . the security could be provided through encryption or some other means . base station 201 and msc 207 could include conventional internet utilities , such as internet ports , firewalls , and internet access software . base station 201 exchanges user communications in a wireless format with the wireless phones over wireless links 211 . the wireless format could be cdma , gsm , wi - fi , wi - max , free - space laser , or some other wireless communication format . base station 201 exchanges the user communications with msc 207 over the tunnel . msc 207 processes the user communications to provide a communication service to the wireless phones . examples of communication services include telephony , instant messaging , push - to - talk , internet access , video downloads , and audio downloads , although there could be alternative communication services . in some variations , base station 201 may not maintain permanent internet connectivity , registration , and / or tunneling with msc 207 . base station 201 and / or msc 207 could establish and de - establish the internet connectivity based on a predetermined schedule likewise , base station 201 and / or msc 207 could register and de - register base station 201 based on a predetermined schedule . base station 201 and / or msc 207 could establish and de - establish the tunnel based on a predetermined schedule . these predetermined schedules for internet connectivity , registration , and tunneling could be the same or different . in some variations , base station 201 and / or msc 207 could establish the internet connectivity , register , and establish the tunnel based on a predetermined schedule , and then de - establish the internet connectivity , de - register , and de - establish the tunnel based on the predetermined schedule . thus , based on a predetermined schedule , base station 201 and msc 207 can transition between a disconnected state where they have no interaction with one another , and a connected state where they interact to deliver the communication service to the wireless phones . in some variations , base station 201 could establish and de - establish the internet connectivity based on end - user activity . likewise , base station 201 could register and de - register with msc 207 based on end - user activity , or base station 201 could establish and de - establish the tunnel based on end - user activity . these end - user activity - based control schemes for internet connectivity , registration , and tunneling could the same or different . in some variations , base station 101 could establish the internet connectivity , register with msc 207 , and establish the tunnel based on an end - user activity control scheme , and then de - establish the internet connectivity , de - register with the service node , and de - establish the tunnel based on the same end - user activity control scheme . based on end - user activity , base station 201 and msc 207 can transition between a disconnected state where they have no interaction with one another , and a connected state where they interact to deliver the communication service to the wireless phones . other techniques to detect end - user activity could be used , such as motion detectors , human proximity detectors , or even a simple on - off switch that the end - user may control manually . a remote control system could transfer control messages to base station 201 and msc 207 to direct these systems to establish and de - establish internet connectivity , registration , and tunneling . the remote control could be based on a predetermined schedule , expected end - user activity , or some other factor . msc 207 is capable of interacting with multiple additional base stations ( not shown ) in a similar manner . thus , msc 207 can register , validate , and establish tunnels to multiple base stations . msc 207 may do so based on differing schedules , end - user activity , or remote control . thus , msc 207 can support a dynamically changing mix of base stations . in some variations , base station 201 is relatively small , which allows for a relatively small bandwidth load on adsl link 213 . base station 201 may be omni - directional meaning the base station has no sectors . base station 201 may have a maximum capacity of 20 simultaneous wireless communication devices . base station 201 may have a maximum of three radio frequency ( rf ) receive channels and three rf transmit channels . fig3 - 4 illustrate communication system 300 in an example of the invention . communication system 300 includes base station 301 , internet interfaces 302 - 303 , and service node 304 . internet interfaces 302 - 303 and service node 304 communicates over the internet . at location “ a ”, base station 301 establishes internet connectivity with internet interface 302 over communication link 312 . base station 301 registers with service node 304 over communication link 312 and the internet . during registration , service node 304 validates base station 301 . base station 301 and service node 304 establish a communication tunnel between one another over communication link 312 and the internet . base station 301 exchanges user communications in a wireless format with wireless communication devices over wireless links 311 . base station 301 and service node 304 exchange the user communications over the tunnel . service node 304 processes the user communications to provide a communication service to the wireless communication devices . in some variations , service node 304 comprises an msc . referring to fig4 , base station has been moved from location “ a ” to location “ b ” as indicated by the dashed lines . at location “ b ”, base station 301 establishes internet connectivity with internet interface 303 over communication link 314 . base station 301 re - registers with service node 304 over communication link 314 and the internet . during registration , service node 304 re - validates base station 301 . base station 301 and service node 304 establish a new communication tunnel between one another over communication link 314 and the internet . base station 301 exchanges user communications in a wireless format with wireless communication devices over wireless links 313 . base station 301 and service node 304 exchange the user communications over the new tunnel . service node 304 processes the user communications to provide a communication service to the wireless communication devices . note that the variations and features described above for examples # 1 and # 2 may also apply to example # 3 . base station 301 could be moved multiple times as needed . at each new location , base station 301 would establish new internet connectivity , re - register with service node 304 , and establish a new tunnel to service node 304 . thus , base station 301 could be moved to an area where wireless communication services are temporarily required , and when that demand goes away , base station 301 could be moved to a new area with a new demand for wireless communication services . for example , base station 301 may be moved to an nfl football stadium on sunday morning to provide added wireless communications capacity or coverage during the football game that day . on monday , base station 301 could be moved to a convention center to provide added wireless communications capacity or coverage during a conference that week . to facilitate such movement , base station 301 may be relatively small , and should be configured in a portable package . in the context of the invention , portable means that a person may physically carry the base station from one location to another , and readily connect and disconnect the power , communication , and control links . communication systems 100 - 300 provide the following advantages ( although all examples of the invention may not provide these advantages ). the problematic cost and delay of using ds1 or ds3 connections to communicate between base stations and service nodes is avoided by using internet access technologies and the internet . internet access and connectivity is lower in cost and more ubiquitous than ds1 or ds3 connections . the lower cost and ubiquity of internet access allows base stations to be placed in more areas to serve increasing demand . in addition , portable base stations may be quickly deployed and moved about to serve areas that require additional capacity or coverage for a temporary amount of time .
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referring now to fig1 a television set ( tv ) 10 is connected to set top box ( stb ) 12 via interconnecting cable 14 . stb 12 is also connected to cable 16 which carries at least one cable program . the tv 10 is any standard tv such as an ntsc , a high definition , or some other standard commercial type for home use . a controller 20 is linked to stb 12 , preferably via a free space optical link 22 for controlling the operation of stb 12 in order to select a program for viewing . referring now to fig2 stb 12 will be described in greater detail . the stb 12 has a cable interface 30 that selects and converts the incoming signals on cable 16 , whether they are digital signals , analog signals , or packet signals , to signals that are compatible with the tv 10 . the cable interface 30 is connected by bi - directional bus 32 to cpu 34 . bi - directional bus 32 carries digital information received over cable 16 for use by cpu 34 and digital information transmitted from cpu 34 to cable interface 30 . if cable 16 is a bi - directional cable , some of the information from cpu 34 will be processed through cable interface 30 to cable 16 . in addition to bi - directional bus 32 , cpu 34 is connected to rom 38 and ram 40 via a memory bus 36 . rom 38 contains an operating program that is executed by cpu 34 to provide most of the functionality of the stb 12 . ram 40 , among other things , provides storage space for intermediate results of the operating program as executed by cpu 34 . ram 40 provides storage for data that is received from cable 16 and filtered in response to the operating program and viewer inputs from controller 20 ( shown in fig1 ). if further storage is needed for data , larger ram devices and / or mass storage devices such as disk drives , may be also connected bi - directional bus 32 ( not shown ). to receive viewer input , cpu 34 is connected to controller interface 44 via bus 42 , and to provide feedback to the viewer , cpu 34 is connected to and drives stb display 48 via bus 46 with channel related information . fig3 illustrates a preferred embodiment of the controller 20 . controller 20 is designed to look and operate like a standard remote control of a tv or a video cassette recorder ( vcr ). controller 20 has a numeric keypad 50 having number keys 0 - 9 . controller 20 has an up arrow 52 , a down arrow 54 , a right pointing arrow 56 , a left pointing arrow 58 , a double up arrow 60 and a double down arrow 62 . controller 20 also has a select (√) button 64 , a cancel ( x ) button 66 and a query (?) button 68 . all interactions with the interface provided by the present invention are controlled by various sequences of these 19 buttons of the controller 20 . further , the result of actuating one of these buttons will be similar the results of a similar action of a standard tv or vcr remote control , so its use will be familiar , predictable and intuitive to the viewer using it . there are two broad classes of graphical components used in the interface of the present invention : those used by the viewer to select a desired data view or to apply a filter to the information being displayed , such as fig4 ; and those components used to actually display the information through which the viewer will progress in order to make a selection of a specific item , such as fig6 . for example , the viewer might view the schedule of tv programs for the next few hours ( all channels ), and filter the display to show only sports , basketball games in particular . these choices fall into the first class . once the display of all basketball shows for the next few hours has been selected , the viewer may progress through it reviewing a text or video digest of each program as selected by the controller 20 . selection of a specific program would typically lead to an action such as videotaping the show or setting an alarm to remind the viewer that the desired program is coming up . the navigation and selection sequences to find and select the desired program are examples of the use of the second class of graphical components . note , that in both cases the viewer is required to navigate through multiple graphic displays in order to ultimately select a desired program . the interfaces are kept conceptually and visually distinct in the interface according to the present invention because they serve different purposes and the viewer is reminded of this by their appearance . in addition , the information involved in the view selection components , i . e ., the first class , falls naturally into the form of hierarchical menus : short lists with complex substructure . in contrast , the data display , i . e ., the second class , components must be able to handle large schedules and arrays of information , which are essentially flat data with simple substructure . additionally , there is a display component in most displays referred to as a ` frame `, which functions as a status display . the frame is used to give the viewer some context ( what view am i displaying ? ), as well as a brief summary of the presently selected item &# 39 ; s characteristics ( what item do i currently have selected ?). typically the latter would be the item &# 39 ; s fill name and useful information such as program start and stop times . the frame will be described further , later . referring now to fig3 and 4 , a top or beginning level display 400 of the viewer interface for use with controller 20 as it appears on the viewer &# 39 ; s tv 10 ( shown in fig1 ) during normal operation . it is depicted as a file card menu 402 having a tab labeled &# 34 ; begin &# 34 ;. on file card menu 402 are interactive buttons labeled movies ( on demand ) 404 , last movie 406 , options 408 , tv 410 , tv now 412 , last tv 414 , shopping 416 , and last shop 418 which when selected by means of the controller 20 cause the next relevant display to be shown along with some sorting and / or filtering to be performed on the data stored in ram 40 ( shown in fig2 ). when the file card menu 402 first appears , an active area , where a selection may be made , is highlighted . this active area may be moved by actuating the arrow buttons 52 - 56 and double arrow buttons 60 , 62 of controller 20 . the file card menu 402 is surrounded by a frame 420 , the top of which indicates the designation of the active area currently highlighted . once an active area has been highlighted , a selection is made by actuating the select (√) button 64 in fig4 the tv button 410 is shown to be active : by actuating the select (√) button 64 , the next display 500 shown in fig5 appears . this appearance is a logical overlaying of the display 500 over the display 400 . although display 400 is not visible while any logically overlaying display is appearing on the screen of the tv 10 , display 400 will become visible again if all of the logically overlaying displays are canceled , i . e . by actuating the cancel ( x ) button 66 . thus , until a program is selected for real time viewing , it is possible for the viewer to work his or her way back to the display 400 by actuating the cancel ( x ) button the appropriate number of times . fig5 shows a second level display 500 which is depicted as a file card menu 502 labeled &# 34 ; tv &# 34 ;, which appears to overlay and occlude all of file card menu 402 except for the label &# 34 ; begin &# 34 ;. the label tv indicates that the items that can be accessed are tv shows , such as dramatic series , situation comedies , serials , regular variety shows , game shows , sports , and so forth . since movies and shopping were topics of other interactive buttons , these types of programs may be filtered out in whole or in part . file card menu 502 has interactive buttons labeled on now 504 , weekdays 506 , coming up 508 , weekend 510 , and search 512 . as with the file card menu 402 , file card menu 502 has an active area that can be moved by the viewer by operation of the arrow buttons 52 - 56 and double arrow buttons 60 , 62 of controller 20 ( shown in fig3 ). each of the interactive button represents another filtering that will be performed if it is selected . in fig5 the on now button 504 is highlighted , and if selected by actuating the select (√) button 64 , causes a third level display shown in fig6 to appear and a further sorting an / or filtering of the data stored within ram 40 ( shown in fig2 ). referring now to fig6 display 600 shows what is on at the present time , which in this illustration is 6 : 30 p . m . a reduced representation 602 of all television shows that are on at the present time appears in fig6 . the reduced representation 602 presents each program that is presently on as a card in a tightly cascaded set of cards . the cards may be gray shade coded to distinguish between news shows , sport shows , dramatic shows , comedy shows , documentary shows and so forth . those skilled in the art will recognize that color would be preferable for color television sets , and a method and apparatus according to the present invention using color to differentiated program types in the reduced representation 602 is contemplated . thus , using visual coding within the reduced representation 602 would allow a sports program to visually stand out from the non - sports tv programming in the example shown . up arrow 52 and down arrow 54 respectively move a selection window 604 , which is slightly wider than the items displayed in reduced representation , up and down the reduced representation 602 of the on now subgroup in single steps . motion of the active area along the reduced representation 602 is one dimensional , either up or down . the up arrows 60 and the down arrows 62 move his selection window 604 respectively up and down the reduced representation 602 in increments of six . the individual items visible and located within the selection window 604 represent a further subgroup of six programs out of the reduced representation 602 on now subgroup . this six program subgroup of the selection window 604 is displayed in larger form in a grid display 606 located next to reduced representation 602 . this larger form allows the viewer to read the titles of the programs presently in grid display 606 . the visible coding , i . e . gray shade coding or color coding , of each item is retained in the larger form in grid display 606 to aid the viewer differentiate between the various types of programming offered . within selection window 604 and grid display 606 are active areas 605 , 607 that highlight one item in their respective portions of display 600 . the active areas 605 , 607 move in coordination with each other in response to the up arrow 52 and the down arrow 54 . when up arrow 52 or down arrow 54 require the active areas 605 and 607 to move above or below the selection window 604 and grid display 606 , a paging occurs which moves the selection window up six or down six . when an item is located within active areas 605 , 607 , further information , such as the tv channel call sign , the cable channel number , and the exact start and stop times , is retrieved from the programming database stored in ram 40 and displayed in the top of a frame 610 of display 600 . if the select (√) button 64 is actuated at this time , a preview of either a short text description or a brief still or motion video replaces the grid display 606 . the data for these previews are stored in ram 40 . a second sequential actuation of the select (√) button 64 actually selects the highlighted program in the active area 604 of reduced representation 602 and formerly highlighted in grid display 606 . if the up arrow 52 or the down arrow 54 is actuated the respective preview for the next program item up or down from the previous previewed item is selected . the information displayed in the top of the frame 610 will change to the next program item up or down also . actuation of the cancel button 66 returns the viewer to the previous arrangement of display 600 . the bottom of the frame 610 lists the characteristics of the display 600 , which are also retrieved from ram 40 . if the query (?) button 68 is actuated , the grid display 606 will be replaced by a generalized help menu . this generalized help menu has many buttons , as explained below , one of which is a view button . if the view button is actuated , the generalized help menu is replaced with the previous select ( i . e . filter ) view . referring now to fig3 and 7 a selection of a program by category will be described . actuation of the query (?) button 68 of controller 20 causes display 700 to appear on the screen of tv 10 ( shown in fig1 ). on display 700 has a help button 702 , a categories button 704 , a view button 706 , a begin button 708 , a favorites button 710 , and a user button 712 . an active area , shown on categories button 704 is moved by the arrow buttons 52 - 58 . the function of the view button 706 has been discussed in regard to fig6 and will not be repeated here . actuation of the help button 702 causes a menu of specific help functions to be displayed . actuation of the begin button 708 causes the beginning menu to be displayed , i . e . it takes the viewer back to the beginning of the selection sequence . actuation of the favorites button 710 brings up a list of favorite programs for the present timeslot , which may either be accumulated by the cpu 32 from viewing data or may be entered by the viewer or viewers . actuation of the viewer button 712 , which causes a display to appear where a viewer may interactively enter his or her status as the principal viewer . this information is used to determine , display a slate of favorite programs customized for each viewer . actuation of the categories button 704 causes a her display 800 , which is shown in fig8 to replace display 700 on the screen of tv 10 . referring now to fig3 and 9 , display 800 has numerous buttons 801 , 802 , 803 , 804 , 805 , 806 , 807 , 808 , and 809 corresponding to favorite , information , entertainment , movies , sports , news , children , series and more categories of programming . the buttons 801 - 809 may be have an active area moved among them using arrows 52 - 58 , or the numeric keypad may be used as a set of hot keys to move the active area to the desired category immediately . the buttons 801 - 809 are laid out in a 3 × 3 row and column arrangement just the same as the 1 - 9 keys of keypad 50 are arranged . thus , without numbering , intuitive hot key navigation is possible . for example to move the active area to the button in the third column and third row , i . e . button 809 , the key in the third column and the third row , i . e . the numeral 9 , of keypad 50 is actuated . the button 809 unlike the other buttons which subsequently provide narrower choices , gives another display of buttons for further category choices ( not shown ). if the active area is around sports button 805 as shown in fig8 and the select (√) button 64 is actuated , the display shown in fig9 would appear . fig9 is arranged with selection buttons 901 - 909 in a 3 × 3 arrangement , similar to that of fig8 . movement of the active area by arrows 52 - 58 or by hot key is available in fig9 as in fig8 . buttons 901 - 909 correspond to baseball , football , basketball , soccer , all , hockey , golf , racing and other respectively . except for all button 905 , each of the buttons in fig9 represents a narrower subgroup of the overall category of sports . actuating all button 905 causes display 1000 , shown in fig1 , to replace , i . e . logically overlay , display 900 . referring now to fig1 , a filtered display for tv programs , that are on now , for 6 : 30 p . m . local time as shown in fig1 , that are sports programs showing all categories in reduced representation 1002 is shown . reduced representation 1002 has so few entries that characteristics of the individual cards that were hidden previously by the sheer number of programs represented can now be discerned . for example , menu card 1003 representing the program this week in the nba is shorter on the left side than menu card 1004 representing the program senior pga golf . the reason for that difference is that the program this week in the nba starts at 6 : 30 p . m ., while the program senior pga golf started at an earlier time as designated by the double left pointing arrows before the title of senior pga golf in selection window 1006 . since this week in the nba and senior pga golf both end at the same time , the right sides of their reduced representations 1003 and 1004 end at the same location . movement or navigation of the active area 1005 along the reduced representation 1002 is by means of controller 20 the same as in fig6 . each of the six titles shown in selection window 1006 has a respective rectangular region 1010 - 1015 thereafter . the rectangular regions 1010 - 1015 are shaded differently according to the type of sports program with which they are associated . these different shades of gray , or different colors if the display is shown on a color tv , are a visual key to the type of sport that corresponds to each of the six titles . actuating the select (√) button 64 of controller 20 causes display 1106 , shown in fig1 , which is a text preview of the program highlighted by the active area , to overlay selection area 1006 . as mentioned above , actuating the select (√) button 64 at this point will cause cpu 34 to instruct cable interface 30 ( shown in fig2 ) to select that tv program for viewing . referring again to fig1 if the status of the method and apparatus is the same as it was just after the selection that caused display 1000 to be shown was made , as described in the previous paragraph , and if the query (?) button 68 is actuated , then the display 700 shown in fig7 with various selections will again be displayed . further , if view button 706 is actuated , display 1200 as shown in fig1 and its filter selections will logically over lay display 700 . display 1200 has numerous interactive buttons : on now 1202 , coming up 1204 , search 1206 , weekdays 1208 and weekend 1210 . since the all sports category has been selected previously , if the active area of display 1200 is moved to highlight the coming up button 1204 and the button 1204 is actuated , display 1300 , shown in fig1 will appear and over lay display 1200 . in display 1300 , two coordinate axes are shown which are respectively labeled with two attributes of the of the selected subgroup of data items . the two attributes shown in display 1300 are channels and timeslots for the next 24 timeslots , i . e . 12 hours , coming up . since the all sports category has been selected , each sports program showing on one of the 300 plus channels within the next 12 hours will be represented in display 1300 . each sports program upcoming is represented by a rectangular ` card ` located in the row corresponding to the channel carrying the program and in the column ( s ) representing the timeslot ( s ) when it will be shown . each ` card ` is a color coded , reduced representation of the data item for its respective program . the viewer may move the active area 1302 among the cards using the up and down arrows 52 , 54 and right and left arrows 56 , 58 for movement vertically and horizontally , respectively . as can be seen from display 1300 , there are still too many data items in the subgroup to individually consider in a reasonable amount of time , so further filtering , either by a shorter time period , i . e . on now , or a narrower category , i . e . basketball , is needed . to change to a narrower category , the viewer presses the query (?) button 68 which causes display 700 ( shown in fig7 ) to be displayed . next , categories button 704 is selected which causes display 900 ( shown in fig9 ) to be displayed . next , basketball button 903 is selected which causes display 1500 of fig1 to be displayed . the coming up time filter of fig1 and 13 has not been changed , so display 1500 shows the basketball programs coming up in the next 12 hours . as can be seen , the two - dimensional grid display 1500 contains approximately sixteen programs , which is sufficiently small to review each item individually in a reasonable time period . moving active area 1502 around two - dimensional grid display 1500 with the up and down arrows 52 , 54 and / or the right and left arrows 56 , 58 , causes the title and channel of each program to be displayed in the top of the frame of display 1500 to assist the reviewing and selection process . for example , the program highlighted by active area 1502 is &# 34 ; this week in the nba &# 34 ; and it is showing on cnn . thus , by selective filtering the unwieldly display 1300 of programs shown in fig1 is reduced to a manageable handful of display 1500 , which the viewer can navigate through individually in a reasonable time . referring now to fig1 - 23 , another aspect of the present invention will be described . in fig1 and the remaining figures , a longer period of time is selected other than the one and a half hours or so retrieved by the on now selection . for example , if the viewer wishes to look at the programming available for the rest of the week in order to select something to record on a vcr ( not shown ). actuating the button having the number zero ( 0 ) of the keypad 50 while watching a program causes the data view menu selection card , such as 900 of fig9 to appear at the point in the menu - display hierarchy where the last selection was made . actuating the zero ( 0 ) button again moves the viewer towards the broadest data view menu 400 of fig4 and the viewer may stop at any display in order to change time or subject matter categories . thus if a viewer were watching this week in the nba , and wanted to find a program of interest that is on later , the viewer would first actuate the zero ( 0 ) button of keypad 50 which would bring up the display of fig1 . actuating the zero ( 0 ) button four more times takes the viewer through displays 900 , 800 , 700 and 500 of fig9 , 7 and 5 respectively . to get a specific program title , the search button 509 is actuated , which causes fig1 to logically overlay the display 500 . fig1 shows a first display 1600 of an interactive alphanumeric selection sequence . first , all alphabetic titles are sorted into groups of five or less . if , for example , nova was the title of the desired program , the active area would be moved from its initial position ( either at the top of the display or at the last group selected ) to the group of letters containing the letter n using the up arrow 52 or the down arrow 54 as shown in fig1 followed by actuation of the select (√) button 64 . this sequence would cause fig1 to logically overlay fig1 . in fig1 , the active area is moved from its initial location at m to the location of n as shown in fig1 followed again by actuation of the select (√) button 64 causes the display 2000 of fig2 to overlay fig1 . in display 2000 are single instances of the first two letters , such as nypd blue is the only instance of n followed by y , and multiple instances of the two letter string as denoted by the double right pointing arrows by no . to continue the search for nova , the active area is moved to the line containing no of display 2000 as shown in fig2 using the down arrow 56 and actuating the select (√) button 64 , which causes display 2200 of fig2 to overlay display 2000 . now , nova is the only instance of a program beginning with nov , so the entire title nova appears in fig2 . by moving the active area to the line labeled nova in display 2200 and actuating the select (√), button 64 causes the display 2300 shown in fig2 to overlay display 2200 with a schedule of times and channels for the program series nova . fig2 is a one week schedule that is laid out as a logical three dimensional grid . the days of the week are displayed along one side , in this case vertically along the left side , of the display 2300 . time of day is displayed along a perpendicular side , in this case horizontally across the top , for a twenty - four hour period . thus , if an episode of nova is scheduled at 8 : 00 p . m . on sunday , a box of contrasting shade will be located in the intersection of the sunday row and in the 8 : 00 p . m . column . the active area 2302 can be moved horizontally by arrows 56 , 58 and vertically by arrows 52 , 54 of keypad 50 . if there are multiple occurrences of nova on a particular night at a particular time , that fact is shown by a box , located at the intersection of the row of that day and the column of that time , having an asterisk (*) located in the box . the asterisk (*) indicates the presence of a logical stack of multiple programs of nova appearing on competing channels , such as occurs on wednesday night at 8 : 00 p . m . to move or navigate through a stack of programs ( or stack of episodes of programs with the same name , for example ) on a particular day at a particular time slot , the viewer uses the double up arrows button 60 and the double down arrows button 62 for this third degree of freedom . because the display 2300 may require greater visual discrimination than program title as a matter of course , the frame information window 1904 is larger than usual for display 2300 . further , frame 2304 is annotated with arrows indicating the existence of program episodes above or below the active areas &# 39 ; position in the stack . if the cable 16 has access to 300 plus ` channels ` of programming , it is conceivable that some programs , such as nova will be offered by more than one channel at the same time . as described previously , once the viewer has moved the active area to a particular entry in two or three dimensions and actuates the select (√) button 64 , a selection is made . in this case , the selection sets an alarm to record a specific channel at a specific time at some day in the near future . referring back to fig1 and 2 , overall operation of the apparatus of the invention is described . program schedule data is supplied via the cable 16 . the program schedule data is either transmitted periodically and the stb 12 receives this program schedule data and stores it in ram 40 . alternatively , all or part of the program schedule data could be dynamically requested and received by stb 12 , which stores it in ram 40 . program data such as this is commercially available from tvdata , inc . and other similar concerns . the data or records of the program schedule data are in a pre - arranged format , such as microsoft access or some other similar database format , to facilitate rapid storage , sorting and retrieval by cpu 34 . each record of a tv program has its date of appearance , its time of appearance , its title , its channel and / or network , its categorizations , and a textual or visual preview ( if any ). a listing of a prototype program that sorts , displays and interactively responds to a viewer &# 39 ; s input is shown in the cpu program listing given below . this listing is in visual basic programming language of microsoft corporation . the visual basic prototype program consists of a collection of forms , each form having its own set of event handlers . in this case , the only significant external events are button actuations because of the remote control interface . a frame form provides the background and information and status bars used by most of the individual displays . a rolodex form provides the menus . the other forms are mostly schedule or list displays of various kinds , including specialized varieties such as the alphanumeric selection list form . the control part of the program begins with a procedure which loads all forms and activates the frame and rolodex , i . e . the top display , to begin . forms hand off control by setting a return code and hiding themselves , thereby activating the form directly beneath ( usually the frame ). both the frame form and the rolodex form perform different actions depending on the value of the return code . the frame form &# 39 ; s most common action is to activate another form , and much of the control flow of the application is handled by the frame form code . the rolodex form is used to display several different menu hierarchies , most importantly view selection and filter choice . thus , it will now be understood that there has been disclosed a method and apparatus of finding and selecting a program to view from a large schedule of tv programs . while the invention has been particularly illustrated and described with reference to preferred embodiments thereof , it will be understood by those skilled in the art that various changes in form , details , and applications may be made therein . for example , color coding of the individual items of the reduced representations and of the various entries in the various grid displays could be used to assist the viewer in making rapid program selections . another example is that it is easily within the capabilities of this art to modify a tv set by integrating the set top box according to the present invention into it . it is accordingly intended that the appended claims shall cover all such changes in form , details and applications which do not depart from the true spirit and scope of the invention . ## spc1 ##
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referring to the drawings and particularly to fig1 and 2 , one form of the display of the invention is shown there and generally designated by the numeral 20 . as best seen in fig1 , display 20 here includes a generally rectangular shaped optical waveguide 21 that is substantially wedge - shaped cross section . waveguide 21 is preferably constructed from acrylic or other optically transparent material , having a refractive index n 1 with a value between approximately 1 . 45 and approximately 1 . 6 and comprises parallel first and second end surfaces 26 and 27 that are joined by parallel side surfaces 28 and 29 ( see fig1 ). waveguide 21 also includes a major upper surface 30 and a lower surface 31 converging with upper surface 30 . the lower surface 31 as generally shown in fig1 is a flat surface and forming an angle 22 ( fig2 ) with a value between approximately 0 . 1 degrees to approximately 2 . 0 degrees with the upper surface 30 . also the lower surface 31 may be a curved surface forming varying angles with the upper surface 30 of the waveguide 21 or include a plurality of stepwise facets for controlling the display light uniformity . a plurality of substantially equally spaced - apart micro - prisms 32 are constructed at upper surface 30 and , as generally shown in fig1 , extend between side surfaces 28 and 29 . micro - prisms 32 may be molded or constructed using lithography from a uv curing polymer having a refractive index n 2 with a value between approximately 1 . 45 and approximately 1 . 6 . led light sources 25 are installed proximate the wide edge 26 of the waveguide 21 and a plurality of tilting micro - shutters 33 are constructed between micro - prisms 32 . in fig2 , one column of the tilting micro - shutters is designated as 33 a , 33 b , and 33 c . fig1 also illustrates a section of a cover assembly 34 . more detailed construction of the cover assembly 34 is illustrated in fig3 . now referring to fig3 of the drawings where more details of multi - layer optical coatings are shown . the first layer is a light reflecting layer 35 constructed from metal or multilayer dielectric materials on the upper surface 30 of the waveguide 21 . the light reflecting layer 35 is patterned to form plurality of light reflecting regions 36 and light transmitting regions 37 . the second optical layer is a light transmitting layer 39 formed from a fluoropolymer or other substantially transparent material having a refractive index n 3 with a value between approximately 1 . 3 and approximately 1 . 4 . the light transmitting layer 39 is formed only in the light transmitting regions 37 as shown in fig3 on the upper surface 30 of the waveguide 21 . also the light transmitting layer 39 may be a continuous layer formed between the light reflecting layer 35 and upper surface 30 of the waveguide 21 . the third optical layer is a light absorbing layer 40 formed from a dielectric material on light reflecting layer 35 and is patterned to partially cover light reflecting layer 35 . a black oxide layer may be formed on upper surface of light reflecting layer 35 instead of light absorbing layer 40 . also the light absorbing layer 40 may be replaced with a light absorbing film and placed below the lower surface 31 of the waveguide 21 . further illustrated in fig3 are micro - prisms 32 . each micro - prism 32 comprises a light input facet 41 which is optically coupled to the upper surface 30 of waveguide 21 via light transmitting layer 39 and a light exit facet 42 which is inclined with respect to the upper surface 30 of waveguide 21 and forms an angle 23 with a value between approximately 45 degrees to approximately 65 degrees . micro - prisms 32 further include a facet 43 which is inclined opposite to the light exit facet 42 and an upper facet 47 which is generally parallel to the light input facet 41 . fig3 also illustrates one of the tilting micro - shutters 33 b which typifies the construction of each of the micro - shutters of the present form of the invention . micro - shutter 33 b comprises a thin aluminum alloy elastic film that is affixed to the upper facet 47 of micro - prism 32 b and it tilts in two directions at about axis 50 that is substantially parallel to the upper surface 30 of the waveguide 21 . for absorbing light , a black oxide layer or a black polymer film may be formed on surfaces of micro - shutters 33 . further illustrated in fig3 is a cover assembly 34 which is affixed to the upper surface 30 of waveguide 21 with spacers 58 ( see fig2 ). cover assembly 34 comprises a substrate 44 made of glass or other substantially transparent material . a light absorbing layer 51 constructed on the lower surface 46 of substrate 44 from conductive light absorbing film or a multilayer film that includes a conductor layer . the light absorbing layer 51 is patterned to form a plurality of display light exit regions 48 located directly above micro - shutters 33 and light absorbing regions 49 . the cover assembly 34 further includes a light shaping diffuser 52 formed on the upper surface 45 of substrate 44 . in the present form of the invention , the tilting micro - shutters 33 operate by electrostatic attraction force . the conductive light reflecting layer 35 and conductive light absorbing layer 51 act as fixed electrodes for the tilting micro - shutters 33 . when a suitable voltage is applied between the conductive light reflecting layer 35 and a micro - shutter 33 , the micro - shutter tilts down by electrostatic attraction force . when a suitable voltage is applied between the conductive light absorbing layer 51 and a micro - mirror 33 , the micro - shutter tilts up by electrostatic attraction force . to prevent micro - shutter stiction , a small gap is required between the edge of the micro - shutters and the landing surfaces . this may be realized by constructing small spacers from a low friction material on landing surfaces or extending small portions of micro - shutters along the edge so the entire edge of the micro - shutters do not touch the landing surfaces . additionally the black polymer coatings on the micro - shutters may be formed from a non stick material . as best seen in fig2 of the drawings , light rays 55 entering from the wide edge 26 of the waveguide 21 reflect from the upper surface 30 and the lower surface 31 by total internal reflections and change angles towards normal with respect to the upper surface 30 . light rays 55 exit the waveguide 21 from the light transmitting regions 37 ( fig3 ) when the incident angle is less than the critical angle 38 defined by the refractive index n 1 of the waveguide 21 and refractive index n 3 of light transmitting layer 39 . light rays passing through the light transmitting layer 39 enter the micro - prisms 32 from the light input facet 41 and change the angle defined by the refractive index n 2 of the micro - prisms . light rays exit the micro - prisms from the light exit facets 42 . depending on the positions of the tilting micro - shutters , light rays are absorbed , or directed to the viewer . when a tilting micro - shutter is in the up position , such as micro - shutter 33 b ( fig2 ), most light rays exiting from light exit facet 42 of micro - prisms 32 are absorbed in light absorber coatings of micro - shutters 33 . any light reflected from the lower surface of the micro - shutters 33 will be absorbed in the light absorbing layer 40 . when a micro - shutter is tilted down , such as micro - shutters 33 a and 33 c , most light rays exiting from light exit facet 42 of micro - prisms 32 exit the display 20 from display light exit regions 48 and are directed to the viewer . referring now to fig4 of the drawings , a cross - sectional view of another embodiment of display of the present invention is there shown and generally designated by the numeral 70 . this latest embodiment is similar in some respect to the embodiment shown in fig1 and 2 of the drawings and like numbers are used in fig4 to identify like components . the display 70 is a full color display wherein each picture element comprises of red , green and blue sub - pixels and includes dichoric filters for separating rgb colors from a white light source or from rgb light sources that are mixed in the waveguide 21 . the display 70 includes optical waveguide 21 and led light sources 25 that are installed proximate the wide edge 26 of the waveguide 21 . display 70 also includes a substrate 72 constructed from a substantially transparent material such as glass having a refractive index n 4 with a value between approximately 1 . 45 and approximately 1 . 6 . the lower surface 74 of substrate 72 is optically coupled to the upper surface 30 of waveguide 21 via an optical layer 71 formed from a substantially transparent material having a refractive index n 3 with a value between approximately 1 . 3 and approximately 1 . 4 . a plurality of equally spaced - apart micro - prisms 32 are constructed at upper surface 73 of substrate 72 and tilting micro - shutters 33 are constructed between micro - prisms 32 . the cover assembly 34 is affixed to the upper surface 73 of substrate 72 with spacers 58 . now referring to fig5 of the drawings where more details of multi - layer optical coatings are shown . the first optical layer is a dichroic filter 75 formed on the upper surface 73 of the substrate 72 . the second optical layer is a light reflecting layer 35 constructed from metal on the dichroic filter 75 . the light reflecting layer 35 is patterned to form plurality of light reflecting regions 36 and light transmitting regions 37 . the third optical layer is a light absorbing layer 40 formed on light reflecting layer 35 and is patterned to partially cover light reflecting layer 35 . also illustrated in fig5 are micro - prisms 32 . each micro - prism 32 comprises a light input facet 41 , which is optically coupled to the upper surface 30 of waveguide 21 via dichroic filter 75 , substrate 72 and optical layer 71 . each micro - prism 32 also includes a light exit facet 42 , a facet 43 which is inclined opposite to the light exit facet 42 and an upper facet 47 which is generally parallel to the light input facet 41 . fig5 also illustrates one of micro - shutters 33 and cover assembly 34 that was described before in fig3 . as best seen in fig4 of the drawings , light rays 55 entering from the wide edge 26 of the waveguide 21 reflect from the upper surface 30 and the lower surface 31 by total internal reflections and change angles towards normal with respect to the upper surface 30 . light rays 55 exit the waveguide 21 from the upper surface 30 and enter substrate 72 through the light transmitting layer 71 when the incident angle is less than critical angle 38 ( fig5 ) defined by the refractive index n 1 of the waveguide 21 and refractive index n 3 of light transmitting layer 71 . dichroic filters selectively pass rgb colors in the light transmitting regions 37 into the micro - prisms 32 . and light exits micro - prisms 32 from the light exit facets 42 . as before depending on the positions of the tilting micro - shutters 33 , light rays are absorbed , or directed to the viewer . to increase the efficiency and reduce light scattering , various anti - reflection coatings may be applied to surfaces where light transitions between two different materials . dichroic layers that comprise a low pass filter for the blue color and a high pass filter for the red color may be formed to overlap in the light reflecting regions 36 . the above described displays will work with infrared , visible and ultraviolet light sources and combinations thereof . depending on the display size and resolution , each picture element of the display panel may include several tilting micro - shutters . reducing the size of individual micro - shutters helps to reduce the required electrostatic actuation voltages . also , micro - shutters for each picture element may be grouped to modulate different levels of light when suitable voltage is applied between the fixed electrodes and a selected group of micro - shutters . this reduces the display addressing constraints . for example , each picture element may include 7 micro - shutters grouped in quantities of 1 , 2 and 4 and selectively addressed to modulate 8 levels of light . additionally , temporal artifacts inherent in pulse - width - modulation displays are reduced . having now described the invention in detail in accordance with the requirements of the patent statutes , those skilled in this art will have no difficulty in making changes and modifications in the individual parts or their relative assembly in order to meet specific requirements or conditions . such changes and modification may be made without departing from the scope and spirit of the invention , as set forth in the following claims .
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referring to the drawings in detail wherein like numerals designate like parts , and referring first to fig1 to establish the environment of the invention , a tilting and sliding bed truck 10 generally of the type disclosed in u . s . pat . no . 3 , 430 , 792 and in the above - referenced application is shown . this truck includes a main chassis frame 11 above which is mounted a sliding and tilting bed 12 . the bed 12 is moved longitudinally forwardly and rearwardly by a centrally located longitudinal power cylinder 13 disposed between the main chassis frame 11 and the sliding bed 12 . a jacking and lift assembly 14 is connected between the bed 12 and depending bracket plates 15 on the rear end of main chassis frame 11 . the sliding and tilting bed 12 includes a pair of lower parallel longitudinal i - beam rails 16 whose lower flanges 17 are slidably held in bearing or wear pad containments 18 , the construction of which forms the main subject matter of this invention . as shown in fig1 there are two units 18 associated with the sliding and tilting truck bed 12 on each side thereof , that is , one pair of units for each i - beam rail 16 of the truck bed . the rearmost units 18 are coupled with the jacking assembly 14 and the forwardmost units 18 are secured to the rear of main chassis frame 11 . each wear pad containment unit 18 includes a lower transverse axis bearing sleeve 19 containing bushings 20 which receive therethrough a pivot pin 21 held in arms 22 rising from the main chassis frame 11 in the case of the two forwardmost units 18 . the two rearward units 18 have their corresponding pivot elements 21 supported through arms or brackets carried by the jacking and lift assembly 14 . each wear pad containment unit 18 further comprises a frame including a horizontal plate 23 resting on a rectangular bar member 24 which is securely welded to the top of sleeve 19 , as best shown in fig3 and 6 . side inclined brace plates 25 are similarly welded between the bottom of horizontal plate 23 and opposite side of sleeve 19 to form a rigid support structure . this support structure or frame further includes spaced vertical side plates 26 welded to the horizontal plate 23 and projecting above it . the lower edges of the side plates 26 are spaced slightly above the top of sleeve 19 , as shown . thus , the support frame composed of welded plates 23 and 26 is bodily and rigidly mounted on the sleeve 19 and can turn with the sleeve around the axis of pivot pin 21 . each containment unit 18 additionally comprises readily separable generally l - shaped wear pad clamps or retainers 27 having diagonal wear pad retainer bars 28 welded across their fore and aft ends . these retainers 27 are held in place on the unit 18 by a pair of spaced parallel transverse bolts 29 located immediately below the flanges 17 of sliding i - beam rails 16 and above horizontal plate 23 . at their far ends , the bolts 29 carry nuts and washers 30 and 31 . upper phenolic wear pads 32 and optional shims 33 are held between the top face of sliding rail flange 17 and the opposing somewhat inclined face of wear pad retainer 27 . the retainer bars 28 prevent displacement of the upper wear pads and shims longitudinally and they are held captive against transverse movement by the i - beam rail 16 and the holding action of retainers 27 . a single lower phenolic wear pad 34 and optional shim 35 are placed between the bottom face of sliding rail flange 17 and the horizontal support plate 23 . the vertical side plates 26 prevent any appreciable displacement of the lower wear pads 34 transversely of the axis of rail 16 , and the two bolts 29 closely straddle the fore and aft ends of the lower wear pads , fig6 and prevent displacement thereof longitudinally . thus , it may be seen that the two bolts 29 serve a dual purpose in the invention of detachably securing retainers 27 in the wear pad units 18 and retaining or holding the lower wear pads 34 against displacement . a chief feature of the invention in contrast to the prior art is that neither the upper or lower wear pads 32 or 34 are pierced by any fastener and the full thicknesses of the pads are available for bearing purposes during gradual wear on the pads thus rendering them useful over a much longer time before shimming or complete replacement becomes necessary . fig7 of the drawings shows the wear pads 32 and 34 somewhat recessed due to wear , as they might be at the time requiring shimming or replacement . the other drawing figures show the upper and lower wear pads without substantial wear . the invention , as described , fulfills its primary objective by rendering servicing or replacement of all of the wear pads simple and economical without the necessity for complete removal of the sliding truck bed 12 from the units or suppots 18 , as was heretofore necessary in all of the known prior art arrangements . instead , by means of the invention , it is only necessary to remove the two bolts 29 of each unit 18 which releases the retainers 27 and allows ready removal of both the upper and lower wear pads 32 and 34 along with their shims , as required . during this operation , the rails 16 are relieved of their weight or loading either by blocking the underside of the bed 12 near its forward end and utilizing the hydraulic jacking assembly 14 of the truck , or an external jacking means if preferred . the installation of new upper and lower phenolic wear pads and the reassembly of the retainers 27 and their bolts 29 is a very simple matter and the necessity for long periods of down time for the truck is avoided . it should be clear , in light of the foregooing description , that the sleeves 19 on which the plate elements 23 and 26 are mounted enable the containment units 18 to pivot around the axes of pins 21 , as required for tilting of the truck bed 12 . the terms and expressions which have been employed herein are used as terms of description and not of limitation , and there is no intention , in the use of such terms and expressions , of excluding any equivalents of the features shown and described or portions thereof but it is recognized that various modifications are possible within the scope of the invention claimed . for instance , the wear pad assemblies or containments may be used in other environments and in an arrangement reverse from that illustrated in the drawings where the longitudinal i - beam rails 16 are stationary and the wear pad containments 18 depend from a slidable frame member , similar to frame member 11 , and engage the top flanges of the i - beam rails , as would be illustrated , for example , by turning fig2 - 7 upside - down . also , in some installations , the support frame composed of plates 23 and 26 may be directly connected to its corresponding frame member 11 rather than being connected thereto through a pivot connection .
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while this invention is susceptible of embodiment in many different forms , there are shown in the drawings , and will be described herein in detail , specific embodiments thereof with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated . fig1 illustrates the accessory organizing device 10 being used on both the driver &# 39 ; s side and passenger side of the golf car , also known as a golf cart . the accessory organizing device 10 comprises a longitudinal member 70 onto which accessory holders 40 are remnovablely attached . the accessory organizing device 10 is mounted to vertical support bars 20 of the golf car through the use of a mounting bracket 30 . the mounting bracket 30 has a longitudinal member support portion 50 , and a vertical support bar 20 mounting portion 60 . fig2 illustrates one embodiment of a longitudinal member 70 . longitudinal member 70 has a rectangular cross section 75 , which as illustrated in fig2 is a square . the cross sectional area is not limited to a four sided regular polygon , and can be any suitable shape . the cross sectional area may have greater or fewer than four sides depending on the number of engagement surfaces desired . a greater number of sides will allow for more surfaces to engage with the accessory holders . each side 72 of the longitudinal member 70 has at least one groove 80 or slot along the length of the longitudinal member ( fig4 ). the longitudinal member may have a t - slot groove as illustrated in fig4 , or the longitudinal member may have a cross sectional area of a different shape , such as a trapezoidal shape . in one embodiment , the longitudinal member is the bar or rail disclosed in u . s . patent application publication 200210122691 or u . s . pat . no . 5 , 429 , 438 , each herein incorporated by reference to the extent not inconsistent with the present description . the longitudinal member can also have more than one groove or slot extending along the length of the longitudinal member on a side of the member . in one embodiment , the longitudinal member 70 is of a length which extends for a portion of the width of the golf car , such as half the width , or a distance which spans one passenger seating area such as the driver or passenger seating areas , or a length which spans a portion of the length of the driver or passenger seating area . in use , each user , such as the driver and the passenger , brings their portable accessory organizing device to be mounted to their respective driver and passenger side vertical supports . each user can adjust the height of the device to suit the user &# 39 ; s positioning needs . each user &# 39 ; s accessory organizing device can be custom configured to have an array of accessory holders customized to each user and custom positioned as desired by the user . accessory holders can be provided for a variety of accessories . fig2 illustrates various accessory holders which can be used with the longitudinal member 70 . accessory holders can be clips 40 a for holding gloves or other accessories such as hats , bags , or food items such as bags of chips . accessory holders can be a platform 40 b to mount a gps or gps bracket or a mobile device . the accessory holders may be specific to particular accessories , such as a sunglasses holder ( not shown ), or the accessory holders may be designed to hold general accessories such as a tray 40 c , a pouch 40 d for holding various items . the accessory holders are attached to the longitudinal member . due to the various types of accessory holders , the weight on the accessory holder and thus its connection with the groove on the longitudinal member may vary to distribute the weight of the holder and prevent the accessory holder from falling out or shaking during use . various mechanisms for providing the desired weight , forces of the accessory holder in securing it to the longitudinal rail along the grooves can be used . as illustrated in fig5 , each accessory holder has a groove engagement portion 90 a , 90 b which is inserted into the groove 80 . accessory holders such as a hook can have a segment which is inserted into the groove by sliding the engagement portion 90 a in from the end of the longitudinal member . other accessories may have a groove engagement component which can be snap fitted into the groove . other accessory holders can have a groove engagement component and also a brace to on the outer surface to balance the force or weight of the accessory . the accessory organizing device is mounted onto the support bars 20 of the golf car via a mounting bracket 30 illustrated in fig3 . the mounting bracket 30 has a longitudinal member supporting portion 50 and a vertical support bar mounting portion 60 . the longitudinal member supporting portion 50 receives the longitudinal member 70 within a bracket 55 or shaft of a shape corresponding to the cross sectional shape of the longitudinal member 70 . a tightening mechanism such as a fastening screw 56 is used to secure the longitudinal member 70 to the bracket 55 by , for example , creating pressure on to the longitudinal member . bracket 55 can also be modified to receive longitudinal members of different cross sectional shapes . the bracket can be modified by use of additional fastening mechanisms to adapt the bracket for receiving longitudinal member of a different cross sectional shape . the longitudinal member 70 may be mounted to the bracket at a distal end of the longitudinal member as illustrated in fig3 . to secure the longitudinal member 70 to the golf car , the bracket 50 holding the longitudinal member is secured to the vertical support bar 20 of the golf car by a securing mechanism on the vertical support bar mounting portion 60 . the vertical support bar securing mechanism may be a u - shaped brace 65 which corresponds to the cross sectional shape of a golf car support bar . the u - shaped brace may be detachably secured to the mounting bracket 30 . the u - shaped brace is wrapped around the support bar and secured to the mounting bracket through the use of a fastening screw 66 by , for example , pressure force on to the u - shaped brace . the interior of the u - shaped brace 65 may be lined with material such a rubber to enhance the grip and connection of the u - shaped brace 65 with the vertical support bar 20 and allow for variations in the size of the golf car support bar 20 . in one embodiment , instead of a u - shaped brace , the securing mechanism may be a c - shaped bracket 65 a ( fig3 a ) which can be opened to receive the vertical support bar 20 of the golf car . the c - shaped bracket 65 a may then be tightened about the vertical support bar 20 using a fastening mechanism such as a fastening screw 66 a . any other mechanism for connecting the longitudinal bar to a vertical support bar known to one skilled in the art may also be used . in another embodiment , the longitudinal member 70 is secured to a vertical support member 20 using a mounting bracket 30 a as illustrated in fig6 . the mounting bracket has a stationary member 31 and a size adapting member 32 , each having an arm 31 a , 32 a between which a region for engaging with a vertical support member 20 is formed . the stationary member 31 has a shaft 55 a for receiving the longitudinal member . a distal end of the longitudinal member is fitted within the shaft , and secured to the shaft 55 a by a fastening mechanism , such as a screw 55 b , illustrated in fig1 which fastens the longitudinal member to the stationary member through aperture 31 c . one or more ends of the longitudinal member may have a threaded opening 71 for receiving the screw 55 b . the stationary member 31 further comprises a receiving shaft 33 for receiving the size adapting member 32 . the depth of the receiving shaft 33 for the size adapting member is of sufficient depth to allow the distance between the arms 31 a and 32 a to vary . a user adjusts the distance between the arms 31 a and 32 a by using a fastening mechanism , such as a screw or bolt ( not shown ) that extends through the aperture 31 b in the top of the stationary member and through the adapting aperture 32 b in the bottom of the adapting member 32 and connects with a nut 55 c ( fig6 ), which is secured against rotation in recess 56 in the bottom of the adapting member 23 . the top of the stationary member may have ridges 57 . the ridges may be interrupted by a screw head platform 35 about the aperture 31 b that may be recessed below the tops of the ridges 57 fig8 illustrates the view along line 8 - 8 ′ of fig7 , and fig9 illustrates the view along line 9 - 9 ′ of fig7 . the arms 31 a and 32 a of the stationary member 31 and the size adapting member 32 comprise size adapting corners 34 ( fig7 and 11 ). the size adapting corners allows for the arms 31 a and 32 a to adapt to vertical supports 20 of various areas . as illustrated in fig1 , the size adapting corners 34 allow for the arms 31 a , 32 a to adapt to vertical supports 20 a having the large cross section ( shown in solid lines ) and to vertical supports 20 b having a smaller cross section ( shown in dashed lines ). the size adapting corners 34 maybe to designed to suit vertical supports of various sizes , such as those formed by 1 inch ( 2 . 5 cm ) tubing , or by inch ( 1 . 875 cm ) tubing . in one embodiment , the receiving shaft 33 for the size adapting member is sized to allow for movement of the size adapting member 32 within the shaft 33 . as illustrated in fig1 , the size adapting member 32 is able to tilt within the shaft 33 within a range to better accommodate connection with various vertical supports . the range extends a predefined number of degrees from vertical alignment with the aperture 31 b . from the foregoing , it will be observed that numerous variations and modifications may be effected without departing from the spirit and scope of the invention . it is to be understood that no limitation with respect to the specific apparatus illustrated herein is intended or should be inferred .
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in the following , description will be given on embodiments of the present invention referring to the attached drawings . first , description will be given on an essential portion of an automatic tilt angle compensator of the present invention referring to fig1 and fig2 . a free interface 4 is formed in a sealed container 1 , and a lower layer transparent liquid 2 and an upper layer transparent liquid 3 are sealed in the container so that an open space 5 is maintained in upper portion of the sealed container 1 . the sealed container 1 comprises a horizontal bottom 1a , a vertical wall 1b running perpendicularly to the bottom 1a , and a reflective wall 1c tilted by 45 degrees with respect to the vertical wall 1b and the bottom 1a respectively . an entry window 6 is disposed on the bottom 1a , a reflective member 7 is arranged on the reflection wall 1c , and an exit window 8 is disposed on the vertical wall 1b . the entry window 6 is immersed in the lower transparent liquid 2 , and the reflective member 7 and the exit window 8 are immersed in the upper layer transparent liquid 3 . a light projecting system 9 is arranged in opposite to the entry window 6 so that a light beam irradiated from the light projecting system 9 passes through the entry window 6 and enters the lower layer transparent liquid 2 . the lower layer transparent liquid 2 or the upper layer transparent liquid 3 is a combination of a polar solvent and a non - polar solvent , e . g . a combination of a fluorine type inactive solution and a non - polar protic solvent , i . e . acetonitrile or n - methyl formamide or pyridine or dimethyl sulfoxide . these substances can dissolve electrolyte such as potassium iodide or potassium chloride and the refractive indices may be changed . when environmental temperature changes , the refractive index of the liquid also changes . by selecting two types of liquids , which have refractive indices changing in the same manner or in almost similar manner to each other depending on temperature , it is possible to maintain change of the optical axis with respect to the tilting of the entire system in the same state or in almost similar state when environmental temperature changes . also , if the open space 5 is disposed at a position out of the optical axis for the case where the volume of the liquid shrinks as temperature changes , it is possible to decrease the change of internal pressure due to expansion or shrinkage of the liquid and to suppress the change of viscosity of the liquid and to maintain durability of the container . instead of providing the open space 5 , if flexibility is given to a part of the container not in contact with the free interface 4 and the change of internal pressure due to expansion or shrinkage of the liquid is absorbed or compensated by deformation of said part of the container , it is possible to suppress the change of viscosity of the liquid or to maintain durability of the container similarly to the case when the open space 5 is provided . in the following , description will be given on automatic compensation in order to maintain an optical axis of an automatic tilt angle compensator in the horizontal direction . here , to facilitate explanation on the change of an optical axis when the main unit is tilted , explanation is given under the assumption that the free interface is tilted . as shown in fig1 when liquid surface is tilted at an angle of α , amount of change of an optical axis ( deflection angle of the optical axis ) after the light passes through the free interface 4 is given by : because the optical axis directed toward the exit window 8 has a deflection angle of &# 34 ; a &# 34 ;, deflection angle θ of the optical axis inside the exit window 8 is given as : ## equ1 ## the deflection angle θ &# 39 ; of the optical axis after passing through the exit window 8 is : ## equ2 ## when θ &# 34 ;= α , an outgoing optical axis ◯&# 39 ; is always maintained in parallel to the free interface 4 regardless of the tilting of the main unit . therefore , if a beam expander ( not shown ) having an angular magnification of 1 /( n - n &# 39 ;) on the outgoing optical axis 603 &# 39 ; is disposed , it is possible to obtain the optical axis , which is always maintained in the horizontal direction regardless of the tilting of the main unit . fig2 shows the entire system rotated by 90 degrees . the two transparent liquids 2 and 3 are also rotated by 90 degrees , and the free interface 4 is also rotated by 90 degrees around the center of gravity . the optical axis from the light projecting system 9 is reflected by the reflective member 7 and passes through the free interface 4 . the amount of change &# 34 ; a &# 34 ; of the optical axis in this case is : because the optical axis directed toward the exit window 8 has a deflection angle of &# 34 ; a &# 34 ;, deflection angle θ of the optical axis in the exit window 8 is given by : ## equ3 ## deflection angleθ &# 39 ; of optical axis after passing through the exit window 8 is : ## equ4 ## therefore , it is the same as the equation ( 3 ), and the outgoing optical axis is compensated by the beam expander and it is possible to obtain an optical axis , which can always be maintained in the vertical direction regardless of the tilting of the main unit . as described above , when environmental temperature changes , refractive indices of the lower layer transparent liquid 2 and the upper layer transparent liquid 3 are changed . by selecting the liquids having refractive indices which vary according to temperature in the same manner or in almost similar manner to each other , it is possible to eliminate or reduce error due to temperature change . the open space 5 absorbs or compensates expansion or shrinkage of the lower layer transparent liquid 2 and the upper layer transparent liquid 3 due to thermal change . fig3 shows an example where the automatic tilt angle compensator is applied to a rotary laser irradiation device . on opposite side to the exit window 8 and on a reflection optical axis of the reflective member 7 , a beam expander 10 is disposed . the beam expander 10 is incorporated in a housing 11 , which is integrated with the sealed container 1 . on opposite side of the beam expander 10 , a rotary pentagonal prism 12 is rotatably arranged on the optical axis of the beam expander 10 , and the rotary pentagonal prism 12 is to be rotated by a rotary driving unit such as a motor ( not shown ). a predetermined light beam from the light projecting system 9 , e . g . a laser beam , entering the sealed container 1 passes through the lower layer transparent liquid 2 and the free interface 4 . then , it is reflected by the reflective member 7 in the upper layer transparent liquid 3 and is emitted from the exit window 8 . the reflected laser beam irradiated from the beam expander 10 is deflected in the vertical direction and irradiated . when the rotary pentagonal prism 12 is rotated by the rotary driving unit ( not shown ), a vertical laser beam irradiation plane is formed by the irradiating laser beam . when the entire system is tilted and the free interface 4 is at the position as shown by two - dot chain line in the figure , an incident light beam is also directed as shown by two - dot chain line in the figure . after passing through the exit window 8 , the light beam is compensated by the beam expander 10 and its irradiating direction is in parallel to the free interface 4 . it is then deflected by the rotary pentagonal prism 12 , and the laser beam irradiated by rotary irradiation forms a vertical plane . fig4 shows the case where the entire system is rotated by 90 degrees in the rotary laser irradiation device as described above . the laser beam entering in the horizontal direction from the light projecting system 9 enters the upper layer transparent liquid 3 and is reflected by the reflective member 7 in the upper layer transparent liquid 3 . then , it passes through the lower layer transparent liquid 2 and the exit window 8 and is compensated by the beam expander 10 . further , it enters the rotary pentagonal prism 12 from the vertical direction and is irradiated after being deflected in the horizontal direction by the rotary pentagonal prism 12 . as the rotary pentagonal prism 12 is rotated , a horizontal irradiation plane is formed . similarly in the case shown in fig3 two - dot chain line in fig4 indicates a variation of the free interface 4 with respect to the sealed container 1 when the entire system is tilted , i . e . it indicates change of the optical axis of the laser beam . fig5 shows the automatic tilt angle compensator of the present invention applied to an angle detector . here , the beam expander 10 is not used , and a planar photodetection element 15 is disposed opposite to the exit window 8 . as described above , the light beam passes through the lower layer transparent liquid 2 and is reflected by the reflective member 7 , and the direction of the optical axis ◯&# 39 ; of the reflected light beam is changed according to the tilting of the free interface 4 with respect to the incident optical axis . therefore , by detecting the irradiating position of the outgoing light beam on the planar photodetection element 15 , it is possible to detect the deflection angle of the optical axis , i . e . the tilting of the entire system . fig6 represents the automatic tilt angle compensator of the present invention rotated by 90 degrees . under this condition , the outgoing light beam is irradiated in the vertical direction . by detecting the irradiating position to the planar photodetection element 15 , deviation of the outgoing optical axis ◯&# 39 ; with respect to the vertical line can be detected , i . e . it is possible to detect the tilting of the entire system . as the planar photodetection element 15 , a 4 - division photoelectric element , or other ccd element or psd element may be used . in this application example again , the entry window 6 , the reflective member 7 , and the exit window 8 are always immersed in the lower layer transparent liquid 2 or the upper layer transparent liquid 3 . as a result , the liquid remains in the transparent member , and diffusion of the light beam caused by the attached liquid can be prevented . as described above , the outgoing light beam passing through the sealed container indicates angular displacement corresponding to the tilting of the entire system . because the incident light beam is reflected in the sealed container and is irradiated , the incident light beam can pass through the transparent liquid , and the outgoing light beam indicates angular displacement corresponding to the tilting of the entire system even when the system is rotated by 90 degrees . because optical components such as the entry window , the reflective member , the exit window , etc . are always immersed in the liquid , it is possible to prevent diffusion of light without worrying about the attachment of the liquid drops or the liquid film , and this contributes to high stability and accuracy of the system .
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as a preliminary matter , a conventional led is formed on a growth substrate . in the example used , the led is a gan - based led , such as an alingan or ingan led , for producing blue light . typically , a relatively thick n - type gan layer is grown on a sapphire growth substrate using conventional techniques . the relatively thick gan layer typically includes a low temperature nucleation layer and one or more additional layers so as to provide a low - defect lattice structure for the n - type cladding layer and active layer . one or more n - type cladding layers are then formed over the thick n - type layer , followed by an active layer , one or more p - type cladding layers , and a p - type contact layer ( for metallization ). for a flip - chip , portions of the p - layers and active layer are etched away to expose an n - layer for metallization . in this way , the p contact and n contact are on the same side of the chip and can be directly electrically attached to the submount contact pads . current from the n - metal contact initially flows laterally through the n - layer . the led bottom electrodes are typically formed of a reflective metal . other types of leds that can be used in the present invention include alingap leds , which can produce light in the red to yellow range . non - flip - chip leds can also be used . the leds are then singulated and mounted on a submount wafer . prior art fig1 illustrates a conventional led 10 flip chip mounted on a portion of a submount wafer 22 . the led 10 is formed of semiconductor epitaxial layers grown on a growth substrate 12 , such as a sapphire substrate . in one example , the epitaxial layers are gan based , and the active layer emits blue light . any other type of led is applicable to the present invention . metal electrodes 14 are formed on the led 10 that electrically contact the p - layer , and metal electrodes 16 are formed on the led 10 that electrically contact the n - layer . in one example , the electrodes are gold bumps that are ultrasonically welded to anode and cathode metal pads on the submount wafer 22 . the submount wafer 22 , in one embodiment , has conductive vias leading to bottom metal pads for bonding to a printed circuit board . many leds are mounted on the submount wafer 22 , and the wafer 22 will be later singulated to form individual leds / submounts . further details of leds can be found in the assignee &# 39 ; s u . s . pat . nos . 6 , 649 , 440 and 6 , 274 , 399 , and u . s . patent publications us 2006 / 0281203 a1 and 2005 / 0269582 a1 , all incorporated herein by reference . a reflective underfill material is prepared . in one embodiment , particles of tio 2 ( appearing white under white light ), or other reflective particles such as zro 2 , are added to a silicone molding compound that is suitable for underfilling . a typical silicone molding compound contains about 82 %- 84 % sio 2 by weight , which creates a very stable material in the high - photon energy , high - heat environment of a power led . to create the reflective properties of the underfill , tio 2 is included in the silicone molding compound to replace some of the sio 2 to cause the tio 2 to be about 5 - 10 % or higher by weight of the total amount of filler in silicone molding compound . the tio 2 plus the sio 2 should equal about 80 %- 84 % by weight of the silicone compound . a 5 % addition of tio 2 results in about an 85 % reflectivity of the silicone compound , and a 10 % addition of tio 2 results in over 90 % reflectivity of the silicone compound . significantly more tio 2 begins to reduce the desirable characteristics of the silicone compound for used as an underfill . other formulations of an electrically insulating , reflective underfill material may be used . fig2 a illustrates one type of suitable injection molding process for creating the underfill and reflective layer for each led . a mold 36 has cavities 38 that define the shape of the hardened underfill material after the molding process . the mold 36 may be formed of aluminum . the mold 36 has a perimeter seal 37 that seals against the submount wafer 22 when the mold 36 is aligned with the wafer 22 and pressed against the wafer 22 . the mold 36 has at least one inlet 40 , for injecting the reflective liquid underfill material 41 , and at least one outlet 42 connected to a vacuum source . once the mold 36 is sealed against the wafer 22 , a vacuum is created within the mold 36 , and the underfill material 41 is injected through inlet 40 . the underfill material 41 flows into all the cavities 38 via channels 44 between the cavities , assisted by the vacuum and the injection pressure of the material 41 . the vacuum removes almost all the air in the mold 36 . ultimately , the entire mold 36 will be filled with the underfill material 41 , including all voids under the leds . the mold 36 is then heated to cure the liquid underfill material . the temperature of the mold 36 during curing is about 150 ° c . alternatively , a transparent mold may be used and the underfill material may be cured with uv light . fig2 b illustrates an alternative wafer - level molding process that does not use pressure injection of the underfill material . in fig2 b , the mold 48 has cavities 50 that are first filled with particles ( e . g ., powder or small tablets ) of solid underfill material 41 at atmospheric pressure . the solid material is then heated in the mold to soften it . the submount wafer 22 is brought against the mold 48 so that the leds are immersed in the underfill material in each cavity 50 . the wafer 22 and mold 48 are pressed together to force the underfill material to fill all voids . a perimeter seal 53 allows the pressure to be high while allowing all air to escape as the underfill material fills the voids . a vacuum may also be pulled between the wafer 22 and the mold 48 using a vacuum source around the seal 53 . the mold 48 is then cooled to solidify the underfill material . certain materials harden automatically after the heating and compression process . handling the underfill material as a solid has various benefits . further , some suitable materials that can be used for an underfill are not a liquid at room temperatures prior to curing , so heating up a solid material in the mold followed by compression greatly increases the number of possible materials that can be used as an underfill . the mold of fig2 a or 2 b is then removed from the wafer 22 , resulting in the structure of fig3 , having the hardened underfill material 54 encapsulating each led . there is also a layer of hardened underfill material 54 on the wafer 22 surface between each led . to perform a laser lift - off process to remove the growth substrates 12 , the underfill material 54 over the growth substrate 12 must first be removed . if the growth substrate 12 will be removed by grinding or another mechanical etch process , such grinding may be used to simultaneously remove the excess underfill material 54 . fig4 illustrates the removal of the excess underfill material 54 by blasting the entire surface of the wafer 22 with high - velocity microbeads 58 . in one embodiment , the microbeads 58 have diameters between 1 - 20 microns and are formed of nahco 3 . the microbeads 58 are accelerated through a nozzle by air at a pressure of about 100 psi or less . the nozzle may be large to etch the underfill material 54 from over the leds 10 without the nozzle moving , or a smaller nozzle may be used to etch the underfill material 54 off only a few leds at a time followed by the nozzle moving to a next position over the wafer 22 . removing excess material of any kind using microbeads is a known process . the underfill material 54 is etched to leave a reflective layer over the submount surface between the leds 10 . the thickness of the remaining layer should be sufficient to reflect at least 80 % of the impinging light . in one embodiment , the thickness of the reflective layer over the submount surface is about 30 - 50 microns ( which may be approximately the thickness of the underfill beneath the led die ), and the overall top surface of the reflective layer is substantially flat , as determined by the mold shape and effects of the microbead blasting . fig5 illustrates a laser lift - off process . the laser pulses are shown by arrows 60 . during the laser lift - off , the surface of the gan absorbs heat , causing the surface layer to decompose into the ga and n 2 . the n 2 pressure pushes the sapphire growth substrates 12 away from the leds . after the growth substrates 12 become detached from the semiconductor led layers during the lift - off process , they are removed by , for example , an adhesive sheet or some other suitable process . the underfill mechanically supports the thin led semiconductor layers during the lift - off process . the exposed led layers are then thinned by , for example , rie or a mechanical etch , since the exposed top layer is a relatively thick n - layer , and the surface has been damaged by the laser lift - off process . the resulting top surface may then be roughened to increase the light extraction efficiency . if it is desired to create phosphor - converted light , a mold similar to mold 48 in fig2 b is then provided to mold a phosphor layer over the leds 10 . for example , the leds 10 may emit blue light and it may be desired to create white light by depositing a layer of yag phosphor ( generates yellow light ) or a layer of red and green phosphors . the blue light leaks through the phosphor to combine with the phosphor - generated light . the phosphor mixture may be phosphor particles infused in a binder such as silicone . the mold cavities then define the shape of the phosphor over the leds 10 , and the phosphor mixture is cured to harden the phosphor layer . fig6 illustrates a molded phosphor layer 62 over the leds . if the tolerances of the mold process cause there to be a thin phosphor layer over the underfill material 54 , such thin phosphor may be removed using a microbead blasting step . a transparent lens 66 ( fig7 ) may then be molded over each led 10 to increase the light extraction from the led , protect the phosphor layer 62 and the led 10 , and create a desired light emission pattern . the lens 66 may be any shape , such as the hemispherical shape shown in fig7 . in one embodiment , the lens 66 is molded from silicone using the same general process shown in fig2 b . in one embodiment , the lens material also contains phosphor particles to wavelength convert the light emitted by the leds 10 . other wafer - level processes may also be performed on the led array while mounted on the submount wafer 22 . the submount wafer 22 is then singulated to form individual leds / submounts , such as shown in fig8 . as shown in fig8 , the entire surface of the submount wafer 22 portion is covered by the reflective underfill material 54 . a light ray 70 is shown being emitted by the phosphor layer 62 in a downward direction and being reflected upward by the underfill material 54 . light rays from the sides of the led 10 will also be reflected upward and exit through the top surface of the underfill material 54 . fig8 also shows the electrodes 72 and 73 on the surface of the submount wafer 22 portion , the vias 76 leading to the bottom electrodes 78 and 79 , and a printed circuit board 82 having pads soldered to the electrodes 78 and 79 . the board 82 may have an aluminum core for sinking heat . the invention also applies to forming a reflective material around leds mounted on a substrate whether or not the reflective material is also used as an underfill . for example , the bottom electrodes on the led may take up virtually the entire backside of the led and an underfill may not be needed . details of a wafer - level lens molding process are described in patent publication us 2006 / 0105485 , entitled overmolded lens over led die , by grigoriy basin et al ., assigned to the present assignee and incorporated herein by reference . while particular embodiments of the present invention have been shown and described , it will be obvious to those skilled in the art that changes and modifications may be made without departing from this invention in its broader aspects and , therefore , the appended claims are to encompass within their scope all such changes and modifications as fall within the true spirit and scope of this invention .
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in order to provide a better understanding of the invention , some prior art ligatures are first discussed . referring first to fig4 , a typical mouthpiece 100 is shown with a reed 104 . the reed 104 is secured to the mouthpiece 100 with a ligature 106 . ligature 106 has a fixed band 108 disposed around mouthpiece 100 . the band 108 is tightened with two screws 110 which hold the reed . all prior ligatures have a fixed band length , and as such only fit one size of mouthpiece . different sized mouthpieces require appropriately sized ligatures . referring to fig5 , mouthpiece 101 is shown with the reed 104 . the reed 104 is secured to mouthpiece 101 with a ligature 112 . ligature 112 has a protrusion 114 that is pressure fit into indentation 116 on mouthpiece 101 . ligature 112 is built specifically for mouthpiece 101 and as such only fits this specific mouthpiece . also , in the attempt to hold the ligature in place , some prior art ligatures utilize large surface areas of tight contact with the mouthpiece body 102 . the vibrations of the reed / ligature combination are dampened by the mouthpiece body 102 creating a deadening effect on the resultant sound produced by the mouthpiece . the invention provides a ligature 118 shown in fig1 - 3 having of a ligature body 120 , a thumbscrew 122 , an adjustable band 124 , and a pressure plate 126 . the body has a generally elongated shape . the band 124 has one end 124 a which is fixed into an inset on one side of the body 120 with a set - screw 128 . alternatively , end 124 a may be permanently fixed by soldering or similar methods to one end of the body 120 . the opposite end of the band 124 slides through a hole 130 in the opposite end of the body 120 . the ligature is adjusted to fit any mouthpiece by sliding an end portion 132 of the band 124 through hole 130 thereby expanding or contracting the size or length of the band 124 . the band 124 is preferably made of steel or brass and is flexible , although it could be made from other materials as well . once the ligature is seated on the respective mouthpiece , the band 124 is tightened by advancing the end 132 through the hole 130 and securing the end 132 to the body 120 . this may be accomplished using an adhesive inserted into the hole , a set - screw 136 ( or thumb screw ) threaded through the side of body 120 and having a tip engaging the end 132 . alternatively , the end 132 and hole 130 are sized and shaped to provide an interference fit there - between . once the length of band 124 forming the loop engaging the mouthpiece body is set , the tip of end 132 extending above the body 120 can be cut off to insure that it does not interfere with the operation of the musical instrument . alternatively , the length of the band is set ( e . g ., its second end 132 is secured to the body 120 ) before the ligature is disposed on the mouthpiece . since the band of the invention is adjustable in length it fits all mouthpieces regardless of width , diameter or shape , including mouthpiece body types 100 and 101 shown in fig4 and 5 . therefore the thumbscrew 122 and pressure plate 126 are used in the same manner as in the prior art ligatures as shown in fig5 to engage and lock the ligature unto the body of the mouthpiece 100 , as clearly illustrated in fig3 . more specifically , once the ligature is mounted or positioned on the mouthpiece 100 , turning the thumbscrew 122 clockwise causes the plate 126 to advance radially thereby tightening the band 130 and causing the ligature and the reed 104 to be firmly secured to the mouthpiece numerous modifications can be made to the invention without departing from the scope defined in the appended claims . for example , band 124 may be fixed at one end 124 a by various fashions . end 124 a may also be allowed to move freely through body 120 as is evident on the other end of the band 124 through hole 130 . whether one end or both ends of band 124 move freely through body 120 is incidental as the invention only requires that the band be adjustable through 120 . the invention does not require it be done in any particular way .
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fig1 shows a stretcher which in its entirety is designated by reference numeral 1 and which comprises on the one hand a thin first layer 2 of an all - round flexible material with large wear and tear strength , and on the other hand a considerably thicker second layer 3 which is permanently joined or integrated with the first layer and consists of a porous or fluffy soft material intended to form a stretcher part that makes it possible to comfortably repose on it . advantageously , the two layers 2 , 3 may be produced in the way disclosed in wo - a - 87 / 04614 , i . e ., of one and the same polymer material , for instance polyethylene or polypropylene , the material in the strong , thin and carrier layer 2 having a density many times larger than the density of the porous layer 3 . however , it is also possible to produce the two layers of different materials and then connect them to each other , for instance by some sort of adhesive or by heat welding . in the shown example , each of the two layers as a rectangular basic form , although it is feasible to confer to them a slightly tapering form . however , in both cases the basic form is elongate in so far as the length of the stretcher always is larger than its largest width . according to the invention , layer 3 forming the soft stretcher part of the stretcher is divided by one or several longitudinal slits 4 , 4 ′ into several elongate sections 5 , 6 , 7 which are jointly held together by the thin carrier layer 2 . more precisely , the holding together of the stretcher sections 5 , 6 , 7 is effected in portions 8 , 8 ′ which form longitudinal folding lines permitting a folding of the stretcher into a package in which the two sections 6 , 7 are folded inwardly towards the middle section 5 , with the carrier layer parts 2 ′, 2 ″, 2 ″′ turned towards each other . according to an embodiment of the invention preferred in practice , the stretcher part 3 has a thickness of at least 30 , suitably at least 50 mm , whereby the stretcher in question is capable of being used as a conventional stretcher , in particular in its folded configuration , for instance in a hospital bed . according to the example in fig1 the stretcher part , i . e . the thick soft layer 3 , is supposed to have a thickness of 50 mm , at the same time as the length of the stretcher amounts to a size of 2000 mm . advantageously , middle section 5 then has a width within the range of 600 to 900 mm , while the width of each separate side section 6 , 7 amounts to about half of the width of middle section 5 . therefore , in the folded state shown in fig3 the stretcher gets the form of about 2000 mm and a width within the range of 600 to 800 mm . of course , also the length , the width and the thickness may deviate from these absolute values . as may be seen in fig1 straps 9 may be connected to the thin and strong carrier layer 2 , which straps on the one hand may consist of carrying straps , on the other hand of straps for holding together the side portions against the body of a lying person . according to a preferred embodiment of the invention , each individual dividing slit 4 has a height equal to the thickness of stretcher part 3 in order to cut the latter down to carrier layer 2 . in other words , the dividing slits keep side section 6 , 7 completely separate from middle section 5 . therefore the user may replace the middle section 5 for her own middle section , such as his own mattress , without affecting the foldability of the present invention . the folding is carried out solely along previously mentioned portions 8 , 8 ′ of carrier layer 2 . although side sections 6 , 7 are equally wide according to the example in fig1 they may also be differently wide . according to a preferred embodiments of the invention , the stretcher being folded along the folding lines in question is packed into an enclosing , flexible envelope . one feasible embodiment of such an envelope 10 is shown in fig2 . in this case , the envelope comprises a large - surface which is placed against the inwardly folded side sections 6 , 7 and against the edge parts 11 extending along both the long and the short sides , which edge parts 11 are kept elastically strained against the upper side of middle section 5 , for instance by a flexible straining bad 12 , for example in the form of a rubber band . advantageously , envelope 10 consists of a suitable textile material , e . g . terry cloth , furniture fabric or similar . it should be obvious that envelope 10 may be easily and quickly pulled off from the packed stretcher in order to make it possible for the later to function as a stretcher . according to an essential aspect of the present invention , the unit 13 shown in fig2 and comprising both the packed stretcher 1 and the enclosing envelope 10 , may be used as an effect in the most diverse circumstances , e . g ., as a support - forming part for the back or as a seat - forming part , for instance in a room or in a vehicle . thus , in its storage or readiness state , the unit may during long times be used as for instance a furniture forming element , whereafter it may be rapidly converted into a rescuing stretcher . this brings about the essential advantage of keeping a large quantity of stretches easily accessible in different public institutions , such as on trains , public buildings , department stores , etc . in fig3 an alternative envelope 14 is shown which encloses and covers the two opposite large - surfaces of the package and at least the longitudinal side edges , in that the envelope is endless . according to this embodiment , the envelope may also cover the short - ends of the package . also in this case , the envelope may consist of a textile material , although also other materials are feasible , e . g ., shrinking plastic , adhering plastic or similar . it should be observed that envelope 14 , equally to envelope 11 , holds together stretcher sections 5 , 6 , 7 and locks these relative to each other in the folded state . in fig5 an alternative embodiment is shown according to which an envelope 15 comprises three different sectors 15 ′, 15 ″, 15 ″′, each separately enclosing the different stretcher sections 5 , 6 , 7 . thus , in this case the envelope is placed on the stretcher when the different stretcher sections are folded out or are in a common plane , the envelope enclosing the stretcher sections all - round and being on contact with their surfaces . in fig5 an embodiment is shown according to which carrier layer parts 2 ″, 2 ″′ have a smaller width than side sections 6 , 7 of the stretcher part . in this embodiment , the outer longitudinal side parts of the side sections become more flexible and softer than at the embodiment according to fig1 . fig6 shows an embodiment according to which each individual side section is divided into two part - sections 6 ′, 6 ″ and 7 ′, 7 ″, respectively , by a corresponding dividing slit 4 ″, 4 ″′. in this embodiment , the side sections are capable of being more easily connected to the body of a patient . in fig7 an embodiment is shown according to which the upper surface 16 on the middle section 5 of the stretcher part has been conferred an uneven surface structure , for instance in the form of longitudinal graining , with the object of reducing the risk for bedsores in cases when the stretcher is used for long periods as a stretcher , for instance in a hospital bed . in fig9 is illustrated an embodiment according to which the different layers in the sections of the stretcher have been made with through aeration channels 17 which promote the evacuation of humidity and vapor from the stretcher and which may bring about a current of air upwards towards a reposing body , for instance by bringing air to the boundary zone between the stretcher sections . fig1 a shows an embodiment according to which two identical stretcher are supposed to be laid adjacent to each other , with the lying surfaces of middle sections 5 in contact with each other . according to this embodiment , the side sections are folded inwardly towards the middle sections , thus forming a package of four - fold thickness in comparison with the individual stretcher layer 3 , and then the package is enclosed in an envelope . fig1 b is very similar to the embodiment shown in fig1 a but has no middle sections 5 so that the user may use his / her own middle section such as a mattress . fig1 shows an embodiment according to which the individual side section is divided into two lamella - like parts 19 , 19 ′ by a slit 18 , 18 ′ parallel to the carrier layer 2 , which parts 19 , 19 ′ are held together along longitudinal side edges by a reinforcing layer 20 which protrudes from carrier layer 2 . as can be seen in fig1 , the lamella part 19 ′ next to the lying surface of middle section 5 may be shorter than the outer lamella part 19 . in this way , the arms of a lying patient or person may be placed between the two lamella parts and be kept locked after the outer lamella parts having been connected to each other , for instance by straps 9 . thus , when the stretcher is used as a stretcher not only the body and the legs of the patient may be held steadily fixed and still , but also the patient &# 39 ; s arms , this being important for instance in connection with rescuing operations and other difficult circumstances . when hands and arms are pressed directly at the body , the ribs of the person may break which may cause a puncture of the lungs . therefore , the foam is an important separator . eventually , in fig1 an embodiment is shown according to which the middle section 5 of the stretcher part is composed of on the one hand a lower partial layer 21 and on the other hand of a plurality of superficial part elements 22 , 22 ′, etc . these separate surface elements 22 , 22 ′ may have different densities in order to satisfy the requirements on the lying surface in the best way , which requirements are different for different parts of the body . in practice , the longitudinal slits that form folding lines at the different embodiments of the invention , along which lines the different sections of the stretcher may be folded inwardly towards each other , may be brought about in the most different ways . one way is cutting or sawing in the porous material , after its production into a homogeneous continuous stretcher part . the porous material may also be cut with a knife or a heated thread . another way is to , already in connection with the producing of the porous layer , form the layer so that dividing slits of desired depth and form are immediately formed . in this context it is pointed out that the cross - sectional form of the individual slit may advantageously be triangular or otherwise tapering , so that wedge - wisely tapering edge parts are formed in the stretcher sections adjacent to each other . the slits may also be made by a melting or pressing operation . it is evident that the invention is not restricted solely to the embodiments described and shown in the drawings . thus , within the scope of the invention it is feasible to integrate electrically conducting material into the stretcher , for instance by using electrically conducting polymer fibers , which conductivity is so chosen that heat is produced when current is provided . other ways include providing the foam with a carbon powder or another electrically conductive material . in other words , the stretcher may be kept warm at a temperature suitable for the purpose by the supply of an electrical current . in practice , the electrically conducting material in question should be located in close proximity to the thin carrier layer , so as to avoid the risk of being compressed or stretched in connection with a possible deformation of the stretcher . in this way it is guaranteed that the material always maintains one and the same electrical resistance , thus producing an even heating temperature . moreover , the geometrical form of the stretcher can vary most considerably . thus , instead of a rectangular basic shape of the respective stretcher sections also a slightly tapering or wedge - like form may occur . it should also be pointed out that the soft and porous stretcher layer may be composed of two or more part layers . it may also be mentioned that the strong carrier layer 2 may in practice be designed with handles or handle - forming recesses in order to make possible the use of the unit as a stretcher . it is further possible to provide the carrier layer with longitudinal pockets in which stiffening bars may be inserted if desired . fig1 is an alternative embodiment of the present invention . the foldable carrier 100 has a continuous flexible thin support layer 102 that may be made of any flexible material that provides sufficient support to carry a person or animal . a thicker soft middle layer 104 may be attached to the layer 102 . on each side of the layer 104 , soft side layers 106 , 108 may be attached to the layer 102 . preferably , the layers 106 , 108 are not attached to the layer 104 so that the carrier 100 may be folded along folding lines 110 , 112 . elongate support members 114 , 116 may be placed along the folding lines 110 , 112 , respectively . the layers 104 , 106 , 108 are soft to make the carrier comfortable for a patient laying in the carrier 100 . fig1 shows a detailed view of the support member 116 . the support member is l - shaped and has a long vertical section 118 and a shorter horizontal section 120 . the l - shape provides extra stiffness . it should be understood that the support member 116 may have any angled shape and is not limited to l - shapes . as best shown in fig1 , the horizontal section 120 may be inserted between the layer 104 and the layer 102 and captured therebetween . the section 118 should be flush or slightly below an upper surface 122 of the layer 104 . as best shown in fig1 , the carrier 100 may be folded into a folded position by turning the side layers 106 , 108 towards one another and against the layer 102 below the middle layer 104 . it should be noted that the support members 114 , 116 may be placed between the side layers 106 , 108 and the layer 102 so that they are not lost . fig1 shows a detailed view of an underside of the layer 102 including two rows of handles 103 . it should be understood that the layers 104 , 106 , 108 may be removably attached to the support layer 102 so that the patient may use his or her own mattress instead of the layers . fig1 shows an alternative embodiment of a carrier 130 enclosing a patient 132 . the carrier 130 has a continuous support layer 134 that is attached to a thick mid - section 136 and outer side sections 138 , 140 . similar to fig1 , the carrier 130 may include elongate support members 142 , 144 that are attachable at the folding lines 146 , 148 . inner side sections 150 , 152 are attached to an upper edge 154 of the mid - section 136 . the sections 150 , 152 may have attachments 156 , 158 , respectively so that the attachment 156 may be attached to attachment 158 , as shown by an arrow a , to permit the arms and hands 160 of the patient to be disposed between the inner and outer side sections . a first handle 162 may be attached to an underside of the layer 102 at the folding lines 146 , 148 to permit the lifting and dragging of the carrier 130 with the patient enclosed inside the inner side sections 150 , 152 and the mid - section 134 . while the present invention has been described in accordance with preferred compositions and embodiments , it is to be understood that certain substitutions and alterations may be made thereto without departing from the spirit and scope of the following claims .
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as used in the specification and appended claims , unless specified to the contrary , the following terms have the meaning indicated : &# 34 ; lower alkyl &# 34 ; refers to a straight or branched chain monovalent radical consisting solely of carbon and hydrogen , containing no unsaturation and having from one to four carbon atoms , e . g ., methyl , ethyl , n - propyl , 1 - methylethyl ( iso - propyl ), n - butyl , 1 , 1 - dimethylethyl ( t - butyl ), and the like . &# 34 ; lower alkoxy &# 34 ; refers to a radical of the formula -- or a where r a is lower alkyl as defined above , e . g ., methoxy , ethoxy , t - butoxy , and the like . &# 34 ; lower haloalkyl &# 34 ; refers to a lower alkyl radical , as defined above , that is substituted by one or more halo radicals , as defined above , e . g ., trifluoromethyl , difluoromethyl , trichloromethyl , 2 - trifluoroethyl , 1 - fluoromethyl - 2 - fluoroethyl , 3 - bromo - 2 - fluoropropyl , 1 - bromomethyl - 2 - bromoethyl , and the like . &# 34 ; aralkyl &# 34 ; refers to a radical of the formula -- r a r b where r a is lower alkyl as defined above and r b is aryl as defined above , e . g ., benzyl . &# 34 ; benzamidine &# 34 ; refers to a phenyl radical substituted by an amidino radical . &# 34 ; naphthamidine &# 34 ; refers to a naphthyl radical substituted by an amidino radical . &# 34 ; optional &# 34 ; or &# 34 ; optionally &# 34 ; means that the subsequently described event of circumstances may or may not occur , and that the description includes instances where said event or circumstance occurs and instances in which it does not . for example , &# 34 ; optionally substituted aryl &# 34 ; means that the aryl radical may or may not be substituted and that the description includes both substituted aryl radicals and aryl radicals having no substitution . &# 34 ; pharmaceutically acceptable acid addition salt &# 34 ; refers to those salts which retain the biological effectiveness and properties of the free bases , which are not biologically or otherwise undesirable , and which are formed with inorganic acids such as hydrochloric acid , hydrobromic acid , sulfuric acid , nitric acid , phosphoric acid and the like , and organic acids such as acetic acid , trifluoroacetic acid , propionic acid , glycolic acid , pyruvic acid , oxalic acid , maleic acid , malonic acid , succinic acid , fumaric acid , tartaric acid , citric acid , benzoic acid , cinnamic acid , mandelic acid , methanesulfonic acid , ethanesulfonic acid , p - toluenesulfonic acid , salicylic acid , and the like . &# 34 ; pharmaceutically acceptable base addition salt &# 34 ; refers to those salts which retain the biological effectiveness and properties of the free acids , which are not biologically or otherwise undesirable . these salts are prepared from addition of an inorganic base or an organic base to the free acid . salts derived from inorganic bases include , but are not limited to , the sodium , potassium , lithium , ammonium , calcium , magnesium , iron , zinc , copper , manganese , aluminum salts and the like . preferred inorganic salts are the ammonium , sodium , potassium , calcium , and magnesium salts . salts derived from organic bases include , but are not limited to , salts of primary , secondary , and tertiary amines , substituted amines including naturally occurring substituted amines , cyclic amines and basic ion exchange resins , such as isopropylamine , trimethylamine , diethylamine , triethylamine , tripropylamine , ethanolamine , 2 - dimethylaminoethanol , 2 - diethylaminoethanol , trimethamine , dicyclohexylamine , lysine , arginine , histidine , caffeine , procaine , hydrabamine , choline , betaine , ethylenediamine , glucosamine , methylglucamine , theobromine , purines , piperazine , piperidine , n - ethylpiperidine , polyamine resins and the like . particularly preferred organic bases are isopropylamine , diethylamine , ethanolamine , trimethamine , dicyclohexylamine , choline and caffeine . &# 34 ; therapeutically effective amount &# 34 ; refers to that amount of a compound of formula ( i ) which , when administered to a human in need thereof , is sufficient to effect treatment , as defined below , for disease - states alleviated by inhibition of factor xa or factor iia . the amount of a compound of formula ( i ) which constitutes a &# 34 ; therapeutically effective amount &# 34 ; will vary depending on the compound , the disease - state and its severity , and the age of the human to be treated , but can be determined routinely by one of ordinary skill in the art having regard to his own knowledge and to this disclosure . &# 34 ; treating &# 34 ; or &# 34 ; treatment &# 34 ; as used herein cover the treatment of a disease - state in a human , which disease - state is alleviated by inhibition of factor xa or by factor iia ; and include : ( i ) preventing the disease - state from occurring in a human , in particular , when such human is predisposed to the disease - state but has not yet been diagnosed as having it ; the yield of each of the reactions described herein is expressed as a percentage of the theoretical yield . the compounds of the invention , or their pharmaceutically acceptable salts , may have asymmetric carbon atoms in their structure . the compounds of the invention and their pharmaceutically acceptable salts may therefore exist as single stereoisomers , racemates , and as mixtures of enantiomers and diastereomers . all such single stereoisomers , racemates and mixtures thereof are intended to be within the scope of this invention . it is understood , for the purposes of this invention , that the compounds of the invention do not include any combination of substituents that may result in unstable compounds . the nomenclature used herein for the compounds of the invention is basically a modified form of the i . u . p . a . c . system , wherein the compounds are named as derivatives of benzamidine or naphthamidine . accordingly , a compound of the invention selected from formula ( iii ), i . e ., ## str3 ## wherein r 1 and r 4 are both -- c ( nh ) nh 2 ; r 7 and r 8 are both phenyl ; for example , a compound of the following formula : ## str4 ## is named herein as 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ). the compounds of the invention are inhibitors of factor xa and factor iia and therefore useful as anti - coagulants in treating disease - states characterized by thrombotic activity based on factor xa &# 39 ; s or factor iia &# 39 ; s role in the coagulation cascade ( see background of the invention above ). a primary indication for the compounds is prophylaxis for long term risk following myocardial infarction . additional indications are prophylaxis of deep vein thrombosis ( dvt ) following orthopedic surgery or prophylaxis of selected patients following a transient ischemic attack . the compounds of the invention may also be useful for indications in which coumadin is currently used , such as for dvt or other types of surgical intervention such as coronary artery bypass graft and percutaneous transluminal coronary angioplasty . the compounds are also useful for the treatment of thrombotic complications associated with acute promyelocytic leukemia , diabetes , multiple myelomas , disseminated intravascular coagulation associated with septic shock , purpura fulminanas associated infection , adult respiratory distress syndrome , unstable angina , and thrombotic complications associated with aortic valve or vascular prosthesis . the compounds are also useful for prophylaxis for thrombotic diseases , in particular in patients who have a high risk of developing such disease . in addition , the compounds of the invention are useful as in vitro diagnostic reagents for inhibiting factor xa or factor iia in the coagulation cascade . the primary bioassays used to demonstrate the inhibitory effect of the compounds of the invention on factor xa or factor iia are simple chromogenic assays involving only serine protease , the compound of the invention to be tested , substrate and buffer ( see , e . g ., thrombosis res . ( 1979 ), vol . 16 , pp . 245 - 254 ). for example , four tissue human serine proteases can be used in the primary bioassay , free factor xa , prothrombinase , thrombin ( factor iia ) and tissue plasminogen activator ( tpa ). the assay for tpa has been successfully used before to demonstrate undesired side effects in the inhibition of the fibrinolytic process ( see , e . g ., j . med . chem . ( 1993 ), vol . 36 , pp . 314 - 319 ). another bioassay useful in demonstrating the utility of the compounds of the invention in inhibiting factor xa demonstrates the potency of the compounds against free factor xa in citrated plasma . for example , the anticoagulant efficacy of the compounds of the invention will be tested using either the prothrombin time ( pt ), or activated partial thromboplastin time ( aptt ) while selectivity of the compounds is checked with the thrombin clotting time ( tct ) assay . correlation of the k i in the primary enzyme assay with the k i for free factor xa in citrated plasma will screen against compounds which interact with or are inactivated by other plasma components . correlation of the k i with the extension of the pt is a necessary in vitro demonstration that potency in the free factor xa inhibition assay translates into potency in a clinical coagulation assay . in addition , extension of the pt in citrated plasma can be used to measure duration of action in subsequent pharmacodynamic studies . for further information on assays to demonstrate the activity of the compounds of the invention , see r . lottenberg et al ., methods in enzymology ( 1981 ), vol . 80 , pp . 341 - 361 , and h . ohno et al ., thrombosis research ( 1980 ), vol . 19 , pp . 579 - 588 . administration of the compounds of the invention , or their pharmaceutically acceptable salts , in pure form or in an appropriate pharmaceutical composition , can be carried out via any of the accepted modes of administration or agents for serving similar utilities . thus , administration can be , for example , orally , nasally , parenterally , topically , transdermally , or rectally , in the form of solid , semi - solid , lyophilized powder , or liquid dosage forms , such as for example , tablets , suppositories , pills , soft elastic and hard gelatin capsules , powders , solutions , suspensions , or aerosols , or the like , preferably in unit dosage forms suitable for simple administration of precise dosages . the compositions will include a conventional pharmaceutical carrier or excipient and a compound of the invention as the / an active agent , and , in addition , may include other medicinal agents , pharmaceutical agents , carriers , adjuvants , etc . generally , depending on the intended mode of administration , the pharmaceutically acceptable compositions will contain about 1 % to about 99 % by weight of a compound ( s ) of the invention , or a pharmaceutically acceptable salt thereof , and 99 % to 1 % by weight of a suitable pharmaceutical excipient . preferably , the composition will be about 5 % to 75 % by weight of a compound ( s ) of the invention , or a pharmaceutically acceptable salt thereof , with the rest being suitable pharmaceutical excipients . the preferred route of administration is oral , using a convenient daily dosage regimen which can be adjusted according to the degree of severity of the disease - state to be treated . for such oral administration , a pharmaceutically acceptable composition containing a compound ( s ) of the invention , or a pharmaceutically acceptable salt thereof , is formed by the incorporation of any of the normally employed excipients , such as , for example , pharmaceutical grades of mannitol , lactose , starch , pregelatinized starch , magnesium stearate , sodium saccharine , talcum , cellulose ether derivatives , glucose , gelatin , sucrose , citrate , propyl gallate , and the like . such compositions take the form of solutions , suspensions , tablets , pills , capsules , powders , sustained release formulations and the like . preferably such compositions will take the form of capsule , caplet or tablet and therefore will also contain a diluent such as lactose , sucrose , dicalcium phosphate , and the like ; a disintegrant such as croscarmellose sodium or derivatives thereof ; a lubricant such as magnesium stearate and the like ; and a binder such as a starch , gum acacia , polyvinylpyrrolidone , gelatin , cellulose ether derivatives , and the like . the compounds of the invention , or their pharmaceutically acceptable salts , may also be formulated into a suppository using , for example , about 0 . 5 % to about 50 % active ingredient disposed in a carrier that slowly dissolves within the body , e . g ., polyoxyethylene glycols and polyethylene glycols ( peg ), e . g ., peg 1000 ( 96 %) and peg 4000 ( 4 %). liquid pharmaceutically administrable compositions can , for example , be prepared by dissolving , dispersing , etc ., a compound ( s ) of the invention ( about 0 . 5 % to about 20 %), or a pharmaceutically acceptable salt thereof , and optional pharmaceutical adjuvants in a carrier , such as , for example , water , saline , aqueous dextrose , glycerol , ethanol and the like , to thereby form a solution or suspension . if desired , a pharmaceutical composition of the invention may also contain minor amounts of auxiliary substances such as wetting or emulsifying agents , ph buffering agents , antioxidants , and the like , such as , for example , citric acid , sorbitan monolaurate , triethanolamine oleate , butylated hydroxytoluene , etc . actual methods of preparing such dosage forms are known , or will be apparent , to those skilled in this art ; for example , see remington &# 39 ; s pharmaceutical sciences , 18th ed ., ( mack publishing company , easton , pa ., 1990 ). the composition to be administered will , in any event , contain a therapeutically effective amount of a compound of the invention , or a pharmaceutically acceptable salt thereof , for treatment of a disease - state alleviated by the inhibition of factor xa in accordance with the teachings of this invention . the compounds of the invention , or their pharmaceutically acceptable salts , are administered in a therapeutically effective amount which will vary depending upon a variety of factors including the activity of the specific compound employed , the metabolic stability and length of action of the compound , the age , body weight , general health , sex , diet , mode and time of administration , rate of excretion , drug combination , the severity of the particular disease - states , and the host undergoing therapy . generally , a therapeutically effective daily dose is from about 0 . 14 mg to about 14 . 3 mg / kg of body weight per day of a compound of the invention , or a pharmaceutically acceptable salt thereof ; preferably , from about 0 . 7 mg to about 10 mg / kg of body weight per day ; and most preferably , from about 1 . 4 mg to about 7 . 2 mg / kg of body weight per day . for example , for administration to a 70 kg person , the dosage range would be from about 10 mg to about 1 . 0 gram per day of a compound of the invention , or a pharmaceutically acceptable salt thereof , preferably from about 50 mg to about 700 mg per day , and most preferably from about 100 mg to about 500 mg per day . of the compounds of the invention as set forth above in the summary of the invention , several groups of compounds are preferred . one preferred group is that group of compounds selected from formula ( i ) wherein r 1 is -- c ( nh ) nh 2 , -- c ( nh ) n ( h ) or 11 or -- c ( nh ) n ( h ) c ( o ) or 11 ; r 2 and r 3 are each hydrogen ; r 4 is -- c ( nh ) nh 2 , -- c ( nh ) n ( h ) or 11 or -- c ( nh ) n ( h ) c ( o ) or 11 ; r 5 , r 6 , r 9 and r 10 are independently hydrogen , halo , or lower alkyl ; and r 11 is hydrogen , lower alkyl , aryl or lower aralkyl . of this group of compounds , a preferred subgroup are those compounds wherein r 1 and r 4 are each -- c ( nh ) nh 2 ; and r 5 , r 6 , r 9 and r 10 are independently hydrogen or halo . of this subgroup of compounds , a preferred class of compounds are those compounds wherein r 5 , r 6 , r 9 and r 10 are each chloro . another preferred group of compounds is that group of compounds selected from the formula ( iii ) wherein r 1 is -- c ( nh ) nh 2 , -- c ( nh ) n ( h ) or 11 or -- c ( nh ) n ( h ) c ( o ) or 11 ; r 2 and r 3 are independently hydrogen , lower alkyl or -- or 11 ; r 4 is -- c ( nh ) nh 2 , -- c ( nh ) n ( h ) or 11 , -- c ( nh ) c ( h ) c ( o ) or 11 , or -- c ( o ) n ( r 11 ) r 12 ; r 7 and r 8 are independently hydrogen , lower alkyl , or aryl ( optionally substituted by one or substituents selected from the group consisting of halo , hydroxy , lower alkyl , lower haloalkyl , lower alkoxy and -- n ( r 11 ) r 12 ); and r 11 and r 12 are independently hydrogen , lower alkyl , phenyl or benzyl . of this group of compounds , a preferred subgroup of compounds is that subgroup wherein r 1 is -- c ( nh ) nh 2 ; r 2 and r 3 are independently hydrogen or -- or 11 ; r 4 is -- c ( nh ) nh 2 or -- c ( o ) n ( r 11 ) r 12 ; r 7 and r 8 are independently hydrogen , lower alkyl or phenyl ( optionally substituted by one or more substituents selected from the group consisting of -- or 11 and -- n ( r 11 ) r 12 ); and r 11 and r 12 are independently hydrogen or lower alkyl . of this subgroup of compounds , a preferred class of compounds is that class wherein r 1 and r 4 are both -- c ( nh ) nh 2 ; r 2 and r 3 are both hydrogen ; r 7 and r 8 are independently phenyl optionally substituted by -- or 11 or -- n ( r 11 ) r 12 ; and r 11 and r 12 are independently hydrogen or lower alkyl . of this class of compounds a preferred subclass is that subclass of compounds wherein r 7 and r 8 are both phenyl . of this subclass of compounds , a preferred compound is 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ). another preferred subclass of compounds from this class is that subclass of compounds wherein r 7 is phenyl ; and r 8 is 4 - dimethylaminophenyl . of this subclass of compounds , a preferred compound is 3 , 3 &# 39 ;- 2 , 3 - dihydro - 4 -( 4 - dimethylaminophenyl )- 2 - oxo - 5 - phenyl - 1h - imidazol - 1 , 3 - diyl ! bis ( methylene )!- bis ( benzamidine ). another preferred group of compounds is that group selected from formula ( iv ) wherein r 1 and r 4 are both -- c ( nh ) nh 2 ; r 2 and r 3 are independently hydrogen or -- or 11 ; r 7 , r 8 and r 9 are independently hydrogen , lower alkyl or phenyl ( optionally substituted by one or more substituents selected from the group consisting of -- or 11 and -- n ( r 11 ) r 12 ); and r 11 and r 12 are independently hydrogen or lower alkyl . of this group of compounds , a preferred subgroup of compounds is that subgroup wherein r 1 and r 4 are both -- c ( nh ) nh 2 ; r 2 and r 3 are both hydrogen ; r 7 and r 8 are both phenyl ; and r 9 is hydrogen . preferred compounds of this subgroup are 7 - 3 - 4 -( amidino ) benzyl !- 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ! methyl !- naphthalene - 2 - carboximidamide and 7 - 3 - 3 -( amidino ) benzyl !- 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ! methyl ! naphthalene - 2 - carboximidamide . another preferred group of compounds is that group selected from formula ( v ) wherein r 1 and r 4 are both -- c ( nh ) nh 2 ; r 2 and r 3 are independently hydrogen or -- or 11 ; r 7 , r 8 , r 9 and r 10 are independently hydrogen , lower alkyl or phenyl ( optionally substituted by one or more substituents selected from the group consisting of -- or 11 and -- n ( r 11 ) r 12 ); and r 11 and r 12 are independently hydrogen or lower alkyl . of this group , a preferred subgroup of compounds is that subgroup wherein r 1 and r 4 are both -- c ( nh ) nh 2 ; r 2 and r 3 are both hydrogen ; r 7 and r 8 are both phenyl ; and r 9 and r 10 are both hydrogen . as a matter of convenience , the following description of the preparation of the compounds of the invention is directed to the preparation of compounds of formula ( iii ), although similar reagents and reaction conditions may be used to produced the other compounds of the invention . compounds of formula ( b ) are starting materials in the prepration of the compounds of the invention and are commercially available or may be prepared according to methods known to those skilled in the art , or may be prepared as illustrated below in reaction scheme 1 wherein r 14 and r 15 are independently hydrogen or arylmethyl ( where the aryl group is substituted by a cyano group and optionally substituted by one or more substituents selected from the group consisting of halo , lower alkyl , lower haloalkyl , -- or 11 , -- c ( o ) or 11 , -- c ( o ) n ( r 11 ) r 12 , -- n ( r 11 ) r 12 ,-- n ( h ) c ( o ) r 11 or -- n ( h ) s ( o ) 2 r 11 where r 11 and r 12 are independently hydrogen , lower alkyl , aryl or lower aralkyl ): ## str5 ## compounds of formula ( a ) are commercially available , for example , from aldrich chemical co ., inc ., or made by prepared by methods known to those of ordinary skill in the art . in general , compounds of formula ( b ) are prepared by reacting a compound of formula ( a ) with cocl 2 ( phosgene ) or a phosgene equivalent under basic conditions , such as utilizing triethylamine under standard conditions to form the intermediate , r 14 -- n ( h )═ c ═ o !, which is then reacted with a compound of formula r 15 -- nh 2 under standard conditions to form a compound of formula ( b ). 1 . compounds of formula ( da ) are intermediates in the preparation of the compounds of the invention . they are prepared from compounds of formula ( c ) and formula ( b ) as illustrated below in reaction scheme 2 where r 7 and r 8 are independently lower alkyl , lower haloalkyl , 4 - pyrdinyl or aryl ( optionally substituted by one or more substituents selected from the group consisting of halo , hydroxy , lower alkyl , lower haloalkyl , lower alkoxy and -- n ( r 11 ) r 12 wher r 11 and r 12 are independently hydrogen , lower alkyl , aryl or lower aralkyl ); and r 14 and r 15 are independently hydrogen or arylmethyl ( where the aryl group is substituted by cyano and optionally substituted by one or more substituents selected from the group consisting of halo , lower alkyl , lower haloalkyl , -- or 11 , -- c ( o ) or 11 , -- c ( o ) n ( r 11 ) r 12 , -- n ( r 11 ) r 12 , -- n ( h ) c ( o ) r 11 or -- n ( h ) s ( o ) 2 r 11 ( where r 11 and r 12 are independently hydrogen , lower alkyl , aryl or lower aralkyl )): ## str6 ## compounds of formula ( c ) may be commercially available or prepared from the appropriate compounds , such as aldehydes , according to methods known to those of ordinary skill in the art . in general , a compound of formula ( da ) are prepared by reacting a compound of formula ( c ) with a compound of formula ( b ) under acidic conditions , such as in refluxing acetic acid . the compound of formula ( da ) is then isolated from the reaction mixture by standard techniques , such as crystallization or chromatography . 2 . compounds of formula ( fa ) are also intermediates in the preparation of the compounds of the invention . they are prepared from compounds of formula ( db ), and from formula ( e ) as illustrated below in reaction scheme 3 where x is chloro , bromo or iodo ; r 2 is hydrogen , halo , lower alkyl , lower haloalkyl , aryl , -- or 11 , -- c ( o ) or 11 , -- n ( r 11 ) r 12 , -- n ( h ) c ( o ) r 11 or -- n ( h ) s ( o ) 2 r 11 ; r 3 is hydrogen , halo , lower alkyl , lower haloalkyl , aryl , or -- or 11 ; r 7 and r 8 are independently hydrogen , lower alkyl , lower haloalkyl , -- c ( o ) or 11 , -- c ( o ) n ( r 11 ) r 12 , or aryl ( optionally substituted by one or more substituents selected from the group consisting of halo , -- or 11 , lower alkyl , lower haloalkyl and -- n ( r 11 ) r 12 ); where each r 11 and r 12 are independently hydrogen , lower alkyl , aryl or lower aralkyl : ## str7 ## compounds of formula ( db ) may be prepared according to the method described in reaction scheme 2 above for a compound of formula ( da ) where r 14 and r 15 are hydrogen , or by methods known to those of ordinary skill in the art . compounds of formula ( e ) may be commercially available or prepared by methods known to those of ordinary skill in the art . in general , a compound of formula ( fa ) are prepared by reacting a compound of formula ( db ) with two or more molar equivalent amounts of a compound of formula ( e ) under standard alkylation conditions to prepare a compound of formula ( fa ). the compound of formula ( fa ) is then isolated from the reaction mixture by standard techniques , such as crystallization or chromatography . 3 . compounds of formula ( l ) are also intermediates in the preparation of compounds of the invention . they are prepared as illustrated below in reaction scheme 4 wherein x is bromo , chloro , iodo ; r 2 is hydrogen , halo , lower alkyl , lower haloalkyl , aryl , -- or 11 , -- c ( o ) or 11 , -- n ( r 11 ) r 12 , -- n ( h ) c ( o ) r 11 or -- n ( h ) s ( o ) 2 r 1 ; r 7 and r 8 are independently hydrogen , lower alkyl , lower haloalkyl , -- c ( o ) or 11 , -- c ( o ) n ( r 11 ) r 12 , or aryl ( optionally substituted by one or more substituents selected from the group consisting of halo , -- or 11 , lower alkyl , lower haloalkyl and -- n ( r 11 ) r 12 ), where each r 11 and r 12 are independently hydrogen , lower alkyl , aryl or lower aralkyl ; and each r 16 is lower alkyl , aryl or lower aralkyl : ## str8 ## compounds of formula ( db ) may be prepared according to the method described in reaction scheme 2 above , or by methods known to those of ordinary skill in the art . compounds of formula ( g ) and formula ( e ) may be commercially available or prepared by methods known to those of ordinary skill in the art . in general , compounds of formula ( l ) are prepared by first treating a compound of formula ( db ) with a compound of formula ( g ) as a limiting reagent under standard alkylation conditions , for example , in an aprotic solvent in the presence of a base such as sodium hydride at temperatures between about 20 ° c . to about 50 ° c ., preferably at about 50 ° c ., to yield a compound of formula ( h ). the compound of formula ( h ) is then treated with one molar equivalent amount of a compound of formula ( e ) under similar alkylation condtions , to yield a compound of formula ( j ). the compound of formula ( j ) is then hydrolyzed under standard basic hydrolysis conditions to yield a compound of formula ( k ), which is then treated with the appropriate amine under standard conditions to yield a compound of formula ( l ). the following reaction scheme is illustrative of the preparation of compounds of the invention , particularly those of formula ( iii ) as described above in the summary of the invention , but similar reagents and reaction conditions may be used to prepared compounds of the other formulae . compounds of formula ( iiia ) are compounds of the invention and are prepared as described below in reaction scheme 5 wherein r 2 , r 3 , r 7 and r 8 are the same as described above in the summary of the invention : ## str9 ## compounds of formula ( fb ) may be prepared according to the methods described above for compounds of formula ( fa ). in general , a compound of formula ( iiia ) is prepared by first dissolving a compound of formula ( fb ) in a lower alkanol , preferably ethanol , and then treating the solution overnight at around 0 ° c . with an anhydrous mineral acid , preferably hcl . the solvent is then removed and the resulting residue dissolved in fresh lower alkanol , preferably ethanol . the resulting solution is then treated with anhydrous ammonia at temperatures from between ambient temperatures and 100 ° c . from about 1 to about 5 hours . the above reactions are carried out in high - pressure glass tubes and vessels . the compound of formula ( iiia ) is then isolated from the reaction mixture by standard techniques . in the following reaction scheme , compounds of formula ( iiib ), which are also compounds of the invention , are similarly prepared from compounds of formual ( l ), as illustrated below in reaction scheme 6 , where r 2 , r 4 , r 7 and r 8 are as described above in the summary of the invention : ## str10 ## compounds of formula ( l ) may be prepared according to the methods described above in reaction scheme 4 . compounds of formulae ( iiia ) and ( iiib ) wherein r 7 or r 8 is -- c ( o ) or 11 , ( where r 11 is lower alkyl ) may be further hydrolyzed to produce compounds of the invention where r 7 or r 8 is c ( o ) or 11 where r 11 is hydrogen . such compounds may be further amidated to produce compounds of the invention wherein r 7 or r 8 are -- c ( o ) n ( r 11 ) r 12 ( where r 11 and r 12 are hydrogen , lower alkyl , aryl or lower aralkyl ). compounds of formulae ( iiia ) and ( iiib ) may be further treated with acid halides , preferably acid chlorides , or with acid anhydrides or equivalents , to yield compounds of the invention where r 1 and r 4 are -- c ( nh ) n ( h ) c ( o ) r 11 . alternatively , compounds of formulae ( iiia ) and ( iiib ) may be further treated with carbamoyl chlorides , or their equivalents , to yield compounds of the invention where r 1 and r 4 are -- c ( nh ) n ( h ) c ( o ) or 11 . compounds of the invention ( as described above in the summary of the invention ) wherein r 1 or r 4 are -- c ( nh ) n ( h ) or 11 are prepared by treating a compound of formulae ( fa ), ( fb ), ( j ), ( k ) and ( l ), as described above , with hydroxylamines of the formula r 11 onh 2 ( where r 11 is as described above in the summary of the invention ) under basic conditions , preferably in the presence of triethylamine . in summary , compounds of the invention , as illustrated above by the preparation of compounds of formula ( iii ), are prepared by : ( 1 ) treating a compound of formula ( c ) with a compound of formula ( b ) to yield a compound of formula ( da ); or ( 2 ) treating a compound of formula ( db ) with a compound of formula ( e ) to yield a compound of formula ( fa ); or ( 3 ) treating a compound of formula ( db ) with a compound of formula ( g ) to yield a compound of formula ( h ); and then treating the compound of formula ( h ) with a compound of formula ( e ) to yield a compound of formula ( j ); and then treating the compound of formula ( j ) to yield a compound of formula ( k ); and then treating the compound of formula ( k ) to yield a compound of formula ( l ); and ( 4 ) treating a compound of formulae ( da ), ( l ), ( fa ) or ( fb ) to form a compound of formula ( iii ). in addition , all compounds of the invention that exist in free base form or free acid form may be converted to their pharmaceutically acceptable salts by treatment with the appropriate inorganic or organic acid , or by the appropriate inorganic or organic base by methods known to those of ordinary skill in the art . salts of the compounds of the invention can also be converted to the free base form or to the free acid form or to another salt by known methods . the following specific preparations and examples are provided as a guide to assist in the practice of the invention , and are not intended as a limitation on the scope of the invention . a . to sodium hydride ( 2 . 4 g , 60 mmol ) in dimethylformamide ( 50 ml ) at 0 ° c . was added imidazolin - 2 - one ( 2 . 6 g , 30 mmol ). after stirring for 20 minutes 4 -( bromomethyl ) benzonitrile ( 13 g , 66 mmol ) was added and the mixture was warmed to ambient temperature . after stirring for 1 hour the reaction was poured into water and a solid formed . the solid was filtered to give 4 , 4 &# 39 ;- ( 2 - oxoimidazolin - 1 , 3 - diyl ) bis ( methylene )!- bis ( benzonitrile ). nmr ( cdcl 3 ) 7 . 65 ( d , 4 ), 7 . 4 ( d , 4 ), 4 . 45 ( s , 4 ), 3 . 2 ( s , 4 ) ppm . 4 , 4 &# 39 ;- ( 1 , 2 , 3 , 4 , 5 , 6 - hexahydro - 2 - oxopyrimidin - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 63 ( d , 4 ), 7 . 4 ( d , 4 ), 3 . 25 ( m , 4 ), 4 . 62 ( s , 4 ), 3 . 25 ( m , 4 ), 1 . 97 ( m , 2 ) ppm ; 3 , 3 &# 39 ;- ( 2 - oxoimidazolin - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 6 ( m , 6 ), 7 . 47 ( m , 2 ), 4 . 45 ( s , 4 ), 3 . 23 ( s , 4 ) ppm ; 3 , 3 &# 39 ;- ( 2 - oxo - 4 , 4 , 5 , 5 - tetramethylimidazolin - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 62 ( m , 4 ), 7 . 55 ( d , 2 ), 7 . 44 ( t , 2 ), 4 . 38 ( s , 4 ), 1 . 05 ( s , 12 ) ppm ; 4 , 4 &# 39 ;- ( 2 - oxo - 4 , 4 , 5 , 5 - tetramethylimidazolin - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 65 ( d , 4 ), 7 . 55 ( d , 4 ), 4 . 4 ( s , 4 ), 1 . 1 ( s , 12 ) ppm ; 1 , 3 - bis ( 3 - cyanobenzyl )- 1 , 2 - dihydro - 5 - ethyl - 2 - oxo - 1h - imidazole - 4 - carboxylic acid , methyl ester ; nmr ( cdcl 3 ) 7 . 4 - 7 . 7 ( m , 8 ), 5 . 3 ( s , 2 ), 5 . 0 ( s , 2 ), 3 . 79 ( s , 3 ), 2 . 7 ( q , 2 ), 1 . 04 ( t , 3 ) ppm ; 1 , 3 - bis ( 3 - cyanobenzyl )- 1 , 2 - dihydro - 2 - oxo - 1h - imidazole - 4 , 5 - dicarboxylic acid , diethyl ester ; nmr ( cdcl 3 ) 7 . 6 ( m , 6 ), 7 . 45 ( m , 2 ), 5 . 15 ( s , 4 ), 4 . 24 ( q , 4 ), 1 . 25 ( t , 6ppm ; 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 4 - methyl - 2 - oxo - 5 - phenyl - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 1 - 7 . 6 ( m , 13 ), 5 . 0 ( s , 2 ), 4 . 87 ( s , 2 ), 1 . 95 ( s , 6 ) ppm ; 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 4 - ethyl - 2 - oxo - 5 - phenyl - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 5 - 7 . 7 ( m , 4 ), 7 . 3 - 7 . 5 ( m , 6 ), 7 . 2 ( s , 1 ), 7 . 15 ( m , 2 ), 5 . 02 ( s , 2 ), 4 . 83 ( s , 2 ), 2 . 3 ( q , 2 ), 0 . 95 ( t , 6 ) ppm ; 3 , 3 &# 39 ;- ( 4 , 5 - bis ( methylethyl )- 2 , 3 - dihydro - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 56 ( m , 2 ), 7 . 5 ( m , 8 ), 5 . 03 ( s , 4 ), 2 . 95 ( m , 2 ), 1 . 13 ( d , 12 ) ppm ; 3 , 3 &# 39 ;- ( 4 , 5 - diethyl - 2 , 3 - dihydro - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 6 ( m , 2 ), 7 . 58 ( m , 8 ), 4 . 95 ( s , 4 ), 2 . 3 ( q , 4 ), 1 . 0 ( t , 6 ) ppm ; and 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 4 , 5 - dimethyl - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 6 ( m , 2 ), 7 . 5 ( m , 8 ), 4 . 93 ( s , 4 ), 1 . 9 ( s , 6 ) ppm . a . to dimethylformamide ( 50 ml ) was added 2 - hydroxy - 1h - benzimidazole ( 2 . 7 g , 25 mmol ), cesium carbonate ( 17 g , 55 mmol ), and 4 -( bromomethyl ) benzonitrile ( 10 g , 50 mmol ). after stirring for 3 hours , the mixture was poured into water . the precipitate was filtered and washed with water . the solid was dissolved in ethyl acetate , dried ( na 2 so 4 ), treated with charcoal , and the solvent was removed in vacuo to give 4 , 4 &# 39 ;- ( 1 , 2 - dihydro - 2 - oxo - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 85 ( d , 4 ), 7 . 6 ( d , 4 ), 7 . 2 ( m , 2 ), 7 . 1 ( m , 2 ), 5 . 25 ( s , 4 ) ppm . 3 , 3 &# 39 ;- ( 1 , 2 - dihydro - 2 - oxo - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 6 ( m , 6 ), 7 . 48 ( m , 2 ), 7 . 07 ( m , 2 ), 6 . 89 ( m , 2 ), 5 . 15 ( s , 4 ) ppm ; 4 , 4 &# 39 ;- ( 1 , 2 - dihydro - 4 - methyl - 2 - oxo - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 65 ( d , 4 ), 7 . 44 ( d , 2 ), 7 . 28 ( d , 2 ), 6 . 95 ( t , 1 ), 6 . 83 ( d , 1 ), 6 . 75 ( d , 1 ), 5 . 4 ( s , 2 ), 5 . 18 ( s , 2 ), 2 . 3 ( s , 3 ) ppm ; 3 , 3 &# 39 ;- ( 1 , 2 - dihydro - 4 - methyl - 2 - oxo - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 6 ( m , 4 ), 7 . 44 ( m , 2 ), 6 . 98 ( t , 2 ), 6 . 83 ( d , 1 ), 6 . 77 ( d , 1 ), 5 . 4 ( s , 2 ), 5 . 18 ( s , 2 ), 2 . 33 ( s , 3 ) ppm ; 3 , 3 &# 39 ;- ( 1 , 2 - dihydro - 4 , 7 - dimethyl - 2 - oxo - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 6 ( m , 2 ), 7 . 45 ( m , 6 ), 6 . 72 ( s , 2 ), 5 . 43 ( s , 4 ), 2 . 33 ( s , 6 ) ppm ; 3 , 3 &# 39 ;- 2 , 3 - dihydro - 4 -( 4 - dimethylaminophenyl )- 2 - oxo - 5 - phenyl - 1h - imidazol - 1 , 3 - diyl ! bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 3 - 7 . 6 ( m , 6 ), 7 . 24 ( m , 5 ), 7 . 03 ( m , 2 ), 6 . 85 ( d , 2 ), 6 . 53 ( d , 2 ), 4 . 9 ( s , 2 ), 4 . 86 ( s , 2 ), 2 . 95 ( s , 6 ) ppm ; 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 2 - oxo - 4 - phenyl - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 4 - 7 . 6 ( m , 5 ), 7 . 24 ( m , 5 ), 7 . 03 ( m , 3 ), 6 . 13 ( s , 1 ), 4 . 85 ( s , 2 ), 4 . 83 ( s , 2 ) ppm ; 3 , 3 &# 39 ;- ( 1 , 2 - dihydro - 2 - oxo - 4 , 5 , 6 , 7 - tetrachloro - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzenecarbonitrile ); nmr ( cdcl 3 ) 7 . 6 ( m , 2 ), 7 . 48 ( m , 6 ), 5 . 6 ( s , 4 ) ppm ; 4 , 4 &# 39 ;- ( 1 , 2 - dihydro - 2 - oxo - 4 , 5 , 6 , 7 - tetrachloro - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ); nmr ( cdcl 3 ) 7 . 65 ( m , 4 ), 7 . 33 ( m , 4 ), 5 . 6 ( s , 4 ) ppm . a . to acetic acid ( 2 ml ) was added urea ( 0 . 6 g , 10 mmol ) and 2 -( 4 - dimethylaminophenyl )- 2 - hydroxy - 1 - phenylethanone ( 2 . 6 g , 10 mmol ). after stirring for 2 hours at 120 ° c ., the reaction was cooled to ambient temperature . the resulting solid was filtered , washed with ether , and dried in vacuo to give 4 -( 4 - dimethylaminophenyl )- 2 , 3 - dihydro - 5 - phenyl - 1h - imidazol - 2 - one ; nmr ( cdcl 3 ) 10 . 98 ( s , 2 ), 7 . 5 ( m , 4 ), 7 . 4 ( m , 5 ), 3 . 18 ( s , 6 ) ppm . 4 , 5 - bis ( 4 - methoxyphenyl )- 2 , 3 - dihydro - 1h - imidazol - 2 - one ; nmr ( dmso - d 6 ) 11 . 0 ( s , 2 ), 7 . 62 ( d , 1 ), 7 . 26 ( d , 4 ), 6 . 9 ( d , 4 ), 3 . 73 ( s , 6 ) ppm ; 2 , 3 - dihydro - 4 - ethyl - 5 - phenyl - 1h - imidazol - 2 - one ; nmr ( dmso - d 6 ) 11 . 02 ( s , 1 ), 10 . 98 ( s , 1 ), 7 . 4 ( m , 4 ), 7 . 3 ( m , 1 ), 2 , 5 ( m , 2 ), 1 . 2 ( t , 3 ) ppm ; and 4 , 5 - diethyl - 2 , 3 - dihydro - 1h - imidazol - 2 - one ; nmr ( dmso - d 6 ) 9 . 5 ( s , 2 ), 2 . 22 ( q , 4 ), 1 . 05 ( t , 6 ) ppm . a . in a manner similar to preparation 1 above , 2 , 3 - dihydro - 4 , 5 - diphenyl - 1h - imidazol - 2 - one ( 1 . 2 g , 5 mmol ) was reacted with 3 -( bromomethyl ) benzonitrile ( 0 . 39 g , 2 mmol ) and sodium hydride ( 0 . 18 g , 5 mmol ) in dimethylformamide ( 20 ml ) to give 3 - ( 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ) methyl ! benzonitrile after chromatography on silica ; nmr ( dmso - d 6 ) 11 . 02 ( s , 1 ), 7 . 4 ( m , 4 ), 7 . 3 ( m , 2 ), 7 . 2 ( m , 7 ), 4 . 75 ( s , 2 ) ppm . 4 - ( 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ) methyl ! benzonitrile ; nmr ( dmso - d 6 ) 11 . 02 ( s , 1 ), 7 . 67 ( d , 2 ), 7 . 4 ( m , 3 ), 7 . 2 ( m , 9 ), 4 . 75 ( s , 2 ) ppm . a . to 2 , 3 - dihydro - 4 , 5 - diphenyl - 1h - imidazol - 2 - one ( 4 . 76 g , 20 mmol ) in 50 ml dmf was added to a suspension of nah ( 0 . 8 g , 20 mmol ) in 25 ml dmf . the suspension was stirred at ambient temperatures for 30 minutes , then heated to 50 ° c . for 30 minutes . a solution of methyl 3 - bromomethylbenzoate ( 2 . 86 g , 12 . 5 mmol ) in 20 ml dmf was then added and the reaction stirred for 10 min at 50 ° c . the mixture was poured into 1n hcl , filtered , washed with water and dried . chromatography on silica gel ( 2 % etoh in 7 : 3 methylene chloride / ethyl acetate ) afforded 1 . 2 g of 3 -( 3 - methoxycarbonylphenyl ) methyl - 4 , 5 - diphenyl - 1h - imidazol - 2 - one as a white solid . a . in a manner similar to preparation 2 above , 3 - ( 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ) methyl ! benzonitrile was reacted with 7 -( bromomethyl ) naphthalene - 2 - carbonitrile to give 7 - 3 -( 3 - cyanophenyl ) methyl - 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ! methyl ! naphthalene - 2 - carbonitrile ; nmr ( cdcl 3 ) 8 . 05 ( s , 1 ), 7 . 9 ( d , 1 ), 7 . 85 ( d , 1 ), 7 . 55 ( m , 3 ), 7 . 4 ( m , 2 ), 7 . 2 ( m , 9 ), 7 . 0 ( m , 3 ), 5 . 1 ( s , 2 ), 4 . 95 ( s , 2 ) ppm . 7 - 3 -( 4 - cyanophenyl ) methyl - 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ! methyl ! naphthalene - 2 - carbonitrile ; nmr ( cdcl 3 ) 8 . 05 ( s , 1 ), 7 . 85 ( d , 1 ), 7 . 8 ( d , 1 ), 7 . 55 ( m , 3 ), 7 . 45 ( d , 1 ), 7 . 4 ( s , 1 ), 7 . 2 ( m , 8 ), 7 . 0 ( m , 4 ), 5 . 1 ( s , 2 ), 5 . 0 ( s , 2 ) ppm ; and a . in a manner similar to preparation 2 above , a suspension of 2 -( 3 - methoxycarbonylphenyl ) methyl - dihydro - 4 , 5 - diphenyl - 1h - imidazol - 2 - one ( 410 mg , 1 . 1 mmol ) ( as prepared above in preparation 5 ), cesium carbonate ( 1 . 5 g ) and 4 - methoxy - 3 - bromomethylbenzonitrile ( 0 . 2 g , 1 mmol ) in 2 ml dmf was stirred at ambient temperature for 3 hours . the mixture was poured into 50 ml water and extracted with ethyl acetate ( 3 × 50 ml ). the ethyl acetate layer was washed with water , dried and evaporated to afford 0 . 55 g of 4 - methoxy - 3 - ( 3 -( 3 - methoxycarbonylphenyl ) methyl - 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ) methyl ! benzonitrile as a white solid . b . to the ester formed above ( 0 . 5 g ) in 5 ml meoh was added 5 ml of 25 % naoh and the reaction stirred at ambient temperatures for 30 minutes . the reaction was acidified to ph 4 with 1n hcl and extracted with ethyl acetate ( 3 × 50 ml ). the ethyl acetate layer was dried and evaporated to afford 0 . 4 g of the acid , 4 - methoxy - 3 - ( 3 -( 3 - carboxyphenyl ) methyl - 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ) methyl ! benzonitrile as a white solid . a . to a solution of 4 - methoxy - 3 - ( 3 -( 3 - carboxyphenyl ) methyl - 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ) methyl ! benzonitrile ( 0 . 39 g , 0 . 72 mmol ), as prepared above in preparation 7 , in 5 ml dmf was added n , n - carbonyldiimidazole ( 166 mg , 1 mmol ) and the reaction stirred at ambient temperatures for 2 hours . dimethylamine ( 0 . 5 ml of 2m solution in thf ) was added and the reaction stirred 10 h at ambient temperatures . the reaction mixture was poured into 50 ml 1n hcl and extracted with etoac . the organic layer was washed with water , dried and evaporated to afford 0 . 17 g of 4 - methoxy - 3 - ( 3 -( 3 - dimethylaminocarbonylphenyl ) methyl - 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ) methyl ! benzonitrile as a white solid . a . to 4 , 4 &# 39 ;- ( 2 - oxoimidazolin - 1 , 3 - diyl ) bis ( methylene ! bis ( benzonitrile ) ( 5 g , 16 mmol ) in ethanol ( 20 ml ) and methylene chloride ( 20 ml ) at 0 ° c . was bubbled hydrochloric acid ( g ). after sealing the reaction vessel and stirring in a high - pressure flask for 16 hours , the reaction mixture was poured into ether to obtain a solid . the solid was collected by filtration and washed with ether . to the solid was added ethanol ( 40 ml ) and the mixture was cooled to 0 ° c . ammonia was bubbled into the reaction mixture . after sealing the reaction vessel , and heating at 55 ° c . for 4 hours , the mixture was cooled , poured into ether and the solid was collected by filtration . recrystallization from ethanol gave 4 , 4 &# 39 ;- ( 2 - oxoimidazolin - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), dihydrochloride . further purification by high performance liquid chromatography ( hplc ) was sometimes necessary to give the final product . in such instances , the dihydrochloride salt was often replaced by trifluoroacetic acid ( tfa ) salt ; nmr ( dmso - d 6 ) 9 . 3 ( s , 4 ), 9 . 0 ( s , 4 ), 7 . 8 ( d , 4 ), 7 . 5 ( d , 4 ), 4 . 45 ( s , 4 ), 3 . 25 ( s , 4 ) ppm . 3 , 3 &# 39 ;- ( 1 , 2 - dihydro - 2 - oxo - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), dihydrochloride ; nmr ( dmso - d 6 ) 9 . 35 ( s , 4 ), 9 . 0 ( s , 4 ), 7 . 8 ( s , 2 ), 7 . 7 ( m , 4 ), 7 . 55 ( t , 2 ), 7 . 1 ( m , 2 ), 7 . 0 ( m , 2 ), 5 . 2 ( s , 4 ) ppm ; 4 , 4 &# 39 ;- ( 1 , 2 - dihydro - 4 - methyl - 2 - oxo - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), dihydrochloride ; nmr ( dmso - d 6 ) 9 . 3 ( s , 4 ), 9 . 0 ( s , 4 ), 7 . 8 ( d , 4 ), 7 . 55 ( d , 2 ), 7 . 35 ( d , 2 ), 7 . 0 ( d , 1 ), 6 . 9 ( t , 1 ), 6 . 75 ( t , 1 ), 5 . 43 ( s , 2 ), 5 . 22 ( s , 2 ), 2 . 25 ( s , 3 ) ppm ; 4 , 4 &# 39 ;- ( 1 , 2 , 3 , 4 , 5 , 6 - hexahydro - 2 - oxopyrimidin - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), dihydrochloride ; nmr ( dmso - d 6 ) 9 . 3 ( s , 4 ), 9 . 0 ( s , 4 ), 7 . 8 ( d , 4 ), 7 . 5 ( d , 2 ), 4 . 6 ( s , 4 ), 3 . 25 ( m , 4 ), 1 . 9 ( m , 2 ) ppm ; 4 , 4 &# 39 ;- ( 1 , 2 - dihydro - 4 , 7 - dimethyl - 2 - oxo - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), dihydrochloride ; nmr ( dmso - d 6 ) 9 . 35 ( s , 4 ), 9 . 05 ( s , 4 ), 7 . 82 ( d , 4 ), 7 . 4 ( d , 2 ), 6 . 7 ( s , 2 ), 5 . 5 ( s , 4 ), 2 . 25 ( s , 6 ) ppm ; 3 , 3 &# 39 ;- ( 1 , 2 - dihydro - 4 - methyl - 2 - oxo - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), dihydrochloride ; nmr ( dmso - d 6 ) 9 . 3 ( br , 8 ), 7 . 6 - 7 . 9 ( m , 6 ), 7 . 45 ( d , 2 ), 7 . 05 ( d , 1 ), 6 . 95 ( t , 1 ), 6 . 8 ( t , 1 ), 5 . 43 ( s , 2 ), 5 . 25 ( s , 2 ), 2 . 3 ( s , 3 ) ppm ; 3 , 3 &# 39 ;- ( 1 , 2 - dihydro - 4 , 7 - dimethyl - 2 - oxo - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), dihydrochloride ; nmr ( dmso - d 6 ) 9 . 35 ( s , 4 ), 8 . 95 ( s , 4 ), 7 . 2 - 7 . 8 ( m , 8 ), 6 . 65 ( s , 2 ), 5 . 45 ( s , 2 ), 5 . 4 ( s , 2 ), 2 . 25 ( s , 3 ) ppm ; 3 , 3 ,&# 39 ;- ( 5 , 6 - dichloro - 1 , 2 - dihydro - 2 - oxo - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), dihydrochloride ; nmr ( dmso - d 6 ) 9 . 38 ( s , 4 ), 9 . 05 ( s , 4 ), 7 . 8 ( s , 2 ), 7 . 72 ( m , 4 ), 7 . 6 ( t , 2 ), 7 . 5 ( s , 2 ), 5 . 2 ( s , 4 ) ppm ; 1 , 3 - bis 3 -( amidino ) benzyl !- 1 , 2 - dihydro - 5 - ethyl - 2 - oxo - 1h - imidazole - 4 - carboxylic acid , methyl ester , dihydrochloride ; nmr ( dmso - d 6 ) 9 . 4 ( s , 4 ), 9 . 15 ( s , 2 ), 9 . 05 ( s , 2 ), 7 . 73 ( m , 4 ), 7 . 58 ( m , 4 ), 5 . 25 ( s , 2 ) 5 . 1 ( s , 2 ), 3 . 7 ( s , 3 ), 2 . 75 ( q , 2 ), 0 . 97 ( t , 3 ) ppm ; 3 , 3 &# 39 ;- ( 4 , 5 - diethyl - 2 , 3 - dihydro - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), dihydrochloride ; nmr ( dmso - d 6 ) 9 . 4 ( s , 4 ), 9 . 1 ( s , 4 ), 7 . 7 ( m , 4 ), 7 . 58 ( t , 2 ), 7 . 44 ( d , 2 ), 4 . 95 ( s , 4 ), 2 . 35 ( q , 4 ), 0 . 9 ( t , 6 ) ppm ; 1 , 3 - bis 3 -( amidino ) benzyl !- 1 , 2 - dihydro - 2 - oxo - 1h - imidazole - 4 , 5 - dicarboxylic acid , diethyl ester , dihydrochloride ; nmr ( dmso - d 6 ) 9 . 35 ( s , 4 ), 9 . 05 ( s , 4 ), 7 . 7 ( m , 4 ), 7 . 58 ( m , 4 ), 5 . 2 ( m , 4 ), 4 . 18 ( q , 4 ), 1 . 15 ( t , 6 ) ppm ; 4 , 4 &# 39 ;- ( 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 3 ( s , 4 ), 9 . 1 ( s , 4 ), 7 . 78 ( d , 4 ), 7 . 25 ( m , 10 ), 7 . 2 ( m , 4 ), 4 . 98 ( s , 4 ) ppm ; 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 2 - oxo - 4 - phenyl - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 35 ( s , 2 ), 9 . 3 ( s , 2 ), 9 . 05 ( s , 2 ), 9 . 0 ( s , 2 ), 7 . 4 - 7 . 8 ( m , 9 ), 7 . 3 ( m , 9 ), 6 . 88 ( s , 1 ), 5 . 03 ( s , 2 ), 4 . 97 ( s , 2 ) ppm ; 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 4 - methyl - 2 - oxo - 5 - phenyl - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 38 ( s , 2 ), 9 . 3 ( s , 2 ), 9 . 05 ( s , 2 ), 9 . 0 ( s , 2 ), 7 . 2 - 7 . 8 ( m , 13 ), 5 . 01 ( s , 2 ), 4 . 9 ( s , 2 ), 2 . 0 ( s , 3 ), ppm ; 3 , 3 &# 39 ;- 2 , 3 - dihydro - 4 -( 4 - dimethylaminophenyl )- 2 - oxo - 5 - phenyl - 1h - imidazol - 1 , 3 - diyl ! bis ( methylene )! bis ( benzamidine ), trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 3 ( s , 4 ), 9 . 03 ( s , 2 ), 9 . 0 ( s , 2 ), 7 . 65 ( m , 2 ), 7 . 5 ( m , 4 ), 7 . 25 ( m , 11 ), 4 . 95 ( s , 4 ), 3 . 03 ( s , 6 ) ppm ; 3 , 3 &# 39 ;- 2 , 3 - dihydro - 4 , 5 - bis ( 4 - methoxyphenyl )- 2 - oxo - 1h - imidazol - 1 , 3 - diyl ! bis ( methylene )! bis ( benzamidine ), trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 3 ( s , 4 ), 9 . 03 ( s , 4 ), 7 . 65 ( d , 2 ), 7 . 52 ( m , 4 ), 7 . 32 ( d , 2 ), 7 . 08 ( d , 4 ), 6 . 9 ( d , 4 ), 4 . 9 ( s , 4 ), 3 . 7 ( s , 6 ) ppm ; 7 - 3 - 3 -( amidino ) benzyl !- 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ! methyl ! naphthalene - 2 - carboximidamide , trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 45 ( s , 2 ), 9 . 35 ( s , 2 ), 9 . 15 ( s , 2 ), 9 . 05 ( s , 2 ), 8 . 4 ( s , 1 ), 8 . 1 ( d , 1 ), 7 . 98 ( d , 1 ), 7 . 8 ( d , 1 ), 7 . 66 ( m , 2 ), 7 . 55 ( m , 2 ), 7 . 45 ( d , 1 ), 7 . 35 ( d , 1 ), 7 . 2 ( m , 10 ), 5 . 05 ( s , 2 ), 5 . 0 ( s , 2 ) ppm ; 7 - 3 - 4 -( amidino ) benzyl !- 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ! methyl ! naphthalene - 2 - carboximidamide , trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 4 ( s , 2 ), 9 . 25 ( s , 2 ), 9 . 1 ( s , 2 ), 9 . 0 ( s , 2 ), 8 . 4 ( s , 1 ), 8 . 05 ( d , 1 ), 7 . 98 ( d , 1 ), 7 . 75 ( m , 3 ), 7 . 65 ( s , 1 ), 7 . 4 ( d , 1 ), 7 . 2 ( m , 12 ), 5 . 05 ( s , 2 ), 5 . 0 ( s , 2 ) ppm ; 7 , 7 &# 39 ;- 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ! bis ( methylene )! bis ( naphthalene - 2 - carboximidamide ), trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 4 ( s , 4 ), 9 . 1 ( s , 4 ), 8 . 4 ( s , 2 ), 8 . 1 ( d , 2 ), 8 . 0 ( d , 2 ), 7 . 8 ( d , 2 ), 7 . 68 ( s , 2 ), 7 . 45 ( d , 2 ), 7 . 2 ( m , 10 ), 5 . 1 ( s , 4 ) ppm ; 3 , 3 &# 39 ;- 2 , 3 - dihydro - 4 - ethyl - 2 - oxo - 5 - phenyl - 1h - imidazol - 1 , 3 - diyl ! bis ( methylene )! bis ( benzamidine ), trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 36 ( s , 2 ), 9 . 3 ( s , 2 ), 9 . 05 ( s , 2 ), 9 . 0 ( s , 2 ), 7 . 78 ( s , 1 ), 7 . 75 ( d , 1 ), 7 . 4 - 7 . 7 ( m , 5 ), 7 . 37 ( m , 3 ), 7 . 23 ( m , 3 ), 5 . 02 ( s , 2 ), 4 . 85 ( s , 2 ), 2 . 35 ( q , 2 ), 0 . 92 ( t , 3 ) ppm ; 3 , 3 &# 39 ;- 4 , 5 - bis ( methylethyl )- 2 , 3 - dihydro - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ! bis ( methylene )! bis ( benzamidine ), trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 38 ( s , 4 ), 9 . 07 ( s , 4 ), 7 . 7 ( m , 4 ), 7 . 6 ( t , 2 ), 7 . 3 ( m , 2 ), 5 . 02 ( s , 2 ), 5 . 03 ( s , 4 ), 3 . 0 ( m , 2 ), 1 . 1 ( d , 12 ) ppm ; 3 , 4 - 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ! bis ( methylene )! bis ( benzamidine ), trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 3 ( s , 2 ), 9 . 28 ( s , 2 ), 9 . 0 ( s , 4 ), 7 . 73 ( d , 2 ), 7 . 66 ( d , 1 ), 7 . 5 ( m , 2 ), 7 . 25 ( m , 9 ), 7 . 18 ( m , 4 ), 4 . 98 ( s , 2 ), 4 . 95 ( s , 2 ) ppm ; 3 , 3 &# 39 ;- ( 1 , 2 - dihydro - 2 - oxo - 4 , 5 , 6 , 7 - tetrachloro - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), dihydrochloride ; nmr ( dmso - d 6 ) 9 . 38 ( s , 4 ), 9 . 1 ( s , 4 ), 7 . 7 ( m , 4 ), 7 . 6 ( m , 4 ), 5 . 58 ( s , 4 ) ppm ; 4 , 4 &# 39 ;- ( 1 , 2 - dihydro - 2 - oxo - 4 , 5 , 6 , 7 - tetrachloro - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), dihydrochloride ; nmr ( dmso - d 6 ) 9 . 20 ( s , 4 ), 8 . 80 ( s , 4 ), 7 . 80 ( d , 4 ), 7 . 40 ( d , 4 ), 5 . 60 ( d , 4 ) ppm ; 3 - ( 3 -( 3 - amidino - 6 - hydroxy ) benzyl - 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ) methyl ! benzamidine , trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 20 ( s , 2 ), 9 . 15 ( s , 2 ), 9 . 00 ( s , 2 ), 8 . 70 ( s , 2 ), 6 . 90 - 7 . 60 ( m , 17 ), 4 . 80 ( s , 2 ), 5 . 00 ( s , 2 ) ppm ; 3 - ( 3 -( 3 - amidino - 6 - methoxy ) benzyl - 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ) methyl ! benzamidine , trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 30 ( s , 2 ), 9 . 20 ( s , 2 ), 8 . 90 ( s , 2 ), 8 . 80 ( s , 2 ), 7 . 00 - 7 . 70 ( m , 17 ), 5 . 00 ( s , 2 ), 4 . 90 ( s , 2 ) 3 . 70 ( s , 3 ) ppm ; 4 , 4 &# 39 ;- bis ( methoxy )- 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 20 ( s , 4 ), 8 . 80 ( s , 4 ), 7 . 10 - 7 . 70 ( m , 16 ), 4 . 80 ( s , 4 ), 3 . 70 ( s , 3 ) ppm ; 4 , 4 &# 39 ;- bis ( hydroxy )- 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 10 . 90 ( s , 2 ), 9 . 10 ( s , 4 ), 8 . 80 ( s , 4 ), 6 . 90 - 7 . 60 ( m , 16 ), 4 . 80 ( s , 4 ) ppm ; 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 4 , 5 - dimethyl - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ); nmr ( dmso - d 6 ) 9 . 40 ( s , 4 ), ( 9 . 20 ( s , 4 ), 7 . 40 - 7 . 80 ( m , 8 ), 4 . 90 ( s , 4 ), 1 . 90 ( s , 6 ) ppm ; 3 , 3 &# 39 ;- ( 2 - oxo - 1 , 3 - diazahepta - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ); nmr ( dmso - d 6 ) 9 . 40 ( br , 8 ), 7 . 40 - 7 . 80 ( m , 8 ), 4 . 50 ( s , 4 ), 3 . 20 ( br , 4 ), 1 . 60 ( b , 4 ) ppm ; m . p . 109 °- 111 ° c . ; 4 , 4 &# 39 ;- ( 2 - oxo - 1 , 3 - diazapenta - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ); nmr ( dmso - d 6 ) 9 . 30 ( s , 4 ), 9 . 20 ( s , 4 ), 7 . 80 ( d , 4 ), 7 . 60 ( d , 4 ), 4 . 30 ( s , 4 ), 3 . 20 ( br , 4 ), 1 . 60 ( br , 4 ) ppm ; and 4 - methoxy - 3 - ( 3 -( 3 - dimethylaminocarbonylphenyl ) methyl - 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ) methyl ! benzonitrile ; nmr ( dmso - d 6 ) 9 . 25 ( s , 4 ), 8 . 80 ( s , 4 ), 7 . 00 - 7 . 70 ( m , 17 ), 4 . 80 ( s , 2 ), 4 . 82 ( s , 2 ), 3 . 70 ( s , 6 ). a . in a manner similar to example 1 above , 4 , 4 &# 39 ;- ( 1 , 2 - dihydro - 2 - oxo - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzonitrile ) ( 1 . 6 g , 4 . 4 mmol ) was reacted sequentially with hydrochloric acid and ethanolic ammonia . the resulting solid was dissolved in water and free - based with sodium hydroxide ( aq ). the solid was collected by filtration and dissolved in methanol . methanesulfonic acid was added to the solution ( 1 : 1 equivalent / amidine ), followed by ether until crystallization . the crystals were collected by filtration and dried to give 4 , 4 &# 39 ;- ( 1 , 2 - dihydro - 2 - oxo - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), methanesulfonic acid salt ; nmr ( dmso - d 6 ) 9 . 3 ( s , 4 ), 9 . 0 ( s , 4 ), 7 . 8 ( d , 4 ), 7 . 55 ( d , 4 ), 7 . 1 ( m , 2 ), 7 . 0 ( m , 2 ), 5 . 22 ( s , 4 (, 2 . 5 ( s , 6 ) ppm . 3 , 3 &# 39 ;- ( 2 - oxoimidazolin - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), dihydrochloride ; nmr ( dmso - d 6 ) 9 . 35 ( s , 4 ), 9 . 05 ( s , 4 ), 7 . 7 ( m , 4 ), 7 . 6 ( d , 4 ), 4 . 42 ( s , 4 ), 3 . 25 ( s , 4 ), 2 . 5 ( s , 6 ) ppm ; 3 , 3 &# 39 ;- ( 2 - oxo - 4 , 4 , 5 , 5 - tetramethylimidazolin - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), methanesulfonic acid salt ; nmr ( dmso - d 6 ) 9 . 25 ( s , 4 ), 8 . 9 ( s , 4 ), 7 . 73 ( s , 2 ), 7 . 65 ( m , 4 ), 7 . 5 ( t , 2 ), 4 . 35 ( s , 4 ), 2 . 55 ( s , 6 ), 1 . 0 ( s , 12 ) ppm ; 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), methanesulfonic acid salt ; nmr ( dmso - d 6 ) 9 . 25 ( s , 4 ), 8 . 98 ( s , 4 ), 7 . 65 ( d , 2 ), 7 . 5 ( m , 4 ), 7 . 1 - 7 . 3 ( m , 12 ), 4 . 95 ( s , 4 ), 2 . 5 ( s , 6 ) ppm . to 50 % aqueous sodium hydroxide was added 1 , 3 - bis 3 -( amidino ) benzyl !- 1 , 2 - dihydro - 5 - ethyl - 2 - oxo - 1h - imidazole - 4 - carboxylic acid , methyl ester , dihydrochloride ( 0 . 20 g , 0 . 46 mmol ). after stirring for 30 minutes , carbon dioxide ( g ) was bubbled through the solution to neutralize excess hydrochloride and methanol ( 1 ml ) was added . the solid was removed by filtration and the filtrate was concentrated in vacuo . after adjusting the ph to 6 with 3n hydrochloric acid ( aq ), the material was purified by high performance liquid chromatography ( hplc ) to give 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 4 - ethyl - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ), trifluoroacetic acid salt ; nmr ( dmso - d 6 ) 9 . 4 ( s , 4 ), 9 . 35 ( s , 4 ), 7 . 65 ( d , 2 ), 7 . 4 - 7 . 9 ( m , 8 ), 6 . 35 ( s , 1 ), 4 . 95 ( s , 2 ), 4 . 9 ( s , 2 ), 2 . 3 ( q , 2 ), 1 . 05 ( t , 3 ) ppm . to 1 , 3 - bis 3 -( amidino ) benzyl !- 1 , 2 - dihydro - 2 - oxo - 1h - imidazole - 4 , 5 - dicarboxylic acid , diethyl ester , dihydrochloride ( 0 . 1 g , 0 . 20 mmol ) in methanol ( 1 ml )/ water ( 1 ml ) at 0 ° c . was added 50 % aqueous sodium hydroxide ( 2 ml ). after stirring for 2 hours , the ph was adjusted to 1 with 3n hydrochloric acid ( aq ). the resulting material was filtered and dried under vacuum to give 1 , 3 - bis 3 -( amidino ) benzyl !- 1 , 2 - dihydro - 2 - oxo - 1h - imidazole - 4 , 5 - dicarboxylic acid , dihydrochloride ; nmr ( dmso - d 6 ) 9 . 35 ( s , 4 ), 9 . 0 ( s , 4 ), 7 . 7 ( m , 4 ), 7 . 58 ( m , 4 ), 5 . 35 ( s , 4 ) ppm . this example illustrates the preparation of representative pharmaceutical compositions for oral administration containing a compound of the invention , or a pharmaceutically acceptable salt thereof , e . g ., 3 , 3 &# 39 ;- ( 1 , 2 - dihydro - 2 - oxo - 4 , 5 , 6 , 7 - tetrachloro - 1h - benzimidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ): ______________________________________a . ingredients % wt ./ wt . ______________________________________compound of the invention 20 . 0 % lactose 79 . 5 % magnesium stearate 0 . 5 % ______________________________________ the above ingredients are mixed and dispensed into hard - shell gelatin capsules containing 100 mg each , one capsule would approximate a total daily dosage . ______________________________________b . ingredients % wt ./ wt . ______________________________________compound of the invention 20 . 0 % magnesium stearate 0 . 9 % starch 8 . 6 % lactose 79 . 6 % pvp ( polyvinylpyrrolidine ) 0 . 9 % ______________________________________ the above ingredients with the exception of the magnesium stearate are combined and granulated using water as a granulating liquid . the formulation is then dried , mixed with the magnesium stearate and formed into tablets with an appropriate tableting machine . ______________________________________c . ingredients______________________________________compound of the invention 0 . 1 gpropylene glycol 20 . 0 gpolyethylene glycol 400 20 . 0 gpolysorbate 80 1 . 0 gwater q . s . 100 ml______________________________________ the compound of the invention is dissolved in propylene glycol , polyethylene glycol 400 and polysorbate 80 . a sufficient quantity of water is then added with stirring to provide 100 ml of the solution which is filtered and bottled . ______________________________________d ingredients % wt ./ wt . ______________________________________compound of the invention 20 . 0 % peanut oil 78 . 0 % span 60 2 . 0 % ______________________________________ the above ingredients are melted , mixed and filled into soft elastic capsules . ______________________________________e . ingredients % wt ./ wt . ______________________________________compound of the invention 1 . 0 % methyl or carboxymethyl cellulose 2 . 0 % 0 . 9 % saline q . s . 100 ml______________________________________ the compound of the invention is dissolved in the cellulose / saline solution , filtered and bottled for use . this example illustrates the preparation of a representative pharmaceutical formulation for parenteral administration containing a compound of the invention , or a pharmaceutically acceptable salt thereof , e . g ., 3 , 3 &# 39 ;- ( 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ) bis ( methylene )! bis ( benzamidine ): ______________________________________ingredients______________________________________compound of the invention 0 . 02 gpropylene glycol 20 . 0 gpolyethylene glycol 400 20 . 0 gpolysorbate 80 1 . 0 g0 . 9 % saline solution q . s . 100 ml______________________________________ the compound of the invention is dissolved in propylene glycol , polyethylene glycol 400 and polysorbate 80 . a sufficient quantity of 0 . 9 % saline solution is then added with stirring to provide 100 ml of the i . v . solution which is filtered through a 0 . 2μ membrane filter and packaged under sterile conditions . this example illustrates the preparation of a representative pharmaceutical composition in suppository form containing a compound of the invention , or a pharmaceutically acceptable salt thereof , e . g ., 3 , 3 &# 39 ;- 2 , 3 - dihydro - 4 -( 4 - dimethylaminophenyl )- 2 - oxo - 5 - phenyl - 1h - imidazol - 1 , 3 - diyl ! bis ( methylene )! bis ( benzamidine ): ______________________________________ingredients % wt ./ wt . ______________________________________compound of the invention 1 . 0 % polyethylene glycol 1000 74 . 5 % polyethylene glycol 4000 24 . 5 % ______________________________________ the ingredients are melted together and mixed on a steam bath , and poured into molds containing 2 . 5 g total weight . this example illustrates the preparation of a representative pharmaceutical formulation for insufflation containing a compound of the invention , or a pharmaceutically acceptable salt thereof , e . g ., 7 - 3 - 4 -( amidino ) benzyl !- 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ! methyl !- naphthalene - 2 - carboximidamide : ______________________________________ingredients % wt ./ wt . ______________________________________micronized compound of the invention 1 . 0 % micronized lactose 99 . 0 % ______________________________________ the ingredients are milled , mixed , and packaged in an insufflator equipped with a dosing pump . this example illustrates the preparation of a representative pharmaceutical formulation in nebulized form containing a compound of the invention , or a pharmaceutically acceptable salt thereof , e . g ., 7 - 3 - 3 -( amidino ) benzyl !- 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 - yl ! methyl ! naphthalene - 2 - carboximidamide : the compound of the invention is dissolved in ethanol and blended with water . the formulation is then packaged in a nebulizer equipped with a dosing pump . this example illustrates the preparation of a representative pharmaceutical formulation in aerosol form containing a compound of the invention , or a pharmaceutically acceptable salt thereof , e . g ., 7 , 7 &# 39 ;- 2 , 3 - dihydro - 4 , 5 - diphenyl - 2 - oxo - 1h - imidazol - 1 , 3 - diyl ! bis ( methylene )! bis ( naphthalene - 2 - carboximidamide ): ______________________________________ingredients % wt ./ wt . ______________________________________compound of the invention 0 . 10 % propellant 11 / 12 98 . 90 % oleic acid 1 . 00 % ______________________________________ the compound of the invention is dispersed in oleic acid and the propellants . the resulting mixture is then poured into an aerosol container fitted with a metering valve . this assay demonstrates the activity of the compounds of the invention towards factor xa , thrombin and tissue plasminogen activator . the activities were determined as an initial rate of cleavage of the peptide p - nitroanilide by the enzyme . the cleavage product , p - nitroaniline , absorbs at 405 nm with a molar extinction coefficient of 9920 m - 1 cm - 1 . 50 mm trishcl , 150 mm nacl , 2 . 5 mm cacl 2 , and 0 . 1 % polyethylene glycol 6000 , ph 7 . 5 . 1 . human factor xa stock solution : 0 . 281 mg / ml in assay buffer , stored at - 80 ° c . ( working solution ( 2 ×): 106 ng / ml or 2 nm in assay buffer , prepared prior to use ). 2 . human thrombin stock solution : stored at - 80 ° c . ( working solution ( 2 ×): 1200 ng / ml or 40 nm in assay buffer , prepare prior to use ). 3 . human tissue plasminogen activator ( tpa ) ( two chains , sigma ) stock solution : 1 mg / ml , stored at - 80 ° c . ( working solution ( 2 ×): 1361 ng / ml in assay buffer , prepare prior to use ). 1 . s2222 ( fxa assay ) stock solution : 6 mm in dh 2 o , store at 4 ° c . ( working solution ( 4 ×): 656 μm in assay buffer ). 2 . s2302 ( thrombin assay ) stock solution : 10 mm in dh 2 o , stored at 4 ° c . ( working solution ( 4 ×): 1200 μm in assay buffer ). 3 . s2288 ( tpa assay ) stock solution : 10 mm in dh 2 o , stored at 4 ° c . ( working solution ( 4 ×): 1484 μm in assay buffer ). assays were performed in 96 - well microtiter plates in a total volume of 200 μl . assay conducted in final concentration of 50 mm trishcl , 150 mm nacl , 2 . 5 mm cacl 2 , 0 . 1 % polyethylene glycol 6000 , ph 7 . 5 , in the absence or presence of the standard inhibitor or the test compounds and enzyme and substrate at following concentrations : ( 1 ) 1 nm factor xa and 164 μm s2222 ; ( 2 ) 20 nm thrombin and 300 μm s2302 ; and ( 3 ) 10 nm tpa and 371 μm s2288 . concentrations of the standard inhibitor compound in the assay were from 5 μm to 0 . 021 μm in 1 to 3 dilution . concentration of the test compounds in the assay typically were from 10 μm to 0 . 041 μm in 1 to 3 dilution . for potent test compounds , the concentrations used in the factor xa assay were further diluted 100 fold ( 100 nm to 0 . 41 nm ) or 1000 fold ( 10 nm to 0 . 041 nm ). all substrate concentrations used are equal to their k m values under the present assay conditions . assays were performed at ambient temperature . the first step in the assay was the preparation of 10 mm test compound stock solutions in dmso ( for potent test compounds , 10 mm stock solutions were further diluted to 0 . 1 or 0 . 01 mm for the factor xa assay ), followed by the preparation of test compound working solutions ( 4 ×) by a serial dilutions of 10 mm stock solutions with biomek 1000 ( or multiprobe 204 ) in 96 deep well plates as follows : ( a ) prepare a 40 μm working solution by diluting the 10 mm stock 1 to 250 in assay buffer in 2 steps : 1 to 100 , and 1 to 2 . 5 . ( b ) make another five serial dilutions ( 1 : 3 ) of the 40 μm solution ( 600 μl for each concentration ). a total of six diluted test compound solutions were used in the assay . standard inhibitor compound ( 5 mm stock ) or dmso ( control ) went through the same dilution steps as those described above for test compounds . the next step in the assay was to dispense 50 μl of the test compound working solutions ( 4 ×) ( from 40 um to 0 . 164 um ), in duplicate , to microtiter plates with biomek or mp204 . to this was added 100 μl of enzyme working solution ( 2 ×) with biomek or mp204 . the resulting solutions were incubated at ambient temperature for 10 minutes . to the solutions was added 50 μl of substrate working solution ( 4 ×) with biomek or mp204 . the enzyme kinetics were measured at 405 nm , at 10 seconds interval , for five minutes in a thermomax plate reader at ambient temperature . enzyme rates were calculated as mod / min based on the first two minutes readings . the ic 50 values were determined by fitting the data to the log - logit equation ( linear ) or the morrison equation ( non - linear ) with an excel spread - sheet . ki values were then obtained by dividing the ic 50 by 2 . routinely , ki ( factor xa ) values lower than 3 nm were calculated from the morrison equation . compounds of the invention , when tested in this assay , demonstrated the ability to inhibit human factor xa and human thrombin . this assay demonstrates the ability of the compounds of the invention to inhibit prothrombinase . prothrombinase ( ptase ) catalyzes the activation of prothrombin to yield fragment 1 . 2 plus thrombin with meizothrombin as the intermediate . this assay is an end point assay . activity of the prothrombinase is measured by activity of thrombin ( one of the reaction products ) or by the amount of thrombin formed / time based on a thrombin standard curve ( nm vs mod / min ). for determination of ic 50 ( ptase ) of the compounds of the invention , ptase activity was expressed by thrombin activity ( mod / min ). 1 . human factor va ( haematologic technologies inc ., cat # hcva - 0110 ) working solution : 1 . 0 mg / ml in 50 % glycerol , 2 mm cacl 2 , stored at - 20 ° c . 2 . human factor xa ( enzyme res . lab . cat # hfxa1011 ) working solution : 0 . 281 mg / ml in assay buffer ( without bsa ), stored at - 80 ° c . 3 . human prothrombin ( fii ) ( enzyme res . lab ., cat # hp1002 ) working solution : diluted fii to 4 . 85 mg / ml in assay buffer ( without bsa ), stored at - 80 ° c . pcps vesicles ( 80 % pc , 20 % ps ) were prepared by modification of the method reported by barenholz et al ., biochemistry ( 1977 ), vol . 16 , pp . 2806 - 2810 . 10 mg / ml in chloroform , purified from brain , stored - 20 ° c . under nitrogen or argon . 50 mg / ml in chloroform , synthetic 16 : 0 - 18 : 1 palmitoyl - oleoyl , stored at - 20 ° c . under nitrogen or argon . spectrozyme - th ( american diagnostica inc ., cat # 238l , 50 μmoles , stored at room temperature ) working solution : dissolved 50 μmoles in 10 ml dh 2 o . assay buffer : 50 mm trishcl , ph 7 . 5 , 150 mm nacl , 2 . 5 mm cacl 2 , 0 . 1 % peg 6000 ( bdh ), 0 . 05 % bsa ( sigma , fr . v , ria grade ). ( a ) 100 μm pcps ( 27 . 5 μl of pcps stock ( 4 . 36 mm ) diluted to final 1200 μl with assay buffer . ( b ) 25 nm human factor va : 5 . 08 μl of va stock ( 1 mg / ml ) was diluted to final 1200 μl with assay buffer . ( c ) 5 pm human factor xa : dilute xa stock ( 0 . 281 mg / ml ) 1 : 1 , 220 , 000 with assay buffer . prepare at least 1200 μl . combine equal volumes ( 1100 μl ) of each component in the order of pcps , factor va and factor xa . let stand at ambient temperature for 5 to 10 minutes and use immediately , or store in ice ( bring to ambient temperature before use ). 2 . 6 μm human prothrombin ( fii ): dilute 124 μl of fii stock ( 4 . 85 mg / ml ) to final 1400 μl with assay buffer . 3 . 20 mm edta / assay buffer : 0 . 8 ml of 0 . 5m edta ( ph 8 . 5 ) plus 19 . 2 ml assay buffer . 4 . 0 . 2 mm spectrozyme - th / edta buffer : 0 . 44 ml of spth stock ( 5 mm ) plus 10 . 56 ml of 20 mm edta / assay buffer . prepare a working solution ( 5 ×) from 10 mm stock ( dmso ) and make a series of 1 : 3 dilution . compounds were assayed at 6 concentrations in duplicate . prothrombinase reaction was performed in final 50 μl of mixture containing ptase ( 20 um pcps , 5 nm hfva , and 1 pm hfxa ), 1 . 2 um human factor ii and varied concentration of the test compounds ( 5 μm to 0 . 021 μm or lower concentration range ). reaction was started by addition of ptase and incubated for 6 minutes at room temperature . reaction was stopped by addition of edta / buffer to final 10 mm . activity of thrombin ( product ) was then measured in the presence of 0 . 1 mm of spectrozyme - th as substrate at 405 nm for 5 minutes ( 10 second intervals ), at ambient temperature , in a theromax microplate reader . reactions were performed in 96 - well microtiter plates . in the first step of the assay , 10 μl of diluted test compound ( 5 ×) or buffer was added to the plates in duplicate . then 10 μl of prothombin ( hfii ) ( 5 ×) was added to each well . next 30 μl ptase was added to each well , mix for about 30 seconds . the plates were then incubated at ambient temperature for 6 minutes . in the next step , 50 μl of 20 mm edta ( in assay buffer ) was added to each well to stop the reaction . the resulting solutions were then mixed for about 10 seconds . then 100 μl of 0 . 2 mm spectrozyme was added to each well . the thrombin reaction rate was then measured at 405 nm for 5 minutes ( at 10 second intervals ) in a molecular devices microplate reader . thrombin reaction rate was expressed as mod / minute using od readings from the five minute reaction . ic 50 values were calculated with the log - logit curve fit program . the compounds of the invention demonstrated the ability to inhibit thrombinase when tested in this assay . the following assay demonstrates the ability of the compounds to act as anti - coagulants . male rats ( 250 - 330 g ) were anesthetized with sodium pentobarbital ( 90 mg / kg , i . p .) and prepared for surgery . the left carotid artery was cannulated for the measurement of blood pressure as well as for taking blood samples to monitor clotting variables ( prothrombin time ( pt ) and activated partial thromboplastin time ( aptt )). the tail vein was cannulated for the purpose of administering the test compounds ( i . e ., the compounds of the invention and standards ) and the thromboplastin infusion . the abdomen was opened via a mid - line incision and the abdominal vena cava was isolated for 2 - 3 cm distal to the renal vein . all venous branches in this 2 - 3 cm segment of the abdominal vena cava were ligated . following all surgery , the animals were allowed to stabilize prior to beginning the experiment . test compounds were administered as an intravenous bolus ( t = 0 ). three minutes later ( t = 3 ), a 5 - minute infusion of thromboplastin was begun . two minutes into the infusion ( t = 5 ), the abdominal vena cava was ligated at both the proximal and distal ends . the vessel was left in place for 60 minutes , after which it was excised from the animal , slit open , the clot ( if any ) carefully removed , and weighed . statistical analysis on the results was perfomed using a wilcoxin - matched - pairs signed rank test . the compounds of the invention , when tested in this assay , demonstrated the ability to inhibit the clotting of blood . while the present invention has been described with reference to the specific embodiments thereof , it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the invention . in addition , many modifications may be made and equivalents may be substituted without departing from the true spirit and scope of the invention . in addition , many modifications may be made to adapt a particular situation , material , composition of matter , process , process step or steps , to the objective , spirit and scope of the present invention . all such modifications are intended to be within the scope of the claims appended hereto .
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please refer to fig1 and 2 . the coin releasing device of the coin stacking machine of the present invention includes a rotary mechanism and a transmission mechanism locked therewith . the rotary mechanism includes a u - shaped frame 12 and a motor 10 connected therewith . the bottom ends of two lateral walls of the u - shaped frame 12 are bent to the same side , each defining a bent section 14 , 15 . one of the lateral walls is formed with a central opening 13 extending from bottom end up to inner side of plane end edge of the u - shaped frame 12 . the plane face of the u - shaped frame 12 near the opening 13 is disposed with a central through hole and several thread holes for locking the motor 10 and for the motor shaft 11 to pass therethrough . the motor shaft 11 is formed with outer thread . each of four corners of the plane face of the u - shaped frame 12 is formed with thread holes . the transmission mechanism is composed of a base board 30 , two locating blocks 32 , a slide block 45 , a resilient plate 40 and a pushing plate 50 . the base board 30 is an irregular plate body . a lower half of the base board 30 is rectangularly shaped and formed with a central through hole 31 . two sides of the lower half are formed with thread holes around the through hole 31 for locking two locating blocks 32 formed with thread holes 33 . each locating block 32 is formed with a slide channel 34 on one side of the bottom end . multiple thread holes are disposed and spaced from the thread hole for locking the locating block 32 by a certain distance . near the end edge is disposed a slot . a t - shaped plate body 35 projects from the edge of upper side of the rectangular plate body between the outermost thread holes . two sides of the t - shaped plate body 35 are upward bent to form a u - shaped frame . the end section of the u - shaped frame is further inward bent to form a bent section 37 . the two bent sections 37 and the base board 30 are formed with corresponding shaft holes in cooperation with c - shaped latch ring 38 . the inner side of the u - shaped frame is disposed with a stopper plate 39 with an angle . the rear side of the u - shaped frame near the bottom end is transversely disposed with a projecting plate 36 parallel to the base board 30 . the upper end of the projecting plate 36 is disposed with an orifice . the arch resilient plate 40 is disposed in accordance with the length of the u - shaped frame . the rear side of the resilient plate 40 encloses a rotary shaft 41 slightly longer than the resilient plate 40 . near the lower end of the resilient plate 40 is disposed a projecting arm 43 . the end of the projecting arm 43 is disposed with a semiarch recess 42 . a stopper plate 44 having a bent section is disposed under the projecting arm 43 . the center of the slide block 45 is formed with an elliptic slot 46 . the front and rear ends of the slot 46 are disposed with projecting t - shaped stopper plates 47 having a width less than the slide block 45 . adjacent to the end of the front stopper plate 47 is formed thread hole for locking the arch pushing plate 50 having a locking ring 51 . please refer to fig1 and 2 . when assembled , the motor shaft 11 is first passed through the central through hole of the u - shaped frame 12 . then the motor 10 is locked on the u - shaped frame 12 . the arch pushing plate 50 with the locking ring 51 is locked on the slide block 45 and then together therewith placed on the base board 30 with the through hole 46 of the slide block 45 overlaid on the through hole 31 of the base board 30 . the arch pushing plate 50 is also placed between the u - shaped frame . also , the slide channels 34 of the locating block 32 are engaged with two sides of the slide block 45 and secured on the base board 30 by screws . the rotary shaft 41 of the resilient plate 40 is passed through the shaft hole of the bent section 37 of the u - shaped frame . the recess 42 of the end of the projecting arm 43 of the resilient plate 40 is hooked with one end of the spring 54 . the other end of the spring 54 is hooked with the orifice of the u - shaped frame . at this time , the stopper plates 39 of the resilient plate 40 are overlaid on the stopper plates 44 of the u - shaped frame . the motor shaft 11 is then passed through the base board 30 in the through hole 46 of the slide block 45 and then locked with the slide block 45 . a fitting ring 53 is fitted around the screw , which locks the base board 30 and the u - shaped frame 12 so as to space the base board from the u - shaped frame . then a transmission plate 49 with a shaft hole 48 at one end is fitted on the motor shaft 11 and tightened by a nut 52 to complete the assembly . as shown in fig1 in normal state , the slide block 45 is slided to rear side , making the two arch resilient plates 40 and the arch pushing plate 50 form a stacking cylinder . in the case of bingo , coins are counted by a counter and dropped and stacked in the stacking cylinder . when the coins drop into the stacking cylinder , the motor 10 is activated and the motor shaft 11 is driven . at this time , the transmission plate 49 is rotated about the motor shaft 11 . when the transmission plate 49 rotates through 1 / 4 circle , the slide block 45 is moved forward along with the transmission plate 49 ( as shown in fig3 ) and the arch pushing plate 50 is also moved forward to slightly stretch open the two arch resilient plates 40 . further , as shown in fig4 when the transmission plate 49 is rotated through 1 / 2 circle , the arch pushing plate 50 and the resilient plates 40 are pushed to the end to make the coins slide down to stack the coins . when the transmission plate 49 is continuously rotated , the slide block 45 is moved back and the resilient plates 40 are restored to home position by the resilient force of the spring 54 . the present invention is widely applicable to game machines to tidily stack coins and release the same . it should be noted that the above description and accompanying drawings are only used to illustrate one embodiment of the present invention , not intended to limit the scope thereof . any modification of the embodiment should fall within the scope of the present invention .
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a circuit 10 for sensing temperature and process variation is shown in fig1 suitable for manufacturing as an integrated circuit using conventional cmos integrated circuit processes . a voltage controlled oscillator ( vco ) 12 has an input coupled to power supply conductor 14 operating a positive power supply potential v dd such as 5 . 0 volts . vco 12 may comprise an odd number of serially coupled controllable inverter stages with an output of the last inverter stage coupled to an input of the first inverter stage . divide - by - 2 circuit 16 reduces the v osc frequency to v osc / 2 for application to a first opposite phase clock generator 18 for providing non - overlapping , opposite phase xclk and yclk clock signals operating an one - half the output frequency of vco 12 . with its input connected to power supply potential v dd , vco 12 oscillates at its maximum output frequency v osc given existing process and temperature conditions and power supply potential . under best case conditions vco 12 may operate at 320 mhz , while under worst case conditions vco 12 may operate at 100 mhz . even after silicon processing , the ic retains certain inherent tracts due to process variables such as gate length , junction depth , gate oxide thickness and threshold voltage which makes the output frequency response of vco 12 unpredictable . a key feature of the present invention is the ability to measure and quantify the response of vco 12 operating dependent on process , temperature and power supply level variation . once temperature and process variation is measured and quantified under real operating conditions , it is possible to compensate another input signal which is presumably experiencing similar variation . a digital input signal - refclk operating at say 5 mhz is applied at a second opposite phase clock generator 20 for providing non - overlapping , opposite phase vx and vy clock signals . the duration of the vx and vy clock signals is 200 ns . the vy clock signal processes through down detector 24 and produces a logic one down -- pulse at each zero - going transition of the vy clock signal . the pulse width of the down -- pulse is one cycle of the v osc / 2 clock signal . the down -- pulse signal is applied at the reset ( r ) input of shift register 26 to reset it at each zero - going transition of the vy clock signal . down detector 24 and shift register 26 receive xclk and yclk clock signals . the down -- pulse signal is also inverted by inverter 28 and &# 34 ; anded &# 34 ; with the vx clock signal through and gate 30 for application to the data ( d ) input of shift register 26 . shift register 26 contains sixteen 1 - bit cells with outputs f1 , f2 through f12 corresponding to the fifth through the sixteenth bit cells . the first four bit cells are used as buffers for the fifth bit cell . data shifts from the data input of shift register 26 into the first data cell then to the second data cell through the sixteenth data cell at each xclk and yclk clock cycle . the number of logic ones clocked into shift register 26 by the xclk and yclk clock signals , which are dependent on temperature and process , is a quantified measure of that temperature and process . buffer circuit 32 buffers outputs f1 - f12 upon receiving the vy clock signal and provides outputs f1 - f12 . compensation circuit 34 makes adjustments to an input signal in response to outputs f1 - f12 for providing an output signal with compensation for temperature and process variation . opposite phase clock generator 18 is shown in fig2 where the v osc / 2 signal is applied through inverters 40 , 42 , 44 and 46 to a first input of and gate 48 . the output of inverter 40 is coupled through inverters 50 and 52 to a first input of and gate 54 . the output of and gate 48 provides the xclk clock signal as applied through inverter 56 to a second input of and gate 54 . likewise , the output of and gate 54 provides the yclk clock signal as applied through inverter 58 to a second input of and gate 48 . the output of inverter 44 at node 60 is coupled through inverter 62 to the input of inverter 52 , while the output of inverter 50 at node 64 is coupled through inverter 66 to the input of inverter 46 . when the v osc / 2 signal switches to logic zero , the output of inverter 40 goes to logic one . inverter 50 attempts to switch node 64 to logic zero before node 60 switches to logic one because node 64 is only two inverter delays away from the v osc / 2 signal while node 60 is three inverter delays away . however , the transition of node 64 to logic zero is slowed by inverter 62 because node 60 is still logic zero two inverter delays after the v osc / 2 signal changes to logic zero . inverter 62 acts to hold node 64 at logic one until the output of inverter 44 changes state . a similar scenario follows when the v osc / 2 signal switches to logic one . thus , the transition of inverters 46 and 52 overlap 180 ° out - of - phase and cross approximately at the 50 % mark , thereby overcoming the delay difference imposed by an unequal number of inverters between the v osc / 2 signal and nodes 60 and 64 . when the output of inverter 46 is logic zero , the xclk clock signal at the output of and gate 48 goes to logic zero . and gate 54 receives logic ones from the outputs of inverters 56 and 52 for providing a logic one yclk clock signal . when the output of inverter 52 goes to logic zero , the yclk clock signal goes to logic zero . and gate 48 receives logic ones from the output of inverters 46 and 58 for providing a logic one xclk clock signal . hence , the xclk and yclk clock signals are non - overlapping and opposite phase switching at substantially the 50 % mark and operating at the frequency of the v osc / 2 signal . turning to fig3 opposite phase clock generator 20 is shown in further detail where the refclk signal is inverted by inverter 70 and applied at a first input of and gate 72 which provides the vy clock signal at its output . the input signal refclk is also applied at a first input of and gate 74 for providing the vx clock signal at its output . the vx clock signal is complemented by inverter 76 and applied at a second input of and gate 72 . the vy clock signal is complemented by inverter 78 and applied at a second input of and gate 74 . when the input signal refclk is logic zero , the vx clock signal at the output of and gate 74 goes to logic zero . and gate 72 receives logic ones from the outputs of inverters 70 and 76 for providing a logic one vy clock signal . when the input signal refclk goes to logic one , the vy clock signal goes to logic zero because of inverter and gate 74 receives logic ones from the input signal refclk and the output of inverter 78 for providing a logic one vx clock signal . hence , the vx and vy clock signals are non - overlapping and opposite phase . in fig4 down detector 24 operates in response to the xclk and yclk clock signals and produces a logic one down -- pulse upon detecting a zero - going transition of the vy clock signal . when the vy clock signal is logic one , the output of inverter 80 is logic zero and the down -- pulse signal at the output of and gate 82 is logic zero . the logic one vy clock signal passes through transistor 84 when the xclk clock signal is logic one . inverter 86 complements the vy clock signal and transistor 88 passes the complemented vy clock signal when the yclk clock signal becomes logic one . the vy clock signal returns to logic one at the output of inverter 90 and passes through transistor 92 during the following high state of the xclk clock signal . after two more inversions through inverters 94 and 96 , the logic one vy clock signal arrives at and gate 82 . the down -- pulse signal remains logic zero because of the logic zero from inverter 80 . when the vy clock signal transitions to logic zero , the output of inverter 80 goes to logic one and the down -- pulse signal at the output of and gate 82 switches to logic one because the output of inverter 96 is still logic one . after one full period of the xclk clock signal ( logic one - to - logic zero - to - logic one ), the logic zero vy passes through transistors 84 , 88 and 92 and inverters 86 , 90 , 94 and 96 and arrives at and gate 82 . the down -- pulse signal returns to logic zero . the vy clock signal must switch back to logic one to preset the output of inverter 96 to logic one before the next logic one down -- pulse signal may occur . thus , the down -- pulse signal goes to logic one for approximately one period of the xclk clock signal at each zero - going transition of the vy clock signal . returning to fig1 the vx signal is applied at the first input of and gate 30 , while the second input of the same received an inverted down -- pulse . shift register 26 receives data from the output of and gate 30 and shifts the data along the sixteen 1 - bit locations in response to the xclk and yclk clock signals . the master - slave operation of shift register 26 requires non - overlapping , opposite phase xclk and yclk clock signals , wherein one clock transition latches the data into the master section while a subsequent clock transfers the data to the output of the slave section . a logic one down -- pulse signal resets all bit cells of shift register 26 to logic zero . when the vx clock signal is logic one and the output of inverter 28 is logic one , the data input of shift register 26 receives a logic one . the xclk and yclk clock signals begin shifting logic ones along shift register 26 during the high state of the vx clock signal . recall the v osc / 2 signal is one - half the output frequency of vco 12 . the vx and vy clock periods are 200 ns , and the high state of the vx clock signal is 100 ns . when down detector 24 detects a zero - going vy clock signal , shift register 26 is momentarily reset with all bit locations at logic zero . since vx clock signal is logic one when vy clock signal is logic zero , shift register 26 begins shifting in logic ones as soon as the down -- pulse returns to logic zero . when the vx clock signal returns to logic zero , and gates 98 and 99 block further xclk and yclk clock signals . shift register 26 stops shifting input data from and gate 30 . if vco 12 operates at 100 mhz because of worst case temperature and process conditions , then xclk and yclk clock signals operate at 50 mhz with 20 ns periods . only output f1 is logic one because shift register 26 receives five xclk and yclk clock signals during the 100 ns high state of the vx clock signal ( 5 × 20 ns = 100 ns ). the first four xclk and yclk clock cycles fill the first four bits cells of shift register 26 but have no output . the fifth xclk and yclk clock cycle shifts a logic one into the fifth data cell and switches output f1 to logic one indicating vco 12 is operating at 100 mhz . if vco 12 operates at 320 mhz in response to best case temperature and process , then xclk and yclk operate at 160 mhz with 6 . 25 ns periods . outputs f1 - f12 are all logic ones because shift register 26 receives sixteen xclk and yclk clock signals during the 100 ns high state of the vx clock signal ( 16 × 6 . 25 ns = 100 ns ). the fifth through the sixteen bit locations of shift register 26 represent 20 mhz steps . thus , circuit 10 measures and quantifies the actual operating characteristics of vco 12 as a function of temperature and process variation . the fifth bit cell ( output f1 ) corresponds to a 100 mhz vco output frequency with 20 mhz steps to the sixteen bit cell ( output f12 ) which represents a 320 mhz vco output frequency . it is understood that shift register may be expanded to achieve greater precision of the actual frequency of vco 12 . buffer circuit 32 is shown is fig5 including twelve buffer blocks . the f1 buffer block is shown in detail and the remaining buffer blocks follow a similar construction . the vy clock signal is applied at a first input of and gate 100 , while a second input of the same receives output f1 . the reset signal is applied through inverter 102 to a third input of and gate 100 . the output of and gate 100 is coupled to the base of transistor 104 . the drain of transistor 104 receives power supply potential v dd , while the source of transistor 104 is coupled through inverters 106 and 108 for providing output f1 . transistor 110 has a base receiving the reset signal , a drain coupled to the input of inverter 106 and a source coupled to power supply conductor 112 operating at ground potential . assume that the output frequency of vco 12 is such that outputs f1 - f2 are logic one and outputs f3 - f12 are logic zero . an active logic one reset signal turns on transistor 110 and pulls the input of inverter 106 to logic zero to reset outputs f1 - f12 to logic zeroes . when the vy clock signal is logic one and output f1 is logic one , the output of and gate 100 goes to logic one ( assuming reset deactivated ) and turns on transistor 104 . output f1 goes to logic one . likewise , output f2 becomes logic one because output f2 is logic one . outputs f3 - f12 remain at logic zero when the vy clock signal is logic one because outputs f3 - f12 are logic zero . to this point , temperature and process sensing circuit . 10 has determined the actual operating frequency of vco 12 . outputs f1 - f12 have been set accordingly . it is understood that devices other than a vco , e . g . a crystal oscillator , may provide similar quantifiable data regarding temperature and process conditions . a key feature of the present invention is using that information to compensate or adjust the input signal to reflect the actual operating conditions . assume that the input signal as applied to compensation circuit 34 operates in a critical timing path . if , for example , the hold time of the input signal is spec &# 39 ; d at 5 ns , it is possible for that hold time to vary between 5 and 20 ns depending on whether the temperature and process yields a best case or worst case scenario . an embodiment of compensation circuit 34 is shown in fig6 to correct for timing error caused by process and temperature variation . outputs f1 - f12 are coupled to thirteen exclusive - or gates 118 - 126 as shown . one input of exclusive - or gate 118 receives a logic one from power supply conductor 14 while one input of exclusive - or gate 126 receives a logic zero from power supply conductor 112 . with output f1 at logic one , the output of exclusive - or gate 118 is logic zero . likewise , the output of exclusive - or gate 120 is logic zero because outputs f1 and f2 are logic one . the output of exclusive - or gate 122 is logic one because output f2 is logic one and output f3 is logic zero . with outputs f3 - f12 at logic zero , the outputs of exclusive - or gates 122 - 126 are logic zero . thus , the configuration provides one and only one logic one from the outputs of exclusive - or gates 118 - 126 for any given combination of logic states from outputs f1 - f12 . an active logic one reset signal is inverted by inverter 128 and produces logic zeroes at the inputs of thirteen nand gates 130 - 138 to disable and reset compensation circuit 34 . when the reset signal returns to logic zero , the logic one from exclusive - or gate 122 forces the output of nand gate 134 to logic zero . the outputs of other nand gates 130 - 136 ( except gate 134 ) are logic one . thirteen inverters 140 - 148 provide complementary outputs of nand gates 130 - 138 . thirteen transmission gates 150 - 158 receive the outputs of nand gates 130 - 138 at their inverted inputs , respectively , and complemented outputs of the same at their non - inverted inputs . transmission gates 150 - 158 may comprise back - to - back p - channel and n - channel transistors ( not shown ) with their drains and sources coupled together , as is well known . the inverted input is the gate of the p - channel transistor , and the non - inverted input is the gate of the n - channel transistor . with the output of nand gate 134 at logic zero , only transmission gate 154 is enabled . the input signal is delayed the appropriate length of time to compensate for temperature and process variation by enabling the corresponding transmission gate to provide the same 2 . 0 ns delay independent of temperature and process conditions . it is important that delay circuits 160 - 168 experience the same temperature and process and power supply potential variation as vco 12 . that is , the inverters in delays circuits 160 - 168 must have same inherent delay and speed as a function of temperature and process as the inverters in vco 12 . thus , for the example of a 5 ns hold - time requirement , under worst case processing , very little if any additional delay is needed , i . e . transmission gate 150 is enabled to activate delay circuit 160 . as process and temperature conditions improve , more delay is necessary to achieve the desired 5 ns hold - time , i . e ., delay circuit 164 activated in response to logic one outputs f1 - f2 as described above . for absolute best case processing , transmission gate 158 is enabled by output f12 to activate delay circuit 168 and slow down the input signal to achieve the desired 5 ns hold - time for the output signal . an alternate embodiment of compensation circuit 34 is shown in fig7 to correct for switching thresholds variation after determining the nature of the process and temperature . exclusive - or gates 170 - 194 operate as described for exclusive - or gates 118 - 126 . or gate 198 provides a logic one to nand gate 208 when any one of exclusive - or gates 170 - 176 goes to logic one . likewise , or gate 202 provides a logic one to nand gate 204 when any one of exclusive - or gates 178 - 182 goes to logic one . or gate 206 provides a logic one to nand gate 208 when any one of exclusive - or gates 184 - 188 goes to logic one , while or gate 210 provides a logic one to nand gate 212 when any one of exclusive - or gates 190 - 194 goes to logic one . inverters 214 - 222 complement the output signals of nand gates 200 , 204 , 208 and 212 , respectively . or gates 198 , 202 , 206 and 210 combine the output signals of exclusive - or gates 170 - 194 into four groups . it is possible to eliminate or gates 198 , 202 , 206 and 210 by including matching nand gates for each exclusive - or gate and correspondingly more transmission gates and buffers . in a similar manner as described for compensation circuit 34 in fig6 only one of or gates 198 , 202 , 206 and 210 produces a logic one at its output . again assuming outputs f1 and f2 are logic one and outputs f3 - f12 are logic zero , exclusive - or gate 174 goes to logic one and the output of nand gate 200 goes to logic zero when the reset signal is logic one following inverter 222 . transmission gate 224 is enabled to activate buffer 226 . transmission gates 228 , 230 and 232 are disabled thereby blocking buffers 234 , 236 and 238 , respectively . it is well known that temperature and process conditions affect switching thresholds . worst case processing causes the widest range of switching thresholds , while best case processing results in the narrowest range of switching thresholds . the difference between buffers 226 , 234 , 236 and 238 is the sizing of the internal drive transistors ( not shown ) and associated switching thresholds . buffer 226 may be sized to switch to logic zero at 0 . 8 volts and to logic one at 2 . 0 volts if driving ttl logic . similarly , buffers 234 , 236 and 238 switch to logic zero at 0 . 8 volts and to logic one at 2 . 0 volts but are sized differently to compensate for process and temperature variation . upon detecting worst case processing , or near worst case , one or more of outputs f1 - f3 are logic one . transmission gate 224 is enabled to activate buffer 226 with its geometry to achieve the desired switching thresholds . under typical case processing , outputs f1 - f3 are logic one and one or more of outputs f4 - f6 are logic one . transmission gate 228 is enabled to activate buffer 234 with its geometry to achieve the desired switching thresholds . alternately , outputs f1 - f6 may be logic one and one or more of outputs f7 - f9 may be logic one to enable transmission gate 228 and activate buffer 236 . finally under best case processing , or near best case , outputs f1 - f9 are logic one and one or more of outputs f10 - f12 are logic one . transmission gate 232 is enabled to activate buffer 238 with its geometry to achieve the desired switching thresholds . controlling switching thresholds works for input buffers and output buffers arrangements . while specific embodiments of the present invention have been shown and described , further modifications and improvements will occur to those skilled in the art . it is understood that the invention is not limited to the particular forms shown and it is intended for the appended claims to cover all modifications which do not depart from the spirit and scope of this invention .
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the figures and the following description relate to preferred embodiments by way of illustration only . it should be noted that from the following discussion , alternative embodiments of the structures and methods disclosed herein will be readily recognized as viable alternatives that may be employed without departing from the principles of what is claimed . fig1 is a logical diagram of a computing architecture and / or methodology described in accordance with an embodiment of the invention . consider an optimization problem being solved . for example , the problem might be : given a set of package delivery drivers with their locations , a set of package delivery destinations , and a set of possible routes between drivers and destinations , what is the set of routes that the drivers can take that will allow all packages to be delivered in the shortest amount of time ? this is a big data problem ( in the domain of graph analytics ) whose solution could well be sought using a distributed computing system and big data compute framework . however , quantum processing devices are potentially very efficient at solving these types of problems . throughout this document , a “ quantum processing device ” may be one or more physical devices that perform processing especially based upon quantum effects , one or more devices that act in such a way , one or more physical or virtual simulators that emulate such effects , or any other devices or simulators that may reasonably be interpreted as exhibiting quantum processing behavior . thus , it might be ideal to solve the entire problem on such a quantum computer . in order to expand the scale of the problem being solved , one way to solve this computational task is to partition the task into smaller sub - problems , some of which are solved on quantum processing devices and some of which are solved on classical distributed computers . referring to the computing system in fig1 , when the end user 110 enters the problem 120 , the big data compute framework 130 distributes pieces of the problem ( for instance , solving the delivery scheduling problem for particular cities rather than an entire state ) to the quantum processing devices 190 a - n as well as to classical distributed computers 150 available to the end user . in this example , the big data computer framework 130 functions as a master machine , and the quantum processing devices 190 and conventional computers 150 function as worker machines . quantum processing devices 190 are employed via an api 170 ( see e . g . fig2 ) in order to solve some or all of these sub - problems , or the entire problem . solutions 187 from the quantum processing devices 190 are returned through the api in an appropriate form 183 for the big data compute framework 130 , allowing seamless execution of the problem in a heterogeneous environment involving both classical distributed computers 150 as well as quantum processing devices 190 . the end result is a solution to the entire delivery scheduling problem , presented in a desired format 183 to the end user . in the architecture of fig1 , an end user 110 describes a computational task 120 , and then loads this problem 120 into a big data compute framework 130 . the big data framework 130 has been extended ( e . g ., via a plugin interface ) with an api 170 and libraries 160 a - n . one or more domain - specific libraries ( such as for machine learning 160 a or for graph analytics 160 b ) may be used by the big data compute framework 130 to perform special operations ( e . g ., specially optimized routines or simplified , more specific versions of general - purpose routines ). the libraries 160 aid or improve the big data compute framework &# 39 ; s ability to solve computational tasks using quantum processing devices 190 . results of library function calls are passed to the provided api 170 , which may also be directly called by the big data compute framework 130 . the api 170 then performs a series of steps in order to execute some or all of the given computational task on one or more quantum processing devices 190 . this involves converting the task to a quantum data model , such that the task may be readily solved on a variety of quantum processing devices and architectures 190 . when the quantum processing devices 190 return solutions 187 to the specified tasks , the provided api 170 returns these solutions in a format 183 amenable to the big data compute framework 130 or in a format that can be converted into a form amenable to the big data compute framework 130 through another software . the distributed computing cluster 150 may directly or indirectly interface with the provided api 170 in order to , for example , communicate information about currently running tasks . one or more quantum processing devices 190 may be used within the architecture , just as any classical computing cluster 150 ( which may be comprised of multiple clusters that the end user can access ) can be used within the architecture . fig2 is a logical diagram of an api described in accordance with one or more embodiments of the invention . in this example , the api 170 includes software 210 that allows integration with various big data compute frameworks ( e . g ., as a plugin for apache spark ). the api 170 also has a manual user interface 220 that allows interaction with the api 170 without a big data compute framework ( and enables development of interfaces to additional big data compute frameworks ). in one embodiment of the invention , the provided api 170 automatically determines 230 how to partition problems into smaller pieces amenable to solution on quantum computing devices 190 , for example , by applying specially adapted classical problem decomposition heuristics for traveling salesman - like problems when the input problem is determined to resemble a traveling salesman problem . in another embodiment , the end user may manually specify some or all of the instructions on how to decompose or partition a larger computational task into smaller pieces that fit within the memory of a quantum computing device . the api 170 also includes an internal task scheduler 240 that is tuned for the many distinguishing characteristics of quantum computing devices . the api 170 also includes a module 250 for conversion of an input computational task into a realization of a quantum data model . this conversion may be fully manual , partially automated , or fully automated , in different embodiments . the realization of the task using quantum data model is a representation of the task in a manner that makes the problem amenable to solution on a particular quantum processing device 190 . for example , in one embodiment , this module might involve automatic conversion of an arbitrary optimization problem into a quadratic unconstrained binary optimization ( qubo ) problem , for solution on a d - wave quantum processing device ( which is largely designed for solving that specific type of problem ). another feature of the api 170 involves a suite of software algorithms and routines 260 for optimizing the realization of the computational task upon the quantum data model for execution upon a particular quantum processing device . this optimization may be fully manual , partially automated , or fully automated , in different embodiments . following the above example , the api may know that one quantum computer has a different architecture than another quantum computer . using this knowledge , the api 170 can tune particular aspects of the problem , the underlying data model , settings of the solution method , etc . so that the task is solved in an optimal or near - optimal way on the quantum processing device . finally , the api 170 includes interfaces 270 to various quantum processing devices . these may include adiabatic quantum computing devices , quantum annealing devices , gate - model quantum computing devices , or other processing devices that use quantum effects in order to obtain solutions to computational problems . this component 270 of the api is capable of both distributing tasks to various quantum processing devices as well as reading returned solutions from the devices . fig2 is just one example of an api 170 . other examples may have less than all the modules 210 - 270 shown in fig2 and / or may have additional modules not shown . typically , the api 170 will include an interface 210 to the master machine , an interface 270 to the quantum processing devices , and some sort of api stack ( modules 220 - 260 in this example ) between the two interfaces . fig3 - 6 are logical diagrams of more example computing architectures and / or methodologies described in accordance with additional embodiments of the invention . in the computing system of fig3 , no classical distributed computers ( 150 in fig1 ) are used . the big data compute framework 130 is used solely in conjunction with quantum processing devices 190 via the provided api 170 and libraries 160 . in the computing system of fig4 , none of the domain - specific libraries ( 160 in fig1 ) are used by the big data compute framework 130 or provided api 170 when performing the given computational tasks . this architecture demonstrates that the api and associated integrations may be used without specific use of the provided domain - specific libraries . in the computing system of fig5 , the provided api 170 and libraries 160 are used to solve a computational problem without use of a big data compute framework ( 130 in fig1 ) or other distributed computing resources ( 150 in fig1 ). in this example , a master machine 530 controls the worker quantum processing devices 190 . this example demonstrates a framework for distributed computation across a set of quantum processing devices 190 without using the integration provided for big data compute frameworks . in the computing system of fig6 , quantum processing simulators 690 are used rather than quantum processing devices 190 . quantum processing simulators 690 are generally virtual quantum processing devices that execute virtually within a classical computing device . quantum processing simulators 690 may be used , for example , to execute quantum algorithms when quantum processing hardware is not available to the end user . since quantum processing simulators 690 behave in the same way as physical quantum processing devices 190 , the api 170 may interoperate with quantum processing simulators 690 or physical quantum computing devices 190 , or a combination of the two . the approaches described above may be used to solve various computational problems and tasks , in whole or in part . in one embodiment , partial components of a larger computational task are executed by the quantum processing devices . in another embodiment , the entire computational task is executed by the quantum processing devices . additionally , while these examples use two specific domain - specific libraries 160 a , b , there is no restriction on what domains may admit useful libraries 160 for inclusion into this computing framework . furthermore , while the drawings display a single computational problem 120 , that computational problem or task may in fact be comprised of many computational problems or tasks that the end user may wish to execute in serial or in parallel . in yet another embodiment shown in fig7 , the computing architecture is composed of a high - level api and library , a quantum data model 765 , and a set of software processes to prepare this data model for computation on a quantum processing device 190 . in this embodiment , the high - level api and library are built as an extension to the existing parallel framework api . this extended api gives the programmer simple control of when to initiate use of the software processes to generate a quantum computational input . in fig7 , the library calls are available at the level of the software blocks 160 a - n titled “ machine learning ” “ graph analytics ” and “ other apps ”. these are application areas that could make use of the quantum processing device as a co - processor . in this embodiment , the existing large scale software framework partitions parallel workloads to worker machines as usual . this is modeled in fig7 by the blocks titled “ big data compute framework ” 130 . internally , the architecture involves modifying the master ( controlling ) machine to contain a quantum data model . in fig7 , the data model is represented by the block 765 titled “ optimization problem .” this data model 765 is stored on the master machine during computation and is used to aggregate computation results from all the worker machines in the system . in this embodiment , the master machine occasionally uses the quantum data model 765 to generate appropriate input for the quantum processing device 190 . a common paradigm in many computer algorithms is to generate quantum inputs ( effectively calling the quantum processing device to perform computation ) once per algorithm iteration . the quantum processing input is generated by running the data model through software processes that automate the generation of the appropriate input for the quantum processing device . in fig1 , these software processes are represented by the flow of data from the “ optimization problem ,” through the “ problem -& gt ; bo / qubo ” and “ operating system ” blocks , and to the “ dwave ” block 190 ( an example of a quantum processing device ). results of computation are then read back from the quantum processing device 190 via the same channel . the results are used to update the quantum data model . finally , the distributed software framework is used to organize the updating of the worker machines with the updated computation model data . although the detailed description contains many specifics , these should not be construed as limiting the scope of the invention but merely as illustrating different examples and aspects of the invention . it should be appreciated that the scope of the invention includes other embodiments not discussed in detail above . for example , one may include multiple large - scale software frameworks in various configurations in the architectures described above . various other modifications , changes and variations which will be apparent to those skilled in the art may be made in the arrangement , operation and details of the method and apparatus of the present invention disclosed herein without departing from the spirit and scope of the invention as defined in the appended claims . therefore , the scope of the invention should be determined by the appended claims and their legal equivalents .
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hereinafter , exemplary embodiments of the present invention will be more fully described with reference to the accompanying drawings . this invention may , however , be embodied in many different forms and should not be construed as limited to the embodiments set forth herein ; rather , these embodiments are provided so that this disclosure will be thorough and complete , and will fully convey the scope of the invention to those skilled in the art . like reference numerals refer to similar or identical elements throughout . fig2 is a perspective view illustrating an apparatus for protecting a pin pad module according to one embodiment of the present invention ; fig3 is a plan view illustrating the rear of a bezel base according to one embodiment of the present invention ; fig4 is a partial perspective view illustrating an apparatus for protecting a pin pad module according to one embodiment of the present invention ; fig5 is a sectional view illustrating an apparatus for protecting a pin pad module according to one embodiment of the present invention ; fig6 is a partially enlarged view of fig5 ; fig7 is a view illustrating the upper surface of a key scan board according to one embodiment of the present invention ; fig8 is a view illustrating the lower surface of a key scan board according to one embodiment of the present invention ; and fig9 is a view illustrating a process of protecting a pin pad module according to one embodiment of the present invention . as illustrated , in order to achieve the above object , an apparatus for protecting a pin pad module according to one embodiment of the present invention comprises a key module 100 including pluralities of buttons 111 and a bezel base 120 wherein the buttons 111 are provided substantially on the front of the key module 100 and pluralities of protruded first rods 122 are formed on the rear of the key module 100 ; a first switching portion 126 for the button 111 of the key module 100 and a second switching point 127 for the first rod 122 of the bezel base 120 ; and a front membrane 125 for transmitting the pressing force of the button 111 and the first rod 122 through the first switching portion 126 and the second switching portion 127 . furthermore , the button 111 provided substantially on the front of the key module 100 is inserted into a front bracket 114 to be close to a protection rubber 113 , the rear of the button 111 passes through the rear of the front bracket 114 tightly , and the protection pad 116 is provided on the rear of the protection rubber 113 , wherein the front bracket 114 is formed into a lattice . at this time , the protection rubber 113 prevents water from penetrating through the space between the button 111 and the front bracket 114 , and the protection pad 116 prevents water from penetrating into the bezel base 120 . furthermore , a transmitting member 118 is positioned substantially at the rear of the protection pad 116 and at the front of the bezel base 120 , for transmitting the pressing force . a switching member 119 is positioned substantially at the rear of the transmitting member 118 , for transmitting the pressing force to the first switching portion 126 of the front membrane 125 through the bezel base 120 . at this time , the button 111 and the front bracket 114 constituting the outer surface of the key module 100 are formed using metal plates , and form a protection wall against the external intrusion . therefore , components provided inside of the key module may be protected . moreover , the bezel base 120 is formed by injecting plastic into an injection module , and one of pluralities of first rods 122 formed on the rear of the bezel base 120 is positioned on one side at the center of the bezel base 120 and another is positioned on the other side at the center thereof 120 , spaced apart by predetermined interval . at this time , the bezel base 120 is positioned at the rear of the transmitting member 118 , and the rear of the button 111 passes through the protection pad 116 , thereby pressing a groove 124 formed on the front of the transmitting member 118 , and then passes through a hole formed on the bezel base 120 , and coupled with the switching member 119 , thereby pressing the first switching portion 126 of the front membrane 125 . furthermore , a key scan board 130 is positioned at the rear of the front membrane 125 , and pluralities of first contacts 132 for connecting the first switching portion 126 and pluralities of second contacts 133 for connecting the second switching portion 127 are positioned on the front of the key scan board 130 . and pluralities of third contacts 134 are further positioned on the rear of the key scan board 130 . at this time , the first and the second switching portions 126 and 127 of the front membrane 125 are formed using a elastic dome , for elastically receiving the pressing force . an electric conductor such as a carbon board is applied on the lower surface of the elastic dome , and electrically connects the first and the second contacts 132 and 133 positioned on the key scan board 130 . furthermore , a plurality of second contacts 133 positioned on the front of the key scan board 130 are provided adjacent to a screw hole 136 for a screw for coupling the key module 100 and the rear case 180 . when the screw is removed , the pressing force of the first rod 122 for the second contact 133 , or the location thereof changes . more particularly , a pair of screw holes 136 for a screw for coupling the key module 100 and the rear case 180 is formed on a vertical line passing the center portion . the second contact 133 is positioned between the screw holes 136 . thus , in case that the screw is removed , the location or pressing force of the first rod 122 for the second contact 133 changes . the electric circuit section 170 detects the change of the voltage or electric current of the second contact 133 and makes information stored in the memory unreadable immediately . furthermore , a rear membrane 140 including a third switching portion 142 for connecting the third contact 134 is positioned at the rear of the key scan board 130 . an electric circuit section 170 including a memory is positioned at the rear of the rear membrane 140 , for performing logic calculation , wherein the memory first receives a value in accordance with connection of contacts of the key scan board 130 and later stores the same . the rear case 180 is positioned at the rear of the electric circuit section 170 , and the rear case 180 includes a second rod 182 for the third switching portion 142 included in the rear membrane 140 and is coupled with the bezel base 120 of the key module 100 . moreover , third contacts 134 positioned on the rear of the key scan board 130 are formed of a pair and positioned on a vertical line passing the center portion . the arrangement of the third contacts 134 like above is to detect that the rear case 180 is removed from the bezel base 120 with the minimum contacts . accordingly , in case that the rear of the rear case 180 moves away from the rear of the bezel base 120 , even a little , the pressing force of the second rod 182 for the third switching portion 142 of the rear membrane changes and the electric current or the voltage changes at the third contact 134 connected to the third switching portion 142 of the rear membrane 140 . furthermore , a circuit connector 172 of the electric circuit section 170 is provided on a vertical line passing through the third contacts 134 and a board connector 135 , so that the board connector 135 , for transmitting the states of connections at contacts of the key scan board 130 , passes through the third contacts 134 . the arrangement of the board connector 135 like above is to prevent the board connector 135 from getting access to the third contacts 134 and prevent a hacker from applying electric conduction liquid ( electric conduction ink ) to the third contact to make it as same as the first state of connection thereof 134 . in case that the hacker attempts to put electric conduction liquid into the terminal of the circuit connector 172 in a state where the circuit connector 172 is coupled with the board connector 135 , the arrangement of the board connector 135 like above is to prevent an instrument including electric conduction liquid from getting access to the circuit connector 172 by the second rod 182 for the third contact 134 . in addition , the third contact 134 includes a first terminal 134 a and a second terminal 134 b , which are electrically connected by the second rod 182 , and the third contact 134 further includes a third terminal 134 c which is formed closely adjacent to the first terminal 134 a and the second terminal 134 b , and the electric circuit section 170 makes the stored information unreadable in accordance with the connection between the second and the third terminals 134 a and 134 b . furthermore , although it is not illustrated , the second contact 133 also includes a first terminal and a second terminal which are electrically connected by the first rod 122 , just like the third contact 134 , and may include a third terminal adjacent to the first terminal or the second terminal . meanwhile , the second rod 182 of the rear case 180 is formed to be protruded in the opposite direction from the first rod 122 , with the similar structure , and includes a tube portion 182 a and a rubber member 182 b for the third switching portion 142 . at this time , the second rods 182 are formed of a pair to correspond to the third contacts 134 and respectively positioned on the upper portion and the lower portion at the center portion of the rear case 180 . furthermore , a first back bracket 150 is positioned at the rear of the rear membrane 140 to support the rear membrane 140 and the key scan board 130 . a second bracket 160 is formed inside the rear case 180 for the electric circuit section 170 , and positioned at the rear of the first back bracket to support the electric circuit section 170 . at this time , it is preferable that the first back bracket 150 and the second back bracket 160 are stuck closely without gap . in addition , the first and the second back brackets 150 and 160 are formed using steel to enhance their strength . therefore , even in case that the rear case 180 is damaged , the first and the second back brackets 150 and 160 protect the electric circuit section 170 substantially . moreover , the external surface of the electric circuit section 170 is molded by epoxy 173 in a state where the electric circuit section 170 is formed inside the rear case 180 . therefore , it is possible to prevent the external access to the electric circuit section 170 . hereinafter , the process for protecting the pin pad module according to the present embodiment will be described . in case that there is any tampering attempt to remove the bezel base 120 or the button 111 of the key module 100 for the purpose of hacking into a password through the electric circuit section 170 or the key scan board 130 of the pin pad module , it is required to unscrew the screw of the bezel base 120 or remove the front bracket 114 on which the button 111 is positioned . at this time , the key module 100 protects the front of the pin pad module . in case that the screw for fixing the bezel base 120 to the rear case 180 is unscrewed , the pressing force or the location changes at any one of the first rod 122 and the second rod 182 for the second and the third switching portions 126 and 142 of the membrane . furthermore , the voltage or the electric current changes at any one of the second and third contacts 133 and 134 for the second switching portion 126 and the third switching portion 142 . at this time , the electric circuit section 170 recognizes the change in the voltage or the electric current of the second and the third contacts 133 and 134 , as hacking for the pin pad module , thereby making the stored information unreadable . fig1 is a perspective view illustrating an apparatus for protecting a pin pad module according to one embodiment of the present invention ; fig1 is a plan view illustrating the rear of a rubber pad including buttons according to one embodiment of the present invention ; fig1 is a sectional view illustrating an apparatus for protecting a pin pad module according to one embodiment of the present invention ; fig1 is a partially enlarged view of fig1 ; fig1 is a view illustrating the upper surface of a key scan board according to one embodiment of the present invention ; fig1 is a view illustrating the lower surface of a key scan board according to one embodiment of the present invention ; and fig1 is a view illustrating a process of protecting a pin pad module according to one embodiment of the present invention . as illustrated , in order to achieve the above object , an apparatus for protecting a pin pad module according to one embodiment of the present inventions comprises a key module 200 including a rubber pad 210 and a bezel base 220 wherein pluralities of buttons 211 are formed on the front of the rubber pad 210 , pluralities of protruded first rods 222 are formed on the rear thereof 210 , and the rubber pad 210 is inserted into the bezel base 220 including holes ; and a front membrane 225 including a first switching portion 226 for the button 211 of the key module 200 and a second switching portion 227 for the first rod 222 , to transmit the pressing force of the button 211 and the first rod 222 to the rear through the first and the second switching portions 226 and 227 . furthermore , a key scan board 230 is positioned at the rear of the front membrane 225 , and includes pluralities of first contacts 232 for the first switching portions 226 , and pluralities of second contacts 233 for the second switching portions 227 on the front of the key scan board 230 and pluralities of third contacts 234 on the rear thereof 230 . in addition , a rear membrane 240 is positioned at the rear of the key scan board 230 , and includes a third switching portion 242 for the third contact 234 , and an electric circuit section 270 is positioned at the rear of the rear membrane 240 and includes a memory for receiving the states of connection of contacts of the key scan board 230 to perform logic calculation . a rear case 280 is positioned at the rear of the rear membrane 240 , includes a pair of second rods 282 for third contacts 242 and is coupled with the bezel base 220 of the key module 200 by screws . at this time , the structure and materials of the front membrane 225 and the rear membrane 240 embodying the present embodiment are similar to those of the previous embodiment . the number of the contacts 226 of the front membrane 225 for the buttons 221 formed on the rubber pad 210 and the number of the first contacts 232 of the key scan board 230 is more than that of the previous embodiment . furthermore , a circuit connector 272 of the electric circuit section 270 is provided on a vertical line passing through the third contacts 234 and a board connector 235 , so that the board connector 235 , for transmitting the states of connection at contacts of the key scan board 230 , passes through the third contacts 234 . the arrangement of the board connector 235 like above is to prevent the board connector 235 from getting access to the third contacts 234 and prevent a hacker from applying electric conduction liquid ( electric conduction ink ) to the third contact to make it as same as the first state of connection thereof 234 . in case that the hacker attempts to put electric conduction liquid into the terminal of the circuit connector 272 in a state where the circuit connector 272 is coupled with the board connector 235 , the arrangement of the board connector 235 like above is to prevent an instrument including electric conduction liquid from getting access to the circuit connector 272 by a second rod 282 for the third contact 234 . in addition , the third contact 234 includes a first terminal 234 a and a second terminal 234 b , which are electrically connected by the first rod 282 , and the third contact 234 further includes a third terminal 234 c which is formed closely adjacent to the first terminal 234 a and the second terminal 234 b , and the electric circuit section 270 makes the stored information unreadable in accordance with the connection between the second and the third terminals 234 a and 234 b . furthermore , although it is not illustrated , the second contact 233 also includes a first terminal and a second terminal which are electrically connected by the first rod 222 , just like the third contact 234 , and may include a third terminal adjacent to the first terminal or the second terminal . meanwhile , the second rod 282 of the rear case 280 is formed to be protruded in the opposite direction from the first rod 222 , with the similar structure , and includes a tube portion 282 a and a rubber member 282 b for the third contact 242 . at this time , the second rods 282 are formed of a pair to correspond to the third contacts 234 and respectively positioned on the upper portion and the lower portion at the center portion of the rear case 280 . furthermore , a first back bracket 250 is positioned at the rear of the rear membrane 240 to support the rear membrane 240 and the key scan board 230 . a second bracket 250 is formed inside the rear case 280 for the electric circuit section 270 , and positioned at the rear of the first back bracket 250 to support the electric circuit section 270 . in addition , the first and the second back brackets 250 and 260 are formed using steel to enhance their strength . therefore , even in case that the rear case 280 is damaged , the first and the second back brackets 250 and 260 protect the electric circuit section 270 substantially . moreover , the external surface of the electric circuit section 270 is molded by epoxy in a state where the electric circuit section 270 is formed inside the rear case 280 . therefore , it is possible to prevent the external access to the electric circuit section 270 . the first , the second , and the third contacts 232 , 233 , and 234 that are formed on the key scan board 230 , and a screw hole 236 are positioned similar to the previous embodiment . hereinafter , the process for protecting the pin pad module according to one embodiment will be described . in case that there is any tampering attempt to remove the bezel base 220 or the button 211 of the key module 200 for the purpose of hacking into a password through the electric circuit section 270 or the key scan board 230 of the pin pad module , it is required to unscrew the screw of the bezel base 220 or remove the rubber pad 210 on which the button 111 is positioned . at this time , the key module 200 protects the front of the pin pad module . in case that the screw for fixing the bezel base 220 to the rear case 280 is unscrewed to remove the bezel base 220 from the rear case 280 , or the bezel base 220 is destroyed , thereby moving the rubber pad 210 , the pressing force or the location changes at any one of the first rod 222 and the second rod 282 for the second and the third switching portions 226 and 242 of the membrane . furthermore , the voltage or the electric current changes at any one of the second and third contacts 233 and 234 for the second switching portion 226 and the third switching portion 242 . at this time , the electric circuit section 270 recognizes the change as hacking for the pin pad module , thereby making the stored information unreadable . as described above , in case that an apparatus for protecting a pin pad module according to the present invention is adopted and there is any tampering attempt to physically disassemble the pin pad module to install hacking equipments for the purpose of finding out a password , the pressing force or location changes at any one of the first and the second rods , wherein the pin pad module is installed in a financial terminal or the like . in addition , the voltage or electric current changes at any one of the second and the third contacts of the key scan board and the electric circuit section detects the event and recognizes the event as hacking for the pin pad module , thereby making the stored information unreadable . therefore , the present invention can enhance the security of the pin pad module . furthermore , the rear of the key scan board embodying the pin pad module is protected by a plurality of metal brackets . therefore , the present invention can prevent a hacker &# 39 ; s intrusion , such as for example , cutting off the rear of the pin pad module and accessing the key scan board . furthermore , a method of detecting hacking that is adopted by the apparatus for protecting the pin pad module , does not electrically connect contacts by fixing components . the method uses contacts of the key scan board in which the electric circuit section detects the states of connection . therefore , in case that an intruder cuts off around the fixing component or cuts off the fixing component , the pressing force or the location of the rod changes at contacts and the electrical change occurs at contacts . thus , the present invention can detect the intrusion immediately through the electric circuit section .
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a well known method for the transmission of digital data over a physical medium ( e . g . a wire ) is the use of line codes . a line code maps the digital levels 1 and 0 to voltage waveforms such that the digital data may be recovered from the signal received at the receiver with minimal error . many different line codes are known , and each line code has its own distinct characteristics . one such characteristic of line codes is the power spectral density ( psd ) which describes the relative power contributed by various frequency components . in accordance with one embodiment of the invention , a first high data rate digital data signal is encoded using a manchester line code and a second low data rate digital data signal is encoded using a polar non - return - to - zero ( nrz ) line code . line codes are well known in the art and various line codes in accordance with particular embodiments of the invention will be described briefly herein . for further information on line codes , see modern digital and analog communication systems , second edition , b . p . lathi , oxford university press , 1995 , chapter 3 . in a polar nrz line code , a digital 1 is encoded as + v volts and a digital 0 is encoded as − v volts . polar nrz is a non - return - to - zero code such that the waveform does not return to 0 volts between symbols . an example waveform for the digital signal 10011 encoded using polar nrz is shown in fig1 . fig2 shown the normalized psd for a signal encoded using the polar nrz line code . as seen from fig2 the psd has a significant dc ( i . e ., 0 frequency ) component . further , for a signaling rate of r bps , a bandwidth null occurs at r hz . a manchester line code is a transition line code wherein waveform transitions between + v and − v encode the digital signal . in a manchester line code , a digital 1 is encoded as a + v →− v transition , and a digital 0 is encoded as a − v →+ v transition . an example waveform for the digital signal 10011 encoded using a manchester line code is shown in fig3 . fig4 shown the normalized psd for a signal encoded using the manchester line code . as seen from fig4 the psd has 0 dc component . further , for a signaling rate of r bps , a bandwidth null occurs at 2r hz . in accordance with one embodiment of the invention , a first low data rate digital signal is encoded using the polar nrz line code , a second high data rate digital signal is encoded using the manchester line code , and the two encoded signals are combined and transmitted over a single physical transmission medium . due to the characteristics of the line codes , the psd &# 39 ; s of the encoded signals at the chosen data rates are substantially orthogonal , and thus the two encoded signals may be combined and transmitted via a single physical medium without interference . fig5 shows the normalized psds for the encoded signals in accordance with this embodiment of the invention in which a high data rate digital signal at a data rate of 4r is encoded using manchester encoding and a low data rate digital signal at a data rate of r / 4 is encoded using polar nrz encoding . the psd for the polar nrz encoded signal is shown as curve 502 and the psd for the manchester encoded signal is shown as curve 504 . as can be seen from fig5 the high data rate manchester encoded signal has a low psd in the low frequency range , and the low data rate polar nrz encoded signal has a high psd in the same low frequency range . further , the high data rate manchester encoded signal has a high psd in the high frequency range , and the low data rate polar nrz encoded signal has a low psd in the same high frequency range . because of the substantial orthogonality of the psds of the two encoded signals , the signals may be combined and transmitted simultaneously over the same physical medium with little or no interference . one embodiment of a system for practicing the invention as described in accordance with fig5 is shown in fig6 . a transmitter 602 receives a low data rate digital signal and a high data rate digital signal . the low data rate digital signal is encoded by polar nrz line coder 604 and the high data rate digital signal is encoded by manchester line coder 606 . the two encoded signals are combined by combiner 608 and transmitted via a wire 610 to receiver 620 . at the receiver 620 the signal is split and provided to a low - pass filter 622 and a high - pass filter 626 . the low - pass filter 622 passes the signal in the low frequency range . as described above in conjunction with fig5 the high data rate encoded signal has a low psd in the low frequency range , and the low data rate encoded signal has a high psd in the same low frequency range . thus , the output of the low - pass filter 622 is provided to a polar nrz line decoder 624 for decoding . the polar nrz line decoder 624 will output the low data rate digital signal . similarly , the high - pass filter 626 passes the signal in the high frequency range . as described above in conjunction with fig5 the high data rate encoded signal has a high psd in the high frequency range , and the low data rate encoded signal has a low psd in the same high frequency range . thus , the output of the high - pass filter 626 is provided to a manchester line decoder 630 for decoding . the manchester line decoder 630 outputs the high data rate digital signal . if appropriate data rates and line codes are chosen , then it is possible to transmit more than two signals over a single physical medium in accordance with the invention . an embodiment in which three signals are transmitted over a single medium will now be described . in accordance with this embodiment , a first high data rate digital signal is encoded using a manchester line code , a second low data rate digital signal is encoded using polar non - return - to - zero ( nrz ) line code , and a third low data rate digital signal is encoded using an alternate mark inversion ( ami ) line code . in an ami line code , a digital 1 is alternately encoded as + v and − v and a digital 0 is encoded as 0 v . an example waveform for the digital signal 10011 encoded using an ami line code is shown in fig7 . fig8 shown the normalized psd for a signal encoded using the ami line code . as seen from fig8 the psd has 0 dc component . further , for a signaling rate of r bps , a bandwidth null occurs at r hz . the ami line code is well known and is further described in modern digital and analog communication systems , second edition , b . p . lathi , oxford university press , 1995 , p . 171 . in accordance with an embodiment of the invention , a first low data rate digital signal is encoded using the polar nrz line code , a second low data rate digital signal is encoded using the ami line code , a third high data rate digital signal is encoded using the manchester line code , and three encoded signals are combined and transmitted over a single transmission medium . due to the characteristics of the line codes in combination with chosen data rates , the psd &# 39 ; s of the encoded signals are substantially orthogonal , and thus the three encoded signals may be transmitted via a single medium without interference . fig9 shows the normalized psds for the encoded signals in accordance with an embodiment of the invention in which a first low data rate digital signal at a data rate of r / 4 is encoded using polar nrz encoding , a second low data rate digital signal at a data rate of r is encoded using ami encoding , and a third high data rate digital signal at a data rate of 4r is encoded using manchester encoding . the psd for the polar nrz encoded signal is shown as curve 902 , the psd for the ami encoded signal is shown as curve 904 , and the psd for the manchester encoded signal is shown as curve 906 . as can be seen from fig9 the psds of the three encoded signals are substantially orthogonal in the frequency domain . all three signals have high psd &# 39 ; s in different frequency ranges . further , in the frequency range in which one of the signals has a high psd , the other signals have low psd &# 39 ; s . as a result , the three signals may be transmitted over the same physical medium with little or no interference . one embodiment of a system for practicing the invention as described in conjunction with fig9 is shown in fig1 . a transmitter 1002 receives a first low data rate ( r / 4 ) digital signal , a second low data rate ( r ) digital signal , and a third high data rate ( 4r ) digital signal . the first low data rate digital signal is encoded by polar nrz line coder 1004 , the second low data rate digital signal is encoded by ami line coder 1006 and the third high data rate digital signal is encoded by manchester line coder 1008 . the three encoded signals are combined by combiner 1009 and transmitted via wire 1010 to receiver 1012 . at the receiver 1012 the signal is split and provided to a low - pass filter 1014 , a band pass filter 1018 , and a high - pass filter 1022 . the low pass filter 1014 , band pass filter 1018 , and high pass filter 1022 are configured to pass the polar nrz encoded signal , the ami encoded signal , and the manchester encoded signal respectively . thus , the output of the low - pass filter 1014 is provided to a polar nrz line decoder 1016 for decoding and the polar nrz line decoder 1016 outputs the first low data rate digital signal . the output of the band pass filter 1018 is provided to an ami line decoder 1020 for decoding and the ami line decoder 1020 outputs the second low data rate digital signal . the output of the high pass filter 1022 is provided to a manchester line decoder 1024 for decoding and the manchester line decoder 1024 outputs the third high data rate digital signal . it is noted that fig6 and 10 are functional block diagrams of apparatuses in accordance with various embodiments of the invention . given the figures and the description herein , one skilled in the art could readily implement the invention . for example , the line coders and line decoders shown in fig6 and 10 could be implemented using programmable processors in conjunction with appropriate software for performing the coding and decoding functions . alternatively , the line coders and decoders could be implemented using hardware , or some combination of hardware and software . the foregoing detailed description is to be understood as being in every respect illustrative and exemplary , but not restrictive , and the scope of the invention disclosed herein is not to be determined from the detailed description , but rather from the claims as interpreted according to the full breadth permitted by the patent laws . it is to be understood that the embodiments shown and described herein are only illustrative of the principles of the present invention and that various modifications may be implemented by those skilled in the art without departing from the scope and spirit of the invention .
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the present invention provides a novel synergistic transformation technique for reducing verification complexity . in particular , the present invention facilitates the synergistic use of a structural overapproximation technique for reducing the size of a sequential design , coupled with the use of a re - encoding technique to render additional property - preserving reductions . the benefit of this synergistic approach is that it enables design reductions far exceeding those possible in the prior art . the result of the present invention is drastic savings in computational resources for the verification process , enabling design flaws to be exposed and proofs to be completed that otherwise would be unfeasible . the present invention relies upon the synergistic application of two techniques to yield increasing reductions of the design under test . first , a logic re - encoding technique simplifies the design under test while preserving its behavior . this re - encoding technique computes the set of values producible at a cut of the design under test as a function of its state elements , then re - encodes the cut by creating logic that produces exactly the same set of values as a function of its state elements . because the re - encoding technique is designed with the freedom to create a completely new , yet behaviorally identical ( with respect to the cut gates ) piece of logic , this technique often offers a superset of the reductions possible using redundant - gate elimination techniques . this technique does not explicitly seek to reduce sequential logic of a design ; it instead attempts to reduce the amount of combinational logic ( and random gates ) in the cut , and to simplify the dependence / correlation of the fan - out side of the cut with the state elements in the fan - in side of the cut . second , a structural overapproximation technique is employed as a way to simplify the design under test while possibly adding randomness to its behavior . such a technique is described in detail in the cross - referenced application described above , which is incorporated by reference in its entirety . this technique often seeks to explicitly eliminate sequential logic from the design by injecting cut - points ( formed from random gates ) in place of other gates in the design . with reference now to the figures , and in particular with reference to fig1 , a simplified block diagram of a data processing system equipped with a computer program product for incremental reduction of a digital design through iterative overapproximation and re - encoding , in accordance with a preferred embodiment of the present invention , is depicted . a data processing system 100 contains a processing storage unit ( e . g ., ram 102 ) and a processor 104 . data processing system 100 also includes non - volatile storage 106 such as a hard disk drive or other direct access storage device . an input / output ( i / o ) controller 108 provides connectivity to a network 110 through a wired or wireless link , such as a network cable 112 . i / o controller 108 also connects to user i / o devices 114 such as a keyboard , a display device , a mouse , or a printer through wired or wireless link 116 , such as cables or a radio - frequency connection . system interconnect 118 connects processor 104 , ram 102 , storage 106 , and i / o controller 108 . within ram 102 , data processing system 100 stores several items of data and instructions , while operating in accordance with a preferred embodiment of the present invention . these items include a design ( d ) 120 and an output table 122 for interaction with a logic verification tool 124 , and a binary decision diagram ( bdd ) builder 126 . other applications 128 and logic verification tool 124 interface with processor 104 , ram 102 , i / o control 108 , and storage 106 through operating system 130 . one skilled in the data processing arts will quickly realize that additional components of data processing system 100 may be added to or substituted for those shown without departing from the scope of the present invention . processor 104 executes instructions from programs , often stored in ram 102 , in the course of performing the present invention . in a preferred embodiment of the present invention , processor 104 executes logic verification tool 124 . logic verification tool 124 incrementally reduces a digital design contained in design ( d ) 120 to create modified design ( d ′) 142 through iterative overapproximation and re - encoding in conjunction with the operation of binary decision diagram builder 126 , re - encoding tool 138 and overapproximation tool 136 . logic verification tool additionally verifies a property ( p ) 134 on design ( d ) 120 . generally speaking , logic verification tool 124 contains rule - based instructions for predicting the behavior of logically modeled items of hardware . binary decision diagram builder 126 converts the structural representation in design ( d ) 120 into a functionally canonical form in bdds 131 . logic verification tool 124 then operates on the series of rules contained in its own instructions , in conjunction with design ( d ) 120 , and associated binary decision diagrams ( bdds ) 131 . design ( d ) 120 may model the designs of many different kinds of logical hardware , such as microprocessors and application specific integrated circuits ( asics ). design ( d ) 120 is represented structurally as a netlist , comprising a directed graph where each node is a gate of some type , e . g . an and gate , an inverter , a primary input ( or random gate ), or a state element . bdd builder 126 transforms design ( d ) 120 into bdds 131 for use with logic verification tool 124 and , where appropriate , re - encoding tool 138 and overapproximation tool 136 . the netlist of design ( d ) 120 is defined in terms of semantic traces , which map the gates to 0 , 1 values in bdds 131 over time . each state element in design ( d ) 120 is associated with a next - state function ( defining what value it will take one time - step in the future ), as well as an initial value ( defining what value it will take at time 0 ), each of which are represented as a gate . design ( d ) 120 is represented as a directed graph with nodes representing gates of various functionality ( e . g ., primary inputs hitherto referred to as random gates , combinational functions such as and gates and inverters , and state elements ), and edges representing interconnections between those gates . interconnections are directed , routing data from “ source ” to “ sink ”. additional items of data stored in ram 102 include property ( p ) 134 , cutpoints 140 , and modified design ( d ′) 142 . property ( p ) 134 contains the behavior to be verified on design ( d ) 120 . cutpoints 140 contains a group of random gate insertion instructions for insertion into modified design ( d ′) 142 , which contains the most current result of the present invention as applied to design ( d ) 120 . cutpoints 140 represent partitions of the netlist of design ( d ) 120 into two graphs , where the only directed path from gates in the “ source ” graph to the “ sink ” graph flow through the gates comprising the cut . “ injecting a cutpoint ” refers to the process of replacing a gate in the netlist with a random gate . a random gate is evaluated as an unconstrained source of random bit - streams in the verification process . logic verification tool 124 records results to output table 122 . logic verification tool 124 may also report the contents of output table 122 or selected indicators of the status of design ( d ) 120 to user i / o 114 or applications 128 . additionally , all or part of logic verification tool 124 , operating system 130 , design ( d ) 120 , output table 122 , re - encoding tool 138 and overapproximation tool 136 may , at times , be stored in storage 106 . additional data structures , which are well known in the art , are used by re - encoding tool 138 and overapproximation tool 136 and are not shown for the sake of illustrative simplicity . in the method of the present invention , logic verification tool 124 relies upon exploiting cutpoint insertion by overapproximation tool 136 to eliminate ( possibly sequential ) logic , then uses a re - encoding method supplied by re - encoding tool 138 and overapproximation tool 136 to reduce the size of the overapproximated design ( d ) 120 , resulting in modified design ( d ′) 142 . logic verification tool 124 then re - applies overapproximation tool 136 to eliminate ( possibly sequential ) logic , followed by a re - encoding method supplied by re - encoding tool 138 and overapproximation tool 136 to reduce the size modified design ( d ′) 142 , to yield incrementally greater reductions . the overapproximation by overapproximation tool 136 synergistically enables greater reductions by re - encoding tool 138 . similarly , the re - encoding by re - encoding tool 138 synergistically enables a greater potential of reductions through the heuristic overapproximation of overapproximation tool 136 by making the “ minimal set ” of gates necessary to preserve the functional behavior of design ( d ) 120 easier to identify ( due to reduced correlation between sequential elements ). the present invention is more robust than the prior art against arbitrarily - selected cutpoint injections causing spurious counterexamples . additionally , the re - encoding by re - encoding tool 138 is useful to offset the increase in the number of random gates of the overapproximated design created by overapproximation tool 136 . one particularly helpful effect of the present invention is that the present invention effectively enables a re - encoding by re - encoding tool 138 of “ sequential ” logic deep in design ( d ) 120 solely by leveraging “ combinational ” algorithms . the overapproximation by overapproximation tool 136 will safely translate certain sequential logic to combinational logic , against which re - encoding by re - encoding tool 138 is particularly effective . this combination , in turn enables “ deep ” reductions by re - encoding tool 138 to design ( d ) 120 , ultimately enabling a conclusive verification result with respect to property ( p ) 134 , even for large and complex problems that otherwise would remain unsolved given prior art techniques . while the technique of the present invention is applicable to rendering sequential reductions of design ( d ) 120 , one may also apply the method of the present invention to yield reductions to combinational designs . broadly , as will be illustrated with respect to fig2 , this overall process of the present invention may be described as a few steps . first , logic verification tool 124 imports design ( d ) 120 , and property ( p ) 134 , a property to verify with respect to that design . second , the overapproximation step is performed in several substeps . logic verification tool 124 uses bdd builder 126 to generate bdds 131 . logic verification tool 124 computes a set of candidate gates for cutpoint insertion , and saves these as cutpoints 140 . overapproximation tool 136 then overapproximates design ( d ) 120 by inserting cutpoints ( random gates ) to those candidate gates to eliminate large portions of design ( d ) 120 , which may include elimination of sequential logic . in one embodiment , the cut - point 140 selection process may be performed using any variety of analysis algorithm ( e . g ., localization refinement , which is discussed briefly below ) to ensure that the overapproximation entailed by the cutpoint 140 insertion in design ( d ) 120 does not yield spurious failures of design ( d ) 120 . third , logic verification tool 124 computes a cut of the netlist graph and saves it as cutpoints 140 . logic verification tool 124 then uses re - encoding tool 138 to apply a re - encoding of design ( d ) 120 at cutpoints 140 to attempt to eliminate logic from the design . the purpose of this third step is to reduce the size design ( d ) 120 ( particularly in terms of combinational gates and random gates ) while preserving its behavior . the reduced design is then saved as modified design ( d ′) 142 . as will be discussed below , the second and third steps of the method of the present invention may be performed in a different order , based on selection criteria discussed with respect to fig2 . fourth , logic verification tool 124 attempts a verification effort with respect to property ( p ) 120 on modified design ( d ′) 142 using any algorithms available . if the verification problem remains unsolved , logic verification tool 124 returns to the second step for additional reductions . turning now to fig2 , a high - level logical flowchart of a process for incremental design reduction via iterative overapproximation and re - encoding is depicted . the process starts at step 200 . the process next moves to step 201 , which depicts logic verification tool 124 receiving design ( d ) 120 and property ( p ) 134 . the process then proceeds to step 202 . step 202 illustrates logic verification tool 124 selecting criteria for deciding which of the available transformation methods to apply to design 120 . examples of such criteria available to logic verification tool 124 include selecting the alternate of the last performed transformation . examples of available criteria also include iterating between transformation types , which would , in one embodiment include iteratively increasing the resources used in each transformation type . if design ( d ) 120 has inputs beyond a threshold number , logic verification tool 124 could automatically choose re - encoding . similarly , if design ( d ) 120 has many state elements , or the property ( p ) 134 for verification is sequentially deep from the inputs , cutpoint 140 insertion could automatically be performed to generate an overapproximation . the process next passes to step 204 , which depicts logic verification tool 124 applying the criteria selected in step 202 to decide which transform to apply . while the method of the present invention as depicted with respect to fig2 reflects the serial use of methods of transformation , one skilled in the art will quickly ascertain that the transformation methods available in the preferred embodiment may also be performed in parallel , with comparison of computing results . if logic verification tool 124 chooses to re - encode design ( d ) 120 , then the process moves to step 206 . at step 206 , logic verification tool 124 employs re - encoding tool 138 to identify a cut of design ( d ) 120 to re - encode , replacing the fan - in side of each cut with minimally sized functionally equivalent logic to create modified design ( d ′) 142 . the re - encoding technique synergistically enhances the ability of the overapproximation technique to eliminate sequential logic by reducing the correlation of state variables in design ( d ) 120 , facilitating the ability of heuristic algorithms in overapproximation tool 136 to identify a smaller “ minimal set ” of adequate gates to preserve . stated differently , by eliminating some connections between sequential elements , re - encoding tool 138 increases the probability that injecting a cutpoint from among cutpoints 140 to an arbitrarily - selected gate will still result in an overapproximated modified design ( d ′) 142 , which satisfies its specification . without such a re - encoding tool 138 , there is a greater chance that an arbitrarily - chosen cutpoint injection from among cutpoints 140 will yield a spurious counterexample . re - encoding tool 138 attempts to render reductions as follows . given a cut within cutpoints 140 of the design ( d ) 120 , re - encoding tool 138 computes the set of values that are producible at those cut gates as a function of state elements in that cut . re - encoding tool 138 then creates new logic that produces exactly the same behavior as the ‘ source ’ side of the cut within cutpoints 140 as a function of the state elements , and replaces the cut gates with this new logic . note that one cannot merely inject cutpoints to the cut gates , as that would generally constitute an overapproximate transformation , whereas the purpose of this transformation by re - encoding tool 138 in the present invention is to render a property - preserving transformation . more specifically , a set of n cutpoints 140 can produce any possible stream of 2 ^ n values over time , whereas the behavior of the original cut gates may be constrained to only produce a subset of the possible values . the advantage of this use of re - encoding tool 138 to produce a reduction is the creation of a simpler yet functionally equivalent replacement logic , reducing the overall size of modified design ( d ′) 142 with respect to design ( d ) 120 . note also that this approach is primarily geared towards reducing combinational logic and random gates , as it directly reuses the state variables when re - encoding over sequential cuts . after step 206 , the process then proceeds to step 210 , which is explained following the discussion of step 208 . returning to step 204 , if logic verification tool 124 determines to transform design ( d ) 120 by overapproximation , then the process moves to step 208 . at step 208 , logic verification tool 124 employs overapproximation tool 136 to overapproximate design ( d ) 120 by injecting cutpoints , ideally assuring that they do not yield spurious assertions of property ( p ) 134 to create modified design ( d ′) 142 . practically , structural overapproximation algorithms employed in overapproximation tool 136 are often heuristic , attempting to discern a minimal set of gates ( particularly state elements ) of design ( d ) 120 , which are needed to ensure that a property under verification will pass and to inject cut - points to the other gates . an “ overapproximate transformation ” is one which may add randomness to the behavior of design ( d ) 120 . for example , if one injects a set of cutpoints 140 into a design , the result is generally overapproximate because cutpoints 140 behave as completely random sources , and hence can ‘ simulate ’ any possible behavior of the original gates being replaced . but those original gates cannot necessarily produce some of the behavior that the random gates can produce . a spurious failure refers to the condition where an overapproximation of design ( d ) 120 causes a failure that would not be possible without the overapproximation . as used in overapproximation tool 136 , a structural overapproximation technique operates by injection of cutpoints 140 . in one embodiment , overapproximation tool 136 eliminates significant portions of design ( d ) 120 by effectively isolating a cut of design ( d ) 120 and injecting cutpoints 140 ( i . e ., random gates ) to those cut gates , the source side of which then drops out of the cone of influence . this method may be deployed in a manner which explicitly seeks to eliminate sequential logic in design ( d ) 120 . in one embodiment , this cutpoint selection process uses some form of analysis of design ( d ) 120 to ensure that the cutpoints 140 being inserted , which overapproximate the behavior of the design under test , do not render spurious failures . one embodiment will employ a scheme termed ‘ localization refinement ’. such a localization refinement includes injecting cutpoints 140 , running some ( possibly underapproximate ) verification to attempt to assess whether the cutpoints 140 cause spurious failures , then if so to “ refine ” the cutpoints 140 by eliminating them and possibly re - inserting them further back in the fan - in cone of the earlier cutpoints 140 to attempt to eliminate the corresponding spurious failure . nevertheless , the particular method used to determine where to inject cutpoints 140 will vary among many possible embodiments . from either of step 206 or step 208 the process then moves to step 210 , which depicts logic verification tool attempting to solve property ( p ) 134 on modified design ( d ′) 142 and / or apply an alternate transformation . the process then moves to step 212 , which illustrates logic verification tool 124 determining whether property ( p ) 134 has been solved with respect to modified design ( d ′) 142 . if property ( p ) has been solved with respect to modified design ( d ′) 142 , then the process ends at step 214 . if at step 212 , property ( p ) has not been solved with respect to modified design ( d ′) 142 , then the process proceeds to step 216 , which depicts logic verification tool substituting the content of modified design ( d ′) 120 for design ( d ) 120 . the process then returns to step 202 , which is described above . by leveraging the above discussed overapproximation tool 136 and re - encoding tool 138 in a synergistic fashion , the present invention enables significantly greater design reductions than possible with the prior art , resulting in greater bug - hunting power in addition to proof capability . the particular synergy between overapproximation tool 136 and re - encoding tool 138 results in several benefits . the structural overapproximation technique employed by overapproximation tool 136 turns sequentially - driven logic into combinationally - driven logic , and more generally injects random gates deeper into the cone of the design ( d ) 120 . this helps the re - encoding technique of re - encoding tool 138 , because the latter is primarily adept at reducing logic near random gates and is the weakest at eliminating purely sequential logic . moreover , the re - encoding technique of re - encoding tool 138 reduces correlation between state variables in the fanin - side of the cut and the fanout - side of the cut . in some cases , certain state variables may be outright eliminated from the problem by the re - encoding ( e . g ., if a gate on the cut is an xor of a primary input and a state element , that xor gate may take any value at any point in time regardless of the value of the state element , and the re - encoding may be able to replace the xor gate safely by a cut - point ). more generally , the reduction minimizes the number of connections between state elements in the fanin - side of the cut and the fanout - side of the cut . one particularly useful advantage of the present invention is that it effectively enables a re - encoding by re - encoding tool 138 of “ sequential ” logic deep in the design solely by leveraging “ combinational ” algorithms . the prior art sequential re - encoding is generally a pspace - complete problem , whereas the latter combinational analysis of the present invention is only a simpler np - complete problem . while in the described embodiment , this invention is to be applied to simplify sequential designs , these techniques may equally well be applied to combinational designs . overall , the combined method of the present invention is more robust against arbitrarily - selected cutpoint injections causing spurious counterexamples . additionally , the re - encoding by re - encoding tool 138 is useful to offset the increase in the number of random gates of the overapproximated design produced by overapproximation tool 136 . while the present invention has been particularly shown as described with reference to a preferred embodiment , it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention . it is also important to note that although the present invention has been described in the context of a fully functional computer system , those skilled in the art will appreciate that the mechanisms of the present invention are capable of being distributed as a program product in a variety of forms , and that the present invention applies equally regardless of the particular type of signal bearing media utilized to actually carry out the distribution . examples of signal bearing media include , without limitation , recordable type media such as floppy disks or cd roms and transmission type media such as analog or digital communication links .
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fig1 illustrates a dialysis system 20 incorporating a differential conductivity recirculation monitor 22 for determining and displaying recirculation efficiency in accordance with the present invention . the dialysis system 20 , which is one example of a medical system with which the present invention may be advantageously used , comprises a dialysis apparatus 24 connected to a fistula 26 surgically formed in a dialysis patient ( not shown ). untreated blood is drawn from the fistula 26 through a dialyzer inlet needle 28 and a dialyzer inlet line 30 . treated blood is returned to the fistula through a dialyzer outlet line 32 and a dialyzer outlet needle 34 . the recirculation monitor 22 is located in the dialyzer inlet and outlet lines 30 and 32 at a point intermediate between the fistula 26 and the dialysis apparatus 24 . the dialysis apparatus 24 comprises a blood pump 36 typically a peristaltic pump , a dialyzer 38 having a blood compartment 40 and a dialysate compartment 42 separated by a semi - permeable membrane 44 , a bubble trap 46 and a dialysate generator 48 . blood is drawn from the fistula 26 by the action of the blood pump 36 and passed through the blood compartment 40 of the dialyzer 38 . the membrane 44 allows transfer of impurities in the blood , such as urea and creatinine , from the blood compartment 40 to the dialysate compartment 42 of the dialyzer 38 . the dialysate compartment 42 is connected to a dialysate generator 48 which generates the dialysate , a liquid isotonic to blood , and circulates it through the dialysate compartment 44 . the principles of operation of the differential conductivity recirculation detector 22 of the present invention are explained in conjunction with fig2 and 3 . the recirculation detector 22 comprises a needle access site 50 in the dialyzer outlet line 32 . a first or outlet conductivity cell 52 is located in the dialyzer outlet line 32 downstream of the needle access site 50 . a second or inlet conductivity cell 54 is located in the dialyzer inlet line 30 . the first conductivity cell 52 comprises an upstream connection 56 , a downstream connection 58 and first and second tubing branches 60 and 62 , respectively , each of which interconnect the upstream connection 56 with the downstream connection 58 . treated blood from the dialyzer flows in the dialyzer outlet line 32 through the needle access site 50 to the upstream connection 56 . at the upstream connection 56 the flow splits approximately equally with a portion of the treated blood flowing in each of the two tubing branches 60 and 62 of the outlet conductivity cell 52 . the flow rejoins at the downstream connection 58 and flows through the dialyzer outlet line 32 to the fistula 26 ( fig1 ). similarly , the inlet conductivity cell 54 comprises an upstream connection 64 , a downstream connection 66 and third and fourth tubing branches 68 and 70 , respectively , which each connect the upstream connection 64 to the downstream connection 66 . untreated blood from the fistula 26 flowing in the dialyzer inlet line 30 , enters the inlet conductivity cell 54 at the upstream connection 64 divides approximately equally between the third and fourth tubing branches 68 and 70 and rejoins at the downstream connection 66 to the inlet conductivity cell 54 . each one of the tubing branches 60 , 62 , 68 and 70 has the same cross sectional area and length as each other one of the tubing branches . the blood , or other biological or medical fluid , flowing in each conductivity cell 52 and 54 comprises an electrical circuit . the electrical circuit is a path for circulation of an electrical current from the upstream connection , through one of the tubing branches , to the downstream connection and from the downstream connection through the other one of the tubing branches to the upstream connection . the outlet conductivity cell 52 and the inlet conductivity cell 54 are positioned adjacent to each other in an angular relationship resembling a pretzel so that the first tubing branch 60 of the outlet conductivity cell 52 is positioned parallel to the third tubing branch 68 of the inlet conductivity cell at an excitation location . the conductivity cells are further positioned so that the second tubing branch 62 of the outlet conductivity cell 52 crosses the fourth tubing branch 70 of the inlet conductivity cell 54 at an angle , approximately sixty degrees in the preferred embodiment , at a sensing location . an excitation coil 72 encircles the first tubing branch 60 of the outlet conductivity cell 52 and the third tubing branch 68 of the inlet conductivity cell 54 at the excitation location . a sensing coil 74 encircles the second tubing branch 62 of the outlet conductivity cell 52 and the fourth tubing branch 70 of the inlet conductivity cell 54 at the sensing location . an electrical circuit , as is illustrated schematically in fig3 is thus formed . the excitation coil 72 is inductively coupled to the outlet conductivity cell 52 and the inlet conductivity cell 54 . when a source of excitation energy 76 causes an alternating excitation current , illustrated by direction arrow 78 , to flow in the excitation coil 72 a changing magnetic field is generated which causes an electrical current , illustrated by the direction arrow 80 , to flow in the blood in the outlet conductivity cell 52 and causes another electrical current , illustrated by direction arrow 82 , to flow in the same electrical direction in the blood in the inlet conductivity cell 54 . since the conductivity cells 52 and 54 are formed to create electrical paths of equal cross sectional area and equal path length the electrical conductance of the paths , as illustrated by the schematic resistors 84 and 86 , and thus the magnitude of the induced currents 80 and 82 , will be related to the conductivity of the blood in the respective conductivity cells 52 and 54 . the induced currents 80 and 82 flowing in the outlet and inlet conductivity cells 52 and 54 generate a changing magnetic field at the sensing location that induces a sensed current , illustrated by direction arrow 88 , in the sensing coil 74 . the induced currents 80 and 82 are in opposite electrical directions so that the magnetic field at the sensing location has a magnitude proportional to the difference between the induced currents . the sensed current 88 is proportional to the magnetic field at the sensing location where the sensing coil 74 encircles the second and fourth tubing branches 62 and 70 , respectively . the sensed current 88 induced in the sensing transformer 74 is therefore proportional to a difference between the induced currents 80 and 82 in the outlet and inlet conductivity cells 52 and 54 , respectively . the induced currents 80 and 82 in the outlet and inlet conductivity cells 52 and 54 , respectively , are related to the conductivity of the fluids in those chambers . therefore , the magnitude of the sensed current 88 induced in the sensing coil 74 will be related to the difference between the conductivities of the fluids in the outlet and inlet conductivity cells 52 and 54 . the sensed current 88 is delivered to , and interpreted by a sensing logic and display circuit 90 , which displays the recirculation efficiency . it should be appreciated that the present invention will function in substantially the same way if the locations of the exciting coil 72 and sensing coil 74 are reversed . referring now to fig1 and 2 , to use the recirculation monitor 22 to perform a recirculation test the dialysis system operator injects a bolus of a marker fluid into the treated blood in the dialyzer outlet line 32 at the needle access site 50 using a typical hypodermic needle 92 . the marker fluid may have an electrical conductivity that is higher or lower than the fluid flowing in the outlet line 32 . in the preferred embodiment a high conductivity marker fluid is used to avoid damaging blood cells . in the preferred embodiment the bolus is 1 milliliter of 24 percent hypertonic saline solution . the conductivity of the treated blood being returned to the patient through the dialyzer outlet line 32 and the outlet conductivity cell 52 of the recirculation monitor 22 is altered . this altered conductivity blood enters the fistula through the outlet needle 34 . if the flow balance in the fistula 26 is such that no flow is recirculating the altered conductivity blood will exit the fistula , as illustrated by the flow circulation arrow 94 , without altering the conductivity of the blood within the fistula . if , however , the flow balance within the fistula 26 is such that blood is recirculating , as illustrated by flow circulation arrow 96 , a portion of the blood withdrawn from the fistula 26 by the pump 36 will be the altered conductivity blood . the recirculation monitor 22 measures the conductivity of the blood flowing in the outlet line 32 and the conductivity of the blood flowing in the inlet line 30 and quantitatively determines the difference between those conductivities continuously throughout the recirculation test . the sensing logic and display circuit 90 interprets the quantitative conductivity differences measured by the recirculation monitor 22 to determine recirculation efficiency . the determination of recirculation efficiency will be explained by reference to fig4 and 6 . the outlet conductivity cell 52 and the inlet conductivity cell 54 may be thought of as signal generators generating the induced currents 80 and 82 in the outlet and inlet conductivity cells . the induced current 82 of the inlet conductivity cell 54 is inverted 98 and added 100 to the induced current 80 in the outlet , conductivity cell 52 , by virtue of the physical relationships between the conductivity cells , excitation coil 72 and sensing coil 74 , to produce the sensed current 88 . the sensing logic and display circuit 90 performs a zeroing operation 102 , a dialyzer outlet flow determining operation 104 , and unrecirculated flow determining operation 106 , and a dividing operation 108 , and includes a visual display device 110 , preferably a liquid crystal display . alternatively the functions of the sensing logic and display circuit 90 may be performed by a digital computer ( not shown ). fig5 is a graph illustrating differential conductivity ( reference 112 ) as a function of time ( reference 114 ) during a typical recirculation test . fig6 is a graph illustrating the integral of differential conductivity ( reference 116 ) as a function of time 114 during the typical recirculation test . prior to the beginning of the recirculation test there may be some normal difference ( reference 118 ) between the conductivity of the treated blood in the dialyzer outlet line 32 ( fig2 ) and the untreated blood in the dialyzer inlet line 30 ( fig2 ). this normal conductivity difference 118 is subtracted from the sensed current 88 by the zeroing operation 102 of the sensing logic and display circuit 90 to remove the effect of the normal difference in conductivity 118 from determination of recirculation efficiency . the recirculation test begins ( reference time t1 ) when the bolus of high conductivity fluid is injected into the dialyzer outlet line 32 ( fig2 ) at the needle access site 50 ( fig2 ). the conductivity of the treated blood in the dialyzer outlet line 32 ( fig2 ) is increased . as the bolus passes through the outlet conductivity cell 52 ( fig2 ) the differential conductivity 112 increases ( reference 120 ) and then decreases ( reference 122 ) until the normal conductivity difference 118 is reached ( reference time t2 ). the outlet flow determining operation 104 calculates the integral of conductivity from the start of the test ( reference time t1 ) until the differential conductivity returns to the normal value 118 ( reference time t2 ). the integral 116 of the conductivity increases ( reference 124 ) until a first steady state value ( reference 126 ) of the integral 116 is reached when the differential conductivity 112 returns to the normal value 118 ( reference time t2 ). the first steady state value 126 is stored by the outlet flow determining operation 104 and is representative of the flow of treated blood in the dialyzer outlet line 32 ( fig2 ). after the treated blood with the altered conductivity enters the fistula 26 ( fig1 ) a portion of it may recirculate and be withdrawn from the fistula 26 ( fig1 ) through the dialyzer inlet line 30 ( fig2 ). the conductivity of the untreated blood in the inlet conductivity cell 54 is increased ( reference time t3 ), causing the differential conductivity to decrease 128 and then increase 130 , returning to the normal value of conductivity difference 118 ( reference time t4 ). the integral of differential conductivity from the beginning of the recirculation test ( reference time t1 ) until the normal value of conductivity difference 118 is reached again ( reference time t4 ) is calculated by the unrecirculated flow determining operation 106 of the sensing logic and display circuit 90 . the integral of differential conductivity 116 decreases ( reference ) to a second steady state value 134 ( reference time t4 . the second steady state value 134 of the integral of differential conductivity is stored by the unrecirculated flow determining operation 106 of the sensing logic and display circuit 90 and is representative of the portion of the bolus of high conductivity liquid that was not recirculated . the second steady state value 134 is thus representative of the unrecirculated portion of the treated blood flow . the dividing operation divides the second steady state value 134 by the first steady state value 126 to calculate a recirculation efficiency 136 . the recirculation efficiency 136 is provided to the operator as a visual output by the display device 110 . it will be apparent to those skilled in the art that the sensing logic and display circuit 90 may be implemented using analog or digital circuit devices and that other calculation algorithms may be used to calculate recirculation efficiency 138 . further , the recirculation efficiency 138 may be calculated in real time or , alternatively , the necessary data stored and the calculations performed on the stored data . further details of the preferred embodiment of the differential conductivity recirculation monitor will be explained by reference to fig7 - 11 . fig7 illustrates a portion of a typical disposable tubing set 140 incorporating conductivity cells 52 and 54 in accordance with the present invention . as is well known in the art , it is highly desirable for all portions of the tubing set 140 to be used with a dialysis system to be disposable , in order to prevent cross contamination and infection between patients . this is true of most blood and other biological or medical fluid processing systems . disposable tubing sets may be formed from a plurality of plastic tubes , connectors , needles and medical devices using techniques that are well known in the art . the discussion of the tubing set 140 will therefore be limited to a discussion of the differential conductivity recirculation monitor 22 ( fig1 ) portion of the tubing set . the dialyzer outlet line 32 is a plastic tube which extends through the needle access site 50 , into the outlet conductivity cell 52 . the outlet conductivity cell 52 comprises a plastic conduit loop and includes the upstream connection 56 , elongated divided first and second tubing branches 60 and 62 , and the downstream connector 58 . the downstream connector 58 has mounted in it an extension of the dialyzer outlet line 32 , which is mounted through a connector 142 to the outlet needle 34 . the dialyzer inlet needle 28 is connected through a connector 144 , to the dialyzer inlet line 30 . the dialyzer inlet line 30 is connected to the inlet conductivity cell 54 , which includes the upstream connection 64 , elongated divided third and fourth tubing branches 68 and 70 respectively , and downstream connector 66 . the dialyzer inlet line 30 extends from the downstream connector 66 to the dialyzer apparatus 24 ( fig1 ). in the preferred embodiment the portion of the dialyzer outlet line 32 between the dialyzer outlet needle 34 and the downstream connector 58 of the outlet conductivity cell 52 and the portion of the dialyzer inlet line 30 between the dialyzer inlet needle 28 and the upstream connector 64 of the inlet conductivity cell 54 must be sufficiently long so that the bolus of marker fluid passes completely through the outlet conductivity cell before any altered conductivity fluid from the fistula 26 enters the inlet conductivity cell . the conductivity cells 52 and 54 have the overall shape of links in an ordinary chain , straight side portions 146 being joined at their ends by semicircular portions 148 . in cross - section at the excitation location , as shown in fig8 the wall of each conductivity cell 42 and 54 defines a d , the insides of the ds providing conduit portions 150 and 152 . a flat portion 154 of the d of the outlet conductivity cell 52 is abutted and adhered to a flat portion 156 of the d of the inlet conductivity cell 54 along one pair of semicircular portions 148 of the conductivity cells . the other pair of circular portions 148 are separated so that axes of the conductivity cells 52 and 54 define therebetween an angle of approximately sixty degrees . the flat portions 154 and 156 of the conductivity cells 52 and 54 are further joined along two of the straight portions 146 at a location along the second and fourth tubing branches 62 and 70 , respectively at the sensing location . an orientation tab 159 is formed on the inlet conductivity cell 54 . mating with tube set 140 is a tubing set acceptor 160 . as shown in fig9 tee tubing set acceptor 160 comprises a portion of an excitation and sensing unit 162 which also includes a logic circuit module 164 . the tubing set acceptor 160 comprises a portion of a first , or rear , acceptor plate 166 and a second , or front , acceptor plate 168 joined by a hinge 169 for motion between open and closed positions and provided with a latch or spring ( not shown ) to hold the acceptor plates in the closed position . the first acceptor 166 plate is relieved to accept into appropriately - shaped indentations 170 thereof the outlet conductivity cell 52 ( fig2 ) and portions the tubing set 140 ( fig7 ). the second acceptor plate 168 is relieved to accept into appropriately - shaped indentations 172 thereof the inlet conductivity cell 54 and portions of the tubing set 140 ( fig7 ). an orientation tab recess 173 is defined by at least one of the appropriately shaped indentations 170 and 172 . the orientation tab recess 173 cooperates with the orientation tab 159 ( fig7 ) of the tubing set 140 ( fig7 ) to assure that the tubing set is correctly oriented when installed in the tubing set acceptor 160 . the tubing set acceptor 160 is sufficiently large to support the conductivity cells 52 and 54 and enough of the dialyzer outlet line 32 and dialyzer inlet line 30 so that fluid flow patterns through the conductivity cells are substantially repeatable , being relatively unaffected by bends , curves , tubing movement , and other disturbances or variations in the positions of the outlet and inlet lines with respect to the conductivity cells during measurement . the excitation coil 72 and sensing coil 74 are mounted to the tubing set acceptor 160 . the excitation coil 72 and sensing coil , 74 are positioned at right angles to each other to minimize magnetic interference between the coils . the excitation coil 72 comprises a first , or rear , and a second , or front , half core 174 and 176 , respectively . similarly the sensing coil comprises a third , or rear , and a fourth , or front , half - core 178 and 180 respectively . the first and third half - cores 174 and 178 , respectively are mounted to the first acceptor plate 166 and the second and third half cores 176 and 180 respectively are mounted to the second acceptor plate 186 . as illustrated in fig8 each half core has a u - shaped configuration , with short legs 182 having ends 184 and connecting legs 186 . the tubing set acceptor 160 holds a portion of the tubing set 140 which includes the conductivity cells 52 and 54 in a fixed relationship with the excitation coil 72 and sensing coil 74 . the first and second half cores 174 and 176 are oriented so that their ends 184 abut when the first and second acceptor plates 166 and 168 are brought to the closed position . the excitation coil 72 thus formed is in the shape of a rectangle defining a rectangular window . the third and fourth half cores 178 and 180 are similarly oriented so that their ends abut when the first and second acceptor plates 166 and 168 are brought to the closed position . the sensing coil 74 thus formed is also in the shape of a rectangular ring defining a rectangular window ( not shown ). when a tubing set 140 is placed in the tubing set acceptor 160 the first and third tubing branches 60 and 68 are engaged in the window of the excitation coil 72 and the second and fourth tubing branches 62 and 70 are engaged in the window of the sensing coil 74 so that the coils encircle the corresponding tubing branches . biasing springs 188 may be provided to hold corresponding half - cores in firm contact when the acceptor plates 166 and 168 are closed . the legs 182 and 186 of the coil 72 and 74 are square in cross - section . at least one connecting leg 186 of each coil 72 and 74 is transformer wire wrapped 190 . the logic circuit module 164 of the excitation and sensing unit 162 may be mounted to one of the acceptor plates 168 or may be separate from the tubing set acceptor 160 with wiring interconnections ( not shown ) to the tubing set acceptor 160 . the logic circuit module houses the sensing logic and display circuit 90 , with the display device 110 and one or more manual input switches 192 to enable the operator to perform such functions as turning the recirculation monitor on and off , testing the operation of the monitor and initiating recirculation test . although the display device 110 and manual input switches 192 are shown in fig9 as being on a side 194 of the logic circuit module 164 adjacent to the second acceptor plate 168 , in the preferred embodiment the display device and manual input switches may be on a side 196 opposite the second acceptor plate 168 , or any other side of the logic circuit module . the circuitry for conductivity measurement and calibration may suitably betas set forth in the ogawa patent incorporated by reference above . the preferred embodiment of the present invention has been described by reference to determination of recirculation efficiency in a surgically created blood access site during , or in conjunction with , a hemodialysis procedure . it should be understood that the present invention is not so limited . the present invention may be used in a variety of medical and non - medical circumstances where it is desirable to determine recirculation efficiency . further , it should be understood that the present invention may be used in a variety of medical and non - medical circumstances where it is desirable to compare the electrical conductivities of two fluids . presently preferred embodiments of the present invention and many of its aspects , features and advantages have been described with a degree of particularity . it should be understood that this description has been made by way of preferred example , and that the invention is defined by the scope of the following claims .
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fig1 is front view of an example embodiment of a digital camera including a led and strobe lighting device according to the present invention . an example embodiment of a camera 100 constructed according to the present invention may include a camera body 102 , a lens 106 , a led and strobe lighting device 104 , an external viewfinder window 108 , a shutter release 110 , and a control 112 . as with all digital cameras , this example embodiment of the present invention includes a circuit 114 electrically connected to the shutter release 110 , electrically connected to the led and strobe lighting device 104 , and configured to control the lighting device 104 by activating either the led or the strobe within the lighting device . this circuit 114 includes a means for detecting when the shutter release 110 is depressed . in some example embodiments of the present invention , the circuit 114 may also be configured to detect when the shutter release 110 is partially depressed . in an example embodiment of the present invention , the control 112 may be used to select a mode of the digital camera . these modes may include a still photo mode and a video mode . fig2 is front view of an example embodiment of a digital camera attached to a lighting device including a led and a strobe according to the present invention . in this embodiment of the present invention the lighting device including a led and a strobe is configured as a separate device from the digital camera . similar to the digital camera of fig1 , this example embodiment of a camera includes a camera body 202 , a lens 206 , an external viewfinder window 208 , a shutter release 210 , a control 212 , a hot shoe 220 including hot shoe electrical contacts 222 . as with all digital cameras , this example embodiment of the present invention includes a circuit 224 electrically connected to the shutter release 210 , electrically connected to the hot shoe electrical contacts 222 and the flash control outputs 218 . the circuit 224 is configured to control one or more external lighting devices through the hot shoe electrical contacts 222 or the flash control outputs 218 . this circuit 224 includes a means for detecting when the shutter release 210 is depressed . in some example embodiments of the present invention , the circuit 224 may also be configured to detect when the shutter release 210 is partially depressed . in an example embodiment of the present invention , the control 212 may be used to select a mode of the digital camera . these modes may include a still photo mode and a video mode . this example embodiment also includes dedicated flash control outputs 218 separate from the hot shoe electrical contacts 222 . both the flash control outputs 218 and the hot shoe electrical contacts 222 may be used to control a mode of the lighting device 200 . this example embodiment of a lighting device 200 includes a combined led and strobe 204 , flash control inputs 216 , and a switch 214 . the flash control inputs 216 and the switch 214 may be used to select a mode of the flash . in a still mode , the strobe of the flash is activated when triggered by the camera . in a video mode , the led is activated when triggered by the camera . in an example embodiment of the present invention , the switch 214 may allow a user to override the mode signal communicated from the camera through the flash control outputs 218 into the flash control inputs 216 of the lighting device 200 . fig3 is a cross - sectional view of a lighting device including two leds , a strobe , and a single reflector according to the present invention . in this example embodiment of the present invention a lighting device 300 is built including a body 302 with supports 312 for a reflector 308 and a lens 310 . in this example embodiment two leds 306 share the common reflector 308 with a strobe tube 304 . those of skill in the art will recognize that many different configurations of leds and strobe tubes may be used within the scope of the present invention . while this example embodiment includes two leds 306 positioned on either side of a strobe tube 304 other embodiments may use any number of leds 306 positioned in widely varying locations with respect to the strobe tube 304 . also , other embodiments of the present invention may use more than one strobe tube 304 . fig4 is a cross - sectional view of a lighting device including one led , a strobe , and two reflectors according to the present invention . in this example embodiment of the present invention a lighting device 400 is built including a body with supports 414 configured to mechanically affix a first reflector 406 , a first lens 410 , a second reflector 408 , and a second lens 412 . a strobe tube 402 is configured to use the first reflector 406 and the first lens 410 , while a led 404 is configured to use the second reflector 408 and the second lens 412 . this embodiment of the present invention includes a hot shoe foot 416 including flash input connections 418 configured to electrically couple to the hot shoe of the camera shown in fig2 . those of skill in the art will recognize that many different quantities and configurations of strobe tubes and leds may be used within the scope of the present invention . while many implementations of the present invention will use white leds for video illumination , other colors of leds may be used either in place of , or in addition to white leds to change the color of the light generated by the lighting device . in other embodiments of the present invention , the led and strobe illumination device may be configured as a device separate from the camera . it may attach to the camera via a hot shoe , and additional signals within the hot shoe may control the mode of the illumination device . in some simple embodiments of the present invention the mode of the illumination device may be controlled by the user of the camera with a switch . the foregoing description of the present invention has been presented for purposes of illustration and description . it is not intended to be exhaustive or to limit the invention to the precise form disclosed , and other modifications and variations may be possible in light of the above teachings . the embodiments were chosen and described in order to best explain the principles of the invention and its practical application to thereby enable others skilled in the art to best utilize the invention in various embodiments and various modifications as are suited to the particular use contemplated . it is intended that the appended claims be construed to include other alternative embodiments of the invention except insofar as limited by the prior art .
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the following description is merely exemplary in nature and is not intended to limit the present disclosure , application , claims , compositions , or uses . while the invention has been particularly shown and described with reference to a number of embodiments , it would be understood by those skilled in the art that changes in the form and details may be made to the various embodiments disclosed herein without departing from the spirit and scope of the invention and that the various embodiments disclosed herein are not intended to act as limitations on the scope of the claims . all percentages and the term “ w / w ” used herein unless specifically stated are percent by weight , and all component amounts recited as “ parts ” are parts by weight and are usually on a basis of parts per part of the active ingredient . the term “ ppm ” is parts per million by weight . when salts of components are mentioned , unless otherwise specifically stated , the composition can contain the acid form of the component , one or more salts of the component , or any mixture thereof . the aprotic solvent is preferably a pyrrolidone such as nmp , though one or more of dimethylsulfoxide ( dmso ), dimethylformamide , and gamma - butyrolactone alone or in mixtures , including mixtures with nmp , are useful . dmso and gamma - butyrolactone dissolve 0 . 24 to 0 . 25 grams prodiamine per gram solvent . nmp dissolves 0 . 68 grams prodiamine per gram solvent . the aprotic solvent is the primary solvent in most embodiments of the ec . there are a number of solvents that are not suitable and would be included only to change the composition . examples , and solubility of prodiamine in grams ai per gram solvent , are shown below for completeness . fatty amides , also called “ fatty acid solvents ” in this application , are amides formed from a fatty acid and an amine , of which many are known . preferred are di - substituted fatty acid amides , which include as non - limiting examples n , n - dimethylcaprylamide ( available from cognis as agnique ™ ke - 3658 ), and n , n - diethyloctanamide ( available as halcomid ™ m8 - 10 ). these compounds can fully or partially replace aprotic solvents , and the solvating capacity approaches that of less - preferred aprotic solvents such as dmso and gamma - butyrolactone , that is , 0 . 24 to 0 . 25 grams prodiamine per gram solvent . a mixture of c8 and c10 fatty acid dimethylamide , ( cas 1118 - 92 - 9 and 14433 - 76 - 2 ) are useful . the alkyl - alkoxylate - based emulsifier is typically an alkyl - based eo / po - containing block copolymer emulsifier , for example an ethylene oxide / propylene oxide alkyl ( e . g ., butyl ) block copolymer . it is possible to use suitable co - polymers of ethylene oxide and propylene oxide , such as aba or bab block copolymer or ba block copolymers . the alkyl group can range from c3 to c7 , for example . a preferred group of ethylene oxide / propylene oxide block copolymers for use in the compositions of this invention are butyl based poly ( oxypropylene ) poly ( oxyethylene ) block copolymers having an average molecular weight in a range of 2 , 400 to 3 , 500 ( e . g . toximul ™ 8320 , stepan chemical co .) also useful is harcros ™ tda - 12 . the hydrophilic non - ionic emulsifier can be a ethoxylated alcohol . a c9 to c18 alcohol can be used , with for example 8 to 20 eo units , for example a tridecyl alcohol hydrophilic non - ionic emulsifier . examples include makon ™ td - 12 , a tridecyl alcohol ethoxylate , poe - 12 available from stepan , or harcros tda - 12 . generally an anionic emulsifier can provide added emulsion stability , and alkyl sulfonates are useful for this purpose , for example a fatty acid benzene sulfonate , particularly calcium salts of dodecylbenzenesulfonate . the following examples are provided for illustrative purposes only and are not limiting to this disclosure in any way . indeed , various modifications of the invention , in addition to those shown and described herein , will become apparent to those skilled in the art from the following examples and the foregoing description . such modifications are also intended to fall within the scope of the appended claims . a first prodiamine ec composition # 1 is shown in table 1 below . various embodiments of the formulations disclosed herein , when formulated into a herbicidal composition , show a surprising and unexpected performance in efficacy and low phytotoxicity for general residential and commercial landscaped herbicide treatment as well as for direct application to urea and other fertilizers for superior pre - emergence weed control . to demonstrate this activity , a series of trials were performed and are described below . field test 1 objective was to evaluate example 1 ( table 1 ) formulation efficacy on pre - emerge crabgrass ( digitaria ischaemum ) against market standard ( s ) in latour , mo . other products tested were barricade 4l at 22 fl . oz ./ acre ( 0 . 68 lb prodiamine / acre ), dimension 40wp at 0 . 6 lb ./ acre ( 0 . 24 lb dithiopyr / acre ), and example 1 at 43 . 56 fl . oz . per acre ( 0 . 68 lb . prodiamine / acre ). test data , percent crabgrass in stand at 58 and 100 days after treatment , are shown below . the differences between treatments were not statistically significant . barricade 4l at 22 fl . oz ./ acre ( 0 . 68 lb prodiamine / acre ): june 5 , 2 %, and july 17 , 39 % dimension 40wp at 0 . 6 lb ./ acre ( 0 . 24 lb dithiopyr / acre ): june 5 , 2 %, and july 17 , 32 % example 1 at 43 . 56 fl . oz ./ acre ( 0 . 68 lb . prodiamine / acre ): june 5 , 2 %, and july 17 , 43 % field test # 2 , to compare barricade to example 1 prodiamine 2 ec for turfgrass safety . 3 × log study on bluegrass poa pratensis in latour , mo . treatments were applied with an application volume of 43 . 56 gallons per acre as a foliar spray . active ingredients were logged at ¼ steps with a reduction in ai by 25 % from the previous step . data at 3 , 7 , and 14 days after treatment are below , with damage on a scale of 0 - 9 . field test # 2 showed no phytotoxicity was observed barricade 4fl , and for example 1 ( prodiamine 2ec ) at 3dat only slightly phytotoxic at step 1 and 2 application rates . step 1 was slightly phytotoxic at 7dat and no phytotoxicity at 14dat . field test # 3 was to compare barricade to experimental prodiamine 2 ec for turfgrass safety . a 3 × log study was done on tall fescue ( festuca arundinacea ) in latour , mo . treatments were applied with an application volume of 43 . 56 gallons per acre via foliar spray . active ingredients were logged at ¼ steps with a reduction in ai by 25 % from the previous step . step 1 is the starting full ai load rate followed by a 25 % ai reduction from the previous step through step 6 . initial application was 72 fl . oz . barricade 4fl per acre ( 2 . 25 lb prodiamine / a ), and example 1 ( prodiamine 2ec ) was applied at 115 fl . oz . per acre ( 1 . 8 lb / a ). conclusion : for barricade 4fl no phytotoxicity was observed , and for prodiamine 2ec at the high rate ( step 1 ) only slight visual phytotoxicity was observed throughout the study . a stable prodiamine ec formulation called pa - 1010 is shown in table 4 below : field test 1 - 2012 evaluated turfgrass phytotoxicity using the example 4 ( table 4 ) formulation . the test was performed by virginia tech university ( blacksburg , va . ), test # 63 - 12 , on kentucky bluegrass ( midnight ) at 0 . 6 ″ fairway mowing height in an irrigated site with irrigation received as needed . the grass was treated may 29 , 2012 . no injury to midnight ky bluegrass observed throughout the study ( 28 days ). no significant differences in % turfgrass cover were noted compared to the untreated control 28 days after the test was initiated . pa - 1010 was applied at 40 fl . oz . per acre . % turfgrass cover days after application ( da - a ) 9 17 28 0 28 pa - 1010 turfgrass injury (%) 0 0 0 % turfgrass cover 71 . 3 61 . 3 untreated turfgrass injury (%) 0 0 0 % turfgrass cover 77 . 5 68 . 8 there was no statistically significant difference between the treated blocks and the control . field test 2 - 2012 evaluated turfgrass phytotoxicity using the example 4 ( table 4 ) formulation . the test was performed by virginia tech university ( blacksburg , va . ), test # 64 - 12 , on perennial ryegrass ( asp6004 ) at 0 . 6 ″ fairway mowing height in an irrigated site with irrigation received as needed . the grass was treated may 29 , 2012 . pa - 1010 was applied at 40 fl . oz . per acre . no injury to perennial ryegrass observed throughout the study ( 28 days ). no significant differences in % turfgrass cover were noted compared to the untreated control 28 days after the test was initiated . % turfgrass cover days after application ( da - a ) 10 17 28 0 28 pa - 1010 turfgrass injury (%) 0 0 0 % turfgrass cover 72 . 5 65 untreated turfgrass injury (%) 0 0 0 % turfgrass cover 72 . 5 63 . 8 there was no statistically significant difference between the treated blocks and the control . field test 3 - 2012 was conducted to test if application of pa - 1010 results in phytotoxicity to desired cool season turfgrasses . the turf species tested was kentucky bluegrass ( poa pratensis ) that had a small amount of perennial ryegrass ( lolium perenne ). the study was conducted at the ohio turfgrass foundation research and education center in columbus , ohio . the sites of the experiment was weed - free . individual treatment plots were 3 × 6 ft and there were treatments and an untreated control ( table 1 ). the experimental design was a randomized complete block with 3 replications . the experiments were all established on jun . 5 , 2012 . pa - 1010 was applied at 40 fl oz per acre . a backpack carbon dioxide sprayer equipped with 6503 nozzles with a spray pressure of 40 psi was used to apply the products with the equivalent of 2 gal h 2 o / 1000 ft 2 . turfgrass phytotoxicity data were collected at 7 , 14 , and 28 days after application of treatments ( dat ) by visually estimating percent injury to the turfgrass on a scale of 0 to 10 with 0 = no injury and 10 = dead turfgrass . the data were analyzed using the general linear models procedure of sas . fishers protected lsd was conducted on the data . barely noticeable injury symptoms were noted in all treated plots at 7 dat ( table 1 ). this was primarily a very light chlorosis . however , none of the differences were statistically significant . the rates tested caused no injury significantly different than the untreated plots at 14 dat . at 28 dat no phytotoxicity was noted . finally , though the rating for plots treated with treatment 4 was numerically lower , there were no significant quality differences observed at 43 dat . pa - 1010 was safe to kentucky bluegrass at all rates tested . treated and control blocks showed 0 . 3 damage at day 7 and 0 . 0 damage at days 14 and 28 , where zero is no damage and 10 is dead turf turf quality for both treated and untreated was rated 7 . 0 at 43 days after testing . field test 4 - 2012 performed at southeastern turfgrass research & amp ; consulting , llc ( lexington , ky .) to evaluate phytotoxicity on a stand of well - managed lawn - height tall fescue turf tall fescue ( barrington / barlexas / barvado tall fescue blend by barenbrug ) at 3 . 5 ″ lawn mowing height was treated on jul . 23 , 2012 . pa - 1010 was applied at 40 fl . oz . per acre . no phytotoxicity was observed at any rating period . turfgrass quality , where 1 = brown , dead turf and 9 = perfect green turf , was 6 . 5 for the treated plots at day 6 versus 6 . 8 for untreated control . at days 20 and 26 after treatment , turfgrass quality was identical between treated and untreated blocks , measuring 7 . 0 in all cases . field test 5 - 2012 by southeastern turfgrass research & amp ; consulting , llc evaluated phytotoxicity at a field between a pond and trees in lexington , ky . tall fescue at 3 . 5 inches was in 44 sand , 48 % silt , 8 % clay , om : 3 . 9 loam with a cec of 9 . 4 and a ph of 6 . 1 . fertilizer level was poor . appliccation was by co2 sprayer at 30 psi , applying 40 fl . oz . per acre of pa - 1010 on may 24 , 2012 . the test showed minor differences in turf quality at day 15 between treated and untreated , and results were identical between treated and untreated on days 21 and 28 after treatment . field test 6 - 2012 was conducted at the landscape horticulture research center at the university of illinois - urbana / champaign in urbana , ill . treatments were applied to a mature stand of kentucky bluegrass l . cv . ‘ bewitched ’ maintained at a 0 . 875 - inch height of cut . the experimental design used was a randomized complete block with four replications and plots measured 4 × 6 feet . treatments were applied with a backpack - type co2 sprayer at 32psi fitted with vs8002 nozzles ( teejet technologies , wheaton , ill .) and a spray volume of 50 gallons acre - 1 . treatments were applied on jun . 27 , 2012 . pa - 1010 was applied at 40 fl . oz . per acre . kentucky bluegrass injury was rated on a scale of 0 - 10 with 0 = none and 10 = dead turf . kentucky bluegrass quality was rated on a scale of 1 - 9 where , 1 = low and 9 = high quality . kentucky bluegrass density was rated on a scale of 1 - 9 where , 1 = open , 6 = typical normal density and 9 = very dense . this study experienced record breaking high temperatures during the first 2 weeks of the trial . the first eleven days of the trial had 5 days over 90 and 6 days at or over 100 degrees f . the average high temperature for the first eleven days was 98 . 5 f ! no phytotoxicity was observed and treated plots showed higher quality and density than untreated control .
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referring now to the drawings , reference numeral 1 indicates one illustrative embodiment of tattooing tool embodying the present invention . the tool 1 includes a motor - driven dental handpiece 3 and a needle / cone assembly 4 . the handpiece 3 includes a motor 5 , a gear drive 7 , and a modified reciprocating head 9 . the motor 5 may be of any standard type , such as air - powered or electrical , and is preferably an electric motor operating at a nominal speed of about 15 , 000 revolutions per minute . the gear drive 7 may be a standard dental handpiece drive , typically having a gear ratio of 1 : 1 . the modified head 9 may be similar to the head shown in u . s . pat . no . 3 , 552 , 022 to axelsson , and will be described in greater detail hereinafter . the motor 5 , drive 7 and head 9 are contained in separate housings all of which are connected to each other by standard fittings to form a handpiece having a housing indicated generally at 11 . the head 9 includes a generally cylindrical housing 13 having at one end a standard connector 15 for connecting the head 9 to the drive 7 . at its free end , the cylindrical housing 13 communicates with a perpendicular oscillator housing 17 . an oscillator mechanism 19 is threaded into the free end of the head housing 13 as shown in fig1 . the oscillator mechanism 19 includes an oscillator bearing 21 , a shaft 23 in the bearing 21 , a connector 25 on the shaft 23 for drivingly connecting the shaft 23 to the drive 7 , and a cam 27 on the free end of the shaft 23 . the cam 27 includes an eccentric lug 29 extending into the oscillator housing 17 . the oscillator housing 17 includes a cylindrical bore 31 having a step 33 at its rearward end and internal threads 35 at its forward end . a bearing 37 is tightly fitted in the bore 31 , against the step 33 . the bearing 37 includes a depending tail 39 . a retaining tube 41 is slidably mounted in the bearing 37 . as shown in greater detail in fig5 and 6 , the retaining tube 41 is in the form of a tube having a forward annular rib 45 and a rearward annular rib 47 , spaced apart sufficiently to receive the lug 29 between them . the rearward rib 47 is cut away to form a flat 49 which cooperates with the tail 39 on the bearing 37 , thereby preventing rotation of the retaining tube 41 in the bearing 37 . the retaining tube 41 is preferably formed of stainless steel . as thus far described , the device 1 is a dental handpiece of a type sold by young dental manufacturing company as its dawn eva handpiece . the retaining tube 41 , as shown in fig5 and 6 , is modified by four longitudinal cuts extending from the rearward end of the retaining tube 41 to the forward rib 45 to form a pair of fingers 51 . the fingers 51 are bent inwardly at their free ends . an adapter 53 is threaded into the forward end of the oscillator housing 17 . the rearward end of the adapter 53 includes an internal bearing 55 for the retaining tube 41 . the forward end of the adapter 53 includes internal threads 57 . the adapter 53 is made of stainless steel . the needle / cone assembly 4 includes a needle assembly 61 and a cone structure 63 . the needle assembly 61 includes a needle carrier 65 and three needles 67 carried by the carrier 65 . the carrier 65 has a thin tubular forward part 69 , an annular shoulder 71 , a rearwardly - facing abutment 73 , a body part 75 , a thin frangible neck 77 , and a cap part 79 having a rim 81 . a blind axial bore 83 extends through the forward end of the carrier 65 into the body part 75 . the three needles 67 are accurately aligned with each other in the form of an equilateral triangle , are fitted snugly into the bore 83 , and are glued into the bore 83 . the needle carrier 65 is machined from aluminum . the needles are nickel - plated carbon steel . the cone structure 63 includes a frustoconical part 85 at its forward end , a collar part 87 , a threaded plug part 89 , and a rearward cylinder 91 . the frustoconical part 85 is turned inwardly somewhat at its forward , free , end to form an ink reservoir . breather holes 93 are provided at the rear of the frustoconical part 85 . the cone structure 63 is formed of aluminum . the needle assembly 61 is assembled to the cone structure 63 , with the shoulder 71 in the cylinder 91 of the cone structure 63 and with the needles in the frustoconical part 85 . the entire free rearward edge of the cylinder part wall is swaged inwardly as shown at 92 , to trap the needle assembly shoulder 71 in the cylinder 91 . the shoulder 71 is somewhat smaller than the inside diameter of the cylinder 91 , to permit free reciprocation of the needle assembly in the cone structure . an installation tube 95 is inserted into the frustoconical part 85 of the cone structure 63 and abuts the forward end of the needle carrier 65 . the tube is pinched slightly out of round , as shown at 96 , to hold it snugly in the frustoconical part , with its end pushing needle assembly to its rearward - most position in the cone structure . the tube 95 performs the dual function of protecting the needles 67 and aiding in the installation of the needle / cone assembly as described hereinafter . the installation tube 95 is made of stainless steel . the needle / cone assembly 4 , including the installation tube 95 , is assembled , sterilized , and packaged in a sterile container . in use , the needle / cone assembly 4 is removed from its packaging and inserted into the adapter 53 and oscillator housing 17 . the threads 89 on the cone structure 63 are threaded into the threads 57 until the collar part 87 abuts the forward end of the adapter 53 . as the cone structure 63 is threaded onto the head 9 , the cap 79 on the needle carrier 61 is forced between the fingers 51 of the needle retaining tube 41 . to ensure complete insertion of the needle assembly 61 into the retaining tube 41 , the installation tube 95 is pushed rearwardly into the oscillator housing 17 before the tube 95 is removed . when the needle assembly 61 is completely inserted into the retaining tube 41 , the abutment 73 on the needle assembly 61 engages the forward end of the retaining tube 41 , and the fingers 51 tightly engage the cap 79 , on the forward side of the rim 81 . the body 75 of the needle carrier 65 fits snugly in the retaining tube 41 . the fingers 51 perform the dual functions of locking the needle assembly axially with respect to the retainer tube 41 and of locking the needle assembly 61 against rotation . upon application of a rotational force on the needle assembly 61 , the stainless steel fingers 51 tend to dig into the softer aluminum to provide positive locking . the tattooing device 1 is used in a conventional manner . rotation of the motor 5 is transmitted through the drive 7 and connector 25 to the cam 27 . the cam lug 29 reciprocates the retaining tube 41 at approximately 15 , 000 cycles per minute , thereby causing the needles 67 to be driven into and out of the frustoconical part 85 . the frustoconical part 85 is dipped in ink in a conventional manner , and the ink is held in the frustoconical part and carried on the tips of the needles 67 . the breather holes 93 prevent the ink from being drawn into the cylinder 91 . at the maximum forward stroke , the needles 67 extend about 1 . 5 millimeters from the end of the frustoconical part 85 . when a particular tattooing job has been completed , the needle / cone assembly 4 is unscrewed from the adapter 53 . when the needle / cone assembly is backed out partially , the turned edge 92 of the cylinder 91 engages the shoulder 71 . continued unscrewing of the needle / cone assembly 4 causes the neck 77 to be snapped . the cap 79 is then able to fall out of the rearward opening of the oscillator housing 17 , when it is pushed by a new needle / cone assembly &# 39 ; s being inserted into the device 3 . it will be seen that the position of the needles is accurately controlled by the bearings 37 and 55 , the fit of the needle carrier 65 in the retaining tube 41 , and the secure permanent bonding of the needles in the bore 83 of the needle carrier 65 . in use , the needle assembly does not touch the cone structure . because the needle / cone assembly may be pre - sterilized and requires no handling of the needles during assembly , sterility is easily maintained . automatic breakage of the frangible neck 77 ensures that needles , once removed , will not be reused . the accidental use of dull or unsanitary needles is thus prevented . the neck may easily be made strong enough for ordinary use , yet readily breakable upon removal of the needle / cone assembly . should the neck break in use , the needles would no longer be driven , but would not fall out of the device . numerous variations in the tool and needle assembly of the present invention , within the scope of the appended claims , will occur to those skilled in the art in light of the foregoing disclosure . for example , other single use tools could be substituted for the needle assembly . other drive devices could be used . other materials may be employed . these variations are merely illustrative .
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[ 0025 ] fig1 shows a cross section of a test substrate ( 10 ) and high density integral rigid test probe ( 12 ) according to the present invention . the test substrate ( 10 ) provides a rigid base for attachment of the probes structures ( 12 ) and fan out wiring from the high density array of probe contacts to a larger grid of pins or other interconnection means to the equipment used to electrically test the integrated circuit device . the fan out substrate can be made from various materials andl constructions including single and multi - layer ceramic with thick or thin film wiring , silicon wafer with thin film wiring , or epoxy glass laminate construction with high density copper wiring . the integral rigid test probes ( 12 ) are attached to the first surface ( 11 ) of the substrate ( 10 ). the probes are used to contact the solder bralls ( 22 ) on the integrated circuit device ( 20 ). the solder balls ( 22 ) are attached to the first surface ( 21 ) of the integrated circuit device ( 20 ). [ 0026 ] fig2 shows an enlarged cross section of the high density integral rigid test probe ( 12 ). the probe tip is enlarged ( 13 ) to provide better alignment tolerance of the probe array to the array of solder balls ( 22 ) on the ic device ( 20 ). the integral rigid test probe ( 12 ) is attached directly to the fan out wiring ( 15 ) on the first surface ( 11 ) of the substrate ( 10 ) to minimize the resistance of the probe interface . the probe geometry includes the ball bond ( 16 ), the wire stud ( 17 ), and the enlarged probe tip ( 13 ). a sheet of polymer material ( 40 ) with holes ( 41 ) corresponding to the probe positions is used to support the enlarged tip ( 13 ) of the probe geometry . it is desirable to match the coefficient of thermal expansion for the polymer sheet ( 40 ) material and the substrate material to minimize stress on the interface between the ball bond ( 16 ) and the fan out wiring ( 15 ). as an example , the bpda - pda polyimide can be used with a silicon wafer substrate since both have a coefficient of thermal expansion ( tce ) of 3 ppm / c . this material is also stable up to 350 c . [ 0027 ] fig3 shows the first process used to fabricate the integral rigid test probe . a thermosonic wire bonder tool is used to attach ball bonds ( 16 ) to the first surface ( 11 ) of the rigid substrate ( 10 ). the wire bonder tool uses a first ceramic capillary ( 30 ) to press the ball shaped end of the bond wire against the first surface ( 11 ) of the substirite ( 10 ). compression force and ultrasonic energy ( 31 ) are applied through the first capillary ( 30 ) tip and thermal energy is applied from thle wire bonder stage through the substrate ( 10 ) to bond the ball shaped end of the bond wire to the first surface ( 11 ) of the substrate . the bond wire is cut , sheared , or broken to leave a small stud ( 17 ) protruding vertically from the ball bond ( 16 ). a first sheet of polymer material ( 40 ) with holes ( 41 ) corresponding to the probe locations on the substrate is placed over the array of wire studs ( 17 ) as shoown in fig4 . the diameter of the holes ( 41 ) in the polymer sheet ( 40 ) is slightly larger than the diameter of the wire studs ( 17 ). a second shect of metal or a hard polymer ( 42 ) with holes ( 43 ) corresponiding to the probe locations is also placed over the array of wire studs ( 17 ). the diameter of the holes ( 43 ) in the metal sheet ( 42 ) is larger than the diameter of the holes ( 41 ) in the polymer sheet ( 40 ). the enlarged ends of the probe tips are formed using a hardened anvil tool ( 50 ) as shown in fig5 . compression force and ultrasonic energy ( 51 ) are applied through the anvil tool ( 50 ) to deform the ends of the wire studs ( 17 ). the size of the enlarged probe tip ( 13 ) is controlled by the length of the wire stud ( 17 ) protruding through the polymer sheet ( 40 ), the thickness of the metal sheet ( 42 ), and the diameter of the holes ( 43 ) in the metal sheet ( 42 ). the enlarged ends of the probes ( 13 ) can be formed individually or in multiples depending on the size of the anvil tool ( 50 ) that is used . also , the surface finish of the anvil tool ( 50 ) can be modified to provide a smooth or textured finish on the enlarged probe tips ( 13 ). fig6 shows the high density integral rigid test probe with the metal mask ( 42 ) removed from the assembly . [ 0029 ] fig7 shows the sputtering or evaporation proces used to deposit the desired contact metallurgy ( 18 ) on the enlarged end ( 13 ) of the probe tip . contact metallurgies ( 18 ) such as pt , ir , rh , ru , and pd can be deposited in the thickness range of 1000 to 5000 angstroms over the probe tip ( 13 ) to ensure low contact resistance with thermal stability and oxidation resistance when operated a elevated temperatures in air . a thin layer of tin , cr , ti , ni , or co can be used as a diffusion barrier ( 19 ) between the enlarged probe tip ( 13 ) and the contact metallurgy ( 18 ) on the surgace of the probe . [ 0030 ] fig8 shows a high density integral test probe ( 12 ) with an additional sheet of polyimide ( 44 ) with enlarged holes ( 45 ) corresponding to the probe location placed on top of the first sheet of polyimide ( 40 ). the enlarged holes ( 45 ) in the second sheet of polyimide ( 44 ) acts as a cup to control and contain the creep of the solder balls at high temperatures . multiple probe arrays can be fabricated on a single substrate ( 60 ) as shown in fig9 . each array of probes is decoupled from the adjacent arrays by using separate polyimide sheets ( 61 , 62 ). matched coefficients of thermal expansion for the plymer sheets ( 61 , 62 ) and the substrate ( 60 ) become increasingly more important for multiple arrays of probes on a large substrate . even slight differences in the coefficient of thermal expansion can result in bowing of the substrate or excessive stresses in the substrate and polymer material over a large area substrate . [ 0032 ] fig1 shows the structure of fig1 with second contact locations ( 70 ) on surface ( 72 ) of substrate 10 . contact locations ( 70 ) can be the same as contact locations ( 13 ). fig1 shows the structure of fig6 with elongated ( 74 ) such as pins fixed to the surface ( 76 ) of pad ( 70 ). [ 0033 ] fig1 shows substrate ( 10 ) disposed spaced apart from the ic device ( 20 ). substrate ( 11 ) is held by arm ( 78 ) of fixture ( 80 ). the ic device ( 20 ) is disposed on support ( 82 ) which is disposed in contact with fixture ( 80 ) by base ( 84 ). arm ( 78 ) is adapted for movement as indicated by arrow ( 86 ) towards base ( 84 ) so that probe tips ( 12 ) are brought into engagement with conductors ( 22 ). an example of an apparatus providing a means for moving substrate ( 10 ) into engagement with the ic device ( 20 ) can be found in u . s . pat . no . 4 , 875 , 614 . while we have described our perferred embodiments of our invention , it will be understood that those skilled in the art , both now and in the future , may make various improvements and enhancements which fall within the scope of the claims which follow . these claims should be constructed to maintain the proper protection for the invention first disclosed .
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fig1 shows the first two units of a typical eo production plant . the first unit is reactor 2 . ethylene feed and a separate oxygen feed are mixed and then reacted in unit 2 to form eo with the consequent formation of by - product as aforesaid . unit 2 forms a first , normally gaseous , reaction product stream 3 that contains a major amount of newly formed eo , a substantial amount of free co 2 and a minor amount of unreacted ethylene . stream 3 is removed from outlet 7 of reactor 2 . the second unit in fig1 is eo absorber 4 which is a water wash scrubber that operates in known manner as a solvent extractor by absorbing ( dissolving ) eo out of stream 3 to form a principally eo / water stream 5 . stream 5 is normally at a temperature of from about 75 to about 105 f under a pressure of about 220 psig , and is primarily a water stream that can contain from about 3 to about 5 weight percent ( wt . %), based on the total weight of stream 5 , eo dissolved therein . stream 5 is then further processed in a manner that is not shown here for sake of brevity , but is shown in its entirety in u . s . pat . no . 6 , 727 , 389 . such further processing recovers , as products of the plant , purified eo and / or derivatives thereof such as one or more glycols . in some processes the eo is not purified , but rather is converted into ethylene glycol . absorber 4 also produces a normally gaseous by - product stream 6 that is part of the plant recycle gas loop . the recycle gas in stream 6 can contain from about 55 to about 97 wt . % methane , from about 20 to about 40 wt . % unreacted ethylene , from about 3 to about 5 wt . % co 2 , and a trace of eo , all wt . % being based on the total weight of stream 6 . ideally , stream 6 is essentially free of c 4 &# 39 ; s . stream 6 is recycled to reactor 2 by way of the plant recycle gas loop for reuse of the unreacted ethylene as feed material in reactor 2 , and in so doing , all or a substantial part of stream 6 can be processed for the removal of co 2 there from . fig2 shows in greater detail a typical recycle gas loop 10 wherein recycle stream 6 from absorber 4 is first passed to a compression unit 11 . the compressed gaseous product of unit 11 is removed by way of line 12 . all or any part of stream 12 can be passed into co 2 absorber 13 for removal of an essentially totally co 2 stream 14 . alternatively , all or any part of stream 12 can by - pass unit 13 by way of line 15 and pass into line 16 . stream 16 , which is essentially of the composition of stream 6 , except it can contain a lesser amount of co 2 , has additional ethylene feed 17 added thereto , after which it passes into an oxygen mix nozzle ( not shown ) by which additional oxygen 18 is added to the mixture of materials . this feed mixture is then passed by way of lines 19 , 20 , and 21 to the inlet 22 of reactor 2 for reaction of ethylene and oxygen therein as aforesaid . lines 19 through 22 can typically carry an array of individual sensors such as a high pressure sensor , high temperature sensor , high oxygen sensor , and high ethylene sensor . these individual sensors are shown collectively as sensor s in fig2 . pursuant to this invention one of these lines , preferably line 21 , carries , in addition to sensors s , a sensor c 4 which sensor is used to detect the c 4 compound content in that stream . this detection step will , by way of this invention , indicate incipient post - ignition developments at or near reactor inlet 22 . the c 4 indicators of this invention can be at least one of n - butane , iso - butane , iso - butylene , butenes , and butynes . a presently preferred marker is n - butane which , for sake of clarity only and not by way of limitation , will be used in the description hereinafter . the sensing equipment for sensor c 4 , and its operation are well known in the art . an example of such equipment is a standard gas chromatograph which is well known in the art and does not require further description to inform the art . as mentioned earlier , stream 21 is ideally devoid of any n - butane . however , there is often a very low background noise for c 4 compounds , typically 0 . 04 parts per million ( ppm ). sensor c 4 is set at a level above this c 4 background noise level for warning purposes . sensor c 4 can also be set to trigger at least one alarm or other warning device once a predetermined level of n - butane is detected in stream 21 . for example , a first alarm or other mechanism can be triggered at a first lower n - butane level to be a warning signal for the operator to watch the n - butane content of the recycle stream more closely , but not necessarily to take any remedial action . a second alarm or other warning device can be triggered at a predetermined higher n - butane level that has been previously determined to indicate that immediate remedial action must promptly be taken by the operator in order to avoid post - ignition at or near intake 22 in the near future . once the remedial action alarm is sounded , the operator then knows to take such action immediately , e . g ., by reducing the oxygen 18 feed rate . once the n - butane content of stream 21 , as detected by sensor c 4 , has decreased to a predetermined level that is below the level set for the first or warning alarm , for example , the feed rate for oxygen 18 can be slowly increased until it is back to its normal feed rate level for the reaction conditions then being present in the reactor . an eo plant as described here in above provides a recycle gas loop stream 6 having a volume of about 2 , 000 , 000 pounds per hour ( pph ) and containing about 50 wt . % methane , about 36 wt . % unreacted ethylene , about 2 . 5 wt . % co 2 , no more than about 0 . 04 ppm n - butane , and about 100 ppm eo , all based on the total weight of stream 6 . about 1 , 000 kpph of recycle loop gas 6 is split off from the recycle loop and passed to co 2 absorber 13 . stream 23 from absorber 13 returns about 960 , 000 pph of recycle gas to the loop . stream 23 has a composition of about 36 wt . % ethylene , about 50 wt . % methane , up to about 1 wt . % co 2 , about 10 wt . % elemental oxygen and argon , and a trace of eo , all wt . % based on the total weight of stream 23 . streams 23 and 15 are combined into stream 16 , and this stream has added thereto ethylene feed 17 and oxygen feed 18 in amounts sufficient to form a feed stream 22 for reactor 2 having a composition of about 40 wt . % ethylene , about 8 wt . % oxygen , about 50 wt . % methane , about 1 . 3 wt . % co 2 , a trace of eo , and no more than about 0 . 04 ppm n - butane . the butane content of this stream is monitored for its n - butane content on a continuous manner using a standard gas chromatograph . when the n - butane content of this stream reaches a level of 0 . 10 ppm , a warning alarm is triggered to focus the operator on this process parameter . when the n - butane content of this stream reaches a level of 0 . 20 ppm second alarm is triggered that signals the operator to take remedial action promptly in order to avoid a post - ignition event . the operator promptly reduces the flow of oxygen 18 into line 19 in order to alter the conditions that were trending toward the formation of a flame front .
| 2 |
the invention relates to 1 - arylalkoxytris ( dialkylamino ) phosphonium salt of the formula i ## str3 ## and also to a process for their preparation and their further reaction to give aromatic compounds having a partially fluorinated side chain . the starting materials used are aromatic aldehydes or ketones which are converted into phosphonium salts of the above formula i by reaction with trifluoromethyl halides and phosphorous triamides . it is known to prepare alkoxytris ( dialkylamino ) phosphonium salts by reaction of the corresponding alcohols with a reactive halotris ( dialkylamino ) phosphonium salt ( synthesis , 1979 , 951 - 2 ). the preparation of trifluormethyl - substituted carbinols , the alcohols on which the phosphonium salts of the formula i are based , by transfer of the trifluoromethyl radical to carbonyl compounds is of great interest and has been investigated in many publications . in this process , organometallic compounds of base metals , which are usually prepared from the corresponding trifluoromethyl halide and a metal , such as magnesium , zinc , manganese , etc ., are used . the disadvantage of this process is the usually expensive preparation and lability of the organometallic compounds which must be prepared initially , which manifests itself in the poor reproducibility of the published results ( tetrahedron lett . 26 , 5243 to 5246 ; specifically p . 5245 footnote 4 ). the invention accordingly relates to compounds of the formula i ( see above ) in which the radicals r 1 to r 5 are identical or different and denote hydrogen , alkyl having 1 to 6 carbon atoms , which can be perfluorinated , alkoxy or alkylthio each having 1 to 6 , in particular 1 to 3 , carbon atoms , and also halogen ( fluorine , chlorine , bromine , iodine ), in which , however , not more than three of the radicals r 1 to r 5 have a meaning other than hydrogen , y denotes hydrogen or a perfluoroalkyl radical c n f 2n + 1 having 1 to 6 carbon atoms , x is bromine or iodine and , &# 34 ; alkyl &# 34 ; stands for an alkyl radical having 1 to 3 carbon atoms . preferably , no more than two substituents r 1 to r 5 having a meaning other than hydrogen are bound to the aromatic ring . the alkyl , alkoxy and alkylthio substituents can be straight - chain or branched and advantageously contain overall a maximum of 6 , in particular a maximum of 4 , carbon atoms . the invention also relates to a simple one - step process for the preparation of the above - mentioned compounds . this can be achieved by transfer of a trifluoromethyl group to aromatic carbonyl compounds , whereby the preparation and use of the above - mentioned organometallic compounds is avoided , and consists in reacting carbonyl compounds of the general formula ii ## str4 ## with trifluoromethyl halides of the formula cf 3 x ( iii ), in which x is bromine or iodine , and phosphorous tris ( dialkylamides ) ( in other words tris ( dialkylamino ) phosphanes ) of the general formula p ( n [ alkyl ] 2 ) 3 ( iv ) to give phosphonium salts of the formula i ( see above ), where in formulae i to iii the radicals are r 1 to r 5 , y and &# 34 ; alkyl &# 34 ; have the above - mentioned meaning . these phosphonium salts are very useful intermediates for syntheses and can be converted - as will be shown later - to aromatics having partially fluorinated side chains , which otherwise are often only accessible with difficulty by other routes . the process according to the invention does not only have the advantage of being simple , but also the advantage that the starting materials are readily accessible and that without exception good yields of phosphonium salts are obtained . trifluoromethyl bromide which is less poisonous and cheaper than trifluoromethyl iodide can be used advantageously for the transfer of the trifluoromethyl radical to the carbonyl compounds . the aromatic carbonyl compounds ( ii ) used can be the aldehydes ( y = hydrogen ) or aryl perfluoroalkyl ketones ( y = perfluoroalkyl radical c n f 2n + 1 where n is 1 to 6 ). the aromatic carbonyl compounds can be unsubstituted or can have one or more identical or different substituents r 1 to r 5 having a meaning other than hydrogen . examples of suitable phosphorous tris ( dialkyl ) amides ( iv ) are tris ( dimethylamino ) phosphane , tris ( diethylamino ) phosphase and tris ( dipropyl - or - isopropylamino ) phosphane ; preferably , tris ( diethylamino ) phosphane p ( n [ ch 2 ch 3 ] 2 ) 3 is used . this phosphane can be produced very easily in high yields by reaction of phosphorus trichloride with diethylamine in a solvent which in inert towards the reactants , for example an aliphatic , cycloaliphatic or aromatic hydrocarbon or a mixture of hydrocarbons . the dialkylamino groups can contain identical or different alkyl groups . in the reaction of the aromatic aldehydes or ketones ( ii ) with a trifluoromethyl halide ( iii ) and phosphorous tris ( dialkyl ) amide ( iv ), initially an adduct of the formula ( vi ) is formed ## str5 ## the existence of this compound and the assignment of structure vi becomes plausible from the reactivity observed . this compound differs from compounds i by its reactivity with carboxylic acid halide with the formation of esters and also by the fact that it is converted to the free alcohol by the addition of a proton acid . compounds i according to the invention do not undergo these reactions . the initially formed adducts vi are subject in the reaction mixture to an exothermic rearrangement to the arylalkoxytris ( dialkylamino ) phosphonium salts ( i ) above a conversion temperature which , depending on the type of the underlying alcohol , is between - 60 ° c . and + 20 ° c . the reaction of the carbonyl compounds with the trifluoromethyl halide and phosphorous tris ( dialkyl ) amide is in general carried out at temperatures of about - 100 ° c . to + 50 ° c ., in particular of - 80 ° to + 20 ° c . in the case of carbonyl compounds of very low reactivity it is advantageous to work at temperatures above - 40 ° c . and , for example , up to + 50 ° c . to achieve a rapid conversion . as is known , the reaction time is dependent on the other conditions , in particular on the reaction temperature . in general , the reaction is completed within a period of a few minutes to several hours . the reaction is in general carried out without applying superatmospheric pressure . however , it may be advantageous to work at elevated pressure , especially if the reaction is carried out above the boiling temperature ( at atmospheric pressure ) of the trifluoromethyl halide . this means that in practice the reaction is carried out at least at the internal pressure . advantageously , the present process is carried out under anhydrous conditions in the presence of a solvent or diluent which is inert towards the reactants . in particular aprotic liquids are used as liquids of this type . the liquids used are , for example , halogenated hydrocarbons , such as methylene chloride , tetrachloroethane , nitriles , for example acetonitrile or homologues thereof , such as butyronitrile or benzonitrile , esters , such as diethyl carbonate or ethylene carbonate , and ethers , such as tetrahydrofuran or dimethoxyethane . the solvent should , if possible , be anhydrous . it is advantageous to ensure that during the entire duration of the reaction it is well mixed , for example by stirring , and to keep the reaction product in solution by choosing a suitable solvent . the method and sequence of combining the three components is not critical . the process according to the invention can be carried out , for example , in such a manner that the solvent , the carbonyl compound and a further component are initially introduced and the third component is metered in . however , it is also possible to combine all three components simultaneously . the other reactants are usually used in at least an equivalent amount with respect to the carbonyl compound ii , but often they are used in an excess of , for example , up to 25 %. the reaction mixture can be worked up , for example , by freeing it from the solvent under reduced pressure and recrystallizing the resulting residue . when isolating the phosphonium salt , it may be advantageous first to remove biproducts and some of the solvent by extraction of the reaction mixture with a non - porous solvent , for example a hydrocarbon such as hexane . in this operation , the bottom layer , which contains mostly the phosphonium salt i , is often already present as a solid . the phosphonium salts according to the invention are fairly stable , hydrolysis - resistant solids , which are readily soluble in water and polar solvent . furthermore , they are preparatively very useful compounds , which can be easily converted in one step to other interesting aromatic compounds having partially fluorinated side chains . thus , when the phosphonium salts i are heated , cleavage of the carbon - oxygen bond at the carbonyl carbon atom takes place , and a molecule of phosphoric triamide p ( 0 ) ( n [ alkyl ] 2 ) 3 is eliminated with substitution by the halide ion . in this reaction , aromatic compounds of the general formula v ## str6 ## which are known per se and contain bromine or iodine at the α - position of the fluorinated side chain and in which r 1 to r 5 and y have the above - mentioned meanings are formed . in most cases , this cleavage proceeds almost quantitatively . for this purpose , the phosphonium salt is heated undiluted or in an inert solvent , for example one having a boiling point of at least the melting temperature of the phosphonium salt , such as methyl isobutyl ketone , tetrahydronapthalene , usually to temperatures above melting point . if a solvent is used , the conversion takes place even at temperatures below the melting point . in the case of individual phosphonium salts , for example the product from example 5 , it is also possible to use fairly low - boiling solvents , such as acetone . the reaction conditions are not critical ; the two reaction products are easily separated by distillation . in a further step , the halides v thus obtained can be easily reduced to the corresponding α - hydrogen perfluoroalkyl aromatics of the formula v in which x denotes hydrogen . the reduction can be carried out by reaction with hydrogen on noble metal catalysts , such as platinum on activated carbon , or more simply by thermal reaction of the halide v with an organic , hydrogen - releasing compound , such as reactive alkyl aromatics , such as tetrahydronaphthalene or diphenylmethane . for this purpose , the compound to be reduced is heated with the alkyl aromatic to temperatures of usually 160 ° c . to 220 ° c . this reduction can also be carried out in one step , starting from the phosphonium salts i , since under these reaction conditions a rapid conversion to the halide v takes place . the reaction product can be isolated , for example by distillation . this reaction sequence provides a conventient access to aromatic compounds of the structure v having fluorinated side chains . these compounds are interesting intermediates , which previously could only be prepared in complicated and multi - step syntheses . the structures of the compounds according to examples 1 to 7 and their most important physical data are summarized in the table . in as far as solvent mixtures were used in the examples for recrystallization , a ratio by volume of 1 : 1 was used , it being possible , however , to achieve optimizations , even with respect to the yield , by changing the ratio . ( 1 ) in a round - bottom flask , 41 g ( 0 . 27 mol ) of trifluoromethyl bromide are condensed in the absence of moisture at about - 70 ° c . into a solution of 26 . 5 g ( 0 . 25 mol ) of benzaldhyde in 150 ml of ch 2 cl 2 . over a period of half an hour , 66 . 7 g ( 0 . 27 mol ) of phosphorous tris ( diethyl ) amide are then metered in with stirring . after 4 hours at - 70 ° c ., the aldehyde had been converted according to ir spectroscopy . the reaction mixture was then slowly heated to room temperature , and the solvent evaporated under reduced pressure . recrystallization of the crude product from methyl t - butyl ether / ethyl acetate gave 97 . 2 g ( 77 % of yield ) of colorless crystals of ( 1 - phenyl - 2 , 2 , 2 - trifluoroethoxy ) tris ( diethylamino ) phosphonium bromide of melting point 129 ° c . ( 2 ) in a round - bottom flask , 61 . 7 g ( 0 . 25 mol ) of phosphorous tris ( diethyl ) amide are added with stirring and in the absence of moisture at about 0 ° c . to a solution of 39 . 6 g ( 0 . 25 mol ) of 2 - chloro - 6 - fluorobenzaldehyde in 150 ml of butyronitrile . 42 . 5 g ( 0 . 28 mol ) of trifluoromethyl bromide are then passed into the solution at 20 ° to 25 ° c . at the rate at which it is consumed . after about 4 hours , the conversion was complete . the reaction mixture was extracted twice with 200 ml each of hexane . the extraction residue was freed from residual solvent under reduced pressure . recrystallization of the residue obtained ( 123 g ) from tetrahydrofuran gave 104 g ( 75 % of yield ) of [ 1 -( 2 - chloro - 6 - fluorophenyl )- 2 , 2 , 2 - trifluoroethoxy ] tris ( diethylamino ) phosphonium bromide in the form of colorless hygroscopic crystals of melting point 123 ° to 124 ° c . ( 3 ) in a round - bottom flask , 41 g ( 0 . 27 mol ) of trifluoromethyl bromide were condensed in the absence of moisture at about - 70 ° c . into a solution of 34 . 3 g ( 0 . 25 mol ) of ω , ω , ω - trifluoroacetophenone in 150 ml of ch 2 cl 2 . at this temperature , 66 . 7 g ( 0 . 27 mol ) of phosphorous tris ( diethyl ) amide were then added dropwise over a period of one hour and with thorough stirring . after a further 6 hours , the reaction mixture was slowly warmed to room temperature and extracted twice with 200 ml each of hexane . the extraction residue was freed from residual solvent under reduced pressure . recrystallization of the residue obtained ( 161 g ) from tetrahydrofuran / acetone gave 121 g ( 85 % of yield ) of [ 1 - phenyl - 2 , 2 , 2 - trifluoro - 1 -( trifluoromethyl ) ethoxy ] tris ( diethylamino ) phosphonium bromide in the form of colorless crystals of melting point 168 ° c . the compounds according to examples 4 to 7 listed in the table were prepared by the process according to example 3 . ( 8 ) in a distillation apparatus , 50 g ( 0 . 1 mol ) of ( 1 - phenyl - 2 , 2 , 2 - trifluoroethoxy ) tris ( diethylamino ) phosphonium bromide ( obtained according to example 1 ) were melted and heated to 140 ° c . for a short time . the subsequent distillation gave 23 . 5 g ( 99 % of yield ) of ( 1 - bromo - 2 , 2 , 2 - trifluoroethyl ) benzene ( b . p . 68 ° c ./ 15 mbar ) and also 24 . 9 g ( 95 % of yield ) of phosphoric tris ( diethyl ) amide as additional product . ( 9 ) in a round - bottom flask equipped with reflux condenser , 53 . 2 g ( 0 . 1 mol ) [ 1 -( 4 - methoxyphenyl )- 2 , 2 , 2 - trifluoroethoxy ] tris ( diethylamino ) phosphonium bromide ( product from example 5 ) were refluxed in 80 ml of methyl isobutyl ketone for 10 minutes . the subsequent distillation gave 22 . 2 g ( 83 % of yield ) of 1 -( 1 - bromo - 2 , 2 , 2 - trifluoroethyl )- 4 - methoxybenzene ( b . p . 108 ° to 110 ° c ./ 8 mbar ). ( 10 ) in distillation apparatus , a mixture of 50 g ( 0 . 1 mol ) of ( 1 - phenyl - 2 , 2 , 2 - trifluoroethoxy ) tris ( diethylamino ) phosphonium bromide according to example 1 and 40 g ( 0 . 3 mol ) of tetrahydronaphthalene were heated for 2 hours at about 200 ° c . after about an hour , the reaction product was slowly distilled off through a small column , in which the boiling temperature at the column head did not exceed 140 ° c . the remaining product was distilled off from the reaction mixture at 40 mbar , after the reaction was completed . repeated distillation of the combined fractions gave 10 . 2 g ( 64 % of yield ) of ( 2 , 2 , 2 - trifluoroethyl ) benzene of b . p . 71 ° to 72 ° c ./ 100 mbar . ( 11 ) in a distillation apparatus , a mixture of 57 g ( 0 . 1 mol ) of [ 1 - phenyl - 2 , 2 , 2 - trifluoro - 1 -( trifluoromethyl ) ethoxy ] tris ( dialkylamino ) phosphonium bromide according to example 3 and 40 g ( 0 . 3 mol ) of tetrahydronaphthalene was heated at 200 ° c . for 3 hours . after about an hour , the reaction product was slowly distilled off through a column , in which the boiling temperature at the column head did not exceed 160 ° c . after the reaction was completed , the remaining product was distilled off from the reaction mixture at 20 mbar . repeated distillation of the combined fractions gave 12 . 8 g ( 56 % of yield ) of 1 , 1 , 1 , 3 , 3 , 3 - hexafluoro - 2 - phenylpropane ( b . p . 83 ° to 84 ° c ./ 100 mbar ). the fact that in the reaction of the starting products used according to the invention initially a salt - like adduct of the formula vi is formed , which differs from the compounds i according to the invention by its reactivity with carboxylic acid halides with a formation of esters , is confirmed by the following comparative experiment with respect to example 3 : as in example 3 , the same amounts of ω , ω , ω - trifluoroacetophenone , ch 2 cl 2 , trifluromethyl bromide and phosphorous tris ( diethyl ) amide are combined . four hours after the addition of phosphorous tris ( diethyl ) amide was complete , 35 . 1 g ( 0 . 25 mol ) of benzoyl chloride were added . the mixture was subsequently stirred at - 70 ° c . for 2 hours . after warming the reaction mixture to room temperature , 300 ml of hexane were added . after phase separation , the bottom layer was again carefully extracted with hexane . the combined hexane layers were concentrated and distilled under reduced pressure . this gave 32 . 5 g ( 75 %) of 1 , 1 , 1 , 3 , 3 , 3 - hexafluoro - 2 - phenylpropyl 2 - benzoate of boiling point 96 ° to 97 ° c ./ 0 . 1 mbar . ______________________________________c h f . sup . 19 f - nmr | ppm | ______________________________________ ( calc .) ( calc .) ( calc .) cf . sub . 3found found found ( 55 . 18 ) ( 2 . 89 ) ( 32 . 74 ) - 70 . 555 . 0 2 . 9 32 . 7______________________________________ in a different experiment , 11 . 4 g ( 0 . 02 mol ) of the phosphonium salt from example 3 and 2 . 8 g ( 0 . 02 mol ) of benzoyl chloride were stirred in a round - bottom flask in 50 ml of ch 2 cl 2 . even after two hours of refluxing , the two starting materials were still present side by side without change ; the formation of the ester described above was not observed . table__________________________________________________________________________ ## str7 ## m . p . [° c .] c h f ( recrystallized ( calc .) ( calc .) ( calc .) . sup . 19 fnmr [ ppm ] ex . r y from ) found found found cf . sub . 3 ( cdcl . sub . 3 ) yield__________________________________________________________________________1 h h 129 ( 47 . 81 ) ( 7 . 22 ) ( 11 . 34 ) - 76 . 4 77 % ( ea / mtbe ) 47 . 7 7 . 4 10 . 72 2 - cl , 6 - f h 123 - 4 ( 43 . 3 ) ( 6 . 18 ) ( 13 . 7 ) - 75 . 4 75 % ( thf ) 43 6 . 1 13 . 63 h cf . sub . 3 168 ( 44 . 22 ) ( 5 . 88 ) ( 19 . 98 ) - 71 . 2 85 % ( thf / acetone ) 43 . 8 6 . 1 19 . 94 4 - ch . sub . 3 h 148 ( 48 . 84 ) ( 7 . 42 ) ( 11 . 03 ) - 76 71 % ( thf ) 49 . 2 7 . 2 11 . 05 4 - och . sub . 3 h 117 - 8 ( 47 . 37 ) ( 7 . 19 ) ( 10 . 7 ) - 76 . 6 81 % ( acetone ) 47 . 1 7 . 1 10 . 66 3 , 4 ( ch . sub . 3 ). sub . 2 cf . sub . 3 118 - 9 ( 46 . 16 ) ( 6 . 57 ) ( 19 . 05 ) - 71 . 0 84 % ( mibk ) 46 . 2 6 . 5 18 . 77 h c . sub . 2 f . sub . 5 137 ( 42 . 59 ) ( 5 . 64 ) ( 24 . 5 ) - 66 . 1 61 % ( mibk ) 43 . 2 5 . 6 24 . 4__________________________________________________________________________ ea = ethyl acetate mtbe = methyl t . butyl ether thf = tetrahydrofuran mibk = methyl isobutyl ketone
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it is to be understood that the figures and descriptions of the present disclosure have been simplified to illustrate elements that are relevant for a clear understanding of the present invention , while eliminating , for the purposes of clarity and brevity , many other elements found in typical network - communicative systems , mobile devices , servers and methods . those of ordinary skill in the art may thus recognize that other elements and / or steps are desirable and / or required in implementing the present invention . however , because such elements and steps are well known in the art , and because they do not facilitate a better understanding of the present invention , a discussion of such elements and steps is not provided herein . the disclosure herein is directed to all such variations and modifications to the disclosed elements and methods known to those skilled in the art . fig1 illustrates a representative service provider or system architecture , which in the preferred embodiment is implemented in or across one or more data centers . a data center typically has connectivity to the internet . in one embodiment , the system provides a web - based hosted solution through which business entities create , manage and monitor their brand integration and product placement activities in an online manner . participants interact with the platform to buy and sell brand integration opportunities as an online marketplace . in an alternative embodiment , the system may be implemented over a private network , or as a product ( as opposed to a hosted or managed service ). a business entity user has a machine such as a workstation or notebook computer . typically , a business entity user accesses the service provider architecture by opening a web browser on the machine to a url associated with a service provider domain or subdomain . the user then authenticates to the managed service in the usual manner , e . g ., by entry of a username and password . the connection between the business entity machine and the service provider infrastructure may be encrypted or otherwise secure , e . g ., via ssl , or the like . although connectivity via the publicly - routed internet is typical , the business entity may connect to the service provider infrastructure over any local area , wide area , wireless , wired , private or other dedicated network . as seen in fig1 , the service provider architecture 100 comprises an ip switch 102 , a set of one or more web server machines 104 , a set of one more application server machines 106 , a database management system 108 , and a set of one or more administration server machines 110 . a representative web server machine 104 comprises commodity hardware ( e . g ., intel - based ), an operating system such as linux , and a web server such as apache 2 . x . a representative application server machine 106 comprises commodity hardware , linux , and an application server such as weblogic 8 . 1 . the database management system 108 may be implemented as an oracle database management package running on solaris . in a high volume use environment , there may be several web server machines , several application server machines , and a number of administrative server machines . although not shown in detail , the infrastructure may include a name service , other load balancing appliances , other switches , network attached storage , and the like . the system typically will also include connectivity to external data sources , such as third party databases that provide historical data . representative third party data sources include , for example , a . c . nielsen placeviews ™ ( for television ), brand cameo ( for film ), american brandstand ( for music ), and the like . each machine in the system typically comprises sufficient disk and memory , as well as input and output devices . generally , the web servers 104 handle incoming business entity provisioning requests , and they export a display interface that is described and illustrated in more detail below . the application servers 106 manage the data and facilitate the marketplace functions of the platform . the administrator servers 110 handle all back - end accounting and reporting functions . the particular hardware and software implementation details described herein are merely for illustrative purposes are not meant to limit the scope of the present invention . as noted above , the system manages avails , wherein an avail is an aspect of a production that is “ available ” for potential product placement and brand awareness . typically , an “ avail ” is an opportunity for an advertiser , advertising agency , media buyer or the like to include a brand as part of a given production . ( a “ brand ” is sometimes used herein to refer to an advertiser itself ). an “ avail ” may also refer to an opportunity that is entered into the system by the seller , or on behalf of the seller , typically a producer , an entertainment network , a film production house , a music video company , a video game producer , or the like . as noted above , any such buyer or seller entity interacts with the platform over the internet or other private network , preferably using a web browser or other graphics display engine . the system allows sellers to create , store , respond to , and transact on new avails . similarly , the buyer uses the system to follow the progress of its offers , to respond to , and to close on avail buying opportunities . as also described above , the system defines a set of one or more product placement - specific metrics that are used on the platform as a standard measure of delivery of exposure across avails . a brand integration unit ( e . g ., a ubi ™, which is a trademark of nextmedium , inc .) preferably is a function of : exposure duration ( typically measured in seconds ) times a given audience size metric ( e . g ., household ( hh ) gross rating points ( grp ), such as available from a . c . neilsen or other sources ) times a given product placement type factor or attribute . the brand integration unit may be normalized , or calculated using other criteria . a “ placement type ” is a type of product placement within a given production , e . g ., a foreground placement , a background placement , a brand mention , a dialogue mention , a dialogue mention by a given character , use as a prop , use in wardrobe , use in a storyline , use as the storyline , or the like . the above product placement types are merely representative . typically , different weights are associated with each placement type , thus influencing the brand integration unit value calculation . thus , for example , a dialog mention has a higher weight than a foreground placement , which has a higher weight than a background placement . the weight values may be informed or influenced by historical data or other statistics . an aggregate of brand integration units , e . g ., over all media , or with respect to a specific media type , over a continuing time period , is as an entertainment integration quotientt ™ ( or e * iq ™). typically , an end user entity buys a ubi and the system measures e * iq , which value typically increases over time and use of the system . e * iq thus is an aggregated view of the effectiveness of a brand across some or all of the media types over time . another metric is a media value , which represents , once again preferably for a given time period , a monetary amount typically calculated as e * iq times a quotient of : average advertising rate and average audience size ( e . g ., measured as hh grp or equivalent ). the media value may be calculated and displayed on an aggregate media basis , or with respect to a specific media type , or the like . business entities access the platform over the web , authenticate , and then access the platform functions by navigating through display pages that comprise a graphical user interface . the following are representative , non - limiting use scenarios for the interactive marketplace of the present invention . a buyer ( an agency media buyer for a brand , such as ford ®) end user logs into the system and wants to find avails for purchase . he or she searches tv avails for a given product category ( e . g ., automobiles ) according to a media type , in this case tv . after finding that a desired show ( e . g ., “ grey &# 39 ; s anatomy ”) has an avail to his or her liking , he or she views its details ( price and placement types ), and places an offer . in another example , a buyer ( revlon ® media buyer ) logs into the system and wants to find out avails to purchase . in this case , however , no seller has entered avails for cosmetics . in this case , the end user does an advanced search entering parameters , such as target demographic ( women 18 - 49 ) and top shows ( per hh grp or e * iq ) in a desired category . the system then performs a data mining function for top shows ( e . g ., based on hh grp or e * iq ) and lists them . the relevant data may be located in the system databases , or the system may execute the search by connecting to remote ( possibly third party ) databases or other data sources . once the search is complete and the results returned , the user is then able to send messages to the seller , e . g ., to initiate integration ( in particular , a dialog between buyer and seller to include avails for revlon ). as yet another example , assume that fox ® racing is a new system customer . the system data mines placement information to find out top exposures , grp , and e * iq for fox racing . it then compares this data with fox racing &# 39 ; s top competitors . assume that the system discovers that , even though fox racing has the highest exposures and grp in a given television show , its e * iq is lower than its competitors . as a result , the system recommends avails that will help fox racing increase its own e * iq . fox racing can then purchase these avails . another example scenario assumes that fox has an exclusive brand integration deal with coke for a television show such as american idol ®. fox wants to ensure that , when coke &# 39 ; s competitors log into the system , they are shown avails for all fox shows except american idol . fox enters this information into the system and the system ensures that when pepsi &# 39 ; s brand manager logs in , it is not shown american idol avails . another example is that the fox tv sales team is creating a new show similar to american idol . it wants to enter avails into the system but needs help in pricing them . the system provides a pricing calculator that then recommends prices based on similar shows and historical data . in another use example , assume that revlon &# 39 ; s brand manager has signed up for a series of avails in the “ cosmetic ” product category for fall tv shows on fox . she wants to audit the exposure . she logs into the system and brings up an exposure history for her deals . the system preferably displays statistics in terms for duration , grp and e * iq , and the page may also includes links to video clips featuring revlon . coke &# 39 ; s brand manager wants to compare how his brand fares in product placements on top shows with respect to pepsi over the past calendar quarter . the end user logs into the system to see this report . the end user can then change dates and captures this information for grp , occurrences , and e * iq . as another example , assume that the “ real world - road rules ” production company wants to sell all avails for a cell phone category for the 2007 television season ( all episodes ). it logs into the system and places this “ brand integration ” sale . the brand manager for t - mobile ® then logs into the system , searches for cell phone integration deals and places an offer for the “ real world - road rules ” program . as still another example , assume that the script in a new tv series calls for the lead actress to drive environmentally friendly cars . the network and production company for this series want to sell automobile avails for all episodes to an automobile brand and feature its various environmentally friendly vehicles . the end user logs into the system and defines the brand integration opportunity . brand managers for toyota , ford , and honda can then access the system and negotiate for the opportunity . another example assumes that a seller receives offers , e . g ., from hyundai and jaguar , with respect to an avail to include cars in a scene with a lead actress in a forthcoming james bond movie . even though the offer from hyundai is more than 30 % higher than that of jaguar , the seller accepts jaguar , because the offer is more in line with the script . however , instead of rejecting hyundai , the seller sends back a counter - offer to include the brand in other parts of the film . as still another example , ford &# 39 ; s brand manager sees a cash offer to include cars as part of a new tv action series . instead , the brand manager responds to the offer with a counterproposal , namely , a lower price per avail and providing all of ford &# 39 ; s 2007 model year cars for free to be used in the show . the seller responds and agrees with this offer . the producer for the “ amazing race ” tv series wants to construct an open - ended offer , as follows . the offer includes an automobile product category opportunity in each weekly show , however , the producer cannot give specifics ( e . g ., duration ) of each occurrence given that the show is loosely scripted . the end user then constructs a deal such that the brand will pay a minimum amount upfront with a remainder paid post - airing of the show , e . g ., based on some metric such as dollars per duration , grp or e * iq . the grp metric can be obtained from a third party measurement source and imported into the system , which can then audit and manage the overall transaction . the system also enables producers to put in a generic description for a series of avails and ask for an upfront fee followed by a pay - for - performance model based on some dollars per duration , grp or e * iq . in this example , cell phones will be used in all episodes for a new tv series . producers can use this feature to sell series of avails without significant upfront work , such as entering specific data ( time , duration , script mention , and the like ), and buyers can use this feature obtain a scientific measurement ( analogous to pay per click ) for avails , as preferably the system has access to third party measurement data , as previously noted . denny restaurant &# 39 ; s brand manager wants to obtain a report on the tv shows and films that have carried the brand and measure their effectiveness . the system &# 39 ; s business intelligence database preferably list all shows , their grp and exposures , including links to clips that feature the brand . the system also exposes the brand &# 39 ; s e * iq with respect to its competition and enables the manager to investigate how to increase the e * iq across all media types . the system then provides this information and lists recommendations . as a final example , assume that the brand manager for ford has $ 1 m to spend on brand integration across various media types ( tv , films , video games , music ). he logs into the system to create a product placement campaign . the system can then recommend a series of avails that will help the manager obtain a maximum return on investment . the above examples are merely illustrative and are not to be taken to limit the present invention in any way . as can be seen , the system provides many advantageous features . in particular , the system automates the key aspects of today &# 39 ; s manual and labor intensive product placement & amp ; brand integration workflow by providing avail listing and search capability , as well as enabling participants to make and respond to offers . the platform provides a central , one stop ( create , manage and transact ) location to manage product placement and brand integration across all media types ( tv , films , music , video games , and the like ). it provides participants with the ability to introduce and execute on new business models , such as pay - for - performance for product placement and brand integration . the system also affords users with access to historical product placement data for business intelligence reports , it provide new metrics ( e . g ., ubi and e * iq ) to measure efficacy of product placements and to define an overall media value for a brand . moreover , the system , through its guided interface to be described below , provides actionable data , tasks and tools to guide the user to intelligently use these metrics . more generally , the system enables participants to increase market size for product placement and brand integration by allowing sellers to target a larger audience of buyers , and vice versa . preferably , participants interact with the system through a web - based portal and , in particular , through a series of display pages exported to a web browser . these display pages are illustrated in fig2 - 22 , by way of example . the particular sequence and organization of these pages is merely representative , as are the particular layouts of each given page . nevertheless , the basic functions of the system can be visualized by navigating through these displays , as will now be described at a high level . fig2 is a representative home or “ portal ” page from which an end user can navigate throughout the system functions . the page comprises a navigation panel 202 with various links to other pages that are described below . a top recent exposure panel 204 exposes details for a highest value product placement for this particular participant ( in this example , the ford brand manager ). this panel includes an embedded media player ( to play the content ), the e * iq , the media value , the brand , the program , the placement type , the duration and its air - time . a top competitors by e * iq panel 206 shows the end user how the company &# 39 ; s branding opportunities are faring with respect to other identified competitors . a top shows by e * iq panel 208 displays the shows that are providing the best return on investment for the brand . an offer status panel 210 displays offer information . a latest avails panel 212 displays one or more recent avails that have been placed or to which the manager has responded . fig3 is a representative page that is displayed by the system when the end user selects the introduction link in the gauge your exposure subdirectory identified in the navigation panel . it includes a number of image links . when the end user selects the e * iq details summary image link 400 , he or she is navigated to the display page in fig4 , which provides a breakdown of the brand &# 39 ; s e * iq score . this page thus shows the number of different programs that the brand &# 39 ; s product has appeared in , the number of seconds the product has aired across all shows , and the number of times the product has been exposed on air ( or the like ). the breakdown your e * iq page in fig4 also shows associated demographic data . referring now back to fig3 , when the end user selects the top shows by e * iq image link 500 , he or she is navigated to the display page in fig5 , which shows the user the brand &# 39 ; s top shows according to their e * iq score in each show . as seen in fig5 , this table also displays additional data such as total occurrences , total duration , total average e * iq , and e * iq broken down by demographics . referring once again back to fig3 , when the end user selects the top competitors by e * iq image link 600 , he or she is navigated to the display page in fig6 , which includes data comparing the brand to its competitors according to e * iq . given temporal and percentage data preferably is also shown , as indicated . as also seen in fig3 , when the end user selects the top placement types by e * iq image link 700 , he or she is navigated to the display page in fig7 , which includes data ( total occurrences , total duration , total average e * iq , and e * iq broken down by demographic ) by one or more placement types : prop , foreground , background , dialogue mention , sponsorship , storyline , and other . the data can be indexed by date , as indicated . fig8 is a representative page that is displayed by the system when the end user selects the introduction link in the find your avails link subdirectory in the navigation panel 202 shown in fig2 . this panel includes a set of image links . when the end user selects the browse open avails image link 900 , he or she is navigated to the display page shown in fig9 , which enables the user to look through open avails in the system , perhaps indexed by category ( e . g ., automobiles ). as seen in fig9 , the avails preferably are also organized by media type , e . g ., television , film music , or video game . the television page is shown by default , but this is not a requirement . by navigating to the desired media type page , the user can review the avails . in this example , there are no television opportunities available for automobiles , which in this example is the relevant category for this particular user . by selecting the film tab , however , the user can navigate to the display page in fig1 , which includes a list of avails , indexed by film name and including associated information such as genre , placement type , a response deadline , a minimum offer , and the number of offers outstanding . selection of a link in this page navigates the user to the display in fig1 , which provides detailed information for the particular offer selected . fig1 includes a make offer button , and selection of this button navigates the user to the display page shown in fig1 , which includes a fill - in form by which the user can enter the offer details . as can be seen in fig1 , preferably the page includes a minimum offer field , a list box that includes a listing from which a product can be selected , an offer field , a promotion field , and a product - in - kind field . the user enters given amounts into these fields as desired , and he or she can add additional comments or integration ideas in the comment field . in the alternative , the end user can select the pay for performance tab and be navigated to the display page in fig1 . this page exposes a fill - in form that enables the user to create a custom pay for performance offer that includes a maximum offer , a desired integration level ( if supported ), a set offer ( preferably measured in $/ sec ) on all placements field , as well as separate placement type fields as indicated . thus , the user can designate a given price that it is willing to pay to get its brand mentioned by a character , or positioned in a foreground shot , or as a part of a character wardrobe , and the like . this pay for performance feature is quite useful , as it enables performance - based bidding and fulfillment . this is desirable , especially for entities that have no control over the execution of a given creative . returning now to fig8 , when the end user selects the find a specific avail image link 1400 , he or she is navigated to the display page shown in fig1 , which enables the user to look through all the avails in the system for a specific avail . as illustrated in fig1 , this page includes a search engine that is indexed by media type , and that includes a set of fill - in options including a response deadline , a top shows list box , a show name field , a network list box , a genre list box , a studio field , a show status list box , a production status list box , and a target demographic list box . entry of data in this fill - in form controls the search engine to return the avails , from which the user can then review and prepare an offer , as has been described above . referring again to fig8 , when the user selects the propose an integration image link 1500 , he or she is navigated to the page shown in fig1 . using this page , the user can enter criteria for a given integration and search through the database , once again indexed by media type and by entering information in the various fields shown . fig1 is a representative page that is displayed by the system when the end user selects the select a program tab from the propose an integration display panel . fig1 is a representative page that is displayed by the system when the end user selects ( e . g ., by clicking on a radio button ) a given program and the clicks the view program details tab . fig1 is a representative page that is displayed by the system when the end user selects the introduction link in the review your offers subdirectory in the navigation bar . this page includes preferably includes a set of image links . a first image link 1900 navigates the user to the display page in fig1 , which shows the user the status of their current offers . he or she can select the view offer history button and be navigated to the display page shown in fig2 . if any of these offers have been pending for a given time period , the user can request feedback from other users using tools accessible through this page . as also seen in fig1 , if the user selects the second image link 2100 , he is she is navigated to the update an offer page shown in fig2 . the user can use this page to update an offer they have already placed . as can be seen , the various display screens can be accessed through the links in the navigation panel 202 , or through the image links on the pages that are exposed during the typical user navigation . as noted above , preferably the web - based marketplace has access to or otherwise integrates with third party sources that include historical product placement data . this information facilitates the generation of the real - time and historical data shown in the representative displays . access to exposure data allows the system to create audit trails and to introduce new business models around product placements and brand integration . the system may also include processing routines that use the historical data ( and perhaps data specific to a particular brand , category , production , or the like ) to predict and recommend avails to the user . access to historical data allows the service provider to data mine for recommendations and to predict trends . further , the product placement - specific metrics ( ubi & amp ; e * iq ) provide the users and others with a standard measure of delivery of exposure across avails . as noted above , preferably e * iq is an aggregated view of the effectiveness of a brand across some or all of the media types . the present invention provides the marketplace participants with the ability to track and manage product placement and brand integration opportunities throughout an entire media production and distribution lifecycle that includes some or all of the following : pre - production , production , post - production , broadcast / distribution , as well as post - broadcast interactivity or other transactional commerce . thus , for example , in pre - production , a seller can reveal an apparel opportunity for a popular television show . in the production phase , a buyer can then bid on the avail and , if the bid is accepted , purchase the opportunity . or , assuming the opportunity is not then closed , an entity may decide to make a bid during the post - production phase . during the broadcast distribution phase , a buyer may even purchase an avail if its brand or branded product can be placed into the production in a “ virtual ” manner . even following broadcast distribution , yet another buyer can purchase an opportunity with respect to downstream distribution ( such as foreign broadcast rights ). thus , using the platform , different buyers can offer different product placements throughout the production and distribution lifecycle of a given creative . as previously noted , the hardware and software systems in which the invention is illustrated are merely representative . the invention may be practiced , typically in software , on one or more machines . generalizing , a machine typically comprises commodity hardware and software , storage ( e . g ., disks , disk arrays , and the like ) and memory ( ram , rom , and the like ). the particular machines used in the network are not a limitation of the present invention . a given machine includes network interfaces and software to connect the machine to a network in the usual manner . as illustrated in fig1 , the present invention may be implemented as a managed service ( e . g ., in an asp model ) using the illustrated set of machines , which are connected or connectable to one or more networks . more generally , the service is provided by an operator using a set of one or more computing - related entities ( systems , machines , processes , programs , libraries , functions , or the like ) that together facilitate or provide the inventive functionality described above . in a typical implementation , the service comprises a set of one or more computers . a representative machine is a network - based server running commodity ( e . g . pentium - class ) hardware , an operating system ( e . g ., linux , windows , os - x , or the like ), an application runtime environment ( e . g ., java , . asp ), and a set of applications or processes ( e . g ., java applets or servlets , linkable libraries , native code , or the like , depending on platform ), that provide the functionality of a given system or subsystem . as described , the service may be implemented in a standalone server , or across a distributed set of machines . typically , a server connects to the publicly - routable internet , a corporate intranet , a private network , or any combination thereof , depending on the desired implementation environment . the previous description of the disclosure is provided to enable any person skilled in the art to make or use the disclosure . various modifications to the disclosure will be readily apparent to those skilled in the art , and the generic principles defined herein may be applied to other variations without departing from the spirit or scope of the disclosure . thus , the disclosure is not intended to be limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein .
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in the above general formula ( ii ) x 1 and x 2 each represents an oxygen atom or a sulfur atom ; r 1 and r 2 each represents a hydrogen atom , an alkyl group ( preferably , an alkyl group having 1 to 4 carbon atoms , such as a methyl group , an ethyl group , a propyl group , an isopropyl group , a butyl group , a t - butyl group , etc . ), an aryl group ( e . g ., a phenyl group , a tolyl group , etc . ), an aralkyl group ( e . g ., a benzyl group , a phenethyl group , etc . ), or a cycloalkyl group ( e . g ., a cyclopentyl group , a cyclohexyl group , etc .). in the above general formula ( ii ) r 3 represents a hydrogen atom , an alkyl group ( suitably , an alkyl group having 1 to 4 carbon atoms , such as a methyl group , an ethyl group , a propyl group , a butyl group , a t - butyl group , etc . ), an aralkyl group ( preferably , a benzyl group , a phenethyl group , etc . ), an aryl group ( preferably , a phenyl group , a tolyl group , etc . ), or a cycloalkyl group ( preferably , a cyclopentyl group , a cyclohexyl group , or the like ); and r 4 represents a hydrogen atom , an alkyl group ( preferably , an alkyl group having 1 to 4 carbon atoms , such as a methyl group , an ethyl group , a propyl group , a butyl group , a t - butyl group , etc . ), or a cycloalkyl group ( e . g ., a cyclopentyl group , a cyclohexyl group , etc .). specific examples of compounds having the general formula ( i ) include hydantoin , thiohydantoin , 5 , 5 - diphenylthiohydantoin , 5 , 5 - dimethylthiohydantoin , 5 - phenyl - 5 - ethylhydantoin , 5 - methyl - 5 - isopropylthiohydantoin , 5 , 5 - diethylhydantoin and 5 - methyl - 5 - cyclohexylhydantoin and examples of compounds having the general formula ( ii ) include 5 - methylthiazoline - 2 - thione , 5 - ethylthiazoline - 2 - thione , 4 , 5 - dimethylthiazoline - 2 - thione , 5 - phenylthiazoline - 2 - thione , 5 - cyclohexylthiazoline - 2 - thione , 5 - benzylthiazoline - 2 - thione . in this invention , the combination of at least one of the compounds of general formula ( i ), the general formula ( ii ), and o - benzoic sulfimide is used , with at least one quinone diazide compound , e . g ., as described hereinbefore . the above - described compounds are suitably added to the light - sensitive composition in an amount of not less than about 0 . 1 % by weight up to less than about 50 % by weight , preferably 1 to 20 % by weight . the quinonediazido type light - sensitive substances which can be used in the present invention include , in general , all of the above - described compounds . the light - sensitive quinone diazide compound and the composition which comprises the compounds of this invention are employed in combination as the light - sensitive composition . if the quinone diazide compound has a film - forming property , an organic solvent solution of the light - sensitive composition is used as a coating solution . if the quinone diazide compound does not have a film - forming property , the coating solution comprises an organic solvent solution of the light - sensitive composition and an additional binder component . suitable examples of binders include phenol - formaldehyde resins , shelac , styrenemaleic anhydride copolymers , methyl methacrylate - methacrylate copolymers , and the binder is suitably added at less than 5 times by weight . suitable solvents which can be used for the coating solution include alcohol solvents such as methanol , ethanol , isopropyl alcohol , and butyl alcohol , dioxane , methyleneglycolmonomethylether , ethyleneglycolmonomethylether , etc . of these , a solvent which disolves the solid components can be employed alone or a mixture of solvents can be employed . the concentration of the solid components of the coating solution normally is about 1 to 20 weight % and the coating amount on the support generally is about 0 . 1 to 10 g per 1 m 2 . the light - sensitive composition of the invention can be applied from solution to a variety of supports . such supports include cloth , paper , ceramics , rubber , wood , metals , plastic films , and the like . the desired image is then produced by image wise exposure to actinic radiation , such as ultraviolet light , and can be used as such as a temporary record or the unexposed materials can be removed by treatment with an appropriate solvent to produce a permanent image . in an embodiment a photoresist composition is prepared employing the light - sensitive composition of the invention mixed with a film - forming resin . for example , the film - forming resin can be a phenol formaldehyde resin such as those known as novolak or resole resins . in a particular , an alkali soluble phenol formaldehyde resin can be used to form a product which is insoluble in alkali but which forms decomposition products which are soluble in dilute alkali upon exposure to actinic rays . the alkali solution may range in strength up to that of 5 % aqueous sodium hydroxide . the light - sensitive composition of this invention can be mixed in any proportion with a film - forming material to form resists or print - out materials . in addition the light - sensitive compositions can be provided in a dry form and mixed with a solvent or as a solvent solution using one or more volatile organic solvents which are solvents for the components of the light - sensitive composition . residual solvent can be removed and the coating is exposed through a pattern to a light source such as a carbon arc . the resist coating , is then placed in a developer such as an aqueous alkaline developer , to remove the exposed areas . the alkaline strength of the developer , as well as the presence of addenda such as solvents , is dependent upon the particular light - sensitive composition employed , any the resin employed and the ratio of the light - sensitive composition to the resin . the developer may also contain dyes and hardening agents . the developed image is rinsed with water , and dried . the substrate can then be etched using conventional techniques such as an acid etching solutions of ferric chloride . in another embodiment a solution containing the light - sensitive composition of this invention is coated upon a lithographic support by using conventional techniques such as whirl coating , flow coating , dip coating , hopper coating , etc . and allowed to dry . the resulting light - sensitive element is then exposed through a negative image to radiation such as that from an ultraviolet light source and subsequently developed with a solvent for the unexposed portions to obtain a positive , highly colored , oleophilic image suitable for use in lithographic printing . the lithographic support materials can be any of those well known in the art such as zinc , anodized aluminum , grained aluminum , copper and specially prepared metal and paper supports ; partially hydrolyzed cellulose ester films ; polymer supports such as polyolefins , polyesters , polyamide , etc . the solvents which can be employed as coating solvents for the light sensitive composition of this invention are preferably those organic solvents which are capable of dissolving at least 0 . 2 % by weight of the light sensitive composition employed but are inert to the components in the light sensitive composition and which are substantially incapable of adversely affecting the substrates employed . suitable solvents include dimethylformamide , cyclohexanone , acetonitrile , 2 - ethoxyethanol and mixtures thereof or with other solvents such as the lower alcohols and ketones . the coating solutions can also contain addenda to improve film formation , coating properties , adhesion to the supports , mechanical strength , etc . examples of such include resins , stabilizers and surface active agents . the light sensitive elements can be exposed using conventional techniques to actinic radiation which is preferably in the ultraviolet range . the exposed elements are then developed by washing , soaking , swabbing , or otherwise treating the light sensitive layers with a solvent or solvent system which acts on the exposed and unexposed areas removing the materials which have not been modified by the action of light . these developing solvents can be organic or aqueous in nature and will vary depending on the composition of the light sensitive layer being developed . examples of developing solvents include water , aqueous acids and alkalis , the lower alcohols and ketones , and aqueous solutions of the lower alcohols and ketones . the images formed can then be treated in any known manner dependent upon the intended end use . the light - sensitive composition of the present invention possesses such high sensitivity that the exposure amount upon exposure can be reduced as compared with the conventional light - sensitive compositions . thus workability is improved . the present invention will now be illustrated in greater detail by reference to the following non - limiting examples of preferred embodiments of the present invention . unless otherwise indicated all parts , percents , ratios and the like are by weight . a 3s 18h aluminum plate was grained on both sides using 25 - mesh alundum , then immersed for 1 minute in a 70 ° c aqueous solution of 20 % sodium tertiary phosphate . after being washed with water , the plate was immersed in a 70 % nitric acid solution , followed by washing with water . thereafter , the plate was immersed for 2 minutes in a bath of 2 % aqueous solution of sodium silicate no . 2 ( made by kanto kagaku co . ; sio 2 / na 2 o ratio : 2 . 45 - 2 . 55 : 1 ) heated to 80 to 85 ° c . after being washed with water and drying the plate , a light - sensitive solution prepared by adding 1 part by weight of polyhydroxyphenyl 2 - diazo - 1 - naphthol - 4 - sulfonic acid ester ( obtained by the polycondensation of acetone and pyrogallol as illustrated in example 1 of u . s . pat . no . 3 , 635 , 709 ) and 2 parts by weight of an oil - soluble novolak - type phenol resin pr - 50904 ( made by sankyo chemical co ., ltd .) to a mixed solution of 10 parts by weight of methyl ethyl ketone , and 10 parts by weight of methoxyethanol for dissolution was applied to the aluminum plate in a dry thickness of 1 . 2 μ to obtain light - sensitive printing plate a . on the other hand , 0 . 18 part by weight of 5 , 5 - diphenylthiohydantoin was further added to the above - described light - sensitive solution , and then applied to the same aluminum plate as described above in the same thickness to obtain light - sensitive printing plate b . the thus obtained light - sensitive printing plates a and b were exposed for the same period of time through a step - wedge using a super - high pressure mercury lamp printing apparatus ( made by orc manufacturing co ., ltd . ; trade name : jet - printer 2000 ), then developed under the same conditions using a 5 % sodium tertiary phosphate aqueous solution . the sensitivity of the light - sensitive printing plate b was found to be enhanced about 1 . 5 times as compared with light - sensitive printing plate a . when printing was effected using the thus obtained printing plates , both printing plates provided excellent impressions . when the same procedures as described in example 1 were conducted except for using 1 part by weight of hydantoin in lieu of 5 , 5 - diphenylthiohydantoin , the sensitivity was similarly enhanced approximately 1 . 5 times . the same procedures as described in example 1 were conducted except for using 0 . 7 part by weight of 2 , 2 - bis [ p -( naphthoquinone -( 1 , 2 )- diazido -( 2 )- 5 - sulfonyloxy )- phenyl ] propane . the same results as in example 1 were obtained . the same procedures as described in example 1 were conducted except for using 0 . 18 part by weight of o - benzoic acid sulfimide in lieu of 5 , 5 - diphenylthiohydantoin . the same results as in example 1 were obtained . the same procedures as described in example 3 were conducted except for using 0 . 18 part by weight of o - benzoic acid sulfimide in lieu of 5 , 5 - diphenylthiohydantoin . the same results as in example 1 were obtained . the same procedures as described in example 1 were conducted except for using 0 . 18 part by weight of 5 - methylthiazoline - 2 - thione in lieu of 5 , 5 - diphenylthiohydantoin . while the invention has been described in detail and with reference to specific embodiments thereof , it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof .
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in fig1 reference 1 indicates a device according to the invention . this device produces at its output 5 a signal whose frequency is determined by a digital code of , for example , n bits applied to the input terminals 10 . this device comprises an accumulator circuit 15 formed by an adder 20 which has two code inputs a and b , and an accumulation register 22 . input a of the adder receives the digital code applied to the terminals 10 and input b is connected to the output of the adder 20 via register 22 . an exclusive - or gate 25 serving as an accumulation decoder produces a logic &# 34 ; 1 &# 34 ; signal to indicate the changing of the value of the most significant bit of the accumulator . therefore , the inputs of this gate are connected , respectively , to the input line ma and to the output line mp of the register 22 while transmitting the most significant bits . according to the invention , a signal indicating certain contents of the accumulator circuit which is , for example , supplied at the output of the exclusive - or gate 25 , is used for activating a variable divider circuit 40 which has an input connected to a reference oscillator 45 and an output 5 which forms the output of the device 1 . circuit 40 is formed by two fixed dividers 51 and 52 for dividing by n 1 and n 2 , respectively , the frequency of the oscillator 45 . the two - position switch 54 connects the signal processed by one of these dividers to output 5 . the choice of these positions is determined by the value of the output signal of gate 25 . the accumulations take place according to an aspect of the invention in time with the signal present on output 5 , which constitutes an accumulation clock signal . for a better understanding of the purpose of the invention , it is appropriate to utilize the following considerations . let m be the number of bits processed by the accumulator circuit 15 . the n - bit code c on input 10 is such that : this code is accumulated in the register 22 and causes the change of the value of the most significant bit in k accumulations when : if t u is called the period of the signal on output 5 , the time interval t sd separating two &# 34 ; 1 &# 34 ; pulses is given by the relation : ## equ1 ## if there is admitted that if sd = 0 , one has : ## equ2 ## and if sd = 1 : ## equ3 ## a relation is formed between the user frequency f u and the code c : during t sd - t u2 , sd is &# 34 ; 0 &# 34 ; and the user frequency f u1 = f r / n1 . during t u2 , sd is &# 34 ; 1 &# 34 ; and the user frequency f u2 = f r / n2 . the mean user frequency has the value of : ## equ4 ## or finally : ## equ5 ## it will be observed thus that the variation step δf becomes : ## equ6 ## and by choosing n1 and n2 this step is controlled as finely as one wishes . fig2 shows an embodiment for a variable divider circuit 40 &# 39 ; where n1 = 16 and n2 = 15 . 5 , thus well adapted to phase controls . this circuit is formed by a divider 60 which divides by n 3 ( n 3 = 16 ) the frequency of the quartz crystal oscillator signals 45 transmitted via an exclusive - or gate 62 which has two inputs of which the first input is connected to the output of the oscillator 45 and the second input is connected to the output of a d - type flip - flop referenced 65 . the output of this flip - flop is further connected to an input of another exclusive - or gate 67 of which another input forms the input of this circuit 40 &# 39 ; and is thus connected to the output of gate 25 . the output of the exclusive - or gate 67 is connected to the input of the flip - flop 65 . the input which permits the change of state of this flip - flop is connected to the output of the divider 60 . the operation of this circuit 40 &# 39 ; will be explained with the aid of fig3 . for this explanation it will be useful to consider the signals , f r , f u , sd , a and b occurring respectively on the outputs of the oscillator 45 , divider 60 , gate 25 , flip - flop 65 and gate 62 . let us consider instant t 0 and assume that signal sd has the &# 34 ; 0 &# 34 ; value as has signal a . therefore , signal b is a copy of signal f r . then one goes to instant t 1 where the signal sd assumes the value &# 34 ; 1 &# 34 ;. the signal on the output of the gate 67 is thus inverted to the input of flip - flop 65 which is prepared to change state . this happens at t 2 when the divider 60 has finished its counting cycle . because of this switching , signals b now represent the inverted signals f r . it will be noted that this inversion never coincides with an edge of the signals f r which is due to the delay caused by the various circuits . in this manner an additional half pulse is created to be divided by the divider 60 . if the signal sd retains its value &# 34 ; 1 &# 34 ;, the end of the dividing cycle of this same divider 60 will entail the switching of the flip - flop 65 and hence the creation of a half pulse for the divider 60 .
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the present invention is a cryogenic distillation process that reduces the methane concentration in a krypton and xenon concentrate stream to below 1 ppm , a level comparable to that attainable using a methane burner . the cryogenic removal of methane would result in reduced capital , less cumbersome operation , and increased recovery of krypton and xenon as compared to the current method . these benefits are in addition to safety concerns . the present invention is a process , which by the means of a distillation column and associated equipment , concentrates krypton and xenon while rejecting methane from a feed stream consisting primarily of oxygen . a schematic diagram of the process of the present invention is illustrated in fig2 . operation of this column as discussed later will result in a product stream that is concentrated in krypton and xenon and that contains less than 1 ppm each of oxygen and methane . with reference to fig2 a liquid feed stream containing oxygen , krypton , xenon , and methane is fed , via line 50 , to an intermediate point of crude krypton column 51 for distillation thereby producing a waste overhead and a krypton / xenon bottoms product . to provide liquid reflux to crude krypton column 51 , a liquid stream is introduced at a location above the intermediate feed , via line 52 , into column 51 . examples of liquid streams suitable for introduction as liquid reflux in line 52 include , but are not limited to , liquid nitrogen produced in a standard double column air separation unit , crude liquid argon produced in an auxiliary argon column , or liquid oxygen from the low pressure column of an air separation that has been passed through an adsorbent vessel . this third option is the one shown in fig2 . the adsorbent removes hydrocarbons , with the exception of methane , and other high - boiling impurities , such as carbon dioxide , that break through the front - end adsorbers . to provide vapor flow up crude krypton column 51 , a bottom gaseous feed , containing less than 1 ppm of oxygen and methane , is introduced to crude krypton column 51 at a location below said intermediate point , preferably a point below the bottom equilibrium stage and above the liquid sump . an example of a stream suitable for the gaseous bottom feed stream is gaseous nitrogen from the top of the high pressure column of a standard air separation unit . crude krypton column 51 operates on the principal of ascending vapor stripping descending liquid of methane , krypton , and xenon preferentially in that order such that the waste overhead , removed via line 62 , contains virtually all of the methane that entered in the feed and is also essentially krypton and xenon - free , whereas liquid bottoms product , removed via line 63 , is concentrated in krypton and xenon and contains less than 5 ppm of methane and preferably less than 1 ppm of methane . crude krypton column 51 operates at a reflux ratio below 0 . 15 . fig2 shows reboiler 55 at the bottom of the crude krypton column 51 , however , it is not essential to use one . the gaseous feed stream , in line 53 , can be at any suitable temperature , for example it can be at its dew point or slightly superheated in a heat exchanger by heat exchange with an appropriate stream . generally , the amount of superheat required is only a couple of degrees above the dew point temperature of the stream and usually this difference is less than 75 ° f . when the gaseous stream , in line 53 , is either superheated or a reboiler is used in the bottom of the crude krypton column 51 , the affect is that the concentration of krypton and xenon in the liquid product , removed in line 63 , is much higher . it does not significantly influence the concentration of methane in the liquid product stream . thus , an oxygen - rich gaseous feed stream , in line 53 , at its dew point is as effective in removing methane as a corresponding slightly superheated stream . the cited prior art was concerned with eliminating the safety risk associated with oxygen - methane mixtures by removing oxygen from the liquid product stream ( analogous to stream 63 ) and replacing it with either argon or nitrogen . this was done since the liquid product streams contained appreciable amounts of methane . the current process described herein , removes essentially all the methane that enters in feed 50 in distillate 62 , such that the concentration of methane in the liquid sump of crude krypton column 51 is less than 1 ppm , a concentration that is not a safety hazard . the use of oxygen in bottom feed 53 ( and hence in the liquid sump of crude krypton column 51 ) is preferable as it will result in capital savings due to the reduced size of crude krypton column 51 . conventional processes for the purification of the krypton and xenon from an air separation plant concentrate methane , as well as krypton and xenon , in an oxygen product stream . the concentration of methane in oxygen must be limited as these two compounds form an explosive mixture if concentration of methane builds up . the limit on methane concentration also limits the extent to which krypton and xenon can be concentrated in the product stream . the invention solves the problem and alleviates safety concerns associated with oxygen / methane mixtures by removing methane from the process by cryogenic distillation such that the product stream contains less than 1 ppm methane . the process of the present invention works by taking advantage of the different relative volatilities of xenon , krypton , and methane . the boiling point of xenon is higher than that of krypton which is higher than that of methane . therefore , for a vapor - liquid mixture at equilibrium at a given temperature ( such a mixture exists on each tray of a distillation column ) there will be a partitioning of xenon , krypton , and methane into both the vapor and liquid phases , with this partitioning governed by the relative volatilities . a larger percentage of the total xenon will be found in the liquid phase as compared to krypton and methane whereas a larger percentage of the total methane will be found in the vapor phase as compared to krypton and xenon . crude krypton column 51 has two sections , a section above intermediate feed 50 ( upper section ) and a section below intermediate feed 50 ( lower section ). both sections operate at a liquid to vapor flow ratio ( l / v ratio ) below 0 . 15 with the upper section operating at a lower l / v ratio than the lower section . vapor in the lower section of the column strips methane , krypton , and xenon ( preferentially in that order ) from the liquid in the lower section . the use of oxygen in bottom feed 53 is preferential to nitrogen as this results in a lower required vapor flow , as demonstrated . the upper section operates on the same principle as the lower section . since the reflux liquid 52 is free of krypton and xenon , the descending liquid removes krypton and xenon from the ascending vapor . the object in this section is to adjust the l / v ratio such that distillate 62 contains no krypton or xenon and all the methane that entered with intermediate feed 50 . computer simulations revealed that it is possible to operate the column to achieve this desired result by operating with a l / v ratio below 0 . 15 . the process of the present invention is of value as it results in the elimination of the methane burner that is required in current processes resulting in capital savings . removal of the methane burner may also entail operating advantages as the invention utilizes a totally cryogenic process whereas the methane burner operates in the vicinity of 800 - 1000 ° f . in order to show the efficacy of the process of the present invention , computer simulations of the process were run using gaseous nitrogen in line 53 and also varying the operation of the column with the use of reboiler 55 . the results of these computer simulations are shown in table i - iii . table i______________________________________100 % nitrogen feed 53 stream no . 50 52 53 62 63______________________________________flow : mol / hr 1 . 00 1 . 25 50 . 0 52 . 0 0 . 25pressure : psia 23 . 4 23 . 1 25 . 3 22 . 8 25 . 2temperature : ° f . - 288 . 6 - 289 . 2 - 311 . 8 - 311 . 6 - 308 . 3compositiono . sub . 2 : % 98 . 2 99 . 93 -- 4 . 29 -- n . sub . 2 : % -- -- 100 . 0 95 . 7 94 . 15ar : ppm 143 400 -- 12 . 4 -- kr : ppm 13664 27 . 1 -- 3 . 7 54021xe : ppm 1113 2 . 05 -- -- 4462ch . sub . 4 : ppm 3978 238 . 1 -- 82 . 2 0 . 1______________________________________ table ii______________________________________no reboiler : bottom vapor feed 53 at dew point stream no . 50 52 53 62 63______________________________________flow : mol / hr 1 . 00 1 . 25 50 . 0 49 . 5 2 . 75pressure : psia 23 . 4 23 . 1 25 . 3 22 . 8 25 . 2temperature : ° f . - 288 . 6 - 289 . 2 - 311 . 8 - 311 . 6 - 311 . 5compositiono . sub . 2 : % 98 . 2 99 . 93 -- 4 . 5 -- n . sub . 2 : % -- -- 100 . 0 95 . 5 95 . 5ar : ppm 143 400 -- 13 . 0 -- kr : ppm 13668 27 . 1 -- 2 . 3 4902xe : ppm 1112 2 . 05 -- -- 402ch . sub . 4 : ppm 3978 238 . 1 -- 86 . 4 0 . 2______________________________________ table iii______________________________________no reboiler : superheated bottom gaseous feed 53 stream no . 50 52 53 62 63______________________________________flow : mol / hr 1 . 0 1 . 25 50 . 0 52 . 0 0 . 24pressure : psia 23 . 4 23 . 1 25 . 0 22 . 8 25 . 2temperature : ° f . - 288 . 6 - 289 . 2 - 296 . 8 * - 311 . 6 - 310 . 4compositiono . sub . 2 : % 98 . 1 99 . 93 -- 4 . 3 -- n . sub . 2 : % -- -- 100 . 0 95 . 7 93 . 8ar : ppm 143 400 -- 12 . 4 -- kr : ppm 13668 27 . 1 -- 3 . 7 57087xe : ppm 1112 2 . 05 -- -- 402ch . sub . 4 : ppm 3978 238 . 1 -- 82 . 2 0 . 1______________________________________ * superheated by 15 ° f . over dew point results of the computer simulation for the process depicted in fig2 is shown in table i . table ii presents results for operation of the crude krypton column without a reboiler . stream numbers correspond to those in fig2 . in this case , the feed to the bottom of the crude krypton column is a 100 % nitrogen vapor at its dew point . methane concentration in liquid product stream 63 is reduced to 0 . 2 ppm and the oxygen content is negligible , comparable to the level obtained using a reboiler . the concentrations of krypton and xenon in product stream 63 are 4902 ppm and 402 ppm respectively . both concentrations are approximately 10 % of the concentrations obtained when a reboiler is used . a method for increasing the concentrations of krypton and xenon in liquid product stream 63 is to introduce bottom feed 53 as a vapor superheated above its dew point . results are presented in table 111 for operation of the crude krypton column without a reboiler in which bottom feed 53 is a 100 % nitrogen vapor superheated by 15 ° f . above its dew point . in this case , the concentrations of krypton , xenon and methane in liquid product stream 63 are 57087 ppm , 4709 ppm , and 0 . 1 ppm respectively . the oxygen concentration is negligible . these concentrations are all comparable to those obtained when a reboiler is employed in the crude krypton column ( compare stream 63 in table i to stream 63 in table 111 ). however , this technique saves the use of an additional heat exchanger . the current invention can be integrated with the main air separation unit as shown in fig3 . this figure represent just one of the numerous ways in which the integration can be achieved . a preferred method of integration is depicted in fig3 . the raw krypton column is refluxed with liquid withdrawn from above the sump of the low pressure column of the main air separation unit . feed to the raw krypton column is provided by liquid oxygen withdrawn from the sump of the low pressure column . reboiling duty in the raw krypton column is provided by gaseous nitrogen from the high pressure column of the main air separation unit . the gaseous nitrogen is condensed to liquid nitrogen in the reboiler at the bottom of the raw krypton column . this liquid nitrogen is returned to the main air separation unit . a portion of the liquid oxygen stream exiting the hydrocarbon adsorber is used as reflux liquid in the crude krypton column . the krypton / xenon concentrate stream withdrawn from the bottom of the raw krypton column serves as feed for the crude krypton column . stripping vapor in the crude krypton column is derived from gaseous nitrogen stream withdrawn from an intermediate location from the high pressure column of the main air separation unit . vapor exiting the top of the crude krypton column is recycled to the low pressure column of the main air separation unit . methane - free and oxygen - free krypton / xenon product is collected from the bottom of the crude krypton column . the present invention has been described in reference to several specific embodiments thereof . these embodiments should not be viewed as limitations of the scope of the present invention . the scope of the present invention should be ascertained by the following claims .
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referring to the drawings , fig1 shows a schematic , perspective view of an actuating device 10 according to the present invention . in this exemplary embodiment , the actuating device 10 is designed as a chain wheel coupling . the actuating device 10 is used to actuate a shading system , which is not shown here in detail . a string element 44 is provided for this . in this exemplary embodiment , the string element 44 is a ball chain . the string element 44 has a first strand 45 and a second strand 46 . the actuating device 10 has a basic structure 11 that has a first partial structure 12 and a second partial structure 13 . here , the first partial structure 12 is designed as a lower housing part and the second partial structure 13 is designed as an upper housing part . an upper area of the first partial structure 12 is inserted partly into a lower area of the second partial structure 13 . the first partial structure 12 has an end 14 facing away from the second partial structure 13 . an access opening 15 , which has a gap - like design , for example , here , is associated with the end 14 . by means of the access opening 15 , the string element 44 can be guided as a first string element 44 into and out of the first partial structure 12 . during use , the string element 44 is suspended from the access opening 15 and forms a loop , not shown in detail here , at its end facing away from the actuating device 10 . the second partial structure 13 has an additional access opening 17 at an end 16 facing away from the first partial structure 12 . the additional access opening 17 has a gap - like design , for example , here and is used for guiding an additional or second string element 47 into or out of the second partial structure 13 . the second partial structure 13 has housing sides 18 , 19 arranged parallel to one another and spaced apart from one another . a side wall 20 is arranged between the housing sides 18 , 19 in the area of the outer circumference of the housing sides 18 , 19 . the side wall 20 of the second partial structure 13 has an essentially u - shaped cross section . furthermore , the first partial structure 12 has two housing sides 21 , 22 arranged parallel to one another and spaced apart from one another . a side wall 33 , which has an essentially u - shaped cross section , of the first partial structure 12 is arranged in the area of the outer circumference of the housing sides 21 , 22 and spaces the housing sides 21 and 22 apart from one another . in this exemplary embodiment , the width of the side wall 23 of the first partial structure 12 is smaller than the width of the side wall 20 of the second partial structure 13 . essentially , the difference of the widths between the side walls 20 , 23 corresponds approximately to the sum of the thickness of the two housing sides 18 , 19 . in addition , the side wall 20 of the second partial structure 13 has a setback in relation to the housing sides 18 , 19 in an area facing the first partial structure 12 . consequently , a partial pushing in of the first partial structure 12 into an area facing away from the end 16 of the second partial structure 13 as shown is made possible . fig2 shows a schematic , perspective , partially open view of the actuating device 10 according to fig1 . a part with the housing side 18 is removed from the second partial structure 13 , as a result of which the second partial structure 13 is opened and the inner structure can be seen . the first partial structure 12 has two webs 24 , 25 aligned in the direction of the second partial structure 13 and essentially parallel to one another . in this exemplary embodiment , the webs 24 , 25 are designed as legs of the essentially u - shaped side wall 23 of the first partial structure 12 . a first coupling element 26 or 27 each is arranged at the free ends of the webs 24 , 25 facing the second partial structure 13 . here , the first coupling elements 26 , 27 are designed as locking hooks . the locking hooks 26 , 27 are aligned facing one another . the second partial structure 13 has second coupling elements 28 , 29 , which are each designed for interacting with one of the first coupling elements 26 , 27 , in an area facing the first partial structure 12 . thus , the second coupling elements 28 , 29 in this exemplary embodiment are designed as locking hook mounts . the second coupling element 28 is associated with the first coupling element 26 and the second coupling element 29 is associated with the first coupling element 27 . the first coupling elements 26 , 27 and the second coupling elements 28 , 29 form a first coupling device and are designed as rigid . according to the view according to fig2 , the first partial structure 12 is located in a released position , in which neither of the first coupling elements 26 , 27 interacts with a second coupling element 28 , 29 . rather , the first coupling elements 26 , 27 are shown in the released position spaced apart from the second coupling elements 28 , 29 in such a way that the two first coupling elements 26 , 27 can be directed in a contactless manner past the second coupling elements 28 , 29 for detaching the first partial structure 12 from the second partial structure 13 . thus , the first coupling elements 26 , 27 in the released position do not mesh with the second coupling elements 28 , 29 . the first partial structure 12 has a groove 30 in an area facing the second partial structure 13 . the groove 30 has an arc - shaped design and is embedded into the outer side of the housing side 21 of the first partial structure 12 . a groove designed analogously hereto is also located in the housing side 22 of the first partial structure 12 . the center of the radius of the arc - shaped groove 30 corresponds to the center of an axle 31 , which is associated with the second partial structure 13 . the inner sides of the housing sides 18 , 19 of the second partial structure 13 have a web , not shown in detail here , which meshes with the groove 30 for establishing a detachable locking connection . the web is designed as sufficiently flexible for establishing and detaching the locking connection . in the released position shown here , the web is arranged essentially centrally in the groove 30 . the arc length of the groove 30 is greater than the width or the arc length of the web . as a result of this , the locking connection makes possible a pivoting of the first partial structure 12 about the center or the central axis of the axle 31 of the second partial structure 13 . fig3 shows a schematic , perspective , open view of the actuating device 10 . a part with the housing side 18 is removed from the second partial structure 13 and a part with the housing side 21 is removed from the first partial structure 12 , as a result of which the two partial structures 12 , 13 are open and their inner structure can be seen . according to this view , the first partial structure 12 is pivoted into a first locking position . in this first locking position , the first coupling element 26 meshes with the second coupling element 28 for establishing a positive - locking connection . as an alternative to the first locking position shown here , the first partial structure 12 can be pivoted in such a way that the first coupling element 27 interacts with the second coupling element 29 for establishing a positive - locking connection , whereby the first partial structure 12 is then located in a second locking position . because of the positive - locking connection between the rigid first coupling element 26 and the rigid second coupling element 28 in the first locking position or between the rigid first coupling element 27 and the rigid second coupling element 29 in the second locking position , an undesired detachment of the first partial structure 12 from the second partial structure 13 with a pull on a single strand of a string element , not shown here in detail , is prevented . the first partial structure 12 has an axle 32 , which is used for the rotatable mounting of a first gear wheel 33 . the first gear wheel 33 is connected in a nonrotatable manner to a coaxially arranged chain wheel 34 . by means of a string element 44 , interacting with the chain wheel 34 and not shown in detail here for better clarity , the first gear wheel 33 can thus be displaced into a rotation about the axle 32 . the first gear wheel 33 is in active connection with a second gear wheel 35 , which is associated with the second partial structure 13 . the second gear wheel 35 is mounted rotatably about the axle 31 of the second partial structure 13 . in this exemplary embodiment , the second gear wheel 35 is connected in a nonrotatable manner to a coaxially arranged chain wheel 36 . thus , a movement of a first string element 44 , which is guided about the first gear wheel 33 , can be transmitted to a second string element 47 , which is guided about the chain wheel 36 . the first gear wheel 33 and the second gear wheel 35 are actively connected to one another in such a way that a pivoting of the first partial structure 12 can be brought about because of the interaction between the two gear wheels 33 , 35 . the stronger the first strand 45 or the second strand 46 of the first string element 44 is pulled , the stronger is the first partial structure 12 pivoted in relation to the second partial structure 13 . in this case , the first gear wheel 33 is coaxially guided about the outer circumference of the second gear wheel 35 or the axle 31 . the second string element 47 may be connected to a drive for driving a shading system . as an alternative , the second gear wheel 35 may have no chain wheel and instead be connected directly to a drive axle . fig4 shows a schematic , cut partial section of an actuating device 10 according to the present invention . the first partial structure 12 has a third coupling element 37 at an end facing the second partial structure 13 . the third coupling element 37 is designed for interacting with a fourth coupling element 38 of the second partial structure 13 . the third coupling element 37 and the fourth coupling element 38 form a second coupling device . in this exemplary embodiment , the third coupling element 37 is designed as an essentially t - shaped locking head . the fourth coupling element 38 is designed here , for example , as an essentially t - shaped locking head mount . the fourth coupling element 38 is arranged at an end of the second partial structure 13 facing the first partial structure 12 . in this exemplary embodiment , the third coupling element 37 is arranged in the plane of the housing surface 18 and the fourth coupling element 38 is arranged in the plane of the housing surface 21 . the third coupling element 37 and the fourth coupling element 38 are arranged essentially centrally to a conceived vertical axis of the first partial structure 12 and of the second partial structure 13 . furthermore , the third coupling element 37 and the fourth coupling element 38 are designed in such a way that the third coupling element 37 can be guided in a contactless manner from the fourth coupling element 38 in the released position , shown here , of the first partial structure 12 in relation to the second partial structure 13 . thus , in the released position , the third coupling element 37 and the fourth coupling element 38 do not mesh with one another . for this , a base or base opening 39 of the fourth coupling 38 is designed as somewhat wider than the t - shaped locking head of the third coupling element 37 . the third and fourth coupling elements 37 , 38 are designed as rigid . in a locking position , not shown in detail here , of the first partial structure 12 , a leg 40 or 41 of the third coupling element 37 meshes with a correspondingly designed leg mount 42 or 43 . a positive - locking connection between the first partial structure 12 and the second partial structure 13 can thus be established in the locking position . the third coupling element 37 is arranged in the area of the housing side 21 of the first partial structure 12 and the fourth coupling element 38 in the area of the housing side 18 of the second partial structure 13 . analogous to the third coupling element 37 and the fourth coupling element 38 , a fifth coupling element designed analogously hereto and a sixth coupling element may be provided , which are arranged in the area of the housing sides 19 , 22 and thus form a third coupling device designed analogously to the second coupling device . fig5 shows a schematic , perspective view of the actuating device 10 according to the present invention according to fig1 with a detached first partial structure 12 . the first partial structure 12 has two assembled housing halves 48 , 49 . the housing halves 48 , 49 are connected to one another by means of a locking connection in this exemplary embodiment . the second partial structure 13 has two assembled housing halves 50 , 51 , which are connected to one another by means of a separate fixing element 52 in this exemplary embodiment . the fixing element 52 may be used as a securing means for a locking connection of the two housing halves 50 , 51 . the fixing element 52 is designed here as a screw , which is guided through the axle 31 . in this case , the axle 31 according to fig2 and 3 is designed as a hollow axle . by means of the fixing element 52 , an especially reliable connection between the housing halves 50 , 51 can be established . as an alternative or in addition , the first partial structure 12 may have an analogously designed fixing element . the housing halves 48 , 49 , 50 , 51 have different designs in this exemplary embodiment . as an alternative , the housing halves 48 , 49 of the first partial structure 12 or the housing halves 50 , 51 of the second partial structure 13 may have an identical design . in the released position , the first partial structure 12 is in active connection or meshes with the second partial structure 13 by means of the groove 30 . with a sufficiently strong pull or essentially equally strong pull on both strands 45 , 46 of the string element 44 , for example , due to the gravity of a child suspended in a loop of the string element 44 , this single connection is detached from the second partial structure 13 by a bending up of the housing sides 18 , 19 at least in the area of the groove 30 , as a result of which the first partial structure 12 is completely detached from the second partial structure 13 as shown here . fig6 shows another sectional view of the schematic , cut partial section according to fig4 . the single detachable connection between the first partial structure 12 and the second partial structure 13 in the released position can be seen in this view . this detachable active connection is designed as a detachable locking connection in this exemplary embodiment . here , a web 53 of the second partial structure 13 meshes with the groove 30 of the first partial structure 12 . the groove 30 is inserted into a front side of the housing side 21 of the first partial structure 12 . the web 53 is arranged on the inner side of the housing side 18 of the second partial structure 13 . analogously hereto , an additional web 55 of the second partial structure 13 meshes with an additional groove 54 of the first partial structure 12 . the additional groove 54 is inserted into a front side of the housing side 22 of the first partial structure 12 . the additional web 55 is arranged on an inner side of the housing side 19 of the second partial structure 13 . as an alternative , the detachable position between the first partial structure 12 and the second partial structure 13 in the released position may have at least one pin or a plurality of pins instead of a web 53 , 55 . the pins or the webs 53 , 55 may have a flexible design in order to guarantee a detachment of the first partial structure 12 in the released position with a sufficient pulling force on both strands 45 , 46 . as an alternative or in addition , the housing sides 18 , 19 may be flexible or elastic in the area of the locking connection or of the webs 53 , 55 . while specific embodiments of the invention have been shown and described in detail to illustrate the application of the principles of the invention , it will be understood that the invention may be embodied otherwise without departing from such principles .
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as used herein , “ long ” micro - channel here means cylindrical hollow micro - channel with ratio of inner diameter to length = 1 / 10 - 1 / 100 . as used herein , “ extremely small ” means volume range 1 - 500 picoliters ( 1 / 10 ^ 9 - 1 / 5 · 10 ^ 7 of one milliliter ). the term “ colony ” or “ micro colony ” in microbiology means a group of cells appearing from one single cell and consisting only from descendants of that cell . as used herein , the term “ cell layers ” refers to cells within a channel that occupy about the same height level , wherein another layer of cells can be supported above the layer . each cell layer in a micro - channel of diameter 10 μm consists of 20 - 80 cells . the shape of a regular prior art micro - colony is usually semi - sphere 101 ( fig1 a ), in contrast to one embodiment of the present disclosure as a long , extremely small micro - channel 102 located on filter 103 , which in turn is located on media , or agar , 104 ( fig1 b ). thus , a micro - colony inside micro - channel 102 in the embodiment of the present invention is notably thinner than the micro - colony of the prior art semi - sphere 101 shown in fig1 a . a colony inside micro - channel 102 ( fig1 b ) reaches height h much quicker than a colony would reach the same height h in semi - sphere 101 ( fig1 a ). the height ( or thickness ) of micro - colonies is important to visibility using microscopy as a high ( thick ) colony has a greater light absorbance , which is the most important optical characteristic of visibility . a long and thin micro - colony has the same light absorbance as a regular semi - spherical colony of the same height - h . at the same time , a volume and number of cells at height h in micro - channel 102 ( fig1 b ) is much less than in semi - sphere 101 ( fig1 a ) at height h , and therefore the time of incubation to create a visible colony is in micro - channel 102 ( fig1 b ). calculations show the advantage in reducing the time of growth in micro - channel 102 ( fig1 b ) compared with semi - sphere 101 ( fig1 a ). a regular shape of colonies growing on flat surfaces of solid nutrient media is , usually , near to semi - sphere . the volume of a semi - sphere ( vss ) is vss =¶· h 2 ·( r − h / 3 ), where vss is the volume of semi - sphere , r is the radius of sphere , ¶ is π or pi , and h is part of radius - height of semi - sphere . the volume of a cylindrical colony ( vcc ) such as in micro - channel 102 ( fig1 b ) is vcc =¶· r 2 · h , where r is the radius of cylinder , and h is the height of cylinder . cylindrical colony with the same height ( h = 10 μm ) and r = 2 . 5 μm has volume : thus , the volume of a cylindrical colony is smaller than the volume of semi - spherical micro - colony with the same height by 27 times , yet both have the same light absorbance . the volume of one cell of escherichia coli ( e . coli ) is near to 1 μm 3 . the speed of multiplying of e . coli is around 20 min at optimal temperature , on optimal media . one cell of e . coli can produce 8 cells in one hour , 64 in two hours , 512 in 3 hours , 4096 in 4 hours and 32768 in 5 hours . thus , one visible micro - colony on a flat surface , containing 5234 cells , can be formed in 4 . 2 hours . the cylindrical colony with the same height and light absorbance ( 196 cells ) can be formed in 2 . 5 hours . therefore , the growth of micro - colonies with a cylindrical shape has a significant advantage as visualization of colonies can be done at much earlier stages . the visualization of microorganisms in one or a multiplicity of micro - channels is much faster than in petri plate , regular laboratory tubes , wells or semi - spheres of an immunological plate , or other known laboratory devices for microorganism growth , because of the very small volume of micro - channels and their long cylindrical shape . thus , one cell trapped in a cylindrical micro - channel , with a length 500 μm and diameter 10 μm ( v = 40 , 000 μm 3 , corresponds to a concentration of 25 million cells per ml ( v = 10 12 μm 3 ). forty cells in a micro - channel correspond to the concentration 10 ^ 9 cells per ml , which is a well - detectable concentration . one cell of e . coli can reach this concentration from one trapped in micro - channel cell ( 40 cells per micro - channel = 10 ^ 9 cells per ml ) in 1 . 7 hours . experiments show that 10 cell layers of colorless small cells ( for example e . coli ) are enough to find visual differences between micro - channels containing cells and empty micro - channels using a regular light microscope , even with a small magnification of × 100 . a smaller diameter of micro - channel requires a smaller amount of cells to create 10 cell layers in the micro - channel . table 1 represents the number of layers of e . coli that can be produced in micro - channels of different diameters between one and five hours . extrapolated , table 1 shows that 10 cell layers will be reached in a micro - channel with a diameter of 2 μm in 1 . 5 hours ; in a 3 μm micro - channel in 2 hours ; in a 4 μm micro - channel in 2 . 3 hours ; in a 5 μm micro - channel in 2 . 7 hours ; in a 7 μm micro - channel in 2 . 9 hours and in a 10 μm micro - channel in 3 . 5 hours . thus , the detection and enumeration of long cylindrical micro - colonies , according this invention , can be done 10 - 20 times faster than regular growth , detection and enumeration of colonies . the growth of a cylindrical micro - colony can be made in a microarray of micro - channels as shown in fig2 . the diameter of each of these micro - channels needs to be very small , only 10 ^ 4 - 10 ^ 5 times larger than the size of the cells . array 201 ( fig2 ) is also called a micro - channel glass plate ( mcgp ). mcgp 201 contains a multiplicity of micro - channels in any required shape . while a round mcgp 201 is depicted in the figures , any shape of mcgp 201 can be used , e . g ., a square or rectangular shape . in one embodiment , mcgp 201 has 700 , 000 micro - channels per cm 2 . preferably , each micro - channel in mcgp 201 has a diameter of about 10 microns , and a length of about 500 microns . in general , mcgp 201 is above filter 103 , wherein filter 103 is porous , such that the pores are smaller than the cells in an aqueous sample ( fig2 ). as the sample is filtrated from above mcgp 201 through both mcgp 201 and filter 103 in a filtration process , a liquid portion of the aqueous sample filters through filter 103 while cells are trapped in micro - channels of mcgp 201 on the surface of the filter 103 . after the filtration is completed , the mcgp 201 and filter 103 are placed on a nutrient agar or agar block of solid nutrient media 104 . nutrient substances from the media penetrate the filter 103 , and fill all micro - channels . growths of micro colonies generally start after this penetration . a micro - colony can start formation regardless of initial trapping position within a micro - channel . fig3 shows three typical positions of a cell in a micro - channel . position 1 : micro - channel 301 — cell was trapped on the surface of the filter 103 and colony formed from the bottom of micro - channel of mcgp 201 . this formation appears when nutrient substances just moistens filter . position 2 : micro - channel 302 — cell was trapped on the wall of micro - channel of mcgp 201 by the force of adhesion or by antibody attached to the wall prior to filtration . position 3 : micro - channel 303 — cell was trapped on the filter 103 , but was later raised up by liquid media and started forming micro - colony in micro - channel of mcgp 201 . the formation of a micro - colony in this embodiment starts only if the micro - channel is filled by nutrient substances from wet agar media , or a thick paper filter filled by a nutrient broth . in all of these cases , one cell formed a micro - colony of cells that were descendants of the first cell in the solid , semi - solid or liquid culture . fig4 a shows a cross - sectional view of a sampling - detection unit ( sdu ) 400 while fig4 b shows isometric view of sdu 400 - 1 , used to trap cells by filtration from liquid or air , grow micro - colonies , and / or treat colonies with chromo - or fluorogenic substrates if needed . sdu 400 preferably includes a removable transparent plate 401 , wherein the plate can be glass , plastic or other transparent substance . transparent plate 401 includes one or more small holes for respiration . sdu 400 further includes mcgp 201 , filter 103 , porous support 104 , a holding device 405 , wherein holding device 405 holds mcgp 201 and filter 103 , and holding device feature 406 , wherein holding device feature 406 , holds porous support 104 adjacent to filter 103 . holding device feature 406 and transparent plate 401 are readily removable from holding device 405 , filter 103 and mcgp 201 . further , porous support 104 can be supported by holding device feature 406 with or without the further inclusion of holding device 405 . as could be readily understood by one skilled in the art , the precise shape and structure of sdu 400 and 400 - 1 can vary while still maintaining the spirit of the invention , particularly with regard to porous support 104 and holding devices 405 and 406 . fig5 shows filtration device 500 consisting from manifold 501 , sdus 400 and holder / funnel support 503 for sdus 400 . one or a multiplicity of sdus 400 are adjusted to manifold 501 as shown in fig5 , wherein sdus 400 are placed on funnel support 503 of manifold 501 after removal of transparent plate 401 ( fig4 ). fig5 shows different adjustments to the sdu 400 mounted on manifold 501 for filtration , wherein sdu 400 can be operated with funnel 504 for filtration of liquid samples which can be adjusted to the sdu 400 , syringe 505 for passing liquids with a help of plunger , or just for passing small samples , or without any additional devices as it is intended for air filtration 506 , for example , for trapping bioaerosols ( cells and spores ) in micro - channels . filtration device 1 500 is shown to include three separate funnel supports , wherein one funnel support 503 a is used to support sdu 400 with a funnel 504 , another funnel support 503 b is used for an sdu 400 with a syringe 505 , and another funnel support 503 c uses neither a funnel nor a syringe . as could be readily understood , filtration device 500 can consist of one or any number of funnels supports 503 a - c in any arrangement , wherein the sdus 400 placed on funnel supports 503 can further include any combinations of funnels 504 , syringes 505 or neither . to use the filtration device , a liquid or air sample containing microorganisms is filtrated through the device adjusted to manifold . after adding sample , transparent plate 401 ( fig4 ) must be placed back on sdu 400 to resist contamination . after filtration , each sdu 400 is removed from funnel support 503 ( fig5 ). porous support 104 and holder 405 are now removed next and transparent plate 401 ( all shown in fig4 ) is returned back on top of sdu 400 . sdu 400 is placed on the surface of an eligible solid nutrient media or in the container with a liquid nutrient media , for example , placed on a petri plate with nutrient media ( bottom left , fig5 ) or nutrient media agar cylinder adjusted to lower side of filter ( bottom right , fig5 ) to initiate micro - colony formation . one embodiment of this is shown in fig2 where liquid from nutrient agar 104 immediately wets filter 103 and penetrates micro - channels of mcgp 201 because of strong capillary forces . the nutrient media is absorbed by the filter and supports the growth of a cylindrical - shaped micro - colony or penetrates through the filter in channels , and supports the growth of suspended microorganisms that later forms cylindrical solid or semi - solid micro - colony as shown on the fig3 . the sdu with nutrient media is incubated at an appropriate temperature for the required time for cell growth , wherein the temperature and time needed will vary as is known in the art with regard to what type of colonies are being grown . in order to reduce the time of analysis by increasing light absorbance or adding fluorescence , the device can be placed in a container with an eligible solution of artificial substrate . otherwise the substrate can be added to solid nutrient media in advance as it is done in chromagars . this invention is capable of detecting a range of cells in a sample from a single cell to several hundreds of thousands or even millions , depending on the number of micro - channels in the mcgp . for example , a 25 millimeter diameter mcgp with micro - channels 10 μm in diameter ( square of plate around 5 cm 2 and 700 , 000 micro - channels per one cm 2 ) contains 3 . 5 millions of micro - channels . in order to have reliability , the number of cells in a sample should be less than the number of micro - channels in mcgp , thereby keeping the allowing no more than one cell per micro - channel . in further preferred embodiments , a ratio of about one cell per five to ten micro - channels is used , to greater ensure that only one cell will enter any particular micro - channel . thus , for example , with a mcgp having 3 . 5 million micro - channels , the number of live microbes in a sample would not exceed 700 , 000 for this plate so that one cell goes to one micro - channel with higher level of reliability . if a sample is expected to contain a higher concentration of microbes , it can be diluted in a manner regularly used in microbiological practice . in comparison , a regular petri plate limits colony growth from one single colony to only 300 colonies recommended by us food and drugs administration , otherwise colonies will begin to overlap each other and decrease the reliability of enumeration . thus , current invention allows grow and detect in around thousand times more concentrated samples without ten - fold dilutions : about 700 , 000 with mcgp and only around 300 by regular petri plate . the micro - channels containing colonies appear as dark dots when a regular light microscope is used , as shown in fig6 a . the addition of artificial chromo - or fluorogenic substrates to micro - colonies can reduce the time between inoculation and detection as they make micro - colonies much more visible at an earlier stage . fig6 shows the differences between natural non - colored micro - colonies ( fig6 a ), micro - colonies colored by chromogenic substrates or absorbent dyes ( fig6 b ), and micro - colonies colored by fluorogenic substrate or fluorescent dye ( fig6 c ). the coloration of micro - colonies inside micro - channels is done by attaching agar or filter paper treated with required substances to the opposite side of the filter attached to the micro - channel plate . a light microscope sends light through the mcgp ( colorless ), filter ( colorless ), and agar ( light transparent ) ( fig6 a and 6b ), revealing long cylindrical shaped micro - colonies because of the natural light absorption of cells , or due to cells colored by chromogenic substrates or absorbent dyes . a fluorescent microscope ( fig6 c ) sends a shorter wave light ( ultra violet , blue or other depending on dye ) and accepts long waves of fluorescence ( blue , green or red ). therefore , micro - channels with micro - colonies will appear as bright dots on a dark background . the structure of the sdu for fluorescent version is : mcgp ( black non fluorescent ), filter ( black non - fluorescent ), and agar ( filled by fluorescent indicator ). fluorescence is considered a much more sensitive type of analysis . thus , the micro - colonies can be much smaller / shorter than those analyzed with the use of light absorbance . fig6 d , 6 e , and 6 f are illustrations of the direction of light travel through the filter and microchannels . whether fluorescent or color indicators are used or not used , and sdu is placed under a light or fluorescent microscope , and the amount of dark , colored or fluorescent channels is detected and enumerated . this amount corresponds to the number of cells trapped on the surface of the filter . the difference between non - colored micro - colonies ( fig6 a and 6 d ,) micro - colonies colored by chromogenic substrates or colored by light absorbent dyes ( fig6 b and 6 e ,) and micro - colonies colored by fluorogenic substrates or fluorescent dyes ( fig6 c and 6f ). many different dyes and indicators used for coloration of micro - colonies . including but not limited to : colorless fluoresceine diacetate or fluoresceine butirate cleaves by esterases with the release of highly fluorescent fluoresceine ( green fluorescence = 515 nm ). fluoresceine collects ( crystallizes ) inside cells and interrupts biochemical pathways , which cause a death of cell . thus , fluoresceine diacetate and other fluoresceine derivatives can be used only after micro - colonies are formed . colorless 4 - methylumbelliferyl acetate , - butyrate , - propionate , or - phosphate cleaves by esterases , lipases or phosphatases with the release of 4 - methylumbelliferone , a highly fluorescent substance ( blue fluorescence = 450 nm ). 4 - methylumbelliferone is secreted from cells and concentrates in extracellular spaces , filling the remaining volume of the micro - channel . fig6 c demonstrate micro - channels filled by 4 - methylumbelliferone appeared after enzymatic reaction of e . coli micro - colony with 4 - methylumbelliferyl - butirate . thus , 4 - methylumbelliferyl derivatives can be used during micro - colony growth . extracellular buildup of fluorescent signal can significantly reduce the time required for analysis as very small micro - colonies ( 10 - 20 cells ) can be detected . to grow micro - colony with 10 - 20 cells needs only 2 - 2 . 5 hours of incubation . a big group of tetrazolium salts — indicators of dehydrogenases ( group of respiratory enzymes of live cells was successfully used to color micro - colonies : thiazolyl blue , tetrazolium iodo ( int ), nitrotetrazolium blue ( nbt ), and bt - tetrazolium . non colored tetrazolium salts produce well colored formazans ( dark violet , blue , red , pink ) in reactions with live cell &# 39 ; s dehydrogenases . our experiments show that thiazolyl blue tertazolium salt is the best and universal for all investigated microorganisms . chromogenic substrates such as 5 - bromo - 4 - chloro - 3 - indoxyl butyrate , - palmitate , - phosphate ( blue precipitates inside cell ) or 6 - chloro - 3 - indoxyl butyrate , - palmitate ( red color precipitates ) for esterases , lipases , or phosphatases , as well as other chromogenic substrates can be used for coloration of formed micro - colonies and as additives to nutrient media chromogenic substrates that are dissolved in nutrient media before application for cell growth are referred to as “ chromagars .” however , chromagars are created for only a few microorganisms : chromagar ™ candida , cromagar ™ 0157 , chromagar ™ salmonella , chromagar ™ staph aureus and chromagar ™. orientation for urinary tract pathogenic microorganisms ( cromagar company , france ). dyes , such as dansylchloride ( dns - chloride ) or fluorescamine , are capable of increasing fluorescence hundreds or even thousands times after attaching to biomolecules such as nh - groups of proteins . these compounds are also useful for marking micro - colonies for further enumeration . some substances are known to change the color of colonies to a dark or even black color , making micro - colonies more visible on a petri plate or under a microscope in micro - channels . for example , iron sulfide in sps agar is known to color clostridia , and xlt4 agar base colors salmonella . likewise , potassium telluride in vj agar colors staphylococcus aureus colonies in well visible black color . some light absorbent and fluorescent substances reveal ability to change color or fluorescence after ph of medium changes . micro - colonies change inner ph in micro - channel that can be found with color or fluorescent indicators . growth of 5 - 6 hours is often enough to produce long micro - colonies , and detect and enumerate a large number of non - colored micro - colonies by their enhanced light absorbance or light scattering . for example growth of e . coli in micro channels on tsa around 6 hours at 37 ° c . is enough to produce micro - colonies visible without of additional coloration . physical factors can also be changed to decrease the time between inoculation and micro - colony detection . for example , heating to coagulate proteins , increasing light absorbance or light scattering , or adding substances to produce gas bubbles within micro - channels that contain live cells — such as oxygen ( o 2 ) from hydrogen peroxide ( h 2 o 2 ) by catalase — can be employed . fig7 demonstrates bubbles of oxygen produced by micro - colonies in reaction catalase — hydrogen peroxide of bacillus megatherium , incubated 3 hours on tsa at 35 ° c . many different kinds of samples , a variety of microorganisms , hundreds of nutrient media , and a multitude of indicator substances opens a huge opportunity for the implementation of this invented technology in the different areas of microbiology . one of the mostly used nutrient solid media for detection of total viable organisms ( mainly bacteria ) is tryptic soy agar ( tsa ). regular growth of colonies on a petri plate filled with tsa requires 24 to 72 hours at 35 ° c . using the proposed invented method ; incubation requires only 4 hours . the procedure for the invented technology is as follows : the sample ( 100 milliliters ) is filtrated through the sdu , trapping cells in micro - channels containing a colorless mcgp and colorless filter ( polycarbonate , 0 . 2 microns pores , osmonics inc , usa ) ( fig4 , fig5 ). live cells , if any in the sample , are trapped in some of the micro - channels . the sdu is removed from the manifold and a nutrient media ( tsa ) agar block is attached to the surface of the filter . nutrient substances from the tsa saturate the filter and penetrate into micro - channels . this process takes around 10 - 30 seconds . the sdu with attached agar block is placed in an incubator for 4 hours at 35 ° c . trapped live cells form long and thin micro - colonies in micro - channels where they were trapped . after incubation , the nutrient media agar block is removed . another agar block containing thiazolyl blue tetrazolium salt ( 3 mg / ml ) is adjusted to the filter . alternatively , a thick filter paper filled by an indicator substance can be used instead of agar block . yellowish molecules of thiazolyl blue penetrates ( diffused ) into the micro - channels . any micro - channels containing micro - colonies become dark violet in color ( fig6 b ). the reaction of tetrazolium salt with cells is well - known and based on respiratory enzymes — dehydrogenases of living cells accepting a hydrogen atom ( h +) from the tetrazolium ring for further use in respiration . this reaction then results in a colored substance — formazan , which is collected inside live bacterial cells , mainly in mesosomes . all known bacterial and fungal cells react with tetrazolium salt to reveal this color reaction . intensely colored long cylindrical micro - colonies are much more visible than the same non - colored micro - colonies or colored flat micro - colonies ( grown without micro - channels ). an agar block ( 2 % in distilled water , 1 cm 3 volume ) can be prepared with thiazolyl blue by adding 3 - 4 drops of a 3 milligrams per milliliter thiazolyl blue in phosphate buffer ( ph = 7 . 2 ). intensively colored cylindrical micro - colonies are visible as colored circles and are easily enumerated in a regular light microscope with a microscopic multiplication from × 40 or larger . the concentration ( cells per milliliter ) of live cells in a sample is enumerated or calculated by regular known methods : direct count , “ most probable numbers ,” or by counting of several microscopic fields , calculate average and recalculate on all surface of mcgp . also automatic count is possible with several modern microscopes equipped by image analyzing programs . thus detection and enumeration of microorganisms in a sample by micro - colonies method and device can be completed many times faster than when depending upon cell growth on a regular petri plate . identification of micro - colony of e . coli o : 157 by enzyme immunoassay in micro - channels micro - colonies can be identified in the micro - channels using enzyme immunological analysis ( eia ). cells are trapped in the micro - channels by filtering a sample as described in example 1 . the use of eia for the identification of micro - colonies is based on the immunological reaction between antigens of the cells ( micro - colony ) and enzyme - antibody conjugates . the conjugate is passed through the micro - channels in order to perform antibody — antigen reactions . the syringe shown in fig5 is suitable for this because it allows a small volume of conjugate to be slowly pressed through the micro - channels . the micro - colonies in this case must be very small , 8 - 32 cells , as larger micro - colonies can clog the micro - channel . after the conjugate attaches to e . coli o : 157 antigens , a block of pure agar filled by tetramethylbenzidine ( a substrate for horseradish peroxidase — an enzyme of the conjugate ) is attached to the filter . tertamethylbenzidine is cleaved by the horseradish peroxidase with creation of a blue - colored dye that collected in micro - channel with e . coli o : 157 . the number of e . coli o : 157 present in the sample corresponds to the number of blue micro - channels . this example is based on a well known color reaction , but fluorescent reactions are also available . thus a conjugate consisting from antibody and β - d - galactosidase gives a fluorescent 4 - methylumbelliferone in reaction with 4 - methylumbelliferyl - β - d - galactose . conjugates consisting from an antibody and phosphatase produce 4 - methylumbelliferone in reaction with 4 - methylumbellyferyl phosphate , disodium salt . micro - channel technology can also be used for the rapid analysis of bioaerosols . air is filtrated through the sdu , which is adjusted to the manifold . the manifold is connected to an air pump ( aircheck hv30 , quicktake 30 or another , skc inc ., usa ). a rotameter for measuring the air volume is installed between the manifold and the pump . a required volume of air is passed through the sdu , and microorganisms present in the air sample are trapped in the micro - channels . bacilli and fungi spores are considered the main microorganisms in bioaerosols . thus , two nutrient media need to be used , tsa for bacilli and sda for fungi spores . this also requires using two sdu . dormant spores of bacilli usually germinate within 0 . 5 - 1 . 5 hours after contact with a nutrient media . this time needs to be added to the regular time of bacilli incubation trapped in micro - channels ( 4 hours ) in order to form a cylindrical micro - colony from the spore . germination of fungi spore requires about 2 - 6 hours , followed by incubation in the sdu of about 12 hours . after micro - colonies from spores appear in the micro - channels , procedures described in example 1 ( detection of the total number of viable microorganisms ) or example 2 ( identification of micro - colonies ) or other procedures developed for micro - channel analysis take place . another version of sampling air microorganisms is by first sampling in liquid ( sodium chloride solution , buffer , liquid nutrient media ) with help of well - known liquid samplers ( e . g ., agi - 30 , skc biosampler , skc inc ., usa ) and then filtrated through the sdu . currently used methods for bioaerosol detection are based on “ landing ” particles on the surface of agar media ( impactor biostage , skc inc .) or inoculating liquid samples with microorganisms sampled beforehand . both methods need a long growth period for the microorganisms in order to form well visible colonies : 24 - 72 hours for bacteria and 72 - 120 hours for fungi . whereas particular embodiments of the invention have been described herein for purposes of illustration , it will be evident to those skilled in the art that numerous variations of the details may be made without departing from the invention as defined in the appended claims .
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in the practice of the present invention , the novel composition hereof contains triethanolamine ( tea ), sodium hydroxide , distilled water , oleic acid , stearic acid , glycerine , ricinoleic acid , coco fatty acids , tallow fatty acids and other minor ingredients such as fragrance , antioxidants , chelating agents , foam stabilizers , colors , germicides , etc . more particularly , the composition hereof contains the following ingredients in the following ranges ( expressed in weight percent ): ______________________________________ranges maxi - minimum optimum mum w / w % w / w % w / w % ______________________________________tea 27 . 0 32 . 5 38 . 0naoh ( 50 %) 7 . 0 8 . 2 9 . 4di - water 1 . 0 2 . 4 7 . 0oleic acid 0 . 0 3 . 4 6 . 0stearic acid 6 . 0 17 . 5 20 . 5cocodiethanolamide ( cdea ) 0 . 0 1 . 5 4 . 0glycerine 0 . 0 11 . 0 25 . 0antioxidant 0 . 0 . 1 . 5fragrance 0 . 0 1 . 0 3 . 0ricinoleic acid 1 . 0 4 . 8 6 . 0coco fatty acid 3 . 0 6 . 3 20 . 2tallow fatty acid 8 . 0 11 . 0 14 . 0laneth - 10 - acetate 0 . 0 2 . 0 4 . 0nonoxylnol - 14 / peg - 4 - octanoate 0 . 0 1 . 0 2 . 0triethanolamine lauryl sulfate 0 . 0 8 . 0 10 . 0acetylated lanolin alcohol 0 . 0 2 . 0 4 . 0witch hazel 0 . 0 1 . 0 3 . 0lauroyl sarcosine 0 . 0 1 . 0 2 . 5citric acid 0 . 0 1 . 0 2 . 0gluconic acid 0 . 0 0 . 2 1 . 5sodium metabisulfite 0 . 0 0 . 5 1 . 54 - chloro - 2 -( 2 , 4 dichloro - 0 . 0 0 . 5 2 . 0phenoxy ) phenol ( irgasan - 300 ) ______________________________________ in addition to the above - listed ingredients , or as alternatives therefor depending on the availability of the reagents and / or the secondary characteristics desired , the following ingredients represent materials which may be incorporated into the blend without diminishing any of the primary characteristics required . thus , satisfactory results are obtained with the addition of an antioxidant such as tocopherol , tocopherol acetate , bha , bht , citric acid , sodium meta - bisulfite , succinic acid and the like ; a chelating agent such as edta , dtpa and similar agents ; commercial grades of triethanolamine ( tea ), such as 85 % tea which can contain both the corresponding secondary and primary amines as impurities ; surfactants and / or foam boosters selected from a wide group of anionic , amphoteric , nonionic , and certain cationic surfactants as exemplified by ( but not limited to ) oleyl betaine , cocamidopropyl betaine , lauramide , c12 - c18 olefin sulfonate , sodium lauryl sulfate , sodium laureth sulfate , cetyltrimethyl ammonium chloride , sodium cocoyl isethionate , tween 20 - 80 , and the like ; fatty acids such as hydrogenated tallow , isostearic acid , lauric acid , palmitic acid , neo - decanoic acid , lanolin fatty acids , palm kernel fatty acids , palm oil fatty acids and the like ; solvents such as diethanolamine , propylene glycol , hexylene , quadrol and the like ; and miscellaneous additives such as polyethylene glycol , lanolin , peg - 20 , hydrolyzed animal proteins , sorbitol and the like . it has also been found , when the exigencies of production require , that potassium hydroxide can be used as a suitable substitute for sodium hydroxide in the neutralization process . the formulation as described above has the unexpected propensity , when introduced into and processed through the equipment shown in the flow diagram of fig1 for substantially instant saponification , as will hereinafter appear , and produces a light colored soap having superior fragrance stability to that obtained by the batch process while achieving at least equivalent physical properties such as hardness , foaming , solubility and clarity . referring to fig1 one practice of the present invention comprises dividing the aforesaid composition into a first and second blend of ingredients , one disposed in each of a first and second discrete tank 11 , 12 . each blend is thereafter pumped from tanks 11 , 12 by speed controlled pumps 13 , 14 , respectively , into a mixing tank 15 surrounded by water jacket 16 . thereafter , the mixture of the first and second blends , whose relationship has been carefully controlled by individually regulating the speed of feed pumps 13 , 14 to create a stoichiometric balance thereof in mixing tank 15 , is pumped by a third speed controlled pump 18 into a second mixing tank 19 which is also surrounded by water jacket 20 . additional specialized ingredients can be added to the formulation at this point of the process . in tank 19 , the mixture receives additional mixing and is thereafter discharged through outlet 21 into suitable molds 22 for further handling as will be hereinafter described in detail . a suitable water heater 23 is disposed adjacent water jacket 16 and supplies jacket 16 with inlet water heated to about 90 ° c . this water from jacket 16 is fed to jacket 20 via suitable piping 24 and the water from jacket 20 is withdrawn therefrom via suitable piping 25 through which it may be directed to a drain ( not shown ) or returned to the reservoir 26 of heater 23 , whatever the exigencies of a particular installation may require . regardless of the blend , the soap bars produced hereby are formed by discharging the warmed ( 60 ° c .- 85 ° c .) soap mixture into the bar molds which are thereafter processed in identical fashion which will now be described . the filled molds 22 are preferably disposed upon a suitable conveyor system 28 which transports the molds 22 into a chiller 29 having a cooling medium of from about - 30 ° to about 6 ° c . provided by refrigeration . the filled molds 22 are maintained in the cooling environment at this temperature for a period of from 5 - 45 minutes whereupon a transparent bar of acceptable hardness ( circa 120 + 40 ), free of crystals and without discoloration is produced . ( see : examples xii and xiii , infra .) the hardness , as reported herein , is measured using a penetrometer ( penetrometer , precision scientific , chicago , il ). it is measured as the depth in millimeters a needle with a 50 gram weight will penetrate the bar in a given time . the greater the penetration , the softer the soap bar . the finished bars are then removed from the molds and packaged in the usual way and are ready for market . to further aid in the understanding of the present invention , and not by way of limitation , the following examples are presented . transparent soap bars were prepared in accordance with the dual tank procedure of the present invention . the first tank was filled with blend a and the second tank was filled with blend b , both shown below . each tank was preheated to 70 °- 80 ° c . and the contents were pumped therefrom in stoichiometric amounts into a mixing vessel surrounded by a hot water jacket wherein saponification occurs during agitation . ______________________________________blend atriethanolamine ( tea ) 4 . 2ricinoleic acid 4 . 8coco fatty acid 6 . 3tallow fatty acid 11 . 0oleic acid 3 . 4stearic acid 17 . 5cdea 1 . 8dl - α - tocopherol 0 . 10fragrance 1 . 0total 50 . 0blend btea 28 . 4naoh 50 % 8 . 2di - water 2 . 4glycerine 11 . 0total 50 . 0______________________________________ thereafter the final mixture is withdrawn from the mixing tank into appropriate molds which are chilled in accordance with example xii . transparent soap bars were prepared in accordance with the dual tank procedure of the present invention . the first tank was filled with blend c and the second tank was filled with blend d , both as reported below . each tank was preheated to 70 °- 80 ° c . and the contents were pumped therefrom in stoichiometric amounts into a mixing vessel surrounded by a hot water jacket wherein saponification occurs during agitation . ______________________________________blend cricinoleic acid 4 . 7coco fatty acid 6 . 3tallow fatty acid 11 . 0oleic acid 3 . 4stearic acid 17 . 5cdea 1 . 8dl - α - tocopherol 0 . 5total 45 . 2blend dtea 32 . 5naoh 50 % 8 . 2di - water 3 . 1glycerine 11 . 0total 54 . 8______________________________________ thereafter the final mixture is withdrawn from the mixing tank into appropriate molds which are chilled in accordance with example xii . transparent soap bars were prepared in accordance with the dual tank procedure of the present invention . the first tank was filled with blend e and the second tank was filled with blend f , both as reported below . each tank was preheated to 70 °- 80 ° c . and the contents were pumped therefrom in stoichiometric amounts into a mixing vessel surrounded by a hot water jacket wherein saponification occurs during agitation . ______________________________________blend ericinoleic acid 4 . 8coco fatty acid 6 . 3tallow fatty acid 11 . 0oleic acid 3 . 4stearic acid 17 . 5cdea 1 . 8glycerine 11 . 0dl - α - tocopherol 0 . 05total 55 . 9blend ftea 32 . 5naoh 50 % 8 . 2di - water 3 . 4total 44 . 1______________________________________ thereafter the final mixture is withdrawn from the mixing tank into appropriate molds which are chilled in accordance with example xii . transparent soap bars were prepared in accordance with the dual tank procedure of the present invention . the first tank was filled with blend g and the second tank was filled with blend h , both as reported below . each tank was preheated to 70 °- 80 ° c . and the contents were pumped therefrom in stoichiometric amounts into a mixing vessel surrounded by a hot water jacket wherein saponification occurs during agitation . ______________________________________blend gtriethanolamine ( tea ) 33 . 3 % ricinoleic acid 4 . 8coco fatty acid 6 . 3tallow fatty acid 11 . 0oleic acid 3 . 4stearic acid 17 . 5dl - α - tocopherol . 1di - water 3 . 4glycerine 12 . 0total 91 . 8blend hnaoh 50 % 8 . 2______________________________________ thereafter the final mixture is withdrawn from the mixing tank into appropriate molds which are chilled in accordance with example xii . transparent soap bars were prepared in accordance with the dual tank procedure of the present invention . the first tank was filled with blend i and the second tank was filled with blend j , both as reported below . each tank was preheated to 70 °- 80 ° c . and the contents were pumped therefrom in stoichiometric amounts into a mixing vessel surrounded by a hot water jacket wherein saponification occurs during agitation . ______________________________________blend itriethanolamine ( tea ) 32 . 5 % ricinoleic acid 4 . 8coco fatty acid 6 . 3tallow fatty acid 11 . 0oleic acid 3 . 4stearic acid 17 . 5lauric diethanolamide 1 . 0glycerine 11 . 8dl - α - tocopherol 0 . 1total 88 . 4blend jnaoh 50 % 8 . 2di - water 3 . 4total 11 . 6______________________________________ thereafter the final mixture is withdrawn from the mixing tank into appropriate molds which are chilled in accordance with example xii . transparent soap bars were prepared in accordance with the dual tank procedure of the present invention . the first tank was filled with blend k and the second tank was filled with blend l , both as reported below . each tank was preheated to 70 °- 80 ° c . and the contents were pumped therefrom in stoichiometric amounts into a mixing vessel surrounded by a hot water jacket wherein saponification occurs during agitation . ______________________________________blend ktriethanolamine ( tea ) 34 . 3 % ricinoleic acid 4 . 8coco fatty acid 6 . 3tallow fatty acid 11 . 0oleic acid 3 . 4stearic acid 17 . 5dl - α - tocopherol . 1total 77 . 4blend lnaoh 50 % 8 . 2di - water 3 . 4glycerine 11 . 0total 22 . 6______________________________________ thereafter the final mixture is withdrawn from the mixing tank into appropriate molds which are chilled in accordance with example xii . transparent soap bars were prepared in accordance with the dual tank procedure of the present invention . the first tank was filled with blend m and the second tank was filled with blend n , both as reported below . each tank was preheated to 70 °- 80 ° c . and the contents were pumped therefrom in stoichiometric amounts into a mixing vessel surrounded by a hot water jacket wherein saponification occurs during agitation . ______________________________________blend mricinoleic acid 4 . 8coco fatty acid 6 . 3tallow fatty acid 11 . 0oleic acid 3 . 4stearic acid 17 . 5cdea 3 . 6dl - α - tocopherol . 1total 46 . 7blend ntea 31 . 7naoh 50 % 8 . 2di - water 3 . 4glycerine 10 . 0total 53 . 3______________________________________ thereafter the final mixture is withdrawn from the mixing tank into appropriate molds which are chilled in accordance with example xii . transparent soap bars were prepared in accordance with the dual tank procedure of the present invention . the first tank was filled with blend o and the second tank was filled with blend p , both as reported below . each tank was preheated to 70 °- 80 ° c . and the contents were pumped therefrom in stoichiometric amounts into a mixing vessel surrounded by a hot water jacket wherein saponification occurs during agitation . ______________________________________blend otriethanolamine ( tea ) 4 . 1 % ricinoleic acid 4 . 8coco fatty acid 6 . 3tallow fatty acid 11 . 0oleic acid 3 . 4stearic acid 17 . 5cdea 1 . 8dl - α - tocopherol . 1total 49 . 0blend ptea 28 . 4 % naoh 50 % 8 . 2glycerine 11 . 0di - water 3 . 4total 51 . 0______________________________________ thereafter the final mixture is withdrawn from the mixing tank into appropriate molds which are chilled in accordance with example xii . transparent soap bars were prepared in accordance with the dual tank procedure of the present invention . the first tank was filled with blend q and the second tank was filled with blend r , both as reported below . each tank was preheated to 70 °- 80 ° c . and the contents were pumped therefrom in stoichiometric amounts into a mixing vessel surrounded by a hot water jacket wherein saponification occurs during agitation . ______________________________________blend qricinoleic acid 4 . 8coco fatty acid 6 . 3tallow fatty acid 11 . 0oleic acid 3 . 4stearic acid 17 . 5cdea 1 . 8glycerine 11 . 0dl - α - tocopherol . 1total 55 . 9blend rtea 32 . 5naoh 50 % 8 . 2di - water 3 . 4total 44 . 1______________________________________ thereafter the final mixture is withdrawn from the mixing tank into appropriate molds which are chilled in accordance with example xii . transparent soap bars were prepared in accordance with the dual tank procedure of the present invention . the first tank was filled with blend s and the second tank was filled with blend t , both as reported below . each tank was preheated to 70 °- 80 ° c . and the contents were pumped therefrom in stoichiometric amounts into a mixing vessel surrounded by a hot water jacket wherein saponification occurs during agitation . ______________________________________blend striethanolamine ( tea ) 30 . 2 % coco fatty acid 20 . 2stearic acid 20 . 2glycerine 12 . 1di - water 7 . 0citric acid 0 . 5gluconic acid 0 . 2sodium metabisulfite 0 . 5total 90 . 9blend tnaoh 50 % 9 . 1 % total 9 . 1______________________________________ thereafter the final mixture is withdrawn from the mixing tank into appropriate molds which are chilled in accordance with example xii . transparent soap bars were prepared in accordance with the dual tank procedure of the present invention . the first tank was filled with blend u and the second tank was filled with blend v , both as reported below . each tank was preheated to 70 °- 80 ° c . and the contents were pumped therefrom in stoichiometric amounts into a mixing vessel surrounded by a hot water jacket wherein saponification occurs during agitation . ______________________________________blend ucoco fatty acid 20 . 2 % stearic acid 20 . 2citric acid . 5gluconic acid . 2sodium metabisulfite . 5total 41 . 6blend vnaoh 50 % 9 . 1di - water 7 . 0 % glycerine 12 . 1triethanolamine ( tea ) 30 . 2total 58 . 4______________________________________ thereafter the final mixture is withdrawn from the mixing tank into appropriate molds which are chilled in accordance with example xii . one hundred grams of the hot soap mixture prepared according to the procedure described in example i , was poured at 85 ° c . into plastic soap molds and subjected to rapid cooling in a variety of controllable media . the internal temperature of the bars was monitored until it reached 25 ° c . at which time the bar was removed from the cooling medium and tested for color , clarity , stability and hardness . the results are shown in table a below . surprisingly , there was no adverse effect on any of the properties of the resultant bars with the exception of hardness at very low temperature & lt ;- 50 ° c . color , clarity , stability and chemical properties all compared favorably with the conventionally prepared transparent soap bars . table a______________________________________ hardnesscooling medium t ° c . ( min ) ( mm ) color clarity______________________________________dry ice / alcohol - 50 15 275 43 . 4 okfreezer - 20 27 194 42 . 2 okrefrigerator 5 35 149 41 . 6 okambient 25 120 132 40 . 4 ok______________________________________ color is recorded as the &# 34 ; l &# 34 ; lightness value , as measured by a macbeth colorimeter , model 1500 , macbeth , inc ., new york , ny . in further cooling experiments , a pvc soap mold ( 8 . 0 cm × 5 . 0 cm × 2 . 5 cm ) containing 100 g of molten soap ( 80 ° c .) from example i , was drawn through a cooling tunnel ( 8 . 5 ft in length and 5 . 5 inch diameter ) with an average temperature of 0 ° to 4 ° c . in these experiments , the molds were drawn through the cooling tunnel at various rates , and the physical properties determined as in example xii . table b______________________________________ initial final bar temp . hardness hardnesstime (° c .) ( mm ) ( mm ) ______________________________________ 5 min 53 . 3 -- 134 7 min 47 . 2 -- 154 9 min 42 . 6 -- 12211 min 39 . 2 -- 12613 min 36 . 1 820 13815 min 33 . 1 420 14217 min 30 . 4 338 13019 min 28 . 4 272 13212 hrs . 22 . 4 126 130 ( control ) ______________________________________time color clarity stability______________________________________ 5 min 44 . 2 ok ok 7 min 44 . 6 ok ok 9 min 44 . 5 ok ok11 min 44 . 7 ok ok13 min 43 . 9 ok ok15 min 44 . 2 ok ok17 min 44 . 2 ok ok19 min 44 . 1 ok ok12 hrs . 43 . 8 ok ok ( control ) ______________________________________ in this experiment , it was found that after 15 to 17 minutes of cooling , the resultant bar was sufficiently solidified to allow handling and initial hardness measurements . in addition , the hardness of these bars was again determined after 12 hours at room temperature ( final hardness ). no significant difference was found between the final hardness of the rapidly cooled bars , and that of the control bars which were cooled at room temperature in a metal frame for 12 hours ( 720 min ). no significant changes in color , clarity , stability , or texture were found in the rapidly cooled bars . in a further series of experiments , the basic formula shown in example i was made 3 times ( experiments 4 , 5 and 6 ) using the continuous process , and compared to 3 batches ( experiments 1 , 2 and 3 ) made using the same formula ( example i ) but prepared using a batch process . in the batch process , the triethanolamine ( 50 % of the total tea ), ricinoleic acid , coco fatty acid , and tallow fatty acids are mixed with the caustic soda and heated at 90 °- 96 ° c . for 30 minutes . after the 30 minute heating , additional triethanolamine is added and the batch cooled to 85 ° c ., followed by the addition of oleic acid , stearic acid , cocodiethanolamine ( cdea ) and glycerine . after the addition of these ingredients , other minor ingredients such as antioxidants , fragrances etc , are added . the soap is then poured into frames or molds and allowed to cool . the resultant soaps were compared for color , appearance , hardness , ph , foaming and stability . table c______________________________________experi - hard - ment process color ness ( mm ) ph foam stability______________________________________1 batch 35 . 97 138 9 . 0 295 ok2 batch 36 . 55 148 9 . 0 300 ok3 batch 35 . 90 124 8 . 9 295 ok4 continuous 43 . 10 130 8 . 9 300 ok5 continuous 42 . 70 138 9 . 0 295 ok6 continuous 43 . 30 120 8 . 9 300 ok______________________________________ foam test results are listed as ml of foam produced , by shaking 50 ml of a 1 . 0 % soap solution with 199 ml of tap water ( 120 ppm of hardness ) and 1 . 0 ml olive oil in a stoppered volumetric flask . the mixture is inverted 10 times in 25 seconds , and the foam height produced , is measured . the two - phase procedure of example i was repeated using the apparatus of fig1 and the blends reported in table b below . in every case , transparent soap bars having the improved characteristics of the present invention were produced . table b - 1______________________________________ingredients examples______________________________________phase i xv xvi xvii xviiitriethanolamine 33 . 5 33 . 8 27 38caustic soda 50 % 8 . 4 8 . 5 8 . 4 8 . 4water 4 . 1 4 . 1 4 . 1 4 . 1glycerine 10 . 2 10 . 4 17 5phase iiricinoleic acid 4 . 8 4 . 8 4 . 8 4 . 8coco fatty acid 5 . 9 6 5 . 9 5 . 9tallow fatty acid 11 . 2 11 . 3 11 11 . 2oleic acid 3 . 5 0 3 . 5 3 . 5stearic acid 17 . 9 18 . 1 17 . 1 17 . 9cdea 0 1 . 9 1 0 . 7antioxidant 0 . 5 0 . 5 0 . 2 0 . 5fragrance 0 . 6total 100 100 100 100phase i xix xx xxi xxiitriethanolamine 33 . 6 37 30 . 6 30caustic soda 50 % 8 . 2 9 . 4 7 . 4 8 . 2water 1 5 3 2glycerine 15 0 11 25phase iiricinoleic acid 3 . 5 6 6 4 . 4coco fatty acid 3 8 . 6 7 4 . 4tallow fatty acid 11 9 8 14oleic acid 3 . 4 5 6 4stearic acid 19 16 . 7 20 . 5 6cdea 1 . 8 1 . 8 0 2antioxidant 0 . 5 0 . 5 0 . 5 0fragrancetotal 100 100 100 100phase i xxiii xxiv xxv xxvitriethanolamine 32 . 5 30 . 2 30 . 2 30 . 5caustic soda 50 % 8 . 2 9 . 1 9 . 1 8 . 1water 2 6 . 8 7 3 . 5glycerine 11 12 . 1 12 . 1 9 . 4phase iiricinoleic acid 4 . 7 0 0 4 . 6coco fatty acid 6 . 3 20 . 2 20 . 2 5 . 6tallow fatty acid 11 -- -- 10 . 5oleic acid 3 -- -- 3 . 3stearic acid 16 . 8 18 . 9 18 . 9 16 . 5cdea 4 -- -- 1 . 5citric acid 1 1gluconic acid 0 . 2 1sodium metabisulfite 1 . 5 0 . 5laneth - 10 - acetate 4nonoxynol - 14 / peg - 4 - 2octanoateantioxidant 0 . 5 0 . 5fragrancetotal 100 100 100 100phase i xxvii xxviii xxixtriethanolamine 28 . 5 30 . 5 32caustic soda 50 % 7 . 7 8 . 1 8 . 2water 3 . 1 3 . 5 3glycerine 8 9 . 5 10phase iiricinoleic acid 4 . 4 4 . 6 4 . 6coco fatty acid 5 . 4 5 . 6 6 . 1tallow fatty acid 9 . 2 10 . 5 10 . 5oleic acid 3 3 . 3 3 . 3stearic acid 14 . 7 16 . 5 17 . 5cdea 1 . 5 1 . 5 1 . 5citric acidgluconic acidsodium metabisulfitelaneth - 10 - acetatenonoxynol - 14 / peg - 4 - octanoatetea - lauryl sulfate 10acetylated lanolin alcohol 4witch hazel 3lauroyl sarcosine 2 . 5antioxidant 0 . 5 0 . 5 0 . 3fragrance 0 . 4 3total 100 100 100______________________________________ from the foregoing , it is apparent that there are several important features associated with the practice of the present invention . thus a process is herein described and illustrated which obtains the production of transparent soap on a continuous basis which soap has improved color , improved fragrance , stability and more uniform quality than was heretofor obtainable by existing batch procedures . in addition to the foregoing , the process of the present invention provides significant economic advantages in reduced processing time and lower labor costs while the composition / process interaction enables rapid cooling from 80 ° c . to 30 ° c . without affecting the basic characteristics of such soap , namely , hardness , solubility , clarity and foaming . it is apparent that the compositions and processes herein described and illustrated fulfill all of the foregoing objectives in a remarkably unexpected fashion . it is of course understood that such modifications , alterations and adaptations , as may readily occur to the artisan skilled in the art to which this disclosure pertains as included within the spirit of this invention which is limited only by the scope of the claims appended hereto .
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in a concrete floor 1 , for example , on which a steel bar or the like is to be fixed in position , the first step is drilling an anchoring bar hole 2 which , in the working example of fig1 to be seen to be stretching in an upright direction from the lower face of the floor 1 thereinto . nextly , a side hole 3 is produced starting at a point some distance from the outer end of anchoring bar hole 2 and at an angle α thereto ( which will generally be less than 90 °) for cutting through anchoring bar hole 2 . to keep these holes true diamond tipped drill bits ( and not impact bits ) will be used . in the next stage of the process ( see fig1 c ) a sprag 4 or anchoring part is slipped into side hole 3 . sprag 4 will be seen somewhat more clearly in fig2 . the sprag 4 is in the present case a sleeve , more specially a cylindrical one , with an opening 6 running therethrough . however , for meeting special needs , the sprag may be made solid and not in the form of a hollow sleeve . using a keeper tool 7 , the sprag 4 or sleeve is pushed from the outside into and along the side hole till the opening 6 is trued up with the anchoring bar hole 2 . the sleeve 4 has a hole 9 with a female - thread in its one end 8 for taking up keeper tool 7 . the female screw - thread of sleeve 4 will have . in each case , a certain number of turns of thread , as for example 21 / 2 . furthermore , the start of the thread in hole 9 has a certain relation to the end ( nearer to the end 8 ) of the opening 6 through the sprag so that , when the tool 7 is screwed as far as it will go into the sprag , it will always have the same position or the same angle in relation to the threaded opening 6 . if , furthermore , as is the case in fig2 a stop plate 19 is fixed at a given distance from the end of tool 7 to the same at an angle the same as the angle between the side hole and the anchoring bar hole , it will be possible for the worker to be certain of getting the sleeve 4 to the right depth in the side hole 2 by using tool 7 , that is to say so that the opening 6 is trued up with the anchoring bar hole 2 and the anchoring bar 11 itself may be screwed home without any trouble at all . in place of this design , it will be possible , however , to have an allen - key or hex socket in the end 8 of sleeve 4 , or to have a hex nut thereon for use with a matching end piece of keeper tool 7 . instead of using regular hex sockets or hex nuts , one - sided sockets or nuts may be used such that the tool 7 may only be joined up with the sprag or sleeve 4 with a certain angle between the two so that , given the right design of the tool 7 , there will be no trouble at all in putting the sprag into the side hole at such an angle that the sideways opening 6 of sleeve 4 is lined up with the anchoring bar hole 2 . after pushing the sprag or sleeve 4 in through the side hole 3 till the threaded opening 6 therein is lined up with the anchoring bar hole 2 , the anchoring bar 11 itself is slipped in and screwed home in the sprag . to make it simpler for the threaded anchoring bar 11 to be lined up with and screwed into the threaded opening in sleeve 4 , threaded anchoring bar 11 is pointed at 12 at its head end and furthermore at least one end 13 of the opening through the sleeve - like sprag 4 is made wider so that if sprag 4 does not have its opening 6 completely lined up with anchoring bar hole 2 , on pushing in the threaded bar 11 , the sprag 4 and the threaded bar 11 will be moved into a position in relation to each other . the threaded bar 11 , which for example may be a screw with a screwhead 16 ( see fig4 ), will be screwed home till a part to be fixed by it ( for example a rail 17 in fig4 ) is positioned on the concrete floor 1 . then tool 7 is undone from sprag 4 , that is to say , in the working example of fig2 the tool 7 is turned so that its threaded end 10 is unscrewed from the threaded hole 9 . it is naturally possible for tool 7 to be undone and taken out without waiting for threaded bar 11 to be screwed fully into screw - threaded opening 6 , because even after the bar has been screwed in only a bit , sprag 4 is kept in position , there being no chance of it falling out . the anchoring system of the invention may be seen from this to be made up of two anchoring parts , that is to say on the one hand the screw - threaded anchoring bar 11 , on whose tail end , sticking out out of the hole 2 , the load is fixed , and the sprag 4 , which is locked in and by the side hole 3 and has the effect of locking or anchoring anchoring bar 11 in position . as has been noted , sprag 4 is kept in the right position with the help of tool 7 while the two anchoring parts are being joined together . after the screw - threaded anchoring bar 11 has been screwed into sprag or sleeve 4 , it may furthermore be locked in place , for example by forcing adhesive or sealant through side hole 3 , threaded hole 9 in the end 8 of sleeve 4 and into the inside of the sleeve so that the threaded bar 11 is then adhesively locked in the sprag 4 . it is furthermore possible for a center - punch - like tool to be slipped in through hole 9 till it is resting against the thread of threaded bar 11 and , using one or two hammer blows on the outwardly running end of the punch - like tool , the thread of anchoring bar 11 is then dented so that it may no longer be unscrewed from sprag 4 . the screw - threaded bar 11 may furthermore be locked in sprag 4 and stopped from being unscrewed therefrom by screwing a screw into threaded hole 9 till its head end comes up against the thread of anchoring bar 11 for fixing the threaded bar 11 in position . lastly , it is possible ( see fig1 f ) for the side hole 2 to be filled up again , for example with concrete . although the process of the invention may be used with good effect with a sprag in the form of a hollow sleeve 4 as the best form of anchoring stop , the sprag may furthermore be in the form of a masonry plug , through which the screw - threaded bar 11 is screwed , the plug being for example in the form of a toggle anchor or expansion anchor , more specially a metal expansion anchor . the working example of the invention to be seen in fig3 and 4 is in connection with fixing a rail , for example for supporting a crane or the like , to which end an anchoring bar hole 2 and then the side hole 3 are produced using for example a drill press having its base - plate fixed in position . after drilling the anchoring bar hole 2 , the drill supporting arm is changed in position or turned and then placed at an angle for drilling the sloping side hole , for producing , in this way , all the fixing or anchoring points to be seen in fig3 . a rail 17 is then fixed in position using screws run into the anchoring sprags or sleeves 4 ( see fig4 ). fig5 is a view of a preferred way of fixing a threaded bar 11 in the invention , for which purpose two side holes 3 and 3 &# 39 ; are produced cutting , at different points , the anchoring bar hole , so that separate anchoring sleeves 4 and 4 &# 39 ; may be slipped into the side holes for the screw - threaded bar 11 to be screwed therethrough keeping them in position , this being a further way of anchoring a threaded bar 11 in position . fig6 is a view of an anchoring system with a better way of guiding and positioning anchoring bar 11 . the step of positioning bar 11 is undertaken in connection with one of the steps 1d and 1e or thereafter . it may be necessary to have a certain amount of play between the anchoring bar 11 and the side of the anchoring hole 2 so that the anchoring bar 11 may be put in position . such play is , however , undesired when the anchoring bar is loaded , for example not axially but sideways with a shearing effect . for cutting down this undesired play it will be seen that in the working example of fig6 a metal sleeve 21 is slipped into the anchoring bar hole at least so far that the sleeve 21 is completely within the hole and no longer running out past the outer face of concrete 1 . the sleeve 21 is best put in position after slipping in the anchoring bar and before the first and second turns on the bar 11 on screwing it into the sprag 4 . because of the presence of metal spacer guide sleeve 21 , the play between the wall of the hole 2 and the outer face of anchoring bar 11 is greatly decreased . so far the figures have been limited for cases in which the anchoring bar 11 is screwed into the anchoring sleeve or sprag 4 . although this is in fact the more specially preferred form of the invention , it would , generally speaking , be possible to have different forms of connection between the anchoring sprag and the anchoring bar , as for example using a bayonet connection or by using hooks or bolts or like stops on the anchoring bar locking into the opening in the anchoring sprag or sleeve . in fig7 a the reader will see an anchoring bar 11 &# 39 ; having a hooked head 22 . the opening 23 in sprag 4 &# 39 ; is not round but is broader in a direction running across the sprag 4 &# 39 ; than it is in a direction measured along the length of sprag 4 &# 39 ;. for slipping in anchoring bar 11 &# 39 ;, the hooked head 22 is turned so as to be across the general direction of sprag 4 &# 39 ; so that it may be pushed through opening 23 and once it is completely through it , the anchoring bar 11 &# 39 ; is turned through 90 ° so that the hooked head 22 is hooked round the wall of opening 23 of sprag 4 &# 39 ; as will be seen in fig7 a . in place of this , the anchoring bar 11 &# 34 ; of fig8 a may have a hammer head , that is to say hooks 24 on its two sides . in this case the opening 25 in the anchoring sleeve or sprag 4 &# 34 ; is placed so as to be lined up parallel with the general direction of sprag 4 &# 39 ;. anchoring bar 11 &# 34 ; with its hooks 24 is then slipped in the way to be seen in fig8 b into and through sprag 4 &# 34 ; in its opening 25 and then , again , turned through 90 ° so that hooks 24 forming a bolt are normal to the general run or direction of opening 25 and sprag 4 &# 34 ; and will be rested against the wall of opening 25 . this makes it clear that there is a further way of producing a trouble - free anchoring connection of the anchoring bar , it being possible in the two designs , that is to say in fig7 a and 8a , to have lock nuts on the anchoring bar resting against the face of the concrete . on producing the anchoring bar hole 2 and the side hole 3 , it is important to see that the two holes are produced completely true with the axis 26 of the side hole as far as possible cutting axis 27 of the anchoring bar hole 2 and meeting it at a point . to make this readily possible without any trouble , the apparatus to be seen in fig9 and 10 may be used , the same forming part of the present invention . the most important part of the apparatus for producing holes in concrete is a plate 31 which , on the one hand may be put in position with a template function for producing the holes and , on the other hand , has an opening or hole 32 , used for guiding a drill bit 33 to make certain that the hole produced thereby will in fact be cut through anchoring bar hole with axis 27 . in fig9 a drill 34 with a drill bit 35 will be seen to be supported on plate 31 in such a way that drill bit 35 and , for this reason , the axis 27 of the anchoring bar hole to be produced , is normal to the working face 36 of plate 31 , that is to say the face placed against the face of the concrete . drill 34 is joined up with plate 31 by way of a drill press 37 which , like the drill 34 itself may , generally speaking , be of normal design and for example have a support rod as part of the press for supporting the drill . however , for stopping any sideways motion , drill press 37 to be seen in fig9 has two support rods 38 and 39 lined up with drill 35 so that they may take up drilling forces in the best possible way . the use of two support rods 38 and 39 in the drill press 37 for drill 34 gives a strong structure which is better than using a single support rod . a further drill bit 33 is used with a drill 40 which may be fixed in more or less the same way as drill 34 on support plate 31 so that no details are given in this respect to make fig9 and 10 clearer . plate 31 may be fixed to the concrete wall 1 by vacuum suckers , by wall anchors or may have parts locking in holes in the concrete . the template system for producing the holes , see fig9 makes certain that the anchoring bar hole and the side hole are produced truly with their axes 26 , 27 cutting and meeting at a single point so that a strong anchoring system may be produced . on using the apparatus of fig9 for producing holes , it may be that one hole or the other comes up against a reinforcement in the concrete . in order to better take into account such reinforcements while at the same time making quite certain that the anchoring hole and the side hole are truly lined up , the further working example of the invention of fig1 for producing holes 42 makes do with one drill 40 with a drill bit 33 , which , once again , is guided by a sleeve 32 through the plate . drill 40 may be fixed to plate 41 in the way to be seen in fig9 . in place of drill 34 the plate 41 only has one opening 42 which is normal to the working face 36 resting on the concrete 1 , of the plate . a screw 43 is slipped in through opening 42 and into an expansion anchor 44 , with which the plate 41 is fixed using a hole 2 in the concrete . for producing the holes , the first step is producing the anchoring hole 2 , which is normal to the face of the concrete wall 1 . then plate 41 is fixed in position using screws and the expansion sleeve on concrete wall 1 and after this , using drill 34 and drill bit 33 , the side hole is produced having an axis 26 , drilling bit 33 being guided through the opening 32 in plate 41 . on the drill bit running against reinforcements in the concrete , screw 43 may be undone somewhat and plate 41 turned round screw 43 , that is to say the axis 27 of the anchoring hole 2 so that the worker may have another go at producing the side hole using drill bit 33 so as to keep clear of reinforcements . this part of the invention is in fact a simple way of producing holes without damaging the reinforcements .
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fig1 illustrates a cross - sectional view of a tft anode / cold cathode field emission display ( fed ) element 100 in accordance with the principles of the present invention . in this exemplary embodiment , the display element 100 is composed of cathode 104 that acts as a low - voltage source of electrons , anode 106 that employs tft technology to control the attraction of electrons 140 to corresponding pixel elements on the surface 160 , and grid 150 between anode 106 and cathode 104 that serves to accelerate electrons to the anode 106 . cathode 104 is fabricated by progressively depositing onto substrate 110 , conventionally a glass , an insulating material 115 , a conductive material 117 , an emitter material 120 operable to emit electrons , a second insulating layer 125 , such as sio 2 , and a second conductive material 130 . emitter material 120 is selected from known materials that have a low work function for emitting electrons 140 . alpha - carbon is a well - known material for emitting electrons 140 . the conductive material 117 beneath the emitter material 120 serves to reduce the resistance of the emitting layer and thus bring the emitter voltage to the edge 135 of emitter material 120 . wells 136 are then etched through the deposited second conductive layer 130 , insulating layer 125 , emitter layer 120 , conductive layer 117 and insulating layer 115 using well - known photoetching methods . in this case , edges 135 of the emitter material 120 are exposed for the generation of electrons 140 . second conductive material 130 operates as a gate to draw electrons 140 from the edges 135 of emitter material 120 when a sufficient potential difference , i . e ., electron extraction voltage or threshold voltage , exists between conductive material 130 and conductive layer 117 . anode 106 is composed of a plurality of conductive pads 170 fabricated in a matrix of substantially parallel rows and columns on surface 160 using known fabrication methods . in this illustrated embodiment material 160 is a transparent material such as glass . conductive pads 170 are also composed of a transparent material , such as ito ( indium titanium oxide ). a matrix organization , as will be shown in fig2 , of conductive pads 170 and phosphor layers 175 allows for known x - y addressing of each of the conductive pads 170 . in this case , conductive pad 170 may be representative of individual pixel element in the display . deposited on each conductive pad 170 is phosphor layer 175 . phosphor layer 175 , in one aspect of the invention , may be selected from materials that emit photons 195 of a specific color for a monochrome display . in a conventional rgb display , phosphor layer 175 may be selected from materials that produce red light , green light or blue light 195 when struck by electrons 140 . as would be appreciated by those skilled in the art , the terms “ light ” and “ photon ” are synonymous and are used interchangeably herein . associated with each conductive pad 170 / phosphor layer 175 pixel element is a tft circuit 180 that is operable to apply a known voltage to an associated conductive pad 170 / phosphor layer 175 pixel element . tft circuit 180 operates to apply either a first voltage to bias an associated pixel element to maintain it in an “ off ” state or a second voltage to bias an associated pixel element to maintain it in an “ on ” state , i . e ., activate . in one embodiment , tft circuit 180 may apply a zero voltage , va = 0 , to bias conductive pad 170 into an “ off ” state , or apply a higher positive bias voltage , in the order of va = 25 - 30 volts , to bias conductive pad 170 into an “ on ” state . in this illustrated case , conductive pad 170 is inhibited from attracting electrons 140 emitted by cathode 104 when in an “ off ” state , and attracts electrons 140 when in an “ on ” state . the use of tft circuitry 180 for biasing conductive pad 170 provides for the dual function of addressing pixel elements and maintaining the pixel element in a condition to attract electrons for a desired time period , i . e . time - frame or sub - periods of time - frame , as will be explained more fully with regard to fig2 and 3 . in the embodiment shown in fig1 , grid 150 is interposed , relatively equidistant , between cathode 104 and anode 106 . grid 150 , having a plurality of grid holes 152 , smaller than the cathode - to - anode distance 190 , unifies the electron distribution in front of the anode plane . in one aspect , electrons 140 emitted by cathode 104 pass through grid 150 and impinge upon phosphor pad 175 when a corresponding conductive pad 170 is biased to an “ on ” state . similarly , electrons are not attracted to the conductive pad 170 when a corresponding conductive pad 170 is biased to an “ off ” state . it would be recognized by those skilled in the art that the role of a positively biased grid 150 is advantageous as it serves to unify the electron distribution in front of the phosphor pads . this operation is applicable when the electron energies are small and can be controlled by the potentials applied to the tft circuitry . for example , when gate voltage for extracting electrons is less than the tft control voltage , i . e ., anode voltage , grid 150 may not be necessary . however , in another aspect , when the gate voltage for electron extraction from emitter edge 135 is higher than voltage applied to the anode , i . e ., phosphor pads 170 , via the tft circuitry , the energies of electron 140 may be too high and not manageable by the relatively low tft voltages . in this case , grid 150 may be used to decelerate the electrons approaching the phosphor pads by lowering the voltage applied to grid 150 . although grid 150 is shown in this exemplary embodiment and has been discussed with regard to controlling emitted electrons , it would be recognized that the operation of display 100 is not dependent upon the presence of grid 150 and the embodiment shown in fig1 represents an exemplary embodiment of the invention . the tft fed 100 shown allows for a low voltage addressing on the anode and the use of inexpensive lcd drivers . furthermore , the addressing circuit ( not shown ) on anode 106 eliminates the need for electron beam focusing methods necessary in conventional fed structures . the use of low voltage further eliminates problems of gas ionization and chamber breakdown characteristically associated with the use of high voltage feds . furthermore , cathode 104 serves as a uniform electron source and provides for high screen brightness and uniformity . the separation of pixel control circuitry from cathode 104 is further advantageous as it makes the fabrication of the device simpler and increases the fabrication yield . fig2 illustrates a top view of an exemplary tft - based anode . in this illustrated example , anode 200 is organized in a matrix of electrically conductive rows , referred to as 210 , and electrically conductive columns , referred to as 220 , electrically insulated from each other . associated with each row / column is an electrically conductive pad or area 170 and phosphor pad 175 that defines a pixel element . as would be appreciated , phosphor pad 175 predominately covers the conductive area 170 and tft 180 is thus shown using dashed lines to indicate that it is located beneath phosphor pad 175 . associated with each conductive pad 170 / phosphor pad 175 and accessed by a row / column designation is tft circuit 180 . tft circuit 180 operates to electrically disconnect an associated conductive pad 170 / phosphor pad 175 when the associated pixel is intended to be in an “ off ” state and connect an associated conductive pad 170 / phosphor pad 175 when it is intended to be in an “ on ” state . a known voltage , referred to as v dd , is applied to each tft circuit 180 . fig3 illustrates a circuit diagram of 1 tft circuit 180 associated with a single element in the matrix shown in fig2 . in this illustrated embodiment , phosphor pad 1754 is shown cut - away to reveal the details of tft circuit 180 . tft circuit 180 is composed of two transistor devices 182 , 186 , electrically cascaded , and capacitor 190 connected between the output of first device 182 and the output of second device 186 . in the illustrated embodiment , devices 182 , 186 are fets ( field effect transistors ). fets are known in the art to possess a high input impendence . in the illustrated embodiment , gate node 183 of fet 182 is electrically connected to and associated with row line 210 , and node 184 of fet 182 is associated with column line 220 . the output node 185 of fet 182 is electrically cascaded to gate electrode 187 of fet 186 , and to capacitor 190 . electrode 188 of fet 186 is electrically connected to constant voltage source , typically v dd , and output electrode 189 is electrically connected to electrically conductive pad 170 . capacitor 190 is also further connected between the gate and the source node of fet 186 . in operation , when fet 182 is in an “ on ” state , by the application of a voltage on row line 210 , a voltage applied to column line 220 is passed through fet 182 and concurrently present at , or applied to , gate node 187 of fet 186 and capacitor 190 . capacitor 190 is charged to substantially the same voltage value as applied to column 220 . when voltage on row line 210 is removed , capacitor 190 operates to substantially maintain the same potential as is on column line 220 to gate electrode 187 . this voltage is maintained for a known period of time , which is based on the value of capacitor 190 and an impedance of fet 182 . capacitor 190 thus operates to substantially “ hold ” the voltage even after the voltage or potential to selected row 210 is removed . as voltage or potential is applied to gate terminal 187 of fet 186 , fet 186 is in an “ on ” state and the constant , fixed voltage or potential , v dd , applied to node 188 , which is also referred to as an anode voltage ( v a ), is passed through fet 186 to node 189 and associated pad 170 . pad 170 then is operable to attract electrons 140 ( not shown ) drawn from cathode 104 . when the gate electrode 187 voltage is removed , the corresponding pixel is switched to an “ off ” state as the potential at electrode 189 is relatively low , i . e ., near zero volts . in one aspect of the invention , the anode voltage may be in the range of about 20 - 30 volts . thus , tft circuit 180 provides for both “ pixel selection ” and “ pixel hold ” functions . accordingly , electrons 140 may continue to be attracted to the corresponding phosphor layer 175 for a desired time frame without the concurrent application of a voltage on a corresponding row line . capacitor 190 is sized to be commensurate with the desired frame time and the input impedance of the second active device 186 . the value of capacitor 190 may be selected such that the decay of the stored charge through the impedance of first device 182 is in the order of or larger than the desired frame time . returning to fig2 , although the exemplary display matrix has been described as a monochromatic display having six pixel elements , those skilled in the art should readily recognize that fig2 may also represent a color display having three color pixels with each color pixel having associated red , green and blue phosphor layers . while the present color display is described with the use of conventional rgb ( red , green , blue ) technology , the use of phosphor layers that emit light of alternate colors , visible and non - visible , is considered within the scope of the inventions fig4 illustrates a second embodiment of the display . in this embodiment , the tft anode structure shown in fig2 is deposited on substrate 110 . in this case , a material such as poly - silicon or amorphone silicon , may be deposited on substrate 110 , that allows for the fabrication of row lines 210 ( not shown ), column lines 220 ( not shown ), conductive pad 170 and tft circuit 180 onto substrate 110 in row / column matrix as shown in fig2 . phosphor layer 175 may then be deposited on corresponding conductive pads 170 . in one aspect a silicon ( si ) single crystal wafer may be used for the active matrix circuitry , wherein the si wafer is attached to a glass substrate . in this case , the phosphor pads are also made on the si wafer . cathode 104 is fabricated on viewing surface 160 and emitter layer 120 and conductive layer 130 operate to draw electrons from edges 135 of emitter layer 120 . emitter layer 120 and conductive layer 130 occupy a significantly small portion of the viewing glass area to allow for photons to be viewed through cathode 104 and transparent viewing glass 160 . as would be appreciated , elements of cathode 104 may be composed of optically transparent materials . as in the embodiment shown in fig1 , grid 150 may have a dual function in both unifying the electron distribution approaching the phosphor pads and decelerating the electron . this latter function may be needed when the threshold voltage for electron extraction from the emitter edge is too high to be controlled by the voltages on the tft circuit . fig5 illustrates a top view of an exemplary cathode 104 in accordance with the principles of the invention . it is desired that cathode 104 serves as a uniform electron source when the voltage applied to conductive layer 130 is sufficiently positive relative to emitter layer 120 . in this exemplary embodiment , wells 136 are formed within the conductive layer 130 as elongated slots 510 , which increase the length of emitter edges 135 ( not shown ). increased emitter edge 135 length provides for an increased edge area for the emission of electrons 140 . in this exemplary view , wells 136 are etched through conductive layer 130 to expose the emitter layer edges . edges 135 ( not shown ) of emitter layer 120 are formed beneath edges 137 of conductive layer 130 . fig6 illustrates another exemplary embodiment of a tft based display 600 wherein cathode 104 a is composed of a plurality of carbon nanotubes 610 placed on conductive material 615 located within well 136 . in this case , conductive layer 130 , electrically isolated from material 615 , operates as a gate that may be used to draw electrons 140 from nanotubes 610 , when the potential difference between gate 130 and nanotube 610 exceeds a threshold for electron extraction . nanotubes 610 are known to possess extremely low threshold voltages in the order of 1 - 3 v / micron for electron emission . cataphoretic deposition or printing of nanotubes 610 , as well as nanotube growth on a metal surface are known in the art . similar to the design shown in fig1 , grid 150 is also shown in this exemplary embodiment to control and decelerate , if necessary , the flow of electrons 140 directed toward phosphor layer 175 . anode 106 is similar to that described with regard to fig1 and its description need not be repeated . fig7 illustrates another exemplary embodiment of a tft - cold cathode based display 700 , wherein cathode 104 c is composed of a plurality of carbon nanotubes 610 that are uniformly distributed on a conductive layer 710 on substrate 110 . grid 150 is also shown in this embodiment and is used for extracting electrons 140 emitted by nanotubes 610 and directed toward phosphor layer 175 . in this embodiment , second grid 155 is included to decelerate electrons so that they are controllable by the tft circuitry . anode 106 is similar to that described with regard to fig1 and its description need not be repeated . fig8 illustrates an embodiment of a tft - cold cathode based display 800 constructed similar to the display shown in fig1 , i . e ., anode on viewing surface . in this embodiment , cathode 104 d is composed of nanotubes 610 deposited on cathode filament 805 . in this case , electrons 140 are emitted from nanotubes 610 when a voltage difference between grid 150 and cathode filament 805 is sufficient to extract electrons 140 . grid 150 is located in the range of 100 - 200 microns above substrate 110 . second grid 810 , which is used to decelerate electrons 140 , is located between grid 150 and anode 106 . anode 106 is similar to that described with regard to fig1 and its description need not be repeated . fig9 illustrates another exemplary embodiment of a tft - cold cathode based display 900 constructed similar to the display shown in fig4 , i . e ., anode on back surface . in this embodiment , cathode 104 is composed of nanotubes 610 on cathode filament 805 as previously described , and grids 150 and 810 are installed between nanotubes 610 and anode 106 , to control and decelerate the flow of electrons to anode 106 . anode 106 is similar to that described with regard to fig4 and its description need not be repeated . fig1 illustrates an embodiment of a tft - cold cathode based display 1000 constructed similar to the display shown in fig4 , i . e ., anode on back surface . in this case , cathode 104 f is composed of nanotubes 610 on narrow stripes of conductive layer 1010 . the area occupied by these stripes is small and does not affect the image quality . grids 150 and 810 are installed between cathode 104 f and anode 106 to extract and control the flow of electrons 140 to anode 106 . grid 810 is used to decelerate the flow of electrons when the electron energies are too high to be controlled by the low anode voltage of the tft circuit 180 . anode 106 is similar to that described with regard to fig4 and its description need not be repeated . although not shown or discussed in detail , it would be understood by those skilled in the art that insulating spacers may be distributed throughout the display to electrically isolate the electrical potential applied to the elements disclosed , to separate two plates from each other and to sustain the evacuated pressure . it should be further understood that the spacers may be used to reduce glass plate thickness and thus decrease both weight and thickness of the display . it should also be understood that the edges of the overall display may be sealed and that the space between the cathode and the anode may be evacuated to a level of at least 10 − 5 tor . while there has been shown , described , and pointed out fundamental novel features of the present invention as applied to preferred embodiments thereof , it will be understood that various omissions and substitutions and changes in the apparatus described , in the form and details of the devices disclosed , and in their operation , may be made by those skilled in the art without departing from the spirit of the present invention . it is expressly intended that all combinations of those elements that perform substantially the same function in substantially the same way to achieve the same results are within the scope of the invention . substitutions of elements from one described embodiment to another are also fully intended and contemplated .
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the structural features of a capacitor of this invention are shown in cross section in fig1 . a rectangular porous tantalum body 10 has a tantalum riser wire 11 partially embedded therein . the tantalum body 10 serves as the anode of the capacitor . more generally , the capacitors of this invention employ porous valve - metal bodies , which valve - metals include tantalum , aluminum , titanium and niobium . a tantalum oxide dielectric film 12 is grown over the surfaces of the body including surfaces within the pores . the oxide 12 is simple represented in fig1 as lying over the outer surface portions of the body 10 . a coating 13 of manganese dioxide lies over and adjacent to the oxide film 12 . this coating is formed by first applying a dilute solution of manganous nitrate in the pores and over the oxide film that conforms to all body surfaces . by subjecting the body to about 300 ° in steam , the manganous salt is pyrolytically converted to a solid semiconducting manganese dioxide ( mno 2 ). pyrolysis may also be accomplished by heating in a dry atmosphere at about 400 ° c . a second application of the manganous salt is again pyrolyzed as before , and yet a third and so on until a sufficiently thick coating 13 of manganese dioxide is formed over the body . up to this point the manufacturing steps are all conventional . a layer of graphite 14 is then applied over the mno 2 coating 13 . another coating of mno 2 15 is then applied over the graphite layer 14 and yet another layer of graphite 16 is formed over the outer mno 2 coating 15 . thus the outer coating 15 of mno 2 is seen as being sandwiched between the two graphite layers 14 and 16 ; however , these two graphite layers are not entirely separate as is shown in the detail of fig2 and as will be explained . over the outer layer 16 of graphite there is a relatively heavy coat 19 of a metal bearing material that serves as the counterelectrode of the capacitor . a metal cathode lead 23 is electrically and physically attached to the counterelectrode 19 by means of a conductive material 22 being bonded therebetween . the anode riser wire 11 is welded or otherwise attached to a metal anode lead 24 . a silicone resin or other suitable organic material serves as the housing encapsulant 20 encompassing the body and a portion of the leads 23 and 24 . thus a basic capacitor section of this invention consists of elements designated 10 through 19 . the section is shown in fig1 encapsulated in housing 20 and having package leads 23 and 24 . the preferred steps for making the capacitor of this invention are as follows : a porous tantalum body is anodized in a conventional manner to form the oxide . this is then coated with mno 2 by pyrolytic decomposition of manganous nitrate using the conventional technique of first applying dilute solutions to penetrate and coat the whole surface of the body followed by more concentrated solutions to achieve the required build up of mno 2 on the outside of the body . in a conventional construction , from 5 to 10 dips in a concentrated solution such as 1 . 78 specific gravity manganous nitrate is typically required to achieve the required build up . in the construction of this invention , a similar , or greater number of top coats is employed . starting with about the fourth or fifth top coat , however , the capacitor of this embodiment is coated with aquadag which is a colloidal graphite suspension . the aquadag is then dried at any suitable temperature , such as 150 ° c for ten minutes . the aquadag is applied an an aqueous solution of about 2 to 4 % solids concentration . after forming this first graphite layer , one or more further coats of mno 2 are pyrolytically deposited . next , another layer of graphite is formed . at this point the capacitor section may be completed by applying a metallic coating to form the counter - electrode and cathode connection . such a unit in the near presence of organic material will show greater impedance stability during 360 ° c exposure than will a prior art unit in which graphite is applied only after completion of pyrolysis . moreover , even greater stability can be achieved by applying further alternating coats of mno 2 and graphite . the number of such coats which may be applied is limited only by the dimension to which the final capacitor has to conform . thus , a to be buried graphite layer is formed , such as layer 14 shown in fig1 . from one to four applications of aquadag are preferably employed to form each such buried layer . it has been observed that the last of a series of pyrolyzed mno 2 layers is porous and friable compared to the relatively dense and nonporous underlying layers of mno 2 . it is postulated that such a porous layer is permeated by a subsequently applied manganous nitrate solution as well as covered by a layer of this solution , such that upon a subsequent pyrolysis step a new porous mno 2 layer is formed over said last layer and said last layer is filled and no longer porous . microscopic views of cross sections of typical mno 2 layers of partially completed capacitors support this hypothesis . in a capacitor of this invention including a layer of mno 2 being sandwiched between two graphite layers , the intervening or sandwiched layer of mno 2 contains enough graphite particles to effectively short circuit this sandwiched mno 2 layer . thus the metal counterelectrode that overlies and electrically contacts the outer graphite layer is always in direct electrical contact with the buried graphite layer without depending upon the intervening mno 2 for this purpose . therefore , when or if the intervening mno 2 is reduced and made highly resistive as by hot organic vapors , the electrical connection , existing between the metal bearing counter - electrode and the dense mno 2 coating that underlies the buried graphite layer , is not lost or substantially degraded . the exact processing point at which the first coat of graphite may be applied is determined by the desirability of keeping the highly conductive carbon from contacting the tantalum oxide surface or from penetrating the mno 2 structure to any point at which it might cause an increase in leakage current . the graphite may be deposited following the first top coat of mno 2 and following each subsequent top coat . however , unless this coat is adequately thick , such a procedure leads to loss of many units due to excessive leakage current . it is therefore desirable that sufficient mno 2 be applied before depositing the graphite to prevent losses due to high leakage current . the number of mno 2 layers required prior to the application of the first graphite layer will depend on the method used to deposit them . thus , in the method described by fournier et al in u . s . pat . no . 3 , 950 , 842 issued apr . 20 , 1976 which deposits heavy layers of mno 2 particles and manganous nitrate , only one such layer might be required . other methods of forming a thick layer of mno 2 are described in u . s . pat . nos . 3 , 481 , 029 , issued dec . 2 , 1969 , and 3 , 241 , 008 , issued mar . 15 , 1966 . using a method in which mno 2 is built up by dipping in a concentrated manganous nitrate solution having a specific gravity of about 1 . 78 g / cc . three to five layers would give a suitable build up before the introduction of the first layer of graphite . this foundation layer of mno 2 is thus preferably thicker than about 0 . 002 inch regardless of how obtained . following pyrolysis of the last mno 2 coat , a final outer layer of graphite is applied which may be formed by applying one or more coats of the graphite suspension . typically the oxide film is reformed after pyrolysis , and good results have been obtained by depositing the graphite either immediately prior to and immediately after this reformation . alternately , only one coat need be applied which may be done either before or after reformation . the capacitor is coated with a conducting layer such as a silver paint or a sprayed metal . it may then be attached by a conducting medium to a solderable metal lead . many such methods of terminating may be used provided they will withstand exposure to 360 ° c . in a preferred embodiment of this invention , the unit is coated with a conducting paint such as eccobond 59c , made by emerson and cumming inc ., canton , mass ., which is a silicone resin containing silver particles that is cured for 30 minutes at 200 ° c . another coat of the 59c is then applied to an area of the capacitor section and is used to cement a suitable termination in place . such termination may typically be a metal can in which the capacitor is contained or a metal lead frame strip or a wire . after thoroughly baking at about 250 ° c to cure and to remove the most volatile organic vapors from the conducting compounds , the capacitor may be hermetically sealed in a metal can , or may be encapsulated in a resin . to illustrate the beneficial effects which may be obtained from the practice of the invention , table i presents impedance values of experimental solid electrolyte tantalum capacitors having various numbers of buried graphite layers . the impedance of each is given for before and after heating at 360 ° c for 3 minutes and again after 6 minutes . the capacitors are 22μf , 10v tantalum capacitors having a counterelectrode of eccobond 59c silver paint and being molded in a silicone resin , namely resin part number 306 made by dow corning corp ., midland , mi . table i______________________________________ impedance ( ohms ) no . of mno . sub . 2 totallayers prior no . of after afterto first graphite 360 ° c / 360 ° c / graphite layers initial 3 min . 6 min . ______________________________________1 . 5 3 0 . 14 0 . 24 0 . 442 . 5 4 0 . 14 0 . 22 0 . 343 . 5 5 0 . 14 0 . 23 0 . 324 . 6 2 0 . 14 0 . 28 0 . 605 . 6 3 0 . 15 0 . 23 0 . 356 . 6 4 0 . 15 0 . 23 0 . 327 . 6 1 0 . 15 4 . 2 -- 8 . 6 1 0 . 15 20 . 4 -- ______________________________________ the experimental capacitors of examples 1 through 6 fall within the scope of this invention . by contrast , data from a capacitor which was constructed in exactly the same manner except that only one layer of graphite was applied , namely after completion of pyrolysis , is exhibited as example 7 . by further way of contrast , data from an experimental capacitor , example 8 , constructed with only a single conventional layer of graphite after completion of pyrolysis and with an epoxy case , gave the results shown . it is concluded that a silicone resin encapsulation is preferred over an epoxy material and that generally only one buried graphite layer is required for a silicone resin encapsulated capacitor . although in making the preferred embodiment of this invention as described , graphite particles are introduced into the sandwiched mno 2 coating by applying aquadag over the porous mno 2 that overlies a buried graphite layer , a variety of other methods may be used to accomplish the same purpose , and are understood to fall within the scope of this invention . for example , the manganous nitrate , that is applied over a to be buried graphite layer , may itself contain graphite particles . as a further example , instead of introducing the graphite by means of a suspension as has previously been described it may be introduced as a dry powder . the units may be coated with a liquid to which the graphite will adhere when it is either sprayed at the units or they are immersed in the powder as for example in a fluidized bed .
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referring now to fig1 , the mixing syringe is a regular syringe with the addition of a mixing disc . a syringe 1 includes a plunger 2 and a seal 3 in order to eject the liquid 6 via tube 4 . a piston - like mixing disc 5 a is added into the syringe . the initial position of disc 5 a is shown as 5 a ′, with plunger seal 3 touching disc 5 a . as liquid and particles are sucked into syringe 1 , seal 3 moves farther from disc 5 a to create a vacuum . disc 5 a moves as well , until stopped by slight ridge 8 . the size of the ridge is exaggerated in fig1 for clarity . it only needs to reduce the inside diameter by about 0 . 2 - 0 . 3 mm . flexible seal 3 easily passes over such a ridge . the particles 7 are sucked into the syringe via tube 4 and quickly settle as shown in fig1 . the particles do not accumulate in the section between plunger seal 3 and disc 5 a as disc 5 a includes a filter with pore sizes smaller than the particles . this is shown in fig2 a and 2b . disc 5 a has one or more holes 9 covered by filter mesh 10 . it is desired to chamfer hole 9 under screen 10 to increase the effective area of the screen . the screen can also be mounted as a flexible flap , being pushed out of the way during ejection of the fluid . the conical shape of disc 5 a is matched to the shape of the conical seal 3 and the conical tip of the syringe . this eliminates trapped fluid between the seal 3 and the syringe outlet at the end of the stroke . the conical shape of disc 5 a also aids the removal of any trapped air bubbles , as they float to the top of disc 5 a and escape when syringe is held vertically . as plunger 3 is moved towards disc 5 a the liquid 6 is ejected via hole 9 at a high velocity , mixing up particles 7 and liquid 6 . this is shown in fig3 . from the moment seal 3 touches disc 8 the disc is pushed forward towards the tube 4 until the syringe is empty and disc 5 a is in position 5 a ′. the operation can now be repeated , if desired . it is desirable to make hole 9 at an angle to the axis of the syringe in order to create a vortex 111 . an even more effective vortex 111 can be created if hole 9 is molded as a curved arc , both in the plane of the drawing and also in the plane perpendicular to the drawing . disc 5 a can be molded in one piece , including screen 10 . alternatively , screen 10 can be bonded to molded disc 5 a . the fit between disc 5 a and bore of syringe 1 is not critical as the particles are relatively large . it was found out that for best results the diameter of disc 5 a should be 0 . 1 - 0 . 2 mm smaller than the inside diameter of syringe 1 . while the example given is for embolization , the invention can be used to mix and two components , including two liquids . the disc 5 can also be made out of pressed sheet metal 11 . this is shown as disc 5 b in fig4 a and 4b . in this case hole 9 and screen 10 are replaced by miniature stamped louvers 12 ( similar to a miniature venetian blind ) acting both as a screen and as a flow director . recommended material is type 316l stainless steel or aluminum , with thickness between 0 . 1 to 0 . 3 mm . the thin wall allows seal 3 to enter into the hollow disc and squeeze out all the liquid . in order to eliminate the need of molding custom syringes it was found out that the slight ridge 8 can be formed in existing syringes by briefly heating up the area of ridge 8 and pressing the walls in slightly , using a split ring slightly smaller than the outside diameter of the syringe . other ways of creating a ridge without molding is pressing into the syringe a thin walled ring , held by friction . if desired the invention can be manufactured out of a standard disposable syringe , without any modifications . the movable disc 5 a is attached to the outlet side of the syringe with a short string that only allows it to move a limited distance . the string 13 is bonded by heat to the syringe or uses an anchor 14 . this is shown in fig5 . in operation tube 4 is first inserted into a mixing bowl where the ingredients are mixed together . the mixture is sucked into the syringe . after filling the syringe is held vertically to help trapped air escape and plunger moved to expel all air . afterwards tube 4 is moved to the catheter or needle used for the procedure and mixture is injected . an additional improvement in mixing is to adjust the density of particles 7 to match the density of liquid 6 , typically a saline solution with a density around 1 . since the materials used to make particles 7 ( plastic , glass or ceramic ) have a density greater than 1 , they have to be made hollow . the technology of manufacturing small hollow spheres , known as micro - balloons , is well known and many polymers as well as glasses are commercially available in micro - balloon form . one supplier is henkel ( http :// www . henkelna . com / cps / rde / xchg / henkel_us / hs . xsl / brands - 1556 . htm ? iname = dualite % 25c2 % 25ae & amp ; countrycode = us & amp ; bu = industrial & amp ; parentreddotuid = 0000000gfr & amp ; reddotuid = 0000000gfr & amp ; brand = 000000qtqe both ideas can be combined : micro - balloon shaped polymer or glass spheres with a density around 1 can be dispensed from a syringe with a mixing disc .
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with initial reference to fig1 - 3 , a dishwasher constructed in accordance with the present invention is generally indicated at 2 . as shown , dishwasher 2 is arranged below a kitchen countertop 6 . also below kitchen countertop 6 is shown cabinetry 8 including a plurality of drawers 9 - 12 , as well as a cabinet door 13 . although the actual dishwasher into which the present invention may be incorporated can vary , the invention is shown in connection with dishwasher 2 depicted as a dual cavity dishwasher 2 having an upper basin or drawer 16 and a lower basin or drawer 18 . in accordance with the embodiment shown , upper drawer 16 includes a front wall 20 , a rear wall 21 , a bottom wall 22 and opposing side walls 23 and 24 that collectively define an upper wash chamber or tub 28 . in a manner known in the art , upper drawer 16 is provided with a handle 29 for accessing an interior of tub 28 . in a manner also known in the art , tub 28 includes a dish rack 30 for supporting various objects , such as glassware , utensils and the like , to be exposed to a washing operation . upper drawer 16 is slidably mounted within a frame 40 through a pair of extendible drawer support glides or rails , one of which is indicated at 41 . the details of frame 40 do not constitute part of the present invention and therefore will not be discussed further here other than to note that frame 40 preferably constitutes an open latticework . in addition , upper drawer 16 is provided with a vertically shiftable lid member 44 that is adapted to selectively seal against an upper portion ( not separately labeled ) of tub 28 . that is , when upper drawer 16 is inserted into frame 40 , lid member 44 is lowered to seal about tub 28 and , when drawer 16 is withdrawn from frame 40 , lid member 44 is caused to be raised so as to enable drawer 16 to be withdrawn from frame 40 and provide access to tub 28 . as the particular manner in which lid member 44 is raised or lowered is not part of the present invention , this aspect of dishwasher 2 will not be detailed further here . in a similar manner , lower drawer 18 includes a front wall 50 , a rear wall ( not shown ), a bottom wall 52 and opposing side walls 53 and 54 that collectively define a lower wash chamber or tub 58 . lower drawer 18 is provided with a handle 59 that enables a consumer to readily access tub 58 , with lower drawer 18 being slidably mounted within frame 40 through a pair of extensible drawer glides or rails ( not shown ). in addition , lower drawer 18 is provided with a shiftable lid member 64 which lowers to selectively seal lower drawer 18 when lower drawer 18 is inserted into frame 40 , and is raised when lower drawer 18 is to be withdrawn from frame 40 . each drawer 16 and 18 includes an associated pump system ( not shown ) that delivers washing fluid to wash arms supported in wash chambers 28 and 58 . actually , the pump systems create a recirculating flow of washing fluid that is directed upon dishware and the like arranged in tub 28 and / or 58 during a washing operation . the entire pump and filtration system is not part of the present invention and therefore will not be discussed further . however , additional details of the pump and filtration system can be found in commonly assigned u . s . patent application ser . no . 10 / 785 , 027 , entitled “ dishwasher pump and filtration system ” filed on feb . 25 , 2004 which is incorporated herein by reference . in general , the above description is provided for the sake of completeness as the present invention is particularly directed to a utility link 70 that connects , for example , wash chamber or tub 28 with a household drain line and / or electrical mains . in accordance with one aspect of the present invention illustrated in fig4 , utility link 70 is constituted by an electrical cable 74 having a first end 80 that extends to a second end 82 through an intermediate portion 84 . in accordance with a preferred form of the invention , intermediate portion 84 includes a first flexible loop section 88 and a second flexible loop section 90 that are joined through a trough section 92 . first and second flexible loop sections 88 and 90 enable , for example , drawer 16 to be fully withdrawn from frame 40 . that is , as drawer 16 is withdrawn from frame 40 , first and second flexible loop portions 88 and 90 begin to straighten . as flexible loop portions 88 and 90 straighten , utility link 70 allows drawer 16 to extend from frame 40 to facilitate loading and unloading of dishware while , at the same time , maintaining a viable utility connection . electrical cable 74 is also shown to include a connector member 94 provided at second end 82 . as will also be discussed more fully below , connector 94 is adapted to interconnect with and provide electrical power to the pump system ( not shown ) for a respective tub 28 , 58 . in accordance with another embodiment of the present invention as shown in fig5 , a utility link 70 ′ is constituted by a drain hose 104 . drain hose 104 includes a first end 110 adapted to extend through frame 40 and connect to a household drain . first end 110 leads to a second end 112 through an intermediate portion 114 . in further accordance with the invention , intermediate portion 114 includes a first section 117 which leads to a first curved portion 119 . leading from first curved portion 119 is a second substantially straight section 121 which terminates in a second curved portion 122 . at this point , second curved portion 122 leads to a third , substantially straight section 123 which terminates at a first flexible loop section 130 . drain hose 104 is also provided with a second flexible loop section 134 which is joined to first flexible loop section 130 through a trough section 136 . in a manner similar to that described above with respect to utility link 70 , first and second flexible loop sections 130 and 134 , as well as trough section 136 , enable drawer 16 to be fully withdrawn from outer housing 70 . as best shown in fig6 , utility link 70 and / or 70 ′ is supported by a utility link carrier 144 . utility link carrier 144 provides support for first and second flexible loops 88 and 90 of cable 74 and / or first and second flexible loops 130 and 134 of drain hose 104 . that is , utility link carrier 144 is designed to support electrical cable 74 or drain hose 104 individually , or both electrical cable 74 and drain hose 104 together . in the embodiment shown in fig6 , utility link carrier 144 includes a first , substantially rigid portion 146 which is mounted to or supported by frame 40 . as shown , first portion 146 includes a first end 147 that leads to a second end 148 through an intermediate portion 149 which , in the embodiment shown , is curvilinear in shape . provided at second end 148 is a flexible joint 154 , formed from plastic spring steel or the like , which serves to interconnect first portion 146 with a semi - rigid support 161 . semi - rigid support 161 is formed from a resilient or elastomeric material that allows utility link carrier 144 to move with utility link 70 and / or 70 ′ yet return to a bowed or curvilinear shape to provide support for flexible loop section 90 and / or 134 . in accordance with the invention , semi - rigid support 161 includes a first end 163 fixedly secured to flexible joint 154 and extending to a second end 164 through an intermediate or support section 166 . intermediate or support section 166 is secured to second loop section 90 and / or 134 of electrical cable 74 and drain hose 104 through the use of , for example , cable ties , clamps or the like . in this manner , when drawer 16 is in a retracted position as shown in fig2 , utility link 70 , 70 ′ is not caused to sag or fall into other portions of dishwasher 2 creating a snag hazard . when drawer 16 is withdrawn from frame 40 , utility link carrier 144 fully supports utility link 70 , 70 ′ while allowing loops 90 and / or 134 to extend . as described above , utility link carrier 144 is formed from resilient or elastomeric material so that , when drawer 16 is shifted between open and closed positions , utility link carrier 144 moves with drawer 16 and , most importantly , returns to an original , at rest state . more specifically , as drawer 16 shifts out from frame 40 , semi - rigid support 161 shifts with drawer 16 . once drawer 16 nears a fully open position , flexible joint 154 stretches as a strain relief , while rigid portion 146 remains fixed relative to frame 40 . also shown in fig6 , second end 164 is provided with a mounting flange 174 that is adapted to interconnect with electrical cable 74 and / or drain hose 104 . mounting flange 174 is fixedly secured to a rear portion of drawer 16 adjacent a utility connection point 175 . in order to properly receive electrical cable 74 and / or drain hose 104 , mounting flange 174 is provided with first and second plate portions 179 and 180 which , in the embodiment shown , are off - set one from the other . first plate portion 179 is provided with a cable receiving section or opening 184 adapted to receive connector member 94 of electrical cable 74 . in this manner , electrical cable 74 can be supported and the connection to drawer 16 maintained while avoiding undo stress on the connection . in a similar manner , second plate 180 is provided with a drain hose receiving tubular section 186 . drain hose receiving tubular section 186 interconnects second end 112 of a drain hose 104 to a hose receiving portion of a drain pump ( not shown ) carried by drawer 16 . based on the above , it should be readily understood that the utility link 70 of the present invention provides a viable and flexible connection between a wash chamber of a drawer - type dishwasher and household utilities , for example , electrical and drain connections . furthermore , utility link 70 , 70 ′ and utility link carrier 144 enable drawer 16 of the wash chamber to be fully withdrawn from frame 40 such that rear wall 21 can extend well beyond countertop 6 so as to enable a consumer to easily insert large kitchenware , such as baking pans and the like , while still maintaining the necessary utility connections . although described with reference to preferred embodiments of the invention , it should be readily understood that various changes and / or modifications can be made to the invention without departing from the spirit thereof . for instance , while described in connection with upper drawer 16 , a corresponding utility link arrangement is also employed in connection with lower drawer 18 . in general , the invention is only intended to be limited by the scope of the following claims .
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turning now to the preferred arrangement for the present invention , reference is made to the drawings to enable a more clear understanding of the invention . however , it is to be understood that the inventive features and concept may be manifested in other arrangements and that the scope of the invention is not limited to the embodiments described or illustrated . the scope of the invention is intended only to be limited by the scope of the claims that follow . this invention is focused on reducing corrosion in hydrocarbon pipelines and especially at the top or twelve o ′ clock position with long pipelines . for example , in a natural gas well , other gases are produced along with methane , ethane , propane , butane , pentane , hexane and other hydrocarbons . such other gases include water vapor , carbon dioxide and hydrogen sulfide and other known organic materials and impurities . as the natural gas is produced , it starts at the temperature of the formation from which it was produced . these temperatures are typically elevated compared to surface air temperatures and can be up to about 300 ° f . in the pipeline , the gases cool and some condense . water condenses below 212 ° f . and hexane and propane are more commonly liquids at temperatures slightly higher than room temperature . as these gases cool because of a cold pipe wall from conduction , condensates are formed . a problem area for condensates is at the very top of the line , in the twelve o ′ clock position , where one or more corrosive condensates tend to form and cause a considerable corrosion risk to the pipeline . in many cases , there is enough h 2 s , co 2 and organic acids in the gas space of the pipeline to create condensed fluids having a ph of as low as 3 . 0 , which is very acidic . the acidic nature can cause rapid corrosion in a carbon steel pipeline and may cause catastrophic breaching of the pipeline within a few months . so , to address the problem , the concept of the invention is to periodically or continuously inject a foam matrix carrying a corrosion inhibitor into the pipeline to mitigate top of the line corrosion . the selection of the foaming agent or surfactant , the foaming gas and the corrosion inhibitor is quite important . for example , focusing on the foaming gas , any oxygen containing gas , such as air , would not be acceptable considering that the pipeline is carrying hydrocarbons . the most preferred gas would be produced gases , most preferably hydrocarbon gases such as methane or ethane gases that are produced and collected at the well head as these are certainly compatible with other hydrocarbons ( will not degrade or cause harm to the hydrocarbons ) and is already at the wellhead and does not need to be purchased or shipped in . nitrogen is the next most logical choice as it is inexpensive , commonly used in the oil field , generally available onsite , and inert . carbon dioxide and oxygen are typically not preferred as the co 2 is one of the causes of corrosion and oxygen is a safety hazard around the hydrocarbons . the first step of the process for providing a corrosion inhibitor for a particular pipeline is to perform an analysis of the constituents of the hydrocarbon mixture that will be flowing in the pipeline during operation . the term “ hydrocarbon mixture ” in this sense includes the hydrocarbons , per se , along with water and the other impurities that are conveyed through the pipeline including gases that may be in the upper portion of the pipeline . the second step of the process is to create , in the lab or at a suitable test station , a test sample for predicting the suitability of a number of combinations of foaming agents and corrosion inhibitors along with foam breaking agents . while it is reasonable to ship samples of the hydrocarbon to the lab or test station , any dissolved gases and impurities are likely to have come out of solution by the time any predictive tests may be carried out . thus , at the end of the process , extended live tests at the pipeline are necessary to confirm the efficacy of the proposed solutions , make changes or , more hopefully , introduce adjustments to the injection rates of the foaming agent and corrosion inhibitors . turning next to making foam , there are a number of known foaming agents that when mixed with water and provided with a bubbling foaming gas may create foam . currently known foaming agents that have been tested are set forth in table 1 below although it is foreseeable that new foaming agents may be created in the future : however , each foaming agent will have a somewhat different performance when mixed with the hydrocarbon mixture that is flowing along the pipeline . the process of the present invention includes undertaking predictive tests with each available foaming agent with a lab created mixture of liquid that may include hydrocarbons , fresh or salt water and other impurities . few foaming agents have been found not to create sufficient foam to justify further study . those that are able to create a stable foam when mixed with the test liquid are then used in a second round of compatibility studies with corrosion inhibitors . there is a number of known corrosion inhibitors for use with carbon steels that mitigate corrosion . for the present invention , the corrosion inhibitors are generally recognized to inhibit corrosion depending upon their concentration in the foam formed with the test liquid . currently known corrosion inhibitors that have been used in testing are set forth in table 2 below although , like foaming agents , new corrosion inhibitors are likely to be created in the future : pursuant to the testing protocol of the present invention , it has been found that the foaming capability of foaming agents that were functional with the test liquids were altered such that more or less foam was measured as compared to the initial round of tests . moreover , the corrosion inhibitor concentration in the foam was not predictable to the inventors in that the only way to determine which foams would appear to provide the most capability to provide substantial or sufficient concentrations of corrosion inhibiting chemicals was by actually performing the tests with the test liquids . a representative example of the measurements one might develop as part of the efficacy assessment of the foaming agent and corrosion inhibitor is shown in fig1 where the clearly preferred choice for the hydrocarbons in the represented pipeline is hiw 85281 with didecyldimethylammonium bromide with distilled water . fig2 provides a similar efficacy assessment where the foaming agent is sles - 70 . one corrosion inhibitor performs better than the others and it is corseline in distilled water . it is interesting to see that the foaming agent sles - 70 performs better with seawater than it does with distilled water , but the best corrosion inhibitor uses distilled water . this shows the unpredictability of these various components when mixed with hydrocarbons . fig3 sets forth the performance of foaming agent dodecylbenzene sulfonic acid with the various corrosion inhibitors . several combinations show good performance where 3 - methoxyproplamine in de - ionized water . based on the concentration of the corrosion inhibiting materials in the foam and the volume of foam present after measured time durations , some initial calculations of how much foaming agent and corrosion inhibitors would provide adequate corrosion protection . based on the likely amounts of foaming agent and corrosion inhibitor that would be used , cost estimates are prepared for each suitable combination . the most economic solution would clearly be preferred , although it should be recognized that that the effectiveness of the most economic solution may be at least slightly different in the field . if a less economical alternative is substantially more capable of controlling corrosion , the cost of changing out the corrosion controlling solutions in the event that the most cost effective choice ends up being ineffective in a particular hydrocarbon solution in an active pipeline . for example , if the lowest cost solution comprises a foaming gas a1 , a foaming agent b1 , a corrosion inhibitor c1 along with a foam breaking agent d1 , and the second but more capable choice uses a1 , b1 and d1 along with a second choice inhibitor c2 , the cost of implementing this backup plan is more likely not very costly as compared with a backup plan that includes a second choice foaming agent b2 and a second choice foam breaking agent d2 where several changes need to be made . it should also be noted that the most cost effective solution may be the most capable solution and no second solution is readily apparent from the lab tests . as noted above , the final step is actual field demonstration of the prime solution with observations and measurements of effectiveness . a delivery system for injecting the foam carried corrosion inhibitor is provided at the pipeline as described below with suitable adjustment capability to provide a preferred performance of the selected solution for the particular pipeline . turning to fig4 of the present invention , a hydrocarbon pipeline carrying primarily gas is indicated with the number 10 . the pipeline has liquid phase in the bottom as indicated by the number 12 and a gas space 15 above the liquid phase . the foam matrix , containing the corrosion inhibitor , is indicated by the arrow 20 and includes an injection nozzle 21 in the wall of the pipeline delivering foam matrix 16 into the gas space of the pipeline 10 . foaming gas is provided from a gas source such as tank 23 through control valve 24 and check valve 25 to a mixing device 28 . mixing device 28 is also provided with foaming agent or surfactant agent from a storage device 33 via pump 34 and check valve 35 and corrosion inhibitor from storage device 43 via pump 44 and check valve 45 . mixing device 28 preferably includes vanes or a tortuous path so that the three components are likely to form a relatively homogeneous blend . injection nozzle 21 is preferably a converging / diverging nozzle which provides back pressure on the fluid flow so that foam may form when the pressure is let down on the diverging or expanding side of the nozzle . alternatively , nozzle 21 may include a fritted filter to create numerous micro - bubbles to form foam . optionally , other known bubbling technology may be employed to form the foam as the fluid enters the pipeline 10 . it should also be noted that storage device 33 includes water with the foaming agent and the two may be combined at the corrosion inhibiting system 20 or may be delivered pre - mixed to the corrosion inhibiting system 20 . at the end of the pipeline , the foam must to be broken as the foaming agents can impact the clean separation of oil , water and gas during production . if foam does not naturally break , it can be broken by addition of an antifoam agent selected for its compatibility with the other components of the system . the amounts of each of the foaming gas , foaming agent , corrosion inhibitor and foaming breaking agent may be independently adjusted to optimize performance for the pipeline 10 . such independent control may be accomplished by speed adjustments on the pumps , by control valves or other known flow regulating technology . finally , the scope of protection for this invention is not limited by the description set out above , but is only limited by the claims which follow . that scope of the invention is intended to include all equivalents of the subject matter of the claims . each and every claim is incorporated into the specification as an embodiment of the present invention . thus , the claims are part of the description and constitute a further description and are in addition to the preferred embodiments of the present invention . the discussion of any reference is not an admission that it is prior art to the present invention , especially any reference that may have a publication date after the priority date of this application .
| 1 |
since the most relevant prior art is devices produced by the assignee of the present invention , the following description is presented of the system used today , in order to better understand the improvements presented later . it should be understood that while the invention is presented in the form of improvements in an existing system , this is only for ease and clarity of description . the present invention , as claimed , has applicability to a wide range of systems , including some systems which may be designed to avoid some of the problems that exist with the present system . an exemplary configuration of existing laser printers is illustrated in a very simplified form in fig1 . a charged photosensitive member 2 is exposed to a light image from a scanning laser 4 controlled by a computer . a similar configuration is used in some copiers , with the scanning laser replaced by a lens focused on a document that is being copied . the areas of the photo - sensitive surface that are exposed to light acquire a different voltage than the parts that are not exposed to light , due to selective discharge of those areas . this voltage difference is used to selectively attract toner particles to parts of the surface , using a developer 3 , producing a toner image that corresponds to the exposure . the toner image is then transferred to an intermediate transfer member 6 , and from there to a printing medium 8 on an impression member 10 in the exemplary form of a roller . although the image could be transferred directly from the photo - sensitive member to the impression member , in some systems better results are achieved by using an intermediate transfer member , which can be heated , resulting in better transfer of the toner ( especially liquid toner ) to the printing media . of course , this drawing is very simplified . the printing media is held to the impression member by printing media grippers 12 . fig2 shows the impression member ( removed from the printer ), seen from one side , and fig3 a and 3b are close - up views of the impression member showing the grippers more clearly . during operation , the opening along the side of the impression member normally has a cover over it , with small openings for the grippers . this cover has been removed in fig2 a , and 3 b , to show a rod 304 ( or rods , optionally connected by a coupler 202 ) which controls the raising and lowering of the grippers . in fig3 a , grippers 12 are in a raised position , while in fig3 b grippers 12 are in a lowered position for holding the printing media . grippers 12 are optionally spring - loaded , and springs 302 are visible in fig3 a . once the media has been printed , grippers 12 are raised , and the printing media is removed from the impression member by a lifting mechanism , for example including suction elements such as suction cups 14 ( shown in fig1 ), and conveyed to an output tray . suction elements 14 may be active , i . e ., they are connected to a vacuum source , or they are passive , i . e ., a vacuum is formed when they are pressed against printing media 8 . generally , active suction elements are preferred . if there is a paper jam , or some other malfunction , and the grippers do not pick up the printing media , then toner will be transferred from the intermediate transfer member directly to the surface of the impression member . because the impression member , which has a metal surface , does not absorb toner as well as the printing media , some toner will remain on the intermediate transfer member . if the intermediate transfer member is not immediately cleaned off , then the toner may dry if it is liquid , or possibly melt if it is solid , which may cause permanent damage to the intermediate transfer member . to prevent this from happening , a piece of media , described herein as impression media or impression paper ( since it is generally of paper ) 9 , is sometimes permanently glued to the surface of the impression member at a point designated as 11 . the forward edge of the impression media is positioned underneath the printing media , i . e ., the forward edge does not extend past the edge 13 of the printing media that is held by the grippers . even if the impression member picks up no printing media , the impression paper surface will absorb all the toner from the intermediate transfer member , and the intermediate transfer member will not be damaged by dried toner . however , the impression paper can create its own problems . first there are the problems connected with gluing . inter alia , since there may be a slight difference in velocity between the impression roller and the intermediate transfer member ( in order to avoid buckling of the paper ), there is significant stress on the glue . therefore , the glue has to be strong . unfortunately , since paper misfeeds do occur , the impression paper must be removable . this mandates a weaker bond for the glue . furthermore , the area available for gluing is limited , in order not to interfere with the printable area of the print media and may sometimes intrude on this area slightly . additionally with time , the impression paper may slide along the impression roller in a direction opposite the direction of motion of the impression roller surface . the differences of height caused by the presence of glue under the impression paper cause poor or sometimes even an absence of transfer from the intermediate transfer member to the print media . if the impression media needs to be replaced , for example because it is worn or torn or because it has been printed on due to a paper misfeed , it can be difficult to remove the old impression paper completely . finally , the smooth surface of the impression paper creates a partial vacuum between the impression paper and the printing media , when the latter is picked up by suction elements to remove it from the impression member . this may cause the printing media to be picked up in an uncontrolled manner , especially if it is thin paper . fig4 shows an impression paper clamp 400 , as seen from below , according to an exemplary embodiment of the invention . here , “ above ” means in a direction away from the impression member when the impression paper clamp is installed , and “ below ” means toward the interior of the impression member when the impression paper clamp is installed . in describing the impression paper clamp , we use terms such as “ above ”, “ below ”, “ upper ”, “ lower ”, “ raised ”, “ lowered ”, “ top ” and “ bottom ” to refer to directions relative to the center of the impression member when the impression paper clamp is installed , even though these terms are only literally true when the impression member is oriented so that the impression paper clamp is uppermost . many of the features of the impression paper clamp shown in fig4 are designed to allow the impression paper clamp to be retrofitted to an existing impression member used in printers manufactured by hewlett - packard . some of these features optionally look quite different , or are absent entirely , in embodiments of the invention designed for use on different impression members , without departing from the teachings of the invention . impression paper clamp 400 comprises an upper portion 402 , in the form of a straight bar , and a lower portion . optionally , upper portion 402 clamps the impression paper directly against an integral part of the impression member , instead of against the lower portion , and in that case there is no need for a lower portion . the lower portion optionally includes a back section 406 , which fits into a slot in the impression member , and a number of teeth 408 , which press against upper portion 402 to hold the impression paper . the spaces between the teeth optionally allow the grippers to open through corresponding apertures in the impression paper , as shown in fig6 and 7 , to hold the printing media . the number of teeth and grippers is different for some embodiments of the invention than the number of teeth and grippers shown in the drawings , but generally there is still one space between the teeth for each gripper . the middle tooth optionally has a clearance hole 410 , for coupler 202 . similarly , back section 406 optionally has a clearance slot 412 for coupler 202 . two captive nut and bolt assemblies 414 can be tightened , through openings 416 ( not visible in fig4 since they are on the hidden top surface of upper portion 402 , but visible in fig5 a and 5b ), to bring upper portion 402 tightly against the lower portion , to hold the impression paper in place . the nuts and bolts need not be captive , but making them captive prevents them from being lost if they come loose , and prevents them from falling into the interior of the impression member and possibly causing damage or malfunction . optionally , the upper and lower portions of impression paper clamp 400 are held against each other by another mechanism , such as a spring or clip , and in some embodiments there is no mechanism for tightening impression paper clamp 400 . two attachment tabs 418 , with holes in them , optionally allow impression paper clamp 400 to be bolted down when it is installed in the impression member . fig5 a and 5b show impression paper clamp 400 installed in impression member 10 . fig5 a shows the grippers in a raised position , and fig5 b shows the grippers in a lowered position . upper portion 402 , one of the openings 416 , one attachment tab 418 , and four of the teeth 408 are visible , as well as printing paper clamps 12 . note that grippers 12 optionally fit into the spaces between teeth 408 . fig6 shows impression paper 600 held at one end by impression paper clamp 400 . trapezoidal apertures 602 in impression paper 600 optionally allow grippers 12 to go through impression paper 600 , and to hold the printing media in place . apertures 602 need not be trapezoidal , but are trapezoidal in this embodiment of the invention to match the shape of grippers in this design of the impression member . circular hole 604 , near the top margin of fig6 , optionally allows clearance for coupler 202 to move when the grippers are raised and lowered . hole 604 is optionally absent in some embodiments of the invention , for example if a mechanism other than coupler 202 is used to connect rods 304 or is no coupler is used or if coupler 202 does not need the clearance . in fig7 , a sheet of printing media 8 is shown held in place by grippers 12 , on top of impression paper 600 . fig8 a shows a bottom view of impression paper clamp 400 , not installed in the impression member , with impression paper 600 adjacent to it . impression paper 600 is shown aligned with impression paper clamp 400 , as it would be before being inserted . note that each of the holes 602 corresponds to one of the spaces between teeth 408 . two slots 802 in impression paper 600 , which are lined up with nut and bolt assemblies 414 . optionally , a different number of nut and bolt assemblies are used in the impression clamp , and optionally one slot 802 is formed in the impression paper , for each nut and bolt assembly . when impression paper 600 is inserted into impression paper clamp 400 , the bolts in the two assemblies 414 each go through its associated slot 802 . optionally , impression paper 600 lacks slots 802 , and is inserted into impression paper clamp 400 only far enough so that its leading edge touches the bolts . however , allowing the bolts to go through slots 802 makes it possible to push impression paper 600 further into impression paper clamp 400 , so that it can be held more firmly . optionally , slots 802 are replaced by bolt holes for the bolts to go through , and the bolts are disengaged from the nuts and raised above the impression paper until the impression paper is fully inserted , at which time the bolts are lowered through the bolt holes and engaged in the nuts . by using slots 802 instead of holes , the bolts can be kept engaged in the nuts while impression paper 600 is being inserted into impression paper clamp 400 . optionally , in embodiments of the invention where a mechanism other than the nut and bolt assemblies is used to tighten the impression paper clamp , or where there is no mechanism to tighten the impression paper clamp , impression paper 600 does not have slots 802 , or bolt holes . fig8 b shows impression paper 600 fully inserted into impression paper clamp 400 , which is seen from below as in fig8 a . note that trapezoidal apertures 602 are now aligned with the spaces between teeth 408 , and circular hole 604 is aligned with hole 410 in the middle tooth . slots 802 are no longer visible , as they are hidden by the lower portion of the impression paper clamp . although fig8 a and 8b show the paper brought adjacent to the impression paper clamp , and then inserted into the impression paper clamp , when the impression paper clamp is not mounted on the impression member , in actual operation , the impression paper is inserted into the impression paper clamp when the impression paper clamp is already mounted on the impression member . the two views of the dismounted mechanism are used to better illustrate the method of mounting the impression paper . fig9 shows a schematic cross - sectional view of impression member 10 , impression paper 600 , printing media 8 , and suction cup 14 . gripper 12 is in a raised position , so that suction cup 14 can pull printing media 8 off impression member 10 . impression paper 600 is held in place by impression paper clamp 400 . dashed lines show trapezoidal hole 602 in impression paper 600 . suction cup may pull the printing media from the impression roller at a distance , as shown or may come into contact with the printing media while it is still flat on the impression media . impression paper 600 is formed with apertures , such as narrow slits 900 or a pattern of small holes , beneath suction cup 14 . when suction cup 14 pulls printing media 8 away from impression paper 600 , a partial vacuum would be created between the smooth surfaces of printing media 8 and impression paper 600 . slits 900 allow air from the space between impression paper 600 and impression member 10 to flow into the space between impression paper 600 and printing media 8 , preventing a significant vacuum from forming , and allowing suction cup 14 to pull printing media 8 away from impression paper 600 and impression member 10 in a controlled , predictable manner . it should be noted that because grippers 12 are no longer holding printing media 8 and impression paper 600 down against impression member 10 , and because the other end of impression paper 600 ( opposite the end held by impression paper clamp 400 ) is free , and because impression paper 600 is somewhat stiff , impression paper 600 may not lie flat against impression member 10 , so there may be a space filled with air between impression member 600 and impression member 10 , which can flow through slits 900 . in other embodiments of the invention , not all these conditions are met , however , even if only some of the conditions are met , there may still be enough air flowing through slits 900 so that suction cups 14 pull media 8 off impression member 10 in a controlled manner . however , as indicated above , while single slits or single or multiple apertures can be used for releasing the vacuum formed , they have a tendency to become clogged with debris , such as paper fibers . thus , for this embodiment , the size of the apertures must be increased , for example greater than 0 . 1 mm and preferably larger , up to a size which interferes with the printing quality , which may be some larger fraction of a mm . in a preferred embodiment of this aspect of the invention , the apertures are slits that are formed in pairs . under these circumstances , the effect of lifting of the printing media is to lift the region between the slits . this allows air to enter the region between the printing media and the impression paper , releasing the vacuum . for this embodiment , the width of the slits is not a factor in the operational life of the impression paper and the slits are preferably made as thin as possible , for example 0 . 1 mm or less ( e . g ., 0 . 05 or 0 . 02 mm ). however , the invention is not limited to such thin slits , which may be difficult to manufacture . in general , it is desirable that the distance between slits be smaller than the size of suction cup 14 . at present a distance of about 7 mm is used . however , smaller distances can be used and more than two slits may be provided beneath each suction cup . furthermore , the length of the slits should be at least as long as the diameter of the suction cups , to aid in the lifting of the portion between the slits . however , this is not absolutely necessary . the one suction cup 14 shown in fig9 optionally represents two or more suction cups arranged in a direction perpendicular to the plane of fig9 . optionally , there are one or more slits 900 in the impression paper beneath each suction cup . in the system where the impression paper slits have been tested by the inventors , for example , there are four suction cups , and there are two slits beneath each suction cup , or a total of eight slits in the impression paper . slits 900 need not be used in conjunction with impression paper clamp 400 , but optionally could be used in impression paper that is attached to the impression member in a different way , for example by gluing . fig1 shows an outline of one end of a piece of impression paper 600 , the end that is held by the impression paper clamp , according to an embodiment of the invention that is being tested . six trapezoidal apertures 602 , circular hole 604 , two slots 802 , and eight slits 900 are visible . the width of slits 900 is exaggerated so that they are visible . in fact , the slits are only 0 . 1 mm wide , in this embodiment of the invention . as noted previously , the number , size and shape of any of these features may be different , and any of these features may not exist , in some embodiments of the invention , depending , among other factors , on the design of the impression member and the impression paper clamp . impression paper preferably has a number of desired characteristics . first , the impression paper should be strong enough so that it can stand the sliding forces induced on it , considering that it contains a series of cut - outs . second , it is desirable that the impression paper be smooth and of uniform thickness . this avoids texturing of the images printed on the printing media . third , it should absorb the ink from the intermediate transfer member , in case of a paper miss - feed . however , since the same impression roller may also be used for printing a second side of duplex , it should not offset ink from the first side , when an image is transferred to the second side from the ( hot ) intermediate transfer member . fourth , while it is desirable that the impression paper be stiff , it is also desirable that the paper conform to the curvature of the impression member . of course , in order to work , impression paper need not be optimized for all or even any of these parameters . it has been found that gardamatt art paper ( garda cartiere , italy ) provides a suitable impression paper , for various thicknesses from nominally 101 micrometers thickness ( gardamatt 115 ) to nominally 313 micrometers thickness ( gardamatt 300 ), although thicker paper (& gt ; 200 micrometers ) are sturdier . the smoothness of this paper veries between 20 ± 5 to 30 or 40 ± 10 or 20 for the thinner papers . however , the smoothness is not critical , so long as there is no texturing of the image . this paper is short fiber paper and is cut so that the stiffer direction is parallel to the axis of the impression roller . this allows the impression paper to conform to the impression roller . the invention has been described in the context of the best mode for carrying it out . it should be understood that not all features shown in the drawings or described in the associated text may be present in an actual device , in accordance with some embodiments of the invention . furthermore , variations on the method and apparatus shown are included within the scope of the invention , which is limited only by the claims . also , features of one embodiment may be provided in conjunction with features of a different embodiment of the invention . furthermore , it should be understood that not all of the embodiments of the invention solve all of the problems that are associated with the prior . it is contemplated that some problems of the prior art will be solved by other means or will not be solved at all . as used herein , the terms “ have ”, “ include ” and “ comprise ” or their conjugates mean “ including but not limited to .”
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in this specification , the devices with the same symbol refer to the devices with substantially the same or similar function , structure , compound or application , but are not necessarily all the same . after reading this specification , persons skilled in the art can replace or alter some devices in the embodiments without departing the essence of the invention . accordingly , the embodiments herein are not used for limiting the scope of the invention . fig3 a demonstrates power controller 22 , which , as an example , is employed in power controller 18 of fig1 . power controller 22 has pulse width modulator 32 and gate - driving circuit 24 . pulse - width signal v pwm is generated according to compensation signal v com at compensation node com . for example , the higher the compensation signal v com , the longer the on time when pulse - width signal v pwm is asserted to make power switch 15 perform a short circuit , the more the electric energy stored in an inductive device , and the higher the power a corresponding power converter converts . gate - driving circuit 24 drives gate node gate of power switch 15 , generating gate signal v gate based on pulse - width signal v pwm and dimming signal v dim . it can be derived from the schematic of gate - driving circuit 24 that , when dimming signal is asserted , gate signal v gate at gate node gate is substantially in phase with pulse - width signal v pwm . gate - driving circuit 24 has driver 26 , which , as an example to compare with embodiments , has a driving force of 4 units to drive gate node gate . fig3 b shows dimming signal v dim , gate signal v gate , and current i in drained to the led chains from input node v in . as shown in fig3 b , when dimming signal v dim is asserted , driver 26 generates gate signal v gate , using its driving force of 4 units , such that power switch 15 is periodically turned on and off , and current i in vibrates within a certain range to power the led chains of fig1 . when dimming signal v dim is deasserted , driver 26 uses its driving force of 4 units to deassert gate signal v gate , whose voltage , as a result , drops quickly and stays around 0 volt , completely turning off power switch 15 . for power switch 15 is turned off , current i in decreases linearly over time and become 0 a eventually . fig4 a demonstrates power controller 30 , which in one embodiment of the invention replaces power controller 18 of fig1 . power controller 30 has pulse width modulator 32 and gate - driving circuit 34 . fig4 a share with fig3 a some common devices , which could be comprehensible to persons skilled in the art and will not be detailed in consideration of brevity . different to gate - driving circuit 24 of fig3 a having a single driver 26 , gate - driving circuit 34 of fig4 a includes two drivers 36 and 38 , having driving force of 1 unit and 3 units respectively . for instance , in one embodiment , the maximum pulling - down current that driver 36 can afford is 10 ma , and the maximum pulling - down current that driver 38 can afford is 30 ma , such that the driving force of driver 38 is three times that of driver 36 . in another embodiment , the pulling - down resistance of driver 36 is three times that of driver 38 to make the driving force of driver 38 three times that of driver 36 . when dimming signal v dim is asserted , gate signal v gate is substantially in phase with pulse - width signal v pwm , and drivers 36 and 38 together use driving force of 4 units in total to generate gate signal v gate . when signal v dim is deasserted , driver 38 is disabled , its output impedance becomes so large , and it drives no more the control gate of power switch 15 . thus , driver 36 alone deasserts gate signal v gate , using driving force of 1 unit . fig4 b shows waveforms of dimming signal v dim , gate signal v gate , and current i in drained to the led chains from input node v in , according to the embodiment of fig4 a . unlike the gate signal v gate in fig3 b , whose voltage , when dimming signal v dim switches to being asserted , drops quickly because of the driving force of 4 units , gate signal v gate in fig4 b drops relatively slower when dimming signal v dim switches to being asserted , because the driving force to pull down gate signal v gate is mere 1 unit . accordingly , current i in in fig4 b can hold for a short period of time and then , when gate signal v gate is surely deasserted to complete turn off power switch 15 , decreases linearly over time and become 0 a eventually . comparing with the waveform of current i in in fig3 b , current i in in fig4 b varies milder , especially when dimming signal v dim is switched to being deasserted . it can be derived from spectrum analysis that a signal that varies relatively milder will have stronger energy to its fundamental frequency and less energy to its harmonic frequencies . as aforementioned , audio noise might happen easily if the energy to the harmonic frequencies of a signal is large even though the fundamental frequency of the signal locates within a frequency range less audible to human . since power controller 30 of fig4 a renders relatively - less energy to harmonic frequencies , it is more - likely that power controller 30 can reduce the audio noise caused by harmonic frequencies . fig5 shows control method 40 adapted to power controller 22 of fig3 a or power controller 30 of fig4 a . control method 40 is used in power controller 30 in one embodiment of the invention . in step 42 , power controller 30 makes sure that operation voltage v cc is well prepared for power controller 30 to properly function . for example , in one embodiment , operation voltage v cc must exceed a certain level to be claimed as being well prepared . step 44 follows , where power controller 30 checks whether it should operate in a dimming - on period or a dimming - off period . for example , if dimming signal v dim is asserted , power controller 30 should operate in a dimming - on period and step 46 follows . in the contrary , if dimming signal v dim is deasserted , power controller 30 should operate in a dimming - off period and step 54 follows . in step 46 , for a predetermined number of subsequent switch cycles , the on time t on in each switch cycle is forced to be a predetermined minimum on time , independent to compensation signal v com at compensation node com . the time period for this predetermined number of subsequent switch cycles could be referred to as a soft - start time . in the meantime , current controller 20 in fig1 starts conducting and spreading current i in through led chains to illuminate . following step 46 is step 48 . in step 48 , power controller 30 controls on time t on of power switch 15 in a following switch cycle according to compensation signal v com , such that the led chains are powered to illuminate . step 50 follows . it can be found from the sequence with steps 44 , 46 and 48 , that step 46 likely provides a soft - start mechanism , which limits the power converted by the voltage - controlled stage during the soft - start time at the beginning of a dimming - on period . the power during the soft - start time is less than the power actually required by the current - controlled stage . after the soft - start time , as being in responsive to compensation signal v com , power controller 30 makes the voltage - controlled stage provide the power substantially required by the current - controlled stage for illuminating the led chains . in step 50 , power controller 30 again checks whether it should operate in a dimming - on period or a dimming - off period . for example , if dimming signal v dim is still asserted , power controller 30 should continuously operate in a dimming - on period and control method 40 proceeds back to step 48 . in the contrary , if dimming signal v pwm is deasserted , power controller 30 should switch to a dimming - off period and control method 40 proceeds to step 52 . step 52 is similar with step 46 . in step 52 , for another predetermined number of subsequent switch cycles , the on time t on in each switch cycle is forced by power controller 30 to be the predetermined minimum on time , independent to compensation signal v com at compensation node com . the time period for this predetermined number of the subsequent switch cycles in step 52 could be referred to as a soft - brake time . during the soft - brake time , current controller 20 in fig1 stops conducting and spreading current i in such that the led chains stop illuminating . following step 52 is step 54 . in step 54 , power controller 30 does not convert electric power and provide current to drive the led chains . in the meantime , the led chains are kept as not illuminating . for example , power controller 30 makes and keeps gate signal v gate deasserted , such that power switch 15 remains as turned off so no electric power is converted . it can be found from the sequence with steps 50 , 52 and 54 , that step 52 likely provides a soft - brake mechanism , which , before power conversion is complete stopped , keeps little but not zero power converted by the voltage - controlled stage during the soft - brake time at the beginning of a dimming - off period , in which no power is actually required as the led chains do not illuminate . after the soft - brake time , power controller 30 constantly turns off power switch 15 , stopping the electric power conversion in the voltage - control stage and current i in to the current - controlled stage . fig6 a shows some signal waveforms around the transition from a dimming - off period to a dimming - on period , while fig6 b does some signal waveforms around the transition from a dimming - on period to a dimming - off period according to control method 40 of fig5 . signal waveforms in each of fig6 a and 6b refer to , from top to bottom , dimming signal v dim , gate signal v gate , current i in , compensation signal v com , and voltage signal v as at current - sense node cs . at time t r in fig6 a , dimming signal v dim is switched to be asserted , such that a dimming - off period ends and a dimming - on period begins . soft - start time t ss , the period from time t r to time t es at the beginning of a dimming - on period , has four switch cycles . during soft - start time t ss , each on time of power switch 15 , as shown in fig6 a , is fixed to be the minimum on time predetermined by power controller 30 , even though compensation signal is demanding longer on time and more power . after time t es , the on time of power switch 15 is determined by compensation signal v com and might be as long as the maximum on time predetermined by power controller 30 . it can found in fig6 a that the power converted during soft - start time t ss is less than what compensation voltage v com corresponds to or demands . at time t f in fig6 b , dimming signal v dim is switched to be deasserted , such that a dimming - on period ends and a dimming - off period begins . soft - brake time t se , the period from time t f to time t se at the beginning of a dimming - off period , has four switch cycles . during soft - brake time t se , each on time of power switch 15 , as shown in fig6 b , is fixed to be the minimum on time predetermined by power controller 30 , even though the led chains stop illuminating and require no power . after time t se , power switch 15 is no more turned on , and gate signal v gate is constantly deasserted . it can found in fig6 b that the power converted during braking time t se is more than 0 , but less than what compensation voltage v com corresponds to or demands . fig7 shows some signal waveforms , including dimming signal v dim , gate signal v gate , compensation signal v com , current i in , around the transition from a dimming - off period to a dimming - on period while no soft - start mechanism is used . in comparison with current i in in fig7 , current i in in fig6 a , due to the introduction of the soft - start mechanism , rises relatively milder around the transition from a dimming - off period to a dimming - on period . accordingly , it is possible that current i in in fig6 a causes relatively less audio noise . similarly , by comparing with current i in in fig3 b , which employs no braking mechanism , current i in in fig6 b , due to the introduction of the soft - braking mechanism , falls relatively milder . accordingly , it is possible that current i in in fig6 b causes relatively less audio noise . during the soft - brake time , the led chains do not illuminate such that the power provided or converted by the voltage - controlled stage during the soft - brake time is not consumed , but stored at output node out . this stored power might make up for the lack during the following soft - start time when the voltage - controlled stage provides power less than that demanded by the led chains . accordingly , employing both the soft - start and soft - brake mechanisms in one embodiment might be beneficial in reducing variation of compensation signal v com . one power controller according to the invention might be configured to perform the soft - start and / or soft - brake mechanisms introduced in fig5 and , as well , the driving - force control introduced in fig4 a . another power controller according to the invention might be configured to perform only the soft - start and / or soft - brake mechanisms , but not the driving - force control . another power controller according to the invention might be configured to perform only the driving - force control , but not the soft - start and / or soft - brake mechanisms . it is not necessary that the on time of a power switch in each switch cycle during the soft - start time and the soft - brake time must be the minimum on time . in another embodiment , what is limited during the soft - start time and the soft - brake time is the peak value of voltage signal v cs , which corresponds to the peak current flowing through inductive device prm . in control method 96 shown in fig8 , voltage signal v cs for each switch cycle during a soft - brake time is forced to be at least a first predetermined value , as indicated by step 98 . similarly , voltage signal v cs for each switch cycle during a soft - start time is forced to be no more than a second predetermined value , as indicated by step 97 in fig8 . the first and second predetermined values are the same in one embodiment , while they might be different in another embodiment . in one embodiment , during a dimming - on period , regardless it is within a soft - start time or not , compensation node com will be charged or discharged according to the feedback voltage at feedback node fb . accordingly , compensation signal v com substantially corresponds to the power required by the led chains to illuminate . during a dimming - off time , nevertheless , compensation node com is isolated or stopped from being charged or discharged , such that compensation signal v com is substantially held or sustained by an external compensation capacitor . when switching to a following dimming - on period , as compensation signal v com substantially keeps its value as of the ending of the previous dimming - on period , a voltage - controlled stage can quickly provide the power actually required by the led chains . according to the aforementioned analysis , embodiments of the invention might render current i in with milder variation , resulting in reduced audio noise caused by harmonic frequencies . even though fig1 exemplifies an embodiment of the invention by way of booster topology , the invention is not limited to . for example , embodiments of the invention might be flyback converters , buck converters , buck - boosters , and the like . while the invention has been described by way of examples and in terms of preferred embodiments , it is to be understood that the invention is not limited thereto . to the contrary , it is intended to cover various modifications and similar arrangements ( as would be apparent to those skilled in the art ). therefore , the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements .
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a process for production of a dynamic ram according to an embodiment of the present invention will first be explained . fig1 a to 1j are cross - sectional views of the process . as shown in fig1 a , a field oxide layer 3 having a thickness of about 6 , 000 å a is formed on a p - type silicon substrate 1 having a specific resistance of about 10 ohm - cm and having a p - type channel cut region 2 . specifically , this is achieved by the steps of forming a silicon nitride ( si 3 n 4 ) layer ( not shown ) on a ram element formation region 4 , implanting boron ions into the p - type silicon substrate 1 at an energy of 60 kev and to a dosage of 2 × 10 13 atoms per cm 2 using the silicon nitride layer as a mask , selectively oxidizing the substrate 1 using the silicon nitride layer as a mask , and then removing the silicon nitride layer . thus the ram element formation region 4 isolated by the field oxide layer 3 is formed . as shown in fig1 b , capacitor oxide layer 5 having a thickness of about 50 to 300 å a is formed on the p - type silicon substrate 1 of the ram element formation region 4 by a usual thermal oxidation process . as shown in fig1 c , a first polycrystalline silicon layer 6 having a thickness of about 500 to 700 å is formed on the obtained structure by a usual chemical vapor deposition ( cvd ) process . as shown in fig1 d , a first resist layer 29 having a thickness of about 10 , 000 å is formed on the first polycrystalline silicon layer 6 . then , the first resist layer 29 is patterned by photolithography on the ram element formation region so that an opening exposing an upper portion of a capacitor formation region 7 is formed . after that , using the resist layer 29 as a mask , first , boron ions ( b + ) are selectively implanted into the substrate 1 through the first polycrystalline silicon layer 6 and the capacitor oxide layer 5 at an energy of 200 kev and to a dosage of 1 × 10 13 atoms per cm 2 . subsequently arsenic ions ( as + ) are implanted at an energy of 150 kev and to a dosage of 5 × 10 13 atoms per cm 2 . thus , a boron region 9 and an arsenic region 10 are formed in the capacitor formation region 7 . in the ion implantation process , contaminants ( not shown ) contained in the implanting chamber may be introduced into the implanting surface by the knock - on phenomena . since the capacitor oxide layer 5 is not exposed to the implanting surface , it is not contaminated . a degenerated layer of the resist layer 29 is formed on the upper surface of the resist layer 8 by the impact of ions on the resist layer 29 . as shown in fig1 e , the first resist layer 29 is removed by a usual ashing process using oxygen gas plasma and a wet treatment using sulfuric acid ( h 2 so 4 ). subsequently , a wet etching process using hydrogen fluoride ( hf ) may be carried out to remove an extremely thin oxide layer which is likely to be formed on the surface of the polycrystalline layer during the implanting process . since the capacitor oxide layer 5 is not exposed to these processes , it is not contaminated and its thickness is not decreased . then , on the first polycrystalline silicon layer 6 , a second polycrystalline silicon layer 11 having a thickness of about 3 , 000 to 4 , 000 å is formed to ensure a sufficient thickness of polycrystalline silicon to make an electrode . impurities of phosphorus ions or the like are implanted into the second polycrystalline silicon layer 11 to give a low resistivity thereto . as shown in fig1 f , a resist layer 12 is formed on the second polycrystalline silicon layer 11 , and then is patterned by a usual photolithography process to leave just the portion directly above the arsenic region 10 and the part of the field oxide layer 3 ranging along the arsenic region 10 . the exposed part of the second polycrystalline silicon layer 11 is etched by a reactive ion etching ( rie ) process using the patterned resist layer 12 as a mask . subsequently , the exposed part of the first polycrystalline silicon layer 6 is etched by the same process . after that , the exposed part of the capacitor oxide layer 5 is etched by the rie process . in the rie process for the polycrystalline silicon layer and the capacitor oxide layer , a mixture of carbon tetra fluoride ( cf 4 ) and oxygen and trifluoromethane ( chf 3 ) are used , respectively , as an etching gas . the etching gas pressure is usually adjusted to about 0 . 01 to 0 . 1 torr , and the high frequency electric power is usually set to 0 . 2 to 0 . 3 watt / cm 2 . as shown in fig1 g , the second resist layer 12 is removed by a usual ashing process whereby a hi - c structure capacitor is realized . the hi - c structure capacitor consists of the arsenic region 10 , which , when activated , becomes an n + - type region and the boron region 9 , which , when activated , becomes a p + - type region ; the capacitor oxide layer 5 positioned above the p - n junction portion ; and a polycrystalline silicon capacitor electrode 13 composed of the first and second polycrystalline silicon layers 6 and 11 . after that , conventional production process are carried out . as shown in fig1 h , a gate oxide layer 14 having a thickness of about 300 to 500 å is formed on the exposed part of the p - type silicon substrate 1 by a usual thermal oxidation process . simultaneously , a second oxide layer 15 is formed over the polycrystalline silicon capacitor electrode 13 . on the obtained structure , a third polycrystalline silicon layer having a thickness of about 4 , 000 to 5 , 000 å is formed by the cvd process . after giving conductivity to the third polycrystalline silicon layer by implanting impurities thereto , the third polycrystalline silicon layer is patterned by the photolithography process to form a polysilicon gate electrode 16 on the gate oxide layer 14 . as shown in fig1 i , high concentration of arsenic ions are implanted into the p - type silicon substrate 1 through the exposed portion of the gate oxide layer 14 using the polycrystalline silicon gate electrode 16 and the polycrystalline silicon capacitor electrode 13 as a mask . after the ion implantation process , the required annealing is carried out so that an n + - type source region 17 and n + - type drain region 18 are formed in the p - type silicon substrate 1 . during the annealing process , the boron region 9 and the arsenic region 10 are activated to become p + - type and n + - type regions , respectively . as shown in fig1 j , on the obtained structure , a phospho - silicate glass ( psg ) layer 19 , for example , is formed by the cvd process . an electrode window is formed by etching the psg layer 19 and the gate oxide layer 14 using a photolithography process . then , an aluminum layer is formed over the obtained structure by vacuum evaporation or sputtering . the aluminum layer is patterned by the photolithography process to form aluminum wiring 20 on the psg layer 19 through the electrode window . the wiring 20 is electrically connected to the drain region 18 , the gate electrode 16 , and the capacitor electrode 13 . the connection of the aluminum wiring 20 to the gate electrode 16 and the capacitor electrode 13 is carried out at another region ( not shown ). thus after the formation of a protective insulating layer on the obtained structure , the production of a dynamic ram is completed . next , a process for production of an eeprom according to an embodiment of the present invention will be explained . fig2 a to 2i are cross - sectional views of the process . first , referring to fig2 a and 2b , the same processes as in fig1 a and 1b are carried out . then , as shown in fig2 c , a part of an oxide layer 5 is etched by a usual photolithography process to form an opening . as shown in fig2 d , a tunnel gate oxide layer 5a having a thickness of about 100 to 200 å is formed on the exposed p - type silicon substrate 1 . after that , on the obtained structure , a first polycrystalline silicon layer 6 having a thickness of 500 to 700 å is formed as shown in fig2 e . then , as shown in fig2 f , a resist layer 9 having an opening is formed on the polycrystalline silicon layer 6 , then arsenic ions are implanted into the p - type silicon substrate 1 through the polycrystalline silicon layer 6 and the tunnel gate oxide layer 5a to form an impurity region 21 for electron injection or discharge . as shown in fig2 g , a second polycrystalline silicon layer 11 having a thickness of about 3 , 000 to 5 , 000 å is formed on the first polycrystalline silicon layer 6 and an ion implantation process is carried out to give the layer 11a low resistivity . subsequently , a patterned resist layer ( not shown ) is formed over the polycrystalline silicon layers 10 and then the polycrystalline layer 6 and 10 are etched , with the resist layer used as a mask to form a preliminary pattern for forming the floating gate pattern . as shown in fig2 h , on the obtained structure , a second gate oxide layer 22 having a thickness of 400 to 700 å is formed by a usual thermal oxidation process . after that , a polycrystalline silicon layer 23 for a control electrode is formed on the second gate oxide layer 22 and an ion implantation process for rendering the layer 23 conductive is carried out . then , a patterned resist layer is formed on the polycrystalline silicon layer 23 above the impurity region 21 for electron injection or discharge . as shown in fig2 i , the polycrystalline silicon layer 23 for a control electrode , the second gate oxide layer 22 , the second polycrystalline silicon layer 11 , the first polycrystalline silicon layer 6 , and the oxide layer 5 are etched in turn by the rie process using the patterned resist layer 12 as a mask . the thus formed floating gate 11a consists of the first and the second polycrystalline silicon layers 11 and 6 . then , arsenic ions are implanted to the p - type silicon substrate 1 to form a source region 24 and a drain region 25 . thus , the eeprom can be obtained according to the present invention . fig3 is a cross - sectional view of an mis transistor according to another embodiment of the present invention . an impurity region 7 for adjusting the threshold voltage is formed by implantation of either boron , arsenic or phosphorus ion through the first polycrystalline silicon layer forming the lower layer of the polycrystalline silicon layer 11a and through a gate oxide layer 5 . in the present invention , the electrode material layer is not limited to polycrystalline silicon . refractory metals , such as molybdenum or tungsten and titanium or metal silicide of these metals , may also be used . the first layer electrode material may also be different from the second - layer electrode material . it will be obvious to those skilled in the art that there are many possible modifications and variations of the above described process . these modifications and variations do not depart from the scope of the invention .
| 8 |
[ 0033 ] fig1 shows a schematic diagram to show a property of an annealing method of a magneto - optical disc of the present invention . it shows a sectional view of a magneto - optical disc 3 at the stage where a step of laying on a magneto - optical disc substrate 1 comprising glass or plastic as a material a magnetic layer 2 which includes at least a domain wall displacement layer where the domain wall displaces , a memory layer which holds information as a recording magnetic domain and a switching layer provided between the domain wall displacement layer and the memory layer and having curie temperature lower than those layers has been completed . while any protective layer is still not formed at the stage of fig1 it does not matter whether the protective layer exists when annealing the disc . here , a character d denotes one of the information recording tracks , and the information track is an area which forms a recording magnetic domain to hold the information such as a user data etc . in general , this convex portion provided on the substrate is referred to as a land . magneto - optical disc of fig1 has a constitution in which the light beam for use of forming an anneal track enters from the back side of the substrate where the magnetic layer 2 is not formed . characters a and a ′ which make an information recording track d exist between them denote anneal tracks , which are formed by a laser annealing with a higher light intensity than that at writing an information on the information recording track d . in the present drawing , the anneal tracks a and a ′ serve also as the guide grooves to control the light beam at the center of the information recording track d in the reproduction step . in general , the concave portion provided on the substrate is referred to as a groove . in the present embodiment , the lands ( convex portions ) on the substrate 1 are taken as information recording tracks and the grooves ( concave portions ) as the anneal tracks , but the constitution of the magneto - optical disc is not limited to this . for example , a constitution wherein the lands ( convex portions ) are taken as the anneal tracks and the grooves ( concaves ) are taken as the information recording tracks is also allowable . the laser spots denoted by characters b and b ′ show the converged light beams when annealing anneal tracks a and a ′, which enter from the back of the substrate . in the drawing , the laser spots of b and b ′ are illustrated as if the two points were irradiated at the same time . this is to clarify that the directions of annealing magnetic fields applied to the two anneal tracks which are adjacent to the information recording track are different . characters c and c ′ show the polarities of applied magnetic fields in the case where the anneal tracks a and a ′ are annealed . in the present embodiment , the direction of the applied magnetic field is from one side of the substrate on which the magnetic layer 2 is provided to the other side of the substrate ( i . e ., the back side of the substrate ) when anneal track a is annealed , and the direction of the applied magnetic field is from the back side of the substrate to the side on which the magnetic layer 2 is provided when anneal track a ′ is annealed . in addition , the annealing magnetic fields at the adjacent anneal tracks with the information recording track d made to exist between them have opposed polarities . in order to form the anneal tracks by applying thus annealing magnetic fields perpendicular to the substrate surface , a device as shown in fig2 is suitable . a magneto - optical disc 100 , wherein a magnetic layer 2 is formed on a magneto - optical disc substrate 1 made of glass or plastic and further a protective layer 3 is formed , is held on a spindle motor with a magnetic chucking and the like , and is constituted such that it is rotatable against an axis of rotation . a laser light for forming the anneal track generated from a semiconductor laser light source 7 is changed to a parallel ray by a collimator lens 8 and passes through a beam splitter 9 and is converged by a condenser lens 6 . then a predetermined position of the magneto - optical disc 100 is irradiated with the converged laser light as a beam from the back . note that the condenser lens 6 is driven by a drive actuator 5 . on this occasion , the condenser lens 6 is constituted such that it is controlled by actuator 5 to move in a focusing direction and a tracking direction so that the laser light successively places a focus on the magnetic layer 2 . the condenser lens 6 also moves along the guide groove engraved on the magneto - optical disc . on the other hand , the reflected light which reflected from the surface of magneto - optical disc surface passes through a route in reverse to the incident light and arrives at the beam splitter 11 and is reflected at a right angle and passes through a λ / 2 plate 10 . this λ / 2 plate is a filter to rotate a the reflected light at 90 ° in the polarizing direction of the incident light . further , the reflected light enters the polarized beam splitter 11 and is put into two condenser lenses 12 by the polarity of the magneto - optical disc magnetization of the magneto - optical disc 100 . two pieces of photo sensors 13 detect the intensities of the incident lights which enter the sensors respectively . the detected resultants are amplified respectively by a differential amplification circuit 14 which differentially amplifies the signal converged and detected respectively according to the polarization direction and by a summing amplification circuit 15 which summing - amplifies the signal converged and detected respectively according to the polarization direction . a light magnetic signal and by a summing signal from the differential amplification circuit 14 and the summing amplification circuit 15 are synthesized and binarized by a digital circuit 200 and outputted to a controller 17 . in addition , the number of rotations of the magneto - optical disc , an annealing radius , an annealing sector information and so forth are inputted to controller 17 , and a signal to control an annealing power is outputted to a ld driver 16 . the ld driver 16 irradiates a laser to a substrate 1 under a predetermined condition according to that signal . further , the controller also controls a magnetic head driver 19 at the same time , and outputs a signal which controls the polarity of the annealing magnetization and the like . reference numeral 18 denotes a magnetic head to apply a magnetic field to a laser - irradiated portion of magneto - optical disc 1 when forming an anneal track , and sandwiches the magneto - optical disc 100 and is arranged in a manner that opposes to condenser lens 6 . magnetic head 18 is used to record information and to reproduce it . in the annealing , a semiconductor laser 7 irradiates the ld driver 16 with an anneal laser power and , at the same time , the magnetic head 18 is allowed to generate a perpendicular magnetic field of a polarity corresponding to a polarity signal of a magnetic field applied for annealing an anneal track ( hereinafter referred to as “ annealing applied magnetic field ”) by magnetic head driver 19 . the magnetic head 18 is constituted such that , coupled with an optical head , it moves in the radial direction of the magneto - optical disc 1 and , at the annealing step , applies a magnetic field successively to the laser - irradiated portion of the magneto - optical disc 3 to perform a desired annealing . however , means which reproduces the information from the reflected light from the magneto - optical disc is not necessarily required . such a means is utilized as means to detect a pre - format and the like and to reproduce a magneto - optical signal when controlling a timing to switch the polarity of the annealing applied magnetic field by the reflected light from the magneto - optical disc , or when checking whether a desired property develops in the information recording track or not after the annealing of the anneal track . in the case , a construction where a parameter such as a laser power according to the annealing , an applied magnetic field or the like is changed into a value relative to the recording or reproduction by the controller 17 is required . in the idea of the above described annealing method and the annealing means , the action of annealing the anneal track will be described by using fig3 a to 3 d . fig3 a shows an annealing power on / off signal which shows the start of the annealing , fig3 b shows an applied magnetic field polarity change timing signal which shows a timing to change the polarity of the applied magnetic field , fig3 c shows an applied magnetic field polarity control signal which controller 17 outputs to magnetic head driver 19 , and fig3 d shows a generated magnetic field of magnetic head 18 . an irradiating power of the laser is set to a desired annealing power by an annealing start command from controller 17 . although the annealing power is different depending on a property of the magneto - optical disc , but it is typically about two times that of the recording power . at the same time of the irradiation of the laser power , the annealing magnetic field is applied by the magnetic head 18 . on this occasion , the polarity of the applied annealing magnetic field is allowed to generate the magnetic field of the polarity corresponding to a polarity of the applied magnetic field control signal from the controller 17 . as described below , the absolute value of the magnetic field intensity is preferable to be larger than about 50 oe . in order to execute the property of the present invention , it is necessary to switch the polarity of the applied magnetic field at least more than one time for one cycle , and this switching timing is controlled by an applied magnetic field polarity change timing signal from the controller 17 . the applied magnetic field polarity change timing signal can be formed by counting a clock for rotation control of the spindle and can be also formed by detecting the reflected light such as a phase pit which causes a change of reflectivity embedded in advance in the anneal track of the magneto - optical disc as an applied magnetic field change timing . the later makes it possible to control the magneto - optical disc by higher position accuracy . since the switched portion of the polarity of the annealing applied magnetic field is considered to have adverse effect on the information recording track , the area where the polarity of the annealing applied magnetic field is switched is preferably the area where the adjacent information recording track is not an user data area , for example , preferably a header area which shows a sector position information and the like . further , an applied magnetic field polarity switching area may be specially provided . by these means and processes , it is possible to control the applied magnetic field to a predetermined magnitude and polarity in annealing the anneal tracks adjacent to both sides of the information recording track . examples of the applied magnetic field polarity change timing in a case where the magneto - optical disc is annealed by these means are shown in fig4 and 5 . in fig4 and 5 , reference numeral 41 denotes the anneal track , and reference numeral 42 denotes the information recording track . among the anneal tracks , the hatching portion shown by t has the applied magnetic field at the time of annealing in the upward direction to the plane of the drawing , and among the anneal tracks , the hatching portion shown by f has the applied magnetic field at the time of annealing in the downward direction to the plane of the drawing . in fig4 switching of the polarity of the annealing magnetic field is performed only when the magnetic field - applying means moves to the next anneal track and the switching is one time for one cycle of the anneal track . in contrast to this , in fig5 since the anneal track of one cycle is divided into four continuous magnetic areas , the switching of the polarity of the applied magnetic field is performed five times . the white portion 42 indicates the information recording track in fig5 . the figure shows that the polarities of the annealing magnetic fields in adjacent portions t and f of the recording tracks are reversed . the timing of switching the applied magnetic field is not limited to the above . the gist of the switching is adaptable not only to cav but also to format , of zone cav , clv and zone clv , assuming that the applied magnetic fields at the time of annealing anneal tracks adjacent to both sides of an information track have opposite polarities . the present invention was executed by the device described in fig2 . the device of fig2 applies an annealing magnetic field perpendicular to the magneto - optical disc surface . [ 0054 ] fig6 and 7 show properties in embodiments of the present invention and the comparative examples , as explained below . after completing the formation of the magnetic layer , the annealing of the anneal track was conducted by laser beam under various conditions . in fig6 the ordinate shows a jitter property . the jitter property is better as the value of the jitter property is smaller . the abscissas of fig6 shows applying methods of the magnetic field at the time of annealing the anneal track . described in order from the left side on the axis of the abscissa are the methods ( 1 ) wherein , as comparative example 1 , the applied magnetic fields at both of the anneal tracks adjacent to the information recording track were taken as − 300 oe and were applied to all the anneal tracks the annealing magnetic field of the same polarity at the same magnitude . ( 2 ) wherein , as comparative example 2 , the applied magnetic fields at both of the anneal tracks adjacent to the information recording track were taken as + 300 oe , which was the same as ( 1 ) in annealing magnetic field . ( 3 ) wherein , as comparative example 3 , the applied magnetic fields at both of the anneal tracks adjacent to the information recording track were taken as 0 oe , and the annealing magnetic field was not applied at the time of forming the anneal track . ( 4 ) wherein , as example 1 , the applied magnetic fields at both of the anneal tracks adjacent to the information recording track were inversed in polarity by one cycle interval , and the generated magnetic field was taken as ± 300 oe , which corresponds to fig4 . [ 0062 ] fig7 is the same as fig6 in axis of abscissas , and the axis of ordinates shows a aberration amount of the reproduction signal pulse width in relation to the regular pulse width in the reproduction signal . if the pulse width is near to “ 0 ”, it shows that it is near to the desired pulse width . table 1 shows annealing magnetic field applied conditions and reproduction properties . the pulse widths regarding the three types of the method for applying the annealing magnetic field were estimated . comparative examples 1 and 2 have large aberrations in the reproduction signal pulse width ( fig7 table 1 ). embodiment 1 has the most excellent performance among the four experiments even in pulse width . from the result of these experiments , it is evident that , in the case where the applied magnetic fields at both of the anneal tracks adjacent to the information recording track are inversed at intervals of every one cycle and the generated magnetic field is taken as ± 300 oe , the jitter property is excellent and the pulse width fluctuation is not generated , and it is the most suitable annealing condition among the above described conditions . in this way , the remanent magnetization at the boundary between the anneal track , where , though there is a deterioration of the magnetic property due to the laser annealing of the present invention , the magnetic property is not lost completely , and the information recording track is taken as a predetermined polarity by both of the adjacent anneal tracks which make the information recording track exist between them , so that the influence for the magnetic recording track in the information recording track is offset and the influence can be equalized . in this way , it is possible to provide the magneto - optical disc , which can obtain the reproduction signal of high quality , and further improve the recording density . the remanent magnetization at the time of the above described annealing has been confirmed not to be inversed by a recording power usually used and a recording magnetic field usually used . in fig8 is shown a schematic diagram to show a property of the second embodiment of the annealing method of a magneto - optical disc of the present invention . in the drawing , what is different from embodiment 1 is that a ring head is used , where the magnetic disc 18 , which applies the magnetic field at the time of annealing , can apply the annealing magnetic field in the in - plane direction of the face of the disc to a heated area on the recording medium . in this way , the magnetic field which is parallel to the magneto - optical disc surface can be applied to a heated annealing portion . in the case where the magnetic field is applied to the inside of the magneto - optical disc surface , there exist two directions parallel and perpendicular to the scanning direction of the light beam . in fig9 an example of the annealing applied magnetic field was shown , where the annealing applied magnetic field is in the in - plane direction to the face of the magneto - optical disc and parallel to the light beam scanning direction . in the case where the annealing magnetic field is applied in this direction , it is not necessary to consider the polarity of the magnetic field and it does not matter whether it is the same polarity or different . in fig1 , an example of the annealing applied magnetic field , where the annealing magnetic field is perpendicular in the plane of the face of magneto - optical disc , is shown . in the case of fig1 , when the annealing magnetic field of the reverse polarity is applied , it is necessary to certainly apply the annealing magnetic field of the same polarity since there is a risk of the magnetic field line loop of the remanent magnetization owned by the adjacent anneal tracks being multiplied on the information recording track . as shown in fig9 and 10 , in order to change the polarity of the generated magnetic field to the scanning direction of the light beam , the direction of the ring head of fig8 may be changed 90 °. as already described as above , in fig1 , although the annealing applied magnetic fields have the same polarity , the polarity of the applied magnetic field does not cause any specific problem in the case where the annealing applied magnetic fields are parallel to the light beam scanning direction . further , in the present embodiment , though the ring head was used in order to generate the magnetic field parallel to the magneto - optical disc surface , there is no limit to this , but it does not matter specifically whatever shape it has , provided the magnetic field parallel to the magneto - optical disc surface can be applied to the laser irradiated portion at the time of annealing . in this way , the remanent magnetization at the boundary between the anneal track , where , though there is a deterioration of the magnetic property due to the laser annealing of the present invention , the magnetic property is not lost completely , and the information recording track is directed to the direction of the inside of the magneto - optical disc surface , so that the influence can be reduced for the magnetic area of the perpendicular direction recorded in the information recording track , and it is further possible to equalize the influence . note that the remanent magnetization at the time of the above described annealing is confirmed not to be inversed by the usually used recording power and the recording magnetic field . as described above , the remanent magnetization at the boundary between the anneal track , where , though there is a deterioration of the magnetic property due to the laser annealing of the present invention , the magnetic property is not lost completely , and the information recording track is equalized and the influence of the remanent magnetization is taken as a predetermined polarity by both of the anneal tracks which make the information recording tracks exist between them , so that a bad influence on the information recording track can be offset , and the jitter property and the pulse width fluctuation can be improved . further , the remanent magnetization at the boundary between the anneal track and the information recording track is directed to the direction of the inside of the magneto - optical disc surface , so that the influence for the magnetic area in the perpendicular direction recorded in the information recording track can be equalized . in this way , the reproduction signal having higher quality than that of the conventional method can be obtained . furthermore , since the information recording track width can be made narrower than that of the conventional method , it is possible to further improve the recording density of the magneto - optical disc .
| 8 |
both the dl and meso configurations of compounds i and ii are preferred . they are conveniently prepared by the following scheme . ## str4 ## in words relative to the above scheme , it should be noted that the dl and s , s forms of 8 ( r 1 = ethyloxycarbonyl ; r 7 = methanesulfonate ) and their synthesis from the corresponding butadiene diepoxide are known . in the general scheme of the present invention , the transformation of dl - butadiene diepoxide ( 1 ) to dl - 8 is accomplished by treating 1 with a strong base , such as , a sodium alhoxide or aryloxide , for example , c 6 h 5 ch 2 ona , or the like , in the presence of the alcohol r 5 oh ( r 5 = alkyl , arylkyl ) at a temperature of from 25 ° to 100 ° c . for from 4 to 48 hours . meso - 2is conveniently prepared by treating the suitably protected trans - 2 - butene - 1 , 4 - diol with an oxidant , such as hydrogen peroxide , in formic acid at 40 ° to 60 ° c . for 1 to 6 hours followed by exposure to aqueous base , such as sodium hydrioxide , at 30 ° to 50 ° c . for 0 . 5 to 2 hours . in addition , d or l - 2 are prepared from diethyl d or l - tartrate in a sequence of four steps involving : acetonide formation utilizing the 2 , 3 - diol functionality , lithuim aluminum hydride reduction of the esters to the 1 , 4 - diol , benzl ether formation , and acetonide hydrolysis . the following transformations involving c - 2 and c - 3 are stereospecific . the transformation 2 to 3 is accomplished by treating 2 with an alkyl - or arylkylsulfonyl halide , such as methanesulfonyl chloride , benzenesulfonyl chloride , toluenesulfonyl chloride , or the like in a solvent , such as diethyl ether , thf , methylene chloride with triethylamine , pyridine or dmap , or the like , at a temperature of from 0 ° to 50 ° c . for from 1 to 24 hours . diazide 4 is obtained from 3 on heating with sodium azide in a solvent such as dimethylformamide ( dmf ), dimethyl sulfoxide , n - methyl pyrrolidinone , or the like , at a temperature of from 25 ° to 150 ° c . for from 4 to 48 hours . the reduction 4 to 5 is accomplished by treating 4 with a reducing agent such as lithium aluminum hydride , or the like , in a solvent such as diethyl ether tetrahydrofuran , dioxane , or the like , at a temperature of from 0 ° to 100 ° c . for from 1 to 4 hours . the n - acylation 5 to 6 is accomplished by treating 5 with the acylating agent of choice , and in a sequence and reaction ratio to achieve n - substituent patterns with r 1 , r 2 , r 3 , and r 4 , above defined , of choice according to acylation procedures well known in the art . representative acylating agents include : ethyl chloroformate , methyl chloroformate , acetic anhydride , acetic - formic anhydride , pivaoyl chloride , boc - on ([ 2 -( t - butoxycarbonyloxyimino )- 2 - phenylacetonitrile ]), or the like . the reaction 6 to 7 is typically accomplished by hydrogenation in the presence of a catalysis such as platinum or palladium or carbon in a solvent such ethanol under a pressure of 1 to 4 atmospheres of h 2 at a temperature of from 25 ° to 50 ° c . for from 1 to 6 hours . the transformation 7 to 8 is accomplished by treating 7 with an alkyl - or arylsulfonyl halide , such as methanesulfonyl chloride , benzenesulfonyl chloride , toluenesulfonyl chloride , or the like , in a solvent , such as pyridine or ether , thf , or methylene chloride in the presence of pyridine , et 3 n or dmap , or the like , at a temperature of from 0 ° to 50 ° c . for from 1 to 12 hours . with respect to radical r 6 of 8 , its precise identity depends on the sulfonating agent taken in reaction . the transformation 8 to 9 ## str5 ## is typically accomplished by treating 8 with potassium thioacetate , potassium ethyl xanthate , or the like , in a solvent such as dmf , dmso , n - methyl prrolidinone , ethanol , or the like , at a temperature of from 0 ° to 50 ° c . for from 1 to 12 hours . the deblocking transformation 9 to i is typically achieved by acid hydrolysis with i being isolated as the n - acid addition salt . mild hydrolysis conditions will convert 9 to the dithiol species leaving the n - acyl groups intact . removal of n - acyl functions in addition to conversion to the dithiol form is accomplished under harsher conditions , for example , on refluxing in concentrated aqueous hcl for 6 to 12 hours . conversion of i to the dithiane ii is accomplished by treating i in the presence of strong base in a solvent such as water , methanol , ethanol , isopropanol , or the like for from 1 to 12 hours at 0 ° to 25 ° c . suitable bases include aqueous naoh , naor , na 2 co 3 , or the like . a preferred scheme involves aqueous naoh in the presence of air . ( r = alkyl having 1 - 4 carbon atoms .) n - alkyl derivatives of i are readily prepared from ii by acylation using acetic anhydride or acetic - formic anhydride , or the like , in a solvent , such as pyridine or ether , thf , or methylene chloride in the presence of pyridine , et 3 n , or dmap , or the like , at 0 ° to 50 ° c . for from 1 to 12 hours followed by lithium aluminum hydride reduction . oxidation of the so derivatized i , as described above , then provides n - alkyl derivatives of ii . repetition of this sequence using a different acylating agent in step one allows the preparation of derivatized i and ii carrying two different n - alkyl groups . the compounds of the present invention are useful as antihypertensives . they may be administered orally , parenterally by injection or by rectal suppository . oral administration by tablet or capsule is preferred ; wherein the final dosage form is prepared according to well known practices to ensure timely dissolution and availability . typically the dose is from 0 . 1 to 10 mg per kg of body weight given 1 to 3 times per day . the exact dosage regimen will be at the routine discretion of clinician taking into account the medical and physical history of the subject . the compounds of the present invention also demonstrate an effect against the damaging effects of high energy , ionizing radiation in mammalian tissue . for humans the effective dosage range is 1 - 20 mg / kg body weight . the following examples illustrate , but do not limit the product , process , compositional or method of treatment aspects of the present invention . in the overall scheme for example 1 , the following abbreviations have been used : bzl for ch 2 c 6 h 5 ; ms for ch 3 so 2 ; and ac for ch 3 co . ## str6 ## dl - butadiene diepoxide ( 1 ) ( 49 . 8 g , 0 . 578 mol ) was added dropwise over 30 minutes at 55 °- 85 ° c . to a stirred solution of sodium ( 15 . 5 g , 0 . 674 mol ) in 348 g benzyl alcohol . after the reaction mixture had been stirred at room temperature for 20 hours , it was transferred to a separatory funnel with 500 ml diethyl ether and 1 l aqueous 1n sulfuric acid . the mixture was shaken well and the aqueous layer was removed . the ether extract was washed ( 1 × 500 ml water ), dried ( mgso 4 ) and concentrated . removal of the benzyl alcohol by high vacuum distillation left the diol 2 , 165 g ( 94 %), which was used in the next step without further purification . methanesulfonyl choride ( 185 g , 1 . 61 mol ) was added dropwise over 2 hours and 20 minutes to a stirred , ice - cold solution of threo - 1 , 4 - dibenzyloxy - 2 , 3 - butanediol ( 2 ) ( 163 g , 0 . 539 mol ) in 490 ml pyridine . after being stirred at room temperature for 20 hours , the reaction mixture was poured into 2 . 2 l of 3n aqueous hydrochloric acid . the majority of the aqueous phase was decanted from the oil that separated and was extracted ( 2 × 200 ml ) with chloroform . the oil was dissolved in 250 ml chloroform , separated from what water was present , and combined with the other chloroform extracts . drying ( mgso 4 ) and concentration left an oil which solidified on standing . recrystallization from ethanol gave 3 , 217 g ( 88 %). sodium azide ( 49 . 6 g , 0 . 763 mol ) was added to a solution of threo - 1 , 4 - dibenzyloxy - 2 , 3 - butanediol 2 , 3 - bismethanesulfonate ( 3 ) ( 100 g , 0 . 218 mol ) in 500 ml dimethylformamide . the mixture was heated to 100 ° c . and maintained at that temperature for 8 hours . after cooling to room temperature , the mixture was filtered and the majority of the dimethylformamide was removed under pressure . the residue was extracted with 500 ml diethyl ether . filtration through celite and concentration left crude 4 , 79 . 1 g ( 103 %), which was used in the next step without further purification . a solution of crude threo - 2 , 3 - diazido - 1 , 4 - dibenzyloxybutane ( 4 ) ( 79 . 1 g , max . theory 0 . 218 mol ) in 200 ml dry diethyl ether was added dropwise over 3 hours to a stirred suspension of lithium aluminum hydride ( 16 . 5 g , 0 . 435 mol ) in 1500 ml dry diethyl ether . after refluxing an additional hour , the mixture was cooled in ice and the excess lithium aluminum hydride was destroyed by cautiously adding water . the ether filtrate obtained after filtration through celite was dried ( mgso 4 ) and concentrated to leave 5 , 59 . 8 g ( 91 % from 3 ). the material was used in the next step without further purification . ethyl chloroformate ( 34 . 0 g , 0 . 314 mol ) was added dropwise over 25 minutes to a stirred , ice - cold mixture of threo - 2 , 3 - diamino - 1 , 4 - dibenzyloxybutane ( 5 ) ( 30 . 0 g , 0 . 100 mol ), 21 g sodium hydroxide , and 300 ml water . after 3 hours on ice , 30 ml of concentrated hydrochloric acid was added slowly and the mixture was extracted ( 3 × 200 ml ) with diethyl ether . drying ( mgso 4 ) and concentration left 6 , 44 . 0 g ( 99 %), which was used in the next step without further purification . a mixture of threo - n , n &# 39 ;- dicarbethoxy - 2 , 3 - diamino - 1 , 4 - dibenzyloxybutane ( 6 ) ( 44 . 0 g , 0 . 100 mol ), 400 ml absolute ethanol , 20 ml concentrated hydrochloric acid , and 2 . 0 g 10 % palladium on carbon was placed in a 1 l bomb and stirred under 40 psi hydrogen for 2 . 5 hours . after removal of the catalyst by filtration through celite , the filtrate was concentrated and the residue was twice taken up in 200 ml chloroform and concentrated to remove trace ethanol . crude 7 , 26 . 9 g ( 100 %), was left as a pale yellow oil and was used in the next step without further purification . methanesulfonyl chloride ( 34 . 4 g , 0 . 300 mol ) was added dropwise over 45 minutes to a stirred , ice - cold solution of threo - n , n &# 39 ;- dicarbethoxy - 2 , 3 - diamino - 1 , 4 - butanediol ( 7 ) ( 26 . 4 g , 0 . 100 mol ) in 130 ml pyridine . after having stirred in ice for 1 hour , 200 ml chloroform was added followed by 410 ml 4n aqueous hydrochloric acid . the mixture was transferred to a separatory funnel , the organic phase was separated , and the aqueous portion was extracted ( 2 × 100 ml ) with chloroform . the combined organic extracts were washed ( 2 × 50 ml ) with 1n aqueous hydrochloric acid and ( 1 × 100 ml ) brine , dried ( mgso 4 ), and concentrated to leave 38 g crude 8 . after triturating with 100 ml absolute ethanol and filtrating , the filter cake was washed with diethyl ether and dried in vacuo to leave 8 , 26 . 1 g ( 62 %), of sufficient purity to be used in the next step . a mixture of threo - n , n &# 39 ;- dicarbethoxy - 2 , 3 - diamino - 1 , 4 - butanediol 4 , 4 - bismethanesulfonate ( 8 ) ( 2 . 28 g , 5 . 43 mmol ) and potassium thioacetate ( 1 . 55 g , 13 . 6 mmol ) in 85 ml of dimethyl - formamide was stirred at room temperature for 15 hours . the majority of the dimethyl - formamide was removed under reduced pressure and the residue was taken up in 50 ml of water and extracted ( 3 × 40 ml ) with chloroform . the combined extracts were dried ( mgso 4 ) and concentrated to leave a residue which was chromatographed ( waters prep 500a , one silica cartridge , 30 % ethyl acetate / hexane ) to provide pure 9 , 1 . 45 g ( 70 %); m . p . 94 °- 97 ° c . a solution of threo - 1 , 2 - dimethylmercaptoethylene dicarbamic acid diethyl ester diacetate ( 9 ) ( 1 . 67 g , 4 . 39 mmol ) in 150 ml of concentrated hydrochloric acid was refluxed under nitrogen for 18 hours . the reaction mixture was evaporated to dryness under reduced pressure and trace water was removed azeotropically with benzene . the residue was recrystallized from methanol / benzene with charcoal treatment to provide 10 , 400 mg ( 41 %). a second crop of less pure material weighing 330 mg was obtained by concentrating the filtrate . a solution of threo - 1 , 2 - dimethylmercaptoethylene dicarbamic acid diethyl ester diacetate ( 9 ) ( 1 . 06 g , 2 . 79 mmol ) in 75 ml of saturated ethanolic hydrogen chloride was refluxed under nitrogen for 12 hours . the mixture was evaporated to dryness and trace ethanol was removed azeotropically with benzene . the residue was flash chromatographed ( 20 mm × 6 in bed of 0 . 040 - 0 . 063 mm silica gel , 1 % methanol / chloroform ) to provide pure 11 , 540 mg ( 65 %); m . p . 107 °- 109 ° c . air was bubbled through a stirred solution of threo - 1 , 2 - dimethylmercaptoethylene dicarbamic acid diethyl ester ( 11 ) ( 1 . 54 g , 5 . 23 mmol ) in 9 ml of 2n aqueous sodium hydroxide for 18 hours . the mixture was diluted with 400 ml of cold water and precipitate was collected by filtration to provide 980 mg of crude product . recrystallization from ethyl acetate / hexane gave pure 12 , 650 mg ( 42 %); m . p . 180 °- 182 ° c . following the foregoing example 1 and text , the compounds of example 2 , table 1 , are prepared by analogy . departures from established procedure are indicated under the heading &# 34 ; remarks &# 34 ;: table 1______________________________________no . compound remarks______________________________________iii ## str18 ## ( meso ) prepared from meso - 2 obtained by the trans hydroxylation of trans - 1 , 4 - dibenzyloxy - 2 - butene . iv ## str19 ## ( d ) prepared from d - 2 derived from d - diethyl tartrate as described in text . ## str20 ## ( l ) prepared from l - 2 derived from l - diethyl tartrate as described in text . vi ## str21 ## ( dl ) obtained by the substitution of acetic anhydride in step e . vii ## str22 ## ( dl ) obtained by the formulation of ii ( r . sup . 1 = h ) with acetic - formic anhydride followed by lithium aluminum hydride reduction . viii ## str23 ## ( dl ) obtained by the acetylation of the oxidized form of vii with acetic anhydride followed by lithium aluminum hydride reduction . ______________________________________ it is understood that the meso , d , and l isomers of compounds vi - viii are prepared by analogy . a dry solid pharmaceutical composition is prepared by mixing the following materials together in the proportions by weight specified : the dry composition is thoroughly blended , and tablets are punched from the resulting mixture , each tablet being of such size that it contains 100 mg of the active ingredient . other tablets are also prepared in a manner containing 10 , 25 , and 200 mg of active ingredient , respectively , by using an appropriate quantity by weight of the active in each case . a dry solid pharmaceutical composition is prepared by combining the following materials together in the weight proportions indicated below : the dried solid mixture is thoroughly mixed until uniform in composition . the powdered product is then used to fill soft elastic and hard - gelatin capsules so as to provide capsules containing 200 mg of the active ingredient .
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the main feature of the current invention is that the more subtle side effects of gut acidity resulting from starch and / or sugar fermentation were previously unknown . the present invention reveals the link between the fermentation of starch and / or sugars in the gastro intestinal tract , low ph and a range of conditions including adverse behaviour , diarrhoea , skin disorders and infections of the hind gut associated with acidic conditions . there is significant variability between individual humans and between individual animals within any species in the efficiency and extent to which different sugars , starches , non - starch polysaccharides and other carbohydrates are digested in the acidic stomach and absorbed from the small intestine . particularly in young animals and humans and in aging humans and animals there may be deficiencies in the gut enzymes responsible for the break down of disaccharides , starches and / or non - starch polysaccharides . there can also be deficiencies in active absorption of sugars from the intestine . these abnormalities can lead to high levels of readily fermentable carbohydrate entering the hind gut . in addition , when there is a sudden change in diet involving the introduction of starch or other fermentable carbohydrate which has not previously been in the diet or which has been in the diet at very much lower amounts , the appropriate endogenous enzymes may not be present in sufficient quantities and / or active absorption mechanisms for simple sugars may not be developed to efficiently digest and absorb all readily fermentable carbohydrate . this may also lead to high levels of fermentable carbohydrate entering the hind gut . there can therefore be considerable variation between individuals in the nature and in the amount of fermentable substrate reaching the hind gut . it is known that some humans , and particularly children , develop adverse behaviour patterns following consumption of particular foods such as those containing sugars and or processed starch . it is also known that animals such as horses develop adverse behaviour such as eating their bedding , coprophagy , chewing wood , and being highly excitable when they consume high levels of cereal grain containing starch . piglets and other animals may develop behavioural problems of chewing tails and &# 34 ; boredom &# 34 ; when they are fed diets based on cereal grain for rapid growth rate and production . poultry can also develop adverse behavioural patterns such as vent pecking and cannibalism when on high grain diets . diarrhoea can be a major problem for all species as it leads to the loss of minerals and electrolytes . it is also a condition which is inconvenient and embarrassing for humans and / or for dogs which are kept indoors . the reason for chronic diarrhoea is often unknown in many situations where clinical disease conditions are not diagnosed . horses on high levels of grain or grazing lush green pasture are given daily doses of virginiamycin , or any other antibiotic compound with a similar or better effect on fermentation and digestion , formulated to reach and mix with the contents of the caecum in order to stop the animal from chewing the wooden rails of the stables and / or those surrounding the paddock and to make the animal easier to handle and more pleasant to ride . piglets are fed diets including virginiamycin , and / or any other antibiotic compound with or without clay and enzyme preparations in order reduce the incidence of tail biting . cattle entering a feedlot and given high levels of grain are fed the concentrate part of the diet containing virginiamycin , or any other antibiotic compound with a similar or better effect on fermentation and digestion , to improve their feeding behaviour and reduce signs of stress and reduce diarrhoea . children displaying hyperactivity and / or attention deficit disorder and / or another conditions or behavioural trait related to intake of a particular sugar , starch or other dietary ingredient containing fermentable carbohydrate are even thiopeptin , or any other antibiotic compound with a similar or better effect on fermentation and digestion , to control fermentation and digestion and restore normal behaviour . compounds such as exogenous enzyme preparations may be consumed with particular foods in order to assist their digestion prior to hind gut fermentation and acid formation . the use of antibiotic feed additives can also be included in order to provide further protection against acidic fermentation in the hind gut in conjunction with food and drinks specially prepared for children with particular problems associated with hyperactivity or other behavioural problems associated with the intake of readily fermentable carbohydrates . there are numerous recorded examples of skin conditions such as psoriasis which respond to changes in the amount and type of carbohydrate consumed . the fermentation and the subsequent acid build up which leads to these conditions are unknown subtle effects of sub - clinical hind gut acidosis . treatment of these conditions involves the administration of an effective antibiotic compound , such as virginiamycin , active against the gram positive bacteria which produce such acid . antibiotic treatment to control acidic fermentation can be used on its own or in conjunction with exogenous enzyme preparations . enzyme preparations may be effective on their own when used with specific feeds or in situations where specific digestive and absorptive deficiencies are known . infections of the hind gut such as wine dysentry can be controlled by preventing acidic conditions in the gut as a result of rapid fermentation of dietary carbohydrates . the use of enzymes to increase the efficiency and extent of starch and other carbohydrate digestion prior to the hind gut may be used as an alternative or an adjunct to the use of antibiotics and / or changing the form of carbohydrate portion of the diet in order to control these hind gut pathogens . the invention will now be described in greater detail by reference to specific examples . the horse was chosen as the primary example for the demonstration of the behavioural ap sects of this invention . the horse has a digestive system similar to many monogastric omnivores such as man , pigs , dogs , poultry etc . it has a hind out which is larger , in proportion to body size , than these other species . eighteen mature standardbred horses were selected on the basis that they showed no signs of lameness and that they had no obvious unusual behavioral characteristics . they were assigned at random to one of three treatment groups ( 6 per treatment ) summarised in table 1 . table 1______________________________________feed intake ( kg / d ) of horses fed hay alone , or hay with increasinglevels of grain - based pellet with or withoutthe addition of virginiamycin ( as founderguard ) week 1 week 2 week 3 week 4treatment group hay hay grain hay grain hay grain______________________________________hay only 8 8 8 8hay and grain 8 6 2 4 4 2 6hay and grain with 8 6 2 4 4 2 6founderguard______________________________________ * founderguard contains virginiamycin at a rate of 1 % and was administered to provide 5 g founderguard / 100 kg liveweight . the &# 34 ; grain &# 34 ; portion of the diet consisted of a pellet containing : wheat ( 72 %); soybean ( 15 %); lupin ( 10 %) and minerals / vitamins ( 3 %). the hay was fed in the long form ( not chaffed ). all animals ate all of the feed offered in two equal feeds in the morning and afternoon . for the week before the experiment started , all of the horses were observed daily when grazing as a single group to determine if there were any abnormal ( background ) behavioural patterns . the horses were then brought into a stable complex with a high overhead walk way from which all of the animals could be observed without being disturbed . behaviour was observed and quantified during a 1 hour session each morning before feeding and a 1 hour session each evening after feeding . every aspect of behaviour was accurately defined before the experiment started and each incident of every type of behaviour was recorded during the periods of observation . in addition to the observations while the animals were in their stalls they were exercised each day and examined for any signs of lameness . samples of faecal material were taken for analysis or ph . blood samples were also taken for measuring ph , blood gas concentrations and lactic acid . the animals were weighed each day . at the end of the experiment all animals were humanely slaughtered in order to take samples of the digestive tract . during this process the digestive tract was weighed . there were marked changes in the behaviour of horses fed increasing levels of grain without founderguard ( fig1 ). during the same time the behaviour of the horses maintained on hay only remained normal indicating that the development of abnormal behaviour was a result of change in diet rather than boredom at being housed in a stable . the behaviour of horses fed grain with founderguard was marginally , but not significantly different from those fed hay . in animals fed grain without founderguard there was a significant decreased in faecal ph with increasing levels of grain in the diet . the faecal ph of horses fed grain with founderguard was similar to those fed hay ( fig2 ). the incidence of adverse behaviour was closely related to faecal ph ( r 2 = 0 . 96 ) ( see fig3 ). with more acidic conditions in the hind gut as indicated by reduced faecal ph , there was a far greater incidence of adverse behaviour . when the horses were weighed each day they were also observed in the yards . all horses seen to be rearing and or kicking during the last week of feeding were identified as being in the group fed grain only . none of the animals fed grain with virginiamycin or hay on it &# 39 ; s own were observed to have this type of behaviour . although the animals fed grain consumed higher levels of digestible energy there was an average weight loss of around 7 kg compared to the horses fed only hay . this difference in liveweight was not statistically significant but the corresponding reduction in the weight of the gut of around 20 kg , in horses fed increasing levels of grain relative to hay , was highly significant . table 2 shows that it was not an empty gut feeling that caused hunger and / or boredom which initiated the abnormal behavioural patterns since both groups of horses which were fed grain had similar changes in the gut weight . table 2______________________________________summary of changes in liveweight of horses during the final 3 weeksof the experimental period and the weight of the gastrointestinal tractat the end of the experiment . grain grain + hay only fg * signif ( p ) ______________________________________average weight change ( kg / 21 d ) 0 . 7 - 7 . 0 - 7 . 5 0 . 2weight of gut ( kg ) 86 63 68 0 . 0002weight of gut as % of live weight 18 13 15 0 . 0001______________________________________ * fg = founderguard contains virginiamycin at a rate of 1 % and was administered to provide 5 g founderguard / 100 kg liveweight . many of the effects of feeding grain to horses are complicated by the fact that there is normally an increase in the amount of digestible energy intake , a reduction in the amount of bulk consumed and a different pattern of fermentation and digestion within the cut . the use of virginiamycin ( as founderguard ) allows us to demonstrate the effects of acid build up in the gut without any confounding factors such as the amount of energy available or the physical nature of the diet when changing from long fibrous roughage to grains or pelleted feed . the results of these studies therefore indicate that the adverse effects of behaviour changes , associated with feeding cereal grain were a direct effect of increased gut acidity due to fermentative digestion and that this problem can be overcome by controlling the build up of acidity in the hind gut . in this study the control of acidity was achieved using virginiamycin . similar effects can be expected with the use of appropriate exogenous enzyme preparations to enhance starch and sugar digestion and thereby reduce hind gut fermentation and the build up of acidity . the use of a combination of enzymes and antibiotic would also be efficacious . a thoroughbred gelding being fed grain supplements in preparation for a show riding event developed behavioural characteristics which made it very hard to handle and ride . before riding the horse it was necessary to lunge the animal for approximately 30 minutes to overcome its urge to buck the rider off . following administration of virginiamycin in the form of founderguard for 1 week it was then possible to ride the horse without any of the adverse behavioural effect such as bucking . the rider reported the horse to be more manageable and far easier to handle . experiments 1 and 2 show that behavioural changes associated with high grain diets in horses can be prevented or reversed through using virginiamycin as founderguard to control gut acidosis . this link between the use of virginiamycin and behavioural changes is completely novel . experiment 3 provides an example of how a number of riders have identified significant changes in the behaviour of horses following treatment with virginiamycin . two paddocks were leased for the experiment on a property in the black mountain area between armidale and guyra , nsw , australia . the rainfall in this area is normally reliable and this factor together with the high altitude 1250 m and the rich basaltic soils were considered to provide a good combination of conditions for the production of pasture with high levels of soluble carbohydrate . conditions for high carbohydrate levels characterised by warm clear days , which facilitate rapid photosynthesis during the day , followed by cold nights . the low night temperatures slow down the process of respiration and retard the break down of carbohydrates . good soil moisture and soil fertility are also important to achieve rapid growth and optimal photosynthetic activity . one paddock was approximately 25 ha and the other around 12 ha . twenty five mature female ponies were selected for the experiment and were identified with numbered tags secured around the neck with a strap and buckle . 20 ponies were selected on the basis of uniform size and signs of fatness ( rib cover and cresting of the neck ). ten of these animals were given founderguard ( 1 % virginiamycin ) at the rate of 5 g / 100 kg live weight by feeding them individually in a race . at the same time a rectal sample of faecal material was taken from each animal for assessment of consistency and for measurement of ph . subsamples were taken for analysis of dry matter , lactic acid and volatile fatty acid concentrations . these subsamples were placed in plastic bags in ice for transport to the laboratory and were then kept at - 20 ° c . prior to analysis . samples of pasture were taken by plucking grass and clover plants in a way which was designed to simulate grazing selection . these samples were also transported back to the laboratory in plastic bags in ice and then stored at - 20 ° c . prior to drying ( 55 ° c .) for analysis of dry matter and soluble carbohydrate content . this experimental period of daily treatment with founderguard and faecal and pasture sampling was continued for a further week . there was a significant ( p & lt ; 0 . 001 ) effect on faecal ph ( fig4 ) and faecal consistency ( fig5 ) as a result of treatment with founderguard . founderguard increased faecal ph by an average of 0 . 1 ph unit which is equivalent to a difference between treatments of 25 % in the concentration of h + ions in faecal material . the difference between treatment groups in the acidity of the faecal material was explained by differences in the concentrations of both lactic and volatile fatty acids ( vfa ). the concentrations of lactic acid . vfa and the proportions of the different acids are summarised in table 3 . there was twice the concentration of vfa in the faecal material of horses without founderguard ( p & lt ; 0 . 001 ). although there was around three times as much lactic acid in horses without founderguard this difference was not significantly different due to the considerable variation between horses in the concentration of lactic acid . there was a significant correlation between faecal ph and faecal consistency ( p & lt ; 0 . 01 ) r 2 = 0 . 151 . table 3______________________________________dry matter content , ph and concentrations of volatile fatty acids ( vfa ) and lactate in faecal samples taken on day 3 of the trial . control founderguard sign mean se mean se p______________________________________dry matter (%) 16 . 6 0 . 6 17 . 1 0 . 9 nslactate mmol / g dm 18 9 . 7 5 3 . 0 nsvfa mmol / g dm 551 37 . 0 257 25 . 6 *** total acid 569 42 . 6 262 26 . 6 ***% acetate 78 0 . 9 75 2 . 3 ns % propionate 11 1 . 2 15 1 . 5 ns % butyrate 5 0 . 3 5 0 . 6 nsph ( day 3 ) 6 . 41 0 . 015 6 . 61 0 . 015 * ______________________________________ the results show that even under conditions which would be considered normal the faecal ph can be lower than ideal and faecal consistency is related to reduced faecal ph . it is very interesting that under these conditions founderguard still has a highly significant effect on faecal ph through reducing the concentrations of acids . soluble carbohydrate and starch entering the hind gut will be rapidly fermented to produce of vfa and lactic acid . the accumulation of acids in the gut in turn increase the rate of flow of digesta and this brings more undigested carbohydrate into the hind gut for fermentation . this cycle is likely to cause chronic acidosis of the hind gut and a pattern of digestion which could be dangerous under conditions of rapidly rising levels of soluble carbohydrate in the diet . in this experiment the levels of soluble carbohydrate in both grasses and clover increased by around threefold in the space of 1 or 2 days and reached concentrations of around 30 % of dry matter . this sudden change in the composition of pasture species is similar to a sudden increase in the amount of starch fed as cereal grain . in horses consuming around 10 kg of pasture dry matter per day 30 % of soluble carbohydrate represents 3 kg of sugars which is equivalent to around 4 kg of barley or wheat . while it is likely that a lot of sugars are digested and absorbed prior to reaching the hind gut there is almost certainly incomplete digestion in the small intestine due to rapid passage of digesta during the intake of large quantities of fresh plant material . there is also likely to be limited capacity of enzyme systems for handling sugars in the small intestine when the dietary conditions change suddenly . the effect of founderguard on faecal ph and the concentration of acids in faecal material is a very interesting and important finding . it is possible that part of the effect of founderguard is to reduce the overall extent of fermentation and digestion but this has not been shown to be significant in monogastric or ruminant animals . the major effect of founderguard is more likely to be due to the specific action of virginiamycin in controlling proliferation of the gram positive lactic acid producing organisms in the hind gut . exogenous enzyme preparations may assist by improving digestion of carbohydrate in the small intestine and reduce the extent of acidic fermentation in the hind gut . in this way antibiotics and enzymes may be used independently or together . the aim of this study was to investigate behavioural changes in race horses on high grain diets with or without founderguard . this experiment introduces the link between faecal consistency , low ph and the control of both of these conditions with virginiamycin to prevent acid accumulation . sixteen trainers in the perth district agreed to select one horse from their stables for the trial . selection was on the basis of the horse being fed high levels of grain and considered to have some behavioural problems such as being difficult to handle , excitable and unpredictable . a placebo batch of founderguard was manufactured which was indistinguishable from the medicated product . the placebo and medicated product ( 1 % virginiamycin ) were packed into identical buckets and were labelled either with letters or numbered in a random way . the labelling code was not known by the person organising the trial who was provided with 16 pairs of buckets , each pair included placebo and active product . each trainer was given one bucket for a two week period and then the second bucket for a further two week period . neither the trainer nor the person organising the trial had any knowledge of which bucket contained the active founderguard ( 1 % virginiamycin ). trainers were asked to record any incident of tying up or any other abnormal development in the health and welfare of the animals involved in the trial . the behaviour of each horse was assessed prior to the start of the trial and at least once during each two week period by both trainer and the veterinarian conducting the trial . in addition the trainers , riders and strappers were asked if they observed any change in behaviour or any adverse effects when the horses were on either of the treatments . there were no veterinary problems or incidents of tying up recorded during the trial period in any of the horses . there was a very wide range in the behavioural idiosyncrasies of individual horses . the best measure was the overall opinion of trainers , veterinarian , riders and strappers as to whether behaviour had improved , got worse , or there was no change when founderguard was given , compared to when the placebo was administered . in cases where there was a range of opinions as to whether any change had taken place this was recorded as no chance . there was always better agreement and more uniformity in rankings involving improved behaviour than there was in assessments involving worse behaviour . ______________________________________response to founderguard number of horses______________________________________no change 5worse 2improved 9______________________________________ the data were analysed using a paired t - test by assigning values of 0 for no change - 1 worse and 1 for improved and were compared against 0 as the control behaviour on placebo . this analysis indicates a significant ( p = 0 . 029 ) improvement in behaviour and handling as a result of using founderguard . the effect of founderguard on behaviour is consistent with the observations of several prominent hack riders who have tried founderguard during the preparation of horses for competition . experiment 5 and 6 demonstrate the efficacy of virginiamycin in controlling diarrhoea in the dog . a golden retriever dog ( approx 43 kg ) with a long history of sporadic diarrhoea was used in an experiment over a period of 12 months . throughout the experimental period the dog was treated with ivermectin in the form of monthly chewable tablets ( merck sharp and dohme ) against heart worm . several dietary regimes and the use of virginiamycin were investigated as a means of controlling hind gut fermentation and the development of acidic conditions in the caecum and colon . pelleted or extruded dog food contains significant levels of cereal grain and starch , mainly in the form of wheat . tinned wet dog food also contains cereal grain . the dog was fed a diet based on either extruded pellets or a mixture of pellets and tinned food for a period of around 18 months prior to the start of the experimental period and faeces during this time were continually soft and unformed with occasional episodes of severe diarrhoea . an investigation of parasitic infection during an episode of diarrhoea indicated nil infection and this was ruled out as a cause of the diarrhoea . no veterinary explanation was available as to the cause of the soft unformed faeces and the episodes of diarrhoea . during the experimental period the diet was changed in a number of ways and treatment with virginiamycin was investigated as a means of controlling the diarrhoea through its effect on fermentation and hind gut acid concentration . the dietary regimes tested and the results are summarised in table 4 . table 4______________________________________dietary treatmentsand their effect on faecal consistency in a golden retriever______________________________________dogboiled rice faeces normally well formed . several incidents of mild diarrhoea . boiled rice faeces well formed and normal . no diarrhoea . and virginiamycinpelleted dog food faeces nearly always soft and unformed . numerous episodes of severe diarrhoea . pelleted dog faeces normally well formed and very rare incidentsfood with of mild diarrhoea . severe diarrhoea whenvirginiamycin virginiamycin accidentally excluded even for short periods . tinned dog food faeces normally soft . only occasional episodes of mild diarrhoea . tinned dog faeces well formed and normal . no diarrhoea . food withvirginiamycinboiled rice faeces normally well formed and normal . occasionaltinned dog food soft faeces and isolated incidents of mild diarrhoea . boiled rice faeces well formed and normal . no diarrhoea . and tinned dogfood withvirginiamycin______________________________________ the dog food were commercial products . the tinned dog food was ` chum ` and the pelleted / extruded dry feed was ` pal `. both products were supplied by uncle ben &# 39 ; s of australia ( kelly street wadonga , victoria 3690 australia ). each treatment was given until there was a clear change in faecal consistency . the treatments were repeated in a randomised design throughout the year . the results are summarised above . virginiamycin was given to a commercial kennel where there was a history of some dogs developing diarrhoea when they first arrived . a number of dogs were treated with virginiamycin at a dose rate of approximately 0 . 4 mg / kg liveweight per day when they developed diarrhoea on arrival at the kennel . these animals all returned to passing normal faeces within 48 hours after first treatment and treatment was stopped after three days . experiment 7 provides further evidence that starch passing undigested to the hind gut is the principle cause of the build up of acid and diarrhoea . piglets were fed diets based on either boiled rice or wheat with a protein supplement based on meat meal . all animals were fed the experimental diets for 4 weeks before being slaughtered at 8 weeks of age . samples of digesta were analysed for ph , dry matter and the concentrations of volatile fatty acids . the dry matter content and the ph of the faeces was significantly higher in the case of pigs fed diets based on boiled rice than those fed wheat - based diets . in this study , the piglets were also challenged with an articial infection of serpulina hyodysenteriae oral administration of the bacteria which produces swine dysentry . the results are summarised in fig6 . these show that there is a very good relationship between acidity in the gut ( ph ) and the dry matter content of the digesta . this relationship changes between diets but within each diet variation in ph explains between 80 and 90 % of the variation in dry matter content . the results also indicate that the difference between diets in the faecal dry matter content can largely be explained by the acidity of the digesta . the average concentration of volatile fatty acids in the colon of pigs fed wheat was 32 . 9 mmol / l compared to 12 . 7 mmol / l in those fed boiled rice . this is one of the major reasons for the difference in ph and dry matter content of digesta and faecal material between the two diets . the change in the source of carbohydrate from wheat to boiled rice prevented the establishment of swine dysentry disease . one of the main differences between wheat and rice is in the non - starch polysaccharides . wheat has much higher levels of non - starch polysaccharides than rice and this reduces the amount of carbohydrate digested and absorbed in the intestines . there is therefore more fermentation of carbohydrate in the large intestines ( hind gut ) and this leads to more accumulation of acids lower ph and lower dry matter content . the use of enzymes to overcome the adverse effects on starch digestion associated with cereal based diets such as wheat , barley and rye , prevents the development of acidic conditions in the hind gut and provides a new way of preventing hind gut diseases such as swine dysentry where the pathogens rely on an acidic environment to establish a competive advantage . experiment 8 provides evidence of the effect of a sudden chance in the source of dietary starch in the human diet on the incidence of diarrhoea . it is common for visitors to mexico to develop diarrhoea shortly after arrival from other countries . it is generally believed that this is a result of poor hygiene . two volunteers , one male and one female around 25 years of age and in perfect health entered mexico to visit merida ( yucatan ) on three separate occasions over period of 18 months from the dominican republic where they were semi - permanent residents . each visit lasted between 10 and 16 days . both the dominican republic and mexico are tropical countries and there is a similar standard of hygiene and standard of living . during each visit the subjects meticulously maintained similar standards of hygiene . when they were not directly responsible for food preparation themselves they ensured that standards of hygiene were in food preparation were to their normal standards . on each visit to mexico both subjects developed chronic diarrhoea for a period of at least one week after which time faecal consistency slowly returned to normal . the major difference in the diet of the subjects was in the source and amount of carbohydrate consumed . in the dominican republic the main source of dietary carbohydrate was wheat ( bread ) and root vegetables such as cassava and sweet potato . in mexico the main source of carbohydrate was maize ( tacos , tortillas etc ). in addition , carbohydrate made up a far greater proportion of the diet in mexico than it did in the dominican republic . it was concluded that the change to high levels of maize in the diet resulted in fermentable carbohydrate passing to the hindgut and that the diarrhoea was of an osmotic nature , from high levels of acid in the hind gut , rather than secretory diarrhoea from the establishment of pathogenic bacteria in the intestine . it is likely that this form of diarrhoea , resulting from excessive hind gut fermentation , can be controlled by antibiotic feed additives such as virginiamycin . exogenous enzyme preparations may also be effective in increasing the digestion of maize starch until the endogenous systems adapt . again antibiotic additives or enzymes can be used independently or together . the presence of β - glucans in cereal grain are known to be responsible for lower nutritive value of grains such as barley . the use of exogenous β - glucanase enzyme is described in this experiment to improve the digestion and absorption of starch before it reaches the hind gut in broiler chickens . broiler chickens were fed diets based on maize or barley grain to supply 60 % of the feed consumed . half of the chickens on each basal diet were given β - glucanase enzyme at a rate of 0 . 129 g enzyme premix per kg of diet dry matter . this was administered by mixing the enzyme into the diet . weight gain in chicks fed barley diets without β - glucanase enzyme were lower than those fed maize or barley with β - glucanase enzyme . the inclusion of β - glucanase enzyme in the barley diets significantly ( p & lt ; 0 . 001 ) improved the digestibility and absorption of starch ( table 5 ). table 5______________________________________pre - ileal digestion of starch (%) in broiler chicks fed diets based onmaize or barley grain with or without the inclusion of β - glucanaseenzyme at 0 or 0 . 129 g / kg dry feed ( from : m . almirall , j . brufau , e . esteve - garcia ( 1993 ) in : enzymes inanimal nutrition ( institut fur nutztierwissenschaften , zurich ) grain type β - glucanase enzyme pre - ileal starch digestion______________________________________maize 0 96maize 0 . 129 94barley 0 89barley 0 . 129 96______________________________________ bentonite , kaolinite , zeolite and other types of clays are able to bind ions reversible and can have a significant effect on ph during fermentation in the gastrointestinal tract . the ability of these clays to absorb ions means that their inclusion in a diet can reduce the osmolarity in the gastrointestinal tract . an experiment was conducted involving the inclusion of bentonite clay in the diets of lambs from weaning at 17 . 5 kg to slaughter at 37 kg . the basal diet consisted of 78 % barley , 16 % soybean 5 % wheat bran and 1 % minerals and vitamins . bentonite was given at a rate of 20kg / tonne of feed , replacing barley , and was administered by mixing with the diet . there was a consistently higher rumen ph in lambs given the diet containing bentonite . the results are summarised in table 6 . similar results are achieved with clays such as kaolinite and zeolites . table 6______________________________________rumen ph and ammonia concentrations of lambs given diets based onbarley with or without bentonite at a concentration of 2 kg / tonneof feed . ( from s . economides , e . georghiades andm . hadjipanayiotou ( 1987 ). effects of bentonite feeding on the pre - and post - weaning performance of chios ewes and lambs ari , cyprus ) parameter without bentonite with bentonite______________________________________rumen ph 5 . 97 5 . 72rumen ammonia ( mg / l ) 97 122______________________________________ the extrapolation of these findings to other species is logical since the same pattern of digestion and fermentation occurs in practically all animals including humans . there are parts of the digestive tract which are designed to support neutral ph and fermentation and there are other compartments which are designed for acid digestion . all species have the capacity for fermentation either prior to the acidic digestion or following acidic digestion and intestinal absorption . the invention therefore extends to any animal , including humans , where the fermentation of starch or sugar occurs in the gastro intestinal tract . in humans , pigs and horses , this fermentation occurs in the hind gut ( caecum and colon ). the present invention makes use of a method for the treatment or prophylaxis of adverse behaviour , diarrhoea , a skin disorder or an infection of the hind gut resulting from the accumulation of acid in the gastrointestinal tract of a human or an animal , said accumulation resulting from the fermentation of carbohydrate in the gastrointestinal tract of said human or animal , which method comprises administering to said human or animal an effective amount of an agent capable of preventing or controlling fermentative acidosis in the gastrointestinal tract .
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the feed starch sugar solution usable in the present invention may be almost any substantially - ketose - free solution of aldoses derived from starch . such a feed solution results in a high - maltose fraction ; and with a maltose content of 90 %, typically 93 % or higher , in a high yield when subjected to the fractionation according to the present invention . for example , feed starch sugar solution may be a saccharified starch solution obtained by subjecting starch to the actions of starch - degrading enzymes , e . g ., α - and α - amylases , and starch - debranching enzyme , or may be an aqueous solution of a commercially - available starch sugar product having a maltose content of at least 70 %. the strongly - acidic cation exchange resin of alkali metal - or alkaline earth metal - form usable in the invention may be , for example , one or more members of styrene - divinylbenzene copolymer resins bearing sulphonyl groups of alkali metal - or alkaline earth metal - form , such as na + , k + , ca 2 + , or mg 2 + . commercially - available resins are , for example , &# 34 ; dowex 50wx2 &# 34 ;, &# 34 ; dowex 50wx4 &# 34 ;, and &# 34 ; dowex 50wx8 &# 34 ;, products of dow chemical company , midland , mich ., u . s . a ., &# 34 ; amberlite cg - 120 &# 34 ;, a product of rohm & amp ; haas company , philadelphia , pa . , u . s . a ., &# 34 ; xt - 1022e &# 34 ;, a product of tokyo chemical industries , kita - ku , tokyo , japan , and &# 34 ; diaion sk 1b &# 34 ;, &# 34 ; diaion sk 102 &# 34 ;, and &# 34 ; diaion sk 104 &# 34 ;, products of mitsubishi chemical industries limited , tokyo , japan . all of these resins have excellent fractionating capability to obtain the high - maltose fraction , and are highly heat - and abrasion - resitant . thus , they are advantageously useful for producing a high - purity maltose on an industrial - scale . in the process according to the present invention , a resin with a nominal particle size of about 0 . 01 - 0 . 5 mm is packed in one or more columns . the bed depth preferred in the invention is generally 7 m or longer . if two or more columns are used , they are cascaded to give a total bed depth of 7 m or longer . as to the column usable in the present invention , any column can be used regardless of its material , size , and shape so far as the objectives of the invention can be attained therewith . the column may be , for example , of glass , plastic or stainless steel , and its shape may be , for example , in cylindrical or square pillar form , but it should be designed to give the most effective laminar flow possible when the feed starch sugar solution is applied to the column packed with the resin . the following description concretely explains in detail the method of the present invention . one or more column ( s ) is packed with a strongly - acidic cation exchange resin of alkali metal - or alkaline earth metal - form , in an aqueous suspension , to give a total bed depth of 7 m or longer . while keeping the temperature in the column ( s ) at 45 °- 85 ° c ., the feed starch sugar solution , at a concentration of about 10 - 70 w / w %, in an amount of about 1 - 60 v / v % against the bed volume , is admitted into the column ( s ) and then charged upwards or downwards with water at a flow rate of about sv 0 . 1 - 2 . 0 to effect fractionation of the material starch sugar solution into a high - dextrin fraction , a high - dextrin .- maltose fraction , a high - maltose fraction , a high - maltose . glucose fraction , and a high - glucose fraction , in the given order . the high maltose - fraction is then recovered . although the eluted fractions are generally collected in about 1 - 20 v / v % against the bed volume , they may be distributed automatically into the fractions . when the feed starch sugar solution is admitted into the column prior to , after , or together with the previously obtained high - dextrin . maltose - and / or high - maltose . glucose - fractions , the amount of water required for substantial fractionation of the feed starch sugar solution can be sharply reduced , and the maltose constituent in the solution can be recovered in higher purity , higher concentration , and higher yield . preferably , the previously obtained high - dextrin . maltose fraction , the feed starch sugar solution , and the previoiusly obtained high - maltose . glucose fraction are applied successively to the column in the given order . although the high - maltose fraction thus obtained can be used intact , it may be , if necessary , treated further as follows . the high - maltose fraction may be subjected to conventional purification steps , e . g ., filtration , decolorization and / or deionization . then , the purified product is , for example , concentrated to obtain a syrup , or crystallized to obtain a mascuit which may be spray - dried into crystalline powder , or separated into mother liquor and maltose crystals of much higher purity . the high - purity maltose thus obtained is extremely useful in various applications , e . g ., for production of food products or pharmaceuticals . the feed starch sugar solutions used in this experiment were prepared from commercially - available starch sugar products as listed in table i , products of hayashibara company , limited , okayama , japan , by dissolving or diluting them in water to give respective concentrations of 45 w / w %. &# 34 ; dowex 50wx4 ( na + )&# 34 ;, a commercially - available strongly - acidic cation exchange resin of alkali metal - form , a product of dow chemical company , midland , mich ., u . s . a ., in an aqueous suspension , was packed in a jacketted stainless steel column , inside diameter , 5 . 4 cm , to give a bed depth of 10 m . while keeping the temperature in the column at 75 ° c ., each feed starch sugar solution listed in table i was admitted to the column in an amount of 5 v / v % against the bed volume , and fractionated by charging 75 ° c . hot water at a flow rate of sv 0 . 4 through the column and the high - maltose fraction , with a maltose content of 93 % or higher , was recovered . the results are given in table ii . the experimental results , as shown in table ii , confirm that when the maltose content in the feed starch sugar solution is 70 % or higher , a high - maltose fraction with a maltose content of 93 % or higher is easily obtainable in an extremely high yield , i . e . 80 % or higher , against the maltose constituent in the feed starch sugar solution . table i______________________________________ sugar composition (%) a b c d______________________________________maltrup 7 . 1 48 . 0 44 . 9malstar 3 . 2 66 . 0 30 . 8hm - 75 1 . 0 76 . 8 22 . 2sunmalt 4 . 3 85 . 0 10 . 7maltose h 0 . 6 91 . 5 7 . 9______________________________________ note : a is the material starch sugar solution ( trade name or registered trade mark ); b , glucose ; c , maltose ; and d , maltotriose and higher oligosaccharides . table ii______________________________________a b c d e______________________________________maltrup 48 . 0 132 . 2 44 . 2 controlmalstar 66 . 0 231 . 7 56 . 3 controlhm - 75 76 . 8 403 . 6 84 . 3 present inventionsunmalt 85 . 0 483 . 8 91 . 3 present inventionmaltose h 91 . 5 548 . 8 96 . 2 present invention______________________________________ note : a is the material starch sugar solution ( trade name or registered trade mark ); b , maltose content in the feed starch sugar solution (%); c , maltose yield in the highmaltose - fraction ( g ); d , maltose yield against the maltose constituent in the feed starch sugar solution (%); and e , remarks . similarly as in experiment 1 , the strongly - acidic cation exchange resin of alkali metal - form was packed in one or two columns to give respective total bed depths in the range of 1 - 20 m as in table iii . while keeping the temperature in the columns of different bed depths at 75 ° c ., 45 w / w % aqueous solution aliquots of &# 34 ; sunmalt &# 34 ;, a commercially - available starch sugar powder with a maltose content of 85 . 0 %, registered trade mark of hayashibara company , limited , okayama , japan , were admitted to the columns in an amount of 5 v / v % against the bed volume , and then fractionated by charging 75 ° c . hot water at a flow rate of sv 0 . 4 through the column and the high - maltose fraction , with a maltose content of 93 % or higher , was recovered . the results are given in table iii . the experimental results , as shown in table iii , confirm that when the bed depth is 7 m or longer , a high - maltose fraction with a maltose content of 93 % or higher is easily obtainable in an extremely high yield , i . e ., 80 % or higher , against the maltose constituent in the feed starch solution . table iii______________________________________a b c d e______________________________________1 1 114 . 5 30 . 1 56 . 93 1 343 . 5 102 . 1 64 . 25 1 572 . 5 192 . 9 72 . 87 1 801 . 5 324 . 9 87 . 610 1 1145 . 0 483 . 8 91 . 315 1 1715 . 5 739 . 3 93 . 020 2 . sup . 6 2290 . 0 994 . 1 93 . 8______________________________________ note : a is total bed depth ( m ); b , number of columns ; c , amount of the feed starch sugar solution applied ( ml ); d , maltose yield in the highmaltose fraction ( g ); e , maltose yield against the maltose constituent in the fee starch sugar solution (%); and . sup . 6 means two columns were cascaded . after packing , the strongly - acidic cation exchange resin of alkali metal - form in columns to give respective bed depths of 10 m , as in experiment 1 , feed starch sugar solution aliquots , prepared similarly as in experiment 2 , were applied thereto , and fractionated similarly as in experiment 1 , except that the columns were kept at different temperatures in the range of 35 °- 95 ° c . during the fractionation . the high - maltose fraction , with a maltose content of 93 % or higher , was recovered . the results are given in table iv . the experimental results , as shown in table iv , confirm that when the column is kept at a temperature in the range of 45 °- 85 ° c ., a high - maltose fraction with a maltose content of 93 % or higher is easily obtainable in an extremely high yield , i . e ., 80 % or higher , against the maltose constituent in the feed starch sugar solution with less browning . table iv______________________________________a b c d e______________________________________35 374 . 7 70 . 7 0 . 023 easy45 430 . 2 81 . 2 0 . 059 easy55 471 . 1 88 . 9 0 . 105 easy65 476 . 9 90 . 0 0 . 150 easy75 483 . 8 91 . 3 0 . 176 easy85 485 . 9 91 . 7 0 . 205 easy95 472 . 2 89 . 1 0 . 496 difficult______________________________________ note : a is the fractionation temperature (° c . ); b total yield of sugar constituents with a maltose content of 93 % or higher ( g ); c , maltose yiel against the maltose constituent in the feed starch sugar solution (%); d , colorization degree , obtained by measuring the absorbance of the highmaltose fraction in 10 cm cell ( a . sub . 420nm - a . sub . 720 nm ), and reducing the obtained value into that in 30 w / w % solution , and e , decolorization using 0 . 1 % activated carbon against sugar constituen ts . a feed starch sugar solution was prepared by diluting &# 34 ; hm - 75 &# 34 ;, trade name of a commercially - available starch sugar syrup with a maltose content of 76 . 8 %, a product of hayashibara company , limited , okayama , japan , in water to give a concentration of 45 w / w %. &# 34 ; xt - 1022e ( na + )&# 34 ;, a commercially - available strongly - acidic cation exchange resin of alkali metal - form , a product of tokyo chemical industries , kita - ku , tokyo , japan , in an aqueous suspension , was packed in four jacketted stainless steel columns , inside diameter , 5 . 4 cm , to give respective bed depths of 5 m , and the columns were cascaded to give a total bed depth of 20 m . while keeping the temperature in the columns at 55 ° c ., the feed starch sugar solution was admitted thereto in an amount of 5 v / v % against the bed volume , and then fractionated by charging 55 ° c . hot water at a flow rate of sv 0 . 13 through the columns and the high - maltose fraction , with a maltose content of 93 % or higher , was recovered . the high - maltose fraction contained 808 . 2 g maltose , and the yield was extremely high , i . e ., 84 . 3 %, against the maltose constituent in the feed starch sugar solution . a feed starch sugar solution was prepared by dissolving &# 34 ; sunmalt &# 34 ;, a commercially - available starch sugar powder with a maltose content of 85 . 0 %, registered trade mark of hayashibara company , limited , okayama , japan , in water to give a concentration of 60 w / w %. the resin , used in example 1 , was converted into k + - form in the usual way and packed in a jacketted stainless steel column , inside diameter , 2 . 2 cm , to give a bed depth of 10 m . while keeping the temperature in the column at 60 ° c ., the feed starch sugar solution was admitted thereto in an amount of 3 v / v % against the bed volume , and then fractionated by charging 60 ° c . hot water at a flow rate of sv 0 . 2 through the column and the high - maltose fraction , with a maltose content of 93 % or higher , was recovered . the high - maltose fraction contained 65 . 7 g maltose , and the yield was extremely high , i . e ., 88 . 3 % against the maltose constituent in the feed starch sugar solution . a feed starch sugar solution was prepared by dissolving &# 34 ; sunmalt &# 34 ;, a commercially - available starch sugar powder with a maltose content of 85 . 0 %, registered trade mark of hayashibara company , limited , okayama , japan , in water to give a concentration of 45 w / w %. &# 34 ; dowex 50wx4 ( mg 2 + )&# 34 ;, a commercially - available strongly - acidic cation exchange resin of alkaline earth metal - form , a product of dow chemical company , midland , mich ., u . s . a ., in an aqueous suspension , was packed in fresh columns of the same material and dimensions as used in example 1 to give a total bed depth of 15 m . while keeping the temperature in the columns at 75 ° c ., the feed starch sugar solution was applied thereto in an amount of 6 . 6 v / v % against the bed volume , and then fractionated by charging 75 ° c . hot water at a flow rate of sv 0 . 13 through the columns and the high - maltose fraction , with a maltose content of 93 % or higher , was recovered . the high - maltose fraction contained 913 . 7 g maltose , and the yield was extremely high , i . e ., 87 . 1 %, against the maltose constituent in the feed starch sugar solution . the first fractionation was carried out as follows . similarly as in example 1 , a feed starch sugar solution was applied to a column , and fractionated except that the feed starch sugar solution was applied to the column in an amount of 20 v / v % against the bed volume . the elution pattern is given in the drawing , where fractions a through e show a high - dextrin fraction , a high - dextrin . maltose fraction , a high - maltose fraction , a high - maltose . glucose fraction , and a high - glucose fraction respectively , and where the elution is effected in the given order . fraction c , the high - maltose fraction , was recovered , and fractions a and e were removed from the fractionation system . the additional fractionation was carried out as follows . fraction b , the feed starch sugar solution in an amount of about 10 v / v % against the bed volume , and fraction d were admitted into the column successively in the given order , and the column then charged with 75 ° c . hot water , as in example 3 , to effect fractionation . the high maltose fractions , with a maltose content of 94 %, were recovered . the additional fractionation was repeated up to 30 batches in total , and the averaged results per batch were calculated . on an average , one high - maltose fraction contained 1483 g maltose , and the yield was extremely high , i . e ., 93 . 3 %, against the maltose constituent in the feed starch sugar solution . a feed starch sugar solution was prepared by dissolving &# 34 ; maltose h &# 34 ;, trade name of a commercially - available starch sugar powder with a maltose content of 91 . 5 %, a product of hayashibara company , limited , okayama , japan , in water to give a concentration of 45 w / w %. &# 34 ; amberlite cg - 120 ( ca 2 + )&# 34 ;, a commercially - available strongly - acidic cation exchange resin of alkaline earth metal - form , a product of rohm & amp ; haas company , philadelphia , pa ., u . s . a ., was packed in fresh columns of the same material and dimensions as used in example 1 to give a total bed depth of 10 m . also , in this example , a dual - stage fractionation was carried out . the first fractionation was carried out as follows . while keeping the temperature in the columns at 80 ° c ., the feed starch sugar solution was applied thereto in an amount of 20 v / v % against the bed volume , and then fractinated by charging 80 ° c . hot water at a flow rate of sv 0 . 6 through the columns to obtain a similar elution pattern as in example 4 . similarly as in example 4 , fraction c , the high - maltose fraction , was harvested , and fractions a and e were removed from the fractionation system . the additional fractionation was carried out as follows . fraction b , the feed starch sugar solution in an amount of 10 v / v % against the bed volume , and fraction d , were admitted into the column successively in the given order , and the column then charged with 80 ° c . hot water at a flow rate of sv 0 . 6 to effect fractionation . the resultant high - maltose fractions , with a maltose content of 96 % or higher , was recovered . the additional fractionation was repeated up to 100 batches in total , and the averaged results per batch were calculated . on an average , one high - maltose fraction contained 1084 g maltose , and the yield was extremely high , i . e ., 95 %, against the maltose constituent in the feed starch sugar solution .
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fig1 shows a turning machine . the headstock is designated by 1 . a turning carriage 2 bearing a cross - slide rest 3 which may be displaced perpendicularly thereto is arranged displaceably on an inclined base . the drive for displacing the cross - slide rest 3 in the direction of the arrow is designated by 4 . a tool revolver 5 is located on the cross - slide rest . two tool - holders 13 are fixed to the tool revolver 5 . one of the tool - holders 13 carries a turning tool 6 . the other tool - holder 13 bears a carrier bolt 7 . the turning chuck designated by 8 is enclosed by a ring magazine 9 . the ring magazine contains a number of storage places for clamping jaws 11 . the clamping jaws 11 are arranged in the ring magazine 9 so as to be radially displaceable in guides 12 . the clamping jaw guides of the turning chuck 8 are designated by 10 . when the cross - slide rest 3 is displaced , the carrier bolt 7 moves radially and perpendicularly to the chuck axis . the clamping jaws 11 are provided with holes 16 into which the carrier bolt 7 may be inserted by displacement of the turning carriage 2 . the subsequent displacement of the cross - slide rest 3 enables the change of clamping jaws between the magazine 9 and the chuck 11 to take place , if the corresponding guides 10 and 12 of the chuck 8 and magazine 9 are in alignment . the magazine 9 may be rotated about the chuck axis , but it does not have its own drive . as described in connection with fig2 it is turned into the suitable position for the change by the drive of the chuck 8 . as will be seen from fig2 the chuck axis 17 is mounted by means of a bearing 18 in a component 22 which is fixed to the machine . the component of the chuck 8 provided with guides 10 is securely connected to the chuck axis 17 via an intermediate ring 33 . an annular holding component 27 is fixed on the headstock 1 by rubber buffers 24 . rotatably mounted thereon by means of a swivelling ball bearing 26 is an annular component 25 which is securely connected to the magazine ring 9 containing the clamping jaw guides 12 . seals 28 and 29 ensure that the swivelling ball bearing 26 does not become dirty . a toothed ring 31 having backwardly directed teeth 35 is disposed on the inner rear periphery of the magazine ring 9 . there is also a toothed ring 32 with teeth 36 also pointing to the rear on the rearward outer periphery of the chuck body bearing the guides 10 . a ring cylinder body 21 , in which a ring piston 23 is rotatably mounted so as to be axially displaceable , is fixed to the headstock 1 . the cylinder chamber may be acted upon by hydraulic fluid via a line 38 . the ring piston 23 is constructed simultaneously as a toothed ring whose teeth 34 are directed towards the front and when the ring piston 23 is displaced to the right , these may engage with the teeth 35 and 36 of the toothed rings 31 , 32 . a sealing ring 30 ensures that the teeth 34 , 35 , 36 remain clean . on the other side a ring seal 37 ensures that no dirt reaches the teeth 34 , 35 , 36 . a spring 20 presses the ring piston 23 back from the toothed rings 31 , 32 if the cylinder chamber is pressureless . if the magazine ring 9 is to be moved into another changing position , hydraulic fluid is supplied to the pressure line 38 . in this way the teeth 34 , 35 , 36 engage with each other . the chuck is now slowly rotated until the magazine ring 9 has reached the required changing position . the teeth 34 , 35 , 36 remain engaged during the changing process . their purpose is not only to turn the magazine ring 9 with the chuck 8 , but they also have an indexing function , i . e ., they should ensure that the guides 10 of the chuck 8 and the guides 12 of the magazine ring 9 are in exact alignment . if another changing position is to be used between the magazine ring 9 and the chuck 8 , the cylinder chamber is emptied so that the ring cylinder 23 may move back . the teeth 34 , 35 , 36 then disengage . other guides 10 and 12 may then be aligned with each other in each case by rotating the chuck 8 relative to the magazine ring 9 . for exact alignment , the teeth 34 , 35 , 36 are then brought to engage again . it is necessary for the changing process for the magazine ring 9 and the chuck 8 to be brought into a rotating position in which the guides 10 and 12 , between which the displacement of the relevant clamping jaws 11 is to be effected , are aligned exactly parallel to the direction of displacement of the cross - slide rest 3 . fig2 shows how the tool - holder 13 , which carries the carrier bolt 7 , is secured to the tool revolver 5 . the tool revolver 5 is provided with a clamp piston 14 which engages in an undercut groove 15 of the tool - holder 13 . the clamp piston 14 thus pulls the tool - holder 13 against the tool revolver 5 . in the embodiment represented in fig3 and 4 , the turning carriage is designated by 102 and the cross - slide rest by 103 . the drive for the cross - slide rest 103 is designated by 104 . a tool revolver 105 which carries two tool - holders 113 is located on the cross - slide rest 103 . a turning tool 106 is located on one of the tool - holders 113 . the other tool - holder 113 carries a carrier bolt 107 directed towards the chuck 108 . the clamping jaws 111 are provided here with grooves 116 , into which the carrier bolt 107 can engage , extending transversely to the direction of displacement . in the case of the embodiment according to fig3 and 4 , bores ( such as 16 in fig2 ) could also be provided in place of the grooves . a holding plate 140 for a drum magazine 109 is fixed to the headstock by means of rubber buffers 124 . the drum magazine 109 is rotatable about the drum axis by means of a rotary drive 141 . the drum magazine has four guides 112 for the clamping jaws 111 . several clamping jaws 111 are arranged one behind the other in the guides 112 . the drum axis extends perpendicularly and radially to the chuck axis . by means of the suitable rotation of the drum magazine one guide 112 can be brought into alignment in each case with a corresponding guide 110 of the chuck 108 . for the changing procedure the carrier bolt 107 is brought by means of the displacement of the turning carriage 102 into the corresponding groove 116 of the clamping jaws 111 of the drum magazine 109 which are positioned next to the chuck 108 . then , by means of the displacement of the cross - slide rest 103 in the direction of the chuck 108 , the clamping jaws 111 are inserted into the guide 110 of the chuck 108 . the clamping jaws 111 in the drum magazine 109 are prestressed in the direction of the chuck 108 by springs 143 . a pressure component 142 , on which the spring 143 bears , rests on those clamping jaws 111 lying the furthest away from the chuck 108 . a separate spring mechanism is provided for each guide 112 . the indexing is also effected by means of a ring piston 123 in the case of the embodiment shown in fig3 and 4 . the ring piston 123 consists of a toothed ring having teeth 134 pointing towards the front . a further toothed ring 131 with teeth 135 pointing towards the rear is arranged , so as to be secured to the machine , on the holding plate 140 . a further toothed ring 132 , similarly with teeth 136 pointing towards the rear , is fixed to the rearward , outer periphery of the chuck 108 . when the ring piston 123 is actuated , the teeth 134 , 135 , 136 engage and fix the chuck 108 so that the selected guide 110 aligns exactly with the guide 112 of the drum magazine 109 which has been brought to the changing position . in fig5 the cross - slide rest 203 is arranged on the turning carriage 202 so as to be displaceable by means of a drive 204 . the cross - slide rest carries a tool revolver 205 with two tool - holders 213 . each tool - holder contains a carrier bolt 207a , 207b . a two - part rod magazine 209 is arranged on both sides of the chuck 208 . each part of the rod magazine 209 has two guides 212 which together form a pointed angle . the angle bisector of this angle extends parallel to the direction of displacement of the cross - slide rest 203 . each guide 212 contains several clamping jaws 212 arranged one behind the other with receiving grooves 216 for the carrier bolts 207a , 207b , extending transversely to the direction of displacement . each guide 212 is provided with a spring mechanism . this consists of a spring 243 which bears on a pressure part 242 . the clamping jaws 211 lying next to the chuck 208 are securely fixed in each groove 212 by a stopping mechanism which prevents the clamping jaws 211 being pushed out of the guide 212 by the spring mechanism . the stopping mechanism consists of a stopping bolt 244 which is pressed against the relevant clamping jaws by a spring 245 . the clamping jaws have a lateral stopping recess 246 for this purpose . the guide 210 of the chuck 208 in which the change is to take place or from which clamping jaws 211 are to be exchanged , must be brought into alignment with the relevant guide 212 of the rod magazine 209 by rotating the chuck 208 . by displacing the turning carriage 202 the relevant carrier bolt 207a , 207b is then inserted into the groove 216 of the clamping jaws lying next to the chuck 208 . in the present case , this is the carrier bolt 207a . this is co - ordinated with the left guide 212 . the carrier bolt 207b is co - ordinated with the right guide 212 . as the two guides 212 do not run parallel to the displacement direction of the cross - slide rest 203 , the carrier bolt 207a , 207b displaces when the cross - slide rest 203 in the relevant groove 216 of the chuck 211 is displaced . it will be seen from fig6 that the rod magazine 209 is fixed to the machine by means of rubber buffers 224 . the indexing mechanism here is similar to that of the embodiment of fig3 and 4 . a toothed ring 232 whose teeth 236 point towards the rear is fixed to the rearward periphery of the chuck 208 . a further toothed ring 231 having teeth 235 which also point towards the rear is attached to the rod magazine 209 . a ring cylinder 223 is arranged so as to be displaceable parallel to the chuck axis , in an annular cylinder component fixed to the machine . the ring cylinder 223 is constructed as a toothed ring having teeth 234 pointing to the front . if the cylinder chamber is acted upon with pressure fluid , the teeth 234 engage in the teeth 235 and 236 , producing indexing . a spring 239 ensures that the annular cylinder 223 is pressed back again when the cylinder chamber is relieved of pressure . a sealing ring 230 prevents the teeth 234 , 235 , 236 becoming dirty . to those skilled in the art to which this invention relates , these and many other such changes in construction and widely differing embodiments and applications of the invention will suggest themselves without departing from the spirit and scope of the invention . the disclosures and the descriptions herein are purely illustrative and are not intended to be in any sense limiting .
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in a television broadcast system , data representing an audio / video content as well as metadata and signalling data are transmitted by a management centre cg to a plurality of multimedia television broadcast receiver units stb . the audio and video stream is transmitted to the core of an mpeg channel , called a programme , according to the signalling in a pmt table ( program map table ) also transmitted by television broadcast . if the programme is encrypted , a confidential stream of control messages ( ecm ) containing the decryption keys is associated to the programme broadcast . the different channels , corresponding to different contents , and their metadata ( such as title , creation year , genre , names of main actors , etc . . . . ) are themselves identified by a set of signalling tables specified partly by the mpeg standard and partly by regional dvb and atsc standards , such as the sdt tables ( service description table ) and eit ( event information table ) also broadcast with the data stream , but in an asynchronous way . in the case of pay television , secure messages for management , control and updating ( emm ), for example transmission keys that encipher the aforementioned ecm stream , are transmitted in the televised data stream , in parallel with the programmes but in an asynchronous way . in particular , these messages allow the establishment of communication channels individually secured with each receiver . furthermore , it is also possible to update the software applied on the receiver units by transmitting with the data stream by television broadcast the updating data necessary to the latter . the stb user unit , also called a master device , receives the data stream and manages the access rights to this data . in order to visualize the data , this type of unit can dispose of several communication means such as an rgb or peritel output . in this case , the signals take an analog form and are protected by different technologies such as macrovision and cgms - a ( copy generation management system - analog ). these technologies do not use any authentication or verification mechanisms as described . another means of communication is disclosed in fig1 that represents wireless means such as wifi . the wifi in interface allows the transmission of the conditional access data towards a dtv television , for example in digital form . this digital form proves very attractive to ill - intentioned individuals and for this reason the data exchanged in the air is encrypted . other transmission forms with wires can be used such as ieee1394 , ethernet , usb , dvi and hdmi . in practice , data encryption rely on a key that is generated dynamically and allows the television set to decrypt this data for processing . if a personal computer that dialogues with the master device in order to store the data in plaintext , takes the place of the dtv television set , the encryption of the data to be transferred fails to provide any protection . for this reason a verification step has been added , namely verification based on the conformity of the certificate stored in each target device . a mutual authentication can be carried out on the basis of the certificate identifier . a key is then generated which serves to encrypt the exchanged data . according to the invention , the data constituting the verification tables ( s ) l 1 , l 2 . . . ln is placed in the data stream dt transmitted from the management centre to the master device . this data can be transmitted in different ways in order to produce the optimal compromise between bandwidth and data security , namely : emm messages : these messages are secure messages for the updating of rights or keys and can be intended for one unit , a group of units or all the units . they can thus contain elements of the verification list , in particular the positive list . this list can be contained in one or more emm messages according to its size . in association with updating software of the receiver by television broadcast , thus benefiting well known associated uploading security mechanisms , such as authentication of the updating and management of the version number by the receiver . data stream : content transmitted during service standby : the periods without diffusion are used , for example between 4 a . m . and 6 a . m . in the morning , to replace the audio / video content with verification lists . signalling table . these tables form part of the descriptive data of the content and can also contain the programme grid data . these tables can contain the verification list ( s ) such as described in this invention , for example in the case of the dvb standard in association with a given content by insertion in the eit table containing the programmes for 8 days and transmitted on a specific channel , with a large bandwidth . in the last two cases , it is necessary to provide mechanisms dedicated to protection of the verification lists , for example by means of specific keys known to the receivers . once received by the master device these lists are stored either in a silicon memory ( flash ) or on hard disk . they can be secured locally by a key pertaining to the user unit or the key of the certificate associated to this unit . as indicated above , these tables can define either the devices capable of processing the conditional access data ( positive list ) or on the contrary those prohibited from said processing ( negative list ). these lists can enumerate each identifier concerned or can define the identifier areas . therefore , if an apparatus is pirated and its identifier reproduced in numerous clones , identified by the anti - piracy control , it is necessary to exclude it from the authorized target devices . an important point in this invention is the flexibility brought by the verification indication . this indication is directly associated to the content and allows , with a minimal cost in terms of bandwidth , a decision to be made during diffusion as to whether a verification must be carried out with reference to one or several previously transmitted verification lists and allows the control of the corresponding version number . these verification indications can be transmitted in several ways in order to render them dissociated from a content at the time of its television broadcast , for example : in a control message ecm , when the content is encrypted ( pay television broadcast applications ). these messages present the advantage of being secured . directly in the description data of the content , such as the programme map table pmt ( program map table ) that describes the organization of the audio and video stream associated to the content . in the description tables of the content regularly transmitted with the latter , such as the eitp / f tables comprising information about the current content and the following contents on a television broadcast channel . in the last two cases , it is necessary to provide dedicated security mechanisms of the verification lists , for example by means of dedicated keys known to the receivers . if several tables are loaded into the master device , the verification indication will specify which table is to be used for verification . thus a content with a low value could specify a different verification table than a high value content . this is applied in particular in the case of a mixed receiver that processes free programmes as well as pay television broadcast programmes . furthermore , the verification indication also allows the identification of the version number of the list transmitted most recently , in order to avoid the possible filtering by the receiver of the new , more restrictive verification lists . this verification indication can define a security level . in a previous step , the master device receives a security list with a definition of list ( s ) to be used for each level . for example , a security level 3 means that for the hdcp protocol , the list hd 12 , version 2 . 23 is specified and for the dtcp protocol , the list dt 8 , version 1 . 17 is specified . for only one security level , the set of protocols as well as the desired version is sent . this intermediate list is preferably secured . according to one embodiment it is possible to transmit a particular list for a particular master device . this can be achieved in a point - to - point way or in diffusion mode with addressing of the related master device . this list takes into account the material environment , for example , of the interface type with target devices . it is not useful to store the identifiers pertaining to an interface type ( for example hdcp for hdmi ) when the only interface provided on this device is of the usb type . according to a different embodiment , the positive list can be limited solely to targets devices previously registered from a management centre , corresponding to target devices effectively connected to a particular master device . in the latter case , an initialization process allows the user to transmit the set of identifiers of his / her target devices . this process can be carried out in an automated way thanks to the feedback channel of the master device and the identifiers , whether they are the serial numbers or the identifier of the certificate , are transmitted to the management centre . a description of the technical capacity of the target devices can complete this data ( television set , computer , pvr with or without recorder , etc .). the transmission of this information can also be made via the telephone ( vocal server ) or the sending of a short message . this initialization process can advantageously use a web ( internet ) service for the registration of the user &# 39 ; s data . the management centre having a black list ( or negative ) will verify if the identifiers received by a user are comprised in this exclusion list and excludes these identifiers from the positive list transmitted to the master device . this verification can be made on the basis of a positive list that lists all the valid certificates . it is possible that the management centre will not able to use a reliable black ( or negative ) list , for example in the case of piracy on a large scale of the hdcp regulation . in this case , the identifiers received by a user must be controlled by an external control centre disposing of a list of valid identifiers . this control centre can pertain to the manufacturer , when the identifier transmitted by the user identifies the manufacturer of the equipment , or directly corresponds to the official certification authority such as one of the associations dtla for dtcp , svpla for svp , or llc for hdcp , responsible for the distribution of valid certificates to all the manufacturers implementing the standards controlled by said associations . furthermore , it is possible that the management centre does not know the exact data , such as the certificate , of a device target of a user . on the basis of the transmission of a material identifier , which could be the serial number of the device or any other indication allowing the identification of this device , the management centre then questions a control centre to obtain the certificate identifiers . this control centre can pertain to a manufacturer or group together several manufacturers , for example it can be the official certification authority such as one of the associations dtla for dtcp , svpla for svp , or llc for hdcp . the certificate of a device is generally directly connected to the communication layer . therefore , if a device contains several communication means such as usb and hdmi , it generally disposes of several certificates corresponding to different standards such as dtcp and hdcp . the verification can be executed on the active communication means for the transmission of the master device data to the target device or on all the certificates . in the case of a content that would be stored in the master device before its transfer towards the target device , the verification information is also stored in order to be able to be executed at the time of the subsequent transmission of the content . according to one embodiment of the invention , the verification in the positive and / or negative lists is carried out previously on the master device . the master device itself will verify the conformity of certificate ( s ) of its communication means . it is possible to verify an identification number that has no relation with the communication means , for example its serial number . according to the chosen operation method , when one means of communication is revoked , the master device is considered as revoked . in the case of a home network , the master device can be connected to a first target device such as a storage unit . verification is carried out by the master device in order to authorize the target device to transfer the data . parallel to the transfer of the data , the verification lists are also transmitted . the verification indication that is associated to the content can thus be carried out by this device that then becomes a master device . the process of the invention is thus noted on all the elements of a home network . this invention also covers a master device disposing of reception means for content ( s ) and reception means of the verification list ( s ) such as that described above . this device comprises verification means in conformity with a target device and storage means called lists . this device includes means for extracting a verification indication associated to the content and for carrying out a verification cycle of the target device on the basis of the verification indication and of the verification list ( s ) previously stored .
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the invention requires that a server using the invention be configured with certain parameters . by way of example , the preferred embodiment requires that a policy be specified that specifies the number of discarded packets that must be detected before detection of a flood event will be performed . further , a minimum number of discarded packets and the relevant discard rate are also specified to declare a flood event . once a flood event has been declared , the policy specifies how often a flood monitor process will be executed and other parameters relating to the monitoring . in fig1 , step 102 represents the normal protocol stack processing operations . there are a number of checks performed by the stack for packets that should be discarded . illustrated are malformed packets , input queue overflow and a catch - all called other discards . when any such packet discard is performed by the stack , entry is made to step 104 where a packet discard counter is incremented . step 106 next determines if a flood event ( a monitoring operation initiated earlier ) is already in progress . if the answer is no , step 110 checks the packet discard counter to determine if the number of discards have exceeded a minimum threshold value x ( taken from system policy in the preferred embodiment ). if not , flood detection is not performed on this discard and processing is returned to stack operations at 102 . if the minimum number of discards x ( min ) is exceeded , then step 112 determines if this number of discards occurred within an interval t . t is also specified by policy in the preferred embodiment . if the answer to step 112 is no , then no flood attack is deemed to exist . in this case , step 122 resets the packet discard counter and an inbound packet counter and exits . at step 106 , if a flood event is already in progress , then step 108 collects and stores a set of information for analysis . by way of example , such information might be the prior hop address ( the mac address of the adapter at the preceding node , the protocol used for the last discarded packet , the reason for the discard , etc . in addition , step 108 initiates a trace of succeeding packets . in the preferred , packet information pertaining to the next one hundred packets is stored for later analysis . returning to step 112 , if the minimum number of discards have occurred in less than the interval t , then a flood attack might be occurring . to determine this , step 116 calculates the rate r of discards by dividing the number of discards x by the number of incoming packets received in the interval . at step 114 , if the rate r does not exceed a threshold y ( also set by policy in the preferred embodiment ), then no attack is in progress and the program resets the counters at step 122 and exits . on the other hand , an attack is deemed to be in progress if the threshold y is exceeded at step 114 . in this event , step 118 initiates a flood event by setting an appropriate marker and sends a report to the system console and error log . step 120 schedules the execution of the flood monitor process of fig2 . step 122 resets the packet discard and inbound packet counters and the program exits . once a flood event has been declared , a policy specifies how often a flood monitor process will be executed and other parameters relating to the monitoring . the preferred embodiment uses a one minute interval for monitoring , but this could also be specified by policy . once a flood event is activated by step 118 , the flood monitor of fig2 is entered later at a scheduled time . in the preferred embodiment , this interval is set at one minute . step 202 first determines if the packet discard count in the last interval ( one minute in the preferred embodiment ) is less than or equal to a minimum number of discards x ( min 2 ). in the preferred embodiment , x ( min ) equals x ( min 2 ); however , this is not a requirement and these two specified thresholds might differ in other embodiments . if the discards at step 202 is less than x ( min 2 ), then the flood attack is deemed to be over . step 204 deactivates the flood event by resetting the flood marker . step 212 analyzes and reports on the set of data collected in step 108 . this set is preferably the last discount count , the discard rate , and the most frequent discard mac address , protocol type and discard type . the counters are reset at 214 and the flood monitoring process is over . returning to step 202 , if x ( min 2 ) is exceeded , then step 206 determines if the rate of discards r in the last monitoring interval is less than one - half of the specified threshold y . if the answer is yes , then this is also used to indicate that the flooding attack is over . if the answer at 206 is no however , the attack is deemed still to be in progress . step 208 analyzes and reports on the same data as reported in step 212 . however , reporting here is done at intervals while the flood event is active . step 210 schedules the next flooding monitoring event so that the flood monitor of fig2 will be executed once again at the expiration of the monitoring interval . again , step 214 resets the counters and exits . eventually the flood will be deemed over either at step 202 or 206 and a final set of data analyzed and reported at step 212 . the invention is able to determine , in some cases , the most likely prior hop that is in the source of attack . once an interface flood event is raised , information about each discard received on the interface is collected . this data includes the prior hop source mac address ( if the interface type provides this information ). at intervals during the flood event and when the flood event ends , information about the flood characteristics is reported . this data includes the prior hop source mac address reported most frequently for the flood event discards . artisans in the field of this invention will quickly realize that the preferred and disclosed embodiment can have many minor variations that are within the intent and scope of the teaching . it is the intent of the inventor to encompass these variations to the extent possible in accordance with the state of the applicable relevant art in the field of the invention .
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by way of introduction , newer prevacuum steam sterilizers use an evacuation cycle that is actually a combination of conditioning and evacuation . this combination compromises the use of a heat sink in its ability to separate air from steam . during this cycle , typically a one minute steam purge is initially conducted with the drain open . then a vacuum pulse and three additional steam and prevacuum pulses are conducted in a closed system . each pulse reaches a critical pressure . the heat transferred from the initial steam purge and subsequent pulses reduces the heat absorptive capabilities of a heat sink . therefore , the present invention employs a material that does not rely on a temperature difference between the steam and a part of the indicator , usually a heat sink , to collapse steam to separate air from it . the present invention employs a material that directly absorbs and / or adsorbs steam without requiring a change of state to liquid , but not air , due to its composition and , in some cases , steam , but not air , due to its structure . thus , any heating of the material during any part of the cycle does not compromise its ability to function . in fact , due to the composition and , in some cases structure of the material , the material has a capacity sufficient to separate air from steam during pre - sterilization cycles and the sterilization cycle itself . any regenerative capabilities of the material simply enhance its capacity . the material can be a desiccant , also called a drying agent and a dehydrating agent , or any other similar material . for example , the metal alumino - silicate crystals that are employed by the preferred embodiments of the present invention instead of a heat sink physically adsorb steam during each conditioning steam pulse . that steam is desorbed to some extent during each vacuum pulse , thereby regenerating the desiccant somewhat before the sterilization cycle is commenced . this desorption actually is aided by the temperature increase of the desiccant during the process . thus , unlike a heat sink , this class of materials can detect all steam - air problems since its utility can extend well into the sterilization portion of the cycle . in the construction of devices 10 , 100 and 200 , which are shown in fig1 through 6 , steam is constrained to follow a prescribed path . steam enters the device through a sealable opening into a receptacle containing a desiccant . the receptacle is designed to provide maximum contact between the steam and the desiccant , and it can define a torturous path to further this purpose . at the distal end of the receptacle is a small opening that provides communication between the receptacle and an air collecting chamber . the chamber contains an indicator . the indicator can be a typical known biological or chemical indicator , or it can be a combination indicator of known type . as is well known in the art , a chemical indicator includes a steam sensitive ink , which changes color upon exposure to steam . as is also well known in the art , a biological indicator includes microorganisms that will be destroyed during steam sterilization . a variety of chemical and biological indicators are commercially available . the top section of the device , which seals the air collecting chamber and covers the indicator , can be peeled or broken away to retrieve the indicator for record purposes . in use , a tab covering the entrance opening to the desiccant receptacle is removed and the device is , typically , placed in the coolest section of the sterilizer , usually over the drain , where air is likely to be present . during the evacuation portion of the cycle , air is withdrawn from the interstices of the desiccant , receptacle and air collecting chamber . entering the sterilization portion of the cycle , steam is forced into the desiccant receptacle where it selectively acts with the desiccant material . any air mixed with the steam is not retained by the desiccant , and is forced further through the receptacle in a progressive manner as areas of the desiccant becomes saturated . when the desiccant is totally saturated , the air and steam are forced into the air collecting chamber . here , if air is present , it will be forced to the end distal from the opening to the receptacle , and it will shield the indicator , thus preventing a uniform change that would show complete reaction with steam . upon completion of the sterilization cycle , the device is withdrawn from the sterilizer and a determination of the effectiveness of the cycle can be made . fig1 through 6 show the preferred embodiments of the indicator provided by the present invention . fig1 through 4 show an indicator 10 , which is typically placed within the chamber of a prevacuum type steam sterilizer ( not shown ) for the purpose of detecting and indicating inadequate air removal during evacuation , and introduction of air during evacuation through a leak or during the sterilization cycle . device 10 includes a top 12 , and a housing 18 , which includes a section 30 that is sealed along its perimeter to housing 18 . the assembly of housing 18 and section 30 is sealed along the perimeter of housing 18 to top 12 . device 10 includes an indicator strip 14 located beneath top 12 , and a grip section 16 , which forms a part of top 12 . referring to fig2 housing 18 defines desiccant receptacle 20 that is adapted to contain a desiccant 22 . housing 18 also defines a portal 24 which allows steam to enter housing 18 . a tab 26 is secured to the bottom of housing 18 over portal 24 . tab 26 maintains the integrity of the interior of housing 18 and desiccant 22 during shipping and storage of device 10 . section 28 , which is defined by housing 18 cooperates with section 16 of top 12 to provide a grip for device 10 . top 12 , including section 16 , is so secured to housing 18 as to permit a user to peel top 12 from housing 18 to gain access to indicator 14 . indicator 14 is , for discussion purposes , a chemical indicator . that is , indicator 14 includes steam sensitive ink . referring to fig3 section 30 is sealed to housing 18 to enclose receptacle 20 . section 30 also cooperates with top 12 to define an air collection chamber 34 , in which indicator 14 is located . desiccant 22 can be loaded into receptacle 20 prior to securing section 30 in place . alternately , desiccant 22 can be loaded into receptacle 20 through portal 24 after section 30 has been secured to housing 18 . air collection chamber 34 is in communication with receptacle 20 through a portal 32 , which is defined by section 30 . preferably , the components shown in fig4 are assembled together by securing section 30 to housing 18 , placing indicator strip 14 on top of section 30 , and securing top 12 to housing 18 . the preferred desiccant 22 for device 10 is crystalline metal alumino - silicates and , more specifically , na 86 [ alo 2 ) 86 ( sio 2 ) 106 ] x h 2 o , which has been activated for water adsorption by removing the water of hydration by heating . crystalline metal alumino silicates of the type preferred can be purchased from union carbide corporation , danbury , conn . the crystal structure of the metal alumino - silicates is a truncated octahedra joined in a cubic array , or honeycomb structure , with relatively large cavities . each cavity is connected with six adjacent cavities through apertures . the efficiency of this material for this application is the selective adsorption of water resulting from water &# 39 ; s unique molecular size and polarity , along with the uniform size and molecular dimensions of the crystal &# 39 ; s cavities , the extremely large surface area resulting from the honeycomb , and the high capacity for adsorption over a wide range of operating conditions including temperatures to over 600 ° f . additionally , the large volume of air within an aggregate of crystals offers a challenge to air removal during the evacuation portion of the steam sterilization cycle . the quantity of desiccant will vary with the application in a manner understood by those of ordinary skill in the art upon reference to manufacturers published information . the sizing of housing 18 will depend on the quantity of material it must contain . to use device 10 , tab 26 is removed from the bottom of housing 18 , and device 10 is placed in the chamber of a prevacuum steam sterilizer . during the newer pulsing prevacuum cycle , the initial steam purge forces some steam through portal 24 and into receptacle 20 , where absorbed and / or adsorbed by desiccant 22 located at proximal end 40 of receptacle 20 . following the initial steam purge , and each subsequent steam pulse cycle , during which steam is absorbed and / or adsorbed by desiccant 22 , an evacuation pulse is produced . during each evacuation pulse , adsorbed moisture can be desorbed to some extent and exits receptacle 20 through portal 24 . thus , desiccant 22 can be regenerated to some extent during each evacuation pulse . the initial steam purge and each subsequent steam pulse occurring during the conditioning - evacuation portion of the cycle increase the temperature of device 10 , including desiccant 22 . during the evacuation pulses , air exits desiccant 22 , through portal 24 , and air collecting chamber 34 , through portal 32 . as steam enters the sterilizer chamber , it is forced into device 10 through portal 24 . upon contacting desiccant 22 , the steam is absorbed and / or adsorbed , leaving any air present in the steam , even if the desiccant 22 is at the sterilization temperature . thus , unlike devices that rely on heat sinks to separate air from steam , the efficacy of device 10 extends throughout the sterilization cycle . as the steam front progresses from proximal end 40 of receptacle 20 to distal end 42 , it forces any accumulated air ahead of it through receptacle 20 . baffles 36 and 38 formed in sections 18 and 30 , respectively , define a tortuous path for steam traveling through receptacle 20 , and create turbulence in the steam . turbulence in the steam flow aids intimate contact between the steam and desiccant 22 . ultimately , the steam forces any accumulated air through portal 32 and into air collecting housing 34 . if air is not present in chamber 34 , which means the sterilization cycle was successful , the ink on chemical indicator will have changed color uniformly . otherwise , the color change will not be uniform . fig5 and 6 show devices 100 and 200 , which include alternative arrangements for providing access to air collecting chamber 34 and indicator strip 14 . elements shown in fig5 and 6 have been assigned the reference characters of the corresponding elements shown in fig1 through 4 . the housing 18 of each of devices 100 and 200 is made from a suitable plastic material . as is well - known to those in the art , a plastic material will exhibit lower tear and crack resistance to forces applied along the molecular orientation of the plastic than to forces applied perpendicular to the molecular orientation . the molecular orientation of housing 18 of each of devices 100 and 200 should be 90 ° to the longitudinal axis of housing 18 . the molecular orientation of top 12 of device 200 should also be 90 ° to the longitudinal axis of device 10 . a detente 46 is formed in the bottom surface of housing 18 of device 100 across its width . access to end 50 of strip 14 is gained by bending end 48 of top 12 and tab 28 of housing 18 upward , relative to the orientation of device 100 in fig5 thereby applying a focused stress along detente 46 , until a fracture occurs . top 12 of device 200 defines a pair of detentes 52 . detentes 52 facilitate tearing end 16 away from housing 18 and the remainder of top 12 to gain access to end 50 of strip 14 . the preferred method provided by the present invention employs devices 10 , 100 , or 200 during sterilization to indicate the effectiveness of the sterilization cycle .
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the foregoing summary , as well as the following detailed description of certain embodiments of the present invention , will be better understood when read in conjunction with the appended drawings . as used herein , an element or step recited in the singular and preceded with the word “ a ” or “ an ” should be understood as not excluding plural said elements or steps , unless such exclusion is explicitly stated . furthermore , references to “ one embodiment ” of the present invention are not intended to be interpreted as excluding the existence of additional embodiments that also incorporate the recited features . moreover , unless explicitly stated to the contrary , embodiments “ comprising ” or “ having ” an element or a plurality of elements having a particular property may include additional such elements not having that property . the invention provides a modified ald chamber featuring an exterior surfaced mounted and accessible oscillating crystal mass measuring device capable of measuring mass changes as little as 0 . 1 ng / cm 2 . an embodiment of the microbalance comprises a sealed qcm integrally molded with the chamber interior . this design contrasts with traditional ‘ fixture - on - a - stick ’ paradigms whereby microbalances , protruding into reaction chambers , alter normal laminar flow patterns , cause dead zones which are insufficiently purged , and ultimately produce distortions in deposition layer thickness . fixture - on - a - stick paradigms also prevent the ability to map the film simultaneously at several locations . instead , the invented paradigm provides improved temperature adjustment and pressure compensation while solving aforementioned problems associated with prior devices . the invented integrated oscillating crystal paradigm is suitable for use with other types of vapor deposition reactors . further , the invented system allows for mapping of a films at several locations across the film . piezoelectrics , and in particular quartz crystal microbalances have been used in conventional vacuum processes where thickness measurements are valuable , for example in thermal evaporation . qcm measurements provide an in situ method for measuring growth rates and nucleation phenomena , optimizing processing conditions , and elucidating surface reaction mechanisms . an embodiment of the invention is a piezoelectric microbalance integrated with an atomic layer deposition device . in an embodiment of the invention , a piezoelectric microbalance is removably integrated with an ald reaction chamber while simultaneously providing a low internal profile . this low profile provides a means to minimize disruption of reactor gas flow this invention envisions the piezoelectric microbalance , such as a qcm crystal , reversibly mounted to a reactor wall , lid , flange or floor of an enclosure defining the reaction chamber of the ald device . as such , the design provides a low internal profile , which is suitable to most reactor geometries . the design allows for thermal equilibration with the crystals and the workpiece being coated . generally , the materials used for these aspects of the system are tolerant at high temperatures ( e . g ., from about 300 to 450 ° c .). in specific embodiments of the invented ald / crystal microbalance system , the microbalance is recessed from the reactor space a distance of between about 1 . 0 mm and 2 . 0 mm . in another embodiment the microbalance is flush with the interior surface of the reactor . the invention allows for modification of the extent of protrusion or recession of the microbalance out of or within the interior surfaces of the walls of the same reaction chamber . as such , the microbalance can be reversibly set to various positions within the ald reaction environment . this allows users to tune the microbalance for optimal reading of the deposited film , depending on gas flow , temperature , reaction rate desired , etc . an embodiment of the invention is designated as numeral 8 in fig1 a . an oscillating crystal microbalance , such as a qcm unit 10 is shown reversibly attached , such as by male - female threaded interaction , to an ald reactor 12 . the ald reactor 12 facilitates vapor deposition of chemical moieties onto a workpiece 14 positioned within the ald reaction chamber 16 . the ald reaction chamber 16 is defined by a wall 18 integrally molded to a base 20 , the combination of which defines a side and bottom surface respectively of the reaction chamber . a top of the reaction chamber is defined by a removably attachable lid 22 , such that an inwardly facing surface 42 of the lid opposes an inwardly facing surface of the bottom surface of the reaction chamber . this inwardly facing surface 42 defines the ceiling of the reaction chamber . in an embodiment of the reaction chamber , the lid 22 is in pivotable communication with a lip defining the periphery formed by the upwardly extending wall 18 . reactants enter the ald reaction chamber 16 through a region of the bottom surface forming an aperture 24 . the reactants originate from a lower preprocessing chamber ( not shown ). optionally , the aperture is in fluid communication with a valve 25 to regulate flow of reactant from its preprocessing chamber to within the chamber 16 . the flow in the ald reaction chamber 16 from the upstream inlet 24 to a downstream outlet 26 , in a generally laminar flow pattern ( as shown by arrows ) which deposits material on all chamber surfaces , including the target workpiece 14 . the target workpiece 14 is supported by the base 20 and in a position to be directly opposed to the underside ( i . e , the inward directed surface ) 42 of the conductive lid 22 . the conductive lid 22 defines one or a plurality of apertures 28 adapted to slidably receive a first end of a hollow annular connector 80 . a myriad of connectors are available including the a standard bayonet nut coupling bayonet neill - concelman ( bnc ) connector , also known as the bayonet neill - concelman connector . a depending or mating end ( mating with lid ) of the connector is in close spatial relationship to a microbalance crystal 30 . in an embodiment of the invention , the crystal 30 is arranged such that the plane defined by the crystal is parallel to the workpiece 14 being coated . this position assures accurate monitoring of material thickness applied to the workpiece 14 during the deposition process while at the same time minimizing modification of the flow patterns within the ald reaction chamber 16 . location of the qcm unit 10 from the workpiece varies from about 1 mm to about 400 mm , and typically the distance is about 40 mm . an exact location is empirically determined , based on reactant type , gas flows , temperatures etc . location selection is made to minimize any impact on reactant flow gas patterns so as to enable accurate thickness monitoring . for a large area workpiece 14 one may utilize several qcm units 10 , while for a small substrate one utilizes a single qcm 10 substantially directly opposing the planar surface defining the workpiece 14 . the qcm units 10 are reversibly mounted to the lid 22 in a transverse configuration so that the distance “ d ” between the crystal and the workpiece 14 can be modified . generally , distances between about 1 and 40 millimeters ( mm ) are suitable distances for “ d ” to afford film growth on the crystal 30 that is similar ( or proportional to ) the growth rate on the opposing workpiece . as used herein , “ chamber - side ” or “ internal ” defines a surface adjacent to or in fluid communication with chamber 16 of the reactor . “ exterior ” or “ external ” descriptors refer to structures not in fluid communication with the reaction chamber . ambient conditions are construed herein as including atmospheric pressure , humidity and temperature . fig1 b depicts the mounting of a qcm unit 10 . each aperture 28 is adapted to slidably receive a disk - like piezoelectric planar disc 30 , as shown in fig1 c and 1 d , having a radially outer edge 32 and coated on the “ chamber - side ” 34 and “ exterior ” 36 surfaces with conductive layers 38 and 40 . the aperture 28 defines a plurality of grooves 48 circumscribing the periphery of the aperture 28 , each of said grooves adapted to receive an o - ring . at least two of the grooves are axially displaced from each other a distance to facilitate a frictional fit of a periphery of the planar disc 30 between o - rings nesting in said at least two of the grooves . more than two grooves can be provided so that several pairs of adjacent grooves can be chosen to removably position the disc 30 . this provides the adjustability of the distance “ d ” discussed supra between the disc 30 and the substrate . in an embodiment of the invention , the aperture 28 has the following structure , as shown in fig1 b . ( in this embodiment , as used herein surfaces parallel to the axis a of the aperture will be described as “ vertical ” and surfaces perpendicular to a longitudinal axis a of the aperture will be described as “ horizontal ” although other orientations for a are possible . ‘ up ” designates a vertical displacement directed towards the exterior to the chamber lid and “ out ” a radial displacement away from the axis . “ down ” and “ in ” are opposite to up and out .) a salient feature of the invention is that all electricity sources to the crystal are integrally formed with the ald body such as its sides , floor or ceiling . this obviates the need for wires to traverse the ald reaction chamber interior , which otherwise may disrupt film forming chemistries . for illustrative purposes only , the accompanying figures show the electricity sources molded with the ceiling or lid of the chamber . a medially facing , transversely extending surface 46 of the lid 22 extends axially ( in relation to line α - α ) and away from the chamber - side surface 42 of the lid 22 . a surface 51 , integrally molded with the transversely extending surface 46 extends laterally from the transversely extending surface 46 and defines a first annular groove 49 . this first annular groove 49 is adapted to frictionally receive a first o - ring 50 . the groove 49 is bordered on its laterally ( i . e . outer ) edge by a conductive ledge 52 . the piezoelectric planar disc 30 is positioned so that its reaction chamber - side surface 34 is in electrical contact with the ledge 52 . alternatively , the inferior face ( i . e ., the reaction side surface ) of the piezoelectric substrate 30 is in electrical contact with an electrically conductive spacer 63 or a plurality of washers , such as a washer . the washer ( s ) 63 in turn are supported by the conductive ledge 52 . these spacers provide additional means to vary the distance d of the piezoelectric substrate 30 from the workpiece 14 . a second retaining wall 54 extends axially from the conductive ledge 52 . the second retaining wall 54 borders a plateau 56 extending horizontally and laterally . the plateau 56 defines the bottom of a cylindrical cavity having an opening facing in a direction opposite the location of the ald chamber . the cavity is dimensioned to removably receive an o - ring compression sleeve 58 . in an embodiment of the invention , the sleeve 58 interacts with the cylindrical cavity in a male - female threaded configuration , or a snap fit configuration . the chamber - side conductive layer surface 38 of the piezoelectric disc 30 is supported by and in electrical contact with the conductive ledge 52 , or alternatively the electrically conductive spacer 63 . the conductive ledge 52 is integrally molded with the lid 22 and thus provides an electrical ground for the system . the chamber - side o - ring 50 contacts a peripheral edge of the chamber - side surface 34 of the piezoelectric disc 30 ( thereby establishing a gas tight seal upon downward compression of the piezoelectric disc 30 upon application of the compression sleeve 58 . the second ( i . e . exterior ) o - ring 60 adjacent to the peripheral edge 32 of the piezoelectric disc 30 provides uniform downward compression to the piezoelectric disc 30 . upon installation to the lid 22 , the exterior chamber - side extending tab 62 of the o - ring compression sleeve 58 provides axial , medially directed ( i . e . inwards ) mechanical pressure to the lid , thereby compressing to the o - rings to form a peripheral seal to both sides of the disc 30 . for example , as depicted in space in fig1 b , a downwardly directed force applied by the compression sleeve 58 toward the chamber on o - ring 60 engages radially the peripheral edge 32 of the piezoelectric disc 30 between the exterior o - ring 60 , the conductive ledge 52 and the chamber - side o - ring 50 , so as to provide a hermetic seal . as the seal is effected via compression of the disc between two reversibly deformable substrates , substrates other than o - rings are suitable , such as gaskets comprised of rubber , silicone , polymer and malleable metal , in the embodiment shown , the two o - rings provide a gas - tight seal and provide a means to maintain the reaction environment at a different pressure , temperature , and / or reactant concentration different than the environment external of the ald chamber . a gap 64 between the upper edge of the inward retaining wall 46 and chamber - side surface 34 of the piezoelectric disc 30 adjacent to the radially outer edge 32 , permits the efficient purge of the surfaces in the vicinity of the contact area between the piezoelectric disc 30 and the chamber - side o - ring 50 . preferrably , the length to height ratio ( l : h ) of the gap 64 is unity . however , a l : h ratio of between 1 : 1 and 10 : 1 is suitable . the system utilizes a resilient / spring electrode manufactured from a metal form having a center aperture therein . a ring in the central region thereof having a plurality of spokes emanating radially there are bent at an angle of about 45 ° from the horizontal . the ends of the spokes are rounded to permit contact with the external conductive surface 40 of the piezoelectric disc 30 without scratching the surface . the resilient / spring electrode 66 engages the exterior surface 36 of the piezoelectric disc 30 to establish electrical contact with the exterior conductive layer 40 of the piezoelectric disc 30 and thus provide power to oscillate the piezoelectric disc 30 . the frusto - conical shaped resilient / spring electrode 66 is fixedly attached to a coupler 68 with a threaded fastener 70 . the void space 72 between the threaded fastener 70 and exterior surface 36 of the piezoelectric disc 30 provides space for undampened oscillation of the piezoelectric disc 30 . the annular void space 74 between the radially inward wall 76 of the o - ring compression sleeve 58 and coupler 68 provides a gas flow path . the resilient / spring electrodes 66 can be in the form of a frusto - conical structure as shown in fig1 b or in the form of a cone or similar structure . the frusto - conical structure can comprise a webbing or sheeting , or a plurality of webs supported by a plurality of radially directed ribs anchored at their proximal ends to the connector when alternating current is provided through the resilient / spring electrode 66 between exterior surface 36 of the piezoelectric film and the conductive ledge 52 , the crystal oscillates transversely , in a direction perpendicular to the axis a , ( i . e ., side - to - side ) as shown by vertical double arrow in fig1 b . variation in qcm oscillation frequency is measured by instrumentation . the qcm unit 10 , as discussed hereinabove is an integral part of the ald reactor 12 as shown in fig1 a . it allows rapid replacement of the piezoelectric disc 30 . the resilient / spring electrode 66 is secured with a threaded fastener 70 to the base of the coupler 68 attached to an axial pin / post 76 of a shaft 78 with threaded fastener 70 . the shaft 78 is contained within a hollow annular connector 80 . the connector 80 is affixed to a mounting plate 82 which is in turn attached to the exterior surface 84 of the ald reactor 12 with mounting fasteners 86 . o - rings 88 provide a gas tight seal between a chamber - side facing surface 90 of the mounting plate 82 and the exterior surface of the ald reactor 24 . the gas - tight seal provides control of the reactor environment . balancing the pressure between the exterior surface 36 and chamber - side surface 34 of piezoelectric disc 30 is performed by two separate components , a pressure equalization means and a purge gas flow means . to equalize pressure on the qcm unit 10 , i . e ., to minimize the effect of a pressure differential between the chamber and the outside on the oscillation of the piezoelectric disc 30 , a channel 92 , integrally formed with the housing of the ald device , and terminates at a first end as an aperture 94 formed in a region of the chamber - side surface 42 of the lid . the aperture 94 serves as a means of egress of pressurized fluid applied to the top side of the crystal . the gas has slightly positive pressure relative to the ald chamber to ensure an inert gas flow always flows out from the exterior surface 36 of the crystal and toward the ald reaction chamber . this provides a means for impeding diffusion of chemicals back to the exterior surface of the crystal 36 ). the aperture 94 is positioned downstream of the deposition zone 98 . however , the aperture may be positioned anywhere along the surface of the reaction chamber so as to facilitate pressure equalization between the chamber side 34 and the exterior side 36 of the piezoelectric substrate 30 . a second end of the channel 92 terminates as an exhaust channel 100 which is hi fluid communication with the exterior surface 36 of the piezoelectric film 30 . in an embodiment of the invention , the channel 92 extends radially through the compression sleeve 58 to the annular void space 74 . this provides a pressure equalization conduit between the chamber - side surface 34 of the piezoelectric film 30 and the exterior surface 36 of the film . an embodiment of the invention comprises an angled channel 92 , whereby the channel extends from the ald chamber side at an angle β . in this embodiment , the angle is chosen to maximize the length of the purge gas channel 92 to prevent backwash of ald moieties to the exterior surface 36 of the crystals . to minimize reactant back - flow through the channel 92 , from the reaction chamber 16 to the annular void space 74 , the channel is charged with an inert gas stream . the inert gas is supplied from an exterior source via a coupler 101 such as a male - female or snap fit coupling . intermediate the coupler and the void space 74 , and in fluid communication therewith is positioned a conduit 102 . a proximal end is removably attached to the coupler 101 while a distal end 105 terminates at a point in close spatial relationship to a purge gas inlet channel 104 . positioned between the distal end 105 and the inlet channel 104 is a purge gas vestibule 103 adapted to receive the incoming purge gas . the vestibule 103 and inlet channel 104 are integrally molded with regions of the o - ring compression sleeve 58 and in fluid communication with each other . the inlet channel 104 extends radially through the compression sleeve 58 and terminates in the void space 74 defining the interior surfaces of the hollow annular connector 80 . in operation , an inert gas flows through the conduit 102 to inlet channel 104 to flow into annular void space 74 . the inert gas exits the annular void space though an exhaust channel 100 integrally molded with the compression sleeve 58 . preferably the exhaust channel is opposed to the inlet channel 104 . this provides a means for assuring thorough purging of the void space prior to the purge gas exiting the void space through the egress channel 100 . upon passing through the egress channel 100 , the gas flows through angled channel 92 and exits the channel via entry port 94 into the ald reaction chamber 16 . a low volume flow of gas prevents back - flow of reactants into the annular void space 74 and deposition onto the exterior surface 36 of the piezoelectric planar disc 30 . in another embodiment of the invention , as shown in fig1 e , an alternate pressure equalization means is illustrated . an exterior pressure equalization conduit 106 establishes fluid communication with the vertical connecting channel 103 , which intersects the inlet channel 104 passing into annular space 74 balancing the pressure between annular chamber 74 and carrier gas line 108 at the entry point 110 upstream of chemical reactant inlets 112 . compared to the effects of the internal pressure equalization conduit 92 depicted in fig1 a , the exterior pressure equalization conduit 106 prevents chemical precursor gases from diffusing to the back side ( i . e ., exterior surface 36 ) of the crystal where coating is undesired . also , the exterior routed conduit 106 provides a simplified fixture where the diagonal channel 92 for backside purge gas need not be drilled at a high angle , thereby simplifying ald chamber lid 22 fabrication . the externally - routed pressure equalization conduit further reduces flow disturbances from the backside purge gas near the workpiece . this is due to a single purge gas source 114 which provides a means for charging both sides of the crystal 30 at the same pressure and volume . the single purge gas source provides a means to for charging the exterior side 36 of the crystal , the interior side 34 of the crystal , and the ald reaction chamber with an inert gas all at the same pressures and volume . the inventors surmise that the external conduit scheme is better at maintaining matching pressure on both side of the crystal , compared to the heretofore described internally routed pressure equalization conduit scheme where the pressure behind the crystal is influenced by both the chamber pressure ( through 94 ) and the steady , externaly provided inert gas flow through 102 . in an embodiment of the invention , the piezoelectric disc 30 is a quartz crystal microbalance ( qcm ) sensor crystal . in another embodiment of the invention , the piezoelectric microbalance is a gapo 4 crystal . the small footprint on the external surface of the ald , approximately between 7 and 20 cm 2 and preferably about 16 cm 2 external to the ald reaction chamber and between 0 . 5 and 1 . 5 cm 2 , and preferably about 0 . 75 cm 2 on the internal surface of the ald chamber — further allows for installation of a plurality of microbalance crystals enabling in situ evaluation of film thickness uniformity profiles over a large expanse of the reactor . a myriad of crystal constituents are suitable for use in the invention . generally , high temperature ( e . g . approximately 50 - 450 ° c .) crystals are suitable , such that the crystals maintain their structural and electrochemical characteristics throughout the deposition temperatures utilized . at - cut crystals , it - cut crystals , fc - cut crystals , rc - cut crystals , sc ( stress compensated )- cut crystals , and super quartz crystals are suitable , among others . at - cut crystals and rc - cut crystals are preferred . also , the inventors found that typography of the crystals plays a role in their suitability . while a myriad of crystal typographies are suitable , polished crystals ( to a roughness of between 1 and 20 nm , are preferable . crystals with a roughness of approximately 5 nm are most preferable . in instances where unpolished crystals are utilized , sealing means other than o - rings are preferable , those sealing means including polymer washers , malleable metal washers , and reversibly deformable substrates , all discussed elsewhere herein . qcms or alternately gallium orthophosphate ( gapo 4 ) crystal microbalances are mass sensors capable of measuring mass fluctuations as low as 0 . 1 ng / cm 2 . based on the piezoelectric effect , the sensors utilize an alternating current applied to the crystal to induce a resonant oscillation at a frequency dependent upon on the crystal thickness . as mass is deposited on ( or removed from ) the surface of the quartz crystal , the frequency of oscillation changes . using the sauerbrey equation , stated below as equation 1 , the frequency change is correlated to a change in mass . δ m a = n q ρ q π z f l tan - 1 [ z tan ( π f u - f l f u ) ] equation 1 where f l frequency of loaded crystal ( hz ), f u — frequency of unloaded crystal , i . e . resonant frequency ( hz ), n q — frequency constant ( for at — cut quartz crystal , n q = 1 . 668 × 10 13 hz å ), δm — mass change ( g ), a is the piezoelectrically active crystal area ( area between electrodes , cm 2 ), ρ q is the density of piezoelectric , and where μ q is the shear modulus of piezoelectric ( for quartz μ q = 2 . 947 × 10 11 g / cm · s 2 ), μ f shear modulus of film ( varies units g / cm · s 2 ), and ρ f is the density of film ( g / cm 3 ) to illustrate the application of the integral qcm design , of the invention , a commercially available aluminum slab lid of an ald ( for example , a savannah 200 ald ( cambridge nanotech , inc ., cambridge , mass .) was modified to accommodate two oscillating crystal fixtures . compression seal sleeves and apertures were machined to appropriate dimensions to produce o - ring compression compatible with published o - ring specifications and qcm crystal thickness . electrical connection to the front of the gold plated qcm crystals is achieved through direct contact with the aluminum ald lid by means of edge 52 , which is in turn grounded to the connector shield by the feed through . electrical connection to the exterior surface of the qcm crystal was achieved with a resilient / spring retainer electrode modified and fitted on a connector shaft . the connector fixture was bolted onto the lid with mounting plate and fasteners were inserted in drilled and tapped holes . tightening of the fasteners compressed a kalrez o - ring in an annular groove , forming an airtight seal . markez 75 d high temperature o - rings on the exterior side of the qcm crystal are compressed by a compression sleeve / seal , as shown in fig1 a to ensure a vacuum - tight seal to the reaction chamber and uniform crystal compression . because qcm crystal interior / flow surface contacts are made directly to the machined medially or inwardly directed edge 38 , there is no need for the conductive epoxy that is required in the prior art ( elam et . al ., rev . sci . instr . 73 , 2981 - 2987 ( 2002 ). as such , the lip / o - ring seal combined with edge and chamber side o - ring allow for clean and rapid crystal exchange in addition to potentially longer crystal lifetimes production of al 2 o 3 in a modified ald reactor as discussed hereinabove was chosen to evaluate the performance of the integral qcm . measurements were carried out in a savannah 200 ald reactor ( cambridge nanotech , inc . ), adapted as discussed hereinabove , using trimethylaluminum ( tma ), and water ( 18 mω , milli - q system ) at a reaction temperature of 190 ° c . the pressure in the ald chamber was maintained at 300 mtorr — when no precursors were pulsing — by the continuous flow of ultra - high purity nitrogen ( 20 sccm ) and rough pumping ( adixen pascal 2500i , hingham , mass .). in continuous flow mode , the conventional ald pulse sequence was used ( t 1 - t 2 - t 3 - t 4 ) where t 1 is the pulse time for the tma , t 3 is the pulse time for h 2 o , and t 2 and t 4 correspond the tma and h 2 o purge times , respectively . all units are given in seconds . in some cases , quasi - static mode was employed to simulate the conditions required for conformally coating high aspect ratio samples . in this mode , the pneumatic valve that provides access to the pump was closed prior to precursor dosing and remained closed while the chemical precursors were allowed to diffuse . here , the timing sequence was [ t 1 - t 1 ′ ]- t 2 -[ t 3 - t 3 ′ ]- t 4 , where t 1 ′ and t 3 ′ refer to the exposure times for the tma and water , respectively . because even the shortest 15 ms pulses of tma and water saturate the relatively small reactor , ald al 2 o 3 was not a suitable choice to evaluate the capability of mapping film growth . instead , the zns ald was selected as it too has a known chemistry and reaction rate and the delivery of 1 % in n 2 h 2 s can be reduced to sub - saturating conditions through the use of a pressure regulator . during the deposition of zns , diethylzinc ( dez ) and h 2 s were maintained at room temperature while the ald chamber temperature set to 140 ° c . ( while 1 % h 2 s in n 2 is highly toxic , it is not flammable . the tool was modified for compatibility with the corrosive gas .) the h 2 s was delivered to the manifold through a 0 . 3 mm orifice ( lenox laser ) with a delivery pressure of − 710 torr gauge pressure . the pulsing sequence was similar to that for tma / h 2 o , where here t 1 = dez pulse time , t 3 is the h 2 s pulse time , and t 2 and t 4 are the purge times for the dez and h 2 s , respectively . a number of disadvantages of the “ fixture on a stick ” or standard straight line qcm probe are its limited utility to monitor routine depositions on sample coupons and devices . additionally , insertion of the probe in an ald reactor alters normal laminar flow patterns , causing dead zones , producing distortions in deposition layer thickness . due to the long equilibration times associated with convective heating and stainless steel construction , temperature - dependent studies or tasks as simple as ex situ sample exchange are burdensome and slow . as such , the “ fixture on a stick ” qcm is restricted to systematic and dedicated studies of ald processes . in contrast , for the design of the invention presented herein , the qcm crystal is mounted directly on the aluminum ald lid , providing rapid thermal equilibration . fig2 a shows the thermal equilibration time — the point at which the signal drift becomes less than a fraction of a monolayer ( a few ng / cm 2 )— for the qcm sensor at 190 ° c . the initial transient in the trace at time = 0 seconds corresponds to when , after samples were exchanged , the reactor lid was closed and the system pumped back down to vacuum . the qcm reached the reaction temperature in a matter of minutes and had sufficiently low baseline drift within approximately 20 minutes — the typical period used for sample warm - up and outgassing — thus introducing no additional delay in the process . the inset shows a zoomed portion of the qcm signal highlighting that the noise is less than 2 ng , with no obvious thermal drift over the 500 s time duration ( for reference , one ald cycle of al 2 o 3 cycles deposits ˜ 32 nm / cm 2 ). to further reduce thermal drift , two additional measures were taken to minimize temperature fluctuations and reduce the temperature sensitivity of the qcm sensor . tuning of the pid temperature controllers through the savannah ald software minimized reactor temperature fluctuations to less than ± 0 . 2 ° c . of the set point temperature . additionally , a fiber insulation pad was placed around the ald chamber and on top of the modified ald lid in order to reduce temperature fluctuations associated with changes in the room ambient . temperature effects may also be minimized by switching to a different sensor crystal with a lower temperature coefficient . fig2 b shows the temperature coefficient as a function of reactor temperature for three different commercially available sensor crystals . the right axis displays the calculation of apparent ald al 2 o 3 thickness change . rc ( colnatec , inc .) and at - cut ( inficon ) crystals were measured independently with the integral qcm , while the gapo 4 data is reproduced from published data ( elam et . al ., rev . sci . instr . 73 , 2981 - 2987 ( 2002 ), the entirety of which is incorporated by reference . a thermocouple was temporarily attached to the lid to accurately measure the temperature of the crystals . a ramp of the ald reactor temperature was executed while monitoring in the sensor frequency , and the temperature coefficients were calculated from the derivative of oscillation frequency versus temperature . an “ apparent al 2 o 3 thickness change ” is plotted on the right axis ( assuming an ald - al 2 o 3 density of 3 . 0 g / cm 3 ) for reference . in the temperature range between 150 and 225 ° c . the rc crystals outperform both the at - cut and the gapo 4 crystals as evidenced by the lower absolute values for the qcm temperature coefficient of the rc crystal in this temperature range . ( the design of the aperture and mounting structure permits quick replacement of the alternative crystals as the need arises .) the right axis displays the calculated apparent al 2 o 3 thickness change . because ald is not a “ line - of - sight ” deposition technique , the precursors can diffuse to every reactive site including the backside of the crystal unless preventative measures are taken . the wall - mounted integral qcm includes a backside purge of ultra - high purity n 2 to prevent growth on the backside of the sensor . to demonstrate the benefit of this active precursor diffusion barrier , al 2 o 3 was deposited using both standard pulse ( continuous flow ) mode and under quasi - static ( exposure mode ) conditions . as high vapor pressure and low molecular weight precursors , both tma and water test the limits of the precursor diffusion barrier strategy . both qcm ports were used : the “ inlet ” qcm port was positioned 2 in from the inlet and the “ outlet ” qcm port was positioned 6 in from the inlet . as the backside purge flow rate was varied , a total of 20 ald cycles were executed at each setting and the growth rate was determined by averaging the rate per step over the last 10 cycles . fig3 a and 3 b show the effects of backside purge rate on the deposition rate for quasi - static and continuous flow mode , respectively . fig3 a is a graph of the process under quasi - static growth conditions ( 0 . 015 second pulse with a 2 second exposure for both water and tma , each followed by a 20 second purge ). the growth rate for al 2 o 3 was determined as a function of the purge flow across the back of the qcm crystals . the left axis is the mass change in nanograms per cycle , while the growth rate of al 2 o 3 — calculated assuming a density of 3 . 0 g / cm 3 — is on the right axis . when the backside purge rate was reduced below 2 . 5 sccm , the growth rate nearly doubled indicating that deposition was occurring on both the front and back of the qcm crystal ( fig3 a ). the growth rate of the inlet qcm port maintained a growth rate of about 2 å / cycle , while the outlet qcm growth rate continued to increase to about 3 å / cycle . that is , in the low flow regime , the rate exceeded twice that expected for al 2 o 3 ald suggesting additional , non - self - limiting growth occurred in the space behind the qcm crystal — likely a result of precursor mixing due to insufficient purging of physisorbed reactants . a means for preventing this film accumulation prevents this from occurring . one such means is increasing the a backside purge rate . for example , of 2 . 75 sccm purge rate is suitable . while the backside purge flow has virtually no effect on the deposition rate under continuous flow conditions ( except under zero back purge flow condition , where the effect is small , fig3 b ( s 2 )), the effect of the backside purge rate during quasi - static conditions is substantial . fig3 b is a graph of the growth rate for al 2 o 3 , in continuous flow ( pulse ) mode . the rate is seen as a function of the purge flow rate over the back ( i . e ., exterior surface 36 ) of the qcm crystals . the timing for the tma / h 2 o cycles was 0 . 015 - 20 - 0 . 015 - 20 . the growth rate remained constant for purge rates & gt ; 0 . 2 sccm over the back of the qcm crystal . the backside purge gas is beneficial for accurate mass calibration . the invented design is such the flow through the entry port 94 does not disturb the normal precursor flow in the ald chamber . to verify that the backside purge gas did not perturb the deposition , a test was performed for 600 cycles of pt ald using ( trimethyl ) cyclopentadienylplatinum ( iv ) ( 99 %, strem ) and molecular oxygen . pt was selected due to its low vapor pressure , sensitivity to substrate cleanliness , and the fact that it provides a distinct change in the reactor appearance with only a few nanometers of film . the pulse sequence was 1 - 10 - 1 - 10 and the reactor temperature was 190 ° c . preventing backside ald is not only key to obtaining accurate mass calibration but also preferable to prevent wrap - around of conductive ald materials . conductive material deposited on the back of the qcm crystal will electrically short the two electrodes that drive the crystal oscillation , rendering it inoperable . fig4 shows the successful in situ qcm monitoring during pt ald using the backside purge . qcm data demonstrates the deposition of pt metal at 190 ° c . using alternating exposures to trimethyl ( methylcyclopentadienyl ) platinum ( iv ) and o 2 . the zoomed region from 0 to 7000 seconds shows the nucleation delay over a period of ˜ 150 cycles , while the region between 1 . 55 × 10 4 and 1 . 575 × 10 4 s highlights a mass gain of 83 . 33 ng / cycle . this corresponds to a growth rate of 0 . 4 å / cycle . fig4 highlights nucleation and steady - state growth . the nucleation region occurs in the first 10000 s and is highlighted in the inset on the bottom right . from this a nucleation delay over a period of ˜ 150 cycles was determined . the steady - state growth region is displayed in the upper left inset and demonstrates the ability of the qcm to resolve the individual steps of each half - reaction . using the bulk density of pt , the growth rate was calculated to be 0 . 4 å / cycle . positive - going transient features accompanying each o 2 exposure likely result from transient heating induced by the exothermic combustion of the organic ligands on the pt surface . a similar transient feature was observed previously during pt and ir ald , but in the negative mass direction . this difference in sign is depicted in fig2 b and also by noting that the earlier application used conventional at - cut sensors which have a temperature coefficient that is opposite in sign as compared to the rc sensors . in the integral wall - mounted qcm design , a lip and o - ring system provide electrical contact to the front of the qcm crystal ( see fig1 b ). a “ purge gap ” between the inner diameter of the lip and crystal has been included to reduce the propensity for dead ends — precursor - accessible portions of the reactor that experience insufficient sweep gas ( purge flow ). dead ends may act as a chemical precursor trap where gas phase mixing of reactants and / or products can occur , the result of which is non - uniform growth and powder formation . to evaluate the extent to which the invented design minimizes dead ends , both tma and water were overdosed by a factor of five , thereby magnifying any effects due to precursor mixing or otherwise non - self - limiting growth . in pure ald , half - reactions will be self - limiting such that introducing additional precursor into the reaction chamber will not increase the growth rate . deposition steps as a function of the number of pulses are shown in fig5 a - 5 d . these figures illustrate al 2 o 3 mass gain at 190 ° c . measured at the outlet using the pulse sequence x ( 0 . 015 - 8 )- y ( 0 . 015 - 8 ), where ( a ) x = 1 = y , ( b ) x = 5 , y = 1 , ( c ) x = 1 , y = 5 , and ( d ) x = 5 = y . each successive pulse was separated by an 8 s purge . the standard 1 : 1 pulse ratio of tma : h 2 o , depicted in fig5 a , yielded a growth rate of 1 . 1 å / cycle . fig5 b , c , and d show the mass deposited using pulse ratios of 5 : 1 , 1 : 5 , and 5 : 5 respectively . in all cases , multiple pulses did not increase the growth rate . furthermore , consecutively pulsing the tma precursor 100 times did not result in additional mass gain . the purge time following both tma and water pulses were also investigated to determine the minimum time required to efficiently remove all unreacted precursor from the reaction chamber . fig6 a and 6 b illustrate the al 2 o 3 growth rate dependence of purge time at 190 ° c . following each half reaction . in ( a ) the purge time following the tma dose was varied using the sequence 0 . 015 - x - 0 . 015 - 8 and in ( b ) the sequence 0 . 015 - 8 - 0 . 015 - y was used to evaluate the effect of h 2 o purge time . purge times are determined empirically . ( the purge time for the al 2 o 3 process at this temperature in an unmodified ald tool is eight seconds .) fig6 display plots of the growth rate versus purge time following a ) tma and b ) h 2 o . the plots show that the integrated qcms do not require additional purge time . the inlet and outlet qcm ports display similar trends ; for purge times greater than 1 s following tma , with the growth rate was maintained at 1 . 1 å / cycle . below one second , the growth rate increased rapidly , suggesting insufficient purging . similarly , at purge times greater than 2 s following a water pulse the growth rate was 1 . 1 å / cycle . at shorter purge times the growth rate increased . these results , in combination with the aforementioned multi - pulse study , indicate that the low profile design and lip and o - ring purge gap produce little to no disturbance to standard reactor operation . due to the small footprint of the integral wall - mounted qcm fixture , both inside and outside the tool , multiple qcm ports may be mounted on a single tool . multi - qcm capabilities provide the opportunity to map the mass deposition as a function of location within the reactor in real time . although ald is designed to produce uniform growth over a wide range of precursor exposures , temperatures , and purge conditions , trade - offs are frequently encountered . for example , higher deposition temperatures may result in better dielectric properties but at the cost of precursor thermal decomposition that results in an exposure - dependent growth rate . exposure - dependent nucleation rates , hot and cold spots , non - uniform flow under increased purge conditions , and precursor consumption by porous or high - surface area substrates can all lead to thickness non - uniformities during ald . typically , the process of identifying and rectifying these problems is laborious and time - consuming requiring many rounds of ald on wafers followed by ex situ thickness measurements . however , this process can be performed rapidly and easily using in situ multi - point mapping such as what are enabled with a multisensor configuration depicted in fig8 and 9 . roughly 23 ports could be packed onto the 30 cm diameter lid depicted in fig1 a . signals are processed by the same sqm - 160 thickness monitor . to evaluate the effectiveness of dual port capability , ald zns was used as a model system . like tma , dez rapidly and completely saturates the commercial ald chamber with even the shortest achievable dose ( 0 . 015 s ); however , the h 2 s dose pressure can be easily reduced to produce sub - saturating conditions by lowering the differential delivery pressure . this allows one to monitor the h 2 s wave front travel through the chamber as function of h 2 s dose time , as depicted in fig7 . the growth rate at the inlet qcm port showed saturation with just a 0 . 5 s h 2 s dose . this compares to an eight second h 2 s pulse required to reach saturating conditions at the outlet qcm port . this difference in the required h 2 s pulse time between the inlet and outlet qcm ports — which were intentionally exacerbated for illustrative purposes — highlights the benefit of dual port capabilities . fig7 illustrates zns growth rate near the inlet ( circles ) and outlet ( squares ). zns was deposited at 140 ° c . using diethylzinc and h 2 s with a pulsing sequence of 0 . 015 - 12 - x - 12 , where x is the h 2 s pulse time . an integral , wall - mounted qcm fixture with a low profile was designed to meet the specific needs of ald systems . the experiments demonstrated the use of the wall - mounted integral qcm design for in situ characterization of films comprised of a myriad of elements and compounds , including , but not limited to , al 2 o 3 , zns , and pt , the invented system is equally applicable for other physical and chemical vapor deposition tools , especially those with the capability to deposit upon and within modest aspect ratio features . several new design elements were incorporated : 1 ) compact electrical and purge gas connections on a single , small bolt - on fixture ; 2 ) the ability to integrate directly into a reactor wall , lid , or flange ; 3 ) a multiple o - ring seal and compression sleeve system that prevents ald on the back of the crystal and allowing rapid and simple crystal exchange ; 4 ) a low - profile lip and o - ring system that affords effective electrical contact to the front of the crystal without increasing the required purge time ; 5 ) a compact footprint that enables multi - point thickness mapping ; 6 ) superior thermal equilibration following sample exchange . when taken together , the design improves the accuracy of and significantly reduces the barrier to routine qcm measurements in a variety of ald tools . it is to be understood that the above description is intended to be illustrative , and not restrictive . for example , the above - described embodiments ( and / or aspects thereof ) may be used in combination with each other . in addition , many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope . while the dimensions and types of materials described herein are intended to define the parameters of the invention , they are by no means limiting , but are instead exemplary embodiments . for example , fig8 a - b are plan and elevated views , respectively , of multi - oscillating crystal configurations for a disk - shaped ald reactor lid geometry . fig9 is a schematic view of a multi - oscillating crystal configuration , wherein the crystals are arranged along a longintudinally extending region of a cylindrically - shaped ald reactor . many other embodiments will be apparent to those of skill in the art upon reviewing the above description . the scope of the invention should , therefore , be determined with reference to the appended claims , along with the full scope of equivalents to which such claims are entitled . in the appended claims , the terms “ including ” and “ in which ” are used as the plain - english equivalents of the terms “ comprising ” and “ wherein .” moreover , in the following claims , the terms “ first ,” “ second ,” and “ third ,” are used merely as labels , and are not intended to impose numerical requirements on their objects . further , the limitations of the following claims are not written in means - plus - function format and are not intended to be interpreted based on 35 u . s . c . § 112 , sixth paragraph , unless and until such claim limitations expressly use the phrase “ means for ” followed by a statement of function void of further structure . the present methods can involve any or all of the steps or conditions discussed above in various combinations , as desired . accordingly , it will be readily apparent to the skilled artisan that in some of the disclosed methods certain steps can be deleted or additional steps performed without affecting the viability of the methods . while the invention has been particularly shown and described with reference to a preferred embodiment hereof , it will be understood by those skilled in the art that several changes in form and detail may be made without departing from the spirit and scope of the invention .
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in this invention , linear polyethylene glycol and 2 , 2 - bis ( hydroxymethyl ) propionic anhydride are used as starting materials . diethylenetriaminepentacetic acid ( dtpa ) is the chelator to stabilize gd . a . preparation of the first generation benzylidene protected chelate p - d 1 -( o 2 bn ) peg diol ( mw 4000 da , 9 . 2 g , 2 . 3 mmol , 1 eq ) and dmap ( 0 . 1670 g , 0 . 39 mmol ) are mixed in a round - bottom conical vial . the mixture is dissolved in a 25 ml of dcm and then the vial is filled with nitrogen gas . benzylidene - 2 , 2 - bis ( oxymethyl ) propionic anhydride ( 4 . 27 g ( 10 mmol )) is dissolved in another vial , and then slowly dripped into the reaction vial . after 24 hours of stirring and reacting in room temperature , 10 ml methanol is added and the reaction is kept for another 6 hours for removing the un - reacted benzylidene - 2 , 2 - bis ( oxymethyl ) propionic anhydride . an excessive amount of ethyl ether ( 700 ml ) is added and the mixture is stirred until white precipitates are released , and the yield rate is about 90 %. among the products , the d n is d 1 with the structure of ( i ) as follows : 1 h nmr ( 400 mhz , cdcl 3 ): δ 1 . 06 ( s , 6 ), 3 . 55 ( t , 6 ), 3 . 61 ( bs ), 3 . 68 ( t , 6 ), 4 . 32 ( t , 4 ), 4 . 64 ( d , 4 ), 5 . 43 ( s , 2 ), 7 . 28 ( m , 6 ), 7 . 42 ( m , 4 ). after the above product ( 11 . 8 g ) is dissolved in 40 ml of 1 : 2 ch 2 cl 2 / meoh solution , 1 . 18 g of pd / c is added , and the mixture is stirred for 24 hours under a hydrogen - saturated environment . when the reaction ends , pd / c is filtrated from dcm , and as described above , an excessive amount of ethyl ether 600 ( ml ) is added to release the white precipitates . the yield rate of the product after freeze - drying is approximately 90 %. 1 h nmr ( 400 mhz , cdcl 3 ): δ 1 . 08 ( s , 6 ), 3 . 67 ( bs ), 4 . 31 ( t , 4 ). p - d 1 - oh ( 2 . 0 g , 0 . 4618 mmol ) and diethylenetriaminepentaacetic acid mono - n - hydroxysuccinimide ester ( dtpa - hsie ) ( 1 . 0871 g , 2 . 2 mmol ) are mixed in a 50 ml round - bottom conical vial and vacuum dried for 3 hours . anhydrous dmso ( 10 ml ) and triethylamine ( 224 μl ) are injected into the mixture and stirred for 48 hours at room temperature under saturated nitrogen gas . acetonitrile / acetone is used to release white residue ; the white solid product after centrifugation and freeze - drying is p - d 1 - dtpa . 1 h nmr ( 400 mhz , cdcl 3 ): δ 1 . 14 ( s , 6 ), 3 . 1 ( t , 16 ), 3 . 4 ( t , 16 ), 3 . 57 ( bs ), 3 . 75 ( s , 8 ), 3 . 8 ( s , 32 ). the principle of preparing the second generation p - d 2 -( o 2 bn ) product is approximately the same as that of the first generation . p - d 1 -( o 2 bn ) ( 95 . 6 g , 0 . 83 mmol , 1 equiv ) and dmap ( 0 . 326 g , 2 . 6 mmol , 3 . 2 equiv ) is mixed and then dissolved in 25 ml dcm . after benzylidene - 2 , 2 - bis ( oxymethyl ) propionic anhydride ( 13 . 3 mmol , 16 equiv , 5 . 69 g ) is added , the mixture is stirred at room temperature for 24 hours . un - reacted benzylidene - 2 , 2 - bis ( oxymethyl ) propionic anhydride is removed with 15 ml methanol . then ethyl ether is used to release the white precipitate at a yield rate of 80 % after freeze - drying . the product d n is d 2 with the structure ( ii ) as follows : 1 h nmr ( 400 mhz , cdcl 3 ): δ 1 . 03 ( s , 12 ), 1 . 26 ( s , 6 ), 3 . 63 ( bs ), 3 . 78 ( t , 4 ), 4 . 03 ( t , 4 ), 4 . 38 ( s , 8 ), 4 . 56 ( d , 8 ), 5 . 41 ( s , 4 ), 7 . 19 ( m , 12 ), 7 . 38 ( m , 8 ). the product ( 5 . 5 g ) from the above process is dissolved in 45 ml of 1 : 2 dcm / meoh solution . the de - protection procedure in step b . of example 1 is repeated , and the final yield rate is about 88 %. 1 h nmr ( 400 mhz , cdcl 3 ): δ 1 . 03 ( s , 12 ), 1 . 19 ( s , 6 ), 3 . 43 ( m , 8 ), 3 . 64 ( bs ), 4 . 08 ( m , 8 ), 4 . 40 ( d , 4 ). the method of synthesizing the second generation p - d 2 - dtpa is approximately the same as that of first generation . p - d 2 - oh ( 0 . 265 mmol , 1 . 3965 g ) and 1 . 2482 g ( 2 . 54 mmol ) dtpa - hsie is mixed in a 50 ml round bottom conical vial and vacuum dried for 4 hours . anhydrous dmso ( 10 ml ) and 350 μl triethylamine is injected into the mixture , and stirred for 48 hours at room temperature under saturated nitrogen gas . acetonitrile / acetone solution is used to release the white precipitate , and p - d 2 - dtpa is produced after centrifugation and freeze - drying . 1 h nmr ( 400 mhz , cdcl 3 ): δ 1 . 04 ( m ), 1 . 18 ( m ), 3 . 07 ( t , 16 ), 3 . 21 ( t , 16 ), 3 . 58 ( bs ), 3 . 68 ( m ), 3 . 79 ( d ), 4 . 21 ( bs ). the preparation process of the third generation p - d 3 -( o 2 bn ) is similar to that of the first and second generations . the product from step b . in example 2 ( 2 . 88 g , 0 . 40 mmol , 1 equiv ), benzylidene - 2 , 2 - bis ( oxymethyl ) propionic anhydride ( 5 . 48 g , 12 . 8 mmol , 32 equiv ), and dmap ( 0 . 3151 g , 2 . 57 mmol , 6 . 4 equiv ) are dissolved in 35 ml dcm at room temperature and reacted for 24 hours . the extracting procedure in step a . of example 2 is repeated , and the final product yield rate is about 89 %. the d n product is d 3 with the structure of ( iii ) as follows . 1 h nmr ( 400 mhz , cdcl 3 ): δ 0 . 89 ( s , 24 ), 1 . 16 ( s , 6 ), 1 . 17 ( s , 12 ), 3 . 57 ( t , 6 ), 3 . 67 ( bs ), 3 . 77 ( t , 3 ), 4 . 15 ( q , 6 ), 4 . 28 ( t , 3 ), 4 . 33 ( m , 16 ), 4 . 55 ( d , 16 ), 5 . 37 ( s , 8 ), 7 . 30 ( m , 24 ), 7 . 35 ( m , 16 ). the product ( 4 g ) from step a . is dissolved in the mixture of dcm and meoh ( 1 : 1 ). pd / c catalyst ( 0 . 4 g ) is added , and stirred for 24 hours under a hydrogen - saturated environment . white powder product ( 1 . 8 g ) is produced after filtering and freeze - drying . 1 h nmr ( 400 mhz , cdcl 3 ): δ 1 . 07 ( s , 24 ), 1 . 27 ( s , 6 ), 1 . 34 ( s , 12 ), 3 . 47 ( t ), 3 . 64 ( bs ), 3 . 76 ( m ), 4 . 26 ( m ), 4 . 32 ( dd , 10 ). the method of synthesizing the third generation p - d 3 - dtpa is the same as aforementioned . p - d 3 - oh ( 1 . 097 g , 0 . 1938 mmol ) and 1 . 814 g ( 3 . 6 mmol ) dtpa - hsie are mixed in a 50 ml round bottom conical vial and vacuum dried for 4 hours . anhydrous dmso ( 10 ml ) and 515 μl triethylamine are injected into the mixture , and stirred for 64 hours at room temperature under saturated nitrogen gas . after white precipitate is released by means of acetonitrile / acetone solution , the white solid product , p - d 3 - dtpa , is produced after centrifugation and freeze - drying . 1 h nmr ( 400 mhz , cdcl 3 ): δ 1 . 03 ( s ), 1 . 25 ( s ), 1 . 29 ( s ), 2 . 7 ( m ), 3 . 16 ( t ), 3 . 46 ( t ), 3 . 79 ( bs ), 3 . 80 ( m ), 3 . 97 ( bs ), 4 . 21 ( m ). in the p - d n - dtpa dendritic compounds of the first , second and third generation , the resonant frequency in nmr spectrum of the methyl on hydrogen is decreased as the generation extends . therefore , it is proved that the dendritic compound of p - d n - dtpa in the present example is the dendritic compound of the first , second and third generations . in addition , infrared spectrum can be applied to verify the structure of dtpa ; in other words , the original c — o bond of dtpa is disappeared at the peak of 1200 cm − 1 , and instead , the carbonyl peak is appeared between signals of 1638 and 1598 cm − 1 . as a result , it is proved that the dendritic compound in the present example possesses the dtpa to chelate gd . p - d 3 - dtpa ( 0 . 066 g , 0 . 005 mmol ) is dissolved in 10 ml water , and a 16 - time amount of gdcl 3 . 6h 2 o ( 0 . 031 g , 0 . 08 mmol ) is added . the ph value is adjusted in neutral ( ph7 ) by 0 . 1 n sodium hydroxide solution . the result of the reaction is verified by ftir and white solid product is produced after freeze - drying . by evaluating the effectiveness of the reacted dendritic compound p - d 3 - dtpa - gd 3 + of the third generation as an agent of enhancing image , it can be compared with the magnetizing relaxation of dtpa - gd ( magnevist ™) by directly comparing the magnetizing relaxation rate via nmr . the results of comparison are showed in table 1 in which r 1 and r 2 respectively represent vertical and horizontal relative relaxation times , and b 0 as the internal magnetic intensity of nmr . the greater volumes of r 1 and r 2 , the stronger image signal will be . therefore , table 1 is clearly indicated the chelating gd element of third generation dendritic compound provides a superior imaging result compared to dtpa - gd ( magnevist ™), and demonstrated distinct progress in nmr imaging . furthermore , conventional imaging agents require high concentration of gd to achieve the ideal image , and it is also a challenge to accumulate the imaging agent on a certain location . the dendritic compound in this invention provides a vivid and clear image with no need to accumulate the image agent on one position and this situation promotes a more suitable clinical application . in addition , each dendritic compound in the present invention contains protected oh functional groups , which extend to a higher generation and possesses the magnifying ability by times . therefore , compared to known imaging agents , a better imaging contrast is provided with the same amount . it is also known that chelator with small molecule weight penetrates vascular endothelial cells easily such that it disperses while circulating ; the dendritic compound is a high molecule carrier which decreases the possibility of being drained away during blood circulation . the “ core ” of the dendritic compound of the present invention is polyethylene glycol and its derivatives . polyethylene glycol , a bio - compatible polymer certified by the fda in the usa , is usually applied to biomedical polymers and can be eliminated spontaneously via circulation . therefore , the dendritic compound of the present invention can be an imaging agent with low toxicity .
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melt film fibrillation nozzles described in the prior art differ from the fiber forming nozzles in the current disclosure in how the fibers are made and the starting melt geometry from which a fibrous web is produced . melt film fibrillation processes of the prior art start with a single phase polymer flow that is impinged by a separate working air stream . the polymer melt film tube is thinned to a polymer film from the shearing action of the air stream . the polymer stream and the working air streams are combined externally to the nozzle at the nozzle exit . the shearing action of the inner gas stream and the effect of the outer gas stream produces a multiplicity of fibers . in contrast , the process of the current disclosure utilizes a mixing chamber to produce a two - phase polymer - gas mixture within the fiber - forming nozzle . the two - phase flow under pressure is then uniformly distributed to and forced through a film forming channel of high length to width ratio . this two phase flow of polymer and working gas in the same narrow long channel within the spin nozzle before the nozzle exit is a novel feature of the disclosure . without being bound by theory , it is believed that in the long narrow channel , the higher viscosity polymer phase forms a film along both surfaces of the channel while the air separates and is forced through the center of the channel . the long narrow channel geometry and control of the magnitude and ratio of polymer melt and gas flows determine the thickness and other attributes of the polymer film . upon exiting the channel , these in combination with the aerodynamic forces of the gas jet cause the polymer film to disintegrate into a multitude of finer filaments . the thinner the polymer film upon exit from the film forming channel , the finer the ultimate fibers produced . thus , by varying the polymer flow rate and the gas velocity , it is possible to control film thickness and hence the fine fiber diameter . in one embodiment the mixing chamber is a two - phase chamber and the long narrow film forming channel has a converging conical geometry . heated pressurized air , together with a polymer melt under pressure are both injected into the two - phase chamber where the mixture combines to form a two - phase flow . the rotational two phase flow in the two - phase chamber is converted into an axial flow along the length of a narrow converging conical channel . as the converging flow geometry decreases flow area , the accelerating gas velocity in turn increases shearing forces on the polymer film as the polymer progresses along the channel tending to thin the polymer film . however , that same converging flow geometry reduces the wall area supporting the polymer film which tends to increase the film thickness . balancing these opposed effects offers unique control over the resulting fiber size and the fiber size distribution . the present disclosure relates to apparatus and methods for forming non - woven nanofibrous materials . the non - woven nanofibrous materials are formed from one or more thermoplastic polymers . generally suitable polymers include any polymers suitable for melt spinning . the melting temperature is generally from about 25 c to 400 c . nonlimiting examples of thermoplastic polymers include polypropylene and copolymers , polyethylene and copolymers , polyesters , polyamides , polystyrenes , biodegradable polymers including thermoplastic starch , pha , pla , pcl , plga , polyurethanes , and combinations thereof . preferred polymers are pcl , pla , plga and other biodegradable linear aliphatic polyesters . optionally , the polymer may contain additional materials to provide additional properties for the fiber . these may modify the physical properties of the resulting fiber such as elasticity , strength , thermal or chemical stability , appearance , liquid absorbency , surface properties , among others . a suitable hydrophilic melt additive may be added . optional materials may be present up to 50 % of the total polymer composition . it may be desired to use a mixture of lower and higher molecular weight polymers in a web . the lower molecular weight polymer will fibrillate easier which may result in fibers having different diameters . if the polymers will not blend , separate nozzles may be utilized for the different molecular weight polymers . the average fiber diameter of a significant number of fibers in the fine fiber layer of the web can be less than one micron and preferably from about 0 . 1 microns to 1 micron , more preferably from about 0 . 5 microns to about 0 . 9 microns . the basis weight of the fine fiber layer can be less than about 25 gsm , commonly from about 0 . 1 to about 15 gsm , preferably less than 10 gsm or 5 gsm . the fine fiber layer may have a basis weight in the range of from about 0 . 5 to about 3 gsm or from about 0 . 5 to about 1 . 5 gsm , depending upon use of the nonwoven web . current fiber spinning methods such as melt spinning , electrospinning , flash spinning , etc ., deposit fibers with a mass distribution centered on the fiber issuing orifice because the probability of fiber deposition is highest at the point of fiber generation . the conical pack of the current disclosure avoids this problem because fiber generation and deposition are distributed uniformly around the circumference of a circle . the result of deposition on a moving take - up device from a single nozzle is a nominally uniform mass profile across the width of the deposition circle . the laws of physics make it increasingly difficult to distribute mass uniformly from a single fiber generating nozzle as throughput increases . this is because more work , faster is required for distribution as throughput increases . this is not the case with the conical pack . because of the geometry the uniformity of fiber distribution is nominally independent of throughput . the nozzle of the current disclosure provides therefore a unique capability to make uniform webs from a single nozzle at high throughput . while current film fibrillation methods typically produce non - uniform non - woven fibrous web , a more uniform fibrous web may be desirable for application such as drug delivery or wound care . a uniform fibrous web may have more controllable and predictable drug or active agent release characteristics . web uniformity can be measured through several methods . ( see description of uniformity index ( ui ) in u . s . pat . no . 7 , 118 , 698 to armantrout et al ). example 21 deposits fibers with mass distribution centered on the fiber issuing orifice , such as other nonwoven processes ; however , the technology of this disclosure lends itself to the design of a fiber forming nozzle with a conical , hollow laydown wherein the fiber generation and deposition are distributed uniformly around the circumference of a circle ( see fig3 ). examples of uniformity metrics include low coefficient of variation of pore diameter , basis weight , air permeability , and / or thermal resistance . uniformity may also be evaluated by the hydrohead or other liquid barrier measurement of the web . the relative distribution of microfibers in the non - woven fibrous web depends on the application and the polymer used . certain thermoplastic polymers such as pcl offer greater compression resistance and elasticity retaining its original shape after compression . the table below compares the uniformity levels of non - woven materials produced with the method of the current disclosure to other nonwoven materials . the uniformity of the produced materials with the methods of the current disclosure approaches that of films . in a preferred embodiment the ui of the material produced is between 2 and 6 . a process for spinning polymer submicron fibers into non - woven webs without the use of solvents according to the present disclosure is shown in fig1 and consists of the following process steps : the two - phase method for spinning polymeric fibers without the use of solvents is shown in fig1 and consisted of the following process steps : polymer was heated and stirred in a reactor vessel 1 to the desired spinning temperature ( the polymer temperature ). the stirrer 2 was stopped and ambient air was fed through a pressurization line 3 to establish a head pressure 4 on the melted polymer ( the polymer pressure ). the valve 5 was opened and pressurized polymer was forced out of the reactor vessel 1 through the valve 5 and then through a filter 6 and into the nozzle 7 . heated , pressurized air was injected through ports 8 ( see fig2 , fig3 , fig4 , and fig5 ) into the mixing chamber 9 of the two phase flow nozzle creating a rotational flow 10 ( see fig4 ). heated polymer was injected into the two - phase chamber 9 through eight orifices 11 ( see fig6 , fig7 ) spaced at 45 degree locations around a cylindrical polymer feed tube 12 . the two - phasing air flow mixed with the polymer creating a two - phase flow which was then forced through a converging channel 13 . the decreasing area of the converging channel 13 forced an increase in air speed along the axis of the nozzle and transitioned the rotational flow in the two - phase chamber into a mainly axial flow as it exited the nozzle through the annular orifice 14 . it is believed that : the polymer is sheared by the accelerating gas flow within the converging channel creating polymeric film layers on both sides of the converging channel 13 . these polymeric film layers were sheared into fibers by the accelerated gas flow such that resulting fiber fineness corresponded to the thickness of the polymeric film . one aspect of the process is that the total volumetric polymer flow can be easily regulated by the number of polymer injection orifices 11 , thus creating a way to vary film thickness at the exit annular orifice 14 and hence fiber size . heated air carrying powder ( s ) was injected 15 ( see fig8 ) into the two - phase nozzle and forced into an annulus 16 such that this flow impinged upon and into 17 the two - phase flow of polymer and heated air while the polymer was still above its melt temperature . the combined flows then mixed and the powder ( s ) became attached to the fibers . in a preferred embodiment , the fibers are collected on a screen at a distance of approximately 12 - 28 in from the exit of the two - phase nozzle . in an alternate embodiment of the process , the solidified issued material is collected at a set distance from the exit of the two - phase nozzle , also referred to herein as the “ collection surface ”. the collector can be a stationary flat porous structure made from perforated metal sheet or rigid polymer . the collector can be coated with a friction - reducing coating such as a fluoropolymer resin , or it can be caused to vibrate in order to reduce the friction or drag between the collected material and the collection surface . the collection surface is preferably porous so that vacuum can be applied to the material as it is being collected to assist the pinning of the material to the collector . in one embodiment , the collection surface comprises a honeycomb material , which allows vacuum to be pulled on the collected material through the honeycomb material while providing sufficient rigidity not to deform as a result . the honeycomb can further have a layer of mesh covering it to collect the issued material . the collection surface can also be a component of the desired product itself . for instance , a preformed sheet can be the collection surface and a thin layer can be issued onto the collection surface to form a thin membrane on the surface of the preformed sheet . this can be useful for enhancing the surface properties of the sheet , such as printability , adhesion , porosity level , and so on . the preformed sheet can be a nonwoven or woven sheet , or a film . in this embodiment , the preformed sheet can even be a nonwoven sheet formed in the process of the disclosure itself , and subsequently fed through the process of the disclosure a second time , supported by the collection belt , as the collection surface . in another embodiment of the present disclosure , a preformed sheet can even be used in the process of the disclosure as the collection belt itself . the collection surface can alternatively comprise a flexible collection belt moving over a stationary cylindrical porous structure . the collection belt is preferably a smooth , porous material so that vacuum can be applied to the collected material through the cylindrical porous structure without causing holes to be formed in the collected material . the collection surface can alternatively further comprise a substrate such as a woven or a nonwoven fabric moving on the moving collection belt , such that the issued material is collected on the substrate rather than directly on the belt . this is especially useful when the material being collected is in the form of very fine particles . in one embodiment of the disclosure in which the material being issued comprises a polymeric fibrous material , the material collected on the collection surface is heated sufficiently to bond the material . this can be accomplished by maintaining the temperature of the atmosphere surrounding the collected material at a temperature sufficient to bond the collected material . the temperature of the material can be sufficient to cause a portion of the polymeric fibrous material to soften or become tacky so that it bonds to itself and the surrounding material as it is collected . a small portion of the polymer can be caused to soften or become tacky either by heating the issued material before it is collected sufficiently to melt a portion thereof , or by collecting the material and immediately thereafter , melting a portion of the collected material by way of the heated gas passing therethrough . in this way , the process of the disclosure can be used to make a self - bonded nonwoven product , wherein the temperature of the gas passing through the collected material is sufficient to melt or soften a small portion of the web but not so high as to melt a major portion of the web . various methods can be employed to secure or pin the material to the collection surface . according to one method , vacuum is applied to the collection surface from the side opposite the collection surface at a sufficient level to cause the material to be pinned to the collection surface . as an alternative to pinning the material by vacuum , the material can also be pinned to the collection surface by electrostatic force of attraction between the material and the collection surface , the collecting cylindrical structure , or the collection belt , as the case can be for a particular embodiment of the disclosure . this can be accomplished by creating either positive or negative ions in the gap between the nozzle and the collection surface while grounding the collection surface , so that the newly issued material picks up charged ions and thus the material becomes attracted to the collection surface . whether to create positive or negative ions in the gap between the nozzle and the collector is determined by what is found to more efficiently pin the material being issued . it has surprisingly been found that the uniformity index of the produced material improves with the application an electrical charge . in order to create positive or negative ions in the gap between the nozzle and the collection surface , and thus to positively or negatively charge the solidified issued material passing through the gap , one embodiment of the process of the present disclosure employs a charge - inducing element installed on the nozzle . the charge - inducing element can comprise pin ( s ), brushes , wire ( s ) or other element , wherein the element is made from a conductive material such as metal or a synthetic polymer impregnated with carbon . a voltage is applied to the charge - inducing element such that an electric current is generated in the charge - inducing element , creating a strong electric field in the vicinity of the charge - inducing element which ionizes the gas in the vicinity of the element thereby creating a corona . the amount of electrical current necessary to be generated in the charge - inducing element will vary depending on the specific material being processed , but the minimum is the level found to be necessary to sufficiently pin the material , and the maximum is the level just below the level at which arcing is observed between the charge - inducing element and the grounded collection belt . all documents cited are , in relevant part , incorporated herein by reference ; the citation of any document is not to be construed as an admission that it is prior art with respect to the present disclosure . a scanning electron microscope ( sem ) was used to take micrographs of polymer fibers . various magnifications were used and a scale watermark of 5 , 10 , 20 , or 100 microns was overlaid onto the sem image accordingly . the sem picture was imported into powerpoint ®, and an x and y axis was placed onto the picture and related to the micron scale using the line drawing tool . the resulting image was captured and imported into digitizelt © ( a software program used to digitize points within an image ). lengths ( in microns ) of the pictured axes were reported to the program relative to the micron scale overlaid onto the sem image , and two ( x , y ) data point . method used to determine the machine direction uniformity index . the md ui of a sheet is calculated according to the following procedure . a beta thickness and basis weight gauge ( quadrapac sensor by measurex infrand optics ) scans the sheet and takes a basis weight measurement every 0 . 2 inches ( 0 . 5 cm ) across the sheet in the cross direction ( cd ). the sheet then advances 0 . 42 inches ( 1 . 1 cm ) in the machine direction ( md ) and the gauge takes another row of basis weight measurements in the cd . in this way , the entire sheet is scanned , and the basis weight data is electronically stored in a tabular format . the rows and columns of the basis weight measurements in the table correspond to cd and md “ lanes ” of basis weight measurements , respectively . then each data point in column 1 is averaged with its adjacent data point in column 2 ; each data point in column 3 is averaged with its adjacent data point in column 4 ; and so on . effectively , this cuts the number of md lanes ( columns ) in half and simulates a spacing of 0 . 4 inch ( 1 cm ) between md lanes instead of 0 . 2 inch ( 0 . 5 cm ). in order to calculate the uniformity index ( ui ) in the machine direction (“ md ui ”), the ui is calculated for each column of the averaged data in the md . the ui for each column of data is calculated by first calculating the standard deviation of the basis weight and the mean basis weight for that column . the ui for the column is equal to the standard deviation of the basis weight divided by the square root of the mean basis weight , multiplied by 100 . finally , to calculate the overall machine direction uniformity index ( md ui ) of the sheet , all of the ui &# 39 ; s of each column are averaged to give one uniformity index . the units for uniformity index are ( ounces per square yd ) ½ . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 70 g of capa 6100 polycaprolactone polymer ( perstorp ) and 30 g of capa 6500 polycaprolactone polymer ( perstorp ). the polymer mixture was heated to 140 c and pressurized to 25 psig . the heated and pressurized polymer was forced through a 140 micron rated filter and then into the two - phase nozzle . heated air was injected into the two - phase chamber at 171 c and 40 psig . fibers were produced at a rate of 0 . 014 g / min . a microscope picture of the fibers produced is shown in fig9 . the fiber size distribution is shown in fig1 . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 70 g of capa 6100 polycaprolactone polymer ( perstorp ) and 30 g of capa 6500 polycaprolactone polymer ( perstorp ). the polymer mixture was heated to 160 c and pressurized to 40 psig . the heated and pressurized polymer was forced through a 140 micron rated filter and then into the two - phase nozzle . heated air was injected into the two - phase chamber at 181 c and 60 psig . fibers were produced at a rate of 0 . 31 g / min . a microscope picture of the fibers produced is shown in fig1 . the fiber size distribution is shown in fig1 . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 70 g of capa 6100 polycaprolactone polymer ( perstorp ) and 30 g of capa 6500 polycaprolactone polymer ( perstorp ). the polymer mixture was heated to 156 c and pressurized to 40 psig . the heated and pressurized polymer was forced through a 140 micron rated filter and then into the two - phase nozzle . heated air was injected into the two - phase chamber at 225 c and 60 psig . fibers were produced at a rate of 0 . 014 g / min . a sem of the fibers produced is shown in fig1 . the fiber size distribution is shown in fig1 . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 100 g of capa 6100 polycaprolactone polymer ( perstorp ), 30 g of capa 6500 polycaprolactone polymer ( perstorp ), 5 g of capa 6800 ( perstop ), and 0 . 5 g of cocamidopropyl betaine . the mixture was heated to 158 c and pressurized to 38 psig to make example 4 - 1 and the mixture was heated to 155 c and pressurized to 38 psig to make example 4 - 2 . the heated and pressurized mixture was forced through a 140 micron rated filter and then into the two - phase nozzle . heated air was injected into the two - phase chamber at 238 c and 40 psig for example 4 - 1 and heated air was injected into the two - phase chamber at 240 c and 40 psig for example 4 - 2 . a sem of example 4 - 1 as spun is shown in fig1 . a flow of air and kaolin powder at 81 c was impinged upon the primary two - phase flow , thereby attaching powder to the polymer mixture melt for example 4 - 1 ; and a flow of air and kaolin powder at 120 c impinged upon the primary two - phase flow , thereby attaching powder to the polymer mixture melt for example 4 - 2 . the production rates where : 0 . 77 g / min for example 4 - 1 and 0 . 81 g / min for example 4 - 2 . the samples as - spun were water washed in stirred beaker to induce some shear on the attached powder . the samples were then “ ashed ” to determine the amount of powder remaining on the samples . another set of the samples were heated in an oven to 55 c for 10 minutes and then subjected to water washing and “ ashed ” to determine the remaining amounts of powder . another set of samples were tested for blood clotting time . for reference , the control clotting time was 7 . 5 minutes , whereby the blood was brought to body temperature and allowed to clot without clotting agents present . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 105 g of capa 6100 polycaprolactone polymer ( perstorp ), 45 g of capa 6500 polycaprolactone polymer ( perstorp ), and 0 . 5 g of cocamidopropyl betaine . the mixture was heated to 157 c and pressurized to 38 psig . the heated and pressurized mixture was forced through a 140 micron rated filter and then into the two - phase flow nozzle . heated air was injected into the two - phase chamber at 220 c and 38 psig . a flow of air and chitosan powder at 105 c impinged upon the primary two - phase flow , thereby attaching the powder to the polymer mixture melt . a sem of the fibers produced is shown in fig1 . the production rate was 1 . 72 g / min . the amount of attached chitosan powder was 10 . 1 % by weight . the blood clotting time was measured to be 4 . 5 minutes . an observation was that chitosan absorbed the blood very well and created a gel although the time to clot was lengthy . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 105 g of capa 6100 polycaprolactone polymer ( perstorp ), 45 g of capa 6500 polycaprolactone polymer ( perstorp ), and 0 . 5 g of cocamidopropyl betaine . the mixture was heated to 154 c and pressurized to 37 - 38 psig . the heated and pressurized mixture was forced through a 140 micron rated filter and then into the two - phase nozzle . heated air was injected into the two - phase chamber at 218 c and 30 - 37 psig . a flow of air , chitosan powder , and kaolin powder at 76 c impinged upon the primary two - phase flow , thereby attaching the powders to the polymer mixture melt . the ratio of powders was : kaolin 75 % and chitosan 25 %. a sem of the collected fibers is shown in fig1 . the production rate was 0 . 7 - 0 . 88 g / min . the amount of attached powder ( chitosan and kaolin ) was 17 % by weight ; chitosan at 14 . 5 % and kaolin at 2 . 5 %. the sample was water washed and amount of attached kaolin after washing was 0 . 9 % and the amount of attached chitosan was found to be approximately unchanged at 14 . 5 %. air washing was observed to create a more “ open ” structure , thereby permitting the blood to flow more freely into the fibrous structure . also , it was observed that the blood began clotting immediately and wetted out the sample due to the chitosan . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 105 g of capa 6100 polycaprolactone polymer ( perstorp ), 45 g of capa 6500 polycaprolactone polymer ( perstorp ), and 0 . 5 g of cocamidopropyl betaine . the mixture was heated to 154 c and pressurized to 40 psig . the heated and pressurized polymer was forced through a 140 micron rated filter and then into the two - phase nozzle . heated air was injected into the two - phase chamber at 228 c and 40 psig . a flow of air , ⅓ mol calcium peroxide powder , and ⅔ mol citric acid powder at 60 c was impinged upon the primary two - phase flow , thereby attaching the powders to the polymer mixture melt . the production rate was 0 . 71 g / min . the attachment of the powders to the fibers is shown in fig1 . the sample was saturated with water and the release rate of oxygen was measured ( see fig1 .) a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 105 g of capa 6100 polycaprolactone polymer ( perstorp ), 45 g of capa 6500 polycaprolactone polymer ( perstorp ), and 0 . 5 g of cocamidopropyl betaine . the mixture was heated to 152 c and pressurized to 40 psig . the heated and pressurized polymer was forced through a 140 micron rated filter and then into the two - phase nozzle . heated air was injected into the two - phase chamber at 212 c and 38 psig . a flow of air , reon powder , copper oxide powder , and chitosan powder at 350 c was impinged upon the primary two - phase flow , thereby attaching the powders to the polymer mixture melt . the weight ratio of the powders was : reon 25 %, copper oxide 25 %, and chitosan 50 %. a sem picture of the collected fibers is shown in fig2 . the production rate was 0 . 6 g / min . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 105 g of capa 6100 polycaprolactone polymer ( perstorp ), 45 g of capa 6500 polycaprolactone polymer ( perstorp ), and 0 . 5 g of cocamidopropyl betaine . the mixture was heated to 154 c and pressurized to 40 psig . the heated and pressurized polymer was forced through a 140 micron rated filter and then into the two - phase flow nozzle . heated air was injected into the two - phase chamber at 228 c and 40 psig . a flow of air , ⅓ mol calcium peroxide powder , ⅔ mol citric acid powder , and chitosan powder at 60 c was impinged upon the primary two - phase flow , thereby attaching the powders to the polymer mixture melt . the weight ratio of the powders was : citric acid 51 %, calcium peroxide 19 %, and chitosan 25 %. a sem picture of the collected fibers is shown in fig2 . the production rate was 0 . 71 g / min . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 105 g of capa 6100 polycaprolactone polymer ( perstorp ), 45 g of capa 6500 polycaprolactone polymer ( perstorp ), and 0 . 5 g of cocamidopropyl betaine . the mixture was heated to 152 c and pressurized to 40 psig . the heated and pressurized polymer was forced through a 140 micron rated filter and then into the two - phase flow nozzle . heated air was injected into the two - phase chamber at 212 c and 38 psig . a flow of air , reon powder , kaolin powder , and chitosan powder at 350 c impinged upon the primary two - phase flow , thereby attaching the powders to the polymer mixture melt . the weight ratio of the powders was : reon 40 %, kaolin 50 %, and chitosan 10 %. the production rate was 0 . 6 g / min . after the sample was formed , a flow of steam was vacuumed through the material . this technique made the reon powder sticky thus forming more of a bond between the powders and the fibers . a sem picture of the material is shown in fig2 . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 105 g of capa 6100 polycaprolactone polymer ( perstorp ), 45 g of capa 6500 polycaprolactone polymer ( perstorp ), and 0 . 5 g of cocamidopropyl betaine . the mixture was heated to 152 c and pressurized to 40 psig . the heated and pressurized polymer was forced through a 140 micron rated filter and then into the two - phase nozzle . heated air was injected into the two - phase chamber at 212 c and 38 psig . a flow of air , reon powder , kaolin powder , and chitosan powder at 350 c was impinged upon the primary two - phase flow , thereby attaching the powders to the polymer mixture melt . the weight ratio of the powders was : reon 25 %, copper oxide 25 %, and chitosan 50 %. a sem picture of the collected fibers is shown in fig2 . the production rate was 0 . 6 g / min . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 100 g of capa 6100 polycaprolactone polymer ( perstorp ), 30 g of capa 6500 polycaprolactone polymer ( perstorp ), 5 g of capa 6800 ( perstop ), and 0 . 5 g of cocamidopropyl betaine . the mixture was heated to 156 c and pressurized to 50 psig . the heated and pressurized mixture was forced through a 140 micron rated filter and then into the two - phase nozzle . heated air was injected into the two - phase chamber at 197 c and 50 psig . a flow of heated air and kaolin powder was impinged upon the primary two - phase flow , thereby attaching powder to the polymer mixture melt . a sem picture of the collected fibers is shown in fig2 . the flowrate was 1 . 89 g / min . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 100 g of capa 6100 polycaprolactone polymer ( perstorp ), 30 g of capa 6500 polycaprolactone polymer ( perstorp ), 5 g of capa 6800 ( perstop ), and 0 . 5 g of cocamidopropyl betaine . the mixture was heated to 130 c and pressurized to 42 psig . the heated and pressurized mixture was forced through a 140 micron rated filter and then into the two - phase nozzle . heated air was injected into the two - phase chamber at 207 c and 38 psig . heated air was impinged onto the 2 phase flow at 400 c . a sem picture of the collected fibers is shown in fig2 . the flowrate of fibers was 0 . 33 g / min . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 50 g of natureworks ® pla polymer 6302d . the polymer was heated to 174 c and pressurized to 42 psig . the heated and pressurized polymer was forced through a 140 micron rated filter and then into the two - phase nozzle . heated air was injected into the two - phase chamber at 278 c and 50 psig . a flow of heated air at approximately 350 c and powder mixture impinged upon the primary two - phase flow , thereby attaching the powder mixture to the polymer mixture melt . the powder mixture was 95 % reon ™ and 2 . 5 % chrysal clear professional 2 . the free jet carrying the pla fibers and the attached reon ™ and chrysal clear professional 2 powder mixture impinged upon the stems of a bouquet of cut flowers . the flowers were rotated slowly under the free jet allowing the fibers and attached powders to form a layer of material for transporting the bouquet . the material covered the cut ends of the stems and a distance of about 6 cm along the stems from the cut ends toward the flowers . the bouquet of flowers with the material is shown in fig2 , 27 , and 28 . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 105 g of capa 6100 polycaprolactone polymer ( perstorp ), 45 g of capa 6500 polycaprolactone polymer ( perstorp ), and 0 . 5 g of cocamidopropyl betaine . the mixture was heated to 150 c and pressurized to 40 psig . the heated and pressurized mixture was forced through a 140 micron rated filter and then into the two - phase nozzle as shown in fig2 . heated air was injected into the two - phase chamber at 210 c and 38 psig . flowrate was 0 . 6 g / min . the issuing fibers were impinged upon a rotating circular plastic drinking straw at a distance of about 8 to 10 inches . the fibers were allowed to collect for about 4 to 4 minutes resulting in the formation of a tubular structure as shown in fig2 . the structure would be useful as a tissue engineering scaffold . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 70 g of capa 6100 polycaprolactone polymer ( perstorp ), 30 g of capa 6500 polycaprolactone polymer ( perstorp ), 25 g of natureworks polylatic acid polymer ( pla grade 6302d ), and 2 . 5 g kaolin powder . the mixture was heated to 165 c and pressurized to 40 psig . the heated and pressurized mixture was forced through a 140 micron rated filter and then into the two - phase nozzle as shown in fig2 . heated air was injected into the two - phase chamber at 265 c and 50 psig . the fibers produced were collected on a screen 12 - 28 inches away . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 105 g of capa 6100 polycaprolactone polymer ( perstorp ), 37 . 5 g of capa 6500 polycaprolactone polymer ( perstorp ), 7 . 5 g of capa 6800 polycaprolactone polymer ( perstorp ), and 0 . 75 g of cocamidopropyl betaine . the mixture was heated to 150 c and pressurized to 50 psig . the heated and pressurized mixture was forced through a 140 micron rated filter and then into the two - phase nozzle as shown in fig2 . heated air was injected into the two - phase chamber at 232 c and 52 psig . the fibers produced were collected on a screen 12 - 28 inches away . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 105 g of capa 6100 polycaprolactone polymer ( perstorp ), 37 . 5 g of capa 6500 polycaprolactone polymer ( perstorp ), 7 . 5 g of capa 6800 polycaprolactone polymer ( perstorp ), 0 . 75 g of cocamidopropyl betaine , and 1 . 5 g sodium percarbonate . the mixture was heated to 80 c and pressurized to 40 psig . the heated and pressurized mixture was forced through a 140 micron rated filter and then into the two - phase nozzle as shown in fig2 . heated air was injected into the two - phase chamber at 240 c and 50 psig . the fibers produced were collected on a screen 12 - 28 inches away . a sem picture of the fibers collected is shown in fig3 . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 25 g of capa 6100 polycaprolactone polymer ( perstorp ), 25 g poly ( 2 - ethyl 2 oxazoline ) polymer , and 2 . 75 g kaolin powder . the mixture was heated to 154 c and pressurized to 32 psig . the heated and pressurized mixture was forced through a 140 micron rated filter and then into the two - phase nozzle as shown in fig2 . heated air was injected into the two - phase chamber at 243 c and 40 psig . the fibers produced were collected on a screen 12 - 28 inches away . a sem picture of the fibers collected is shown in fig3 . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 25 g of capa 6100 polycaprolactone polymer ( perstorp ), 27 . 3 g of capa 6500 polycaprolactone polymer ( perstorp ), 10 g poly ( 2 - ethyl 2 oxazoline ) polymer , and 5 g water . the mixture was heated to 151 c and pressurized to 32 psig . the heated and pressurized mixture was forced through a 140 micron rated filter and then into the two - phase nozzle as shown in fig2 . heated air was injected into the two - phase chamber at 222 c and 40 psig . the fibers produced were collected on a screen 12 - 28 inches away . a stainless steel reactor vessel ( volume = 0 . 5 l ) was charged with 105 g of capa 6100 polycaprolactone polymer ( perstorp ), 45 g of capa 6500 polycaprolactone polymer ( perstorp ), the mixture was heated to 160 c and pressurized to 60 psig . the heated and pressurized mixture was forced through a 140 micron rated filter and then into the two - phase nozzle as shown in fig3 . heated air was injected into the two - phase chamber at 245 c and 80 psig . the fiber flowrate was 0 . 141 g / min . the fibers produced were collected on a moving scrim of reemay ® as it passed over a vacuum box . the exit of the two - phase nozzle was 18 inches from the collecting surface . the machine - direction ( md ) uniformity of the collected sheet material was measured by weighing 0 . 5 inch squares in lanes in the md . three lanes were measured , each with 14 squares . the sample uniformity index , ui , was calculated to be 5 . 6 ( see definition of ui .)
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other than in the operating examples , or where otherwise indicated , all numbers expressing quantities of ingredients and / or reaction conditions are to be understood as being modified in all instances by the term “ about ” which encompasses ± 10 %. “ keratinous substrate ” may be chosen from , for example , hair , eyelashes , lip , and eyebrows , as well as the stratum corneum of the skin and nails . “ polymers ” as defined herein , include homopolymers and copolymers formed from at least two different types of monomers . as used herein , the expression “ at least one ” means one or more and thus includes individual components as well as mixture / combinations . the “ wear ” of compositions as used herein , refers to the extent by which the color of the composition remains the same or substantially the same as at the time of application , as viewed by the naked eye , after a certain period or an extended period of time . wear properties may be evaluated by any method known in the art for evaluating such properties . for example , wear may be evaluated by a test involving the application of a composition to human hair , skin or lips and evaluating the color of the composition after a specified period of time . for example , the color of a composition may be evaluated immediately following application to hair , skin or lips and these characteristics may then be re - evaluated and compared after a certain amount of time . further , these characteristics may be evaluated with respect to other compositions , such as commercially available compositions . “ tackiness ” as used herein refers to the adhesion between two substances . for example , the more tackiness there is between two substances , the more adhesion there is between the substances . to quantify “ tackiness ,” it is useful to determine the “ work of adhesion ” as defined by iupac associated with the two substances . generally speaking , the work of adhesion measures the amount of work necessary to separate two substances . thus , the greater the work of adhesion associated with two substances , the greater the adhesion there is between the substances , meaning the greater the tackiness is between the two substances . work of adhesion and , thus , tackiness , can be quantified using acceptable techniques and methods generally used to measure adhesion , and is typically reported in units of force time ( for example , gram seconds (“ g s ”)). for example , the ta - xt2 from stable micro systems , ltd . can be used to determine adhesion following the procedures set forth in the ta - xt2 application study ( ref : mati / po . 25 ), revised january 2000 , the entire contents of which are hereby incorporated by reference . according to this method , desirable values for work of adhesion for substantially non - tacky substances include less than about 0 . 5 g s , less than about 0 . 4 g s , less than about 0 . 3 g s and less than about 0 . 2 g s . as known in the art , other similar methods can be used on other similar analytical devices to determine adhesion . “ substituted ” as used herein , means comprising at least one substituent . non - limiting examples of substituents include atoms , such as oxygen atoms and nitrogen atoms , as well as functional groups , such as hydroxyl groups , ether groups , alkoxy groups , acyloxyalky groups , oxyalkylene groups , polyoxyalkylene groups , carboxylic acid groups , amine groups , acylamino groups , amide groups , halogen containing groups , ester groups , thiol groups , sulphonate groups , thiosulphate groups , siloxane groups , and polysiloxane groups . the substituent ( s ) may be further substituted . the composition according to the invention comprises at least one supramolecular polymer comprising a polyalkene - based supramolecular polymer . in particular , the polyalkene - based supramolecular polymer is obtained by a reaction , especially the condensation , of at least one polyalkene polymer functionalized with at least one reactive group , with at least one junction group functionalized with at least one reactive group capable of reacting with the reactive group ( s ) of the functionalized polyalkene polymer , said junction group being capable of forming at least three hydrogen bonds and preferably at least four hydrogen bonds , preferentially four hydrogen bonds . the terms “ polyalkene ” and “ polyolefin ” mean a polymer derived from the polymerization of at least one monomer of alkene type , comprising an ethylenic unsaturation , the said monomer possibly being pendent or in the main chain of the said polymer . the terms “ polyalkene ” and “ polyolefin ” are thus directed towards polymers that may or may not comprise a double bond . preferably , the supramolecular polymers used according to the invention are prepared from a polymer derived from the polymerization of an alkene comprising at least two ethylenic unsaturations . the supramolecular polymer according to the invention is capable of forming a supramolecular polymer chain or network , by ( self ) assembly of said polymer according to the invention with at least one other identical or different polymer according to the invention , each assembly involving at least one pair of paired junction groups , which may be identical or different , borne by each of the polymers according to the invention . for the purposes of the invention , the term “ junction group ” means any group comprising groups that donate or accept hydrogen bonds , and capable of forming at least three hydrogen bonds and preferably at least four hydrogen bonds , preferentially four hydrogen bonds , with an identical or different partner junction group . these junction groups may be lateral to the polymer backbone ( side branching ) and / or borne by the ends of the polymer backbone , and / or in the chain forming the polymer backbone . they may be distributed in a random or controlled manner . the polyalkene polymers are functionalized with at least one reactive group and preferably with at least two reactive groups . the functionalization preferably occurs at the chain ends . they are then referred to as telechelic polymers . the functionalization groups , or reactive groups , may be attached to the polyalkene polymer via linkers , preferably linear or branched c 1 - c 4 alkylene groups , or directly via a single bond . preferably , the functionalized polyalkene polymers have a number - average molecular mass ( mn ) of between 1000 and 8000 . even more preferably , they have a number - average molecular mass of between 1000 and 5000 , or even between 1500 and 4500 . even more preferably , they have a number - average molecular mass of between 2000 and 4000 . preferably , the functionalized polyalkene polymer , capable of forming all or part of the polymer backbone of the supramolecular polymer according to the invention ( preferably , it forms all of the backbone of the polymer ), is of formula ho — p — oh in which : p represents a homo - or copolymer that may be obtained by polymerization of one or more linear , cyclic and / or branched , polyunsaturated ( preferably diunsaturated ) c 2 - c 10 and preferably c 2 - c 4 alkenes . p preferably represents a homo - or copolymer that may be obtained by polymerization of one or more linear or branched , c 2 - c 4 diunsaturated alkenes . more preferably , p represents a polymer chosen from a polybutylene , a polybutadiene ( such as a 1 , 4 - polybutadiene or a 1 , 2 - polybutadiene ), a polyisoprene , a poly ( 1 , 3 - pentadiene ) and a polyisobutylene , and copolymers thereof . the preferred poly ( ethylene / butylenes ) are copolymers of 1 - butene and of ethylene . they may be represented schematically by the following sequence of units : [— ch 2 — ch 2 —] and [— ch 2 ch ( ch 2 — ch 3 )—]. according to a second preferred embodiment , p is a polybutadiene homopolymer , preferably chosen from a 1 , 4 - polybutadiene or a 1 , 2 - polybutadiene . the polybutadienes may be 1 , 4 - polybutadienes or 1 , 2 - polybutadienes , which may be represented schematically , respectively , by the following sequences of units : preferably , they are 1 , 2 - polybutadienes . preferably , p is a 1 , 2 - polybutadiene homopolymer . according to another embodiment , p is a polyisoprene . polyisoprenes may be represented schematically by the following sequences of units : a mixture of above units may obviously also be used , so as to form copolymers . the functionalized polyalkene polymers may be totally hydrogenated to avoid the risks of crosslinking . preferably , the functionalized polyalkene polymers used in the compositions according to the invention are hydrogenated . preferably , the polyalkene polymers are hydrogenated and functionalized with at least two oh reactive groups , which are preferably at the ends of the polymers . preferably , they have functionality as hydroxyl end groups of from 1 . 8 to 3 and preferably in the region of 2 . the polydienes containing hydroxyl end groups are especially defined , for example , in fr 2 782 723 . they may be chosen from polybutadiene , polyisoprene and poly ( 1 , 3 - pentadiene ) homopolymers and copolymers . mention will be made in particular of the hydroxylated polybutadienes sold by the company sartomer , for instance the krasol ® resins and the poly bd ® resins . preferably , they are hydrogenated dihydroxylated 1 , 2 - polybutadiene homopolymers , such as nisso - pb 1 , gi3000 , gi2000 and gi1000 sold by the company nisso , which may be represented schematically by the following formula : these polymers have the following number - average molecular masses : gi3000 of mn = 4700 , gi2000 of mn = 3300 and gi1000 of mn = 1500 . these values are measured by gpc according to the following protocol . determination of the number - average molecular mass mn , the weight - average molecular mass mw and the polydispersity index mw / mn in polystyrene equivalents . ps 6035000 - ps 3053000 - ps 915000 - ps 483000 - ps 184900 - ps 60450 - ps 19720 - ps 8450 - ps 3370 - ps 1260 - ps 580 inject 100 μl of each of the solutions into the calibration column . prepare a solution with a solids content of 0 . 5 % in thf ( tetrahydrofuran ). prepare the solution about 24 hours before injection . filter the solution through a millex fh filter ( 0 . 45 μm ). columns : pl rapid m ( batch 5m - poly - 008 - 15 ) from polymer labs pl - gel hts - d ( batch 5m - md - 72 - 2 ) from polymer labs pl - gel hts - f ( 10m - 2 - 169b - 25 ) from polymer labs pl - rapid - f ( 6m - 0l1 - 011 - 6 ) from polymer labs length : 150 mm — inside diameter : 7 . 5 mm pump : isocratic m1515 waters eluent : thf injection : 100 μl at 0 . 5 % am ( active material ) in the eluent detection : ri 64 mv ( waters 2424 refractometer ) the average molar masses are determined by plotting the calibration curve : log molar mass = f ( illusion volume at the top of the ri detection peak ) and using the empower option gpc software from waters . among the polyolefins with hydroxyl end groups , mention may be made preferentially of polyolefins , homopolymers or copolymers with α , ω - hydroxyl end groups , such as polyisobutylenes with α , ω - hydroxyl end groups ; and the copolymers of formula : where ( m + n ) is from 1 to 100 and 0 & lt ; n & lt ;( m + n ), more preferably ( m + n ) is from 5 to 50 and 0 & lt ; n & lt ;( m + n ); most preferably ( m + n ) is from 9 to 35 and 0 & lt ; n & lt ;( m + n ). in a preferred embodiment , the copolymers of the above formula are those sold by mitsubishi under the brand name polytail . the supramolecular polymers according to the invention also have in their structure at least one residue of a junction group capable of forming at least three hydrogen bonds and preferably at least four hydrogen bonds , said junction group being initially functionalized with at least one reactive group . unless otherwise mentioned , the term “ junction group ” means in the present description the group without its reactive function . the reactive groups are attached to the junction group via linkers l . l is a single bond or a saturated or unsaturated c 1 - c 20 divalent carbon - based group chosen in particular from a linear or branched c 11 - c 20 alkylene ; a c 5 - c 20 ( alkyl ) cycloalkylene alkylene ( preferably cyclohexylene methylene ), a c 11 - c 20 alkylene - biscycloalkylene ( preferably alkylene - biscyclohexylene ), a c 6 - c 20 ( alkyl ) arylene , and an alkylene - bisarylene ( preferably an alkylene - biphenylene ); the linker l possibly being substituted with at least one alkyl group and / or possibly comprising 1 to 4 n and / or o heteroatoms , especially in the form of an no 2 substituent . preferably , the linker is a group chosen from phenylene ; 1 , 4 - nitrophenylene ; 1 , 2 - ethylene ; 1 , 6 - hexylene ; 1 , 4 - butylene ; 1 , 6 -( 2 , 4 , 4 - trimethylhexylene ); 1 , 4 -( 4 - methylpentylene ); 1 , 5 -( 5 - methylhexylene ); 1 , 6 -( 6 - methylheptylene ); 1 , 5 -( 2 , 2 , 5 - trimethylhexylene ); 1 , 7 -( 3 , 7 - dimethyloctylene ); - isophorone -; 4 , 4 ′- methylene bis ( cyclohexylene ); tolylene ; 2 - methyl - 1 , 3 - phenylene ; 4 - methyl - 1 , 3 - phenylene ; and 4 , 4 - biphenylenemethylene . c 1 - c 20 alkylene such as —( ch 2 ) 2 —; —( ch 2 ) 6 —; — ch 2 ch ( ch 3 )— ch 2 — c ( ch 3 ) 2 — ch 2 — ch 2 —, and preferably , l is chosen from : - isophorone -; —( ch 2 ) 2 —; —( ch 2 ) 6 —; — ch 2 ch ( ch 3 )— ch 2 — c ( ch 3 ) 2 — ch 2 — ch 2 —; 4 , 4 ′- methylene biscyclohexylene ; and 2 - methyl - 1 , 3 - phenylene . according to one particularly preferred embodiment , the linker is an alkylcycloalkylene alkylene . preferably , according to this embodiment , the linker is an isophorone group . the term “ isophorone ” means the following group : the said reactive groups functionalizing the junction group must be capable of reacting with the — oh reactive group ( s ) borne by the functionalized polyalkene . reactive groups that may be mentioned include isocyanate (— n ═ c ═ o ) and thioisocyanate (— n ═ c ═ s ) groups . preferably , it is a group — n ═ c ═ o ( isocyanate ). the functionalized junction groups capable of forming at least three h bonds may comprise at least three identical or different functional groups , and preferably at least four functional groups , chosen from : the junction groups capable of forming at least three hydrogen bonds form a basic structural element comprising at least three groups , preferably at least four groups and more preferentially four functional groups capable of establishing hydrogen bonds . said basic structural elements capable of establishing hydrogen bonds may be represented schematically in the following manner : in which each of x 1 to x i is an hydrogen - bond accepting functional group ( identical or different ) and each of y 1 to y i is an hydrogen - bond donating functional group ( identical or different ). thus , each structural element should be able to establish hydrogen bonds with one or more partner structural elements , which are identical ( i . e . self - complementary ) or different , such that each pairing of two partner structural elements takes place by formation of at least three hydrogen bonds , preferably at least four hydrogen bonds and more preferentially four hydrogen bonds . a proton acceptor x will pair with a proton donor y . several possibilities are thus offered , for example pairing of : preferably , the junction groups may establish four hydrogen bonds with an identical ( or self - complementary ) partner group among which are two donor bonds ( for example preferably , the junction groups capable of forming at least four hydrogen bonds are chosen from : in this formula , r 1 , r 2 and r 3 have the following meanings : r 1 ( or r 1 and r 2 ) are single bonds constituting the point of attachment of the junction group to the linker capable of forming at least three ( preferably four ) hydrogen bonds to the rest of the graft . preferably , the said point of attachment is borne solely by r 1 , which is a single bond . r 2 represents a single bond or a divalent group chosen from a c 1 - c 6 alkylene or a monovalent group chosen from a hydrogen atom , or a linear or branched , saturated c 1 - c 10 monovalent hydrocarbon - based group , which may contain one or more heteroatoms such as o , s or n , these groups being optionally substituted with a hydroxyl , amino and / or thio group . preferably , r 2 may be a single bond or a monovalent group chosen from h , ch 2 oh , ( ch 2 ) 2 — oh and ch 3 . according to one particularly preferred embodiment , r 2 is h . r 3 represents a monovalent or divalent group , in particular , r 3 is chosen from a hydrogen atom or a linear or branched c 1 - c 10 saturated monovalent hydrocarbon - based group , which may contain one or more heteroatoms such as o , s or n , these groups being optionally substituted with a hydroxyl , amino and / or thio function . preferably , r 3 may be a monovalent group chosen from h , ch 2 oh , ( ch 2 ) 2 — oh and ch 3 . according to one particularly preferred embodiment , r 3 is a methyl group . according to one preferred embodiment , the junction groups are chosen from 2 - ureidopyrimidone and 6 - methyl - 2 - ureidopyrimidone . preferably , the preferred junction group is 6 - methyl - 2 - ureidopyrimidone . the junction groups , and especially the ureidopyrimidone junction groups , may be added directly or may be formed in situ during the process for preparing the supramolecular polymer . the first and second preparation methods described below illustrate these two alternatives , respectively . in particular , the functionalized junction groups capable of reacting with the functionalized polyalkene polymer to give the supramolecular polymer according to the invention are preferably of formula : c 1 - c 20 alkylene such as —( ch 2 ) 2 —; —( ch 2 ) 6 —; — ch 2 ch ( ch 2 )— ch 2 — c ( ch 2 ) 2 — ch 2 — ch 2 —, and preferably , l is chosen from : - isophorone -; —( ch 2 ) 6 —; and 4 , 4 ′- methylene biscyclohexylene . according to one particularly preferred embodiment , the junction group is of formula in one particularly preferred embodiment , the supramolecular polymer of the invention corresponds to the formula : l ′ and l ″ have , independently of each other , the following meaning : a single bond or a saturated or unsaturated c 1 - 20 divalent carbon - based group chosen in particular from a linear or branched c 1 - c 20 alkylene ; a c 5 - c 20 ( alkyl ) cycloalkylene alkylene ( preferably cyclohexylene methylene ); a c 11 - c 20 alkylene - biscycloalkylene ( preferably alkylene - biscyclohexylene ); a c 6 - c 20 ( alkyl ) arylene ; and an alkylene - bisarylene ( preferably an alkylene - biphenylene ); wherein one or both of l ′ and l ″ are possibly substituted with at least one alkyl group and / or possibly comprising 1 to 4 n and / or o heteroatoms , especially in the form of an no 2 substituent ; x and x ′═ o ; and p has the meaning given above for the functionalized polyalkene polymer . preferably , l ′ and l ″ each independently represent a saturated or unsaturated divalent c 1 - c 20 carbon - based group chosen in particular from a linear or branched c 1 - c 20 alkylene ; a c 5 - c 20 ( alkyl ) cycloalkylene ; an alkylene - biscycloalkylene ; and a c 6 - c 20 ( alkyl ) arylene . preferably , l ′ and l ″ each independently represent a group chosen from : - isophorone -; —( ch 2 ) 2 —; —( ch 2 ) 6 —; — ch 2 ch ( ch 3 )— ch 2 — c ( ch 3 ) 2 — ch 2 — ch 2 —; 4 , 4 ′- methylene biscyclohexylene ; and 2 - methyl - 1 , 3 - phenylene . preferably , p is hydrogenated and represents a polyethylene , a polybutylene , a polybutadiene , a polyisoprene , a poly ( 1 , 3 - pentadiene ), a polyisobutylene , or a copolymer thereof , especially a poly ( ethylene / butylene ). in one particularly preferred embodiment , the supramolecular polymer of the invention corresponds to the formula ( i ) below : wherein n can be an integer from 20 to 70 ; most preferably an integer from 30 to 40 . the polymer according to the invention may be prepared via the processes usually used by a person skilled in the art , especially for forming a urethane bond between the free oh functions of a polyalkene , and the isocyanate functions borne by the junction group . by way of non - limiting illustration , a first general preparation process consists in : optionally ensuring that the polymer to be functionalized does not comprise any residual water ; heating the said polymer comprising at least two reactive oh functions to a temperature that may be between 60 ° c . and 140 ° c . ; the hydroxyl number of the polymer possibly serving as a reference in order to measure the degree of progress of the reaction ; adding , preferably directly , the ureidopyrimidone junction group bearing the reactive functions , especially isocyanate such as those described in patent wo 2005 / 042 641 ; especially such as the junction groups having the cas numbers 32093 - 85 - 9 and 709028 - 42 - 2 ; optionally stirring the mixture , under a controlled atmosphere , at a temperature of about 90 - 130 ° c . ; for 1 to 24 hours ; optionally monitoring by infrared spectroscopy the disappearance of the characteristic isocyanate band ( between 2500 and 2800 cm − 1 ) so as to stop the reaction on total disappearance of the peak , and then allowing the final product to cool to room temperature . the reaction may also be monitored by assaying the hydroxyl functions ; it is also possible to add ethanol in order to ensure the total disappearance of the residual isocyanate functions . the reaction may be performed in the presence of a solvent , especially methyltetrahydrofuran , tetrahydrofuran , toluene , propylene carbonate or butyl acetate . it is also possible to add a conventional catalyst for forming a urethane bond . an example that may be mentioned is dibutyltin dilaurate . the polymer may finally be washed and dried , or even purified , according to the general knowledge of a person skilled in the art . according to the second preferred mode of preparation , the reaction may comprise the following steps : functionalization of the polymer , which has preferably been dried beforehand , with a diisocyanate according to the reaction scheme : the diisocyanate may optionally be in excess relative to the polymer . this first step may be performed in the presence of solvent , at a temperature of between 20 ° c . and 100 ° c . this first step may be followed by a period of stirring under a controlled atmosphere for 1 to 24 hours . the mixture may optionally be heated . the degree of progress of this first step may be monitored by assaying the hydroxyl functions . this second step may optionally be performed in the presence of a cosolvent such as toluene , butyl acetate or propylene carbonate . the reaction mixture may be heated to between 80 ° c . and 140 ° c . for a time ranging between 1 and 24 hours . the presence of a catalyst , especially dibutyltin dilaurate , may promote the production of the desired final product . the reaction may be monitored by infrared spectroscopy , by monitoring the disappearance of the characteristic peak of isocyanate between 2200 and 2300 cm − 1 . at the end of the reaction , ethanol may be added to the reaction medium in order to neutralize any residual isocyanate functions . the reaction mixture may be optionally filtered . the polymer may also be stripped directly in a cosmetic solvent . according to one particular mode , the said supramolecular polymer is dissolved in a hydrocarbon - based oil , which is preferably volatile , in particular isododecane . thus , the composition of the invention will comprise at least one hydrocarbon - based oil , which is preferably volatile , in particular at least isododecane , especially provided by the supramolecular polymer solution . in particular , the supramolecular polymer ( s ) may be present in a composition according to the invention in an amount ranging from about 1 % to about 60 % by weight , preferably from about 3 % to about 45 % by weight , more preferably from about 5 % to about 20 % by weight , based on the total weight of the composition . in another particular embodiment of the invention , a makeup composition is in the form of a lipstick and the supramolecular polymer ( s ) may be present therein in a content ranging from about 1 % to about 40 % by weight , preferably from about 3 % to about 30 % by weight , more preferably from about 5 % to about 15 % by weight , based on the total weight of the composition . hyperbranched polymers are molecular constructions having a branched structure , generally around a core . their structure generally lacks symmetry , the base units or monomers used to construct the hyperbranched polymer can be of diverse nature and their distribution is non - uniform . the branches of the polymer can be of different natures and lengths . the number of base units , or monomers , may be different depending on the different branching . while at the same time being asymmetrical , hyperbranched polymers can have : an extremely branched structure around a core ; successive generations or layers of branching ; a layer of end chains . hyperbranched polymers are polymers that are highly branched and contain large number of end groups . hyperbranched polymer usually contains a central core and the growth of the polymer emanates from this central core . the growth of the polymer is made possible by repeating units of single monomers or linear chains added onto the central core . the end unit of the single monomer or linear chain can be functionalized which can become junction points ( i . e ., linkage points ) for further growth of the polymer . the final form of the hyperbranched polymer exhibits a tree - like structure without any symmetry or regularity . the synthesis of hyperbranched polymer can be produced by single monomer methodology ( smm ) or double monomer methodology ( dmm ) ( gao and yan , 2004 ). for smm , polymerization involves an ab x , ab * or a latent ab x monomer through generally four different types of reaction mechanism : polycondensation of ab x monomers , self - condensing vinyl polymerization ( scvp ), self - condensation ring opening polymerization ( scrop ) and proton transfer polymerization ( ptp ). for dmm , a direct polymerization is possible with two types of monomers or monomer pairs , the most notable being the polymerization of “ a 2 + b n , n ≧ 2 ”, and the couple - monomer methodology ( cmm ) has also been used . there are several ways to characterize the topology of a hyperbranched polymer , such as , by its degree of branching and the wiener index . the degree of branching is defined as b = 2d /( 2d + l ) where d is the number of fully branched units and l is the number of partially reacted units ( holter et al ., 1997 ). for a completely linear polymer , b = 0 and for a fully branched hyperbranched polymer b = 1 . the wiener index states the sum of paths or branches between all pairs of non - hydrogen atoms in a molecule ( wiener , 1947 ). it is defined as w = 1 2 ∑ j = 1 n s ∑ i = 1 ns d i j where n is the degree of polymerization and d ij is the number of bonds separating site i and j of the molecule . for two polymers with equal number of molecular weight , the linear polymer will have a smaller wiener number than the hyperbranched polymer . an end group can be reacted with the hyperbranched polymer to obtain a particular functionality on the ends of chains . “ hyperbranched functional polymers ” refers to polymers comprising at least two , for example three , polymeric branches , forming either the main branch or a secondary branch , and each comprising at least one at least trifunctional branch point , which may be identical or different , and which is able to form at least two at least trifunctional branch points , different from and independent of one another . each branch point may be , for example , arranged in the interior of at least one chain . the branches may be , for example , connected to one another by a polyfunctional compound . as used herein , “ trifunctional branch point ” means the junction point ( i . e ., linkage point ) between three polymer branches , of which at least two branches may be different in chemical constitution and / or structure . for example , certain branches may be hydrophilic , i . e . may predominantly contain hydrophilic monomers , and other branches may be hydrophobic , i . e ., may predominantly contain hydrophobic monomers . further branches may additionally form a random polymer or a block polymer . as used herein , “ at least trifunctional branch ” means the junction points ( i . e ., linkage points ) between at least three polymeric branches , for example n polymeric branches ( wherein n = 3 or more ), of which n − 1 branches at least are different in chemical constitution and / or structure . as used herein , “ chain interior ” means the atoms situated within the polymeric chain , to the exclusion of the atoms forming the two ends of this chain . as used herein , “ main branch ” means the branch or polymeric sequence comprising the greatest percentage by weight of monomer ( s ). suitable hyperbranched functional polymers include , but are not limited to , hyperbranched polyols and hyperbranched polyacids . the at least one hyperbranched functional polymer may be present in the composition of the present invention in an amount ranging from about 0 . 1 to about 30 % by weight , more preferably from about 1 to about 20 % by weight , most preferably from about 2 to about 10 % by weight , relative to the total weight of the composition . according to the present invention , compositions comprising at least one hyperbranched polyol compound are provided . the at least one hyperbranched polyol compound of the present invention has at least two hydroxyl groups . preferably , the hyperbranched polyol has a hydroxyl number of at least 15 , more preferably of at least 50 , more preferably of at least 100 , and more preferably of at least about 150 . “ hydroxyl number ” or “ hydroxyl value ” which is sometimes also referred to as “ acetyl value ” is a number which indicates the extent to which a substance may be acetylated ; it is the number of milligrams of potassium hydroxide required for neutralization of the acetic acid liberated on saponifying 1 g of acetylated sample . according to preferred embodiments , the at least one hyperbranched polyol has a hydroxyl number between 50 and 250 , preferably between 75 and 225 , preferably between 100 and 200 , preferably between 125 and 175 , including all ranges and subranges therebetween such as 90 to 150 . in accordance with the present invention , “ hyperbranched polyol ” refers to dendrimers , hyperbranched macromolecules and other dendron - based architectures . hyperbranched polyols can generally be described as three - dimensional highly branched molecules having a tree - like structure . they are characterized by a great number of end groups , at least two of which are hydroxyl groups . the dendritic or “ tree - like ” structure preferably shows irregular non - symmetric branching from a central multifunctional core molecule leading to a compact globular or quasi - globular structure with a large number of end groups per molecule . suitable examples of hyperbranched polyols can be found in u . s . pat . no . 7 , 423 , 104 , and u . s . patent applications 2008 / 0207871 and 2008 / 0286152 , the entire contents of all of which are hereby incorporated by reference . other suitable examples include alcohol functional olefinic polymers such as those available from new phase technologies . for example , olefinic polymers can include a functionalized polyalphaolefin comprising the reaction product of admixing an alpha - olefin monomer having at least 10 carbon atoms and an unsaturated functionalizing compound . non - functionalized olefins that may be used in accordance with the present invention include , but are not limited to , 1 - decene , 1 - dodecene , 1 - tetradecene , 1 - hexadecene , 1 - octadecene , 1 - eicosene , as well as such commercial mixtures sold as alpha - olefins including those having mainly c10 - c13 , c20 - c24 chain lengths , c24 - c28 chain lengths and c30 and higher chain lengths . unsaturated functionalizing compounds useful with the present invention are chosen from alcohols , including olefinic alcohols such as allyl alcohol , 9 - decen - 1 - ol , 10 - undecylenyl alcohol , oleyl alcohol , and erucyl alcohol . the molar ratio of alpha - olefin monomer to unsaturated functionalizing compound can range from about 20 : 1 to 1 : 20 such as from about 10 : 1 to 1 : 10 or such as from about 8 : 1 to 1 : 2 . after the polymerization , the alcohol functional olefinic polymers preferably have molecular weights , determined using gel permeation chromatography procedure and a polystyrene standard , of from about 200 daltons to about 150 , 000 daltons , such as from about 400 daltons to about 80 , 000 daltons or such as from about 600 daltons to about 6 , 000 daltons . according to certain embodiments , the alcohol functional olefinic polymer has a dynamic viscosity ranging from 0 . 1 pa · s to 100 pa · s , such as from 0 . 1 pa · s to 50 pa · s , or such as from 0 . 1 pa · s to 10 pa · s at room temperature . according to particularly preferred embodiments of the present invention , the at least one hyperbranched polyol compound comprises a hydrophobic chain interior . preferably , the chain interior comprises one or more hydrocarbon groups , one or more silicon - based groups , or mixtures thereof . particularly preferred chain interiors comprise olefinic polymers or copolymers and / or silicone polymers or copolymers . suitable olefinic monomers include , but are not limited to , compounds having from about 2 to about 30 carbon atoms per molecule and having at least one olefinic double bond which are , for example , acyclic , cyclic , polycyclic , linear , branched , substituted , unsubstituted , functionalized or non - functionalized . for example , suitable monomers include ethylene , propylene , 1 - butene , 2 - butene , 3 - methyl - 1 - butene , and isobutylene . suitable silicone groups for inclusion into the interior chain include , but are not limited to , m , d , t , and / or q groups in accordance with commonly used silicon - related terminology ( m = monovalent ; d = divalent ; t = trivalent ; and q = quadvalent ). particularly preferred monomers are “ d ” groups such as dimethicone or substituted dimethicone groups . such groups can help form , for example , suitable dimethicone copolyols in accordance with the present invention . a preferred structure of the at least one hyperbranched polyol of the present invention is as follows : where x corresponds to hydroxyl functionality and r corresponds to a methyl group or an alkyl group preferably containing 2 - 30 atoms . according to preferred embodiments , the at least one hyperbranched polyol compound has a molecular weight ( mw ) between about 1 , 000 and about 25 , 000 , preferably between about 2 , 000 and about 22 , 000 , preferably between about 3 , 000 and about 20 , 000 , including all ranges and subranges therebetween such as about 4000 to about 5500 . according to preferred embodiments , the at least one hyperbranched polyol compound has a viscosity at 90 ° f . of between 0 . 01 pa · s and 10 pa · s , such as between 0 . 02 and 7 pa · s , and such as between 0 . 03 and 6 pa · s , including all ranges and subranges therebetween . the viscosity is determined using brookfield viscometer at 90 ° f . by astmd - 3236mod method . a particularly preferred at least one hyperbranched polyol compound for use in the present invention is c20 - c24 olefin / oleyl alcohol copolymer , commercially available from new phase technologies under the trade name performa v ™- 6175 . the at least one hyperbranched polyol compound may be present in the composition of the present invention in an amount ranging from about 1 to about 30 % by weight , more preferably from about 5 to about 25 % by weight , most preferably from about 10 to about 20 % by weight , relative to the total weight of the composition . according to the present invention , compositions comprising at least one hyperbranched polyacid compound are provided . the aforementioned “ hyperbranched polyol ” refers to the hyperbranched functional polymer wherein the functional groups are substituted with hydroxyl groups . similar definition applies to the term “ hyperbranched polyacid ” wherein the functional groups of the hyperbranched functional polymer are substituted with carboxylic acid groups . the at least one hyperbranched polyacid compound of the present invention has at least two carboxyl groups . preferably , the hyperbranched polyacid has a carboxyl number of at least 3 , more preferably of at least 10 , more preferably of at least 50 , and more preferably of at least about 150 . according to preferred embodiments , the at least one hyperbranched polyacid has a carboxyl number between 50 and 250 , preferably between 75 and 225 , preferably between 100 and 200 , preferably between 125 and 175 , including all ranges and subranges there between such as 90 to 150 . suitable examples of hyperbranched polyacids can be found in u . s . pat . no . 7 , 582 , 719 , and ep1367080 , the entire contents of all of which are hereby incorporated by reference . unsaturated functionalizing compounds useful with the present invention include , but are not limited to , carboxylic acids , carboxylic acid esters , amides , ethers , amines , phosphate esters , silanes and alcohols . examples of such carboxylic acids include , but are not limited to , 5 - hexenoic acid , 6 - heptenoic acid , 10 - undecylenic acid , 9 - decenoic acid , oleic acid , and erucic acid . also useful are esters of these acids with linear or branched - chain alcohols having from about 1 to about 10 carbon atoms , as well as triglycerides containing olefinic unsaturation in the fatty acid portion such as tall oil , fish oils , soybean oil , linseed oil , cottonseed oil and partially hydrogenated products of such oils . other useful materials include olefinic alcohols such as allyl alcohol , 9 - decen - 1 - ol , 10 - undecylenyl alcohol , oleyl alcohol , erucyl alcohol , acetic acid or formic acid esters of these alcohols , c1 - c4 alkyl ether derivatives of these alcohols and formamides or acetamides of unsaturated amines such as oleylamine , erucylamine , 10 - undecylenylamine and allylamine . a particularly preferred acid functional olefinic polymer is c30 + olefin / undecylenic acid copolymer available from new phase technologies under trade name performa v ™- 6112 . according to preferred embodiments , the at least one hyperbranched acid compound has a molecular weight ( mw ) between about 500 and about 25 , 000 , preferably between about 800 and about 10000 , preferably between about 1000 and about 8000 , including all ranges and subranges there between such as about 1000 to about 6000 . according to preferred embodiments , the at least one hyperbranched polyacid compound has a viscosity at 210 ° f . of between 0 . 01 pa · s and 10 pa · s , such as between 0 . 02 and 7 pa · s , and such as between 0 . 03 and 6 pa · s , including all ranges and subranges there between . the viscosity is determined using brookfield viscometer at 210 ° f . by astmd - 3236mod method . according to preferred embodiments , the at least one hyperbranched acid compound has an acid number between about 20 and about 400 mg / koh , more preferably between about 30 and about 300 mg / koh , and even more preferably between about 50 and about 100 mg / koh . the at least one hyperbranched polyacid compound is present in the composition of the present invention in an amount ranging from about 0 . 1 to about 20 % by weight , more preferably from about 0 . 2 to about 10 % by weight , most preferably from about 0 . 5 to about 5 % by weight , relative to the total weight of the composition . a composition according to the invention further comprises a fatty phase . this fatty phase may comprise oils , waxes and / or pasty compounds and / or silicone compounds as defined below . the fatty phase ranges from 1 % to 97 % by weight , especially 5 % to 95 % by weight or even 10 % to 90 % by weight , relative to the total weight of the composition . thus , a composition according to the invention may advantageously comprise one or more oils , which may be chosen especially from hydrocarbon - based oils and fluoro oils , and mixtures thereof . the oils may be of animal , plant , mineral or synthetic origin . the term “ oil ” means a water - immiscible non - aqueous compound that is liquid at room temperature ( 25 ° c .) and at atmospheric pressure ( 760 mmhg ). for the purposes of the invention , the term “ volatile oil ” means any oil that is capable of evaporating on contact with keratin materials in less than one hour , at room temperature and atmospheric pressure . volatile oils preferably have a non - zero vapour pressure , at room temperature and atmospheric pressure , ranging from 0 . 13 pa to 40 , 000 pa , in particular from 1 . 3 pa to 13 , 000 pa and more particularly from 1 . 3 pa to 1 , 300 pa . the term “ fluoro oil ” means an oil comprising at least one fluorine atom . the term “ hydrocarbon - based oil ” means an oil mainly containing hydrogen and carbon atoms . the oils may optionally comprise oxygen , nitrogen , sulfur and / or phosphorus atoms , for example in the form of hydroxyl or acid radicals . the volatile oils may be chosen from hydrocarbon - based oils containing from 8 to 16 carbon atoms , and especially c 8 - c 16 branched alkanes ( also known as isoparaffins ), for instance isododecane , isodecane and isohexadecane . the volatile hydrocarbon - based oil may also be a linear volatile alkane containing 7 to 17 carbon atoms , in particular 9 to 15 carbon atoms and more particularly 11 to 13 carbon atoms . mention may be made especially of n - nonadecane , n - decane , n - undecane , n - dodecane , n - tridecane , n - tetradecane , n - pentadecane and n - hexadecane , and mixtures thereof . hydrocarbon - based oils of animal origin , hydrocarbon - based oils of plant origin , such as phytostearyl esters , such as phytostearyl oleate , phytostearyl isostearate and lauroyl / octyldodecyl / phytostearyl glutamate ; triglycerides formed from fatty acid esters of glycerol , in particular whose fatty acids may have chain lengths ranging from c 4 to c 36 and especially from c 18 to c 36 , these oils possibly being linear or branched , and saturated or unsaturated ; these oils may especially be heptanoic or octanoic triglycerides , shea oil , alfalfa oil , poppy oil , pumpkin oil , millet oil , barley oil , quinoa oil , rye oil , candlenut oil , passionflower oil , shea butter oil , aloe oil , sweet almond oil , peach stone oil , groundnut oil , argan oil , avocado oil , baobab oil , borage oil , broccoli oil , calendula oil , camellina oil , carrot oil , safflower oil , hemp oil , rapeseed oil , cottonseed oil , coconut oil , marrow seed oil , wheatgerm oil , jojoba oil , lily oil , macadamia oil , corn oil , meadowfoam oil , st - john &# 39 ; s wort oil , monoi oil , hazelnut oil , apricot kernel oil , walnut oil , olive oil , evening primrose oil , palm oil , blackcurrant pip oil , kiwi seed oil , grape seed oil , pistachio oil , pumpkin oil , quinoa oil , musk rose oil , sesame oil , soybean oil , sunflower oil , castor oil and watermelon oil , and mixtures thereof , or alternatively caprylic / capric acid triglycerides , such as those sold by the company stearineries dubois or those sold under the names miglyol 810 ®, 812 ® and 818 ® by the company dynamit nobel , synthetic ethers containing from 10 to 40 carbon atoms ; synthetic esters , for instance the oils of formula r 1 coor 2 , in which r 1 represents a linear or branched fatty acid residue containing from 1 to 40 carbon atoms and r 2 represents a hydrocarbon - based chain , which is especially branched , containing from 1 to 40 carbon atoms , on condition that r 1 + r 2 ≧ 10 . the esters may be chosen especially from fatty acid esters of alcohols , for instance cetostearyl octanoate , isopropyl alcohol esters , such as isopropyl myristate , isopropyl palmitate , ethyl palmitate , 2 - ethylhexyl palmitate , isopropyl stearate , isopropyl isostearate , isostearyl isostearate , octyl stearate , hydroxylated esters , for instance isostearyl lactate , octyl hydroxystearate , diisopropyl adipate , heptanoates , and especially isostearyl heptanoate , alcohol or polyalcohol octanoates , decanoates or ricinoleates , for instance propylene glycol dioctanoate , cetyl octanoate , tridecyl octanoate , 2 - ethylhexyl 4 - diheptanoate , 2 - ethylhexyl palmitate , alkyl benzoates , polyethylene glycol diheptanoate , propylene glycol 2 - diethylhexanoate , and mixtures thereof , c 12 - c 15 alcohol benzoates , hexyl laurate , neopentanoic acid esters , for instance isodecyl neopentanoate , isotridecyl neopentanoate , isostearyl neopentanoate , octyldodecyl neopentanoate , isononanoic acid esters , for instance isononyl isononanoate , isotridecyl isononanoate , octyl isononanoate , hydroxylated esters , for instance isostearyl lactate and diisostearyl malate , polyol esters and pentaerythritol esters , for instance dipentaerythrityl tetrahydroxystearate / tetraisostearate , esters of diol dimers and of diacid dimers , copolymers of diol dimer and of diacid dimer and esters thereof , such as dilinoleyl diol dimer / dilinoleic dimer copolymers , and esters thereof , copolymers of polyols and of diacid dimers , and esters thereof , fatty alcohols that are liquid at room temperature , with a branched and / or unsaturated carbon - based chain containing from 12 to 26 carbon atoms , for instance 2 - octyldodecanol , isostearyl alcohol , oleyl alcohol , 2 - hexyldecanol , 2 - butyloctanol and 2 - undecylpentadecanol , c 12 - c 22 higher fatty acids , such as oleic acid , linoleic acid and linolenic acid , and mixtures thereof ; dialkyl carbonates , the two alkyl chains possibly being identical or different , such as dicaprylyl carbonate ; oils with a molar mass of between about 400 and about 10 , 000 g / mol , in particular about 650 to about 10 , 000 g / mol , in particular from about 750 to about 7 , 500 g / mol and more particularly ranging from about 1 , 000 to about 5 , 000 g / mol ; mention may be made especially , alone or as a mixture , of ( i ) lipophilic polymers such as polybutylenes , polyisobutylenes , for example hydrogenated polydecenes , vinylpyrrolidone copolymers , such as the vinylpyrrolidone / 1 - hexadecene copolymer , and polyvinylpyrrolidone ( pvp ) copolymers , such as the copolymers of a c 2 - c 30 alkene , such as c 3 - c 22 , and combinations thereof ; ( ii ) linear fatty acid esters containing a total carbon number ranging from 35 to 70 , for instance pentaerythrityl tetrapelargonate ; ( iii ) hydroxylated esters such as polyglyceryl - 2 triisostearate ; ( iv ) aromatic esters such as tridecyl trimellitate ; ( v ) esters of fatty alcohols or of branched c 24 - c 28 fatty acids , such as those described in u . s . pat . no . 6 , 491 , 927 and pentaerythritol esters , and especially triisoarachidyl citrate , pentaerythrityl tetraisononanoate , glyceryl triisostearate , glyceryl 2 - tridecyltetradecanoate , pentaerythrityl tetraisostearate , poly ( 2 - glyceryl ) tetraisostearate or pentaerythrityl 2 - tetradecyltetradecanoate ; ( vi ) diol dimer esters and polyesters , such as esters of diol dimer and of fatty acid , and esters of diol dimer and of diacid . in particular , one or more oils according to the invention may be present in a composition according to the invention in a content ranging from 1 % to 90 % by weight , preferably ranging from 2 % to 75 % by weight or even from 3 % to 60 % by weight relative to the total weight of the composition . it is understood that the above - described weight percentage of oil takes into account the weight of oil used for the formulation of the associated supramolecular polymer , if present . for the purposes of the present invention , the term “ silicone oil ” means an oil comprising at least one silicon atom , and especially at least one si — o group . in particular , the volatile or non - volatile silicone oils that may be used in the invention preferably have a viscosity at 25 ° c . of less than 800 , 000 cst , preferably less than or equal to 600 , 000 cst and preferably less than or equal to 500 , 000 cst . the viscosity of these silicone oils may be measured according to standard astm d - 445 . the silicone oils that may be used according to the invention may be volatile or non - volatile or mixtures of volatile and non - volatile silicone oils . thus , a composition according to the invention or under consideration according to a process of the invention may contain a mixture of volatile and non - volatile silicone oils . in a preferred embodiment , the term “ volatile silicone oil ” means an oil that can evaporate on contact with the skin in less than one hour , at room temperature ( 25 ° c .) and atmospheric pressure . the volatile silicone oil is a volatile cosmetic oil , which is liquid at room temperature , especially having a non - zero vapour pressure , at room temperature and atmospheric pressure , in particular having a vapour pressure ranging from 0 . 13 pa to 40 , 000 pa ( 10 − 3 to 300 mmhg ), preferably ranging from 1 . 3 pa to 13 , 000 pa ( 0 . 01 to 100 mmhg ) and preferentially ranging from 1 . 3 pa to 1 , 300 pa ( 0 . 1 to 10 mmhg ). the term “ non - volatile silicone oil ” means an oil whose vapour pressure at room temperature and atmospheric pressure is non - zero and less than 0 . 02 mmhg ( 2 . 66 pa ) and better still less than 10 − 3 mmhg ( 0 . 13 pa ). in one embodiment of the present invention , compositions according to the invention comprise at least one volatile silicone oil . the volatile silicone oils that may be used in the invention may be chosen from silicone oils especially having a viscosity ≦ 8 centistokes ( cst ) ( 8 × 10 − 6 m 2 / s ). furthermore , the volatile silicone oil that may be used in the invention may preferably be chosen from silicone oils with a flash point ranging from 40 ° c . to 102 ° c ., preferably with a flash point of greater than 55 ° c . and less than or equal to 95 ° c ., and preferentially ranging from 65 ° c . to 95 ° c . volatile silicone oils that may be mentioned include : volatile linear or cyclic silicone oils , especially those with a viscosity ≦ 8 centistokes ( cst ) ( 8 × 10 − 6 m 2 / s at 25 ° c . ), and especially containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms , these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms . more particularly , the volatile silicone oils are non - cyclic and are chosen in particular from : a saturated or unsaturated hydrocarbon - based radical , containing from 1 to 10 carbon atoms and preferably from 1 to 6 carbon atoms , optionally substituted with one or more fluorine atoms or with one or more hydroxyl groups , or a hydroxyl group , one of the radicals r possibly being a phenyl group , n is an integer ranging from 0 to 8 , preferably ranging from 2 to 6 and better still ranging from 3 to 5 , further wherein none of the r groups in the silicone compound of formula ( d ) contain more than 15 carbon atoms ; a saturated or unsaturated hydrocarbon - based radical , containing from 1 to 10 carbon atoms , optionally substituted with one or more fluorine atoms or with one or more hydroxyl groups , or a hydroxyl group , one of the radicals r possibly being a phenyl group , x is an integer ranging from 0 to 8 , further wherein none of the r groups in the silicone compound of formula ( e ) or ( f ) contain more than 15 carbon atoms . preferably , for the compounds of formulae ( d ), ( e ) and ( f ), the ratio between the number of carbon atoms and the number of silicon atoms is between 2 . 25 and 4 . 33 . the silicones of formulae ( d ) to ( f ) may be prepared according to the known processes for synthesizing silicone compounds . among the silicones of formula ( d ) that may be mentioned are : the following disiloxanes : hexamethyldisiloxane ( surface tension = 15 . 9 mn / m ), sold especially under the name dc 200 fluid 0 . 65 cst by the company dow corning , 1 , 3 - di - tert - butyl - 1 , 1 , 3 , 3 - tetramethyldisiloxane ; 1 , 3 - dipropyl - 1 , 1 , 3 , 3 - tetramethyldisiloxane ; heptylpentamethyldisiloxane ; 1 , 1 , 1 - triethyl - 3 , 3 , 3 - trimethyldisiloxane ; hexaethyldisiloxane ; 1 , 1 , 3 , 3 - tetramethyl - 1 , 3 - bis ( 2 - methylpropyl ) disiloxane ; pentamethyloctyldisiloxane ; 1 , 1 , 1 - trimethyl - 3 , 3 , 3 - tris ( 1 - methylethyl ) disiloxane ; 1 - butyl - 3 - ethyl - 1 , 1 , 3 - trimethyl - 3 - propyldisiloxane ; pentamethylpentyldisiloxane ; 1 - butyl - 1 , 1 , 3 , 3 - tetramethyl - 3 -( 1 - methylethyl ) disiloxane ; 1 , 1 , 3 , 3 - tetramethyl - 1 , 3 - bis ( 1 - methylpropyl ) disiloxane ; 1 , 1 , 3 - triethyl - 1 , 3 , 3 - tripropyldisiloxane ; 3 , 3 - dimethylbutyl ) pentamethyldisiloxane ; ( 3 - methylbutyl ) pentamethyldisiloxane ; ( 3 - methylpentyl ) pentamethyldisiloxane ; 1 , 1 , 1 - triethyl - 3 , 3 - dimethyl - 3 - propyldisiloxane ; 1 -( 1 , 1 - dimethylethyl )- 1 , 1 , 3 , 3 , 3 - pentamethyldisiloxane ; 1 , 1 , 1 - trimethyl - 3 , 3 , 3 - tripropyldisiloxane ; 1 , 3 - dimethyl - 1 , 1 , 3 , 3 - tetrakis ( 1 - methylethyl ) disiloxane ; 1 , 1 - dibutyl - 1 , 3 , 3 , 3 - tetramethyldisiloxane ; 1 , 1 , 3 , 3 - tetramethyl - 1 , 3 - bis ( 1 - methylethyl ) disiloxane ; 1 , 1 , 1 , 3 - tetramethyl - 3 , 3 - bis ( 1 - methylethyl ) disiloxane ; 1 , 1 , 1 , 3 - tetramethyl - 3 , 3 - dipropyldisiloxane ; 1 , 1 , 3 , 3 - tetramethyl - 1 , 3 - bis ( 3 - methylbutyl ) disiloxane ; butylpentamethyldisiloxane ; pentaethylmethyldisiloxane ; 1 , 1 , 3 , 3 - tetramethyl - 1 , 3 - dipentyldisiloxane ; 1 , 3 - dimethyl - 1 , 1 , 3 , 3 - tetrapropyldisiloxane ; 1 , 1 , 1 , 3 - tetraethyl - 3 , 3 - dimethyldisiloxane ; 1 , 1 , 1 - triethyl - 3 , 3 , 3 - tripropyldisiloxane ; 1 , 3 - dibutyl - 1 , 1 , 3 , 3 - tetramethyldisiloxane and hexylpentamethyldisiloxane ; the following trisiloxanes : octamethyltrisiloxane ( surface tension = 17 . 4 mn / m ), sold especially under the name dc 200 fluid 1 cst by the company dow corning , 3 - pentyl - 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyltrisiloxane ; 1 - hexyl - 1 , 1 , 3 , 3 , 5 , 5 , 5 - heptamethyltrisiloxane ; 1 , 1 , 1 , 3 , 3 , 5 , 5 - heptamethyl - 5 - octyltrisiloxane ; 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyl - 3 - octyltrisiloxane , sold especially under the name silsoft 034 by the company osi ; 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyl - 3 - hexyltrisiloxane ( surface tension = 20 . 5 mn / m ), sold especially under the name dc 2 - 1731 by the company dow corning ; 1 , 1 , 3 , 3 , 5 , 5 - hexamethyl - 1 , 5 - dipropyltrisiloxane ; 3 -( 1 - ethylbutyl )- 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyltrisiloxane ; 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyl - 3 -( 1 - methylpentyl ) trisiloxane ; 1 , 5 - diethyl - 1 , 1 , 3 , 3 , 5 , 5 - hexamethyltrisiloxane ; 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyl - 3 -( 1 - methylpropyl ) trisiloxane ; 3 -( 1 , 1 - dimethylethyl )- 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyltrisiloxane ; 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 , 3 - bis ( 1 - methylethyl ) trisiloxane ; 1 , 1 , 1 , 3 , 3 , 5 , 5 - hexamethyl - 1 , 5 - bis ( 1 - methylpropyl ) trisiloxane ; 1 , 5 - bis ( 1 , 1 - dimethylethyl )- 1 , 1 , 3 , 3 , 5 , 5 - hexamethyltrisiloxane ; 3 -( 3 , 3 - dimethylbutyl )- 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyltrisiloxane ; 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyl - 3 -( 3 - methylbutyl ) trisiloxane ; 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyl - 3 -( 3 - methylpentyl ) trisiloxane ; 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyl - 3 -( 2 - methylpropyl ) trisiloxane ; 1 - butyl - 1 , 1 , 3 , 3 , 5 , 5 , 5 - heptamethyltrisiloxane ; 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyl - 3 - propyltrisiloxane ; 3 - isohexyl - 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyltrisiloxane ; 1 , 3 , 5 - triethyl - 1 , 1 , 3 , 5 , 5 - pentamethyltrisiloxane ; 3 - butyl - 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyltrisiloxane ; 3 - tert - pentyl - 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyltrisiloxane ; 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 , 3 - dipropyltrisiloxane ; 3 , 3 - diethyl - 1 , 1 , 1 , 5 , 5 , 5 - hexamethyltrisiloxane ; 1 , 5 - dibutyl - 1 , 1 , 3 , 3 , 5 , 5 - hexamethyltrisiloxane ; 1 , 1 , 1 , 5 , 5 , 5 - hexaethyl - 3 , 3 - dimethyltrisiloxane ; 3 , 3 - dibutyl - 1 , 1 , 1 , 5 , 5 , 5 - hexamethyltrisiloxane ; 3 - ethyl - 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyltrisiloxane ; 3 - heptyl - 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyltrisiloxane and 1 - ethyl - 1 , 1 , 3 , 3 , 5 , 5 , 5 - heptamethyltrisiloxane ; the following tetrasiloxanes : decamethyltetrasiloxane ( surface tension = 18 mn / m ), sold especially under the name dc 200 fluid 1 . 5 cst by the company dow corning ; 1 , 1 , 3 , 3 , 5 , 5 , 7 , 7 - octamethyl - 1 , 7 - dipropyltetrasiloxane ; 1 , 1 , 1 , 3 , 3 , 5 , 7 , 7 , 7 - nonamethyl - 5 -( 1 - methylethyl ) tetrasiloxane ; 1 - butyl - 1 , 1 , 3 , 3 , 5 , 5 , 7 , 7 , 7 - nonamethyltetrasiloxane ; 3 , 5 - diethyl - 1 , 1 , 1 , 3 , 5 , 7 , 7 , 7 - octamethyltetrasiloxane ; 1 , 3 , 5 , 7 - tetraethyl - 1 , 1 , 3 , 5 , 7 , 7 - hexamethyltetrasiloxane ; 3 , 3 , 5 , 5 - tetraethyl - 1 , 1 , 1 , 7 , 7 , 7 - hexamethyltetrasiloxane ; 1 , 1 , 1 , 3 , 3 , 5 , 5 , 7 , 7 - nonamethyl - 7 - phenyltetrasiloxane ; 3 , 3 - diethyl - 1 , 1 , 1 , 5 , 5 , 7 , 7 , 7 - octamethyltetrasiloxane ; and 1 , 1 , 1 , 3 , 3 , 5 , 7 , 7 , 7 - nonamethyl - 5 - phenyltetrasiloxane ; the following pentasiloxanes : dodecamethylpentasiloxane ( surface tension = 18 . 7 mn / m ), sold especially under the name dc 200 fluid 2 cst by the company dow corning ; 1 , 1 , 3 , 3 , 5 , 5 , 7 , 7 , 9 , 9 - decamethyl - 1 , 9 - dipropylpentasiloxane ; 3 , 3 , 5 , 5 , 7 , 7 - hexaethyl - 1 , 1 , 1 , 9 , 9 , 9 - hexamethylpentasiloxane ; 1 , 1 , 1 , 3 , 3 , 5 , 7 , 7 , 9 , 9 , 9 - undecamethyl - 5 - phenylpentasiloxane ; 1 - butyl - 1 , 1 , 3 , 3 , 5 , 5 , 7 , 7 , 9 , 9 , 9 - undecamethylpentasiloxane ; 3 , 3 - diethyl - 1 , 1 , 1 , 5 , 5 , 7 , 7 , 9 , 9 , 9 - decamethylpentasiloxane ; 1 , 3 , 5 , 7 , 9 - pentaethyl - 1 , 1 , 3 , 5 , 7 , 9 , 9 - heptamethylpentasiloxane ; 3 , 5 , 7 - triethyl - 1 , 1 , 1 , 3 , 5 , 7 , 9 , 9 , 9 - nonamethylpentasiloxane and 1 , 1 , 1 - triethyl - 3 , 3 , 5 , 5 , 7 , 7 , 9 , 9 , 9 - nonamethylpentasiloxane ; the following hexasiloxanes : 1 - butyl - 1 , 1 , 3 , 3 , 5 , 5 , 7 , 7 , 9 , 9 , 11 , 11 , 11 - tridecamethylhexasiloxane ; 3 , 5 , 7 , 9 - tetraethyl - 1 , 1 , 1 , 3 , 5 , 7 , 9 , 11 , 11 , 11 - decamethylhexasiloxane and tetradecamethylhexasiloxane . hexadecamethylheptasiloxane ; octadecamethyloctasiloxane ; eicosamethylnonasiloxane . among the silicones of formula ( e ) that may be mentioned are : the following tetrasiloxanes : 2 -[ 3 , 3 , 3 - trimethyl - 1 , 1 - bis [( trimethylsilyl ) oxy ] disiloxanyl ] ethyl ; 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 -( 2 - methylpropyl )- 3 -[( trimethylsilyl ) oxy ] trisiloxane ; 3 -( 1 , 1 - dimethylethyl )- 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 -[( trimethylsilyl ) oxy ] trisiloxane ; 3 - butyl - 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 -[( trimethylsilyl ) oxy ] trisiloxane ; 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 - propyl - 3 -[( trimethylsilyl ) oxy ] trisiloxane ; 3 - ethyl - 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 -[( trimethylsilyl ) oxy ] trisiloxane ; 1 , 1 , 1 - triethyl - 3 , 5 , 5 , 5 - tetramethyl - 3 -( trimethylsiloxy ) trisiloxane ; 3 - methyl - 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 -[ trimethylsilyl ) oxy ] trisiloxane ; 3 -[( dimethylphenylsilyl ) oxy ]- 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyltrisiloxane ; 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 -( 2 - methylpentyl )- 3 -[( trimethylsilyl ) oxy ] trisiloxane ; 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 -( 4 - methylpentyl )- 3 -[( trimethylsilyl ) oxy ] trisiloxane ; 3 - hexyl - 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 -[( trimethylsilyl ) oxy ] trisiloxane and 1 , 1 , 1 , 3 , 5 , 5 , 5 - heptamethyl - 3 -[( trimethylsilyl ) oxy ] trisiloxane ; among the silicones of formula ( f ), mention may be made of : 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 , 3 - bis ( trimethylsiloxy ) trisiloxane . use may also be made of other volatile silicone oils chosen from : the following tetrasiloxanes : 2 , 2 , 8 , 8 - tetramethyl - 5 -[( pentamethyldisiloxanyl ) methyl ]- 3 , 7 - dioxa - 2 , 8 - disilanonane ; 2 , 2 , 5 , 8 , 8 - pentamethyl - 5 -[( trimethylsilyl ) methoxy ]- 4 , 6 - dioxa - 2 , 5 , 8 - trisilanonane ; 1 , 3 - dimethyl - 1 , 3 - bis [( trimethylsilyl ) methyl ]- 1 , 3 - disiloxanediol ; 3 - ethyl - 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 -[ 3 -( trimethylsiloxy ) propyl ] trisiloxane and 1 , 1 , 1 , 5 , 5 , 5 - hexamethyl - 3 - phenyl - 3 -[( trimethylsilyl ) oxy ] trisiloxane ( dow 556 fluid ); the following pentasiloxanes : 2 , 2 , 7 , 7 , 9 , 9 , 11 , 11 , 16 , 16 - decamethyl - 3 , 8 , 10 , 15 - tetraoxa - 2 , 7 , 9 , 11 , 16 - pentasilaheptadecane and the tetrakis [( trimethylsilyl ) methyl ] ester of silicic acid ; the following hexasiloxanes : 3 , 5 - diethyl - 1 , 1 , 1 , 7 , 7 , 7 - hexamethyl - 3 , 5 - bis [( trimethylsilyl ) oxy ] tetrasiloxane and 1 , 1 , 1 , 3 , 5 , 7 , 7 , 7 - octamethyl - 3 , 5 - bis [( trimethylsilyl ) oxy ] tetrasiloxane ; the heptasiloxane : 1 , 1 , 1 , 3 , 7 , 7 , 7 - heptamethyl - 3 , 5 , 5 - tris [( trimethylsilyl ) oxy ] tetrasiloxane ; the following octasiloxanes : 1 , 1 , 1 , 3 , 5 , 5 , 9 , 9 , 9 - nonamethyl - 3 , 7 , 7 - tris [( trimethylsilyl ) oxy ] pentasiloxane ; 1 , 1 , 1 , 3 , 5 , 7 , 9 , 9 , 9 - nonamethyl - 3 , 5 , 7 - tris [( trimethylsilyl ) oxy ] pentasiloxane and 1 , 1 , 1 , 7 , 7 , 7 - hexamethyl - 3 , 3 , 5 , 5 - tetrakis [( trimethylsilyl ) oxy ] tetrasiloxane . volatile silicone oils that may more particularly be mentioned include decamethylcyclopentasiloxane sold especially under the name dc - 245 by the company dow corning , dodecamethylcyclohexasiloxane sold especially under the name dc - 246 by the company dow corning , octamethyltrisiloxane sold especially under the name dc - 200 fluid 1 cst by the company dow corning , decamethyltetrasiloxane sold especially under the name dc - 200 fluid 1 . 5 cst by the company dow corning and dc - 200 fluid 5 cst sold by the company dow corning , octamethylcyclotetrasiloxane , heptamethylhexyltrisiloxane , heptamethylethyltrisiloxane , heptamethyloctyltrisiloxane and dodecamethylpentasiloxane , and mixtures thereof . it should be noted that , among the above - mentioned oils , the linear oils prove to be particularly advantageous . the non - volatile silicone oils that may be used in the invention may be chosen from silicone oils with a viscosity at 25 ° c . of greater than or equal to 9 centistokes ( cst ) ( 9 × 10 − 6 m 2 / s ) and less than 800 , 000 cst , preferably between 50 and 600 , 000 cst and preferably between 100 and 500 , 000 cst . the viscosity of this silicone oil may be measured according to standard astm d - 445 . among these silicone oils , two types of oil may be distinguished , according to whether or not they contain phenyl . representative examples of these non - volatile linear silicone oils that may be mentioned include polydimethylsiloxanes ( i . e ., pdms ); alkyl dimethicones ; vinyl methyl methicones ; and also silicones modified with optionally fluorinated aliphatic groups , or with functional groups such as hydroxyl , thiol and / or amine groups . pdmss comprising alkyl or alkoxy groups , which are pendent and / or at the end of the silicone chain , these groups each containing from 2 to 24 carbon atoms , pdmss comprising aliphatic groups , or functional groups such as hydroxyl , thiol and / or amine groups , polyalkylmethylsiloxanes optionally substituted with a fluorinated group , such as polymethyltrifluoropropyldimethylsiloxanes , polyalkylmethylsiloxanes substituted with functional groups such as hydroxyl , thiol and / or amine groups , polysiloxanes modified with fatty acids , fatty alcohols or polyoxyalkylenes , and mixtures thereof . according to one embodiment , a composition according to the invention contains at least one non - phenyl linear silicone oil . the non - phenyl linear silicone oil may be chosen especially from the silicones of formula : r 1 , r 2 , r 5 and r 6 are , together or separately , an alkyl radical containing 1 to 6 carbon atoms , r 3 and r 4 are , together or separately , an alkyl radical containing from 1 to 6 carbon atoms , a vinyl radical , an amine radical or a hydroxyl radical , x is an alkyl radical containing from 1 to 6 carbon atoms , a hydroxyl radical or an amine radical , n and p are integers chosen so as to have a fluid compound . as non - volatile silicone oils that may be used according to the invention , mention may be made of those for which : the substituents r 1 to r 6 and x represent a methyl group , and p and n are such that the viscosity is about 500 , 000 cst ( measured by brookfield viscometer using astmd - 445 method ), such as the product sold under the name se30 by the company general electric , the product sold under the name ak 500 , 000 by the company wacker , the product sold under the name mirasil dm 500 , 000 by the company bluestar , and the product sold under the name dow corning 200 fluid 500 , 000 cst by the company dow corning ( viscosity determined by brookfield viscometer using astmd - 445 method ), the substituents r 1 to r 6 and x represent a methyl group , and p and n are such that the viscosity is about 60 , 000 cst ( measured by brookfield viscometer using astmd - 445 method ), such as the product sold under the name dow corning 200 fluid 60 , 000 cs by the company dow corning , and the product sold under the name wacker belsil dm 60 , 000 by the company wacker , the substituents r 1 to r 6 and x represent a methyl group , and p and n are such that the viscosity is about 350 cst ( measured by brookfield viscometer using astmd - 445 method ), such as the product sold under the name dow corning 200 fluid 350 cs by the company dow corning , the substituents r 1 to r 6 represent a methyl group , the group x represents a hydroxyl group , and n and p are such that the viscosity is about 700 cst ( measured by brookfield viscometer using astmd - 445 method ), such as the product sold under the name baysilone fluid t0 . 7 by the company momentive . according to one embodiment variant , a composition according to the invention contains at least one phenyl silicone oil . representative examples of these non - volatile phenyl silicone oils that may be mentioned include those oils of formulae ii to vii described below . in which the groups r represent , independently of each other , a methyl or a phenyl , with the proviso that at least one group r represents a phenyl . preferably , in this formula , the phenyl silicone oil comprises at least three phenyl groups , for example at least four , at least five or at least six . in which the groups r represent , independently of each other , a methyl or a phenyl , with the proviso that at least one group r represents a phenyl . preferably , in this formula , the phenyl silicone oil comprises at least three phenyl groups , for example at least four or at least five . mixtures of these phenyl silicone oils may be used . examples that may be mentioned include mixtures of triphenyl , tetraphenyl or pentaphenyl organopolysiloxanes . in which me represents methyl , ph represents phenyl . such a phenyl silicone oil is especially manufactured by dow corning under the reference ph - 1555 hri or dow corning 555 cosmetic fluid ( chemical name : 1 , 3 , 5 - trimethyl - 1 , 1 , 3 , 5 , 5 - pentaphenyltrisiloxane ; inci name : trimethyl pentaphenyl trisiloxane ). the reference dow corning 554 cosmetic fluid may also be used . in which me represents methyl , y is between 1 and 1 , 000 and x represents — ch 2 — ch ( ch 3 )( ph ). in which me is methyl and ph is phenyl , or ′ represents a group — osime 3 and y is 0 or ranges between 1 and 1000 , and z ranges between 1 and 1000 , such that compound ( vi ) is a non - volatile oil . according to a first embodiment , y ranges between 1 and 1000 . use may be made , for example , of trimethyl siloxyphenyl dimethicone , sold especially under the reference belsil pdm 1000 sold by the company wacker . according to a second embodiment , y is equal to 0 . use may be made , for example , of phenyl trimethylsiloxy trisiloxane , sold especially under the reference dow corning 556 cosmetic grade fluid . r 1 , r 2 , r 5 and r 6 are , together or separately , an alkyl radical containing 1 to 6 carbon atoms , r 3 and r 4 are , together or separately , an alkyl radical containing from 1 to 6 carbon atoms or an aryl radical , x is an alkyl radical containing from 1 to 6 carbon atoms , a hydroxyl radical or a vinyl radical , n and p being chosen so as to give the oil a weight - average molecular mass of less than 200 , 000 g / mol , preferably less than 150 , 000 g / mol and more preferably less than 100 , 000 g / mol . mixtures of the phenyl silicone oils corresponding to formulae ( ii ) to ( vii ) are also useful . the phenyl silicone oils that are most particularly suitable for use in the invention are those corresponding to formulae ( iii ), ( iv ) and ( vi ), especially to formula ( iv ) and ( vi ) hereinabove . more particularly , the phenyl silicone oils are chosen from phenyl trimethicones , phenyl dimethicones , phenyl - trimethylsiloxydiphenylsiloxanes , diphenyl dimethicones , diphenylmethyldiphenyltrisiloxanes and 2 - phenylethyl trimethylsiloxysilicates , and mixtures thereof . preferably , the weight - average molecular weight of the non - volatile phenyl silicone oil according to the invention ranges from 500 to 10 , 000 g / mol . the composition of the present invention contains at least one polyethylene wax . the polyethylene wax may be present in the composition of the present invention in an amount ranging from about 1 to about 25 % by weight , more preferably from about 2 to about 20 % by weight , most preferably from about 4 to about 15 % by weight , relative to the total weight of the composition . the cosmetic compositions of the present invention may also contain at least one cosmetically acceptable colorant such as a pigment or dyestuff . examples of suitable pigments include , but are not limited to , inorganic pigments , organic pigments , lakes , pearlescent pigments , iridescent or optically variable pigments , and mixtures thereof . a pigment should be understood to mean inorganic or organic , white or colored particles . said pigments may optionally be surface - treated within the scope of the present invention , including but not limited to , surface treatments with compounds such as silicones , perfluorinated compounds , lecithin , and amino acids . representative examples of inorganic pigments useful in the present invention include those selected from the group consisting of rutile or anatase titanium dioxide , coded in the color index under the reference ci 77 , 891 ; black , yellow , red and brown iron oxides , coded under references ci 77 , 499 , 77 , 492 and 77 , 491 ; manganese violet ( ci 77 , 742 ); ultramarine blue ( ci 77 , 007 ); chromium oxide ( ci 77 , 288 ); chromium hydrate ( ci 77 , 289 ); and ferric blue ( ci 77 , 510 ) and mixtures thereof . representative examples of organic pigments and lakes useful in the present invention include , but are not limited to , d & amp ; c red no . 19 ( ci 45 , 170 ), d & amp ; c red no . 9 ( ci 15 , 585 ), d & amp ; c red no . 21 ( ci 45 , 380 ), d & amp ; c orange no . 4 ( ci 15 , 510 ), d & amp ; c orange no . 5 ( ci 45 , 370 ), d & amp ; c red no . 27 ( ci 45 , 410 ), d & amp ; c red no . 13 ( ci 15 , 630 ), d & amp ; c red no . 7 ( ci 15 , 850 ), d & amp ; c red no . 6 ( ci 15 , 850 ), d & amp ; c yellow no . 5 ( ci 19 , 140 ), d & amp ; c red no . 36 ( ci 12 , 085 ), d & amp ; c orange no . 10 ( ci 45 , 425 ), d & amp ; c yellow no . 6 ( ci 15 , 985 ), d & amp ; c red no . 30 ( ci 73 , 360 ), d & amp ; c red no . 3 ( ci 45 , 430 ) and the dye or lakes based on cochineal carmine ( ci 75 , 570 ) and mixtures thereof . representative examples of pearlescent pigments useful in the present invention include those selected from the group consisting of the white pearlescent pigments such as mica coated with titanium oxide , mica coated with titanium dioxide , bismuth oxychloride , titanium oxychloride , colored pearlescent pigments such as titanium mica with iron oxides , titanium mica with ferric blue , chromium oxide and the like , titanium mica with an organic pigment of the above - mentioned type as well as those based on bismuth oxychloride and mixtures thereof . the precise amount and type of colorant employed in the compositions of the present invention will depend on the color , intensity and use of the cosmetic composition and , as a result , will be determined by those skilled in the art of cosmetic formulation . a composition according to the invention may also comprise at least one surfactant , which may be present in a proportion of from about 0 . 1 % to about 10 % by weight , especially from about 0 . 5 % to about 8 % by weight , or even from about 1 % to about 6 % by weight relative to the total weight of the composition . the surfactant may be chosen from amphoteric , anionic , cationic and nonionic , preferably nonionic , surfactants . mention may especially be made , alone or as a mixture , of : a ) nonionic surfactants with an hlb ( i . e ., hydrophilic - lipophilic balance ) of less than 8 at 25 ° c ., optionally combined with one or more nonionic surfactants with an hlb of greater than 8 at 25 ° c ., as mentioned below , for instance : saccharide esters and ethers such as sucrose stearates , sucrose cocoate and sorbitan stearate , and mixtures thereof ; fatty acid esters , especially of c 8 - c 24 and preferably of c 16 - c 22 fatty acids , and of polyol , especially of glycerol or sorbitol , such as glyceryl stearate , glyceryl laurate , polyglyceryl - 2 stearate , sorbitan tristearate and glyceryl ricinoleate ; lecithins , such as soybean lecithins ; oxyethylenated and / or oxypropylenated ethers ( which may comprise 1 to 150 oxyethylene and / or oxypropylene groups ) of fatty alcohols ( especially of c 8 - c 24 and preferably c 12 - c 18 fatty alcohols ) such as stearyl alcohol oxyethylene ether containing two oxyethylene units ( ctfa name : steareth - 2 ); silicone surfactants , for instance dimethicone copolyols and alkyldimethicone copolyols , for example the mixture of cyclomethicone / dimethicone copolyol sold under the name q2 - 3225c ® by the company dow corning ; b ) nonionic surfactants with an hlb of greater than or equal to 8 at 25 ° c ., for instance : saccharide esters and ethers such as the mixture of cetylstearyl glucoside and of cetyl and stearyl alcohols , for instance montanov 68 from seppic ; oxyethylenated and / or oxypropylenated glycerol ethers , which may comprise 1 to 150 oxyethylene and / or oxypropylene units ; oxyethylenated and / or oxypropylenated ethers ( which may comprise from 1 to 150 oxyethylene and / or oxypropylene units ) of fatty alcohols , especially of c 8 - c 24 and preferably of c 12 - c 18 fatty alcohols , such as stearyl alcohol oxyethylene ether containing 20 oxyethylene units ( ctfa name : steareth - 20 ), cetearyl alcohol oxyethylene ether containing 30 oxyethylene units ( ceteareth - 30 ) and the oxyethylene ether of the mixture of c 12 - c 15 fatty alcohols comprising seven oxyethylene units ( c 12 - 15 pareth - 7 ); esters of a fatty acid , especially of c 8 - c 24 and preferably of c 16 - c 22 fatty acids , and of polyethylene glycol ( or peg ) ( which may comprise 1 to 150 oxyethylene units ), such as peg - 50 stearate and peg - 40 monostearate ; esters of a fatty acid , especially of c 8 - c 24 and preferably of c 16 - c 22 fatty acids , and of oxyethylenated and / or oxypropylenated glycerol ethers ( which may comprise from 1 to 150 oxyethylene and / or oxypropylene units ), for instance glyceryl monostearate polyoxyethylenated with 200 oxyethylene units ; glyceryl stearate polyoxyethylenated with 30 oxyethylene units , glyceryl oleate polyoxyethylenated with 30 oxyethylene units , glyceryl cocoate polyoxyethylenated with 30 oxyethylene units , glyceryl isostearate polyoxyethylenated with 30 oxyethylene units and glyceryl laurate polyoxyethylenated with 30 oxyethylene units ; esters of a fatty acid , especially of c 8 - c 24 and preferably of c 16 - c 22 fatty acids , and of oxyethylenated and / or oxypropylenated sorbitol ethers ( which may comprise from 1 to 150 oxyethylene and / or oxypropylene units ), for instance polysorbate 20 and polysorbate 60 ; dimethicone copolyol , especially the product sold under the name q2 - 5220 ® from dow corning ; dimethicone copolyol benzoate , such as the products sold under the names finsolv slb 101 ® and 201 ® from finetex ; copolymers of propylene oxide and of ethylene oxide , also known as eo / po polycondensates , which are copolymers formed from polyethylene glycol and polypropylene glycol blocks , for instance polyethylene glycol / polypropylene glycol / polyethylene glycol triblock polycondensates . salts of c 16 - c 30 fatty acids , especially amine salts , such as triethanolamine stearate or 2 - amino - 2 - methylpropane - 1 , 3 - diol stearate ; polyoxyethylenated fatty acid salts , especially animated salts or salts of alkali metals , and mixtures thereof ; phosphoric esters and salts thereof , such as dea oleth - 10 phosphate ( crodafos n 10n from the company croda ) or monopotassium monocetyl phosphate ; sulfosuccinates such as disodium peg - 5 citrate lauryl sulfosuccinate and disodium ricinoleamido mea sulfosuccinate ; alkyl ether sulfates such as sodium lauryl ether sulfate ; isethionates ; acylglutamates such as disodium hydrogenated tallow glutamate ( amisoft hs21 r ® from ajinomoto ) and sodium stearoyl glutamate ( amisoft hs11 pf ® from ajinomoto ); soybean derivatives , for instance potassium soyate ; citrates , for instance glyceryl stearate citrate ; proline derivatives , for instance sodium palmitoyl proline or the mixture of sodium palmitoyl sarcosinate , magnesium palmitoyl glutamate , palmitic acid and palmitoyl proline ( sepifeel one from seppic ); lactylates , for instance sodium stearoyl lactylate ; sarcosinates , for instance sodium palmitoyl sarcosinate or the 75 / 25 mixture of stearoyl sarcosine and myristoyl sarcosine ; sulfonates , for instance sodium c 14 - 17 alkyl - sec - sulfonate ; glycinates , for instance sodium cocoyl glycinate . ammonium salts such as ( c 12 - 30 alkyl ) tri ( c 1 - 4 alkyl ) ammonium halides , for instance n , n , n - trimethyl - 1 - docosanaminium chloride ( or behentrimonium chloride ); e ) amphoteric surfactants , for instance n - acylamino acids , such as n - alkylaminoacetates and disodium cocoamphodiacetate , and amine oxides such as stearamine oxide . a makeup and / or care composition according to the invention may also comprise at least one agent usually used in cosmetics , chosen , for example , from : reducing agents ; thickeners ; film - forming agents that are especially hydrophobic , or are softeners , antifoams , moisturizers , or uv - screening agents ; ceramides ; cosmetic active agents ; peptizers ; fragrances ; proteins ; vitamins ; propellants ; hydrophilic or lipophilic , film - forming or non - film - forming polymers ; and lipophilic or hydrophilic gelling agents . the above additives are generally present in an amount for each of them of between 0 . 01 % and 10 % by weight relative to the total weight of the composition . a person skilled in the art will take care to select the constituents of the composition such that the advantageous properties associated with the invention are not , or are not substantially , adversely affected . the ready - to - use composition according to the disclosure can be in various forms , such as in the form of liquids , creams , gels , lotions or paste . the ready - to - use composition can comprise other compounds constituting the cosmetically acceptable medium . this cosmetically acceptable medium comprises water or a mixture of water and at least one cosmetically acceptable organic solvent . as examples of cosmetically acceptable organic solvents , non - limiting mentions can be made of alcohols such as ethyl alcohol , isopropyl alcohol , benzyl alcohol and phenylethyl alcohol , or glycols or glycol ethers such as , for example , ethylene glycol , propylene glycol , butylene glycol , hexylene glycol or dipropylene glycol , or ethers thereof such as , for example , monomethyl , monoethyl and monobutyl ethers of ethylene glycol or propylene glycol , such as , for example , monomethyl ethers of propylene glycol , butylene glycol , hexylene glycol or dipropylene glycol , as well as alkyl ethers of diethylene glycol , for example monoethyl ether or monobutyl ether of diethylene glycol . the composition of the present invention may be in any form , either liquid or non - liquid ( semi - solid , soft solid , solid , etc .). for example , it may be a paste , a solid , a gel , or a cream . it may be an emulsion , such as an oil - in - water or water - in - oil emulsion , a multiple emulsion , such as an oil - in - water - in - oil emulsion or a water - in - oil - in - water emulsion , or a solid , rigid or supple gel . the composition of the invention may , for example , comprise an external or continuous fatty phase . the composition can also be a molded composition or cast as a stick or a dish . lip compositions control control inci us example 1 example 2 example 1 c30 + olefin / undecylenic 17 0 4 . 25 acid copolymer ( performa v ™- 6112 ) supramolecular polymer of 8 . 75 8 . 75 8 . 75 formula ( i ) ( n = 30 - 40 ) red 7 pigment 6 6 6 isododecane qs qs qs polyethylene 500 0 9 . 71 7 . 29 polyethylene 400 0 7 . 29 5 . 46 tio2 4 . 3 4 . 3 4 . 3 all numerical values in the above table are weight percent active . all materials were mixed with moderate agitation at 80 degrees celsius until all waxes have melted and contents looked uniform . the mixture was then cooled to room temperature while mixing before pouring to suitable size containers for future testing . the formulations of the examples above were tested on forearm for rub test . they were also subjected to a texture test upon application on the lips . three subjects evaluated the formulations of control examples 1 and 2 and example 1 on the inner forearm on the same day . each formulation was applied with a lip gloss applicator for 5 strokes and allowed to dry for 10 minutes on forearm and then a drop of olive oil was added to each patch of test area and allowed to rest for 5 minutes before rubbing with kimwipe 5 times to measure color transfer . then a visual evaluation score was given to each kimwipe with a range between 1 and 5 where 5 represents high transfer of color and is undesirable and 1 represents no transfer of color and is highly desirable . three subjects evaluated the formulations of control examples 1 and 2 and example 1 on their lips on the same day . each formulation was applied with a lip gloss applicator for 5 strokes and allowed to dry for 10 minutes . sensorial evaluation was recorded based on the application of the product on the lips . the results above show that , the inventive formulation provided a creamy film texture and a comfortable feeling on the lip with the addition of two polyethylene waxes . at the same time , they provided high oil resistance . it is to be understood that the foregoing describes preferred embodiments of the invention and that modifications may be made therein without departing from the spirit or scope of the invention as set forth in the claims .
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referring now to fig1 of the drawings , wherein a preferred embodiment of the invention is represented in block diagram form , municipal waste materials are collected at a central collection site 10 , to which they are transported by various methods including , for example , using a trash collection truck 12 which deposits waste material in a temporary deposit area 14 . the waste materials thus collected may include articles of many various types , such as discarded paper and fabric goods derived from normal residental household waste . additionally such items as tires 16 , discarded household appliances 18 , and other materials such as scrap wood , plywood , corrugated paper board 20 or tin cans 22 may be included among the waste materials normally expected to be collected . because some of these materials are useful otherwise , but not useful as fuel , a first step in the process of disposal of such waste materials is to sort the materials , as indicated at 24 , removing magnetic materials to the extent possible by the use of magnets , and performing other sorting operations which do not form a part of the present invention . such sorting may need to be done manually , or may be performed mechanically , at least in part . the materials thus removed , indicated at 26 , may be handled as desired , and their disposal is not a part of the present invention . the waste materials 28 remaining after the sorting operation indicated at 24 are first treated according to the present invention by being reduced in size mechanically , as by being passed through a primary shredder 30 . it will be understood that such a primary shredder may be machinery of any construction capable of reducing such waste materials of assorted types into smaller pieces , but is called a shredder herein for the sake of convenient reference . one type of apparatus which is suitable for this purpose , with respect to most materials to be expected to be collected in municipal wastes , is described in rouse , et al ., u . s . pat . no . 4 , 560 , 112 , whereof the disclosure is hereby incorporated herein by reference . depending on the design of the primary shredder 30 , it may be desirable to pass the waste materials more than once through the primary shredder , or through two or more successive stages of similar machinery , the object being to reduce the size of large pieces of waste materials somewhat , to produce pieces small enough to settle closely together as a significantly denser quantity of coarsely shredded wastes 32 , having pieces of more uniform size whose maximum dimension is , for example , no more than 18 inches , but the majority of whose pieces have no dimensions greater than , for example , about 8 inches . such coarsely shredded wastes 32 may be handled easily as bulk materials , using conventional belt or pan conveyors , or bucket loaders , rather than handling individual pieces of waste material separately . the coarsely shredded wastes are transported from the primary shredder 30 , or from an accumulation of such coarsely shredded wastes in the vicinity of the primary shredder 30 , to the location of a burner 34 in which the coarsely shredded waste materials are to be consumed as combustion fuel , before any further processing of the materials is accomplished . however , the sorting operation described above may , optionally , be carried out after the collected waste materials 14 have been treated in the primary shredder 30 . an additional step of sorting may also be performed , after primary shredding has been performed , to remove additional non - combustible material which may have been separated from combustible material as a result of operation of the primary shredder 30 on the waste materials . because the coarsely shredded wastes 32 have been increased in density , relative to their density when collected , it is more economical to transport them by truck to the site of the burner 34 , as indicated at 36 , than if those materials had not been reduced to smaller sized pieces by the primary shredder 30 . the coarsely shredded wastes 32 are preferably delivered to a storage and feed bin 38 located closely adjacent the burner 34 . they are delivered from the storage and feed bin 38 ( see fig2 ) by a metering feed apparatus 40 , to a secondary size reduction apparatus 42 . the secondary size reducing apparatus is preferably of a type including a size - limiting screen member , for example , the granulator manufactured by cumberland engineering company , a division of leesona corp ., of attleboro , mass ., as its model 3250 granulator , or it may be of a design similar to that of the primary shredder 30 , but of smaller dimensions . the capacity of the secondary apparatus 42 is chosen so that it is capable of reducing the size of individual pieces of the coarsely shredded wastes 32 most economically in view of the fuel demands of the burner 34 . the secondary size reduction apparatus 42 is preferably of a design particularly adapted to reduce the size of pieces of coarsely shredded wastes of the predominant type of material available . as shown more particularly in flg . 2 , the metering feed apparatus 40 may include an upwardly inclined pan conveyor 41 to carry the coarsely shredded waste materials 32 upward from the collection bin 38 , while a pair of leveling screws 43 , located a predetermined distance above the upper end of the pan conveyor 41 , are rotated continuously so as to oppose the movement of the coarsely shredded waste materials 32 above a certain height relative to the pan conveyor 41 , to maintain the rate of delivery of coarsely shredded wastes 32 to the secondary size reducing apparatus 42 . coarsely shredded waste materials 32 are thus delivered to the secondary size reduction apparatus 42 at the rate established by the speed of the pan conveyor 41 . the objective of the secondary size reduction is to reduce the size of individual pieces of the coarsely shredded wastes 32 , so that the total surface area of the pieces is increased , promoting better combustion , and to make individual pieces small enough to be transported in a stream of gas . the coarsely shredded wastes 32 are thus transformed in the secondary size reduction apparatus 42 into waste - derived , prepared fuel 44 with substantially all of the pieces of the prepared fuel 44 having maximum dimensions less than a maximum size which is determined by the type of material and the type of burner . the prepared fuel 44 is transported in a stream of moving gas produced by a blower 45 , through a conduit system 46 arranged to deliver the waste - derived , prepared fuel 44 from the secondary size reduction apparatus 42 immediately and directly to the burner 34 . preferably , at least part of the stream of gas used to transport the prepared fuel 44 is made up of air drawn from an enclosure 47 at least partially covering the pan conveyor 41 and the secondary size reduction apparatus 42 . this helps to reduce the amount of dust which might otherwise be produced as a result of the operation of the pan conveyor 41 and secondary size reduction apparatus 42 . additionally , any odors produced by the prepared fuel 44 and coarsely shredded wastes 32 may be controlled thereby . similarly , portions of the stream of gas may be provided by drawing air into the blower 45 from the vicinity of other nearby odor - producing factories , etc ., as indicated schematically at 39 . the prepared fuel 44 would ordinarily be introduced into the stream of gas in a zone of low pressure developed in the conduit 46 as by a venturi nozzle arrangement located at 49 in fig2 or through a device such as , for example , the triple gate valve disclosed in rouse , et al ., u . s . pat . no . 4 , 561 , 467 . a secondary venturi nozzle effect is provided at 60 , downstream from the last point of introduction of any material into the stream of gas , by a slight constriction in the conduit 46 , which provides resistance against minor backpuffs from the burner 34 , to prevent disruption of the flow of materials included in the stream of gas and wastes being sent into the burner 34 . gaseous or liquid hazardous wastes which can be rendered harmless by exposure to sufficiently high temperature conditions of sufficient duration may be introduced into the stream of gas at this point , preferably through an injection nozzle 68 as shown in fig2 to be carried into the burner 34 to be rendered safe by such incineration , or they may be introduced in a zone of low pressure on the intake side of the blower 45 . the rate of introduction of such hazardous materials is preferably controlled , as by the valve 37 . solid or semi - solid hazardous wastes capable of being rendered harmless by incineration may be introduced by appropriately controllable apparatus designated as 55 , which delivers such materials to the secondary size reducing apparatus 42 in small quantities , so that it becomes a small part of the prepared fuel 44 . ideally , a pair of similar machines 42 are provided so that one can be used during repair or adjustment of the other , as shown schematically in fig3 with a split conduit or chute down from the feed conveyor 41 being provided and having a diverter gate 64 to permit selection of either shredder . appropriate sections of conduit 66 are provided , and cut - off valves 67 are provided below each of the machines 42 to isolate either of the secondary size reduction machines 42 during maintenance and repair work . the sections of conduit 66 , below the cutoff valves 67 , join each other in a &# 34 ; y &# 34 ; upstream of the conduit 46 . as shown in fig4 it may be desirable to introduce prepared fuel 44 into the conduit 46 by introducing it directly into the intake of a blower 61 , from the secondary size reducing machine 42 , which serves the purpose of positively accelerating motion of the prepared fuel 44 as it enters the conduit 46 , and also enhances the efficiency of operation of the secondary size reduction apparatus 42 as a result of the flow of the air through it into the blower 61 . the burner 34 may be a municipal waste incinerator adapted to produce heat useful for generating steam for municipal heat generation or for generation of electrical power . alternatively , the burner 34 may be the furnace of a lime kiln or a cement kiln producing clinker from which cement may be produced , in which case it may be desired to use such waste derived , prepared fuel 44 only as a supplement for a primary fuel 51 such as coal , oil , or gas , with quantities of the waste - derived , prepared fuel 44 used being limited to that which can be incorporated in the product of the cement or lime kiln without detriment to the quality of the product resulting from the ash produced by combustion of the waste - derived , prepared fuel 44 . the combustion process in the burner 34 is monitored by appropriate exhaust gas analyzing sensors and combustion zone temperature sensors indicated collectively as a combustion monitor 48 , which is connected to provide appropriate electrical indications of the observed conditions within the burner 34 to a feed control device 50 . such a feed control device 50 may be of known design , including programmable apparatus arranged to provide controlling electrical output signals to the metering feed apparatus 40 , as by electrically controlling the speed of operation of the pan conveyor 41 , in response to the conditions sensed by the combustion monitor 48 , so as to provide a proper rate of delivery of waste - derived , prepared fuel 44 to develop and maintain the required combustion temperature and fuel - air mixture required for complete and acceptably clean combustion of the waste - derived , prepared fuel 44 and any other fuel 51 used to fire the burner 34 , or to control the amount of useful heat output 52 produced by the burner 34 . the feed control apparatus 50 may also be connected electrically to control the feed apparatus 55 for introduction of solid or semi - solid hazardous waste materials into the secondary size reduction apparatus 42 . it can also be connected to operate the valve 37 or other feed controlling apparatus to regulate the delivery of liquid or gaseous hazardous wastes into the stream of gas used to deliver prepared fuel 44 to the burner 34 . additionally , sensors for detection of excessive pressure or temperatures are desirably provided in the conduit 46 adjacent the burner 34 , as at 65 , so as to transmit signals electrically to the feed control apparatus 50 so that feed can be stopped and the blower 45 shut down thereby in response to indications of backpuffing , explosions within the burner 34 , or other unsafe conditions thus detectable . an emergency shut - off valve 69 , preferably including provision for relieving dangerously excessive pressure from within the burner 34 , is provided at the point of entry of the conduit 46 into the burner 34 , and is controllably connected to the feed control apparatus 50 to be closed , interrupting the stream of material in the conduit 46 in response to detection of unsafe conditions by the sensor 65 . in order further to promote efficiency and completeness of combustion , a significant part of the stream of gas used to convey the prepared fuel 44 into the burner 34 is preferably heated gas . some of such heated gas may be provided by using a portion of the exhaust gas from the burner 34 , conducting it through a conduit 53 to the blower 45 . this heated gas preheats the prepared fuel 44 and permits the size of the stream of gas used to carry prepared fuel 44 to be larger than otherwise would be practical because of the cooling effect of too much air introduced from the atmosphere at ambient temperatures , given the requirement for high combustion temperatures required to produce cement and lime , and to break down certain chemical compounds which would otherwise be dangerous if allowed to become part of the ash residue which must be disposed of , either as a component of cement produced or to be disposed of as landfill . it will be understood by one skilled in the field that the temperature of the stream of gas must not be high enough to ignite the prepared fuel 44 prematurely , and that the oxygen required for combustion of the prepared fuel 44 is not available in the exhaust gases which might be recycled directly . it may , then , be necessary in some cases to utilize a heat exchanger 56 to extract heat from gases exhausted from the burner 34 to preheat air in order to provide enough oxygen to combine with the fuel of the burner 34 without cooling the combustion zone unduly . since the coarsely shredded wastes 32 are denser than the prepared fuel 44 , they are more accurately measureable and more easily metered during delivery into the secondary size reduction apparatus 42 than would be the prepared waste - derived fuel 44 whose smaller particle size typically results in lesser density and less uniformity because of the resiliency of paper and other fabric and fiber materials usually forming a large portion of metropolitan waste materials . by delivering the waste - derived , prepared fuel 44 immediately to the burner 34 after reduction to small particles in the secondary size reduction apparatus 42 , however , the responsiveness of the feed control system including the feed controller 50 and the metering feed apparatus 40 is made to be adequate , particularly in the case of a continuously fed and operated limestone kiln or cement kiln fired only secondarily by the use of waste - derived , prepared fuel 44 . the terms and expressions which have been employed in the foregoing specification are used therein as terms of description and not of limitation , and there is no intention in the use of such terms and expressions of excluding equivalents of the features shown and described or portions thereof , it being recognized that the scope of the invention is defined and limited only by the claims which follow .
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fig1 illustrates the preferred embodiment of the invention . scan - compatible analog differential driver circuit 100 comprises differential driver 110 , programmable termination impedance network 120 , up - channel receiver 130 and lssd test mode control circuit 140 . differential driver 110 may be any differential driver circuit incorporating a digital - to - analog converter ( dac ) and having large dynamic gain . in the preferred embodiment , driver 110 is a high - speed ( e . g . 6 gbps or higher ) differential finite - impulse - response ( fir ) i / o driver with large dynamic gain as described in u . s . pat . no . 6 , 680 , 681 , entitled high speed fir transmitter , by hsu et al ., the subject matter of which is hereby incorporated by reference in its entirety . data inputs ap and an to differential driver 110 represent differential data inputs . programmable termination impedance network 120 sets the termination impedance at differential output nodes zp and zn . during digital scan test mode ( e . g . lssd testing ), programmable termination impedance network 120 skews the termination impedance at differential output nodes zp and zn in response to signals resctrl_p & lt ; 5 : 0 & gt ; and resctrl_n & lt ; 5 : 0 & gt ;. when the termination impedance is skewed at differential output nodes zp and zn , the differential output of driver 110 ( dop and don ) is skewed , and thus , up - channel receiver 130 is capable of detecting the full dynamic range of driver 110 . skewing the output termination impedance serves to covert dop and don into a common - mode signal . during normal operation , programmable termination impedance network 120 programs the termination impedance at output nodes zp and zn in response to signals resctrl_p & lt ; 5 : 0 & gt ; and resctrl_n & lt ; 5 : 0 & gt ; to the appropriate termination resistance for optimum transmission ( e . g . matched 50 ohm impedance at zp and zn ). up - channel receiver 130 may be any receiver circuit with voltage offset such that when inputs to the receiver are equal , the receiver reliably outputs a low voltage . alternatively , up - channel receiver 130 may incorporate hysteresis for improved noise immunity during up - channel signaling . up - channel signaling is well known in the art . for example , see u . s . patent application ser . no . 10 / 604025 , entitled data transceiver and method for equalizing the data eye of a differential input data signal , assigned to ibm corporation . in the preferred embodiment , up - channel receiver 130 is a differential receiver with a built - in offset voltage and hysteresis , and is capable of receiving signals transmitted up - channel ( i . e . in the opposite direction as the data being transmitted ). such receivers are incorporated in high speed serializer - deserializer ( serdes ) circuit designs for up - channel signaling , and thus , circuit area may be minimized when an up - channel receiver with hysteresis is already present in a design . up - channel receiver 130 is used to complete the observation path from the output of driver 110 to a srl or a primary output during digital scan - based testing . during normal operation , up - channel receiver 130 may sense a signal as low as 70 mv . however , there will be some ambiguity at these low levels . since digital scan - based test mode requires deterministic results of either a logic ‘ 1 ’ or ‘ 0 ’ without ‘ x ’ propagation , the area of ambiguity must be removed . this is accomplished by changing the characteristics of up - channel receiver 130 during test mode . when up - channel receiver 130 is placed in test mode by lssd_en , offset and gain characteristics of the receiver are changed such that the receiver now requires a 150 mv signal or the output will result in a ‘ 0 ’. this increased voltage offset (˜ 70 mv ) guarantees that when all dacs are turned off in driver 110 , there will be a logic ‘ 0 ’ output from up - channel receiver 130 at node z . additionally , by skewing the termination impedance at nodes zp and zn during test mode , the lsb of driver 110 can be observed as a logic ‘ 1 ’ at the output of up - channel receiver 130 . lssd test mode control block 140 enables scan - compatible driver circuit 100 of fig1 for digital testing by overriding the nominal control signals resctrl_p & lt ; 5 : 0 & gt ; and resctrl_n & lt ; 5 : 0 & gt ; and by overriding the nominal segment control vector seg_disable & lt ; 7 : 0 & gt ;. by overriding the nominal control signals resctrl_p & lt ; 5 : 0 & gt ; and resctrl_n & lt ; 5 : 0 & gt ;, the output termination impedance at nodes zp and zn may be skewed , thus allowing observation of the lsb of the differential driver . by overriding the nominal segment control vector seg_disable & lt ; 7 : 0 & gt ;, each segment of differential driver 110 may be tested one at a time , thus assuring the lsbs of the driver are effectively tested for faults . these signals are overridden in response to lssd_en . in the preferred embodiment , lssd_en signal is a primary input . a detailed description of the aforementioned signals follows . during digital test mode , up - channel receiver 130 is enabled for digital testing by lssd_en and powered on by pdwn . up - channel receiver 130 functions as an analog - to - digital converter ( adc ) and is capable of passing a digital value z , which represents the output of differential driver 110 , to a shift register latch (“ srl ”) which is observable during digital testing . during digital test mode , the termination impedance is skewed , thus enabling up - channel receiver 130 to detect the full dynamic range of differential driver 110 even though the least - significant - bits ( lsbs ) effect a much smaller change than up - channel receiver 130 could detect during normal operation . detecting the lsb of differential driver 110 enables the digital - to - analog converters ( dacs ) residing within differential driver 110 to be fully digitally modeled ( e . g . as a number of n - bit or gates ), thus enabling an automatic test pattern generator to generate test patterns for the entire dac circuit . if the termination impedance is not skewed , the voltage offset of up - channel receiver 130 will be much larger than the lsb of driver 110 , making the receiver &# 39 ; s interpretation of the output of driver 110 unreliable . by skewing the termination impedance , the lsb of the dac may be tested using a scan - based digital test methodology . during normal operation , up - channel receiver 130 is taken out of digital test mode by disabling lssd_en . additionally , up - channel receiver 130 may be powered down by activating pdwn or may remain powered on by leaving pdwn deactivated . fig2 illustrates in further detail differential driver 110 of fig1 . finite impulse response ( fir ) latches 210 store differential data inputs ap & lt ; 3 : 0 & gt ; and an & lt ; 3 : 0 & gt ; and present ap & lt ; 3 : 0 & gt ; and an & lt ; 3 : 0 & gt ; to driver logic 220 . xnor circuits 230 may invert ap & lt ; x : 0 & gt ; and an & lt ; x : 0 & gt ; in response to data polarity signal tx_polarity & lt ; 3 : 0 & gt ; or may disable ap & lt ; x : 0 & gt ; and an & lt ; x : 0 & gt ; in response to data disable signal tapdis 0 / 2 / 3 . buffer circuits 240 buffer the output of xnor circuits 230 . predriver circuits 250 amplify the differential data signals . each predriver circuit contains one or more preamplifiers (“ segments ”). as illustrated in fig2 , predriver circuit 250 a comprises one segment , predriver circuit 250 b comprises four segments , predriver circuit 250 c comprises two segments , and predriver circuit 250 d comprises one segment . if a differential data bit is preamplified by more than one segment , driver output stages 260 are paralled per segment for that differential data bit . as illustrated in fig2 , predriver circuit 250 b contains four segments , and therefore , driver 260 b will have four parallel differential inputs from each of the four segments contained in predriver circuit 250 b . each paralleled output stage has a separate predriver , driven from the same driver logic ( xnor circuits 220 and buffer circuits 240 ). the number of segments per differential data bit determines the drive strength for that differential data bit . the more segments , the higher the drive strength for the programmed current . any segment may be disabled via the seg_disable & lt ; x : 0 & gt ; signal . the output drive strength of output drivers 260 a - 260 d is set by current dac ( idac ) circuit 270 . idac circuit 270 comprises idacs 270 a - 270 d . the value of each idac 270 a - 270 d is set by tx_coeffx & lt ; x : 0 & gt ;. as illustrated in fig2 , the value of idac 270 a is determined by tx_coeff 3 & lt ; 3 : 0 & gt ;. the range of the current reference ( iref ) for each idac 270 a - 270 d is set by the output of power dac 280 , which is controlled by tx_power & lt ; 6 : 0 & gt ;. the differential output of drivers 260 a - 260 d are tied together at differential output nodes zp and zn to form the final pair of output signals , dop and don . during digital testing , signals tx_coeffx & lt ; n : 0 & gt ;, tapdiso / 2 / 3 , tx_power & lt ; 6 : 0 & gt ;, tx_polarity & lt ; 3 : 0 & gt ;, ap & lt ; 3 : 0 & gt ;, and an & lt ; 3 : 0 & gt ; are supplied from srls , thus making the differential driver digitally testable . fig3 illustrates in further detail programmable termination impedance network 120 of fig1 . programmable termination impedance network 300 , which corresponds to programmable termination impedance network 120 of fig1 , comprises programmable resistor circuits 310 and 320 . resistor circuit 310 comprises a number of resistor components 312 and number of transistor switches 314 , wherein one transistor of transistor switches 314 is electrically coupled in series with one resistor of resistor components 312 . resistor circuit 320 also comprises a number of resistor components 322 and number of transistor switches 324 , wherein one transistor of transistor switches 324 is electrically coupled in series with one resistor from resistor components 322 . when a particular resistor is switched into the resistor network by a transistor , that resistor component is electrically coupled in parallel with all other resistors that are also switched into the network . when a particular resistor is switched out of the resistor network , it is electrically isolated from the impedance network . in the preferred embodiment , resistor circuits 310 and 320 each comprise six resistors , the value of which are as follows : rp 1 = 53 . 65 ohms , rp 2 = 71 . 15 ohms , rp 3 = 144 . 35 ohms , rp 4 = 286 . 95 ohms , rp 5 = 554 ohms , and rp 6 = 3001 ohms , where : rn 1 = rp 1 , rn 2 = rp 2 , rn 3 = rp 3 , rn 4 = rp 4 , rn 5 = rp 5 , and rn 6 = rp 6 . in the preferred embodiment , transistor switches 314 and 324 comprise six p - fet transistors . resistor circuit 310 provides termination impedance to output node zp of differential driver 110 of fig1 and resistor circuit 320 provides termination impedance to output node zn of differential driver 110 of fig1 . control signal resctrl_p & lt ; 5 : 0 & gt ; programs resistor circuit 310 and control signal resctrl_n & lt ; 5 : 0 & gt ; programs resistor circuit 320 by either activating or deactivating the transistor electrically in series with a certain resistor . both resctrl_p and resctrl_n are determined by lssd test mode control block 140 of fig1 . resctrl_p and resctrl_n switch in or out resistor components within resistor circuits 310 and 320 , thus programming the termination impedance at nodes zp and zn , respectively . during digital scan test mode , the termination impedance provided by resistor circuits 310 and 320 is programmed so that the termination impedance of programmable termination impedance network 300 is skewed at nodes zp and zn . for example , the termination impedance at node zp , determined by those resistors in resistor circuit 310 which are switched in to the network by corresponding transistor switches 314 and those that are not , may be programmed to 54 ohms while the termination impedance at node zn is programmed to 554 ohms . this occurs when resctrl_p & lt ; 5 : 0 & gt ;=“ 011111 ” and resctrl_n & lt ; 5 : 0 & gt ;=“ 111101 ”. when the termination impedance is skewed in such a manner , the differential output of driver 110 in fig1 is converted to a common mode signal because the differential signal at node zn of the driver will be 10 × larger than the same signal at node zp , thus resulting in a differential - to - common mode gain of 5 ×. during normal operation , signals resctrl_p & lt ; 5 : 0 & gt ; and resctrl_n & lt ; 5 : 0 & gt ; program transistor switches 314 and 324 so that the output termination impedance at nodes zp and zn match . this occurs when resctrl_p & lt ; 5 : 0 & gt ;= resctrl_n & lt ; 5 : 0 & gt ;. for illustrative purposes , consider a differential driver that comprises a seven - bit dac where : the lsb of the 7 bit dac = 1 . 2v / 127 = 9 mv in terms of driver output differential amplitude at 50 ohms and 90 mv at 500 ohms . lsb of 4 / 5 / 6 bit dac = 19 mv of driver output differential amplitude at 50 ohms and 190 mv at 500 ohms . up - channel receiver 130 of fig1 is capable of detecting these amplitudes for a termination resistance of 500 ohms , but can not detect these amplitudes at 50 ohms , because the amplitude is less than the receiver &# 39 ; s offset voltage . as dacs are designed more precisely , the lsb will become smaller and more difficult to detect in a digital test framework . a number of resistor / transistor combinations as well as resistor values are possible and within the scope of the invention . fig4 illustrates in further detail up - channel receiver 400 , which corresponds to up - channel receiver 130 of fig1 . up - channel receiver 400 comprises a hysteresis comparator circuit 402 and a common level shifter 404 . common level shifter 404 provides transition from an analog power supply domain (“ vtt ”) to a digital power supply domain (“ vdd ”). level shifters are well known to those skilled in the art , and therefore , no further description is necessary . hysteresis comparator circuit 402 comprises reference current source 406 , first built - in offset voltage comparator 408 , second built - in offset voltage comparator 410 , differential amplifier circuit 412 , and output stage 414 . reference current source 406 comprises p - fet transistor tpl 2 and n - fet transistor t 1 and generates reference current ioref . current sources are well known to those skilled in the art , and therefore , no further description is necessary . first built - in offset voltage comparator 408 comprises p - fet transistors tel , tpl , and tnl . the comparator has a built - in offset voltage (“ vth −”). the value of vth − is dependent upon the ratio of tnl to tpl as well as the biasing current ibias . in general , the higher the ratio or higher the biasing current , the higher vth − becomes . as previously stated , this offset voltage provides improved noise immunity . without this offset voltage , a comparator would output a high when vinp & gt ; vinn , output a low when vinp & lt ; vinn , and output an unknown value when vinp = vinn . such a comparator has zero noise margin due to the fact that a minimal amount of noise triggers a response . first built - in offset voltage comparator 408 addresses low to high transitions at vinp and vinn . vinp corresponds to dop and vinn corresponds to don as illustrated in fig1 , where dop and don represent the differential output of differential driver 110 of fig1 . second built - in offset voltage comparator 410 comprises p - fet transistors ter , tpr , and tnr . the comparator has a built - in offset voltage (“ vth +”). the value of vth + is dependent upon the ratio of tnr to tpr as well as the biasing current ibias . in general , the higher the ratio or higher the biasing current , the higher vth + becomes . as previously stated , this offset voltage provides improved noise immunity . second built - in offset voltage comparator 410 addresses high to low transitions at the inputs vinp and vinn . differential amplifier circuit 412 comprises n - fet transistors tinp , tinn and tbias . output stage 414 comprises p - fet transistor tnr 2 , n - fet transistor t 2 , and inverter circuit 416 . transistors tnr 2 and t 2 supply an input signal to inverter circuit 416 and the inverter inverts that signal . differential amplifiers , output stages and inverters are all well known to those skilled in the art , and therefore , no further description is necessary . common level shifter 404 transitions the output of inverter circuit 416 from vtt to vdd and outputs a signal z . up - channel receiver 400 is either disabled , enabled during up - channel signaling ( e . g . while performing equalization ), or enabled during digital scan - based testing . the receiver is disabled when vbias is a logic ‘ 0 ’. vbias is an inverted version of the pdwn signal as illustrated in fig1 . when the pdwn signal is active ( i . e . logic ‘ 1 ’), vbias is pulled to ground and n - fet transistor tbias is turned off , which cuts off the tail bias current ibias , thus effectively disabling receiver 400 . when pdwn is deactive ( i . e . logic ‘ 0 ’), vbias is pulled to vdd and n - fet tbias is turned on , thus enabling receiver 400 . when up - channel receiver 400 is enabled during up - channel signaling , both first built - in offset voltage comparator 408 and second built - in offset voltage comparator 410 are enabled . first built - in offset voltage comparator 408 is enabled when lssd_en signal is deactive ( logic ‘ 0 ’). second built - in offset voltage comparator 410 is always enabled because the gate of p - fet transistor ter is tied to ground . in this mode , up - channel receiver 400 outputs a logic ‘ 1 ’ at z when vinp − vinn & gt ; vth +, outputs a logic ‘ 0 ’ when vinp − vinn & lt ; vth −, and remains in its previous state when vth −& lt ; vinp − vinn & lt ; vth +. first built - in offset voltage comparator 408 and second built - in offset voltage comparator 410 both have memory , which is desired for improving noise immunity , but not permitted during digital scan - based testing . when up - channel receiver 400 is enabled during digital scan - based testing , first built - in offset voltage comparator 408 is disabled and second built - in offset voltage comparator 410 is enabled . first built - in offset voltage comparator 408 is disabled when lssd_en signal is active ( logic ‘ 1 ’). by disabling first built - in offset voltage comparator 408 , hysteresis is turned off , thus satisfying the digital scan - based methodology requirement of not having memory . when first built - in offset voltage comparator 408 is disabled , second built - in offset voltage comparator 410 functions as a built - in offset - voltage comparator . therefore , up - channel receiver 400 outputs a logic ‘ 1 ’; if and only if vinp − vinn & gt ; vth +. due to process , temperature , and supply variation , vth + will vary with some range ( e . g . vth + _lower to vth + _upper ). for illustrative purposes , vth + _lower = 70 mv and vth + _upper = 150 mv . this variation in vth + is addressed by skewing the output termination impedance as previously described and as illustrated in fig3 . for illustrative purposes , the output termination impedance at node zp of fig1 is set to 500 ohms and the output termination impedance at node zn of fig1 is set to 50 ohms . thus : a ) when a logic ‘ 1 ’ is scanned in , if any bit of the differential driver idac is on , vinp − vinn will always be greater than vth + _upper and thus will always guarantee a logic “ 1 ” at up - channel receiver output z ; b ) when a logic “ 0 ” is scanned in , if any bit of the differential driver idac is on , vinp − vinn will always be less than vth + _lower and thus will always guarantee a logic “ 0 ” at up - channel receiver output z ; and c ) when all bits of the differential driver idac are off , regardless of scanning a logic ‘ 1 ’ or logic “ 0 ”, vinp − vinn is equal to zero ( and always less than vth + _lower ) and thus will always guarantee a logic ‘ 0 ’ at up - channel output z . therefore , the lsb of a differential driver is capable of being digitally tested in a repeatable , predictable , and reliable manner . alternatively , if up - channel signaling is not required , hysteresis is not needed and only second built - in offset voltage comparator 410 is required . fig5 illustrates in further detail lssd test mode control circuit 500 , which corresponds to lssd test mode control circuit 140 of fig1 . multiplexer circuits (“ mux ”) 502 , 504 , 510 and 512 are controlled by the lssd_en signal . when the scan - compatible analog differential driver circuit of the present invention is placed in digital test mode , lssd_en is active , thus enabling muxs 502 , 504 , 510 and 512 to select test signals for the purpose of digitally testing the driver circuit . during normal operation , lssd_en is deactive , thus enabling muxs 502 , 504 , 510 and 512 to select signals that correspond to normal functional operation of the driver circuit , which have been previously described . mux 502 selects either nominal_resctrl_p & lt ; 5 : 0 & gt ; or hard - wired value ‘ 011111 ’ in response to lssd_en . mux 504 selects either nominal_resctrl_n & lt ; 5 : 0 & gt ; or hard - wired value ‘ 111101 ’ in response to lssd_en . during normal operation , lssd_en is deactivate ( logic ‘ 0 ’) and mux 502 selects nominal_resctrl_p & lt ; 5 : 0 & gt ; and mux 504 selects nominal_resctrl_n & lt ; 5 : 0 & gt ;. as previously described , nominal_resctrl_p & lt ; 5 : 0 & gt ; and nominal_resctrl_n & lt ; 5 : 0 & gt ; program the output termination impedance so that the impedance matches at nodes zp and zn of fig1 . this occurs when nominal_resctrlp & lt ; 5 : 0 & gt ;= nominal_resctrln & lt ; 5 : 0 & gt ;. during digital scan - based testing , lssd_en is activate ( logic ‘ 1 ’). when lssd_en is active , mux 502 selects a hardwired value for resctrl_p & lt ; 5 : 0 & gt ; and mux 504 selects a hardwired value for resctrl_n & lt ; 5 : 0 & gt ;. in the preferred embodiment , when lssd_en is activate , resctrl_p & lt ; 5 : 0 & gt ; is set to ‘ 011111 ’ and resctrl_n & lt ; 5 : 0 & gt ; is set to ‘ 111101 ’. these values allow the output termination impedance of programmable termination network 120 of fig1 to be skewed in accordance with the present invention and as previously described . the values corresponding to resctrl_n / p & lt ; 5 : 0 & gt ; may be supplied from any storage element which is accessible during digital testing ( i . e . embedded dram , fuses , rom , etc .) so long as those values do not switch during digital testing . switching of these signals can produce unpredictable test results . or circuits 506 and 508 are optional and allow leakage testing to be performed by setting resctrl_p & lt ; 5 : 0 & gt ; and resctrl_n & lt ; 5 : 0 & gt ; to lt which equals ‘ 111111 ’. leakage testing is well known in the art , and thus , is not discussed in further detail . mux 510 selects the drive strength signal to be supplied to power dac 280 of fig2 . during digital scan - based testing , the power to idac circuit 270 of fig2 is limited so as to not overpower the 3 k ohm resistor components rn 6 and rp 6 of fig3 . when lssd_en is active , mux 510 selects the hardwired value ‘ 0100000 ’ to be tx_power & lt ; 6 : 0 & gt ;. this value programs the idac circuit of the differential driver as illustrated in fig2 to a quarter of the normal operating power . during normal operation , mux 510 selects nominal_tx_power & lt ; 6 : 0 & gt ; to be tx_power & lt ; 6 : 0 & gt ;. mux 512 selects either nominal_seg_disable & lt ; 7 : 0 & gt ; or a decoded signal supplied from decoder 514 in response to lssd_en . during digital testing , only one segment of the differential driver may be tested during a test sequence ( e . g . load test patterns , run system clock , unload test results ). test patterns that represent which segment is to be tested during a test sequence are provided to decoder 514 from srls 516 during digital testing . decoder 514 may be any standard 3 to 8 decoder and decodes the signals provided by srls 516 . for a differential driver that contains eight segments , three srls ( i . e . 2 { circumflex over ( )} 3 2 { circumflex over ( )} 2 2 { circumflex over ( )} 1 ) supply test patterns to decoder 514 . these three inputs to decoder 514 enable the decoder to provide eight outputs to the differential driver when being tested , each output representing which one of eight segments within the differential driver will be activated during a particular test time . test patterns are loaded into the srls , or “ scanned in ”, each time a different segment is to be tested . for example , when 2 { circumflex over ( )} 3 2 { circumflex over ( )} 2 2 { circumflex over ( )} 1 = 0 0 0 , seg_disable & lt ; 7 : 0 & gt ;=& lt ; 11111110 & gt ;; when 2 { circumflex over ( )} 3 2 { circumflex over ( )} 2 2 { circumflex over ( )} 1 = 0 0 1 , seg_disable & lt ; 7 : 0 & gt ;=& lt ; 11111101 & gt ;; when 2 { circumflex over ( )} 3 2 { circumflex over ( )} 2 2 { circumflex over ( )} 1 = 0 1 0 , seg_disable & lt ; 7 : 0 & gt ;=& lt ; 11111011 & gt ;; etc . ; and finally when 2 { circumflex over ( )} 3 2 { circumflex over ( )} 2 2 { circumflex over ( )} 1 = 1 1 1 , seg_disable & lt ; 7 : 0 & gt ;=& lt ; 01111111 & gt ;. the decoded signal is selected by mux 512 and transmitted to the differential driver when lssd_en is active . during normal operation , mux 512 selects nominal_seg_disable & lt ; 7 : 0 & gt ;. the number of srls required to provide test input to the decoder and the size of the decoder depend upon the number of segments contained within the differential driver . thus , any size decoder and number of srls for inputting test signals to the decoder are within the scope of this invention . or circuit 518 is optional and allows the differential driver to be placed in tristate mode when ts is active . placing a driver in tristate mode is well known in the art , and thus , is not discussed in further detail . logic circuit 520 either inhibits or gates nominal_pdwn signal depending upon the value of lssd_en . when in digital scan - based test mode , lssd_en is active and inverted to a logic ‘ 0 ’ at the input to logic circuit 520 , thus inhibiting nominal_pdwn and resulting in pdwn being a logic ‘ 0 ’. this assures that up - channel receiver 130 of fig1 remains powered on during digital testing as previously described and as illustrated in fig4 . during normal operation , the receiver may be powered down by activating the nominal_pdwn signal ( i . e . a logic ‘ 1 ’). lssd_en does not inhibit nominal_pdwn when lssd_en is deactivate . instead , logic circuit 520 gates nominal_pdwn when lssd_en is deactive . fig6 illustrates a method of digitally testing differential driver 110 of fig1 in accordance with the present invention . digital scan - based test mode is activated at 600 by activating the lssd_en signal illustrated in fig1 . in the preferred embodiment , this signal is a primary i / o signal that electrically configures the scan - compatible analog differential driver circuit 100 of fig1 for digital testing . the lssd_en signal adjusts the electrical properties of programmable termination impedance network 120 of fig1 at 610 by programming resctrl_p & lt ; 5 : 0 & gt ; to ‘ 0111111 ’ and resctrl_n & lt ; 5 : 0 & gt ; to ‘ 111101 ’, thus skewing the output impedance of the programmable termination impedance network in accordance with the present invention and as previously described . the lssd_en signal also adjusts the offset voltage of up - channel receiver 130 of fig1 and selects a suitable power range for idac circuit 270 of fig2 at 620 in accordance with the present invention and as previously described . for illustrative purposes , the power to the idac circuit is set to a quarter of the normal operating power by setting tx_power & lt ; 6 : 0 & gt ; to ‘ 0100000 ’ as previously described and as illustrated in fig5 so as to not overpower the 3k ohm resistor components rn 6 and rp 6 of fig3 . the power range selectable by the lssd_en signal is dependent upon the configuration of the programmable termination impedance network and any range selected is within the scope of the invention . additionally , lssd_en also enables decoder 514 of fig5 at 630 . in accordance with the present invention and as previously described , the decoder activates only one segment of the differential driver during any one test sequence , thus preventing segment contention at the output of the differential driver under test . during digital scan - based testing , the decoder determines which segment is to be activated and activates that segment at 640 in accordance with the present invention and as previously described . the differential driver circuit is stimulated from srls ( e . g . lssd or gsm ) at 650 . during digital scan - based test modeling , the differential driver is modeled , for example as a number of n - bit or gates , and digital test patterns are automatically generated ( atpg ) for testing the components of the driver for stuck - at ‘ 1 ’ or ‘ 0 ’ faults . these test patterns provide stimulus to the driver circuit at 650 during digital scan testing . the stimulus represented by the tx_coeffx & lt ; x : 0 & gt ; signals , which are generated during atpg , are stored in srls and stimulate the differential driver circuit during digital scanbased testing . the four bits of differential data input signal ap & lt ; 3 : 0 & gt ; as illustrated in fig2 are supplied from srls . the four bits of differential data input signal an & lt ; 3 : 0 & gt ; as illustrated in fig2 are also supplied from srls . the input stimulation signals to the differential driver ( tx_coeffx & lt ; x : 0 & gt ;, ap & lt ; 3 : 0 & gt ;, an & lt ; 3 : 0 & gt ;, tx_polarity & lt ; 3 : 0 & gt ;, tapdiso / 2 / 3 , and seg_disable & lt ; 7 : 0 & gt ;) will all be observed at the output z of up - channel receiver 130 of fig1 , which is connected to a srl . thus , the idacs comprising the differential driver are digitally testable and observable during digital scan testing at 660 . each segment is activated in accordance with the present invention and as previously described and tested until all segments have been tested or until a fail occurs at 670 . the lsb of the differential driver is stimulated and observed by stepping through each segment and testing each idac input bit . when testing is complete , digital test mode is deactivated at 680 by deactivating the lssd_en signal . when lssd_en is deactivate , the nominal values for resctrl_p / n , tx_power , and seg_disable as illustrated in fig5 are supplied to scan - compatible analog differential driver circuit 100 of fig1 in accordance with the present invention and as previously described . digital scan testing methodologies are well known in the art , in particular , the incorporation of a digital scan architecture into a design , the generation of patterns for testing the design , and the stimulation and observation of circuits within the design . in an alternate embodiment , up - channel receiver 130 of fig1 is capable of being powered down when not in use . when digital scan - based test mode is activated at 600 , nominal_pdwn signal as previously described and as illustrated in fig5 is inhibited by lssd_en . when lssd_en is active , pdwn is a logic ‘ 0 ’, thus ensuring that the receiver remains powered on during testing . after testing is complete and digital test mode is deactivated at 680 , nominal_pdwn is no longer inhibited by lssd_en and may be activated to power down the differential receiver . the description of the present invention has been presented for purposes of illustration and description but is not intended to be exhaustive or limited to the invention in the form disclosed . many modifications and variations will be apparent to those of ordinary skill in the art . the embodiment was chosen and described in order to best explain the principles of the invention and the practical application , and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated .
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with reference to fig1 , the majority of computer systems can be characterised as comprising : an application layer 1 comprising one or more applications , such as web browsers , word processors , administration tools ( e . g . anti - virus software ) and web servers , that provide an interface between individual users 2 and the rest of the computer system or automatically access the computer system themselves ; an operating system ( os ) 3 ; and a resource layer 4 including hardware such as modems , processors and memory devices . generally speaking , the control and management of the file system and resources is performed by the operating system . this is a piece of resident software on the computer system and provides an interface between the relatively high level commands and requests issued by the users and applications and the hardware specific commands required by the resources and file system to perform those requests . a mechanism by which this occurs is for each request from a user or application , the operating system issues one or more system calls . a system call is a low level command to which the system resources are directly responsive . consequently , it is within the operating system , at the system call level that the access control process of the present invention is preferably implemented . a schematic illustration in the form of a flow chart is illustrated in fig2 that represents a mode of operation of an access control system operating in accordance with an embodiment of the present invention . the process is instigated by a system request 21 being issued by an application , either directly in response to a user operation or as part of one or more functions automatically executed by the application in question . an example of such a request would be to open a particular data file . the request is next compared to a defined permission set , step 22 , to determine if the user or application has the required permissions to access the requested data file . this permission set is predefined and definite , in the sense that a system request will either fall within the permission set or not . if the issued system request 21 does not fall within the predefined set of permissions , the request is denied , with a suitable warning or notification being preferably issued to the user . the set of permissions , or privileges , is preferably defined both in terms of the particular data items that an application can access and also the particular applications that a user is allowed to use . with respect to the second restriction , it will be appreciated that , as previously mentioned , an application may be responsive to both a direct command from a human operator or may be responsive to some other automatic process . an example of the latter occurrence would be the use of a internet dial up application to establish a connection with an internet server in response to an anti - virus software application running an automatic scheduled virus update procedure . in this instance , the operation of the dialup application occurs not in response to direct user demand , but in response to a request from the anti - virus software . consequently , a “ user ” can be both a human operator and another software application . the set of defined privileges may additionally be defined in terms of particular operations on data items that individual applications are allowed to perform , for example an application may have permission to read a particular data file but not to edit or delete it . the data files may be defined in terms of their own characteristics , for example all pdf files may be accessed by an identified pdf reader , or alternatively , the data files may be characterised in terms of their location , for example all data files of any type within an individual users home directory may be fully accessible by that user . this first stage , as explained above , follows known prior art techniques . however , in embodiments of the present invention additional steps are taken . if the system request does comply with the defined permission set it is subsequently determined , at step 23 , whether or not the request is deemed to be abnormal or unusual . to determine what is abnormal or unusual a system monitor 24 is provided . the system monitor is capable of learning the normal activity profile of a user . the learning process may occur over a fixed initial period during which the user is prompted after every system request to indicate whether this is a usual or unusual activity . however , a preferred mode of learning involves maintaining a continuously updated record of each user request and determining whether or not they are abnormal or unusual from various characteristics , such as the frequency with which a user makes a request , the data types most often accessed by the user , the time of day , and other such attributes . the precise learning model of the system monitor is not particularly germane to the present invention and is therefore not discussed in any further detail herein . if the system request is considered to be a normal request by the system monitor , the request is allowed and the desired operation of the computer system proceeds as expected . on the other hand , if the system monitor 24 determines that the system request is abnormal any one or combination of a number of conditions are applied that have to be satisfied for the execution of the system request to be completed . these conditions are referred to herein as benign responses . in the context of this specification , a benign response is one that impedes a suspected unauthorised operation but ultimately does not completely prevent it . an advantage of such benign responses is that they can be set to occur automatically safe in the knowledge that even if the response turns out to be a false alarm there are no significant or lasting detrimental effects . this is in comparison to prior art systems in which the responses tend to be much more drastic , e . g . the termination of a communication session . possible conditions , as represented at step 25 , include prompting the user for a password . the password may be the user &# 39 ; s conventional computer access password as used to initially log in to the computer system , or may be a further password that is used only when an abnormal system request is detected . it will be appreciated that other possible permutations of password authorisation may be applied , for example requesting a different predetermined password depending upon the level of “ abnormality ” determined by the system monitor or , for example , subsequent passwords may be requested depending upon the frequency of abnormal system requests being made over a given period of time . a further alternative may be that as part of the prompt for authorisation , a newly created password is presented to the user which must be entered in response to the prompt . preferably , the password is presented to the user as an image that whilst possible for a human operator to distinguish , is extremely difficult for a machine to detect . this approach , known generally as a reverse turing test , is designed to ensure the intervention of a human is required and to help prevent automatic password generating algorithms bypassing a predetermined password system . whilst not preventing an abnormal system request , by requesting a further password or other form of authorisation , a malicious user may be prevented or delayed from gaining access to the computer system , whereas the genuine authorised user is merely slightly inconvenienced . as an alternative , or in conjunction with asking for a password when an abnormal system request is made , other conditions , or benign responses , may be applied . for example , a time delay may be applied before the system request is actioned . for example , the user may be requested to wait 30 seconds before the system request is actioned . a variation to this may be that user is presented with the choice of allowing the delay to expire naturally , or entering a password as previously discussed to circumvent the delay . again , whilst this does not prevent a determined malicious user from gaining access to the computer system , in the case that the malicious user is in fact an automated virus , or other such similar software , the imposed delay may well be sufficient to hinder the virus from performing its design operation as the automated nature of virus software may not be capable of dealing with an unexpected time delay . in a further variation , the imposed time delay may be progressively increased for each subsequent abnormal system request in any given period of time . on completion of the re - authorisation process 25 and or completion of the system request itself , a “ learning ” process 26 is performed , in which the system monitor 24 is updated in an appropriate manner to reflect any changes in a users pattern or operation of the computer system . as touched upon above , the number of abnormal requests made in any given period of time may be taken into consideration when applying an appropriate response . an illustration of how this may be achieved is shown schematically in fig3 a to 3 c . fig3 a schematically illustrates the system requests issued by a user or application during for substantially equal time periods t 1 to t 4 . in the first time period t 1 , three system requests 30 are issued , referenced a to c . in the example shown , system request c is considered to be an abnormal request . fig3 b illustrates those system requests that are processed within any given time period and it will be seen that during the first time period t 1 system requests a and b , which are considered normal requests , are processed immediately . fig3 c schematically represents a buffer in which the abnormal requests are stored for a single predetermined time period . hence , in time period t 1 the abnormal system request c is stored in the buffer . in the subsequent time period t 2 three further system requests , d , e and f are issued , with system request e being considered an abnormal request . consequently request e is placed in the buffer , shown in fig3 c , whilst request d and f are processed immediately , together with request c which has now been retrieved from the buffer . in the example shown , only a single abnormal request per time period is retrieved from the buffer illustrated by fig3 c . at the next time period , t 3 , it will be seen from fig3 a that a large number of system requests have been issued , only one of which g is considered to be a normal request . the large number of abnormal system requests h to p may be issued due to the actions of a malicious user or malicious piece of software such as a virus . consequently , the large number of abnormal requests h to p are placed in the buffer , with only the abnormal request e from the previous time period t 2 and the normal request g being processed in the third time period t 3 . during the fourth time period , t 4 , no new system requests are issued and the single abnormal request h is retrieved from the buffer and processed , with the remaining abnormal requests i to p remaining in the buffer . the system may be arranged to provide a warning to an appropriate user if the number of abnormal requests in the buffer exceeds the predetermined number , as this would indicate attempted access to the computer system by a malicious user or piece of malicious software . even if no such warning was given , or no action taken in response to the warning , the restricted number of abnormal system requests that are processed from the buffer during each time period is likely to significantly hamper the operations of a malicious user , and in particular hamper the operation of a piece of malicious software . as mentioned previously , the most appropriate place to implement embodiments of the present invention is in the kernel of the computer operating system . the basic implementation in respect of a unix base computer system is described below by way of illustrative example only . the unix os has two modes — user mode and kernel mode . applications run as tasks in user mode . tasks on the unix operating system are represented by the process ( or thread ) abstraction . a running application may have one of more tasks associated with it . the operating system runs in kernel mode . tasks running in user mode are unprivileged and have no direct access to the system resources . the operating system running in kernel mode is privileged and can access system resources directly . the unprivileged application tasks get access to system resources ( such as files or network connections ) by the system call , also referred to herein as function requests , mechanism . to access a particular resource a task makes a system call . for example , to read from a file the task makes the “ read ” system call , to run another application the task calls the fork system call ( explained further below ) followed by the exec system call . these system calls cause the operating system kernel to carry out the corresponding system resource operations on behalf of the calling process . to implement embodiments of the present invention it is possible to add checks at the point where an application makes a system call so that a check can be made whether the requested operation fits within its normal use profile . an example of the operation of a unix operating system in accordance with embodiments of the present invention is illustrated in fig4 . fig4 schematically shows a segment within the flow of execution of the operating system , with individual processes shown as boxes and system calls as lines . matt is a computer user and is allowed to use frontpage for editing html ( web ) pages , but does not usually do so . when he attempts to run frontpage , the first system call is a fork . to process this command , the kernel creates an identical copy of the current process . the second call is an exec . to process this command , the kernel will copy the binary for frontpage into the second process , so that frontpage can run . according to embodiments of the present invention , the fork will succeed , but when the exec is attempted , the system will notice that matt does not unusually run frontpage , and jump out of processing the exec command , to running the response code . this will contain some policy configurable responses , for example popping up a window to ask for a password , logging , sending a message to an admin ( alert ), delaying , or delaying and asking for a password . depending on the result of the response , the system call that is waiting ( exec in this case ) will be allowed . a further example is illustrated in a similar manner in fig5 . matt usually uses excel , usually using it to read and write x 1 files in his home directory . at the end of each month he edits the payroll spreadsheet in a different directory . matt then attempts to read the payroll spreadsheet in the second week of the month . the process forks successfully and the exec system call is allowed , ( because matt usually uses excel ). however , when he tries to open the payroll file , the system intercepts the “ read ” system call , i . e . read ( payroll . xls ), and jumps out to run the response . depending on the reply from the response , the read will either return a handle to the file , or return an error . thus there is a need to examine calls ( and arguments ) to exec , read and write when controlling which applications a user uses on what data . this is in contrast to , and is advantageous over , other known approaches that need to examine all system calls . as embodiments of the present invention examine significantly fewer system calls , they provide more efficient implementations . processes have an attribute identifying the owner associated with them ( uid ). for interactive applications the owner will typically be the user who is currently running the application . server type applications are often run as the root user . the root user is a special user on unix and has access to all the system resources . typically , administration of the system is done using the root account . however , often server applications are run as root since they may need to carry out certain privileged operations . for the purposes of embodiments of the present invention it is important that we can distinguish between root when running as user doing administration versus root running a server program . the root server permission set is preferably more restrictive than the root administrator set . one mechanism for making this distinction according to embodiments of the present invention is described below . each process has an additional attribute associated with it via its ‘ task_struct ’ data structure . the ‘ task_struct ’ is a record of information about a particular process on the system and is held in the kernel . this attribute is simply 1 or 0 . processes that belong to an admin user of the system have this bit set to 1 . all other processes on the system have this bit set to 0 . when deciding which permission set / behaviour to apply to a particular process this extra attribute can be taken into account . in the kernel startup code ( pre - user space operation ) the attribute for all tasks is set to 0 . the bit is then turned on within the init kernel_thread prior to it invoking the init user space program . init is the first user space process and all other user space processes are forked / exec - ed from it . under unix , processes that are subsequently forked / exec - ed by init are controlled by the / etc / inittab file . this file is used to specify which processes should have the bit unset and which processes should have it left set . it is important to note that no method is provided to set the attribute to 1 after it has been set to 0 from userspace . it is only possible to unset the attribute or query its value from user space . the attribute value is inherited and its value preserved through fork / exec . so , with this new attribute the init program can launch new processes that are either admin processes or not by either unsetting or not unsetting the attribute . for example , processes , such as a web server running as root will have the attribute unset , marking it as a server process . even though a service may be running as root they cannot modify the attribute , as there is simply no mechanism to do this from user space . on the other hand , processes launched by a user from certain physical terminals will have the attribute marked as set , marking all processes launched from those terminals as a user doing administration . this allows it to determine whether somebody running as root entered the system via a legitimate route ( such as logging on via the system console ) or via a compromised web server , say . a schematic representation of a dataprocessor configured in accordance with embodiments of the present invention is shown in fig6 . requested function commands received at an input 31 of the dataprocessor are distributed to a main processing unit 32 , responsible for the execution of the function command , and to a function command monitor 33 . the function command monitor 33 determines if the requested function command conforms to a set of parameters , i . e . if the function command is abnormal or not . the set of parameters may be stored in a memory device 34 within the function command monitor 33 , as shown in fig6 , or may be stored elsewhere within the dataprocessor or remotely from the dataprocessor . the function command monitor 33 is coupled to a function command controller 35 , represented in fig6 as embedded within the main processing unit 32 . the function command controller 35 is configured to halt the execution of a function command by the main processing unit 32 in response to receiving a control signal from the function command monitor 33 . the function command controller is also configured to allow the resumption by the main processing unit 32 of the function command in response to one or more resumption conditions being satisfied , as previously discussed herein . the generation of user prompts and the management of time delays is also controlled by the function command controller .
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[ 0029 ] fig1 a through 7 illustrate one preferred embodiment of the invention wherein hemispheroidal , parabolic , conical or other tapered bowl members 1 are provided with a central eyelet or bore 2 and may be mounted on a cylindrical and circular ring 3 , as shown in fig3 a through 4b , as well as fig5 . the bowl members 1 may be secured to the ring 3 spaced apart by an adhesive and are arranged to face in the same direction , as illustrated . the ring apparatus comprising bowl members 1 of the configuration shown in either fig1 a and 1b or 2 a and 2 b are secured spaced apart on ring 3 which may be mounted on an insulator 4 of the type shown in fig6 . [ 0030 ] fig7 shows the cleaning ring apparatus of the embodiment of fig1 a through 7 mounted on the insulator whereby the ring assembly may be constantly driven by available wind to scrape dirt off the surface of the insulator and keep it sufficiently clean to prevent electrical sparking . the cleaning ring apparatus shown in fig7 may be formed from electrical insulating type materials such as plastic , rubber , nylon and similar electrical insulating materials . the cleaning ring apparatus shown in fig7 can be secured on a porcelain insulator 4 or similar insulator used in electrical systems . as shown in fig8 a through 9b , hemispheroidal shaped bowl members or conical shaped bowl members 1 may be modified to include a peripheral edge 5 which facilitates scraping dirt off of an insulator , such as the insulator 4 , if these bowl members are substituted for the bowl members 1 of the type shown in fig1 a through 2b . the peripheral edges 5 formed on the hemispheroidal or conical shaped bowl members are indicated to be favorable for removing dirt from an insulator . referring to fig1 , 11 and 12 , another embodiment of the invention is illustrated wherein hemispheroidal bowl members 1 may be mounted on a ring 3 spaced apart by spherical beads 6 each having a central bore or eyelet . the beads 6 are provided to fix the distance between the bowl members 1 . fig1 illustrates a cleaning ring apparatus using spherical spacer beads 6 and hemispheroidal shaped bowl members 1 arranged to face in the same direction and held spaced apart by the beads 6 . as shown in fig1 , the beads 6 may also assume a cylindrical or cannular shape for maintaining the bowl members 1 spaced apart . another embodiment of the invention is illustrated in fig1 , wherein bowl members 1 are mounted on a modified ring 3 which includes circumferential ring - like protuberances formed thereon to secure the bowl members spaced apart , as shown . referring to fig1 , 15a and 15 b , a cylindrical or circular brush 8 may be mounted between bowl members 1 and supported on the ring 3 . the brushes 8 are provided with eyelets or bores so that they may be sleeved over the ring 3 spaced apart between the bowl members 1 as shown . the brushes 8 improve the speed with which an insulator may be cleaned by a cleaning ring apparatus in accordance with the invention . referring to fig1 , 17a and 17 b , another preferred embodiment of the invention is illustrated wherein hemispheroidal bowl members 1 are supported spaced apart on the cleaning ring 3 and a scraper member 9 is supported between the bowl members . referring to fig1 a through 19b , another embodiment of the invention is illustrated wherein the bowl members 1 are formed integral with a ring 3 . still further , referring to fig2 and 21 , another embodiment of the invention is illustrated wherein the bowl members are formed integral with the ring and the ring is provided with a joint 10 which is secured by a connector 11 which may be bonded or welded to the cleaning ring to form it as a circular ring assembly . referring still further to fig2 , another embodiment of the invention is illustrated , which is different from the cleaning ring assemblies described above , wherein the bowl members 1 are not sleeved or threaded centrally on the ring 3 but are fixed to the ring radially outwardly on one side thereof , as illustrated . although preferred embodiments of the invention have been described and illustrated herein , those skilled in the art will recognize that various substitutions and modifications may be made to the invention without departing from the scope and spirit of the appended claims .
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the invention is further described in details by reference to examples , but the invention is not limited to the following embodiments . in this example , water - soluble polymer emulsion used for lithium - ion battery membrane was prepared through polymerization reaction generated by hydrophilic polymer polyvinyl alcohol ( pva ) 1750 and lipophilic monomer vinyl acetate ( vac )/ ethylacrylate ( ea )/ acrylonitrile ( an ) in water solution . the composing of copolymer was pva : vac : ea : an = 10 : 2 : 2 : 5 ( weight ratio , the same hereinafter ). the content of copolymer is 17 %. the product was white opaque emulsion . the polymer emulsion was prepared through following steps : 1000 g distilled water and 100 g polyvinyl alcohol ( pva ) 1750 were added to four - neck reaction vessel fixed condenser . the temperature of the reaction vessel was heated to 75 ° c . under stirring at 100 rpm . after 3 h , the material was transparent like can be regarded as dissolved finished . after natural cooling to 55 ° c ., 40 g mixture of lipophilic monomer vinyl acetate ( vac ) and ethyl acrylate ( 1 : 1 ) was added in one time . after stirring for 10 min , 0 . 5 g of water - soluble initiator ( ammonium peroxydisulphate ) was added . about 20 minutes later , the material was light blue . the color of the mixture changed into a white emulsion after 30 minutes . the reactive intermediate was obtained after 2 h copolymerization . the above reaction mixture and 50 g of lipophilic monomer acrylonitrile ( an ) were mixed . 1 . 5 g of initiator and 0 . 5 g weakly acidic lithium vinyl sulfonic acid were added . after 10 h reaction , polymer colloidal emulsion was obtained . 19 g of filler ( zirconium dioxide ) and 160 g of plasticizer ( benzyl alcohol ) were added to the polymer colloidal emulsion prepared according to step 1 . the mixture was grinded with a ball grinder for 5 h . the viscosity of the slurry at the temperature t slurry of 35 ° c . was 2500 mpa · s measured at the temperature of 20 . 6 ° c . and the relative humidity ( rh ) of 64 %. tape - casting equipment was used . polymer colloidal emulsion was coated on bopp plastic baseband . the microporous polymer membrane was obtained after the water and plasticizer of the bopp baseband coated the polymer colloidal emulsion was volatilized through the heated - air drying tunnel . the temperature of heated - air drying was 60 - 130 ° c ., preferably , 80 - 100 ° c . the reaction steps are basically the same as example 1 the only difference is that the lipophilic monomer ethyl acrylate ( ea ) was replaced by acrylamide ( am ). the composing of copolymer was pva : vac : am : an = 10 : 2 : 1 : 8 . the concrete preparation method of the polymer emulsion is as follows : all monomers were added in one time . the concentrations of materials were adjusted to about 13 %. initiator was added directly . the slurry experienced colorless - light blue - white emulsion process . the reaction rate was faster than example 1 . after 12 h reaction , polymer emulsion used for lithium batteries was obtained . the amount of filler is the same as example 1 . the materials are titanium dioxide and benzyl alcohol . the mixture was grinded with a ball grinder for 5 h . the viscosity of the slurry was kept at 2500 mpa · s by adjusting the solid content at the temperature t slurry of 35 ° c . in this example , polyvinyl alcohol 1788 ( pva ) was added to lipophilic monomer styrene ( st )/ butyl acrylate ( ba )/ acrylonitrile ( an ). water - soluble polymer emulsion used for lithium - ion battery membrane was prepared by ternary polymerization in aqueous phase . the composing of copolymer was pva : st : ba : an = 10 : 2 : 4 : 5 ( weight ratio , the same hereinafter ). the content of copolymer is 17 %. the product was white opaque emulsion . the polymer emulsion was prepared through following steps : 1000 g distilled water and 100 g polyvinyl alcohol ( pva ) 1788 were added to four - neck reaction vessel fixed condenser . the temperature of the reaction vessel was heated to 90 ° c . under stirring at 100 rpm . after 3 h , the material was transparent like can be regarded as dissolved finished . after natural cooling to 65 ° c ., styrene monomer and a little initiator were added . about 20 minutes later , the mixture became a white emulsion . in the meantime , butyl acrylate ( ba ) was added . the reaction was continued for 2 h . acrylonitrile monomer was added dropwisely to the above prepared emulsion ( the dropwise speed was controlled by peristaltic pump . the material was added to the emulsion during 5 h ). 1 . 5 g of initiator was replenished and the polymerization reaction was continued for 12 h to obtain polymer membrane emulsion used for lithium battery . 15 % of filler ( silicon dioxide ) and 100 % of plasticizer ( tributyl phosphate ) were added to the prepared polymer colloidal emulsion . the mixture was grinded with a ball grinder for 5 h . the viscosity of the slurry was kept at 2500 mpa · s by adjusting the solid content at the temperature t slurry of 35 ° c . in this example , polyvinyl alcohol 1788 ( pva ), hydrophilic monomer n - vinyl pyrrolidone ( nvp ), lipophilic monomer butyl acrylate ( ba ) and acrylonitrile ( an ) were used as materials for preparation of water - soluble polymer emulsion used for lithium battery membrane . the composing of copolymer was pva : nvp : ba : an = 10 : 2 : 4 : 5 ( weight ratio ). the polymer emulsion was prepared by one - step polymerization . the monomers and initiators were added simultaneously . the redox system of ammonium sulfite - potassium peroxydisulfate was used as initiator . the reaction temperature was 72 ° c . and the reaction time was 12 h . the concentration of copolymer is 19 . 5 %. the product was white colloidal emulsion . 15 % of filler ( silicon dioxide treated with 3 - aminopropyltriethoxysilane ) and 100 % of plasticizer ( tributyl phosphate ) were added to the prepared polymer colloidal emulsion . the viscosity of the slurry was kept at 2500 mpa · s by adjusting the solid content . in this example , pva , hydrophilic monomer lithium acrylate ( maali ) and lipophilic monomer acrylonitrile ( an ) were polymerized in aqueous phase to form water - soluble polymer emulsion used for lithium battery membrane . the composing of copolymer was pva : maali : an = 10 : 2 : 5 ( weight ratio ). the polymer emulsion was prepared through following steps : first , polyvinyl alcohol 1788 was dissolved in water at 50 ° c . lithium acrylate ( maali ) and acrylonitrile ( an ) were added in one time . the polymerization method is the same as foregoing example . after 12 h , polymerization reaction was completed . 30 % of filler ( aluminum oxide ) and 120 % of plasticizer ( triethyl phosphate ) were added to the prepared polymer colloidal emulsion . in order to improve the adhesiveness of membrane with bopp substrate , 35 % of oxidized polyethylene wax emulsion was added . the mixture was grinded with a ball grinder for 5 h . the viscosity of the slurry was kept at 2500 mpa · s by adjusting the solid content . in this example , aqueous polymer emulsion used for lithium battery membrane was obtained by graft polymerization of polyvinyl alcohol 1799 ( pva ), hydrophobic monomer vinyltriethoxysilane ( 151 )/ acrylonitrile ( an ) in aqueous phase . the composing of copolymer was pva : 151 : an = 10 : 4 : 5 ( weight ratio ). the polymer emulsion was prepared through following steps : 1000 g distilled water and 100 g polyvinyl alcohol ( pva ) 1799 were added to four - neck reaction vessel fixed condenser . the temperature of the reaction vessel was heated to 90 ° c . under stirring at 100 rpm . after 3 h , the material was transparent like can be regarded as dissolved finished . after natural cooling to 60 ° c ., 40 g of vinyltriethoxysilane 151 , 50 g of acrylonitrile ( an ) and 1 . 9 g of ammonium peroxydisulphate were added . the graft polymerization time was 12 h . the concentration of copolymer is 17 . 4 %. the product was white colloidal emulsion . the polymer colloidal emulsion is adjusted to be weakly acid by diluted hydrochloric acid . 20 % of filler ( silicon dioxide ) filler and 100 % of plasticizer ( triethyl phosphate ) was added . in order to improve the shrinkage performance of membrane , 30 % alkali free fiberglass ( micron - sized ) was attempted added . the fiberglass was sintered at temperature 500 ° c . before use , then natural cooling . the mixture was grinded with a ball grinder for 5 h . the viscosity of the slurry was kept at 2500 mpa · s by adjusting the solid content . the microporous polymer membranes prepared by example 1 - 6 were dried for 3 - 8 h in a vacuum at 90 ° c . the whole testing process was carried out in dry air atmosphere ( the relative humidity of dry air atmosphere was below 3 %). the membranes were taken out after 2 , 4 , 6 , 12 h dipping in electrolyte , respectively . the residual electrolyte on surface was blotted up by filter paper . the sample was weighed using analytical balance of 0 . 01 g accuracy . the weight difference before and after dipping in the electrolyte is the absorption amount . after 12 h dipping in electrolyte , the membranes were taken out and deposited for 3 h . the electrolyte conservation rate of water - soluble polymer membranes was determined ( the absorption amount to the weight difference of 12 h dipping ). the results of contrast experiment of example and pp membrane are shown in table 1 . the microporous polymer membrane prepared in example 6 was assembled into a lithium - ion battery . the battery was composed of the limn 2 o 4 cathode material , graphite anode materials , and electrolyte lipf 6 consisting of ethylene carbonate / diethyl carbonate . the battery is subject to a dod 100 % charge - discharge cycle under a condition of 1 c . the results of experiments showed that the capacity of battery remained over 75 % than initial capacity after 1500 charge - discharge cycle . the increase of internal resistance in battery was less than 10 %. as a contrast , the lithium - ion battery assembled by commercial microporous polypropylene film under the same conditions has the capacity about 75 % of initial capacity and the internal resistance increases more than 35 % after 400 cycles under the same condition . the lithium - ion battery assembled by microporous polymer membrane prepared in present invention has long cycle life and smaller battery polarization attributed to the microporous polymer membrane has excellent affinity with the polar electrolyte solution and excellent liquid retention property which is made from a high - polarity polymer material .
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referring now to fig2 which illustrates a control system for the motor antenna of the present invention . the control system includes a battery b , a control circuit 10 , an ignition key 20 , a radio receiver 30 , a motor m , and an antenna 40 . the control circuit 10 controls the starting of the motor m and detects electric current and branch current of the motor m . based upon the result thus detected , the control circuit 10 stops the motor m . the control circuit 10 includes a + b terminal and an rx terminal which receives a + b voltage through a power switch 31 of the radio receiver 30 . the control circuit 10 further includes an acc terminal , an ig terminal , and a ground terminal e . fig1 is a circuit diagram showing the control circuit shown in fig2 in a more detail manner . the circuit of fig1 includes a relay rl1 which changes over and controls a relay contact s1 , a relay rl2 which changes over and controls a relay contact s2 , a transistor tr1 which controls the relay rl1 , and a transistor tr2 which controls the relay rl2 . the transistor tr1 is turned on when the ignition key 20 and the power switch 31 of the radio receiver 30 are turned on . the transistor tr1 excites the relay rl1 by way of the power from the rl terminal which is connected to the rx terminal or the acc terminal ; and when the relay rl1 is excited , the relay contact s1 is changed over from the point b to the point a . the relay rl2 is excited when the transistor tr2 is turned on ; and when the relay rl2 is excited , the relay contact s2 is changed over from the point b to the point a . a positive line from the battery b is connected to the point a of the relay contact s1 and the point a of the relay contact s2 . one terminal m1 of the motor m is connected to point c of the relay contact s1 , and the other terminal m2 of the motor m is connected to point c of the relay contact s2 . a positive characteristic thermistor rp1 , which possesses a positive resistance - temperature characteristics , is interposed between the point b of the relay contact s1 and the ground . another positive characteristic thermistor rp2 is interposed between the point b of the relay contact s2 and the ground . the relay contacts s1 and s2 are respectively changed over to the point b when the relays rl1 and rl2 are not excited . diodes d1 , d2 , d3 , and d4 are electric current blocking diodes , and these diodes control the current for exciting the relays which is supplied from the + b power source or the rl power source so that the relay exciting current does not flow into the other power sources . condenser c3 is provided in the circuit so that it supplies a power to the relay rl2 for a short period of time when the supply of the rl power is stopped . the electric current from the condenser c3 is blocked by the diodes d1 and d2 and flows only to the relay rl2 . the transistor tr3 starts to function when the voltage at both ends of the positive characteristic thermistor rp1 is higher than a predetermined level . the positive pulses , which are generated at the moment the relay rl1 is excited and the contact s1 is changed over from the point b to the point a , passes through the condenser c2 , and with this positive pulse the transistor tr3 is turned on and the transistor tr2 turns off . on the other hand , the negative pulses , which are generated at the moment the contact s1 is changed over from the point a to the point b , passes through the condenser c1 , and with this negative pulses the transistor tr4 is turned on and the transistor tr2 is turned off . a motor branch current amplifying and detecting circuit 11 includes an alternating current amplifier and a rectification circuit , and this circuit 11 amplifies the branch current generated at the both ends of the positive characteristic thermistor rp1 or rp2 and outputs a negative voltage element . the negative signals thus outputed are fed to the base of the transistor tr2 and also to the base of the transistor tr3 . the operation of the above embodiment will be explained in the below . first , when the antenna 40 is retracted and the ignition key 20 is not turned on , the voltage at the rl terminal is zero , and therefore , neither the relay s1 nor s2 are excited . thus , the relay contacts s1 and s2 are connected to the points b , respectively , and no current flows to the motor m . accordingly , the antenna 40 stays retracted . this is shown in fig3 ( 1 ). when the ignition key 20 is turned on and the switch 31 of the radio receiver 30 is switched on , the + b voltage is applied to the rx terminal . then , the transistor tr1 is turned on , and the relay rl1 is excited through the rl terminal and the diode d4 . as a result , the relay contact s1 is changed over from the point b to the point a , and an electric current flows to the motor m through the + b terminal , the relay contact s1 , the terminals m1 and m2 , the relay contact s2 , and the positive characteristic thermistor rp2 . thus , the antenna 40 is extended . this is shown in fig3 ( 2 ). when the antenna is fully extended , it is mechanically locked and an excess current flow through the motor m . thus , the voltage at the both ends of the positive characteristic thermistor rp2 is increased , and the transistor tr2 is turned on , and as a result the relay rl2 is excited . accordingly , the relay contact s2 is changed over from the point b to the point a , and the current flowing to the motor m is stopped . as a result , the extension of the antenna 40 is stopped . this is shown in fig3 ( 3 ). in this case , the relay contact s2 has been changed over to the point a , and a base current flows to the transistor tr2 through the points a and c of the relay contact s2 and the resistance r1 ; therefore , the relay rl2 is self - held . on the other hand , since the transistor tr1 stays turned on as long as the power switch 31 stays on , the relay rl1 is also kept excited , and as a result the relay rl1 is self - held . in other words , if the power switch 31 is on when the antenna has been fully extended , the antenna stays in the fully extended position . then , when the power switch 31 is turned off , the transistor tr1 is turned off and the relay rl1 turns off , and the relay contact s1 is changed over to the point b . as a result , as shown in fig3 ( 4 ), since the current flows in the direction from the terminal m2 to the terminal m1 of the motor m , the motor m reverses its direction of rotation , and the antenna 40 is retracted . when the antenna 40 is completely retracted , it is mechanically locked . then , the electric current in the motor m becomes very large , and the terminal voltage of the positive characteristic thermistor rp1 is increased . as a result , the transistor tr3 is turned on and drops the base electric potential of the transistor tr2 . the transistor tr2 is turned off , the relay rl2 is turned off , and the relay contact s2 is changed over to the point b . thus , the current flowing in the motor m is stopped , in other words , the antenna 40 is retracted . this is shown in fig3 ( 1 ). the circuits for the condensers c1 and c2 eliminate the malfunction , which is caused by a rush electric current which occurs when the motor m is started , as a timer . thus , with the condensers c1 and c2 , the motor m , which works to extend and retract the antenna , receives the signal which is opposite to the signal being received . as mentioned above , the antenna 40 is fully extended and then locked , and this control is brought by applying the changes ( increase ) in the terminal voltage of the positive characteristics to the base of the transistor tr2 , and by exciting the relay rl2 when the terminal voltage is increased over the predetermined level . on the other hand , the control to retract and then lock the antenna is brought by applying the changes ( increase ) in the terminal voltage of the positive characteristic thermistor rp1 to the base of the transistor tr3 , turning on the transistor tr3 when the terminal voltage becomes higher than the predetermined level , turning off the transistor tr2 , and then turning off the relay rl2 . further , when the motor antenna 40 is locked , the terminal voltage in the positive characteristic thermistors rp2 and rp1 is immediately increased . thus , it is possible to design a system such that only the increased amount of the voltage is applied to the base of each transistor . with this arrangement , the chances for the antenna to be influenced by the steady - state current is less likely , and the antenna is extended and retracted without failure . in the above embodiment , when the motor m is running , the branch current generated by the commutator is picked up by the positive characteristic thermistors rp1 and rp2 and detected and amplified by the motor branch current amplifying and detecting circuit 11 . as a result , a negative direct current is generated , and this negative direct current is applied to the bases of the transistors tr2 and tr3 . thus , when the motor m is running , it does not receive the direct current elements of the positive characteristic thermistors rp1 and rp2 . as a result , the functional errors caused by the changes in the load on the motor m which is derived from the deformation of the antenna 40 can be prevented . further , the functional errors caused by the increase in the motor current , which is generated when the load at the motor driving section is increased in the low ambient temperature , can be also prevented . since the above embodiment uses positive characteristic thermistors rp1 and rp2 , the control errors can be prevented . the possible control errors and the solution thereof will be explained below . the functional errors could occur in the mechanical system , and the motor m could stop with an excessive current which flows into the motor m . in this case , the excess current also flows into the positive characteristic thermistors rp1 and rp2 which are connected in series to the motor m . if the excess current flows into the motor m for a few minutes , heat is generated in the positive characteristics thermistor rp1 or rp2 , and as shown in fig4 the resistance level increases and the motor current can be restricted . further , since the terminal voltage at the positive characteristics thermistor rp1 or rp2 increases sharply , the transistors tr2 and tr1 function smoothly . thus , control errors can be prevented . when the control cannot be resumed smoothly due to the malfunction in the control circuit , etc ., it is impossible to block the motor current . however , since the current can be restricted by the positive characteristic thermistors , the motor m is prevented from burning out . instead of the positive characteristic thermistors rp1 and rp2 , a fixed resistance may be used in the present invention . in case that the ignition key 20 is turned off when the switch 31 of the radio receiver 30 is left on ( and the antenna 40 is left extended ), it is necessary to retract the antenna . to retract the antenna , in the conventional device , the power for the control circuit is directly taken from the battery b so that the control circuit is kept connected to the power source . as a result , a battery discharge caused by a dark current in the control circuit occurs occasionally , and also the semiconductor malfunctions when struck by the lightning . however , in the embodiment of the present invention , the power from the battery is used until the antenna is retracted , and once the antenna is retracted completely , the power supply from the battery is stopped . in order to smoothly accomplish such a power supply control , the control power source maintaining circuit ( which comprises the two diodes d1 and d2 and the large capacity condenser c3 ) is employed . more specifically , when the ignition key 20 is turned off while the antenna 40 is being retracted , the relay rl2 is being excited at this moment and the + b power from the battery b is supplied to the relay rl2 and the control circuit through the diode d1 so that the antenna 40 is kept retracting . when the antenna is completely retracted , the relay rl2 and the control circuit are disconnected from the + b power . on the other hand , when the ignition key 20 is turned off while the antenna is being extended by the electrical charge of the condenser c3 , although at this moment the relay rl2 is not being excited , the control circuit and the relay rl2 are instantly rendered to function . in other words , the contact s1 is changed over from the point a to the point b ; therefore , at this moment , the transistor tr4 is begun to be turned on by the condenser c1 , and the transistor tr4 successively begins to turn on , and then the relay rl2 momentarily functions . as a result , the contact s2 of the relay rl2 is changed over to the point a , and the + b power is supplied to the relay rl2 and the control circuit through the diode d1 until the antenna 40 is completely retracted . the above embodiment can be automatically controlled electronically without using mechanical limit switches , mechanical clutches , etc . as mentioned in detail in the above , according to the present invention , the control device for motor driven antenna for automobiles has a simple structure and a high motor antenna reliability , and is easy to design the overall size small .
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in the following descriptions , the present invention will be explained with reference to various example embodiments ; nevertheless , these example embodiments are not intended to limit the present invention to any specific example , embodiment , environment , application , or particular implementation described herein . therefore , descriptions of these example embodiments are only provided for purpose of illustration rather than to limit the present invention . the invention is to cover all modifications , equivalents , and alternatives falling within the scope of the invention as defined by the appended claims . referring to fig1 and fig2 , a knee pad assembly 100 is shown . the assembly generally comprises a base 102 and a removable cover 104 . the base 102 fastens to the user &# 39 ; s knee using fastening straps 106 , such as the ratcheting adjustable straps as shown in these figures with ratcheted fastener 109 . an upper and a lower strap are shown but more or fewer straps are within the scope of the invention . the base 102 presents a forward facing cover receiving portion 108 . the cover 104 is disposed over the forward facing portion 108 of base 102 as indicated in these figures and secured via attachment means , in this example via corner hooks 110 disposed at the corners of base 102 . the assembled knee pad 100 is shown in fig2 . the knee pad base can be configured in short or long versions as appropriate for the particular application and a user &# 39 ; s desired level of coverage . the cover is correspondingly sized . the cover may be formed from any suitable material , including rubber and plastic , and formed in any suitable shape . in addition , the cover may fully or partially comprise multirole materials such as leather , cloth , plastic , fiber glass , foam , rubber , carbon fiber , composites , metal or any other material that is designed for the end user &# 39 ; s specific job requirements . a wide variety of cover attachments means are within the scope of the invention . such means include , but are not limited to hooks , snaps , clips , hook and loop components ( e . g . velcro fasteners ) on respective portions of the base and cover , and combinations of two or more different attachment means . the user &# 39 ; s ability to change covers on the knee pad bases allows for a single pair of knee pads to be adapted to a wide variety of surface types . the ability to change covers also provides the user with the option to replace individual worn covers , wash soiled covers , and / or use job specific covers as needed , avoiding the need to purchase a replacement or additional set of knee pads . referring to fig3 and 4 , another example embodiment of a knee pad assembly 200 is shown . the base 202 is provided with one or more front facing suspension components 212 , such as rubber or foam pads . in this example embodiment , base 202 is slideably engaged with pad 204 by straps 214 that are integrated into the corners of pad 204 . straps 214 secure the knee pad assembly 200 to a user by wrapping straps 214 securely around the back of the users knee . it should also be noted that straps 214 could also be integrated with base 202 and slide through corresponding openings ( not shown ) in pad 204 to also achieve the floating suspension effect . cords may also be used instead of straps . while secured , the back surface of pad 204 engages the suspension member 212 of base 202 , and slides on guide rails 216 , allowing pad 204 to float on suspension member 212 and remain aligned via guide rails 216 , without being fixably connected to base 202 . this allows pad 204 to move in toward the knee and out away from the knee , depending on the pressure exerted on the front surface of pad 204 while in use . this provides cushioned suspension for the knee while the improved knee pad assembly is in use . the spring force of the compression component 212 may be adapted to a desired range of cushioning or compression based upon a user &# 39 ; s weight , and / or the conditions of use of the knee pad , and / or the length of time of intended use . preferably a material with an ild ( indention load deflection ) of between 45 and 100 may be used . urethane and other foams may also be used with densities of weights between 1 and 10 pounds per square foot of material . the outer cover 204 may comprise a semi - rigid or a hard plastic shell ( or similar material ) that will compress one or more of the suspension components 212 and distribute the force over the cover 204 . the cover 204 cooperates with a plurality of integrated straps 214 , guide rails 216 and guide plate 218 to facilitate slideable engagement , and uniform alignment , of the cover to the base . this example embodiment also illustrates a tension / release mechanism or feature . when kneeling , compression placed on the cap 204 would compress suspension components 212 and release strap tension on straps 214 and when standing , compression would be released and strap tension would be allowed to return . the purpose is to release strap tension on the back of the worker &# 39 ; s leg , nerves and blood vessels while the worker is kneeling , yet maintain security of the knee pad when the worker is standing or walking . the cap 204 , straps 214 , suspension components 212 , guide rails 216 and guide plate 218 cooperate to achieve this feature , as well as providing a uniform alignment of the cap 204 with the base 202 , and providing extended comfort to the user . referring to fig5 and 6 , another embodiment of a knee pad assembly 300 is shown . the base 302 comprises a knee cup 304 and a suspension member 306 disposed on the outer front surface of the base . an outer cover or shell 308 is disposed over knee cup 304 and suspension member 306 by straps 310 . this arrangement allows force applied to the cover to compress the collapsible or suspension member towards the base to provide cushioning . the edges of the cover 308 slide toward the user &# 39 ; s knee along the outer perimeter surface of the base . when the pressure on the cover is released , the suspension member 306 expands to its original shape . in one variant , the suspension member 306 is partially collapsible in order to provide adequate support and air space while collapsible enough to provide desired cushioning . in addition open areas 312 in suspension member 306 allow additional cushioning and support for the knee . similar to the embodiments described and depicted in fig3 and 4 , the contact and cooperation between cover or shell 308 and suspension member 306 provides a floating type suspension for the knee while the knee pad 300 is strapped to a user by straps 310 . referring to fig7 , depicted is yet another exemplary embodiment where knee pad assembly 400 is comprised of base 402 , which is a partial shell that is disposed behind the user &# 39 ; s leg , such as on the calf and behind the knee , and cap 404 . for example , straps or a neoprene back of leg wrap 402 may be substituted for the base and straps described in the preceding examples . the cover 404 is then placed over the knee cap and restrained in place via tension members 418 , such as cords , on either side of the base spanning between the base and the cover . this arrangement promotes good pressure management on the user &# 39 ; s knee and leg . the cover 404 is shown with a honeycomb pattern 420 in a soft rubber material in order to enhance traction and provide cushioning for the user . a further feature illustrated in this example is the ratchet system 422 disposed on top of cover structure 404 and functionally connected to the tension members 418 . via the ratchet system 422 , the wearer has the ability to tighten or loosen strap pressure ( snugness ) of the knee pad . a dial 424 or other user actuator is provided to allow the user to actuate the ratchet system . referring to fig8 through 15 , depicted are various means to removeably attach a pad to a base . fig8 provides a base 502 with one or more sleeves or pockets 504 to receive the tongues 508 of cover 506 . the front receiving surface 510 of the base 502 and back surface 511 of cover 506 , may further be provided with a respective portion of a hook and loop fastener 512 to further secure the cover to the base . the cover 506 shown in this example is a generally rectangular and slightly curved semi - rigid board comprising a polyethylene material . however , the board can vary in size , shape and material as appropriate for the particular usage . referring to fig9 , an exemplar knee pad assembly is shown with another cover fastening means . an elastic hem 522 is provided around the perimeter 524 of the cover receiving surface 526 of the base 520 . the perimeter 528 of the cover 530 includes corresponding protruding tabs or projections 532 that are sized and shaped for being received in the elastic hem 522 . hook and loop 527 may also be used as shown in fig8 , and can further be used with all embodiment disclosed herein . referring to fig1 , a further embodiment of a knee pad assembly is shown . the base and cover is shown in fig9 . in addition , an overlay cover 534 is now provided . the overlay cover 534 is disposed over the cover 530 and then secured to the base with a plurality of reinforced strap loops 536 . the straps 538 used to secure the base to the knee region of the user are placed through the reinforced loops 536 of the overlay cover 534 to secure the cover and overlay in place . referring to fig1 , another embodiment of a knee pad assembly is shown . the cover or overlay 540 includes a plurality of elastic bands or cords 542 . the cords 542 can extend through the cover 540 for better securement . a tab 544 is provided at an approximate mid - point of each band 542 . the cover 540 is secured to the base 546 by inserting the tabs 544 into respective slots or pockets 548 in the base 546 . channels 550 in the outer perimeter surface 552 of the base 546 may be provided to further retain the bands in place . hook and loop fasteners 554 may further be provided on respective portions of the cover and base to further secure the cover to the base . fig1 illustrates a cord - lock means 562 for securing the cover 564 to the base 566 . raised corners 568 on the cover are inserted behind portions of the locking cord 570 . the locking cord or cords 570 are then tightened by pulling on cords 563 and retainer 562 is then used to maintain the tension in the retaining cord ( s ). fig1 through 15 illustrate other exemplar attachment embodiment means for a knee pad assembly . the cover or overlay 578 includes a plurality of elastic bands or cords 572 shown at the corners of the cover 578 . the cords can extend through the cover in a crossing pattern or “ x ” shape 574 for better securement , as shown in fig1 . a tab 576 is provided at an approximate mid - point of each band 572 . the cover 578 is secured to the base 580 by inserting the tabs 576 into respective slots or pockets 582 in the base at the corners thereof . the corner pockets may be raised to facilitate insertion and removal of the tabs . fig1 further illustrates that cover 578 may be used to secure pads used in previous embodiments to a base such as base 580 . note that the underlayment of pad 584 of fig1 includes a plurality of slots 586 for receiving the knee pad retaining straps 581 . the compressibility factor ( including material property and physical dimensions and shape ) of the collapsible or suspension members disclosed herein can be varied to accommodate different user weight ranges and to accommodate a user &# 39 ; s desired cushioning factor . the cover can be secured using a variety of means as discussed in this disclosure . alternatively , the cover may include straps that secure the assembly directly to the user &# 39 ; s knees , such as elastic cord or adjustable straps that extend behind the knee of the user . the collapsible or suspension members may comprise a wide variety of materials , including , springs , pen cell foam , closed cell foam , air bag , molded eva , soft 3d fabric ( spacer mesh ), a resilient honeycomb structure , rubber , or any combination of these or other materials . the cushioning factor can also be selected according to body weight or according to average time spent kneeling / hour . for example , body weight ranges of 80 to 150 lb , 150 to 225 lb , and over 225 lb ; kneeling 10 min ./ hour , 30 min ./ hour and 50 min ./ hour . however more or fewer ranges may be specified . features of the various embodiments discussed herein can be mixed and matched in any manner of additional embodiments that are all within the scope of the invention regardless of whether or not explicitly discussed herein . while the invention has been described in connection with what is presently considered to be the most practical and preferred embodiments , it will be apparent to those of ordinary skill in the art that the invention is not to be limited to the disclosed embodiments . it will be readily apparent to those of ordinary skill in the art that many modifications and equivalent arrangements can be made thereof without departing from the spirit and scope of the present disclosure , such scope to be accorded the broadest interpretation of the appended claims so as to encompass all equivalent structures and products . moreover , features or aspects of various example embodiments may be mixed and matched ( even if such combination is not explicitly described herein ) without departing from the scope of the invention . for purposes of interpreting the claims for the present invention , it is expressly intended that the provisions of section 112 , sixth paragraph of 35 u . s . c . are not to be invoked unless the specific terms “ means for ” or “ step for ” are recited in a claim .
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fig1 is a cross - sectional side view to show a laser printer as an example of an image forming device according to one embodiment of the invention . fig2 shows the laser printer shown in fig1 in which a process cartridge is attached to and detached from a main body casing as an example of a main body . fig3 is a perspective view of a drum shutter . a laser printer 1 includes a main body casing 2 and a sheet feed unit 3 , an image formation unit 4 , and a sheet discharge unit 5 provided in the main body casing 2 as shown in fig1 . the main body casing 2 has a substantially box shape and has an opening 6 formed through one side wall of the main body casing 2 . the main body casing 2 includes a front cover 7 configured to open and close the opening 6 . in a state where the front cover 7 is opened , a process cartridge 17 ( described later ) can be attached to or detached from the main body casing 2 . in the description to follow , the side where the front cover 7 is provided is “ front ” and the opposite side is “ rear .” the front in the sheet thickness direction in fig1 is the left and the back in the sheet thickness direction in fig1 is the right . the left and right direction ( side to side direction ) is synonymous with the width direction . the sheet feed unit 3 includes a sheet feed tray 9 , a sheet feed roller 10 , a sheet powder removing roller 12 , a pair of registration rollers 14 , and a sheet press plate 15 . the sheet feed roller 10 is configured to feed a sheet at the top of stack of sheets placed on the sheet press plate 15 one by one at one time . the sheet 8 fed by the sheet feed roller 10 passes through the sheet powder removing roller 12 and the registration rollers 14 and then is conveyed to a transfer position ( described later ) of the image forming unit 4 . the image forming unit 4 includes a scanner unit 16 , the process cartridge 17 , and a fixing unit 18 . the scanner unit 16 is provided in an upper portion of the main body casing 2 and includes a laser beam emission unit ( not shown ), a rotated polygon mirror 19 , a plurality of lenses 20 , and a plurality of reflecting mirrors 21 . a laser beam emitted from the laser beam emission unit based on image data is reflected on the polygon mirror 19 and then passes through the lenses 20 and reflected on the reflecting mirrors 21 . thereafter , the laser beam is scanned over the surface of a photoconductive drum 25 serving as an example of a rotation body ( described later ) of the process cartridge 17 , as indicated by the dashed line in fig1 . the process cartridge 17 is detachably attachable to the main body casing 2 and is placed below the scanner unit 16 in the main body casing 2 when the process cartridge 17 is attached to the main body casing 2 . the process cartridge 17 includes the drum cartridge 22 and the developer cartridge 31 . the developer cartridge 31 is detachably attachable to a cartridge storing portion 33 of the drum cartridge 22 . the drum cartridge 22 and the developer cartridge 31 are an example of a cartridge . the drum cartridge 22 has a substantially box shape as shown in fig3 . the drum cartridge 22 includes a drum frame 23 forming the contour of the drum cartridge . a roughly rear side half of the drum frame 23 is adopted as a drum storing portion 32 and a roughly front side half is adopted as the cartridge storing portion 33 . the drum storing portion 32 has a substantially box shape with an opening formed through both front and rear side faces and includes the photoconductive drum 25 , a scorotron charger 26 , and a transfer roller 27 . an opening formed through the rear face of the drum storing portion 32 is called a drum rear opening 77 and an opening formed through the front face of the drum storing portion 32 is called a drum front opening 63 . each of the drum rear opening 77 and the drum front opening 63 has a substantially rectangle relatively long in the width direction . the photoconductive drum 25 is relatively long in the width direction and is placed so that it is partially exposed from the drum frame 23 to the rear in the drum rear opening 77 . the portion exposed from the drum rear opening 77 in the photoconductive drum 25 is called a drum exposure portion 75 as an example of an exposure portion . the photoconductive drum 25 is rotatably supported on the drum frame 23 . the scorotron charger 26 is supported on the drum frame 23 with a spacing from the photoconductive drum 25 above the photoconductive drum 25 . the transfer roller 27 is placed facing the photoconductive drum 25 from below the photoconductive drum 25 and is rotatably supported on the drum frame 23 . the cartridge storing portion 33 is formed to have a closed - end frame with the upper face opened . a drum grip 24 extending to the front is formed in the upper end portion of the front end portion of the cartridge storing portion 33 . by grasping the drum grip 24 , the user can attach or detach the drum cartridge 22 to or from the main body casing 2 singly or as the process cartridge 17 with the developer cartridge 31 attached to the cartridge storing portion 33 . the drum front opening 63 of the drum storing portion 32 is exposed in the cartridge storing portion 33 , and the front portion of the photoconductive drum 25 is exposed to the inside of the cartridge storing portion 33 through the drum front opening 63 . the upper registration roller 14 of the paired registration rollers 14 described above is rotatably supported on the bottom of the cartridge storing portion 33 . the developer cartridge 31 is detachably attached to the drum cartridge 22 in the cartridge storing portion 33 . the developer cartridge 31 has a substantially box shape . the developer cartridge 31 includes a developing frame 28 as an example of a case forming the contour of the developer cartridge 31 . an opening ( called a developing opening 59 ) of almost the same shape as the drum front opening 63 is formed through the rear face of the developing frame 28 . the inside of the developing frame 28 is partitioned into a toner storage chamber 29 on the front and a developing chamber 30 on the rear . the toner storage chamber 29 and the developing chamber 30 communicate with each other . a developing grip 35 extending to the front is formed in the upper end portion of the front end portion of the developing frame 28 . by grasping the developing grip 35 , the user can attach or detach the developer cartridge 31 to or from the drum cartridge 22 . the developing chamber 30 includes a supply roller 36 , a developing roller 37 as an example of a developer carrier , and a layer thickness regulation blade 38 . the developing roller 37 is relatively long in the width direction and is placed so that the developing roller 37 is partially exposed from the developing frame 28 to the rear in the developing opening 59 . the portion exposed from the developing opening 59 in the developing roller 37 is called a developing exposure portion 76 as an example of an exposure portion . the developing opening 59 and the drum front opening 63 face each other in a state where the developer cartridge 31 is attached to the drum cartridge 22 . in this state , the developing roller 37 is in contact with the photoconductive drum 25 from the front in the developing exposure portion 76 . the developing roller 37 and the supply roller 36 are rotatably supported on the developing frame 28 . both end portions in the width direction of the rotation shaft of the developing roller 37 are exposed from both side walls in the width direction of the developing frame 28 . the layer thickness regulation blade 38 includes a plate spring member 45 formed like a thin plate and press contact rubber 46 provided in a lower end portion of the plate spring member 45 . an upper end portion of the plate spring member 45 is fixed to the developing frame 28 and the press contact rubber 46 presses the surface of the developing roller 37 by the elastic force of the plate spring member 45 . an agitator is rotatably provided in the toner storage chamber 29 . nonmagnetic single - component toner having positive electrostatic property as an example of a developer is stored in the toner storage chamber 29 . the toner in the toner accommodation chamber 29 is agitated by rotation of the agitator 40 and is released into the developing chamber 30 and is supplied to the supply roller 36 , as shown in fig1 . the toner supplied to the supply roller 36 is supplied to the developing roller 37 by rotation of the supply roller 36 . at this time , the toner is frictionally charged to the positive polarity between the supply roller 36 and the developing roller 37 . subsequently , the toner supplied to the developing roller 37 enters the nip between the press contact rubber 46 and the developing roller 37 with rotation of the developing roller 37 and is carried on the surface of the developing roller 37 as a thin layer while the layer thickness is regulated between the press contact rubber 46 and the developing roller 37 . the surface of the photoconductive drum 25 is positively charged uniformly by the scorotron charger 26 with rotation of the photoconductive drum 25 and then is exposed to light by a laser beam from the scanner unit 16 and an electrostatic latent image based on the image data is formed . next , when the toner carried on the surface of the developing roller 37 faces the photoconductive drum 25 and comes in contact therewith by rotation of the developing roller 37 , the toner is supplied to the electrostatic latent image formed on the surface of the photoconductive drum 25 . accordingly , the electrostatic latent image is developed ( is made visible ) and the toner image is carried on the surface of the photoconductive drum 25 . the toner image is transferred onto the sheet 8 conveyed to the nip between the photoconductive drum 25 and the transfer roller 27 ( transfer position ). the sheet 8 onto which the toner image is transferred is conveyed to the fixing unit 18 . the fixing unit 18 is provided at the rear of the process cartridge 17 . the fixing unit 18 includes a heating roller 48 , a pressurization roller 49 pressed against the heating roller 48 from below , and a pair of conveying rollers 50 placed at the rear of them . in the fixing unit 18 , the toner transferred onto the sheet 8 at the transfer position is thermally fixed while the sheet 8 passes through the nip between the heating roller 48 and the pressurization roller 49 and then the sheet 8 is conveyed to the sheet discharge unit 5 by the pair of conveying rollers 50 . the sheet discharge unit 5 includes a sheet discharge path 51 , a sheet discharge roller 52 , and a sheet discharge tray 53 . the sheet 8 conveyed from the fixing unit 18 to the sheet discharge path 51 is conveyed from the sheet discharge path 51 to the sheet discharge roller 52 and is discharged onto the sheet discharge tray 53 by the sheet discharge roller 52 . in the main body casing 2 , a guide wall 39 extending substantially along the back and forth direction is provided slightly above the process cartridge 17 attached to the main body casing 2 . the lower face of the guide wall 39 is partitioned by a horizontal portion 41 and an inclined portion 42 . the inclined portion 42 is a slope extending downward to the slanting rear from the opening 6 to the inside of the main body casing 2 , and the front end corresponds to the upper end of the opening 6 . the horizontal portion 41 is a substantially horizontal plane extending from the rear end of the inclined portion 42 to the rear along the back and forth direction ( or slightly downward inclined ). a main body terminal 54 as an example of a first terminal is provided in the vicinity of the rear end of the horizontal portion 41 . the main body terminal 54 is formed of an electrical conductive plate spring having elasticity or the like and projects downward from the horizontal portion 41 . the main body terminal 54 is connected to a cpu ( not shown ) provided in the main body casing 2 . the drum cartridge 22 includes a drum cover 44 as an example of a cover member on the rear face of the drum frame 23 ( drum storing portion 32 ). the drum cover 44 is formed like a thin plate having a substantially inverted - j shape in the left sectional view , for example , as shown in fig3 . for the convenience of the description , the upper flat portion of the drum cover 44 is called as a flat portion 47 and the lower bent portion of the drum cover 44 is called as a bend portion 55 . the bend portion 55 is bent downward in a direction toward the rear face of the drum frame 23 ( namely , the front in fig3 ). in the drum cover 44 , a memory device 64 and a drum terminal 65 as an example of a second terminal electrically connected to the memory device 64 are provided on a side face on the opposite side to the side opposed to the rear face of the drum frame 23 ( namely , the rear face in fig3 ). the memory device 64 is memory for storing information concerning the drum cartridge 22 ( for example , drive condition of the photoconductive drum 25 , etc .,) in such a manner that the information can be read and can be written . the memory device 64 and the drum terminal 65 may be formed in one piece , i . e ., the drum terminal 65 may be integrated with the memory device 64 . the memory device 64 may be provided in the drum frame 23 rather than the drum cover 44 . in this case , the memory device 64 is electrically connected to the drum terminal 65 of the drum cover 44 by an electric wire or a plate . a swing shaft 56 extending in the width direction is inserted into the drum cover 44 . the drum cover 44 is supported in the rear end portion of the upper wall of the drum frame 23 through the swing shaft 56 and swingable around the swing shaft 56 ( see fig1 ). in particular , the drum cover 44 can move between a cover position ( an example of a first position ) and an exposure position ( an example of a second position ) described later . the swing shaft 56 is roughly at the center position in the up and down direction of the flat portion 47 ; hereinafter , in the flat portion 47 , the portion above the swing shaft 56 will be referred as an upper portion 57 and the portion below the swing shaft 56 will be referred as a lower portion 58 . when the drum cover 44 is positioned at the cover position , the lower end portion of the bend portion 55 abuts the rear end portion of the bottom wall of the drum frame 23 from the rear , and the drum cover 44 covers the drum rear opening 77 formed through the drum frame 23 and the drum exposure portion 75 exposed from the drum rear opening 77 from the rear , as indicated by the solid line in fig2 . at this time , the drum cover 44 is made upright roughly along the up and down direction so that the upper portion 57 projects upward to the slanting front from the upper wall of the drum frame 23 . the drum terminal 65 faces backward . on the other hand , when the drum cover 44 is positioned at the exposure position , the lower end portion of the bend portion 55 is away from the rear end portion of the bottom wall of the drum frame 23 to the rear and the drum cover 44 exposes the drum rear opening 77 and the drum exposure portion 75 to the rear , as shown in fig1 . the drum cover 44 is inclined roughly along the back and forth direction so that the flat portion 47 is almost along the upper wall of the drum frame 23 . when the drum cover 44 is positioned at the exposure position , the drum terminal 65 faces upward . thus , the drum cover 44 can move relative to the drum frame 23 . a spring 66 ( an example of an urging member ) is intervened between the rear end portion of the upper wall of the drum frame 23 and the upper portion 57 of the drum cover 44 for urging the upper portion 57 of the drum cover 44 so as to project upward from the upper wall of the drum frame 23 , as shown in fig2 . accordingly , the drum cover 44 is urged so as to position at the cover position normally ( namely , when the drum cartridge 22 is outside the main body casing 2 ). the drum cover 44 protects the drum exposure portion 75 of the photoconductive drum 25 in a state where it positions at the cover position . ( 3 ) attaching and detaching of process cartridge to and from main body casing the drum cartridge 22 including the drum cover 44 is attached to the main body casing 2 . for the convenience of the description , the description shows an example where the drum cartridge 22 to which the developer cartridge 31 is attached , namely , the process cartridge 17 is attached to the main body casing 2 , rather than the drum cartridge 22 is solely attached to the main body casing 2 . however , the drum cartridge 22 solely may also be attached to and detached from the main body casing 2 . the drum cover 44 is positioned at the cover position when attachment of the process cartridge 17 is started . first , the front cover 7 is opened for opening the opening 6 and the process cartridge 17 is inserted into the main body casing 2 from the front roughly along the horizontal direction . at this time , the upper portion 57 of the drum cover 44 at the cover position is opposed to the inclined portion 42 of the guide wall 39 with a spacing in the back and forth direction . thus , if the process cartridge 17 is continuously inserted into the main body casing 2 roughly along the horizontal direction , the upper portion 57 is abutted against the inclined portion 42 . accordingly , the drum cover 44 starts to swing toward the exposure position against the urging force of the spring 66 ( see the drum cover 44 indicated by the dotted line in fig2 ). if the process cartridge 17 is continuously inserted into the main body casing 2 roughly along the horizontal direction , the upper portion 57 is abutted against the horizontal portion 41 following the inclined portion 42 and the drum cover 44 swings to the exposure position ( see the drum cover 44 indicated by the alternate long and short dash line in fig2 ). since the horizontal portion 41 is a roughly horizontal plane as described above , the drum cover 44 is maintained at the exposure position while the upper portion 57 is abutted against the horizontal portion 41 . when inserting of the process cartridge 17 into the main body casing 2 stops , placing the process cartridge 17 in the main body casing 2 is complete as shown in fig1 . at this time , the drum cover 44 is positioned at the exposure position and thus the drum terminal 65 faces upward as described above and abuts the main body terminal 54 . accordingly , the drum terminal 65 and the main body terminal 54 are electrically connected , so that the cpu ( not shown ) and the memory device 64 provided in the main body casing 2 are electrically connected . in this state , the cpu ( not shown ) can read the information stored in the memory device 64 and can rewrite the information stored in the memory device 64 in response to the image formation operation . on the other hand , the front cover 7 is opened in a state where the process cartridge 17 is attached to the main body casing 2 , and the process cartridge 17 is drawn out to the front . accordingly , the drum terminal 65 is brought away from the main body terminal 54 and thereby electrically disconnected from the main body terminal 54 . the drum cover 44 is continuously at the exposure position as indicated by the alternate long and short dash line in fig2 in a state where the upper portion 57 is abutted against the horizontal portion 41 . when the process cartridge 17 is drawn out to the front and the upper portion 57 passes through the horizontal portion 41 and is abutted against the inclined portion 42 , the drum cover 44 starts to swing toward the cover position by the urging force of the spring 66 ( see the drum cover 44 indicated by the dotted line in fig2 ). when the upper portion 57 passes through the inclined portion 42 , the drum cover 44 swings to the cover position . when the process cartridge 17 is completely drawn out from the main body casing 2 , detaching the process cartridge 17 from the main body casing 2 is complete . as shown in fig1 , when the drum cover 44 is moved in one direction ( in particular , to the exposure position ) at the attachment completion position of the process cartridge 17 ( in particular , the drum cartridge 22 ) in the main body casing 2 , the drum terminal 65 provided on the drum cover 44 abuts the main body terminal 54 . then , the drum terminal 65 and the main body terminal 54 are electrically connected and information can be transferred between the memory device 64 and the cpu ( not shown ) provided in the main body casing 2 . when the drum terminal 65 abuts the main body terminal 54 , the abutment pressure received by the drum terminal 65 from the main body terminal 54 is received at the drum cover 44 , so that the abutment pressure can be prevented from acting directly on the drum frame 23 and the drum frame 23 can be prevented from moving from a predetermined attachment completion position . thus , shift of the attachment position of the process cartridge 17 ( drum cartridge 22 ) relative to the main body casing 2 can be prevented . consequently , positioning the process cartridge 17 to the main body casing 2 can be reliably executed without affecting connection of the main body terminal 54 and the drum terminal 65 . the drum cover 44 can move between the cover position for covering the drum exposure portion 75 of the photoconductive drum 25 ( see the solid line portion in fig2 ) and the exposure position for exposing the drum exposure portion 75 ( see fig1 ). thus , when the drum cover 44 is moved to the exposure position , a toner image can be transferred from the photoconductive drum 25 to a sheet 8 , and the sheet 8 with the toner image can pass through the drum rear opening 77 uncovered with the drum cover 44 . on the other hand , when the drum cover 44 is moved to the cover position , the drum exposure portion 75 can be protected ( see fig2 ). thus , the photoconductive drum 25 as a rotation body rotatably supported on the drum frame 23 is covered with the drum cover 44 at the cover position . when the drum cover 44 is positioned at the exposure position , the drum terminal 65 abuts the main body terminal 54 and thus information can be transferred between the memory device 64 and the cpu ( not shown ) in the main body casing 2 at the same time as the transfer operation described above , so that operability can be improved . a developing cover 60 may be provided as an example of a cover member in addition to or in place of the drum cover 44 . the developer cartridge 31 and the drum cartridge 22 when the developing cover 60 is provided will be discussed below . fig4 is a side view of the process cartridge in which the developer cartridge is attached to and detached from the drum cartridge . fig5 a shows the developing cover positioned at a cover position and fig5 b shows the developing cover positioned at an exposure position . the developing cover 60 is included in the developer cartridge 31 and is formed like a thin plate relatively long in an up and down direction and roughly rectangular in the front view , for example , as shown in fig5 a and 5b . the upper end portion and the lower end portion of the developing cover 60 are formed so as to project one step to both sides in the width direction . the portions projecting to both sides in the width direction in the upper end portion of the developing cover 60 are called upper projection portions 62 ( an example of a distal end portion ), and the portions projecting to both sides in the width direction in the lower end portion of the developing cover 60 are called lower projection portions 67 . in the developing cover 60 , a through hole 61 of almost the same shape as the developing opening 59 is formed at a position slightly shifted to the lower side from the center of the developing cover 60 in the up and down direction thereof . the developing cover 60 is slidably supported in the up and down direction by the rear end portions of both side walls in the width direction of the developing frame 28 . in particular , the portion of the developing cover 60 between the upper projection portions 62 and the lower projection portions 67 in the up and down direction is sandwiched between the rear end portions of both side walls in the width direction of the developing frame 28 . in this state , the developing cover 60 can move between a cover position described later and an exposure position above the cover position . when the developing cover 60 is positioned at the cover position , the developing opening 59 is covered with the upper portion above the through hole 61 in the developing cover 60 from the rear , as shown in fig5 a . accordingly , the developing exposure portion 76 is also covered with the developing cover 60 from the rear . that is , when the developing cover 60 is positioned at the cover position , the developing cover 60 covers the developing opening 59 formed through the developing frame 28 and the developing exposure portion 76 exposed from the developing opening 59 from the rear . the roughly lower half portion of the developing cover 60 projects downward from the developing frame 28 . when the developing cover 60 moves down to the cover position , the upper projection portions 62 abut the rear end portions of both side walls in the width direction of the developing frame 28 from above , so that the developing cover 60 is prevented from further moving from the cover position and dropping out from the developing frame 28 . the developing cover 60 is normally positioned at the cover position under its own weight . on the other hand , when the developing cover 60 is positioned at the exposure position , the developing opening 59 faces the through hole 61 in the back and forth direction and communicates with the through hole 61 as shown in fig5 b . accordingly , the developing exposure portion 76 is exposed to the front through the developing opening 59 and the through hole 61 . that is , when the developing cover 60 is positioned at the exposure position , the developing cover 60 exposes the developing exposure portion 76 to the rear . the roughly upper half portion of the developing cover 60 projects upward from the developing frame 28 . thus , when the developing cover 60 moves from the cover position to the exposure position , the developing cover 60 moves up ( an example of a first direction ) relative to the developing opening 59 ; when the developing cover 60 moves from the exposure position to the cover position , it moves down relative to the developing opening 59 . this means that the developing cover 60 can make a relative movement to the developing frame 28 containing the developing opening 59 . in the developing cover 60 , the above - described memory device 64 is provided above the through hole 61 on a side face on the opposite side to the side opposed to the developing opening 59 ( namely , the rear face in fig5 a and 5b ). the memory device 64 according to modified example 1 stores information concerning the developer cartridge 31 ( for example , the toner storage amount , etc .,). a developing terminal 68 as an example of a second terminal electrically connected to the memory device 64 is provided on the upper end face of the developing cover 60 . the memory device 64 and the developing terminal 68 may be formed in one piece . the memory device 64 may be provided in the developing frame 28 rather than the developing cover 60 . in this case , the memory device 64 is electrically connected to the developing terminal 68 of the developing cover 60 by an electric wire or a plate . as shown in fig4 , in the drum cartridge 22 , the upper end faces of both side walls of the cartridge storing portion 33 in the width direction thereof ( called guide rails 69 ) are formed so as to incline downward to the slanting rear . the rear end margins of the guide rails 69 are connected roughly to the center in the up and down direction of the front end margins of both side walls of the drum storing portion 32 in the width direction thereof . a concave portion 70 recessed downward to the slanting rear continuous from the rear end margin of the guide rail 69 is formed on both side walls of the drum storing portion 32 in the width direction thereof . each concave portion 70 pierces the corresponding width direction side wall in the drum storing portion 32 in the width direction . a guide groove 71 is formed on the width direction inner faces of both side walls of the drum cartridge 22 in the width direction thereof corresponding to the developing cover 60 . the guide grooves 71 are formed by notching the width direction inner faces of both side walls of the drum cartridge 22 in the width direction thereof from the upper end margins to the lower side . in particular , the groove bottom ( lower end face ) of each guide groove 71 is formed so that it extends like a circular arc from the rough center position in the back and forth direction of the corresponding guide rail 69 to the rear lower side ( this portion is called a circular arc groove bottom 73 ) and then extends to the rear roughly horizontally ( this portion is called a horizontal groove bottom 74 ). the direction in which the developer cartridge 31 is attached to and detached from the drum cartridge 22 is a direction crossing the horizontal direction ( see the thick arrow in fig4 ). the developer cartridge 31 with the developing cover 60 at the cover position ( see the solid line indication portion in fig4 ) is inserted into the cartridge storing portion 33 of the drum cartridge 22 downward to the slanting rear . at this time , first , the corresponding lower projection portions 67 are accepted in the guide grooves 71 . portions exposed from both side walls of the developing frame 28 in the width direction thereof in the rotation shaft of the developing roller 37 ( called exposure shafts 72 ) are placed in the corresponding guide rails 69 . in this state , if the developer cartridge 31 is inserted into the cartridge storing portion 33 , the lower projection portions 67 are guided along the guide grooves 71 ( in particular , the circular arc groove bottoms 73 ), the exposure shafts 72 are guided along the guide rails 69 , and the developer cartridge 31 moves downward to the slanting rear . when the lower projection portions 67 pass through the circular arc groove bottoms 73 and arrive at the horizontal groove bottoms 74 , the positions of the lower projection portions 67 in the up and down direction are fixed and it is made impossible for the developing cover 60 to further move down . thus , if the developer cartridge 31 ( in particular , the developing frame 28 ) is further moved down , the developing frame 28 moves down relative to the developing cover 60 of which the downward movement is regulated ( see the alternate long and short dash line portion in fig4 ). accordingly , the developing cover 60 moves up relative to the developing frame 28 and moves to the exposure position . when the exposure shafts 72 pass through the corresponding guide rails 69 and are fitted into the corresponding concave portions 70 , placing the developer cartridge 31 in the drum cartridge 22 is complete ( see the dotted line portion in fig4 ). at this time , the through hole 61 of the developing cover 60 at the exposure position , the developing opening 59 , and the drum front opening 63 face each other and the developing exposure portion 76 of the developing roller 37 comes in contact with the photoconductive drum 25 . the upper end portion of the developing cover 60 , in particular the developing terminal 68 projects upward from each upper wall of the drum frame 23 and the developing frame 28 . thus , if the drum cartridge 22 to which the developer cartridge 31 is attached , namely , the process cartridge 17 is attached to the main body casing 2 , the developing terminal 68 abuts the main body terminal 54 . accordingly , the cpu ( not shown ) provided in the main body casing 2 and the memory device 64 are electrically connected and the cpu ( not shown ) can read and rewrite the information stored in the memory device 64 as described above . if the process cartridge 17 is detached from the main body casing 2 , the developing terminal 68 is brought away from the main body terminal 54 and thereby electrically disconnected from the main body terminal 54 . on the other hand , when the developer cartridge 31 attached to the drum cartridge 22 is drawn out to the front , the developer cartridge 31 moves up to the slanting front . at this time , the lower projection portions 67 are guided along the guide grooves 71 ( in particular , the horizontal groove bottoms 74 ) and the exposure shafts 72 are placed out of the concave portions 70 and are guided along the guide rails 69 . the developing cover 60 cannot move up under its own weight ; whereas , the developing frame 28 moves up and thus the developing cover 60 moves down relative to the developing frame 28 and moves to the cover position . when the exposure shafts 72 are placed out of the guide rails 69 and the lower projection portions 67 are placed out of the guide grooves 71 ( in particular , the circular arc groove bottoms 73 ) and the developer cartridge 31 is completely drawn out from the cartridge storing portion 33 , detaching the developer cartridge 31 from the drum cartridge 22 is complete . in modified example 1 , the developing cover 60 can move between the cover position for covering the developing exposure portion 76 of the developing roller 37 ( see fig5 a ) and the exposure position for exposing the developing exposure portion 76 ( see fig5 b ). thus , if the developing cover 60 is moved to the exposure position , toner can be supplied from the developing exposure portion 76 to the photoconductive drum 25 ( see the dotted line portion in fig4 ) and if the developing cover 60 is moved to the cover position , the developing exposure portion 76 can be protected ( see the solid line portion in fig4 ). thus , the developing roller 37 as a rotation body rotatably supported on the developing frame 28 is covered with the developing cover 60 at the cover position . when the developing cover 60 is positioned at the exposure position , the developing terminal 68 abuts the main body terminal 54 and thus information can be transferred between the memory device 64 and the cpu ( not shown ) in the main body casing 2 at the same time as the toner supply described above , so that operability can be improved . in the embodiment described above , as the process cartridge 17 , the drum cartridge 22 and the developer cartridge 31 can be separated . however , the process cartridge 17 into which the drum cartridge 22 and the developer cartridge 31 are combined as one piece may be adopted as an example of a cartridge . in this case , the process cartridge 17 is provided with the drum cover 44 , but not with the developing cover 60 . as information concerning the process cartridge 17 , both the information concerning the drum cartridge 22 described above and the information concerning the developer cartridge 31 are stored in the memory device 64 of the drum cover 44 . in the embodiment described above , the toner storage chamber 29 and the developing chamber 30 are provided in the developing frame 28 of the developer cartridge 31 , but the portion corresponding to the toner storage chamber 29 may be attached to and detached from the developing frame 28 as a toner cartridge . the developer cartridge 31 may also be detachably attachable to the drum cartridge 22 in a state where the drum cartridge 22 is attached to the main body casing 2 . the photoconductive drum 25 , the scorotron charger 26 , and the transfer roller 27 may be provided in the main body casing 2 and the developer cartridge 31 may be detachably attachable to the main body casing 2 . in the embodiment described above , the monochrome laser printer 1 is illustrated ; however , for example , the image forming device can also be implemented as a color laser printer ( containing tandem type , intermediate transfer type ).
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the closing part of the bottom closure herein is preferably covered by a cap , a free space being provided between the closing part and the cap so that the cap is only lifted when the packings are outside the range of the issuing solid . the advantage of this embodiment is that , first of all , the cylindrical sealing surfaces on the closing part are already completely covered by the cap before the bottom closure is opened , which prevents it from coming in contact with the issuing product , and second , the cap prevents the further discharge of the solid before the bottom closure is completely closed , so that the complete closing of the closure is not prevented by solid particles between the conical surfaces of the closing part and attachment opening . in this embodiment the closing part has preferably a bottom sealing surface , a central section widening conically upward which bears in the closed position on the conically widening attachement opening of the cylinder extension , and a conical top which engages the cap after the closure has been partly opened . in another preferred embodiment , the bottom closure contains a protective packing sleeve which is pressed by compression springs etc . from the bottom against the cylindrical , sealing surfaces of the closing part and moved completely during the opening of the closure over o - rings arranged in grooves in the upper straight section of the cylinder extension before the closing part has engaged the cap . in this embodiment , the o - rings provided for sealing do not come directly in contact with the solid , so that they cannot be destroyed by it or impaired in their function . in another embodiment , the o - rings are arranged in grooves which are provided in the central conical section of the closing part , these grooves narrowing preferably to the outside and thus preventing the o - rings from falling out . for cleaning the closing part and the surfaces of the closure on which the closing part bears can be provided a means for rinsing the closing part . this rinsing liquid can also be supplied through a line inside the control rod of the closing part and issue through openings in the conical region of the closing part . referring now to fig1 reactor 1 has a cylindrical extension 2 , a conical surface being provided at the point of transition from the reactor to the cylinder extension on which closing part 3 bears , thus sealing the reactor . closing part 3 can have a conically tapering bottom end , similar to the tapering section in fig2 . the closing part protrudes through a cylindrical extension into the interior of the reactor , approximately up to the level where the straight section of the reactor begins . the cylindrical extension of the closing part is terminated by a top which destroys during its opening any bridges and arches formed by solids within the reactor . the closing part is moved up by control rod 12 for opening the closure , and down for closing . according to fig2 the closing part can be covered by a cap 4 protruding into the interior of the reactor . in the closed state there is a free space between the closing part and the cap . only when the closing part is lifted so far that it engages the cap 4 does the discharge of the solid begin . when the bottom closure is closed , the cap already rests on the bottom of the reactor before the downward movement of the closing part 3 is completed . this has for its effect the prevention of adhesion of any solid during the last stage of the closing movement on the sealing surfaces , e . g . the conical section 7 of the closing part and the conical region of the attachment opening of the cylinder extension 2 , which adhesion could otherwise prevent complete closing . in the upper region of cylinder extension 2 are provided circular grooves in which are arranged o - rings . these o - rings are made of a suitable elastic , and possibly reinforced plastic , and ensure complete sealing . in order to prevent these o - rings from being damaged during the discharge of the solid , the protective packing sleeve 5 moves during the opening of the closure from the bottom over the o - rings 10 . the protective packing sleeve 5 is urged by compression spring 9 against the closing part 3 . the sleeve follows the closing part 3 so far that the o - rings are covered . ( in fig2 the protective packing sleeves and the compression springs are illustrated to be of shorter length ). the distance between the cap and the closing parts in the direction of the closing movement is therefore so great that the cap is only lifted when the protective packing sleeve has moved over the o - rings and the cap has also sealed the cylindrical sealing surface 6 on the closing part . the issuance of the solid thus starts only when the cylindrical sealing surface 6 on the closing part is also covered by the cap in such a way that the solid can not reach it . according to fig3 grooves 13 can be provided in the central conical region 7 of the closing part , and o - rings are arranged in these grooves . in this embodiment a particularly good seal is achieved . in order to prevent fouling of the o - rings 11 , a means for rinsing this region of the closing part is provided , where the rinsing liquid is supplied through a line which opens into the lower region of the reactor and directs through a plurality of openings , jets of a rinsing liquid toward the conical region 7 of the closing part when the closure is opened . the rinsing liquid can also be supplied through a line inside the control rod 12 and issue directly through openings inside the conical section 7 . particularly in bottom closures in extractors which are used for decaffeinating raw coffee , it is important to clean the sealing surfaces and the o - rings by rinsing , otherwise the operation of the closure would be impaired . suitable materials for the o - rings are , for example , reinforced or unreinforced polytetrafluoroethylene copolymers of vinylidene fluoride and hexafluoropropylene ( respectively , teflon and viton , trademarks of dupont ). the conical section 7 of the closing part can also contain metal sealing ring 14 in divided grooves . this type of seal is shown in fig4 . the gas - and liquid - tight bottom closure is suitable for a pressure of up to 400 bar . if teflon or viton are used for the o - rings , the admissible temperature is about 160 ° c . if metal seals 14 are used , the temperature may rise up to 325 ° c .
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fig1 a shows a perspective view of a belleville washer . the washers are manufactured using materials , such as alloy steels , to meet specific material requirements . they should exhibit good fatigue life and minimum relaxation . a high alloy content material is commonly used as the spring steel . fig1 b identifies dimensions of belleville springs commonly used . spring 10 is shown in fig1 a and fig1 b . d 1 is the diameter of the opening , d 2 is the external diameter of the spring , t is the thickness of the spring material , d is the maximum deflection of the spring when it is compressed , and e is the overall thickness of the spring in the uncompressed state . d = e − t . the spring may contain special properties for corrosion or other properties and may be coated with a number of different materials such as phosphate , galvanizing , mechanical zinc plating and electroless nickel plating . it may also be coated with the coating to minimize friction , which is discussed further below . referring to fig2 a , spring stack 20 is shown in cross section , including springs 22 in series configuration on spring carriers 24 , which are guided by mandrel 26 . forces are applied to the springs through load ring 28 ( a ) and load base 28 ( b ). referring to the inset of fig2 a , spring carrier 24 is formed by sleeve 21 and circumferential flange 25 . fig2 b depicts spring stack 20 in the state of maximum compression . springs 22 have been deflected to the point where the cone is collapsed ( i . e ., deflected by the distance “ d ” of fig1 b ). spring carriers 24 are in contact on mandrel 26 . fig2 c shows a perspective view of the washers and spring carrier 24 of fig2 a and 2b . carrier 24 is formed from sleeve 21 and circumferential flange 25 on the outside surface of the sleeve . flange 25 allows the washers to be spaced at a selected location on carrier 24 , normally at an equal distance from each end of the sleeve . spring carrier 24 is adapted to fit slidably on mandrel 26 . the outside diameter of spring carrier 24 is adapted to fit in the inside diameter ( d 1 of fig1 b ) of belleville spring 22 . referring to fig3 a , belleville springs 32 on one side of mandrel 36 are shown in a partial cross - sectional view . spring carrier 34 is placed between mandrel 36 and springs 32 . spring carrier 34 includes sleeve 31 and circumferential flange 35 . in fig3 a , springs 32 are either in a relaxed state or in a compressed state less than maximum compression . fig3 b shows spring 32 in the state of maximum compression allowed when springs are employed on spring carrier 34 . spring carrier 34 has an axial dimension , as measured from flange 34 to an end of sleeve 31 , greater than the maximum deflection (“ d ” of fig1 b ) of spring 32 . when the apparatus is deployed on mandrel 36 and load is applied , spring carrier 34 may serve to limit the deflection and the load applied to springs 32 . this load - limiting feature may be selected over a broad range of load from zero deflection or the relaxed state to maximum deflection of the springs . the width of circumferential flange 35 may also be selected to maintain an optimum spacing of springs 32 . flange 35 serves primarily to control the placement of springs 32 on spring carrier 34 . it preferably has enough width to provide the needed mechanical strength of the flange . referring to fig4 a , springs 42 are deployed on mandrel 46 using spring carriers 44 . as seen more clearly in the center inset , spring carrier 44 is made up of sleeve 41 . the outside surface of sleeve 41 includes an annular recess 43 ( a ) extending axially from the upper end of sleeve 41 , and the inside surface of sleeve 41 includes an annular recess 43 ( b ) extending axially from the lower end of sleeve 41 . recesses 43 ( a ), 43 ( b ) define annular shoulders 47 ( a ), 47 ( b ), respectively , on the outside and inside surfaces , respectively , of sleeve 41 . consequently , the outside surface of sleeve 41 has a smaller diameter portion and a larger diameter portion that intersect at a shoulder 47 ( a ), and the inside surface of sleeve 41 has a smaller diameter portion and a larger diameter portion that intersect at a shoulder 47 ( b ). flange 45 extends radially outward from the larger diameter of the outside surface of sleeve 41 . the smaller diameter of the inside surface of sleeve 41 is sized to fit slidably over mandrel 46 and the larger diameter of the outside surface of sleeve 41 is sized to fit in the inside diameter of springs 42 . as previously described , spring carrier 44 has inside and outside surfaces of different diameter on each side of shoulders 47 ( a ) and 47 ( b ), which are placed at selected locations on the outside surface and inside surface , respectively , of carrier 44 . shoulder 47 ( a ) separates the larger and small diameter on the outside surface and shoulder 47 ( b ) separates the larger and smaller diameter on the inside surface of sleeve 41 . circumferential flange 45 may be used to facilitate placing springs 42 on carrier 44 . load ring 48 ( a ) and load base 48 ( b ) may be used to apply load to stack 40 . the outside diameter of one segment of carrier 44 is selected to fit in the inside diameter of another segment of carrier 44 . the carriers are disposed on mandrel 46 such that adjacent carriers overlap and thereby decrease lateral or bucking loads on mandrel 46 as springs 42 are compressed . overlapping of adjacent carriers creates rigidity to the stack of carriers and provides significant friction reduction in stack 40 as it is compressed and decompressed . a hysteresis curve for the compression and decompression will have significantly smaller area in the presence of overlapping carriers 44 than in the absence of such carriers . carriers 44 may be truncated so that an end carrier may allow the end spring to compress against load ring 48 ( a ) or load base block 48 ( b ). truncated carriers 49 ( upper inset and lower inset ) illustrate a preferred configuration of a spring carrier to be placed at the end of a stack . in fig4 b compressive load has been applied to deflect springs 42 to the point where adjacent springs carriers 44 are completely interlocked or overlapping and springs 42 have reached maximum deflection . spring carriers 44 have moved along their axis as each spring has been deflected a distance equal to the maximum deflection (“ d ” of fig1 b ). as discussed above with respect to fig3 a and 3b , the distance from an end of sleeve 41 to shoulder 47 ( a ) or 47 ( b ) may be less than the maximum deflection of spring 42 . in this case , when the apparatus is deployed on mandrel 46 and load is applied , then spring carrier 44 may serve to limit the deflection and the load applied to springs 42 . this load - limiting feature may be selected over a broad range of load from zero deflection or the relaxed state to maximum deflection of the springs . referring to fig4 c , a perspective view is shown of springs 42 on carriers 44 and mandrel 46 . sleeve 41 has shoulder 47 ( a ) on the outside surface and shoulder 47 ( b ) on the inside surface . circumferential flange 45 is placed at a selected position , preferably in the center of the larger diameter surface on the outside surface of sleeve 41 . shoulders 47 ( a ) and 47 ( b ) may be placed equal distances from the opposite ends of sleeve 41 . alternatively , the shoulders may be placed at different distances from the opposite ends of sleeve 41 . these distances will be shown in more detail in fig6 a . referring to fig5 spring stack 50 guided by cylinder 56 is shown . springs 52 are sized to fit the inside diameter of spring carriers 54 . the larger outside diameter of spring carrier 54 is sized to slidably fit inside cylinder 56 . spring carriers 54 are made of sleeve 51 ( see inset ) and have circumferential ledge 55 on the smaller diameter area of the inside surface . the inside surface of sleeve 51 includes an annular recess 53 ( a ) extending axially from the upper end of sleeve 51 , and the outside surface of sleeve 51 includes an annular recess 53 ( b ) extending axially from the lower end of sleeve 51 . recesses 53 ( a ), 53 ( b ) define annular shoulders 57 ( a ), 57 ( b ), respectively , on the inside and outside surfaces , respectively , of sleeve 51 . consequently , the inside surface of sleeve 51 has a smaller diameter portion and a larger diameter portion that intersect at a shoulder 57 ( a ), and the outside surface of sleeve 51 has a smaller diameter portion and a larger diameter portion that intersect at a shoulder 57 ( b ). flange 55 extends radially outward from the smaller diameter of the inside surface of sleeve 51 . load blocks 58 ( a ) and 58 ( b ) transmit force to the stack of springs 52 . overlapping spring carriers for use inside a cylinder guide or on a mandrel may be designed to provide complete interlocking or overlapping when springs reach maximum deflection or may be designed to provide load - limiting capabilities by selection of axial dimensions . fig6 a illustrates dimensions of overlapping carriers . as can be noted in the figure , for the carriers to be moved with the springs to maximum spring deflection ( d ) when the carriers are completely overlapping or interlocked , dimensions may be selected such that : where t is spring thickness , w is width of the circumferential ledge , c is the distance between the inside and outside shoulders , l is the overlap of the carriers at the initial deflection of the springs and r is the remaining overlap from the initial deflection of the springs . if we dimension the spring carrier so that r = 2d , then : the carriers then would move from the position shown in fig6 a to that shown in fig6 b ( completely overlapping ) if d and t are spring properties that will be supplied by the manufacturer of the selected spring . c and l are design options for the carriers , which will determine the value of w if the springs are to reach maximum deflection when the carriers are completely interlocked . if load - limiting of the springs is to be provided by the carriers , the value of r ( along the inside surface ) under no - load conditions may be decreased , for example . alternatively , dimensions of the carriers may be adjusted along the outside surface . preferably , the spring carriers disclosed herein are coated with an anti - friction coating . many such coatings are available . a suitable coating is provided by the kolene qpq process , which is a product of kolene corporation . another suitable process is the armorall process . other known friction - reducing coatings , polymers , oils or additives may be used . embodiments disclosed heretofore employed a guide for the springs , either a mandrel or a cylinder . in other embodiments , a guide is not employed and the carriers are placed such that overlapping of adjacent carriers is sufficient to form a rigid structure that prevents sidewise movement of springs or buckling of a stack of springs . fig7 a illustrates such a stack , stack 70 . springs 72 are deployed on spring carriers 74 . note the absence of a mandrel , but adjacent carriers overlap sufficiently to provide a rigid structure , preventing buckling of the stack of springs . overlapping may be provided by pre - loading springs or by adjusting carrier dimensions to allow sufficient overlapping a zero spring deflection . carriers 74 have inside and outside surfaces of different diameter on each side of shoulders , as explained above for fig4 a . circumferential flange 73 facilitates placing springs 72 on carriers 74 . end pieces 78 ( a ) and 78 ( b ) may be used to apply force to the stack and to confine lateral movement of the end pieces of the carriers . fig7 b shows stack 70 in the totally compressed state . stack 70 of fig7 is similar to stack 40 of fig4 , except a mandrel guide is not present in fig7 . fig5 shows a stack using a cylinder as a guide . of course , a stack can be formed using the guides of fig5 without a cylinder guide if carriers are initially overlapped . such a stack may have the guide and spring configuration of fig5 with load blocks at the ends of the stack and no cylinder guide outside . although the present disclosure has been described in detail , it should be understood that various changes , substitutions and alterations can be made thereto without departing from the scope and spirit of the invention as defined by the appended claims .
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as described above , the precise placement of electro - optical components is a critical issue . organic optical waveguides on electrical flexible substrates with electrical fine - pitch conductor technologies can be used as an alternative to build the interface between electrical circuits and optical data - transport - media ( e . g . fibres or other waveguides ). with the specific aim of create a path of easy integration of optics into it systems the use of cheap processes to build electro - optical “ flexible ” modules is a very powerful tool . typically , components are assembled to electrical flex - circuits while they &# 39 ; re still flat . only after assembly , the flex circuits are deformed to meet very special spatial requirements ( e . g . to “ re - orient ” optical components , pressure sensors , microphones , or just to tightly pack components into 3 - d like assemblies ). fig1 shows a typical flip - chip bonder installation for flat mounting and not belonging to the present invention . as shown , there is provided a substrate 130 upon which a flip - chip component 120 is to be installed . the flip - chip bonder itself comprises bond head 110 and x - y stage 140 . the substrate 130 is mounted on the x - y stage 140 , which is adapted to coarsely position the substrate in the x - y plane . the flip - chip component 120 meanwhile is held by bond head 110 . the bond head 110 is mounted for precise movement in the z - axes . as shown , the bond head is provided with airtight channels 111 which in use contain a partial vacuum , thereby retaining the flip - chip component in position on the die head . the bond head 110 and x - y stage 140 are moved so as to precisely align the substrate 130 and flip - chip component 120 in the desired relationship , and then the bond - head is moved in the z axis so as to bring the flip - chip component into contact with the substrate 130 such that optical apertures on the flip - chip component 130 are exactly aligned with corresponding apertures of the waveguides . the flip - chip component 120 is then bonded to the substrate 130 by any one of a number of standard techniques such as use of thermal curing glue , use of uv curing glue , use of rapidly curing glue etc . the bond head 110 then pressurises the channels 111 so as to release the flip - chip component and withdraws . a standard flip - chip bonder of the kind described above has the required precision to position optical components , and present the further advantage of being readily available and relatively inexpensive . the very high placement accuracy , inherent to flip - chip bonders is used to directly attach optical devices to the optical facet , or terminal of a waveguide or waveguide array and to use the flexible nature of flex - prints to orient the latter in a suitable way to be processed with standard equipment , that is connected to an electro - optical chip die ( e . g . a vcsel or a photodiode ) by means of a standard flip - chip bonder . the optical wave - guides are manufactured on either side of the substrate or fully embedded . the expression “ optical device ” electro - optical component such as for example a photodiode or vcsel , or a passive component such as a lens or mirror . unfortunately many optical components are intended for mounting in the z - y plane , i . e . at right angles to the plane of the substrate , so as to receive or transmit an optical signal arriving through a waveguide oriented in the plane of the substrate . embodiments described herein seek to exploit the intrinsic flexibility of flex - circuits , even before certain components have yet been assembled , i . e . to use the flexibility of the substrate to enable a simpler and higher throughput assembly operation . fig2 a , 2 b , 2 c , 2 d , 2 e and 2 f show an optical assembly and flip - chip bonder in different configurations in accordance with a first embodiment of this invention . as shown in fig2 a there is provided a rectangular , planar , flexible substrate 230 , comprising one or more waveguides 235 . the flexible substrate is provided with a reinforcing layer 231 . as shown , a u shaped section is cut out from the substrate 230 to leave a tongue 234 fixed to the substrate at one edge . to guarantee the terminal remain properly aligned ( i . e . no warping ) and increase the surface available for bonding , a further reinforcing section in the form of a piece of rigid pcb material 232 is added / left underneath the tongue portion 234 , but there is provided an un - reinforced , flexible portion 233 extending across the width of the tongue 234 . as a preliminary step , the x - y stage ( not shown ) positions the planar substrate 230 on the panel underneath the bond - head 260 , which as shown includes the optical component 250 . as shown , there is further provided a clamp element 240 , situated below the bond head 260 , which once the planar substrate 230 is correctly positioned with respect to the x - y plane starts to rise upwards towards the planar substrate 230 and bond head 260 in the z axis . as shown in fig2 b , the clamp element 240 , has risen upwards to the bond head 260 in the z axis so as to engage the planar substrate 230 and by the pressure exerted thereon has deformed at least a part of the flexible portion , so that the terminal 235 of the waveguide comprised therein is oriented away from the substrate 230 so as to expose the terminal 235 . in particular as shown the terminal 235 is positioned in a bonding plane 237 substantially parallel to the plane of the substrate 230 , and elevated above it . the x - y stage ( not shown ) is formed to permit the passage of the clamp , for example by the provision of an aperture of suitable dimensions . as shown , the clamp element 240 is shaped so to as to exactly conform to the outer contour of the flexible portion of the planar substrate in its deformed configuration , so as to ensure that the terminal 235 is precisely and securely positioned with respect to the x - y stage , and thereby the bond head 260 . to further avoid undesired deformations of the substrate , the x - y stage and / or the clamping element may be provided with gripping means such as an adhesive or high friction coating , suction cups or vacuum channels , similar to those provided in the bond head . according to an optional variation of the embodiment of fig2 , there may be provided a second clamp element . this second clamp element is preferably shaped so as to exactly conform to the inner contour of the flexible portion , of the planar substrate in its deformed configuration , that is , on the opposite side of the substrate to the first clamp element . by this means , any residual freedom for the terminal to stray from the required position is removed , so as to ensure that the terminal 235 ( not shown ) is precisely and securely positioned with respect to the x - y stage , and thereby the bond head 260 . where such a second clamp element is provided , it may advantageously be brought into contact with the substrate by sliding in sideways parallel the substrate , or more preferably by arriving obliquely from above so as to clear any components on the substrate surface . in certain embodiments , the x - y stage and / or the bond - head may also be able to correct angular errors with respect to the orientation of the planar substrate ( i . e . tilt and rotation ). as shown in fig2 c , once the terminal 235 ( not shown ) is correctly positioned with regard to x - and y and θ , t , and where appropriate tilt and rotation , the bond head positions the optical component in the z axis so as to placing the electro - optical component on the waveguide component by means of a flip - chip bonder so as to abut the terminal , as shown in fig2 d . the bond head is provided with airtight channels 261 which in use provide a partial vacuum , thereby retaining the flip - chip component in position on the die head as discussed above with respect to fig1 . it is at this stage that the electro - optical component is coupled to the terminal , as described in more detail hereafter . as shown in fig2 e , the bond head 260 then pressurises the channels 261 so as to release the optical component 250 and withdraws . meanwhile , the clamp element 240 is also withdrawn , so that the flexible portion so as to resume its position aligned with the plane of the substrate , as shown in fig2 f . this deformation preferably occurs due to the elasticity of the flexible substrate . fig2 f thus shows the optical assembly in its final form , with the optical component 250 positioned so as to receive an optical signal from a waveguide oriented in the plane of the substrate , and to transmit a signal away from that plane , for example at right angles thereto . it will be appreciated that the configuration of the substrate may be subject to many variations . for example , the reinforcing layer may be omitted altogether , or may take a different form to that described above . the reinforcing layer may include only the main section 231 , or the part reinforcing the tip of the tongue 232 . the reinforcing layer may be disposed on either or both sides of the flexible substrate . rather than comprising a cutout defining a tongue 234 as described above , the flexible portion may be a protuberance extending from the edge of the substrate , or indeed the whole width of the flexible substrate may constitute the flexible portion , in which case the deformation strep would involve the bending of the whole substrate across its width . fig3 is a flowchart of the steps of the process described with respect to fig2 a - 2 f . there is accordingly defined a method for fabricating an optical assembly comprising an optical component . as shown in fig3 , the method starts at step 300 , at which a planar substrate 230 comprising a waveguide portion 234 through which a waveguide extends is provided . the waveguide portion comprises a flexible portion 233 such that by deformation of at least a part of the flexible portion 233 , the substrate 230 may be arranged in an operational configuration with a terminal 235 of the waveguide positioned within the plane so as to interface an installed optical component in operation , and an installation configuration with the terminal of the waveguide oriented away from the substrate so as to expose the terminal 235 for installation of the optical component 250 . the method then proceeds to step 305 , at which the flexible portion 233 is deformed so as to adopt the installation configuration . the method then proceeds to step 310 at which the electro - optical component placed on the waveguide portion 234 by means of a flip - chip bonder 260 so as to abut the terminal 235 . the method then proceeds to step 315 at which the electro - optical component is coupled to the terminal , before finally proceeding to step 320 of deforming the flexible portion so as to adopt the operational configuration . as described with reference to fig2 a - 2 f , the waveguide portion preferably comprises a tongue fixed to the substrate at one edge , and wherein the flexible portion 233 extends across the width of the tongue . as described with reference to fig2 b , the installation configuration of the terminal 235 is preferably positioned in a plane substantially parallel to the plane of the substrate . as described with reference to fig2 f , in the operational configuration the terminal is preferably positioned in a plane substantially orthogonal to the plane of the substrate . as described with reference to fig2 e and 2 f , the step of deforming the flexible portion so as to adopt the operational configuration preferably comprises allowing the flexible portion to elastically resume its original configuration . the step of coupling as described above with regard to fig2 d may be implemented using a variety of techniques . the term coupling includes the establishment of different types of relationship between the optical component 250 and the terminal and the waveguide portion 234 . these relationships may include the mechanical bonding of the optical component 250 to the terminal and / or the wave - guide portion 234 , the optical coupling of the optical component 250 to the terminal or terminals , and / or the electrical connection of electrical contacts of the optical component 250 to electrical contacts of the wave - guide portion 234 . electrical connections need only be formed where the optical component incorporates electrical circuitry . different coupling techniques may be envisaged in which two or more of the above kinds of coupling are achieved by the same process . a number of exemplary coupling strategies are described in more detail hereafter ; however the skilled person will appreciate that other approaches or different combinations of the described techniques may also be effective . fig4 a , 4 b , and 4 c show a first coupling technique . fig4 a , 4 b and 4 c show an expanded view of the elements of the optical assembly at the interface between the optical component 250 and the substrate 230 . in particular , the free end of the flexible portion 234 is shown in the installation configuration , together with the reinforcing part 232 . fig4 a further shows the waveguide 400 , and the terminal 235 . in fig4 a , the optical component 250 has not yet been brought into contact with the terminal 235 . the optical device and the bond - surface are prepared . the lower surface of the optical component 250 has been provided with a plurality of stand - off bumps 410 , which may comprise electrical contacts e . g . gold - stud - bumps and / or mechanical stand - offs . on the flexible substrate a fast curing glue ( e . g . photosensitive glue ) for the mechanical fixation is deposited . to reduce the impact of potential spill - over of this mechanical glue over the optical interface , an optically transparent glue is preferable . the contact material for the electrical contacts ( e . g . conductive epoxy ) is deposited by e . g . stencil printing . as shown , an electrically conductive glue 420 has been applied to the substrate 230 , in electrical contact with conductive tracks embedded in said substrate or disposed on the surface thereof . still further , an optically curable glue 430 has been applied to the substrate 230 and / or preferably to the reinforcing layer 232 . in fig4 b , the optical component 250 has been brought into contact with the substrate , or more precisely certain stand - off pumps 410 mounted the optical component 250 have been brought into contact with the substrate , thereby spacing the optical component itself at a precisely controlled distance from the terminal 235 . certain stand - off bumps 410 are in contact with optically curable glue 430 , and others are in contact with the electrically conductive glue 420 , so that certain stand - off bumps also form part of the electrical contact between the optical component 250 and the substrate 230 . at this stage the glues are cured . by exposure to suitable radiation such as ultra - violet light in the case of optically curable glues , or by exposure to heat in the case of thermally cured glues , or otherwise as appropriate . the optical component is now physically secured to the substrate , and the bond head 260 may withdrawn as described above . in fig4 c , an optical underfill 440 is injected between the electro - optical component 250 and the terminal 235 , in the cavity created by the stand - off bumps 410 . the optical underfill 440 is then cured . once cured , the optical underfill optically couples the optical component and the terminal 235 , and is thus preferably selected to have suitable transparency and refractive properties to ensure proper transmission of optical signals once cured . thus with respect to mechanical coupling , there are accordingly provided steps of applying a glue to the flexible portion in the vicinity of the terminal , wherein the step of placing the electro - optical component comprises bringing the electro - optical component into contact with the glue , and wherein in the step of coupling the electro - optical component to the terminal comprises the further step of physically securing the electro - optical component to the terminal by curing the glue . the glue is preferably substantially transparent , so that in the event of a spill of glue into the vicinity of the terminal , the glue will present a minimal interference to correct signal transmission . the glue is preferably optically curable , since this permits excellent control of the timing of the curing process , without exposing assembly to undesirable thermal or chemical environments . thus with respect to electrical coupling , there are accordingly provided steps of providing an interface surface of the electro - optical component with a plurality of stand - off bumps , and of applying an electrically conductive glue to the flexible portion in electrical connection with the terminal , wherein the step of placing the electro - optical component comprises bringing at least one of the stand - off bumps into contact with the electrically conductive glue , and wherein in the step of coupling the electro - optical component to the terminal comprises the further step of electrically connecting the electro - optical component to the terminal by curing the glue . the glue may be a solder , in which case a reflow or other processing method may be appropriate . this step need not be performed on the flip - chip bonder because mechanically the device may already be secured mechanically by the mechanical glue . thus with respect to optical coupling , there are accordingly provided steps of injecting and subsequent curing an optical underfill between the electro - optical component and the terminal . another approach to establishing electrical coupling may comprises the further steps of bringing at least one of the contacts in close proximity to a corresponding electrical contact on the terminal and depositing an electrically conductive material such as a conductive ink . the deposition of electrically conductive ink may advantageously be achieved by inkjet - printing . there may optionally be provided cleaning steps . these steps may advantageously be implemented after the mechanical securing of the optical component 250 to the substrate 230 , and before the optical interface is sealed by applying an optically transparent underfill material , which also further improves the mechanical attachment / stability . fig5 shows an expanded view of the elements of the optical assembly at the interface between the optical component 250 and the substrate 230 . in particular , the free end of the flexible portion 234 is shown in the installation configuration , together with the reinforcing part 232 . fig5 further shows the waveguide 400 , and the terminal 235 . in fig5 a , the optical component 250 has not yet been brought into contact with the terminal 235 . the optical device and the bond - surface are prepared . the lower surface of the optical component 250 has been provided with electrical conductor contacts 540 . the contact material for the electrical contacts ( e . g . conductive epoxy ) is deposited by e . g . stencil printing . the upper surface of the flexible substrate 230 has similarly been provided with electrical conductor contacts 520 . the contact material for the electrical contacts ( e . g . conductive epoxy ) are again deposited by e . g . stencils printing . on the flexible substrate a fast curing glue 530 ( e . g . photosensitive glue ) for the mechanical fixation is deposited . since this glue also fulfils the role of optical coupling agent , this material must also have suitable optical properties once cured . the fast curing glue may equally be provided either on the optical device or on the substrate or on both . in fig5 b , the optical component 250 has been brought to a precisely controlled distance from the terminal 235 , with the glue 530 sandwiched between the substrate and the optical component so as to substantially fill all of the space between the two elements . in fact it is only necessary that contact is made , and that a maximum distance , for example smaller than ˜ 50 microns ), is preferably not exceeded . the electrical contacts 540 and 520 are in close proximity , but may be separated by a bead of glue 530 squeezed from between the substrate and the optical component . at this stage the glues are cured , by exposure to suitable radiation such as ultra - violet light in the case of optically curable glues , or by exposure to heat in the case of thermally cured glues , or otherwise as appropriate . the optical component is now physically secured to the substrate , and the bond head 260 may be withdrawn as described above . the bead of glue 530 squeezed from between the substrate and the optical component may be excised by means of a laser or otherwise , so as to leave the electrical contacts 540 and 520 separated by a mere film of glue . in fig5 c , a connecting film of conductive ink or other electrically conductive material 550 is printed for example by means of an inkjet printer so as to brides the gap between electrical contacts 540 and 520 . fig6 shows parts of a flip - chip bonder adapted for carrying the steps of the method of fig3 . as shown , the flip - chip bonder comprises a bond head 260 comprising channels 261 as described above , and a lower clamp element 240 . the flip - chip bonder further comprises an x - y stage 610 , and an upper clamping element 620 . the x - y stage is moveable such that a planar substrate mounted thereon can be positioned in the x - y plane with respect to the other components , and is provide with an aperture for the passage of a lower clamp element 240 . an optional upper clamp element is articulated so as to move inward the other components being articulated so as to engage the surface of a substrate mounted on the x - y stage , that by trapping the substrate between the upper and lower clamp elements at least a part of a flexible portion deformation of the substrate may be arranged in an installation configuration with the terminal of the waveguide oriented away from the substrate so as to expose the terminal for installation of the optical component , whereupon the bond head 260 is adapted to descend in the z axis to bring an optical component into contact with the substrate . by withdrawing the bond head and upper and lower clamp elements , the flexible portion is allowed to resume its original configuration . the flip - chip bonder may additionally be provided with means for the injection or placement of glues or solders for coupling of the optical component to the substrate . the flip - chip bonder may additionally be provided with means for the curing of glues used in the coupling of the optical component to the substrate , such as ultra - violet lamps or heaters . as described above , a single optical assembly is formed from a given substrate , by coupling a single optical component thereto . it will be appreciated that a given assembly comprise a plurality of optical components , in which case a corresponding plurality of bond heads , or a specially adapted composite bond head , or a single bond head controlled so as to sequentially place each of the plurality of optical components will be required . it will furthermore be appreciated that a plurality of assemblies may be formed on the same substrate , for later separation , thereby making better use of the relatively large range of travel of the x - y stage . as shown in fig7 there is provided a substrate 730 bearing eight cut - out tongue portions 731 to 738 , ready for installation of optical components as described above . the eight cut - out tongue portions 731 to 738 are arranged in a 2 × 4 matrix . the x - y stage of the flip - chip bonder would preferably be adapted to mirror this configuration , in particular by being sufficiently large to support the entire substrate , and providing an aperture corresponding to each assembly for the passage of the lower clamp element 240 as described above . such a “ panel level assembly ” promises to be more efficient and allows for a higher assembly throughput . still further , the substrate of fig7 may constitute a continuous web . by further adaptations to the flip - chip bonder it is then possible to produce optical assemblies in a continuous process , rather than the batch process described heretofore . fig8 shows a flip - chip bonder adapted for continuous processing . the flexible waveguide is processed in sequence in different process stations . a continuous reel of flexible substrate 861 is provided . in the place of the x - y stage there is provided a conveyor belt 869 , which is provided with regularly spaced aperture for the passage of the lower clamp element 240 . material is drawn from this reel 861 through the various stages of the adapted flip - chip - bonder to produce complete a continuous stream of complete optical assemblies at the output . on leaving the reel , a particular section of substrate material first passes dispensing steps 863 and 862 which in accordance with the foregoing embodiments dispense optical glue for mechanical attachment and optical coupling and electrically conductive glue such as epoxy , respectively . the substrate material next arrives between the bond head 260 and the lower clamp 240 , whereupon the optical component is positioned and coupled as described above . a flash curing station 865 radiates the assembly with a suitable ( ultra - violet ) radiation to cure optically curable glues etc . as appropriate . the assembly is moved on to a further optical sealing polymer dispenser 866 which dispenses optical underfilling on the case of mechanical stand - offs in accordance with foregoing embodiments , and then cut from the continuous substrate web to form an individual assembly by cutter unit 867 . the assembly then passes through an oven 868 for thermal curing of thermally activated glues as appropriate , in particular for the applied optical polymer dispensed by dispenser 866 as well as any other curable glues , e . g . uv curable glues , to which no uv could be applied because they were masked by the components themselves at the earlier step . this approach makes it possible to manufacture flexible cables of any given length bearing optical and opto / electrical conversions at either ends of the cable . optical waveguide can be produced of pre - configured customised lengths onto a flexible tape or reel this approach can be highly efficient , since the rough - alignment requirements ( i . e . through the part - feeder ) is not very high and the fine - adjustments is done by the flip - chip bonder , which have usually usable path lengths in the order of 25 mm . by using butt - coupling as described above with regard to the second embodiment , directly to the waveguides with minimum distance between the optical components and the waveguides , it is very likely that the alignment accuracy can be relaxed from ˜ 5 μm to somewhere between 10 to 20 cm . according to further embodiments , a flip - chip bonder is used to mount optical components including electro - optical components a flexible substrate bearing waveguides by bending a part of the substrate out of its plane so as to expose the waveguide terminals , positioning the optical component on the exposed terminal , bonding it in place and then allowing the substrate to return to its plane . to facilitate this approach the flip - chip bonder may be adapted to incorporate one or more clamp elements to deform the substrate in the appropriate manner to correctly expose and position the terminal . the bonder x - y stage may be provided with an aperture to allow the passage of such clamp elements . a continuous reel process is also provided , capable of producing substrates or cables of any arbitrary length with optical components mounted at either end . the invention can take the form of an entirely hardware embodiment , as embodied in the flip - chip bonder , an entirely software embodiment as embodied for example in software controlling the flip - chip bonder , or an embodiment containing both hardware and software elements . in a preferred embodiment , the invention is implemented in software , which includes but is not limited to firmware , resident software , microcode , etc . furthermore , the invention can take the form of a computer program product accessible from a computer - usable or computer - readable medium providing program code for use by or in connection with a computer or any instruction execution system . for the purposes of this description , a computer - usable or computer readable medium can be any apparatus that can contain , store , communicate , propagate , or transport the program for use by or in connection with the instruction execution system , apparatus , or device . the medium can be an electronic , magnetic , optical , electromagnetic , infrared , or semiconductor system ( or apparatus or device ) or a propagation medium . examples of a computer - readable medium include a semiconductor or solid state memory , magnetic tape , a removable computer diskette , a random access memory ( ram ), a read - only memory ( rom ), a rigid magnetic disk and an optical disk . current examples of optical disks include compact disk - read only memory ( cd - rom ), compact disk - read / write ( cd - r / w ) and dvd . accordingly there is provided a computer program comprising instructions for controlling a flip - chip bonder so as to install an optical component in an optical assembly , said assembly comprising : a planar substrate - comprising a waveguide portion through which a waveguide extends , said waveguide portion . comprising a flexible portion such that by deformation of at least a part of the flexible portion , the substrate may be arranged in an operational configuration with a terminal of the waveguide oriented within the plane so as to interface an installed optical component in operation , and an installation configuration with the terminal of the waveguide oriented away from the substrate so as to expose the terminal for installation of the optical component , said computer program causing said flip - chip bonder suitably coupled to a computer executing said program to implement the steps of : placing the electro - optical component on the waveguide component by means of a flip - chip bonder so as to abut the terminal ; the computer may of course be embedded in the flip - chip , bonder , or be a stand alone computer coupled to the flip - chip bonder by any appropriate means , for example via an ethernet or wireless network connection , usb , bluetooth etc as appropriate . a data processing system suitable for storing and / or executing program code will include at least one processor coupled directly or indirectly to memory elements through a system bus . the memory elements can include local memory employed during actual execution of the program code , bulk storage , and cache memories which provide temporary storage of at least some program code in order to reduce the number of times code must be retrieved from bulk storage during execution . input / output or i / o devices ( including but not limited to keyboards , displays , pointing devices , etc .) can be coupled to the system either directly or through intervening i / o controllers . network adapters may also be coupled to the system to enable the data processing system to become coupled to other data processing systems or remote printers or storage devices through intervening private or public networks . modems , cable modem and ethernet cards are just a few of the currently available types of network adapters . the flowchart and block diagrams in the figures illustrate the architecture , functionality , and operation of possible implementations of systems , methods and computer program products according to various embodiments of the present invention . in this regard , each block in the flowchart or block diagrams may represent a module , segment , or portion of code , which comprises one or more executable instructions for implementing the specified logical function ( s ). it should also be noted that , in some alternative implementations , the functions noted in the block may occur out of the order noted in the figures . for example , two blocks shown in succession may , in fact , be implemented substantially concurrently , or the blocks may sometimes be implemented in the reverse order , depending upon the functionality involved . it will also be noted that each block of the block diagrams and / or flowchart illustration , and combinations of blocks in the block diagrams and / or flowchart illustration , can be implemented by special purpose hardware - based systems that perform the specified functions or acts , or combinations of special purpose hardware and computer instructions . while particular embodiments of the present invention have been shown and described , it will be obvious to those skilled in the art that based upon the teachings herein , that changes and modifications may be made without departing from this invention and its broader aspects . therefore , the appended claims are to encompass within their scope all such changes and modifications as are within the true sprit and scope of this invention . furthermore , it is to be understood that the invention is solely defined by the appended claims . it will be understood by those with skill in the art that if a specific number of an introduced claim element is intended , such intent will be explicitly recited in the claim , and in the absence of such recitation no such limitation is present . for non - limiting example , as an aid to understanding , the following appended claims contain usage of the introductory phrases “ at least one ” and “ one or more ” to introduce claim elements . however , the use of such phrases should not be construed to imply that the introduction of a claim element by the indefinite articles “ a ” or “ an ” limits any particular claim containing such introduced claim element to inventions containing only one such element , even when the same claim includes the introductory phrases “ one or more ” or “ at least one ” and indefinite articles such as “ a ” or “ an ”; the same holds true for the use in the claims of definite articles .
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it is noted that in the accompanying drawings , only main facilities are shown and accessory facilities are omitted . in the drawings , tanks , bulbs , pumps , blowers and heat exchangers are provided as required . further , two turbines are usually provided in pairs as each of a low pressure turbine , a medium pressure turbine and a high pressure turbine , but each pair of the turbines is also represented by a single reference numeral . as shown in fig1 , the carbon dioxide recovery type power generation system according to the present invention comprises a boiler 1 having a reheating unit 5 , a high pressure turbine 3 which is driven by steam of the boiler 1 , a medium pressure turbine 7 which is driven by steam discharged from the high pressure turbine 3 and heated by the reheating unit 5 , a low pressure turbine 8 which is driven by steam discharged from the medium pressure turbine 7 , and a generator 13 which generates electric power by the rotation of these turbines . the exhaust side of the low pressure turbine 8 is connected to the boiler 1 via a line 11 provided with a condenser 10 which condenses the exhaust , and an overhead condenser 25 which effects heat exchange between condensed water and recovered co 2 , in this sequence . further , on the combustion exhaust gas outlet side of the boiler 1 , a blasting blower 14 which pressurizes of a combustion exhaust gas , a cooler 15 which cools the combustion exhaust gas , and a co 2 absorption tower 18 which is filled with co 2 absorption liquid for absorbing and removing co 2 from the combustion exhaust gas are successively arranged in this sequence from the side of the boiler . it is noted that as the co 2 absorption liquid , an alkanolamine such as , for example , monoethanolamine , diethanolamine , triethanolamine , methyldiethanolamine , diisopropanolamine , diglycolamine , is preferred , and an aqueous solution of one of these compositions or an aqueous solution obtained by mixing two or more of these compositions can be used . the co 2 absorption tower 18 is installed in combination with a regeneration tower 24 which regenerates the loaded adsorption liquid with co 2 absorbed therein . these towers are connected by a line 20 which supplies the loaded absorption liquid to the regeneration tower 24 , and by a line 19 which supplies a reproduced adsorption liquid to the co 2 absorption tower 18 . a rich / lean solvent heat exchanger 23 which effects heat exchange between the line 20 and the line 19 is provided for the line 20 and the line 19 . further , a lean solvent cooler 33 which further cools the regenerated adsorption liquid is provided for the line 19 between the co 2 absorption tower 18 and the heat exchanger 23 . in the regeneration tower 24 , as shown in fig2 , a nozzle 56 for spraying the loaded adsorption liquid downward from the line 20 is provided . underneath the nozzle 56 , a lower filling section 52 filled with a filler is provided in order to make the sprayed loaded adsorption liquid easily brought into contact with steam . further , above the nozzle 56 , an upper filling section 51 filled with a filler is provided in order to remove adsorption liquid steam and mist . a first reboiler 41 for heating the loaded absorption liquid is provided for a bottom part of the regeneration tower 24 . the first reboiler 41 and the regeneration tower 24 are connected by a line 47 , which leads the loaded adsorption liquid stored in the tower bottom part to be heated by the first reboiler and then returns the heated absorption liquid again to the tower bottom part . further , the first reboiler 41 and the low pressure turbine 8 are connected by a line 44 which supplies steam extracted from the low pressure turbine 8 as a heating source of the first reboiler 41 . further , in the regeneration tower 24 , a liquid storage section 61 for storing the loaded adsorption liquid which flows down is provided between the nozzle 56 and the tower bottom part . thus , the lower filling section 52 is vertically divided into two parts which are positioned above and below the liquid storage section 61 . further , a second reboiler 42 for heating the loaded adsorption liquid is provided for a preceding stage of the first reboiler 41 . the second reboiler 42 and the regeneration tower 24 is connected by a line 48 , which leads the loaded adsorption liquid stored in the liquid storage section 61 to be heated by the second reboiler and then returns to the lower part of the liquid storage section 61 . further , the second reboiler 42 and the low pressure turbine 8 are connected by a line 45 which supplies , as a heating source of the second reboiler 42 , steam with a pressure lower than the pressure of the steam which is extracted to be supplied to the first reboiler 41 . it is noted that a nozzle 58 for spraying the heated loaded adsorption liquid downward is provided for the line 48 . further , a vent hole 62 for allowing co 2 gas ascending from the lower part of the tower to pass upward is provided for the liquid storage section 61 . above the vent hole 62 , there is provided a top plate 63 for preventing the loaded adsorption liquid , which flows down from the upper part of the tower , from passing to the lower part of the tower . further , a line 28 is provided for the co 2 gas outlet side of the tower top part of the regeneration tower 24 , the line 28 being successively provided with an overhead condenser 25 for effecting heat exchange between co 2 gas and condensed water , an overhead cooler 26 for cooling co 2 gas , and a separator 27 for separating water content from co 2 gas , in this sequence . in addition , a line 30 which supplies the water separated by the separator 27 again to the tower top part of the regeneration tower 24 is provided for the separator 27 . a nozzle 57 for spraying the reflux water downward is provided for the line 30 . with the above configuration , steam which is generated and heated to a high pressure and a high temperature ( of about 250 kg / cm 2 g , about 600 ° c .) by the boiler 1 is introduced into the high pressure turbine 3 via a line 2 to drive the high pressure turbine 3 . steam ( of about 40 kg / cm 2 g , about 300 ° c .) discharged from the high pressure turbine via a line 4 is heated by the reheating unit 5 in the boiler 1 . the steam discharged from the high pressure turbine which is reheated ( to about 600 ° c . ), is introduced into the intermediate pressure turbine 7 via a line 6 , to drive the medium pressure turbine 7 . steam ( of about 10 kg / cm 2 g ) discharged from the intermediate pressure turbine is introduced into the low pressure turbine 8 via a line 9 to drive the low pressure turbine 8 . in this way , the turbines are driven to enable the generator 13 to generate electric power . further , a part of the steam is extracted from the low pressure turbine and supplied via the line 44 to the first reboiler 41 provided for the tower bottom part . further , a part of steam with a pressure lower than the pressure of the steam supplied to the first reboiler is extracted from the low pressure turbine and supplied to the second reboiler 42 via the line 45 . the two kinds of extracted steam are respectively used to heat the loaded absorption liquid in the first reboiler 41 and the second reboiler 42 , so as to be condensed . further , the two kinds of extracted steam are pressurized by a reboiler condensate pump 32 , and then mixed with boiler feed water of the line 11 . thereby , the boiler feed water is heated up and transferred to the boiler 1 . here , the steam which is extracted to be supplied to the first reboiler 41 provided for the tower bottom part , preferably has a temperature which makes it possible to remove almost all co 2 from the loaded absorption liquid to regenerate the absorption liquid , and which for example preferably ranges from 130 to 160 ° c ., although the temperature may be different depending upon the kinds of co 2 absorption liquid . it is noted that the absolute pressure of the steam corresponding to this temperature ranges from 2 . 75 to 6 . 31 ata . further , the steam which is extracted to be supplied to the second reboiler 42 preferably has a temperature lower than the above described temperature , that is , an absolute pressure lower than the above described absolute pressure , in order to heat the loaded absorption liquid in stages . it is noted that when supplied into the regeneration tower 24 , the loaded absorption liquid is depressurized to release a part of co 2 and cooled ( for example , by a temperature about 20 ° c .). therefore , the lower limit value of the steam is preferably set to a temperature which makes it possible to effect heat exchange with the absorption liquid with the temperature when it is introduced into the tower ( for example , a temperature higher by about 10 ° c . compared with the temperature of the absorption liquid after it is introduced into the tower , or a temperature lower by about 10 ° c . compared with the temperature of the absorption liquid when it is supplied to the tower ), that is , preferably set to an absolute pressure corresponding to the steam temperature . the exhaust ( of about 0 . 05 ata , about 33 ° c .) of the low pressure turbine 8 is introduced into the condenser 10 via the line 11 and condensed . a boiler feed pump 12 makes the condensed water preheated through the overhead condenser 25 and then transferred to the boiler 1 as the boiler feed water . on the other hand , the boiler combustion exhaust gas containing co 2 discharged from the boiler 1 is first pressurized by the blasting blower 14 , and then transferred to the cooler 15 so as to be cooled by cooling water 16 . the cooled combustion exhaust gas is transferred to the co 2 absorption tower 18 , and cooling wastewater 17 is discharged to the outside of the system . in the co 2 absorption tower 18 , the combustion exhaust gas is brought into contact in counterflow with co 2 absorption liquid based on the alkanolamine , so that co 2 in the combustion exhaust gas is absorbed by the co 2 absorption liquid through a chemical reaction . the combustion exhaust gas 21 with co 2 removed therefrom is discharged from the tower top part to the outside of the system . the loaded absorption liquid ( rich absorption liquid ) with co 2 absorbed therein is pressurized by a rich solvent pump 22 via the line 20 connected to the tower bottom part , and heated by the rich / lean solvent heat exchanger 23 , and thereafter is supplied to the regeneration tower 24 . in the regeneration tower 24 , the loaded absorption liquid is sprayed from the nozzle 56 , and flows downward through the lower filling section 52 b so as to be stored in the liquid storage section 61 . then , the loaded absorption liquid in the liquid storage section 61 is extracted by the line 48 , and heated by the low pressure steam of the line 45 in the second reboiler 42 , and thereafter returned again to the regeneration tower 24 . the loaded absorption liquid thus heated is sprayed by the nozzle 58 , and a co 2 gas partially separated from the absorption liquid by the heating operation ascends upward in the tower as shown by a dotted line in fig2 , while the loaded absorption liquid still containing co 2 flows down in the tower . further , the loaded absorption liquid , which passes through the lower filling section 52 a and is stored in the tower bottom part , is extracted by the line 47 to be heated by the higher pressure steam of the line 44 in the first reboiler 41 , and thereafter is returned again to the tower bottom part . the residual co 2 is almost separated from the absorption liquid by this heating operation in the first reboiler 41 of the tower bottom part . the separated co 2 gas ascends in the tower in the same way as described above . the co 2 gas which ascends in the tower is discharged from the tower top part of the regeneration tower 24 . the discharged co 2 gas passes through the line 28 , to preheat the boiler feed water of the line 11 in the overhead condenser 25 , and is further cooled by the overhead cooler 26 . thereby , the water content in the co 2 gas is condensed . the condensed water is removed by the separator 27 . the high purity co 2 gas with water content removed therefrom is discharged to the outside of the power generation system , so as to be able to be used effectively for other applications . further , the condensed water separated by the separator 27 is refluxed by a condensed water circulation pump 29 into the regeneration tower 24 through the line 30 . the reflux water is sprayed by the nozzle 57 to wash co 2 gas ascending through the upper filling section 51 , thereby making it possible to prevent the amine compound contained in the co 2 gas from being discharged from the tower top part . on the other hand , almost all co 2 is separated from the loaded absorption liquid by the heating operation in the first reboiler of the tower bottom part , so that the absorption liquid is regenerated . the regenerated absorption liquid ( lean absorption liquid ) is extracted by the line 19 , and pressurized by a lean solvent pump 31 . then , the regenerated absorption liquid is cooled by the loaded absorption liquid in the rich / lean solvent heat exchanger 23 and is further cooled by the lean solvent cooler 33 so as subsequently to be supplied to the co 2 absorption tower 18 . thus , the co 2 absorption liquid can be used in circulation in the power generation system . in this way , high pressure steam is extracted from the low pressure turbine 8 as a heating source of the first reboiler 41 of the tower bottom part , and steam with a pressure lower than the pressure of the high pressure steam is extracted from the low pressure turbine 8 as a heating source of the second reboiler 42 between the nozzle 56 and the tower bottom part , as a result of which the loaded absorption liquid can be heated in stages by the steam extracted in the two stages . thus , instead of a part of the high pressure steam extracted from the low pressure turbine 8 , which part is to be supplied to the first reboiler 41 of the tower bottom part , steam with a lower pressure can be extracted from the low pressure turbine 8 , as a result of which output decrease of the low pressure turbine 8 can be suppressed as a whole and power generation output of the generator 13 can be improved . it is noted that in fig1 and fig2 , the reboiler is constituted in two stages by providing the second reboiler 42 between the nozzle 56 and the tower bottom part so as to extract steam from the low pressure turbine 8 in two stages . however , the reboiler provided for the regeneration tower 24 may be constituted in three or more stages to extract steam from the low pressure turbine 8 in three or more stages . in this case , the line which supplies the extracted steam to the reboiler is connected so as to make the pressure of supplied steam increased from the reboiler in the preceding stage of the regeneration tower 24 ( the tower top part side ) to the reboiler in the post stage of the regeneration tower 24 ( the tower bottom part side ). for example , as shown in fig3 , a liquid storage section 66 , a vent hole 67 and a top plate 68 are additionally provided between the nozzle 56 and the liquid storage section 61 , and a third reboiler 43 is also provided in the preceding stage of the second reboiler 42 , so that steam with a pressure further lower than the pressure of the steam supplied to the second reboiler 42 is extracted from the low pressure turbine 8 and is supplied to the third reboiler 43 via a line 46 . thereby , the loaded absorption liquid in the added liquid storage section 66 is heated by the third reboiler 43 via a line 49 . as a result , the loaded absorption liquid in the regeneration tower 24 can be heated in more stages . therefore , instead of a part of the high pressure steam supplied to the first reboiler 41 and the second reboiler 42 , the steam with further lower pressure is extracted from the low pressure turbine 8 , so that output decrease of the low pressure turbine 8 can be further suppressed . a rich absorption liquid with co 2 absorbed therein is regenerated by using a steam system consisting of the regeneration tower and the low pressure turbine shown in fig3 . the result is shown in table 1 . further , a result of the case where the steam system consisting of the conventional regeneration tower and the low pressure turbine shown in fig4 is used , is also shown in table 1 as a comparison example . as shown in table 1 , in the conventional system , it is necessary to supply high pressure steam of 3 . 6 ata to the reboiler of the tower bottom part at a rate of 417 ton / h , in order to make the rich absorption liquid of a predetermined amount heated to 120 ° c . and regenerated . as a result , the output of the low pressure turbine from which the steam is extracted , is lowered by 76 , 330 kw . on the other hand , in the system according to the present invention shown in fig3 , steam with a lower pressure of 2 . 73 ata and steam with a lower pressure of 3 . 16 ata are supplied to the third reboiler and the second reboiler at a rate of 107 ton / h and at a rate of 138 ton / h , respectively , so that even when the rate of the high pressure steam of 3 . 6 ata supplied to the first reboiler of the tower bottom part is reduced to 174 ton / h , the rich absorption liquid can be regenerated similarly to the conventional system . therefore , the total amount of heat supplied to the first to third reboilers is approximately equal to the amount of heat supplied to the reboiler of the tower bottom part in the conventional system , but the output of the low pressure turbine is lowered only by 73 , 756 kw . as a result , the turbine output can be improved by about 3 . 4 % in comparison with the conventional system .
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a device 1 for injecting fuel which is under high pressure is described in greater detail below with reference to fig1 . as is apparent in fig1 , device 1 includes an electrodynamic actuator 30 , a needle 2 , and a fuel supply line 19 . a fuel under high pressure is supplied to device 1 via fuel supply line 19 . electrodynamic actuator 30 includes a first permanent magnet 4 , a second permanent magnet 6 , a spacer disk 5 , a movable coil 7 , and a casing 8 . spacer disk 5 is made of a magnetically conductive material , and is situated between first permanent magnet 4 and second permanent magnet 6 . movably situated coil 7 is situated at the outer periphery of first and second permanent magnets 4 , 6 and of spacer disk 5 . casing 8 is likewise made of a magnetically conductive material , and encloses coil 7 at the periphery as well as the two end faces of first permanent magnet 4 and second permanent magnet 6 in axial direction x - x . the two permanent magnets 4 , 6 are situated in such a way that the same poles face spacer disk 5 . permanent magnets 4 , 6 thus form a magnetic field over spacer disk 5 which extends radially outwardly toward casing 8 . when coil 7 is then supplied with current , coil 7 experiences a lorentz force which , depending on the current direction , acts in an opening or a closing direction of the needle ( i . e ., in axial direction x - x ). this causes coil 7 to move in the appropriate direction in each case . device 1 also includes a closing spring 3 which exerts a closing force on needle 2 . for this purpose , a spring washer 13 on which closing spring 3 is supported at one end is fastened to needle 2 . the other end of closing spring 3 is supported on a housing component 14 a . in addition , a pinhole disk 11 is fastened to needle 2 , at an end of needle 2 remote from spray holes 18 . spray holes 18 are provided in housing 14 and oriented at a predetermined angle with respect to axial direction x - x . movable coil 7 is connected to needle 2 via a connecting device 9 . connecting device 9 includes multiple fingers 10 which engage in openings 11 a in pinhole disk 11 . in addition , a tube 12 is provided which is guided through electrodynamic actuator 30 . tube 12 is used for conducting fuel from fuel supply line 19 . the fuel is led into a fuel chamber 16 , flowing between fingers 10 of connecting device 9 . this is indicated by arrows b in fig1 . arrow a characterizes the flow direction of the fuel into fuel supply line 19 . a rear portion of needle 2 as well as closing spring 3 are situated in fuel chamber 16 . in addition , an annular pressure chamber 15 is provided upstream from spray holes 18 . pressure chamber 15 is connected to fuel chamber 16 via a supply line channel 17 . thus , when needle 2 is opened , as indicated by arrow d in fig1 , fuel is able to flow from fuel chamber 16 into supply line channel 17 , as indicated by arrow c , and from there flows to pressure chamber 15 . device 1 according to the present invention functions as follows . fuel which is already under pressure is supplied , as indicated by arrow a , for fuel supply line 19 , and tube 12 is supplied to fuel chamber 16 . a connection to annular pressure chamber 15 is provided in fuel chamber 16 via supply line channel 17 . electrodynamic actuator 30 is activated if fuel is to be injected . for this purpose , coil 7 is supplied with current in such a way that the coil moves , as indicated by arrow e . thus , needle 2 also moves in the direction of arrow d , via connecting device 9 and fingers 10 . this causes needle 2 to be lifted off from valve seat 2 a , thus opening spray holes 18 and allowing fuel to be injected from the spray holes into a combustion chamber or an intake manifold . closing spring 3 is compressed by the motion of needle 2 . to conclude the injection , the current direction at movable coil 7 is reversed , causing the coil to move in the opposite direction . active closing of needle 2 is thus achieved , with the assistance of tensioned closing spring 3 in the closing operation . needle 2 is thus actively closed as a result of the fixed connection between movable coil 7 and needle 2 . the injection of fuel is thus concluded . according to the present invention , for an inwardly opening valve , needle 2 may thus be actively opened and closed , using an electrodynamic actuator 30 , by reversing the current direction at a movable coil 7 . very brief closing times may be achieved which are significantly shorter than closing times for electromagnetic actuators , for example . this is achieved with a compact design of device 1 as well as very cost - effective manufacturability of device 1 . by providing a plurality of spray holes 18 , large quantities of fuel may be injected , even with short opening times . in particular , a spray with very good distribution may thus be achieved . further preferred exemplary embodiments of the present invention are described in greater detail below with reference to fig2 and 3 . identical or functionally equivalent parts are denoted by the same reference numerals as in the first exemplary embodiment . fig2 shows a device 1 according to a second exemplary embodiment , except that , in contrast to the first exemplary embodiment , in the second exemplary embodiment the fuel is supplied to annular pressure chamber 15 via a central needle hole 21 and a transverse hole 22 . thus , fuel may be conducted through entire device 1 to annular pressure chamber 15 without large pressure losses . electrodynamic actuator 30 is centered over housing region 14 a on which tube 12 is supported , electrodynamic actuator 30 being fixed to tube 12 . fig3 shows a device 1 according to a third exemplary embodiment which essentially corresponds to the second exemplary embodiment . in contrast to the second exemplary embodiment , in the third exemplary embodiment no fuel chamber 16 is present . the fuel is conducted in the axial direction by fuel supply line 19 , through tube 12 and central through hole 21 as well as transverse holes 23 , to annular pressure chamber 15 . closing spring 3 is situated in tube 12 . in addition , tube 12 has a guide section 12 a , at the end facing needle 2 , on which needle 2 is guided . tube 12 itself is centered over a base region 8 a of casing 8 . a further transverse hole 22 also provided in needle 2 establishes a connection to a second pressure chamber 24 . this connecting hole 22 thus ensures that electrodynamic actuator 30 itself is situated in the fuel . as the result of using electrodynamic actuator 30 , device 1 described in the exemplary embodiments thus has characteristics which very closely approximate the characteristics of piezoelectric actuators . named in particular are a very short switching time and multiple injections during a cycle . devices 1 according to the present invention are nevertheless very compact and cost - effective .
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in order that the invention may be fully understood , preferred embodiments thereof will now be described with reference to the accompanying drawings . the present invention comprises the random id code generation and circle path authentication . a random id code is generated at one point of a close circle of the transaction communication . the rid can travel through one direction and return to the original point in the circle or travel from two directions and meet at one point in the circle . at this point , the rids will be checked against each other . the two rids should be exactly the same . fig1 is the illustration of the network of system embodying the preferred embodiment of the present invention . fig1 shows the mobile terminal 100 , mobile wireless network 200 , user &# 39 ; s account server 300 , terminal 400 , terminal transaction server 500 , wire or wireless network 600 between 300 and 500 . fig1 also shows the path of the rid , which is generated in the account server , passed through a circle and sent back to the original account server . fig2 is a block diagram of the user account server 300 of fig1 . the account server consists a network interface 310 to the mobile wireless network 200 to communicate with the mobile terminal , a network interface 320 to the network 500 to communicate with transaction server , a random id generator 330 , a database 340 containing subscribed user account information , subscribed terminal account information , transaction records and all pending transaction and their rid , a module to verify the terminal &# 39 ; s account 340 when the terminal did not subscribed to it , a module to track and match all pending transactions &# 39 ; rid 350 . fig3 is a functionality block diagram of the transaction terminal 400 and the transaction server 500 . the terminal server consists of an interface between the transaction terminal and transaction server 510 , a network interface that communicates with the users &# 39 ; account server 520 ; a transaction request module 530 to pack the terminal account information , action request , and the user &# 39 ; s account information and send to the user account server , a module to locate the user &# 39 ; s account server 540 , a database 550 which save the transaction records , account server information and the terminal information . the transaction terminal consists of an interface to the terminal server 410 , a user interface with the user or the mobile terminal 420 , which can be a keyboard , an infrared or contactless ( rfid ) smart card reader , a barcode reader , a web page , and etc . the connection between the transaction terminal and the terminal server can be a network connection , through which the transaction server could manage multiple terminals or an internal bus if they &# 39 ; re physically built in the same machine . fig4 and fig5 show the flowchart of the preferred embodiment of the present invention . referring the network configuration of fig1 and 3 , the example sequences of the id authentication or payment charge method will be explained in detail . first , a person with a mobile communication tool , such as a mobile phone , subscribes to a service provide , such as his / her wireless carrier say verizon , or a third party who &# 39 ; s going to authenticate the person or authorize an action / transaction say direct a payment through debit or credit account . the service provider for payment can be a debit / credit account issuer like mbna or an essential account verifier such as visa international . in the case of id authentication for secure access , many times a private party which holds both the user and terminal account is involved . after subscription , the mobile terminal can interface with a transaction terminal when an authentication or authorization is needed . the account number and the service provider id ( if multiple service providers are available ) are passed to the transaction terminal . there are several ways to pass this information : ( b ) a barcode which contains both the account and server information is provided to the user as a label than can be sticked on the mobile or an image that can be display on a screen , the terminal can scan the barcode to get the information ; and / or ( c ) the information is saved in the mobile phone &# 39 ; s non - volatile memory , such as flash , and then can be passed to the terminal wirelessly ( infrared or near field rf ). after the transaction terminal receives the account information , it will send them to the transaction server . the transaction server may needs to locate the service provider from a third party if it doesn &# 39 ; t have the service provider &# 39 ; s information . the transaction server sends the user account information , terminal information and the action request to the account server . the account server will verify the user &# 39 ; s account information , check the terminal &# 39 ; s credibility , and verify the feasibility of the action request . if it &# 39 ; s an access request , the server will check if the user has the right of accessing the specified the resource . if it &# 39 ; s a payment request , the server will check if the account has enough balance or credit line for paying the request amount of money . after the server verifies every thing , it will generate a random id code . this rid code is the core element of the authentication process . this rid will be sent to the mobile terminal . the account serer also sends a transaction sequence number back to the transaction server referring the current transaction request . this sequence number can also be generated by the transaction server and sent to the account server with the action requestion . to prevent mishandling of a lost mobile terminal , the account server may require the user to key in a password to retrieve the rid . the password can be either sent back to the account server or handled internally inside the mobile terminal . there are numerous ways of detecting the mobile terminal lost or personation . they are not covered in this application . when a mobile terminal is determined as lost or misused , the account server will lock the account for any further action until contacting the user for clarification . the mobile wireless network can easily find out if there &# 39 ; s a personate mobile terminal if two different base stations ( not adjacent to each other ) report the presentation of the same terminal id ( such as the phone number ). another way to detect terminal personation is to send an id request to the terminal . the terminal should response back with the correct id and a random number . this random number is generated per id request . there could be multiple responses to one id request , but the random number should be the same . if for one id request , two different random numbers were received . the network can determine there &# 39 ; s a personate terminal . after received by the mobile terminal , the rid will be passed to the transaction terminal by method discussed before ( manual key in , rf , barcode , and etc .). when the transaction server receives the rid from the transaction terminal , it will pass it back to the account server with the original transaction sequence number . the server check if the received rid is exactly the same as that sent out for this transaction . if yes , the further action will be confirmed . and the server may also check the terminal who sent back the rid is the same one who initialized this transaction . the rid code can be sent to the mobile terminal by simple text message or through other protocols . the account server can also generate a 2d barcode image based on the rid which can be displayed on the mobile phone and scanned by a terminal . in addition to the rid information , the account server can optionally send the transaction terminal / server &# 39 ; s information to the mobile terminal for review . it &# 39 ; s better not to send any sensitive information . if the account server received a wrong rid or hasn &# 39 ; t received it in a certain period , say one minute , it may deny the transaction and lock the user &# 39 ; s account . alternatively the account server may recreates a new rid and then send it through the same path . after tried a specified times and failed , the server may deny the transaction and determine the user &# 39 ; s account may be stolen . the account may be locked until contacting the user for clarification . the key innovation of the present invention is the random id generation and circle verification procedure . fig6 shows the travel path of the rid . by sending the rid code through this circle , the account server verifies both the user who carries the mobile terminal and the transaction terminal , which directly interfaces with the mobile terminal and its user . as the rid is complete random and only used once , not even for a short period time , the eavesdropping of the whole process of the transaction is totally useless . beside the account server , the transaction server can also be used for generating and verifying rid . and the rid is still being transfer through the circle . fig7 shows a possible embodiment of pending transaction records and rids in the account server . the server will use these records to keep track of all pending transaction . the transaction server can keep these records if it generates the rids . it may be simpler to generate the transaction s / n at the same place the rid is generated . fig8 shows a way of passing rid reversely . the rid is generated in the account server and then sent to the transaction server and terminal . the user &# 39 ; s mobile phone passes the rid received from the terminal to the account server for verification . fig9 shows another alternative rid passing method of sending the rid to both directions . if the account server generates the rid , the rid will be sent to the transaction server and the mobile terminal . the transaction server will perform the rid verification instead of the account server . if the transaction server generates the rid , the rid will be sent to the account server and the mobile terminal . the account server performs the rid verification . there is a way of not using rid but still taking advantage of the mobile wireless network . the account server can call the mobile terminal and prompt confirmation of the ongoing transaction . this method demands human intervening and can not be fully implemented electronically . and there is sensitive transaction and account information sending to the mobile phone . even a special design of secured link may still be vulnerable to some eavesdropping practices . it is also inconvenient and not user friendly as the user has to confirm all the detail transaction information . there may be more than two servers involving a transaction . for example , the account server may request a third party , the mobile phone &# 39 ; s wireless carrier or a security service provider , to generate , send and verify the rid and return authentication to the account server . fig1 shows an example of online credit card payment : 1 . the e - commerce server prompts the buyer to input the credit card type and credit card number . based on the credit card type , the server will send a request to the specified credit card network , say visa network . this request will be first sent to the card issuer and then to visa &# 39 ; s account server ; 2 . visa account server verify the credit number and find out the associated mobile phone number to this credit card ( the visa card issuer , say mbna , or visa itself may keep this information ). the account server send an authentication request with the user &# 39 ; s mobile phone number and a request number to the user &# 39 ; s mobile network carrier , say verizon ; 3 . the mobile account server of verizon receives the request and generates a rid and sends the user &# 39 ; s mobile phone ; 4 . this rid will be input into the e - commerce web page and sent back to the visa account server ; 5 . visa account server send the rid and original request number back to the mobile account server ; 6 . the mobile account server check if the rid received matches to the one saved for the specified request number . if match , it send a authentication message back to the visa account server ; fig8 shows a possible implementation of a pending transaction table kept in the account server database for online credit card payment . the account server retrieves the original rid by looking after this table . there could be more columns in this table ; and the credit card issuer can verify and authenticate the user account before sending information to visa &# 39 ; s account server . it will send the authentication request to the mobile phone carrier . the mobile phone carrier can itself be a credit card issuer , so the whole verification and authentication processes can be done with its account server . definition list 1 term definition random id code a code that is generated randomly as a ( rid ) identification number passed to the mobile phone rid circle the rid travel through a circle path of originate authentication server , mobile , terminal and transaction server . by going through the circle , the account server verifies the elements on the whole path . the rid can travel from one direction and return to the start point . it also can travel on two direction from one point and meet at another point on the circle . transaction user interface of the transaction server terminal transaction the server which process the transaction request server coming from the terminal and send the request to the account server . account server the server which holds the user &# 39 ; s account information and mobile phone number . mobile terminal a mobile communication tool within a mobile wireless network . one skilled in the art will understand that the embodiment of the present invention as shown in the drawings and described above is exemplary only and not intended to be limiting . it will thus be seen that the objects of the present invention have been fully and effectively accomplished . it embodiments have been shown and described for the purposes of illustrating the functional and structural principles of the present invention and is subject to change without departure from such principles . therefore , this invention includes all modifications encompassed within the spirit and scope of the following claims .
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this disclosure broadly relates to roof systems and methods of using such roof systems . various exemplary embodiments of the disclosure will now be described with particular reference to the drawings . embodiments of this disclosure may take on various modifications and alterations without departing from the spirit and scope of the disclosure . accordingly , it is to be understood that the embodiments of this disclosure are not to be limited to the following described exemplary embodiments , but is to be controlled by the limitations set forth in the claims and any equivalents thereof . an appreciation of various aspects of the invention will be gained through a discussion of the examples provided below . the following description should be read with reference to the drawings , in which like elements in different drawings are numbered in like fashion . the drawings , which are not necessarily to scale , depict selected illustrative embodiments and are not intended to limit the scope of the disclosure . although examples of construction , dimensions , and materials are illustrated for the various elements , those skilled in the art will recognize that many of the examples provided have suitable alternatives that may be utilized . unless otherwise indicated , all numbers expressing feature sizes , amounts , and physical properties used in the specification and claims are to be understood as being modified in all instances by the term “ about .” accordingly , unless indicated to the contrary , the numerical parameters set forth in the foregoing specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by those skilled in the art utilizing the teachings disclosed herein . the recitation of numerical ranges by endpoints includes all numbers subsumed within that range ( e . g . 1 to 5 includes 1 , 1 . 5 , 2 , 2 . 75 , 3 , 3 . 80 , 4 , and 5 ) and any range within that range . as used in this specification and the appended claims , the singular forms “ a ,” “ an ,” and “ the ” encompass embodiments having plural referents , unless the content clearly dictates otherwise . for example , reference to “ a layer ” encompasses embodiments having one , two or more layers . as used in this specification and the appended claims , the term “ or ” is generally employed in its sense including “ and / or ” unless the content clearly dictates otherwise . the term “ polymer ” will be understood to include polymers , copolymers ( e . g ., polymers formed using two or more different monomers ), oligomers and combinations thereof , as well as polymers , oligomers , or copolymers that can be formed in a miscible blend . additionally , the terms “ attic ” and “ unconditioned space ” are used interchangeably herein . referring to fig1 , a traditional roof 10 generally includes one or more roof portions 12 extending between a soffit 14 and a roof peak or ridge 16 . roof 10 includes a protective covering 18 , such as concrete or clay tiles or asphalt shingles , on a roof board or deck 20 that covers an unconditioned space or attic 22 . attic 22 can serve as a buffer to a living space 24 below the attic . roof 10 can include vents 26 on the soffit and also vents on the roof ( not depicted ) and / or a ridge vent 28 . referring to fig2 , the roof system 110 according embodiments of this disclosure can include one or more roof portions 112 , each having a roof board or deck 120 , a soffit 114 having a soffit duct or vent 126 ( which vent 126 can include an air router ), a roof peak or ridge 116 , and a protective covering 118 , such as concrete or clay tiles or asphalt shingles , on deck 120 . roof system 110 further includes one or more passive or active roof management components . such components can include , for example , vent open / close components 130 on the top and / or bottom of the soffit vent 126 , one or more blowers or fans 132 ( such as , for example , variable speed / high pressure fans and can be used to effect movement of air , such as the pushing and / or pulling of various air movements ), one or more ridge air routing members or air routers 134 for routing air flow in the roof system 110 ( see fig1 a - 10f ), sensors or sensing members 136 , such as , for example , moisture , temperature , heat flow , impact , fire , and carbon monoxide sensors . in embodiments , sensors 136 can be moisture , temperature , heat flow , impact , fire , and carbon monoxide sensors . those skilled in the art will recognize that other sensors can be used without departing from the spirit and scope of this disclosure . in embodiments of roof system 110 , protective covering 118 can include roof system including one or more channels 119 running partially or fully from the soffit region to or near the ridge or peak of the roof , such as that described in pct international publication no . wo 2012 / 033816 a1 , entitled “ above - deck roof venting article ” and u . s . patent application no . 61 / 579 , 297 , entitled “ above - deck roof venting article ,” both of which are incorporated herein by reference in their entirety . roof system 110 can further include one or more solar cells 138 and each of the roof system management components can , optionally , be solar - powered . air routers 134 can be or include one or more air ducts that run along , such as parallel , ridge 116 of roof system 110 . the cross section and / or shape of the ducts can vary with size and shape . the materials of air router 134 can be any of a number of materials , including , for example , lightweight , non - rusting metals and or various low - high temperature polymers , although those skilled in the art would recognize that other materials can be used . electric - actuated linear actuators can be included to create various valve ports of air router 134 . other methods of mechanical gating can be used in air router 134 are contemplated . output from software can close or open the respective gates to enable natural and or forced air flow through air router 134 . depending on climate zone location and secondary operations tied to roof system 110 , air router 134 can have multiple ports . the examples have been shown for four - way and six - way ports , although other air router 134 configurations , including more than six ports or less than four ports are contemplated . the roof system 110 of embodiments can include controls ( including , for example , hardware and / or software , not depicted ) to enable further optimization of the thermal energy management of a building and for controlling the roof system management components . for example , the temperature and relative humidity / dew point temperature of an unconditioned attic space can automatically effect air flow movement using roof system . likewise , structure ventilation could trigger air flow movements to mechanical devices or buffering heat / cold air . referring to fig3 a and 3b , in a first embodiment , radiant energy is depicted as impinging upon the right roof portion 112 of roof system 110 . positions 1 , 2 , 5 and 6 of air router 134 can be open ( see fig1 a ), which routes warmer air from both roof portions 112 of roof system 110 up to ridge 116 , such as through a channel or channels 119 included in at which point the warmer air exits . air router 134 generally extends along substantially the entire length of ridge 116 . referring to fig4 a and 4b , in a second embodiment , radiant energy is depicted as impinging upon the right roof portion 112 of roof system 110 . blower 132 on right roof portion 112 can be set to push soffit air and the blower 132 on left roof portion 112 can be set to pull warmer air . positions 2 and 5 of air router 134 can be open ( see fig1 b ). the warmer air is then routed from the warmer right roof portion to cooler left roof portion . referring to fig5 a and 5b , in a third embodiment , to transfer air to a cooler side of a roof using a below - deck solution , blower 132 on right roof portion 112 can be set to push soffit air and blower 132 on left roof portion 112 can be set to pull air . positions 2 and 4 of air router 134 can be open ( see fig1 c ). the air is then routed from the right roof portion 112 to the left roof portion 112 . the air is then pushed through channels 119 provided in or with protective covering 118 . referring to fig6 a and 6b , in a fourth embodiment , all positions of air router 134 can be closed ( see fig1 d ) and the right and left blowers 132 can be set to pull outside air using , for example , variable blower speed . this will cause air to be blown onto the roof system 110 through vents ( not depicted ) included in protective covering 118 . this configuration can be useful , for example , when it is desired to blow water , snow , or other debris ( such as leaves ) off of roof system 110 . referring to fig7 a and 7b , in a fifth embodiment , radiant energy is depicted as impinging upon the right roof portion 112 of roof system 110 . in this embodiment , positions 2 and 3 of air router 134 can be open ( see fig1 e ) the soffit ducts ( air routers ) and blowers / fans are controlled through the software for force air convection direction ( pushing or pulling ), natural convention in the soffit and attic areas , and balance system ventilation . the left and right blowers 132 can be set to re - circulate warmer air through the channel 119 included in or with the protective covering . the unconditioned space can be used as a buffer to store warm air or cool air depending on the season . referring to fig8 a and 8b , in a sixth embodiment , in a cold climate case , radiant energy is depicted as impinging upon the right roof portion 112 of roof system 110 . in this embodiment , positions 2 , 3 , 4 and 5 of air router 134 can be open ( see fig1 f ) and the soffit ducts ( air routers ) and blowers / fans are controlled through the software for force air convection direction ( pushing or pulling ), natural convention in the soffit and attic areas , and balance system ventilation . the left blower 132 can , optionally , be set to push soffit air and the right blower 132 can be set to push soffit air . new air is routed to flow into a home air make - up unit 140 and old air flows out of unit 140 . referring to fig9 a and 9b , in a seventh embodiment , in a warm climate case , radiant energy is depicted as impinging upon the right roof portion of roof . in this embodiment , positions 2 , 3 , 4 and 5 of air router 134 can be open ( see fig1 f ) and the soffit ducts ( air routers ) and blowers / fans are controlled through the software for force air convection direction ( pushing or pulling ), natural convention in the soffit and attic areas , and balance system ventilation . the left blower 132 can , optionally , be set to push soffit air and the right blower 132 can be set to push soffit air . new air is routed to flow into unit 140 and old air flows out of unit 140 . referring to fig1 a - 10f , the various air router 134 configurations are depicted schematically for each of the embodiments depicted and described with respect to fig3 - 9 . referring to fig1 a and 11b , a soffit duct ( air router ) is depicted . in a first configuration , the soffit duct can be open , by opening a first gate 140 , such as an electric - actuated “ air gate or linear actuator ,” to the channel 119 for air flow . it is depicted with open gates for natural convection in the bottom or closed gates for force convection through the respective blowers . in another embodiment , a second gate 142 , such as an electric - actuated “ side gate ,” can be open for below deck air flow management . referring to fig1 , in embodiments , a blower 144 can be located or positioned in attic 122 and in fluid ( air ) communication , such as through ductwork 146 , with air routers 134 and air gates 140 and , optionally , second air gates 142 to manage airflow by or within the roof system 10 , the environmental thermal loads of the roof system 10 , the temperature of conditioned and / or unconditioned spaces in a building , and the ventilation of the conditioned and / or unconditioned spaces in a building , such as , for example , as described above with respect to fig3 - 9 . to do so , blower 144 can be controlled to selectively push and / or pull air to or from air routers 134 and air gates 140 and , optionally , second air gates 142 — depending upon what result is desired . in embodiments , such as those depicted in fig3 - 9 and 11 , channels 119 , such as those included in above - deck protective covering , that extend up the slope of the deck mate or align with dedicated ports on air router 134 , such as the # 2 port ( right ) or # 5 port ( left ) of the air router 134 , as depicted in fig1 a - f . the embodiments of this invention should not be considered limited to the particular examples described herein , but rather should be understood to cover all aspects of the invention as fairly set out in the attached claims . various modifications , equivalent processes , as well as numerous structures to which the embodiments of this invention can be applicable will be readily apparent to those of skill in the art to which the embodiments of this invention are directed upon review of the instant specification .
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fig1 a shows a concentrator and booster assembly generally designated by the reference numeral 10 . the concentrator assembly 10 comprises a concentrator unit 15 , a pressure booster 16 , a bos storage plenum 17 , and a monitor controller 18 . the concentrator assembly 10 is coupled to one or more panel mounted regulators 19 shown in fig1 b by a plurality of pneumatic and electric lines . it will be understood by those skilled in the art that each panel mounted regulator 19 is coupled to masks ( not shown ) which deliver product gas to the crew . as shown in fig1 a , the concentrator unit 15 comprises an air inlet 21 coupled to a filter 22 and a shut - off valve and regulator 23 . a differential pressure indicator 24 is coupled to the filter 22 and to a line 25 including a control relief valve 26 , and a flow restrictor 27 . a regulator control valve 28 with a vent 29 senses the pressure in the plenum 17 as more fully described below and is coupled to the flow restrictor 27 , the control relief valve 26 , and the regulator 23 . an electrical motor 30 drives a rotary valve 31 which alternately directs air to the two beds 32 of molecular sieve material . the outlets of the beds 32 are coupled to check valves 33 and a purge line 34 including a flow restrictor 36 ; the inlets of the beds 32 are alternately coupled to a purge vent 35 by the rotary valve 31 . the check valves 33 are coupled to the concentrator outlet 37 and to a pressure switch 38 . the concentrator outlet is coupled to a two - way bos - fill solenoid valve 41 , a line 40 , a three - way self - test solenoid valve 42 in the monitor controller 18 , and a three - way product - delivery solenoid valve 43 coupled to an outlet filter 45 ( seen in fig1 b ). the bos - fill solenoid valve 41 is coupled by a line 45 to two check valves 44 which admit product gas to the compression cylinder 46 of the pressure booster 16 . a compression piston 47 in the compression cylinder 46 is coupled by a rod 48 to a larger driver piston 49 in a driver cylinder 51 . the driver cylinder 51 alternately receives air from the rotary valve 31 by means of two lines 52 and 53 , one of which includes a check valve 54 and a vent line 56 coupled to a booster control valve 57 . two outlets 58 from the compression cylinder 46 are coupled to check valves 59 and to a booster outlet 61 . a pressure tap 62 from the booster outlet 61 is coupled to the booster control valve 57 and to the regulator control valve 28 . the booster outlet 61 is coupled to the plenum 17 , to a pressure relief valve 64 through a pressure tap 63 and through a conduit 97 , to the product - delivery solenoid valve 43 , and to a pressure indicator 87 in the panel mounted regulator 19 . the monitor controller 18 includes the self - test solenoid valve 42 which is coupled to an oxygen sensor 66 through a flow restrictor 67 and is vented to ambient through an absolute pressure regulator 68 and a vent 69 . a pressure transducer 70 is coupled to the cockpit 80 by means of a pressure sensing line 71 , and an air line 72 couples the self - test solenoid valve 42 to the inlet of the rotary valve 31 . the monitor controller 18 is coupled to a power source 73 , and to a calibration check switch 75 , a built - in - test ( bit ) switch 88 , a mode selection switch 89 and an on - off switch 86 located in the cockpit 80 ( fig1 b ). the monitor controller sends signals to a warning light 93 in the cockpit 80 which indicates both low oxygen and low pressure , and to the shut - off valve and regulator 23 , the motor 30 for the rotary valve 31 , the bos - fill solenoid valve 41 , and the product - delivery solenoid valve 43 . a more detailed description of the monitor controller 18 is given in conjunction with the description of fig4 - 7 . turning now to fig1 b , the panel mounted regulator 19 , the warning light 93 , and the calibration check switch 75 are all mounted in the cockpit 80 . the panel mounted regulator 19 includes the on - off switch 86 , the plenum pressure indicator 87 , the bit switch 88 with a bit light 91 , and a mode selection switch 89 . turning now to fig2 the oxygen sensor 66 in the monitor controller 18 is shown in greater detail . the oxygen sensor 66 includes a zirconia electrolyte element 76 comprising zro 2 - y 2 o 3 and having electrodes 77 attached to either side thereof . a hollow cap 78 having a diffusion hole 79 is mounted on the element 76 , and a heater 81 having leads 82 for attachment to a power source is mounted on the cap 78 . turning now to fig3 the pressure booster 16 is shown immediately adjacent to the molecular sieve filled plenum 17 . the plenum 17 is fitted with a conduit 97 for the removal of product gas as required and for connection to additional plenum volume at either adjacent or remote locations . as shown , the diameter of the driver piston 49 is greater than the diameter of the compression piston 47 to accomplish the compression of the product gas in the compression cylinder 46 by the air delivered to the driver cylinder 51 by the rotary valve . fig4 a and 4b show the monitor controller 18 and the connections to the panel mounted equipment in the cockpit 80 in greater detail . two or more regulators 19 may be provided and an on - off switch 86 on each regulator 19 is coupled to a network of relays and phasing capacitors 106 which in turn is coupled to a power converter 107 . the relays and phasing capacitors 106 are coupled to the shut off valve 23 and the motor 30 for the rotary valve 31 shown in fig1 . the power converter 107 provides + 5 volt and ± 15 volt power to various portions of the concentrator where needed . the on - off switch 86 is also coupled to a three - way solenoid controller 111 which in turn is coupled by a line 109 to the three - way solenoid valve 43 seen in fig1 . a built - in - test switch 88 is coupled to a self - test timer 112 having a time period of 20 seconds and a light 91 on the switch is coupled to a latch 133 . a mode selector switch 89 is coupled to a mode selection with delay 113 , which in turn is coupled to a reference o 2 level approximation circuit 114 . the level approximation circuit 114 is additionally coupled to the pressure transducer 70 which measures the pressure in the cockpit 80 through the sensing line 71 and develops a signal representative of aircraft cockpit altitude . the output of the pressure transducer 70 is also coupled to a high altitude detector 117 . the level approximation circuit 114 is coupled to a network of level comparators 118 which receives a signal from the oxygen sensor 66 through the signal conditioning circuit 121 . the oxygen sensor 66 receives either product gas or air through the three - way solenoid valve 42 and is vented to ambient through the regulator 68 . the oxygen sensor 66 includes the heater 81 which is powered through a heater controller 83 . the level comparator network 118 provides a control signal on line 120 to the two - way solenoid valve 41 which controls the filling of the plenum 17 , as well as a low oxygen signal on line 122 and a calibration signal on line 123 to a logic circuit 131 . the logic circuit 131 is coupled to the calibration check switch 75 through the calibration check timer 132 . the logic circuit 131 provides a warning signal on line 146 to the three - way solenoid controller 111 , to the warning light 93 in the cockpit , and to a latching circuit 133 . the latching circuit 133 has a first input 138 coupled to the output of an and gate 143 , a second input 139 coupled to the warning output 146 of the logic circuit 131 , a latch input 140 , and a negative latch input 141 . the output 142 of the latch 133 is coupled to the bit lights 91 in the cockpit . the inputs of the and gate 143 are coupled to the oscillator 136 , and the output of the or gate 144 and the inputs of the or gate 144 are coupled to the cal - check timer 132 and the self - test timer 112 . the output of the or gate 134 is also coupled to the three - way solenoid valve 42 . the self - test timer 112 is coupled to a power up circuit 137 which has inputs coupled to the power converter 107 . turning now to fig5 the curve 150 shows the minimum oxygen output requirements for the system in either , dilution mode ( less than 100 percent concentrator output ) or the 100 percent mode ( pure oxygen ) as a function of altitude . the curve 151 shows minimum oxygen concentration to the regulator as a function of altitude for a system output in the dilution mode which is maintained at an oxygen partial pressure ( po 2 ) of 330 mm hg . the curve 152 shows minimum oxygen concentration as a function of altitude for a system output in the 100 percent mode which is maintained at 263 mm hg po 2 . the curve 153 shows the maximum oxygen which may be delivered by the system in the dilution mode . fig6 shows the voltage output vo 2 of the oxygen sensor 66 as a function of time during the built - in - test . the voltage output curve 156 falls below the warning level 157 within the 20 second test period to show that the system is functioning properly . fig7 shows the voltage output vo 2 of the oxygen sensor as a function of time during a calibration check . the curve 156 falls below the warning level 157 and enters the calibration threshold between the limits 162 and 163 during the 2 minute test period . pressurized air is coupled to the inlet 21 , filtered to remove moisture and particulate matter in the filter 22 , pressure regulated by the regulator 23 , and ducted to the rotary valve 31 . the regulator 23 maintains the pressure of the air to the rotary valve 31 at one of two pressures , depending on whether or not the booster 16 is operating to pressurize the product gas in the plenum 17 as more fully explained below . the rotary valve 31 alternately feeds the pressurized air to the beds 32 of molecular sieve , and oxygen - enriched product gas passes through the check valves 33 to the concentrator outlet 37 . a portion of the product gas from one of the beds 32 passes through the flow restrictor 36 to back flush through the other bed in order to desorb nitrogen therefrom and vent the same to ambient through the purge vent 35 . the booster driving piston 49 is driven by air from the concentrator rotary valve 31 . referring to fig1 a when the rotary valve is charging molecular sieve bed 1 , air pressure from the line 53 forces the driver piston to the left . at the same time , the rotary valve allows the air on the other side of the piston 49 to escape through the valve 57 , the line 56 , and the purge vent 35 . at the same time , product gas from the valve 41 enters the compressor cylinder 46 through the right - hand inlet check valve 44 , and the compressor piston 47 compresses the product gas which flows through the left - hand outlet 58 , the check valve 59 , and the booster outlet 61 to the product gas storage plenum 17 . after completion of the stroke , the booster pump will delay the return stroke until the rotary valve 31 starts charging sieve bed 2 ; and air through line 52 and valve 54 will force the driver piston 49 to the right . this will compress another charge of product gas on the right side of compressor piston 47 . thus , each stroke of the piston 47 to the left or to the right compresses product gas and is a compression stroke . as long as the two - way solenoid valve 41 stays open , this process will continue until the plenum is fully charged . if the two - way solenoid valve 41 closes , no product gas will flow to the compressor cylinder 46 ; and no additional product gas will be stored in the plenum 17 . the maximum plenum pressure is limited by the pressure relief valve 64 and is determined by both the peak inlet air pressure and the ratio of the size of the driver piston 49 to the compressor piston 47 . when the maximum plenum pressure is reached , the pressure booster is automatically shut off to conserve inlet air which is not needed as long as the bos 17 remains fully charged . the booster is shut off by the increased plenum pressure in the lines 61 and 62 forcing the booster control valve 57 to a closed position , thus preventing the left side of the driver cylinder 51 from venting . the piston 49 then remains at the right side of the booster chamber until the plenum pressure drops , thus opening the shut - off valve 57 and resuming pressure cycling of the driver piston 49 . this arrangement insures that the plenum stays fully charged with pressurized gas . in actual practice , it has been found that increasing the pressure of the product gas in the molecular sieve filled plenum by a factor of approximately 5 increases the storage capacity of the plenum by a factor of approximately 3 . those skilled in the art will recognize that although the proportional storage capacity increase of the sieve filled plenum at increased pressure is not as great as the proportional capacity increase of a plenum at increased pressure without sieve , the total capacity of the sieve filled plenum at increased pressure is greater than the total capacity of a plenum without sieve at increased pressure . the regulator control valve 28 is mechanically linked to the booster control valve 57 ; and when the booster control valve 57 closes because the plenum 17 is fully charged , the regulator control valve 28 vents pressure regulator air pressure from line 25 to ambient through the vent 29 . the regulator control valve 28 is coupled to the shut - off valve and regulator 23 by the line 25 , and ordinarily , the pressure in the line 25 controls the operation of the regulator 23 . when the regulator control valve 28 closes the vent 29 , the pressure in the line 25 will build to about 30 psig at which point the pressure is relieved by the relief valve 26 . this allows the regulator 23 to regulate at about 55 psig . when control valve 28 opens the vent 29 to ambient , however , the regulator 23 will regulate at 25 psig . this operation provides product gas at the concentrator outlet 37 at slightly less than 55 psig for pressurizing by the booster 16 and storage in the plenum 17 , and reduces air consumption by the concentrator by reducing the concentrator bed inlet pressure to 25 psig when the plenum 17 is fully charged and at the same time shutting the booster off . the active element in the oxygen sensor , the zirconia electrolyte element 76 , is a solid state current limiting oxygen sensor which is commercially available ; but since the output of the element varies with temperature and pressure , modifications are necessary in order to obtain satisfactory performance in an aircraft environment . the heater 81 is used to maintain the element 76 at an operating temperature range of 400 ° c . to 600 ° c ., independent of ambient temperature and it has been determined that a temperature close to 600 ° c . is preferable , since the response of the sensor is faster at the higher temperature . the flowrate of product gas to the sensor 66 is controlled by the flow restrictor 67 to isolate the oxygen sensor 66 from sudden and periodic pressure variations which may exist at the concentrator outlet 37 . the absolute pressure regulator 68 is vented to ambient by the vent 69 and maintains a constant pressure at the sensor in order to avoid ambient pressure dependent fluctuation in the sensor output caused by changes in altitude . in operation , a voltage potential applied to the electrodes 77 causes oxygen ions to conduct through the element 76 to provide an electro chemical pumping of the oxygen ions , and a limiting current is developed through the element 76 which at a constant temperature is proportional to the net diffusion rate of oxygen molecules through the diffusion hole 79 . at the constant pressure which is maintained by the regulator 68 , the diffusion rate of oxygen molecules is a function of oxygen concentration of the gas from the valve 42 . the output current of the oxygen sensor 66 is processed to give a voltage which is a function of oxygen concentration in the product gas admitted to the sensor 66 from the concentrator outlet 37 . this voltage is compared by the level comparator 118 in the monitor controller 18 to reference levels to activate the control and warning signals . for example , a 93 percent o 2 reference voltage may be used to control the plenum filling two - way solenoid valve 41 . the solenoid valve 41 is energized to allow flow through the compressor 16 to the plenum 17 when the product gas oxygen concentration is above 93 percent . the warning light 93 is lit when the oxygen concentration is below the minimum value for pilot breathing requirements as measured by the sensor 66 , or when low pressure at the concentrator outlet 37 trips the switch 38 . the product - delivery valve 43 is de - energized to provide product gas to the crew from the plenum 17 in order to provide fail - safe operation in the event of electrical failure . the self - test solenoid valve 42 is ordinarily de - energized and conducts product gas from the concentrator output 37 to the oxygen sensor 66 . in order to test the operation of the oxygen sensor 66 , depression of the built - in - test button 88 or the calibration check switch 75 causes the solenoid valve 42 to admit air through the line 72 from the rotary valve 31 to the oxygen sensor 66 . once the test has been completed the self - test valve 42 is returned to its normal state allowing product gas to flow to the sensor 66 . whenever the concentrator product gas oxygen concentration is below required minimum levels , the oxygen monitor controller 18 activates the warning light 93 and de - energizes the three - way solenoid valve 43 to deliver breathing gas to the pilot from the stored gas in the bos 17 . the control scheme is fail safe in that the two - way valve 41 closes and the three - way valve 43 automatically provides flow to the pilot from the plenum 17 during emergency conditions , ( loss of electrical power , low oxygen , etc .). referring to fig4 two diluter demand breathing regulators 19 control and regulate the breathing gas supplied to the pilot &# 39 ; s mask . the regulators 19 are electrically connected to the oxygen concentrator assembly and the setting of the off - on switch 86 on the regulators control actuation of the system . with both switches 86 in the off position , the regulators are closed to maintain pressure in the plenum 17 , and the oxygen concentrator assembly is unpowered . switching either regulator to the on position applies power to the concentrator assembly through the relays 106 and the power converter 107 and allows the pilot with the on regulator to breathe from the plenum 17 until the composition of the concentrator product gas at the oxygen sensor 66 is above the appropriate levels for the dilution and 100 percent breathing modes described below . the monitor controller 18 then energizes the three - way solenoid valve 43 to provide breathing gas to the pilots directly from the oxygen concentrator . the system includes a low - pressure switch 38 coupled to the output of the concentrator which , through the controller , turns on the warning light 93 and provides breathing gas from the bos 17 in response to low pressure at the concentrator inlet 21 or a clogged inlet filter 22 . the product gas oxygen concentration is measured by the zirconia solid - state oxygen sensor shown in fig2 . the output of the oxygen sensor is processed by the signal conditioning circuit 121 and compared to the appropriate reference levels in the level comparators 118 and if appropriate to activate the warning signal and specific control functions . when the built - in - test ( bit ) is used for either the self - test or calibration check , the logic circuit 131 receives the low oxygen signal 122 and the calibration signal 123 from the level comparator 118 , and the latch circuit 133 latches the result at the end of the bit operation . the bit light 91 flashes during a test , and a warning signal on line 146 illuminates the warning light 93 if the unit fails the self - test or calibration check . the warning signal 146 goes to the off condition and the bit light 91 goes out when the unit passes the test . the output signal of the oxygen sensor 66 is processed by the signal conditioning circuit 121 to give a voltage as a function of the product gas oxygen concentration . this voltage is compared in the level comparator 118 to reference levels programmed into the level comparator 118 to activate the control and warning signals . a 93 percent oxygen reference voltage is used to regulate filling of the plenum by the two - way solenoid valve 41 . the solenoid valve 41 is energized by the control line 120 from the level comparator 118 to allow flow to the plenum 17 when the product gas oxygen concentration is above 93 percent . referring to fig5 control and warning levels are provided following the curves 152 and 151 . in the preferred embodiment , the minimum oxygen concentration to be delivered by the system in either the dilution or the 100 percent mode is 21 percent at sea level and 93 percent above 25 , 000 feet . between sea level and 25 , 000 feet , the curve 150 defines the minimum . the curve 153 defines the maximum oxygen concentration which may be delivered by the system in the dilution mode . the curve 152 is a plot of oxygen concentration vs . altitude for a constant oxygen partial pressure of 263 mm hg . it will be seen that the oxygen concentration levels defined by the curve 152 at all altitudes are greater than the oxygen concentration levels defined by the curve 150 at the same altitudes . accordingly , the curve 152 can be followed in order to deliver oxygen at a concentration which is always greater than the minimum shown by curve 150 . since the partial pressure of oxygen is the product of the oxygen concentration multiplied by the total pressure ( po 2 =% o 2 × p ), the % o 2 can be determined by dividing fixed po 2 signal by the cabin pressure signal derived from the pressure transducer 70 . this reference level limit is compared to the measured % o 2 level in the level comparators 118 ; and if the measured product is less than 263 mm hg , a low o 2 signal 122 is sent to the logic circuit 131 . the curve 151 is a plot of oxygen concentration vs . altitude for a constant oxygen partial pressure of 330 mm hg . this curve is used as a lower limit for oxygen concentration in product gas supplied to the panel regulator 19 when the system is operating in the dilution mode , and accordingly , the addition of air by the regulator to the breathing mixture will reduce the oxygen concentration of the gas actually delivered to the crew . it has been determined that the addition of air by the regulator will not reduce the oxygen concentration to a value below the minimum shown by the curve 150 . as in the explanation of system operation in the 100 percent mode given immediately above , the % o 2 value corresponding to 330 mm hg can be determined by dividing the fixed reference ppo 2 signal by the altitude signal derived from the pressure transducer 70 . this reference % o 2 level is compared to the measured % o 2 in the level comparator 118 ; and if the measured product is less than 330 mm hg ppo 2 , a low o 2 signal 122 is sent to the logic circuit 131 . in the dilution mode , below 23 , 000 feet cabin altitude the reference levels follow the 330 mm hg po 2 curve 151 or 90 percent oxygen curve 154 , whichever is less as shown in fig5 . above 23 , 000 feet , the 100 percent mode reference levels are used since the breathing regulators 19 automatically switch over to the 100 percent mode above 23 , 000 feet cabin altitude . in the 100 percent mode , the reference levels for warning and control follow the 263 mm hg curve 152 or 93 percent oxygen curve 155 whichever is less . product gas oxygen concentration below the appropriate reference levels given for the regulator operating mode ( dilution or 100 percent ) generates the low - oxygen signal 122 at the level comparator 118 . the logic circuit 131 detects this low - oxygen signal and generates the warning signal on line 146 . the warning signal activates the three - way solenoid controller 111 to de - energize the three - way solenoid valve 43 and light the warning lamp 93 . in this event breathing gas is provided to the crew from the bos plenum 17 . to summarize , the three - way solenoid valve 43 is deactivated to provide plenum gas to the crew members , and the warning signal 146 is activated when the concentrator output product composition drops below the level defined by the 263 mm hg po 2 curve 152 in fig5 when the breathing regulators are operated in the 100 percent mode . the plenum gas is provided to the crew members and the warning signal 146 is provided when the concentrator product gas composition falls below the level defined by the 330 mm hg po 2 curve 151 and 90 percent oxygen curve 154 below 23 , 000 feet altitude when the breathing regulators are operated in the dilution mode . the breathing regulators automatically switch over to the 100 percent mode above 23 , 000 feet as detected by the high altitude detector 117 independent of the position of the mode selection switch 89 . the oxygen monitor controller built - in test ( bit ) function provides the capability to conduct a system self - test for preflight and an oxygen sensor calibration check for oxygen level maintenance . the purpose of the system preflight self - test is to ensure that the monitor controller is operating and provides a low - oxygen warning signal and automatically switches over to the plenum when the concentrator product gas composition drops below the minimum levels . after the system has been on for a minimum 90 second warm - up time , a self - test can be initiated by momentarily pushing the bit switch 88 . simultaneously the self - test timer 112 is started , the three - way bit solenoid valve 42 is energized to allow air to flow through the sensor , and the bit light 91 flashes to indicate that a self - test is in progress . once the air reaches the oxygen sensor 66 the sensor output begins to drop approaching the warning level 157 . for the self - test regardless of whether the regulator is in the dilution or 100 percent mode , the mode selection with delay 113 signals the reference oxygen level approximation circuit 114 to provide the 263 mm hg po 2 warning level , v ref , to the level comparator . when the sensor output vo 2 drops below the warning level , the level comparator 118 provides a low - oxygen signal on line 122 to the logic circuit 131 . the logic circuit in turn initiates the following : a . sends a signal to the input 139 of latch 133 to stop the flashing of the bit light 91 indicating the test has been passed and momentarily activates flow from the bos 17 and turns on the warning light 93 in the cockpit indicating low oxygen ; c . uses the output of the self - test timer to the or gate 133 to de - energize the three - way self - test valve 42 allowing product gas to flow through the oxygen sensor 66 . the warning light 93 will be on briefly ( less than five seconds ) until the output 156 of the sensor 66 ( vo 2 ) increases to above the warning level in route to the value corresponding to the product gas oxygen concentration . upon initiating a self - test , if the output 156 of the sensor 66 does not drop below the warning level 157 within 20 seconds as shown on fig6 the self - test is considered as failed and the bit light 91 will remain on as controlled by the latch 133 shown in fig4 . a self - test is also initiated automatically at start - up by the power up circuit 137 which is activated by the power converter 107 and which provides a signal to the self - test timer 112 . this test follows the same steps as above except the bit light 91 is not energized unless the self - test fails . the oxygen sensor calibration check is based on an air calibration and when passed verifies that the oxygen sensor output is calibrated over the 20 - 95 percent range in oxygen concentration . this test is initiated by means of the calibration check switch 75 . upon initiating the check , the calibration check timer 132 generates a pulse to energize the three - way valve 42 in order to flow air through the oxygen sensor for two minutes and also to flash the bit light 91 via the oscillator 136 and latch 133 to indicate that a calibration check is in progress . if during the test the output 156 of the sensor falls to within the calibration threshold between the values 162 and 163 as shown on fig7 the cal signal on line 123 is activated and the sensor has passed the calibration check . after two minutes the calibration check timer 132 de - energizes the three - way valve 42 and allows the product gas to pass through the oxygen sensor 66 . the warning light 93 will be on from the end of the calibration check until the output of the sensor 66 increases above the 263 mm hg po 2 warning level at which time the warning light 93 will turn off and the test will be complete . if at the end of the two - minute calibration check the cal signal on line 123 is not detected by the logic circuit 131 ( thus meaning the output of the sensor 66 did not enter and remain within the calibration threshold ), the sensor has failed the calibration check and the warning light 93 will remain on . having thus described the invention , various alterations and modifications will be apparent to those skilled in the art , which modifications and alterations are intended to be within the scope of the invention as defined by the appended claims .
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in our experiments carried out with the aim of extending the duration of the effect of carbamate , thiolcarbamate , chloroacetanilide and dichloroacetanilide herbicides , optionally combined with antidotes we have surprisingly found that the thio - and dithiophosphoric acid ester derivatives according to the invention prolong the action of said herbicides , increase their activity and improve their selectivity . in addition , we have found , that the action of the simultaneously used antidotes is also extended and their activity is increased . by using the thio - and dithiophosphoric acid ester derivatives according to the invention the duration of herbicidal effect can be optimalized , the doses of the herbicides employed can be reduced , their selectivity can be increased , and similar favorable effects can be achieved also when the compounds according to the invention are employed in association with antidotes . by employing the extenders according to the invention , the herbicidal compositions comprising carbamates , thiolcarbamates , chloroacetanilides and / or dichloroacetanilides as herbicidally active ingredient and optionally antidotes can be used more advantageously in maize , sunflower , cereals , soya , sugar beet , vegetables and fruits than the hitherto employed compositions containing the above - mentioned active ingredients and optionally antidotes . the extenders according to the invention are particularly effective in combination with s - ethyl bis -( 2 - methylpropyl )- carbamothioate , s - ethyl cyclohyxythyl - carbamothioate , s -( 2 , 3 - dichloroallyl )- diisopropylthio - carbamate , s - ethyl dipropylcarbamothioate , s - ethyl - n , n - hexamethylene - thiocarbamate , s - propyl - dipropylthiocarbamate , 2 - chloroallyl - diethyl - dithioarbamate , 1 - methylethyl - 3 - chlorophenylcarbamate , 4 - chloro - 2 - butinyl - 3 - chlorophenyl - carbamate , 2 - chloro - 2 , 6 - diethyl - n - methoxymethyl - acetanilide , 2 - chloro - 2 - methyl - 6 - ethyl - n - methoxyethyl - acetanilide , n - butoxymethyl - 2 - chloro - 2 , 6 - diethyl - acetanilide , n - chloroacetyl - n -( 2 , 6 - diethylphenyl )- glycine , 2 - chloro - n -( 1 , 6 - dimethylphenyl )- n -( methoxyethyl )- acetamide , n -( 2 - chloroethyl )- 2 , 6 - dinitro - n - propyl - 4 -( trifluoromethyl )- aniline , 2 - chloro - n -( 2 , 6 - dimethylphenyl )- n -( lh - pyrazol - l - yl - methyl )- acetamide , 2 - chloro - n -( 2 - ethyl , 6 - methylphenyl ) n -( 2 - methoxy - 1 - methylethyl )- acetamide , 2 - chloro - n -( 2 , 6 - diethylphenyl )- n -( 2 - propoxyethyl )- acetamide , 2 - chloro - n -( 1methylethyl )- n - phenyl - acetamide and n , n - diallylchloroacetanilide , and optionally antidotes . the compositions containing the compounds of formula ( i ) as extenders in combinations with the above - mentioned herbicides and optionally antidotes can be applied to the soil or the plants or incorporated into the soil prior to or after sowing , pre - or postemergently , depending on the properties of the herbicides present in the compositions . alternatively , the herbicides , antidotes and the compounds according to the invention may be formulated separately and can be employed simultaneously or subsequently , but the time interval between the application of the individual components should be minimalized . the dose of the compounds according to the invention and the mutual proportions of the various components may be varied within a wide range . the actual dose is a function of the chemical and physical properties of the herbicides , the cultivated plants , weeds , type of the soil , climatic factors and further similar conditions which are well known for those skilled in the art . in the combinations according to the invention the ratio of the herbicidally active component to the thio - or dithiophosphoric acid esters of the formula ( i ) generally is between 30 : 1 and 1 : 1 , preferably 10 : 1 and 3 : 1 , most preferably 6 : 1 and 5 : 1 . the quantity of the thio - or dithiophosphoric acid ester component in the first line depends on the microbial activity of the soil . generally it is employed in an amount of 0 . 1 to 8 . 0 kg , preferably 0 . 2 to 3 . 0 kg , most preferably 0 . 5 to 3 . 0 kg per hectare . in the combinations according to the invention the antidotes are generally used in the usual ratios related to the herbicides , but lower doses are also possible . the total active ingredient concentration in the compositions according to the invention is 0 . 1 to 95 % by mass , preferably 1 to 90 % by mass . from the concentrated compositions according to the invention the ready - to - use formulations are prepared by dilution . the formulation prepared by the admixture of the herbicides , the extenders according to the invention and optionally the antidotes directly prior to application ( e . g . tank mixtures ) which are , if desired , diluted , are also within the scope of the invention . the compositions containing the extender alone generally contain 0 . 1 to 95 % by mass , preferably 1 to 90 % by mass of active ingredient . the compositions according to the invention may be formulated as solid or liquid preparations conventionally used in the agriculture , depending on the physical and chemical properties of the active ingredient ( s ). the compositions contain the active ingredient ( s ) in association with acceptable , non - phytotoxic solid or liquid carriers and optionally surfactants . the compositions optionally contain further additives , which have a favorable influence on the activity , e . g . decrease the volatility of the active ingredients or facilitate the application . such additives include protecting colloids , thickening agents , adhesives , stabilizers and solid carriers with high adsorption capacity . the compositions according to the invention generally contain in addition to the above - defined amount of active active ingredient ( s ) 1 to 99 % by mass of solid or liquid carriers and optionally surfactants . as a carrier any non - phytotoxic inorganic or organic material of natural or synthetic origin may be employed . solid carriers include clays , natural or synthetic silicates , silicic acid , dolomite , kaoline , diatomaceous earth , flour of vegetable products , starch , etc . as a liquid carrier for example water , alcohols , esters , ketones , mineral oil fractions , aromatic , aliphatic or cyclic hydrocarbons , halogenated hydrocarbons , dimethyl sulfoxide , etc . can be employed . the surface active agents include emulsifying , dispersing and wetting agents , which are of ionic and / or non - ionic character . typical representatives of surfactants are the salts of ligninesulfonic acid , salts of phenol - and naphthalinesulfonic acids , polycondensation product of ethylene oxide with fatty alcohols or fatty acids or fatty acid amides , arlalkylsulfonates , substituted phenols , e . g . alkyl - and arylphenols . the solid compositions according to the invention may be finished as powders , dusting powders , granulates , etc ., while the liquid formulations include solutions , emulsifiable concentrates , emulsions , concentrated suspensions , wettable powders , sprays or pastes . the concentrated formulations may be diluted as desired , and are prepared in a conventional manner . the compositions according to the invention may be employed simultaneously with other plant protecting agents , e . g . herbicides , pesticides , fungicides , bactericides , and plant growth regulators . generally any plant protecting agent which is compatible with the chloroacetanilide , dichloroacetanilide , carbamate and thiolcarbamate herbicides is suitable for simultaneous application . according to the invention the formulations containing an effective amount of one or more herbicides of the carbamate , thiolcarbamate , chloroacetanilide and dichloroacetanilide type and optionally antidotes in association with the thio - and dithiophosphoric acid esters of the formula ( i ) are applied to the plants or the soil containing the seeds of the plants . alternatively , the herbicidally active ingredients and / or the antidotes and / or the extenders according to the invention may be formulated separately , and applied to the plants or to the soil either simultaneously or subsequently . the active ingredients are employed in an effective amount . the formulations are applied to the plants or the soil for example by spraying , dusting , vaporization , etc ., using conventional techniques . the invention is elucidated in more detail by the aid of the following non - limiting examples . 30 g of chloroacetic acid - n -( 2 - propenyl )- amide in 200 ml of acetonitrile are stirred with 40 g of 0 - ethyl - s - n - propyl - thiophosphoric acid potassium salt at room temperature for 12 hours . after stirring , the reaction mixture is refluxed for 3 hours . the salts precipitated upon cooling are eliminated from the solution , and the solvent is distilled off under reduced pressure . the residue is taken up in 100 ml of methylene chloride and washed with 30 ml of 1 n sodium hydroxide and subsequently 30 ml of water . the solvent is then distilled off on a bath of 40 ° to 50 ° c . to yield the title compound with a good yield . into a flask equipped with a stirrer , thermometer and dropping funnel there are added 25 . 5 g ( 0 . 1 mole ) of o , s - di - 2 - chloroethyl - dithiophosphoric acid , 17 . 3 g of diallyl - chloroacetamide and 100 ml of benzene . to the mixture 11 g of triethyl amine are slowly added , under vigorous stirring . a rapid reaction takes place , which results in the precipitation of the amine hydrochloride formed . when the addition is complete , the mixture is refluxed for 3 to 4 hours . the hydrochloride formed in the theoretical amount is eliminated by filtration . the filtrate is washed with 50 ml of a 20 % sodium hydroxide solution and subsequently with water . the solvent is distilled off in vacuum , and the title compound is obtained with a good yield . 18 . 4 g of o , s - diethyl - dithiophosphoric acid are dissolved in 50 ml of water , and the solution is neutralized with 6 . 8 g of potassium carbonate . in a flask equipped with a stirrer , thermometer and dropping funnel 17 . 3 g of diallyl chloroacetamide in 50 ml of acetone are added to the above solution dropwise , at 20 ° c . when the addition is complete , the mixture is stirred at 45 ° to 50 ° c . for 4 to 5 hours , whereupon it is poured into 500 ml of water and the precipitated oily product is separated . the aqueous phase is extracted with benzene twice , dried over sodium sulfate , and the solvent is distilled off . the title compound is obtained with a good yield . ______________________________________substituentsno . r r r &# 39 ; r &# 39 ; n . sub . d . sup . 25______________________________________1 methyl methyl propenyl propenyl 1 . 43382 n - propyl n - propyl propenyl propenyl 1 . 52423 propenyl propenyl propenyl propenyl 1 . 53984 2 - chloro - 2 - chloro - 4 - propyl 4 - propyl 1 . 5282 ethyl ethyl5 ethyl 3 - chloro - propenyl propenyl 1 . 5065 propyl6 ethyl i - propyl propenyl propenyl 1 . 51377 ethyl ethyl 2 - chloro - 2 - chloro - 1 . 5886 ethyl ethyl8 2 - chloro - 2 - chloro - ethyl n - propyl 1 . 5183 ethyl ethyl9 2 - chloro - 2 - chloro - n - propyl i - butyl 1 . 5344 ethyl ethyl10 2 - chloro - 3 - chloro - propenyl propenyl 1 . 5013 ethyl propyl______________________________________ in the biological tests the active substances according to examples 1 , 2 and 3 and the compound no . 10 were used in the following manner : 40 parts by weight of active ingredient are dissolved in a mixture of 32 parts by weight of xylene and 22 parts by weight of dichloromethane , and to the solution an emulsifying agent containing the mixture of 6 parts by weight of alkylarylsulfonic acid calcium and fatty acid - polyglycol ester is added . the solution is homogenized by stirring and is then filtered . an emulsion concentrate containing 40 % by weight of active ingredient is obtained . examination of the duration of activity and increase in herbicidal effect of chloroacetanilide herbicides when combined with the compounds of formula ( i ) test were carried out under foil preemergently , in pots of 12 cm diameter , on &# 34 ; chernosiom &# 34 ; brown forest soil containing 1 . 63 % of humus . ( 4 ) o , s - diethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester ( product according to example 3 ) 200 g / ha ( 5 ) o , s - diethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester ( product according to example 3 ) 500 g / ha ( 6 ) 2 - chloro - 2 &# 39 ;, 6 &# 39 ;- diethyl - n -( methoxymethyl )- acetanilide 1 kg / ha ( lasso )+ o , s - diethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester ( product according to example 3 ) 500 g / ha ( 7 ) 2 - chloro - 2 &# 39 ;, 6 &# 39 ;- diethyl - n -( methoxymethyl )- acetanilide 2 kg / ha ( lasso )+ o , s - diethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester ( product according to example 3 ) 200 g / ha the compositions were used as a tank mixture and applied to the pots in an amount of 220 lit / ha by spraying . as a test plant maize was used . into each pot 5 seeds were sown . as a weed wild millet ( panicum ssp ) was employed , since of the monocotyledonous weeds grown from seeds wild millet is the most resistent to herbicides . therefore , this test weed is excellently suitable for evaluation of the efficiency of a herbicidal agent or combination . of wild millet 20 seeds were sown into each pot . after spraying , the pots containing the cultivated plants and weeds , respectively were kept at 23 to 30 ° c ., the soil was calibrated to a water capacity of 70 to 80 % in order to increase the decomposition rate of herbicides . 15 and 30 days after sowing and spraying , the overground vegetable parts were removed and new seeds were sown without substantial admixture of the surface . in this way the activity increasing and herbicide action extending properties of the compounds according to the invention were tested under &# 34 ; provocative &# 34 ; conditions . evaluation was carried out on the 15th day . in the case of wild millet the killing ratio (%), in the case of maize the phytotoxicity ( ewrc scale ) were calculated . on the ewrc scale the score 1 means that there is no phytotoxicity , while the score 9 represents total weed killing . tests were carried out in four repetitions . ______________________________________effect of the active ingredients on the killing ratio ofwi1d millet ( panicium spp ) no . oftreatment killing in % of the control on theaccording to 30thexample 5 15th day 45th______________________________________1 0 0 02 0 0 03 13 0 04 0 0 05 0 0 06 100 100 677 100 100 100______________________________________ ______________________________________the effect of active ingredients on the injury of maize ( zea mays ) no . of treat - ment accord - phytotoxicity ( ewrc - scale ) on theing to 30thexample 5 15th day 45th______________________________________1 1 1 12 1 1 13 1 1 14 1 1 15 1 1 16 1 1 17 1 1 1______________________________________ the test results show that when employed alone both 2 - chloro - 2 &# 39 ;, 6 &# 39 ;- n -( methoxymethyl )- acetanilide and the product according to example 3 ( representing the compounds according to the invention ) are ineffective against wild millet . but their efficiency has surprisingly been increased , when the two compositions were employed together . while a 2 kg / ha dose of 2 - chloro - 2 &# 39 ;, 6 &# 39 ;- diethyl - n -( methoxymethyl )- acetanilide showed a slight effect against wild millet on the 15th day only , the test combinations resulted in a 67 to 100 % killing of wild millete even according to the evaluation performed on th 45th day . the increase of herbicidal activity had no injurious effect on maize . accordingly , it can be established that the compounds according to the invention when employed alone in the given doses could not control the most resistant monocotyledonous weed , wild millet . their combinations with chloroacetanilide herbicides ( which are ineffective or have only a slight effect alone ), however , are capable of an effective control of wild millet and show an increased duration of activity , i . e . a clear synergism is observed . examination of the extension of activity , the extent of the reduction of dose , the possibility of combination of antidotes in case of combinations of chloroacetanilide herbicides with the compounds of formula ( i ) the test conditions were identical with those described in example 5 . the following treatments were carried out : ( 20 ) alachlor 1 . 0 kg / ha + the product according to example 2 500 g / ha ( 21 ) acetochlor 1 . 0 kg / ha + the product according to example 2 500 g / ha ( 22 ) butachlor 2 . 0 kg / ha + the product according to example 2 500 g / ha ( 23 ) diethatyl 2 . 0 kg / ha + the product according to example 2 500 g / ha ( 24 ) dimethachlor 1 . 0 kg / ha + the product according to example 2 500 g / ha ( 25 ) pretylachlor 1 . 5 kg / ha + the product according to example 2 500 g / ha ( 26 ) propachlor 3 . 0 kg / ha + the product according to example 2 500 g / ha ( 27 ) methazachlor 1 . 5 kg / ha + the product according to example 2 500 g / ha ( 28 ) metholachlor 1 . 0 kg / ha + the product according to example 2 500 g / ha ______________________________________effect of the active ingredients on the killing ratio ofwild millet ( panicum spp ) no . oftreatments killing in % of the control on theaccording to 30thexample ( 5a ) 15th day 45th______________________________________ 1 0 0 0 2 15 0 0 3 0 0 0 4 26 0 0 5 0 0 0 6 0 0 0 7 0 0 0 8 0 0 0 9 0 0 010 37 0 011 6 0 012 16 0 013 0 0 014 0 0 015 0 0 016 0 0 017 0 0 018 17 0 019 0 0 020 100 84 5221 100 100 8122 100 17 4023 100 63 3924 100 100 8625 100 86 7726 100 100 8827 100 92 7128 100 88 7329 0 0 0______________________________________ the results set forth in the table show that the test herbicides were practically ineffective against wild millet ( panicum ssp .) when employed in the test doses alone . by combining the test herbicides with the compound according to example 2 of the instant invention their efficiency could considerably be improved . according to the evaluations carried out on the 15th day the herbicidal effect was 100 % in case of each combination , while even the results observed on the 45th day show that in spite of the lower doses employed , the activity was increased to an unexpected extent , which could not be foreseen on the basis of the individual activities of the components combined . the biological activity of acetochlor was examined alone and in combination with the product according to example 3 in maize . the test conditions were identical with those described in example 5 . the following treatments were carried out : ( 5 ) acetochlor 2 . 0 kg / ha + compound according to example 3 400 g / ha + n - dichloroacetyl - 1 - oxy - 4 - aza - spiro - 4 , 5 - decane 200 g / ha during evaluation the height of maize was measured to determine whether the compound according to example 3 reduced the toxic effect of acetochlor on maize or had any effect on the similar effect of antidote ( n - dichloroacetyl - 1 - oxa - 4 - aza - spirodecane ). ______________________________________effect of the active ingredients on the height of maizein % of the controlno . of alteration in height in maize culturetreatments on theaccording to 30thexample ( 5b ) 15th day 45th______________________________________1 100 100 1002 56 87 1003 124 115 1034 109 103 1015 116 109 1056 92 101 100______________________________________ the results show that the compounds according to the invention counterbalance the toxicity of acetochlor and increase the efficiency of the antidote tested . 2 &# 39 ;- methyl - 6 &# 39 ;- ethyl - n - ethoxymethyl - chloroacetanilide ( acetochlor ), 2 - chloro - n - isopropylacetanilide ( propachlor ) and 2 - chloro - 2 &# 39 ;, 6 &# 39 ;- diethyl - n -( methoxymethyl )- acetanilide as typical representatives of chloroacetanilide herbicides were combined with the compound according to example 3 and a herbicidally active urea derivative , chlorobromuron ( 3 -( 4 - bromo - 3 - chlorophenyl )- 1 - methoxy - 1 - methyl - urea ). the test conditions were identical with those described in example 5 , except that in addition to monocotyledonous weeds also dicotyledons ( amaranthus retroflexus ) were sown . ( 7 ) 2 &# 39 ;- methyl - 6 &# 39 ;- ethyl - n - ethoxymethyl - chloroacetanilide 2 . 0 kg / ha + 3 -( 3 - bromo - 3 - chlorophenyl )- 1 - methoxy - 1 - methyl - urea 1 . 5 kg / ha + compound according to example 3 1 . 0 kg / ha ( 8 ) 2 - chloro - n - isopropylacetanilide 4 kg / ha + 3 -( 4 - bromo - 3 - chlorophenyl )- 1 - methoxy - 1 - methyl - urea 1 . 5 kg / ha + compound according to example 3 1 . 0 kg / ha ( 11 ) 2 &# 39 ;- methyl - 6 &# 39 ;- ethyl - n - ethoxymethyl - chloroacetanilide 2 . 0 kg / ha + 3 -( 4 - bromo - 3 - chlorophenyl )- 1 - methoxy - 1 - methyl - urea 1 . 5 kg / ha + compound according to example 3 0 . 4 kg / ha ( 12 ) 2 - chloro - n - isopropylacetanilide 4 . 0 kg / ha + 3 -( 4 - bromo - 3 - chlorophenyl )- 1 - methoxy - 1 - methyl - urea 1 . 5 kg / ha + compound according to example 3 0 . 4 kg / ha the effect of the active ingredients on the killing rate of wild millet ( panicum ssp ) and amaranth ( amaranthus ssp ). ______________________________________no . of killing in % of the control on thetreatments 30thaccording to 15th day 45thexample ( 5c ) w . m . a . r . w . m . a . r w . m . a . r . ______________________________________1 0 0 0 0 0 02 26 67 0 37 0 03 0 51 0 19 0 04 15 60 0 23 0 05 0 82 0 19 0 06 11 0 0 0 0 07 100 100 100 81 62 588 76 100 57 83 41 549 83 100 61 78 50 5110 0 0 0 0 0 011 92 100 75 78 54 5312 59 100 43 81 29 6013 77 100 56 74 37 62______________________________________ w . m . = wild millet a . r . = amaranth from the results it can be concluded that the compounds according to the invention improve the duration and extent of activity of chloroacetanilide herbicides also in combination with herbicidally active urea derivatives . under similar conditions to those described in example 5 we examined the herbicidal activity of combinations of herbicidally active chloroacetanilides and triazines in association with the compound according to example 1 . as weeds wild millet ( panicum ssp ) and amaranth ( amaranthus ssp ) were employed . ( 9 ) 2 &# 39 ;- methyl - 6 &# 39 ;- ethyl - n - ethoxymethyl - chloroacetanilide 2 . 0 kg / ha + 2 - chloro - 4 - ethylamino - 6 - isopropylamino - 1 , 3 , 5 - triazine 1 . 0 kg / ha + compound according to example 1 1 . 0 kg / ha ( 10 ) 2 &# 39 ;- methyl - 6 &# 39 ;- ethyl - n - ethoxymethyl - chloroacetanilide 2 . 0 kg / ha + 2 - chloro - 4 - ethylamino - 6 - isopropylamino - 1 , 3 , 5 - triazine 1 . 0 kg / ha + compound according to example 1 0 . 4 kg / ha ( 11 ) 2 &# 39 ;- methyl - 6 &# 39 ;- ethyl - n - ethoxymethyl - chloroacetanilide 2 . 0 kg / ha + 2 - ethylamino - 4 - isopropylamino - 6 - methylthio - 1 , 3 , 5 - triazine 1 . 0 kg / ha + compound according to example 1 1 . 0 kg / ha ( 12 ) 2 &# 39 ;- methyl - 6 &# 39 ;- ethyl - n - ethoxymethyl - chloroacetanilide 2 . 0 kg / ha + 2 - ethylamino - 4 - isopropylamino - 6 - methylthio - 1 , 3 , 5 - triazine 1 . 0 kg / ha + compound according to example 1 0 . 4 kg / ha ( 13 ) 2 &# 39 ;- methyl - 6 &# 39 ;- ethyl - n - ethoxymethyl - chloroacetanilide 2 . 0 kg / ha + 2 , 4 - bis ( isopropylamino )- 6 - methoxy - 1 , 3 , 5 - triazine 1 . 0 kg / ha + compound according to example 1 1 . 0 kg / ha ( 14 ) 2 &# 39 ;- methyl - 6 &# 39 ;- ethyl - n - ethoxymethyl - chloroacetanilide 2 . 0 kg / ha + 2 , 4 - bis ( isopropylamino )- 6 - methoxy - 1 , 3 , 5 - triazine 1 . 0 kg / ha + compound according to example 1 0 . 4 kg / ha ( 15 ) 2 &# 39 ;- methyl - 6 &# 39 ;- ethyl - n - ethoxymethyl - chloroacetanilide 2 . 0 kg / ha + 2 -( 4 - chloro - 6 - ethylamino - 1 , 3 , 5 - triazine - 2 - ylamino )- 2 - methyl - propionitrile 1 . 0 kg / ha + compound according to example 1 1 . 0 kg / ha ( 16 ) 2 &# 39 ;- methyl - 6 &# 39 ;- ethyl - n - ethoxymethyl - chloroacetanilide 2 . 0 kg / ha + 2 -( 4 - chloro - 6 - ethylamino - 1 , 3 , 5 - triazine - 2 - ylamino )- 2 - methyl - propionitrile 1 . 0 kg / ha + compound according to example 1 0 . 4 kg / ha ______________________________________the effect of the active ingredients on killing rate (%) of wild millet ( panicum ssp ) and amaranth ( amaranthus ssp ) killing ratio (%) related to the controlno . of on thetreatments 30thaccording to 15th day 45thexample ( 5 d ) w . m . a . r . w . m . a . r . w . m . a . r . ______________________________________1 0 0 0 0 0 02 26 67 0 37 0 03 14 92 6 61 0 484 19 94 4 70 0 535 20 89 11 66 0 446 16 98 7 72 0 567 11 0 0 0 0 08 0 0 0 0 0 09 100 100 100 100 66 8710 100 100 87 100 59 7411 100 100 100 100 61 8112 100 100 80 95 54 7013 100 100 100 100 52 7714 100 100 79 92 46 7015 100 100 95 100 62 7916 100 100 76 96 57 71______________________________________ w . m . = wild millet a . r . = amaranth as the results set forth in the table above the compound according to example 1 increased the activity and extended the duration of activity of combinations containing chloroacetanilides ( 2 &# 39 ;- methyl - 6 &# 39 ;- ethyl - n - ethoxymethyl - chloroacetanilide ) and various triazines in the usual doses and mutual proportions . in this experiment the effect of the compound according to the invention on the duration of activity of thiolcarbamate herbicides and on their combinations with antidotes was tested . tests were carried out as described in example 5 , except that , as usual in case of thiolcarbamate herbicides , the compositions were admixed with the soil prior to sowing . ( 4 ) s - ethyl - dipropylthiocarbamate ( eptc ) 5 kg / ha + o , s - di - 2 - chloroethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester 500 g / h ( compound according to example 2 ) ( 5 ) s - ethyl - dipropylthiocarbamate ( eptc ) 5 kg / ha + n - dichloroacetyl - 1 - oxa - 4 - azaspiro - 4 , 5 - dicane 350 g / ha ( ad - 67 )+ o , s - di - 2 - chloroethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester 600 g / ha ( compound according to example 2 ) ( 6 ) n - dichloroacetyl - 1 - oxa - 4 - azaspiro - 4 , 5 - decane 350 g / ha ( ad - 67 )+ o , s - 2 - chloroethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester 500 g / ha ( compound according to example 2 ) ( 8 ) o , s - di - 2 - chloroethyl - s -( di - propenylamino )- dithiophosphoric acid ester 500 g / ha ( compound according to example 2 ) ______________________________________the effect of active ingredients on the killing rate (%) of wild millet ( panicum ssp ) no . of killing rate in %- age of the controltreatments on theaccording to 30thexample 6 15th day 45th______________________________________1 0 0 02 100 0 03 100 0 04 100 100 905 100 97 806 0 0 07 0 0 08 0 0 0______________________________________ ______________________________________the effect of active ingredients on the extent of injuryof maize ( zea mays )- phytotoxicityno . of alteration in height in %- age of thetreatments controlaccording to 30thexample 6 15th day 45th______________________________________1 100 100 1002 69 100 1003 82 100 1004 94 100 1005 121 110 1066 134 118 1117 102 100 1008 129 120 108______________________________________ the results show that under the provocative conditions described in example 5 the test compound of formula ( i ) extended the duration of activity of s - ethyl - dipropyl - thiolcarbamate to three - fold of the activity observed when the herbicide was used either alone or in combination with the given antidote in the usual doses . it can be concluded , too , that the compound according to example 2 , selected as a representative of the compounds of formula ( i ), has no effect on the test weed when employed alone , in the given dose . it is highly surprising that the compound according to example 2 substantially extends the active period of thiolcarbamate herbicides even under provocative conditions ( acceleration of decomposition ). evaluation of the phytotoxicity studies shows that the test compound according to the invention reduces the undesired effect of thiolcarbamate herbicides on the cultivated plant testes ( maize ). the same effect was observed when the combinations were antidoted . it can further be concluded that compounds of formula ( i ) are not phytotoxic themselves . the antidotal activity of the compounds according to the invention as well as their effect on the efficiency of a known antidote were tested by measuring the height of maize treated , and calculating the change related to the control . it can be seen that eptc when used without any antidote decreased the height of maize by 31 % according to the evaluation performed on the 15th day . in case of antidoted eptc combinations the reduction in height was 18 % only . in case of later sowings ( evaluations carried out on the 30th and 45th days , respectively ) there was no change in height . the combination of eptc with the compound according to example 2 resulted in a further reduction of the decrease in height : the decrease was only 6 % according to the evaluation performed on the 15th day . when the antidoted eptc formulation and the active ingredient according to the invention were sprayed together on maize ( treatment no . 5 ), the height of the maize exceeded the height of the control . combined application of the test antidote and the active ingredient according to the invention resulted in a further increase in the growth of maize . from the results it can be concluded that the compounds according to the invention increase the efficiency of antidotes of herbicidally active thiolcarbamates ( n - dichloroacetyl - 1 - oxa - azaspiro - 4 , 5 - decane ; n , n - diallyl - 2 , 2 - dichloroacetamide ; 3 -( dichloroacetyl )- 2 , 2 - dimethyl - 1 , 3 - oxazolidine ). the results discusses in example 6 unambiguously prove that the active ingredients according to the invention on the one hand increase the activity of herbicidally active thiolcarbamates and extend the duration of their activity , on the other hand , improve the selectivity of said herbicides and their combinations with antidotes and extend the period within which said formulations can be used safely . in this example the herbicidal activity , and the effective doses of herbicidally active thiolcarbamates alone and in combination of compounds according to the invention were examined . the test conditions were identical with those described in examples 5 and 6 , except that the herbicidal activity and the duration of activity were examined . the compositions were thoroughly admixed with the soil prior to sowing . ______________________________________the effect of the active ingredients on the killingratio (%) of wild millet ( panicum ssp ) no . of killing rate in %- age of controltreatments on theaccording to 30thexample ( 6a ) 15th day 45th______________________________________1 0 0 02 100 11 03 75 0 04 10 7 05 63 0 06 100 0 07 66 0 08 100 100 869 100 77 5210 100 100 8111 100 80 6012 100 100 5413 100 83 5914 0 0 015 0 0 0______________________________________ the test results show that the duration of the activity of herbicidally active thiolcarbamates can be expanded and their dose can be reduced , if they are combined with the active ingredients according to the invention . the increase in the duration of herbicidal activity and the decrease of their effective dose were tested in case of thiolcarbamate herbicides , which need not be admixed with the soil prior to sowing in order to achieve the desired effect . unlike in the previous tests instead of wild millet ( panicum ssp ) wild oat ( avena fatua ) was used as a test plant , since the above - mentioned herbicides are particularly effective against wild oat , though they are active also against other monocotyledonous weeds . ______________________________________the effect of the compounds according to the invention onthe killing rate (%) of wild oat ( avena fatua ) no . of killing rate in %- age of the controltreatments on theaccording to 30thexample ( 6b ) 15th day 45th______________________________________ 1 0 0 0 2 79 0 0 3 31 0 0 4 83 5 0 5 42 0 0 6 67 0 0 7 22 0 0 8 71 0 0 9 26 0 010 88 11 011 41 0 012 100 100 6913 100 69 5114 100 100 10015 100 89 6616 100 100 9217 100 81 5918 100 100 7119 100 76 6120 100 100 10021 100 84 75______________________________________ examination of the thiolcarbamate herbicides shows that they are ineffective two weeks after the treatment . if , however , they are combined with compound no . 1 according to the invention , their activity lasts more than two - times as long as originally . in addition , their activity is also increased . decreasing the dose of the thiolcarbamate herbicides tested but combining them with the compound no . 1 , the death of wild oat is 100 % at the first evaluation even if the dose of the herbicide is decreased to half of its original amount . a more than 50 % death is observed even during the third evaluation ( 45th day ) when a combination was employed , while the herbicides alone , even in the complete original doses , were ineffective ( 0 %) 45 days after treatment . the test conditions were the same as in examples 5 and 6 , except that in addition to wild millet ( panicum ssp ) amaranth ( amaranthus ssp ) was used as a test weed . ( 9 ) s - ethyl - dipropylcarbamothioate 5 . 0 kg / ha + n - dichloroacetyl - 1 - oxa - 4 - azaspiro - 4 , 5 - decane 0 . 5 kg / ha + 2 - chloro - 4 - ethylamino - 6 - isopropylamino - 1 , 3 , 5 - triazine 1 . 5 kg / ha + compound according to example 3 1 . 0 kg / ha ( 10 ) s - ethyl - dipropylcarbamothioate 5 . 0 kg / ha + n - dichloroacetyl - 1 - oxa - 4 - azaspiro - 4 , 5 - decane 0 . 5 kg / ha + 2 - chloro - 4 - ethylamino - 6 - isopropylamino - 1 , 3 , 5 - triazine 0 . 75 kg / ha + compound according to example 3 1 . 0 kg / ha ( 11 ) s - ethyl - dipropylcarbamothioate 5 . 0 kg / ha + n - dichloroacetyl - 1 - oxa - 4 - azaspiro - 4 , 5 - decane 0 . 5 kg / ha + 2 -( 4 - chloro - 6 - ethylamino - 1 , 3 , 5 - triazine - 2 - yl - amino )- 2 - methyl - propionitrile 1 . 5 kg / ha + compound according to example 3 1 . 0 kg / ha ( 12 ) s - ethyl - dipropylcarbamothioate 5 . 0 kg / ha + n - dichloroacetyl - 1 - oxa - 4 - azaspiro - 4 , 5 - decane 0 . 5 kg / ha + 2 -( 4 - chloro - 6 - ethylamino - 1 , 3 , 5 - triazine - 2 - ylamino )- 2 - methyl - propionitrile 0 . 75 kg / ha + compound according to example 3 1 . 0 kg / ha ( 13 ) s - ethyl - diisobutyl - thiocarbamate 5 . 0 kg / ha + n , n - diallyl - 1 , 2 - dichloroacetamide 0 . 5 kg / ha + 2 - chloro - 4 - ethylamino - 6 - isopropylamino - 1 , 3 , 5 - triazine 1 . 5 kg / ha + compound according to example 3 1 . 0 kg / ha ( 14 ) s - ethyl - diisobutyl - thiolcarbamate 5 . 0 kg / ha + n , n - diallyl - 2 , 2 - dichloroacetamide 0 . 5 kg / ha + 2 - chloro - 4 - ethylamino - 6 - isopropylamino - 1 , 3 , 5 - triazine 0 . 75 kg / ha + compound according to example 3 1 . 0 kg / ha ( 15 ) s - ethyl - diisobutyl - thiolcarbamate 5 . 0 kg / ha + n , n - diallyl - 2 , 2 - dichloroacetamide 0 . 5 kg / ha + 2 -( 4 - chloro - 6 - ethylamino - 1 , 3 , 5 - triazine - 2 - yl - amino )- 2 - methylpropionitrile 1 . 5 kg / ha + compound according to example 3 1 . 0 kg / ha ( 16 ) s - ethyl - diisobutyl - thiolcarbamate 5 . 0 kg / ha + n , n - diallyl - 2 , 2 - dichloroacetamide 0 . 5 kg / ha + 2 -( 4 - chloro - 6 - ethylamino - 1 , 3 , 5 - triazine - 2 - yl - amino )- 2 - methylpropionitrile 0 . 75 kg / ha + compound according to example 3 1 . 0 kg / ha ______________________________________no . of killing rate in % age of the control on thetreatments 30thaccording to 15th day 45thexample ( 6c ) w . m . a . r . w . m . a . r . w . m . a . r . ______________________________________1 0 0 0 0 0 02 100 67 0 0 0 03 100 59 0 0 0 04 34 93 11 60 0 315 11 49 0 21 0 06 38 90 13 64 0 257 14 42 0 25 0 08 0 0 0 0 0 09 100 100 100 100 69 7810 100 100 100 100 57 7111 100 100 100 100 72 7612 100 100 100 100 51 6913 100 100 100 100 71 7414 100 100 100 100 56 6715 100 100 100 100 67 7016 100 100 100 100 41 56______________________________________ thiolcarbamate herbicides are often combined with herbicidally active triazine derivatives , to widen their activity spectrum . examination of the activity of the combinations containing herbicidally active thiolcarbamates , triazines and compounds according to the invention shows that the compound according to the invention extend the duration of activity and increase the activity of the test combinations . accordingly , compounds of the formula ( i ) excert their favourable effects not only in combination with thiolcarbamate herbicides alone but also if they are combined with various herbicidally active triazine derivatives . the effect of the compounds according to the invention on the duration and extent of herbicidal activity of various herbicidally active thiolcarbamates were examined . the test were carried out essentially as described in example 6 , except that as a cultivated plant 5 pieces of soya were cultivated in each pot . ______________________________________the effect of active ingredients on the killing rate (%) of wild millet ( panicum ssp ) no . of killing rate in % age of the control ontreatments theaccording to 30thexample 7 15th day 45th______________________________________1 0 0 02 23 0 03 8 00 04 95 64 405 74 53 296 97 73 557 66 41 30______________________________________ the results set forth in the above table show that 1 - methylethyl - 3 - chlorophenyl - carbamate alone is practically ineffective against wild oat in the test doses . the addition of the compound according to example 1 has considerably increased the herbicidal activity in each combination tested , and the combinations which contained the compounds according to the invention were considerably more effective even on the 45th day after treatment than those containing the above - mentioned carbamate derivative as a sole active ingredient on the 15th day . the effect of the above combinations on cultivated plants was tested on soya . injury rating was carried out on the basis of ewrc scale . 1 means that there was no injury observed , 9 stands for total killing . ______________________________________phytotoxicity on soya using the combinations according tothe inventionno . oftreatments phytotoxicity ( ewrc ) on theaccording to 30thexample 7 15th day 45th______________________________________1 1 1 12 2 1 13 1 1 14 2 1 15 1 1 16 1 1 17 1 1 1______________________________________ it can be seen that the combination of 1 - methylethyl - 3 - chlorophenyl - carbamate with the compound according to the invention resulted in no increase in phytotoxicity . the effect of the combinations of thiolcarbamate and chloroacetanilides with compounds of formula ( i ) was examined . though they are generally applied to the fields differently ( thiolcarbamates are to be incorporated into the soil while acetochlor should be sprayed on the surface ), a common feature of thiolcarbamates and acetochlor is that both should be antidoted to avoid the undesired injury of cultivated plants ( e . g . maize ). tests were carried out in pot having a diameter of 12 cm filled with meadow chernosiom soil , in 6 repetitions . the corns of maize ( 5 pieces into each pot ) were placed ia a depth of 8 cm measured from the top of the pots . corns were then covered with a 5 to 6 cm thick soil layer admixed with the seeds of various weeds ( cocksfoots weed , amaranth ). weeds were admixed with the soil in separate pots , each with 1 cm 3 of soil . the combinations tested were then sprayed on the pots as a tank mixture , in an amount of 220 lit ./ ha . after spraying , the soil was covered with a 2 to 3 cm thick fresh soil layer , and the water capacity of the soil was adjusted to 65 to 70 %. on the 20th day after treatment the degree of weed control and the injury of cultivated plants were examined . on the 20th day the test plants were eliminated , and new weed seeds were admixed with the upper 3 to 5 thick layer of soil . the degree of weed control was examined and the efficiency of weed control was examined on the 40th day . ( 8 ) treatment no . 2 + o , s - di - 2 - chloroethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester ( compound according to example 2 ) 0 . 8 kg / ha ( 9 ) treatment no . 3 + o , s - di - 2 - chloroethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester ( compound according to example 2 ) 0 . 8 kg / ha ( 10 ) treatment no . 4 + o , s - di - 2 - chloroethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester ( compound according to example 2 ) 1 kg / ha ( 11 ) treatment no . 5 + o , s - di - 2 - chloroethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester ( compound according to example 2 ) 1 kg / ha ( 12 ) treatment no . 6 + o , s - di - 2 - chloroethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester ( compound according to example 2 ) 0 . 7 kg / ha ( 13 ) treatment no . 7 + o , s - di - 2 - chloroethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester ( compound according to example 2 ) 0 . 7 kg / ha ______________________________________the effect of combinations on the killing rate ofcocksfoot weed ( echinochloa ssp ) and amaranth ( amaranthusssp ) killing in %- age of the control on the 20th 40thno . of daytreatments ec . am . ec . am . ______________________________________1 0 0 0 02 100 100 32 143 100 100 27 314 100 100 27 295 100 100 35 366 100 100 28 217 100 100 36 338 100 100 72 699 100 100 88 7410 100 100 79 7111 100 100 87 7812 100 100 64 7913 100 100 67 76______________________________________ ec = cocksfoot weed am = amaranth the killing rate was examined on the basis of green weight . killing rate (%) = green weight in % age of the control . ______________________________________effect of the combinations on the height of maize andthe ratio of malformation height of plant in %- age of the ratio ofno . of control malformationtreatments on the basis of the average of 6 × 5______________________________________ plants1 100 . 0 -- 2 94 . 5 13 86 . 6 -- 4 90 . 5 -- 5 93 . 8 -- 6 86 . 3 27 89 . 7 18 95 . 7 -- 9 93 . 6 -- 10 94 . 5 -- 11 96 . 9 -- 12 91 . 7 -- 13 93 . 2 1______________________________________ evaluation of the activity of antidoted combinations of various thiolcarbamates ( butylate , eptc , vernolate ) and acetochlor shows that they have no substantial phytotoxic effect on maize , if they are incorporated into the soil not too deeply . in addition , these combinations show an excellent herbicidal activity according to the evaluation carried out on the 20th day . the results of the second evaluation show , however , that their herbicidal activity considerably decreases as a function of time . on the 40th day they can control only 14 to 36 % of the weeds tested . on the other hand , when o , s - di - 2 - chloroethyl - s -( di - 2 - propenylamino )- dithiophosphoric acid ester according to the invention was added to the test combinations , they killed 64 to 88 % of the weeds at the time of second evaluation , too . moreover , the compound according to the invention did not increase the phytotoxicity of the test combinations .
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the present invention discloses a 2 × vdd - tolerant mixed - voltage i / o buffer , wherein the circuit thereof adopts transistors with a thinner gate oxide layer . refer to fig2 a diagram schematically showing the circuit of the mixed - voltage i / o buffer according to a first embodiment of the present invention . in fig2 , the mixed - voltage i / o buffer 20 comprises two nmos transistors 22 and 24 , a dynamic gate - controlled circuit 26 , an input circuit 30 , an output circuit 32 and a pre - driver circuit 34 . the dynamic gate - controlled circuit 26 is coupled to the gates of the two nmos transistor 22 and 24 , and externally coupled to a high - level voltage vddh . an i / o pad 28 is coupled to the dynamic gate - controlled circuit 26 and the drain of the nmos transistor 24 . the output circuit 32 is coupled to the input circuit 30 and the source of the nmos transistor 22 at node 1 , and is externally coupled to a low - level voltage vdd . the pre - driver circuit 34 is coupled to the output circuit 32 and the gate - controlled circuit 26 . according to an output - enable signal oe , the pre - driver circuit 34 outputs a pull - up signal pu to control a pull - up pmos transistor 322 , and outputs a pull - down signal pd to control a pull - down nmos transistor 324 of the output circuit 32 . the nmos transistor 22 is coupled to the nmos transistor 24 at node 2 . the input circuit 30 comprises a pmos transistor 302 and two inverters 304 and 306 . the drain of the pmos transistor 302 and the input the inverter 304 are coupled to node 1 . the output end of the inverter 304 is coupled to the gate of the pmos transistor 302 and the input end of the inverter 306 . in the output circuit 32 , the pull - up pmos transistor 322 is externally coupled to a low - level voltage vdd , and the pull - down nmos transistor 324 is grounded . refer to fig3 a diagram schematically showing the dynamic gate - controlled circuit according to the first embodiment of the present invention . in fig3 , the dynamic gate - controlled circuit 26 comprises a level shifter 36 , two coupled inverters 38 and 40 , a nmos transistor 42 , and a gate - tracking circuit 44 . a level shifter 36 is coupled to the pre - driver circuit 34 and receives a voltage signal pub output by the pre - driver circuit 34 and pulls up the voltage signal pub to be a voltage signal puh . the input end of the inverter 38 is coupled to the level shifter 36 , and the output end of the inverter 38 is coupled to a gate of the nmos transistor 42 and the inverter 40 . the gate - tracking circuit 44 further comprises two coupled pmos transistors 441 and 442 . the gate - tracking circuit 44 is coupled to the inverter 40 , the drain of the nmos transistor 42 , the gate of the nmos transistor 22 , the gate of the nmos transistor 24 , and the i / o pad 28 . the bulks of the pmos transistors 441 and 442 are coupled to the gate of the nmos transistor 24 to maintain the bulks at a high - level voltage lest current leakage occur . when the output - enable signal oe received by the pre - driver circuit 34 is a low - level voltage ( 0v ), the mixed - voltage i / o buffer 20 is in a receive mode , and the i / o pad 28 receives an input signal and transmits the signal to the input end din of the input circuit 30 . in the receive mode , the pre - driver circuit 34 turns off the pull - up pmos transistor 322 and the pull - down nmos transistor 324 of the output circuit 32 and outputs a 0v voltage signal pub to the dynamic gate - controlled circuit 26 , and the level shifter 36 of the dynamic gate - controlled circuit 26 transforms the voltage signal pub into a vdd - level voltage signal puh . thus , the gate of the nmos transistor 22 is biased at a voltage of vdd via the inverter 40 , and the nmos transistor 42 makes the gate of the nmos transistor 22 more stably biased at a voltage of vdd . consequently , the gate voltage of the nmos transistor 22 is always biased at vdd in the receive mode . the gate - tracking circuit 44 is coupled to the gate of the nmos 24 transistor , and the gate voltage of the nmos transistor 24 thus is dependent on the voltage of the i / o pad 28 in the receive mode . refer to table . 1 . when the i / o buffer 20 receives a 0v input signal in the receive mode , the gate of the nmos transistor 22 is biased at a voltage of vdd , and the gate of the nmos transistor 24 is also biased at the voltage of vdd ; node 1 and node 2 are discharged to 0v via the nmos transistors 22 and 24 , and a 0v input signal is transmitted from the i / o pad 28 to the input end din of the input circuit 30 . when the i / o buffer 20 receives a 2 × vdd input signal in the receive mode , the gate of the nmos transistor 22 is still biased at the voltage of vdd , but the gate of the nmos transistor 24 is biased at a voltage of 2 × vdd ; node 1 is biased at the voltage of vdd via the feedback operation of the pmos transistor 302 of the input circuit 30 and node 2 is biased at a voltage of ( 2 × vdd − δv ) to enable 1 × vdd input signal transmitted from the i / o pad 28 to the input end din of the input circuit 30 via the nmos transistors 22 and 24 . when the output - enable signal oe received by the pre - driver circuit 34 is a high - level voltage signal ( vdd ), the i / o buffer 20 is in a transmit mode , and an output signal is transmitted from the output end dout of the pre - driver circuit 34 to an output signal to the i / o pad 28 . when the output end dout of the pre - driver circuit 34 sends out a 0v output signal in the transmit mode , the pre - driver circuit 34 turns off the pull - up pmos transistor 322 of the output circuit 32 and turns on the pull - down nmos transistor 324 and then a 0v voltage signal pub is transmitted to the dynamic gate - controlled circuit 26 and transformed into a vdd voltage signal puh by the level shifter 36 of the dynamic gate - controlled circuit 26 . the gates of the nmos transistors 22 and 24 are biased at a voltage of vdd , as shown in table . 1 , to enable a 0v output signal transmitted from the output end dout of the pre - driver circuit 34 to the i / o pad 28 . when the output end dout of the pre - driver circuit 34 sends out a vdd output signal in the transmit mode , the pre - driver circuit 34 turns on the pull - up pmos transistor 322 of the output circuit 32 and turns off the pull - down nmos transistor 324 and then a vdd voltage signal pub is transmitted to the dynamic gate - controlled circuit 26 and transformed into a 2 × vdd voltage signal puh by the level shifter 36 of the dynamic gate - controlled circuit 26 . as shown in table . 1 , the gates of the nmos transistors 22 and 24 are biased at a voltage of 2 × vdd to enable a vdd output signal transmitted from the output end dout of the pre - driver circuit 34 to the i / o pad 28 . during the transition from receiving a 2 × vdd input signal to transmitting a 0v output signal in the mixed - voltage i / o buffer 20 , node 1 and node 2 are respectively at voltages of vdd and ( 2 × vdd − δv ) initially . during the transition , the pull - down signal pd generated by the pre - driver circuit 34 turns on the nmos transistor 324 of the output circuit 32 and the nmos transistor 22 is turned on when its source voltage is pulled down by the nmos transistor 324 . then , the nmos transistor 24 is turned on and the voltage at the i / o pad 28 is pulled down . the drain - source voltages vds of the nmos transistors 22 and 24 will not exceed the maximum voltage defined in a given fabrication process . therefore , no matter whether it is in the receive mode , in the transmit mode or during the transition from receiving a 2 × vdd input signal to transmitting a 0v output signal , the mixed - voltage i / o buffer 20 of the present invention is free from gate - oxide deterioration and hot - carrier degradation . refer to fig4 a diagram schematically showing the circuit of the mixed - voltage i / o buffer 50 according to a second embodiment of the present invention , wherein a voltage slew - rate control output circuit 52 replaces the output circuit 32 shown in fig2 . in fig4 , the mixed - voltage i / o buffer 50 of the present invention is a mixed - voltage i / o buffer with a voltage slew - rate control function and implemented with a voltage slew - rate control output circuit 52 , which has a plurality of parallel pull - up pmos transistors and a plurality of parallel pull - down nmos transistors . thereby , the mixed - voltage i / o buffer 50 improves the problem of the ground bounce effect . in summary , the present invention proposes a 2 × vdd - tolerant mixed - voltage i / o buffer . no matter whether it is in the receive mode , in the transmit mode or during the transition from receiving a 2 × vdd input signal to transmitting a 0v output signal , via two nmos transistors and a dynamic gate - controlled circuit , the mixed - voltage i / o buffer of the present invention is free from the problems of gate - oxide reliability , current leakage and hot - carrier degradation . further , the present invention incorporates a voltage slew - rate control output circuit in the mixed - voltage i / o buffer to realize a mixed - voltage i / o buffer with a voltage slew - rate control function . those described above are the embodiments to clarify the characteristics and technical thought of the present invention to enable the persons skilled in the art to understand , make and use the present invention . however , it is not intended to limit the scope of the present invention . any equivalent modification or variation according to the spirit of the present invention is to be also included within the scope of the present invention .
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referring first to fig1 there is shown a simplified block diagram of the dual channel neuromuscular stimulator system of the present invention . the overall unit 10 has a pair of output jacks 12 and 14 which can be connected to suitable stimulation electrodes , such as medtronic conductive carbon electrodes # 3791 , 3793 , 3794 or 3795 , through normal plug - in cables such as medtronic # 3781 cable . the electrodes are affixed to the skin over the muscle and nerve tissue to be stimulated using neuromod ® tens electrode gel and tape patches for the selected carbon electrode . the circuitry providing the excitation at output jacks 12 and 14 is identical for channels 1 and 2 . each channel has a constant current output circuit 16 and 18 . individual patient adjusted amplitude controls 20 and 22 provide an adjustment of stimulation pulse amplitude which is accessible to the patient . additionally , a physician or clinician controlled amplitude limit adjustment 24 and 26 is also provided for each channel . the clinician controls are located under a protective cover in the device to limit their accessibility to the patient . the physician accessible limit controls 24 and 26 allow the physician to establish an upper limit for stimulation amplitude as well as allowing the patient adjusted amplitude controls 20 and 22 to be adjustable over the most desirable part of the range of operating amplitudes . the drive signals 28 and 30 to the output circuits 16 and 18 are provided by identical channel 1 and channel 2 pulse width circuits 32 and 34 . the pulse width circuits are driven by input signals 36 and 38 which are supplied respectively by a rate oscillator 40 and a phase inverter 42 which receives its input signal 44 from rate oscillator 40 . rate oscillator 40 has a physician controlled adjustment means 46 to alter the oscillation rate . in the preferred embodiment shown , the pulse rate is adjustable between 3 and 50 pulses per second . additional inputs to the pulse width circuits 32 and 34 are provided by pulse width ramp generation circuits 48 and 50 . the ramp circuits 48 and 50 are adjustable by clinician controlled ramp time adjustment means 52 and 54 , respectively . the pulse width ramp circuits 48 and 50 also receive inputs from a momentary &# 34 ; on &# 34 ; switch 56 which is also referred to herein as a &# 34 ; constant stimulation &# 34 ; actuating switch . further inputs to the pulse width ramp circuits 48 and 50 are provided through accessory jack 58 . the accessory jack may be connected to an external switch such as a physician controlled switch which may be used during calibration of the stimulator to apply pulses independent of the status of separate &# 34 ; on &# 34 ; and &# 34 ; off &# 34 ; time controls discussed below . signals controlling the pulse width ramp circuits from the treatment timer 60 and on / off cycler 62 are also passed through the accessory jack 58 as shown more fully in the detailed schematic of fig2 a through 2c . treatment timer 60 receives an input from a patient control 64 to set the length of the treatment time and shut down the operation of the stimulator after the selected treatment time has elapsed . the on / off cycler 62 provides for intermittent operation of the circuitry during a treatment to apply pulses in bursts having a predetermined time duration and to suppress the pulse output during a predetermined &# 34 ; off &# 34 ; time or rest interval as established by physician actuated adjustment controls 66 and 68 . the treatment timer provides for treatment time of 15 , 30 or 60 minutes or continuous operation while the on / off cycler provides alternative stimulation and resting intervals of 2 to 25 seconds and 2 to 50 seconds , respectively . referring now to fig2 a through 2c , there is shown a detailed schematic diagram of the dual channel neuromuscular stimulator system according to the present invention . the broken line boxes in fig2 a through 2c correspond generally to the similarly numbered boxes in the functional block diagram of fig1 . box 72 encloses power source circuitry not explicitly shown in fig1 . the details of construction and operation of the various block elements shown in fig1 and fig2 a through 2c is described below . the dosage timer 60 utilizes as the principal timing means a 14 - stage binary cmos counter u3 manufactured by fairchild and others as a model 4020 . the numbers at the outside of the box u3 denote the manufacturer &# 39 ; s pin designations for the various terminals and the lettering on the inside of the box indicates the functional description of the various u3 terminals utilized in dosage timer 60 . the three outputs from the counter u3 at pins 1 , 2 and 3 are from the 12th , 13th and 14th counter stages , respectively , and are connected to diodes cr4 , cr5 and cr6 . the input to u3 at terminal 10 is provided by a schmitt trigger circuit u2a utilizing one element of a schmitt trigger module such as a model 40106 unit manufactured by rca , national semiconductor and others which contains six schmitt triggers . the adjustable feedback resistor r3 and timing capacitor c3 operate to establish the frequency of schmitt trigger u2a as an oscillator to provide a clock signal to the input to u3 . in a preferred embodiment of the stimulator , the clock signal is selected to provide outputs at stages 12 , 13 and 14 of the binary counter at 15 , 30 and 60 minutes , respectively . by selecting the appropriate output from counter u3 , it is then possible to obtain a logic signal at either 15 , 30 or 60 minutes for use in terminating the treatment . the treatment timer is reset as the unit is initially powered up by the voltage divider comprised of capacitors c1 , diode cr1 and resistor r1 . when the &# 34 ; power on &# 34 ; switches s1 and / or s2 are closed , the + v voltage is applied to the various circuits to which it is connected and a regulated v1 voltage is developed across cr3 . in the preferred embodiment shown , s1 and s2 are included in the patient amplitude controls 20 and 22 , respectively . capacitor c2 is charged almost instantaneously through limiting resistor r2 and provides a filtering effect for the regulated voltage v1 across cr3 . when v1 is applied to c1 as either s1 or s2 is closed to energize the stimulator , c1 begins with no stored voltage so that the charging current passing from v1 to ground through cr1 and r1 develops a positive voltage across r1 to apply a reset signal to terminal 11 of u3 . after c1 is fully charged , the charging current drops to zero and thereby removes the reset signal to allow the input clock signal at terminal 10 of u3 to begin the counting operation . a reset signal can also be applied to the dosage counter u3 by conductor 76 which is connected to terminal 86 of a four - position slide switch 64 which provides the adjustment to select the desired treatment time . slide switch 64 has terminals 78 , 80 , 82 , 84 and 86 . in the first position , the movable conductive element 87 in the slide switch shorts terminals 78 and 80 together ; in the second position it shorts terminal 80 to 82 ; and , in a third position , shorts terminal 82 to 84 and finally , in the fourth position , shorts terminal 84 to terminal 86 . in the first position , a 15 - minute time interval is selected , in the second , a 30 - minute time interval , in the third , a 60 - minute time interval and , in the fourth position , because terminal 84 is connected to regulated supply at v1 , a positive voltage is connected to the reset input of timer u3 to cause the stimulator to operate in a continuous mode since the treatment timer counter has been disabled by application of constant voltage to its reset terminal . it is particularly convenient to have the continuous operating mode switch position available when the physician is adjusting the various physician controlled parameters of the stimulator to avoid having the stimulator shut off by the treatment timer 60 while adjustments are being made . in the schematic in fig2 a , terminals 78 and 80 are shown shorted together , representative of the switch being in position 1 selecting 15 - minute operation . the other switch positions for wiper 87 are shown in phantom or dotted line form in fig2 a . when the count in counter u3 reaches the 12th stage of the 14 - stage counter , a positive voltage is applied through cr4 to terminal 78 , through the switch contact to terminal 80 and through cr7 to the input at terminal 13 to the schmitt trigger oscillator u2a to stop operation of the oscillator after the desired time has been reached . this is done for the three time intervals of 15 , 30 and 60 minutes so that the &# 34 ; end of treatment command &# 34 ; signal will not be erroneously removed by the count advancing to the next stage in the 14 - stage binary counter u3 . the output signal from the selected 12th , 13th or 14th stage of the 14 - stage binary counter u3 is connected through diode cr10 and normally closed switch contact of accessory jack j5 to the remainder of the circuit where it is used , as described below , to disable the application of stimulation pulses by the circuitry after the desired treatment time has elapsed . the normally closed contact 90 in accessory jack j5 is opened when an accessory switch is used to bypass the treatment timer . in addition to the treatment timer reset pulse which is generated by c1 , cr1 and r1 when the system is powered up , a reset signal can also be applied to the treatment timer counter by switching the selector switch 64 to the fourth position to bridge contacts 84 and 86 and apply the voltage v1 directly to the reset input terminal 11 of the dosage timer . when the switch is set in this position , the stimulation circuit is in continuous operation at the selected pulse rate and at the selected on and off cycle time and the treatment time is not being measured by the counter u3 . of course , the resetting of counter u3 removes any positive output signals from the 12th , 13th and 14th binary stages to allow the schmitt trigger oscillator u2a to resume operation at the beginning of its timing cycle . in addition to the treatment timer 60 , the circuit 10 includes a cycle timer 62 , the details of which are shown in fig2 b . the cycle timer 62 establishes the &# 34 ; on &# 34 ; or stimulation and &# 34 ; off &# 34 ; or resting time intervals which alternate during the selected treatment time in accordance with clinician adjustable controls 66 and 68 which are variable resistors appearing in the circuit of the cycle timer 62 as shown in fig2 b . the variable resistor 66 is in the feedback circuit of schmitt trigger u2d in series with a calibration resistor r10 . in order to have schmitt trigger u2d operate as an oscillator , a capacitor c5 is connected from its input terminal 1 to ground . the output of the schmitt trigger oscillator u2d is passed through diode cr13 to terminal 10 of u4 which is the input to a 14 - stage binary counter of the same type as u3 . counter u4 is reset when a positive voltage is applied to reset terminal 11 . a reset signal is provided by the capacitor c1 resistor r4 voltage divider when the circuit is powered up . the output of u4 at the 14th stage of the binary counter at pin 3 is connected through diodes cr9 and or &# 39 ; ed with the end of treatment command signal from treatment timer 60 and the resultant signal is passed through resistor r43 to indicator circuit 70 . the signal is also provided , as indicated above , through j5 and resistor r43 and diode cr2 to inhibit generation of pulses when either the selected time for the treatment timer has elapsed or when the stimulator is in the &# 34 ; off &# 34 ; time interval . the &# 34 ; off &# 34 ; timer is mechanized in fig2 b utilizing schmitt trigger circuit u2b . the feedback resistors include a calibration resistor r7 and the physician controlled resistor 68 . capacitor c4 causes the circuit to oscillate in the same manner as the &# 34 ; on &# 34 ; timer , but at a slower rate to allow for the longer off intervals utilized in the preferred embodiment . the output signal of oscillator u2b at terminal 8 is connected through diode cr12 to the input to counter u4 . oscillators u2b and u2d do not operate at the same time . the circuitry comprised of diode cr14 , diode cr11 and schmitt trigger u2c operates as a toggle to enable either u2b or u2d to oscillate at any one time . u2c is connected as an inverter . when the stimulation device is in the &# 34 ; on &# 34 ; cycle , pin 3 of u4 is at a low voltage so that the u2d oscillator is operating as the binary counter u4 counts until the output of binary stage 14 at pin 3 switches to a high voltage . when that voltage switches , it shuts down the stimulator by feeding the positive voltage through cr9 and jack j5 in the same way that the end of treatment command from treatment timer 60 is fed . the high voltage at pin 3 of u4 feeds through cr14 to stop the operation of oscillator u2d . that high voltage is also conducted through resistor r44 to u2c which inverts it to remove the high logic signal that was conducted through cr11 to keep oscillator u2b stopped . thus , u2b starts to operate when u2d is shut down . by adjustment of the operating frequencies of u2d and u2b , the on and off times of the preferred embodiments shown can be adjusted over ranges of 2 to 25 and 2 to 50 seconds , respectively . the constant stimulation momentary on switch block 56 has a switch designated s3 in fig2 a . when switch s3 is actuated , it connects the cathode of cr8 to ground . this inhibits signals coming from jack j5 , preventing output circuit to turn off . the treatment timer 60 and the cycle timer 62 are inhibited from shutting the circuit off during the time that the momentary contact switch s3 is closed . the closure of switch s3 also applies a ground to the input of u2c which puts a high logic signal on the output of u2c to stop oscillator u2b . this operational feature allows oscillator u2d to keep running until u4 reaches the end of its time cycle so that when the pressure on the constant stimulation button s3 is removed , the cycle time is in the &# 34 ; off &# 34 ; position and at the beginning of the &# 34 ; off &# 34 ; cycle . this is an important operational feature because after continued stimulation under control of the constant stimulation switch has been applied to a muscle group , it is extremely desirable to allow the muscle to recover in a nonstimulated condition . allowing the &# 34 ; on &# 34 ; cycle timer to continue to run to bring the circuit back into the beginning of the &# 34 ; off &# 34 ; cycle during the time that constant stimulation is applied accomplishes this desirable objective in the preferred embodiment of the stimulator shown . it should also be noted that actuation of the constant stimulation button s3 does not reset the treatment timer 60 . the output signal at terminal 3 of counter u4 is connected through j5 to the cycler indicator lights 70 . the signal passes through resistor r5 to the base of npn transistor q1 which has its base connected to ground through resistor r41 . the collector of q1 is connected to the base of q2 through resistor r12 . a green light emitting diode cr15 is connected to the collector of q1 while a red led cr16 is connected to the collector of q2 . the anodes of cr15 and cr16 are connected through a current limiting resistor r11 to the unregulated supply voltage + v . the emitters of q1 and q2 are tied together and connected to the collector of npn transistor q9 which receives an input signal through r42 . either q1 or q2 is turned on , depending upon whether the output of u4 is in a high or low condition . q9 is turned on for each half cycle of the output of rate oscillator 40 . the leds thus operate to indicate whether the stimulation is &# 34 ; on &# 34 ; or &# 34 ; off &# 34 ;. during the &# 34 ; on &# 34 ; cycle or when s3 is pushed for constant stimulation , the red light of cr16 will come on . during the &# 34 ; off &# 34 ; cycle or once the treatment timer shuts the device down , the green light of cr15 comes on . since q9 is turned on and off at the rate of the rate oscillator , the light emitting diodes cr15 and cr16 are blinked at a rate corresponding to the rate of the oscillator and the power consumption to drive the indicators is substantially reduced . if the rate of oscillator 40 is set at a very low rate , the blinking is visible to the user &# 39 ; s eye . the signal from the output of timers u3 and u4 after passing through the normally closed contacts 90 of j5 is conducted through resistor r43 , cr2 , conductor 93 and resistor r16 to the base of npn transistor q3 . the base of q3 is connected to ground through r15 . the collector of q3 is connected through r22 to the base of q8 . the emitter of npn transistor q8 is connected to the regulated supply + v1 . the base of q8 is connected to the regulated supply + v1 through resistor r45 and the collector of q8 is connected through r23 to diodes cr26 and cr23 at the inputs of identical channel 1 and channel 2 ramp circuits 48 and 50 , respectively , as shown in fig2 c . the detailed circuitry of pulse width circuits 32 and 34 are also identical . accordingly , it is necessary only to describe the operation of the channel 1 output circuitry since the channel 2 output circuitry is essentially identical . when the u3 or u4 timers switch to a positive signal , that signal charges capacitor c9 of ramp circuit 48 rapidly through resistor r23 which has a low impedance . the positive voltage applied at noninverting input terminal 5 of u1c produces a positive voltage at the output terminal 7 of u1c which is connected through resistor r25 to the noninverting input of u1d in the channel 1 pulse width circuit . thus , when a positive voltage is applied to cr26 , a positive signal is applied at the input of pulse width circuit 32 which , as described below , turns off the channel 1 output . when the positive signal holding channel 1 off is removed from the anode of cr26 , capacitor c9 , which had been previously charged to a high logic signal , begins to discharge through the series combination of adjustable resistor 52 and fixed resistor r18 . since u1c is connected as a voltage follower , the positive output of u1c gradually diminishes . the diminishing ramp signal from the output of ramp circuit 48 is summed in the pulse width circuit 32 with a rate signal on conductor 36 produced by rate oscillator 40 , the operation of which is discussed below . the square wave rate signal on conductor 36 is passed through capacitor c10 to the wiper of variable resistor r38 and through resistor r27 to the noninverting input terminal 3 of u1d . a diode cr25 has its anode connected to ground and its cathode connected to pin 3 of u1d . the values of r38 , r27 and c10 are selected to give a time constant which , when applied to the square wave signal at the output of oscillator 40 , produces a nominal 225 microsecond pulse width for the output pulses . the pulse width of the drive signal on conductor 28 is inversely dependent upon the magnitude of the ramp input to u1d produced by the ramp circuit 48 . as the output of u1c follows c9 to zero , + v1 divides across r26 and r25 to ground through u1c to provide a fixed bias to pin 2 of u1d . the signal on conductor 28 is connected to the output circuit 16 of channel 1 . the signal is an increasing pulse width signal beginning from a very narrow signal when the positive voltage is removed from the anode of cr26 and increasing to the full nominal pulse width after the ramp signal at the output of the ramp circuit 48 decreases to zero in accordance with the setting of ramp adjustment control 52 . as the output of u1c follows c9 to zero , + v1 divides across r26 and r25 to ground through u1c to provide a fixed bias to pin 2 of u1d . the leading edge of the pulse occurs at intervals determined by the square wave signal produced by oscillator 40 so the leading edges of the drive pulses on conductor 28 occur at a fixed pulse rate . rate oscillator 40 is based on schmitt trigger u2e and its adjustable feedback resistors r13 and 46 and timing capacitor c6 . the drive signal to channel 1 is inverted by schmitt trigger u2f so that the identical drive circuitry of channels 1 and 2 is not in the &# 34 ; on &# 34 ; condition at the same time . this is necessary to avoid undesirable overloading of the power supply . cells bt1 , bt2 and bt3 provide the power for the device . capacitors c11 and c12 are large capacitors used to facilitate driving the output current . they are back - to - back to prevent damage due to improperly installed batteries . because the output circuits 16 and 18 are identical , only the channel 1 output circuit 16 is described in detail . the drive signal on conductor 28 is passed through a variable calibration resistor r28 , the physician amplitude control 24 and the drive signal for q4 is taken from the wiper of the patient adjustment amplitude control 20 . the winding of potentiometer or a variable resistor 20 is connected to the base of a grounded emitter open collector npn transistor q11 to provide temperature and base - emitter voltage compensation for q4 . the collector of q4 is connected to the base of pnp darlington transistor pair q5 which has its emitter connected to the + v supply . the darlington base junction is also connected to the positive supply through r33 . the collector of q5 is connected through the primary winding of isolation transformer t1 and a current measuring resistor r31 to ground . r31 has an extremely low resistance and serves as a current sensor to force q5 to drive a constant current in the primary of t1 . the current feedback is obtained as follows . the base - emitter voltage of q4 and q11 are matched so that the voltage from control 20 is applied to r31 to drive a current therein proportional to the setting of 20 . thus , the t1 primary current is fixed at a selected current . t1 acts as a current transformer to produce a constant current output for load impedance from 100 to 1 , 000 ohms . a flyback diode cr17 suppresses the inductive surge voltage across the primary winding of transformer t1 when q5 shuts off at the completion of a pulse . the secondary winding of transformer t1 is connected to output terminals 12 . zener diode cr19 is a safety diode to prevent the voltage across output terminals 12 rising to an excessive value if the output impedance across terminals 12 is extremely high due to a loose electrode or some similar kind of open circuit condition . diode cr18 is used to keep cr19 from forward conducting during the negative or biphasic portion of the pulse , thus maintaining a zero net dc output to the patient . the transformer produces a balanced biphasic rectangular waveform with a zero net dc component to minimize the possibility of skin rash developing from stimulation . the device is operated as follows . fresh , fully - recharged batteries bt1 , bt2 and bt3 are installed . both amplitude controls 20 and 22 are set with s1 and s2 in the off position and at minimum resistance and the clinician or physician operated amplitude limit controls 24 and 26 are set at initially 50 % of appropriate levels . these and other clinician controls are set to produce minimal muscle fatigue while comfortable to the patient . the on and off time controls are also preset . generally , on off - time of twice the on - time will avoid fatigue and a ramp time of approximately two seconds will produce a good , comfortable contraction . a selected pulse rate of 30 - 35 pulses per second will produce a fused contraction with minimal fatigue . if the amplitude settings of controls 24 and 26 are insufficient to produce an adequate muscle contraction , then they may be adjusted upward until a good contraction is achieved . after the clinician controls are initially adjusted , the cables and electrodes are connected at jacks 12 and 14 and the electrodes are attached to the patient . the treatment time switch 64 is set in the continuous position and the constant stimulation button s3 is depressed while the patient amplitude adjustments 20 and 22 are advanced to produce a fused , but comfortable , contraction . if an adequate contraction is not achieved , even when the amplitude knobs are set to their maximum setting , the controls are returned to the minimum setting and the physician amplitude controls 24 and 26 are advanced by another increment before the patient adjusted amplitude controls 20 and 22 are again adjusted . when an adequate contraction is achieved , the constant stimulation s3 is released and the treatment time switch is set for the desired time interval , allowing treatment to begin .
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the present invention will now be more particularly described with reference to and as illustrated in the following figures : fig1 shows a cross - sectional view of a prior art laminated film as commonly used for flow - wrapping products , such as chocolate bars ; fig2 shows a cross - sectional view of a second prior art laminated film as used for wrapping stacks of tissue paper or trays of biscuits ; fig3 shows a cross - sectional view of an embodiment of the present invention where a metallic ink has been employed as a laser retardant material ; fig4 shows a cross - sectional view of a second embodiment of the present invention where an adhesive layer incorporates a laser retardant material ; fig5 shows a cross sectional view of a third embodiment of the present invention where a metallic ink has been laid onto a substrate along with non - metallic inks ; fig6 shows a plan view of a web of laminated material a fourth embodiment of the present invention ; fig7 shows a cross - sectional view of the web of laminated material through the dotted line marked x - x as illustrated in fig6 ; fig8 shows a plan view of a packaged product made using a portion of a web of material as shown in fig6 ; and fig9 shows a side view of a packaged product as illustrated in fig8 . with reference to fig3 , there is shown a laminated material 100 having five layers : a clear opp layer 102 ; an ink layer 104 ( which includes portions of metallic ink 106 ); an adhesive layer 108 ; a metallic foil layer 110 ; and a white opp layer 112 . the laminated material 100 is produced by bonding together the two separate webs of material by using adhesive . a first web of material 111 is formed by reverse printing the ink 104 which incorporates a number of portions having a metallic ink 106 onto the clear opp layer 102 . the second web 113 of material is formed by applying a metallic foil layer 110 to the white opp layer 112 by means of vacuum or vapour deposition ( however , the foil layer may simply be a foil which is bonded to the white opp by means of an adhesive ). the two webs 111 , 113 of material are then adhered to one another such that a layer of adhesive 108 binds the ink layer 104 to a position adjacent to and above the metallic foil layer 110 . a laser is used to produce offset scores or cuts in the first and second webs 111 , 113 of material . as can be seen in fig3 , the first laser 114 is able to penetrate the clear opp layer and the ink layer 104 . however , the power of the laser 114 is attenuated by a first portion of metallic ink 116 and whilst the path of the laser still continues to some degree through the adhesive layer 108 , it is unable to penetrate the metallic foil layer 110 . the second web 113 of material can be cut by the second laser 118 which is able to penetrate the white opp layer 112 and whilst the path of the laser is attenuated by the metallic foil layer 110 , it also passes to some extent through the adhesive layer 108 until it reaches a second portion of metallic ink 120 . the offset cuts ( denoted 122 and 124 ) formed by the first and second lasers ( 114 and 118 ) do not impair the sealing characteristics of the laminated material , but allows for the first and second webs to be peeled away from one another in the area between the cuts , if the adhesive layer 108 is a peelable and / or re - sealable adhesive . the laminated material 100 can be fed through a flow - wrap machine in order to produce packaging similar to that shown in fig8 and 9 ( which will be described in more detail later on ). the embodiment as shown in fig4 , is formed in a similar manner as to the laminated material shown in fig3 . however , rather than the laminated material having an ink layer 104 having portions of metallic ink , a laser - retardant material is placed within the adhesive layer . similar layers in fig3 will be denoted with the same reference numeral prime (‘) for fig4 . the laminated material 150 is formed having a clear opp layer 102 ′, and ink layer 104 ′, an adhesive layer 108 ′, a metallic foil layer 110 ′ and a white opp layer 112 ′. the ink layer 114 ′ does not contain any portions of metallic ink , but rather the adhesive layer 108 has a laser - retardant material 152 disposed therein . the laser - retardant material 152 may be any number of materials known to have laser - attenuating or retarding properties . for example , a laser - retardant material may simply be small metallic particles . as can be seen in fig4 , a first laser 154 is able to penetrate the clear opp layer 102 ′, the ink layer 104 ′ and whilst it passes through a laser - retardant particle 156 , the laser is ultimately prevented from passing further than the metallic foil layer 110 ′. a second laser 158 can pass through the white opp layer 112 ′, and whilst it is attenuated to some degree as it passes through the metallic foil layer 110 ′, it is ultimately prevented from passing further than through the laminated material by means of a metallic particle 160 . the metallic particles 156 , 160 , may be dispersed randomly or universally throughout the adhesive layer 108 ′. it will be apparent that if desired , using metallic particles which are uniformly dispersed throughout the adhesive layer 108 ′ will allow for the attenuation of the laser to the same degree as to that of the metallic foil layer 110 ′ depending on the concentration and how the metallic particles are dispersed throughout the adhesive layer . alternatively , the metallic particles may be placed in certain locations around the area intended to be cut by the laser so as to reduce costs of producing the material . with reference to fig5 , there is shown a further laminated material 200 again having a similar construction as to the materials 100 and 150 shown in fig3 and 4 . similar features in the laminated material 200 to those shown in the laminated materials of fig3 and fig4 are denoted with same reference numeral double prime (‘ ’). the laminated material 200 has a plurality of layers consisting of a clear opp layer 102 ″, an ink layer 104 ″, an adhesive layer 108 ″, a metallic foil layer 110 ″, and a white opp layer 112 ″. the adhesive layer 108 ″ does not contain any metallic particles as shown in fig4 , but in common with fig3 , it has portions of metallic ink 202 located within the ink layer 104 ″. during the print process of the ink layer onto the clear opp layer 102 ″, metallic ink 202 is layered on the clear opp layer 102 ″, along with non - metallic coloured ink 204 so as to produce the printed image seen on the outside of the laminated film . as in common with the laminated materials 100 and 150 as shown in fig3 and fig4 , the laminated material 200 is formed of two webs 111 ″, 113 ″ of material which are made prior to being bonded together by means of the adhesive layer 110 ″. also , the adhesive 108 ″ may be a re - sealable adhesive , so that after the offset cuts have been made , the two webs can be pulled apart from one another and resealed if necessary . in fig5 , a first laser 206 is shown to be able to penetrate the clear opp layer 102 ″, and is attenuated by a layer of metallic paint 208 and whilst the laser passes through the adhesive layer 108 ″, the metallic layer 110 ″ prevents further penetration . a second layer 210 penetrates the white opp layer 112 ″, and is attenuated by the metallic foil 110 ″ and passes through the adhesive 108 ″ and ultimately a metallic ink 212 prevents the laser from penetrating further through the laminated material . fig5 illustrates the feature that when applying the image to the clear opp layer 102 ″, a range of different inks ( metallic , non - metallic and coloured ) can be used so as to produce differential colour throughout the laminated material so as to provide the colours or images applied to a particular pack . the ease with which a metallic ink can be included in standard apparatus , so as to produce a laser - retardant layer , results in a laminated material which is thin and easy to produce using standard equipment , thus reducing the cost of producing the overall laminated material . with reference to fig6 and 7 , there are shown a continuous web of laminated material 300 which , after processing , is cut and run through a flow - wrap machine so as to flow - wrap a particular product , such as a chocolate bar . in common with earlier embodiments , the laminated material generally comprises an upper web 301 and a lower web 305 which are bonded together with adhesive . the continuous web 300 contains a number of “ v ” cut sections 302 which are areas that are processed by means of a laser prior to the material being used to wrap a given product . the “ v ” sections shown in fig6 with a solid line correspond to laser score lines 302 for the upper web 301 , whilst the dotted line corresponds to the lower score lines 303 for the lower web 305 . the web of laminated material 300 is formed of five layers : a clear opp layer 304 , an ink layer 306 ( which includes areas of metallic ink 308 , an adhesive layer 310 , a metallic foil layer 312 , and a white opp layer 314 . along either edge of the web , a permanent adhesive 316 is also provided beneath the white opp layer 314 . as in common with the laminated materials illustrated in fig3 - 5 , the laminated material shown in fig6 - 7 is formed by reverse printing an ink layer 306 to a clear opp layer 304 . the portions of the ink layer 306 incorporating metallic ink 308 correspond to the edges of the “ v ” portion 302 in the web of material 300 , as these are the areas which will be subjected to laser scoring . the ink layer 306 will be reverse printed onto the clear opp layer 102 and forms a first web which is bonded to a white opp layer 314 to which a metallic foil 312 has been applied . the two webs are adhered to one another by means of the adhesive layer 310 . in order to allow the laser scored “ v ” to form a re - sealable flap in the packaging when formed , the laminated material is adhered with permanent adhesive 318 throughout the majority of the material 300 . however , the areas between the offset cut ( between the “ v ”) will be formed with a re - sealable adhesive 330 , 332 so that once the offset cuts have been made , a re - sealable flap is formed within the material . the dotted lines shown in fig7 illustrate the cuts which will be made by the laser and the laser beam will penetrate the material in a similar manner as described with reference to fig3 - 5 . the addition of the permanent adhesive 316 along the edges of the material are used to bind the edges to themselves , when a product is placed centrally in the material during the packaging step so as to farm a thin seal as shown in fig9 . transverse bands 322 of permanent adhesive will also form the transverse sealed edges of the package when formed . with reference to fig8 and 9 , there is shown a pack 400 which has been formed from a section 320 of the material so as to encase a chocolate bar . the web 300 is formed around the product so as to encase it and the edges are bound to one another by means of the permanent adhesive 316 so as to form the “ fin ” 410 . transverse lines of permanent adhesive 322 are brought together so as to form the upper and lower sealing ends for 412 , 414 , and thus form a sealed pack . when the product is ready to be removed from the pack , the tip 416 of the “ v ” shaped score line 302 is lifted . the areas of re - sealable adhesive 330 , 332 allow the upper portion of the laminated material to be removed from the lower portion of the laminated material so as to form a flap and allow entry inside the package . if the entire product has not been consumed or removed , the flap can be re - adhered to the lower portion of the material so that the flap from a re - sealable flap . by removing the requirement to have two continuous metallic foil layers in the laminated material , the laminate can be formed much thinner and also at a reduced cost . the laminated material is also compatible with existing machinery , therefore removing the requirement to adapt or modify current flow - wrap machinery . the foregoing embodiments are not intended to limit the scope of protection afforded by the claims , but rather to describe examples how the invention may be put into practice .
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in order to be able to crosslink by disulfide bridging , the modified mercaptoamino functionalities according to the invention need to be in reduced form , that is to say in thiol form (— sh ). it is thus when they are in this form that the modified collagenic peptides may be termed “ crosslinkable ”. this term reflects the ability of the modified collagenic peptides to self - crosslink spontaneously in the presence of atmospheric oxygen , at ambient temperature and optionally in the presence of auxiliary agents such as oxidizing agents . the mercaptoamino residues bearing crosslinking functions of free thiol type or precursors thereof in substituted thiol form are advantageously residues that are closely or remotely derived from cysteine or analogues thereof : cysteamine and homocysteine . it is interesting to note that these various mercaptoamino residues are of biological nature . in the present specification , two types of monovalent mercaptoamino residues or grafts are distinguished , namely those bearing directly crosslinkable thiol functions and those bearing mercapto functions that are precursors of said thiol functions . as regards the mercaptans that are thiol precursors , they define a first subfamily of modified collagenic peptides according to the invention characterized in that at least some of the mercaptoamino residues , grafted onto the carboxylic acids of the aspartic acids and glutamic acids , correspond to the general formula ( i ) below : x = 1 or 2 ; r 0 = h or ch 3 ; r 1 represents h or coor 3 with r 3 corresponding to a hydrocarbon - based radical of aliphatic , aromatic or alicyclic type , preferably alkyl , alkenyl , aryl , aralkyl , alkylaryl , aralkenyl or alkenylaryl type and even more preferably of methyl or ethyl type ; r 2 is an aliphatic and / or alicyclic and / or aromatic radical , preferably an alkyl or an acyl optionally containing sulfur and / or amino , and even more preferably r 2 corresponds to formula ( ii ) below : with y , r 00 and r 4 corresponding to the same definition as that given in the legend in formula ( i ) for x , r 0 and r 1 . more specifically , the grafted mercaptoamino residues of these collagenic peptides , that are not immediately crosslinkable , are chosen from the group of monovalent radicals comprising : these are grafts derived from cystine and thus comprising a disulfide bridge which may be reduced with known reducing agents such as mercaptans ( mercaptoethanol , mercaptoacetic acid , mercaptoethylamine , benzyl mercaptan , thioresol , dithiothreitol , etc .) and / or reductive salts ( nabh 4 , na 2 so 8 , etc .) and / or organic reducing agents ( phosphine ). these novel modified collagenic intermediates according to this first subfamily are stable and soluble in water and more generally in aqueous medium and / or in polar solvents . in addition , they are readily purifiable and isolable , which makes them products that are practical for packaging , storage and use . the second subfamily of modified collagenic peptides according to the invention combines those in which the carboxyls of the glutamic acids and aspartic acids have reacted with the amine functions of the mercaptoamino residues of formula ( i ) in which the substituent r 2 corresponds to hydrogen . the modified collagenic peptides according to the second subfamily may be prepared by reducing the collagenic peptides according to the first subfamily , using reducing agents such as those defined above . these reduced collagenic peptides are readily purifiable and isolable . since they are obtained in dry form after an isolation in acidic medium , these peptides are stable . finally , they are soluble in water and more generally in aqueous medium and / or in polar solvents and are easy to use . the mercaptoamino residues of these peptides containing free thiol functions are defined by formula ( ii ) below : in which r 1 may correspond to h or coor 3 , with x , r 1 , r 0 and r 3 as defined above , and also r 3 may represent hydrogen or a cation to form a salt with coo − , this cation preferably being na + , k + or li + , when a step of deprotection of the ester is provided . the graft thus used is derived directly from cysteine . collagenic peptides comprising such mercaptoamino residues containing thiol reactive functions have the characteristic of being crosslinkable within the meaning of the invention . the crosslinking is carried out by oxidizing the thiols to disulfide bridges , which makes it possible to obtain a chemically crosslinked three - dimensional collagenic network , which is insoluble in physiological media and entirely stable . this oxidation may be obtained , for example , with atmospheric oxygen in weakly basic medium , with aqueous hydrogen peroxide solution or with iodo derivatives ( iodine , betadine ). among the modified collagenic peptides in accordance with the invention , it is possible to isolate those which exist in crosslinked form and which compose a third subfamily of collagenic peptides comprising collagenic chains linked together via disulfide bridges , in which the constituent sulfur atoms belong to mercaptoamino residues grafted onto the aspartic acids and glutamic acids of the collagenic chains , exclusively via amide bonds . these crosslinked collagenic peptides of the third subfamily may be advantageously obtained from the modified collagenic peptides of the second subfamily . these crosslinked collagenic peptides are novel , stable products whose mechanical and biological qualities make them biomaterials of choice for producing medical or surgical articles such as implants , prostheses , dressings or artificial skin . since it is possible to vary the degree of substitution of the carboxylic moieties of the aspartic acids and glutamic acids , there is certain room for maneuver in choosing the appropriate mechanical quality and the appropriate rate of biodegradation . moreover , the crosslinked form which is of concern for these collagenic peptides belonging to the third subfamily described in the present specification , is reversible . specifically , it is possible to reduce the disulfide bridges using suitable reducing agents . examples of these reducing agents are given above . in accordance with the invention , the free carboxylic residues of the aspartic acid and glutamic acid monomers of the collagenic chain are mobilized for the grafting of crosslinking functionalities . however , the fact nevertheless remains that at least some of the other free functions of the collagenic chain , such as , for example , the amine functions lysine residues , may serve as sites of attachment for groups other than the mercaptoamino residues as defined above and which afford diverse and varied functionalities , that are useful in the intended applications . as a result , the collagenic peptides as defined above may comprise , according to one variant , grafts g attached to at least some of the free amine moieties of the collagenic chain , via amide bonds , g being an acyl comprising a hydrocarbon - based species , with the exclusion of the mercaptoamino residues , in particular those as defined above , this species optionally comprising hetero atoms ( advantageously o and / or n ) and preferably being chosen from alkyls and / or alkenyls and / or alicyclics and / or aromatics and even more preferably from groups comprising an optionally unsaturated alkyl chain , containing from 1 to 22 carbon ( s ) or corresponding to the formula ( iii ) below : r 6 = h or a linear or branched alkyl radical and preferably a methyl ; the number of repeating units n is chosen such that the molecular weight of the polymer chain is between 100 and 15000 , preferably between 200 and 8000 , and is , for example , about 4000 . this additional functionalization on the amine sites of the lysines may give the modified collagenic peptide a hydrophilic or hydrophobic nature , or even a surfactant nature , which allows the swelling , mechanical strength and degradation kinetics properties to be modified . it is also conceivable for this functionalization to have therapeutic aims by means of the attachment of an active principle . in addition to the collagenic product aspect taken as such , the present invention also relates to the production of modified collagenic peptides , and in particular those as defined above and even more particularly those belonging to the three subfamilies presented above . the invention thus relates to a process for obtaining a collagenic peptide modified by grafting free or substituted thiol functions borne by mercaptoamino residues . this process consists essentially in reacting the collagenic peptide in solution with at least one precursor of a mercaptoamino residue in which the thiol function and the possible carboxylic function are blocked , in the presence of at least one grafting agent preferably chosen from the group of products for activating carboxylic groups and even more preferably from carbodiimides . the production conditions are chosen such that the grafting of the mercaptoamino residue is carried out on the free carboxylic moieties of the aspartic acids and glutamic acids of the collagenic chain . this process is particularly novel and advantageous in that it can be performed in aqueous medium in which the starting materials and / or the intermediate products and / or the final modified collagens are at least partially dissolved . in practice , all the products contained in the aqueous reaction medium are dissolved therein , from the first to the last step . this synthesis in aqueous medium , in accordance with the invention , is particularly advantageous industrially , since it is very simple to carry out , inexpensive and nonpolluting . specifically , it is easy , for example , to remove the reagents ( e . g . by diafiltration ) and to recover the targeted modified collagen . the process according to the invention is all the more advantageous since it makes it possible to achieve high degrees of grafting of mercaptoamino residues ( e . g . 12 %). preferably , the mercaptoamino residues ( monovalent groups ) which are grafted onto the collagenic peptide are those as defined above , in particular in formulae ( i ), ( i . 1 ), ( i . 2 ) and ( i . 3 ). in practice , the collagenic peptides thus obtained correspond , for example , to the precursors as targeted above , of crosslinkable collagenic peptides . these precursors are included in the first subfamily of modified collagenic peptides according to the invention . in order to be able to react with the free carboxylic moieties of the collagenic peptide , the mercaptoamino graft has a free amine function capable of reacting with the coohs to form an amide bond . this precursor is , for example , a cysteine , a homocysteine or a cysteamine in which the thiol function and the possible carboxylic acid function is ( are ) correctly protected . an efficient means for protecting the thiol function is to choose as precursor for the mercaptoamino residue to be grafted , cystine , homocystine or cystamine , which comprise a disulfide bridge that stabilizes the mercapto function . another means for protecting said function which may be chosen is any conventional function for protecting thiols that is known in the prior art ( see , for example , “ greene : protecting groups in organic chemistry , wiley , 1975 ”). the possible cooh functions of the graft may themselves be protected with a protecting group or any other organic function which may provide an advantageous property of any nature ( pegs or hydrophobic or hydrophilic or charged groups ). according to one advantageous arrangement of the invention , the precursor of the mercaptoamino residue corresponds to a formula ( iv ) corresponding to formula ( i ) given above and in which the free valency is replaced with a substituent capable of reacting with the carboxylic functions of the aspartic acids and glutamic acids of the collagenic chain , this substituent preferably being hydrogen , such that the reactive function is a primary amine . the precursors of formula ( iv ) that are most especially preferred are cystamine ( i . 1 ), cystine dimethyl ester ( i . 2 ) and cystine diethyl ester ( i . 3 ), all three of which comprise a disulfide bridge that protects the thiol function . in practice , the grafting of the - mercaptoamino residue is carried out by dissolving the collagenic peptide and then the precursor of the mercaptoamino residue to be grafted in a suitable solvent . this solvent may be , for example , water ( preferably ) and / or an organic solvent , for instance dimethyl sulfoxide ( dmso ), n - methylpyrrolidone ( nmp ) or the like . the reaction conditions are chosen so as to prevent the activated collagen from reacting with the amines contained in its own skeleton . a coupling agent , such as a carbodiimide , is then added to the reaction solution and the grafting is left to proceed while stirring the medium for a few hours , at ambient temperature . the process according to the invention makes it possible to obtain collagenic peptides substituted with mercaptoamino residues that are precursors of the crosslinkable thiol residues . the peptides thus obtained are novel intermediate products that are stable and soluble in water . they may be isolated and purified , for example by dialysis or diafiltration and then lyophilization or by precipitation in organic medium and then drying . a subject of the present invention is also a process for preparing a crosslinkable collagenic peptide modified by grafting free thiol functions borne by mercaptoamino residues . this process is characterized in that it consists essentially : 1 . in reacting in solution the collagenic peptide with at least one precursor of a mercaptoamino residue whose thiol function and possible carboxylic function are blocked , in the presence of at least one grafting agent preferably chosen from the group comprising products that activate carboxylic groups , preferably carbodiimides , 2 . and in deprotecting ( conversion to thiols ) the mercapto functions of the mercaptoamino residues grafted onto the modified collagenic peptides obtained in step 1 . the crosslinkable collagenic peptides thus prepared correspond , for example to the products containing free thiol functions included in the second subfamily of modified collagenic peptides , as defined above . when the protection or masking of the mercapto functions is provided by a disulfide bridge ( that is to say when the graft precursors are , for example , cystamine or cystine ), the thiol function is regenerated by reduction . this reduction may be carried out using reducing agents such as mercaptans ( mercaptoethanol , mercaptoacetic acid , mercaptoethylamine , benzyl mercaptan , thiocresol , dithiothreitol , etc .) and / or reductive salts ( nabh 4 , na 2 so 3 , etc .) and / or organic reducing agents ( phosphine ). according to one preferred characteristic of the present invention , the protective disulfide bridge is reduced in basic aqueous medium using dithiothreitol . after this step , the thiolated collagen obtained is purified by dialysis / diafiltration and may be isolated , for example by lyophilization . the invention also relates to a process for preparing a crosslinked collagenic peptide , from a collagenic peptide modified by grafting free thiol functions borne by mercaptoamino residues . this process is characterized in that it consists , essentially : 1 . in reacting in solution the collagenic peptide with at least one precursor of a mercaptoamino residue whose thiol function and possible carboxylic function are blocked , in the presence of at least one grafting agent preferably chosen from the group comprising products that activate carboxylic groups , preferably carbodiimides , 2 . and in deprotecting ( conversion to thiols ) the mercapto functions of the mercaptoamino residues grafted onto the modified collagenic peptides obtained in step 1 , 3 . and in oxidizing the thiol functions of the crosslinkable modified collagenic peptide obtained in step 2 , so as to form intercatenary disulfide bridges . this oxidation may be carried out , for example , using atmospheric oxygen in weakly basic medium , or using aqueous hydrogen peroxide solution or iodo derivatives ( iodine , betadine ). the crosslinked collagenic peptides , as prepared by the above process , correspond in particular to the crosslinked products of the third subfamily of modified collagenic peptides as defined above . according to one advantageous characteristic which is intrinsic to the three processes described above , an additional step f is envisaged , this being a step of functionalization with grafts g that are different in nature from the grafts attached to the carboxylic functions of the aspartic acids and glutamic acids , this step f consisting essentially in carrying out an acylation of at least some of the free amine functions of the collagenic chain , so as to attach thereto grafts g comprising a hydrocarbon - based species , with the exclusion of mercaptoamino residues , in particular those as defined above , this species optionally comprising hetero atoms ( advantageously o and / or n ) and preferably being chosen from alkyls and / or alkenyls and / or alicyclics and / or aromatics , and even more preferably from groups comprising an optionally unsaturated alkyl chain or corresponding to formula ( iii ) below : r = h or ch 3 ; r 6 = h or a linear or branched alkyl radical and preferably a methyl ; z = 0 , 1 or 2 and n & gt ; 0 . in order to be able to react by acylation with the three amine functions of the residue of the collagenic chain , the precursors of the grafts g advantageously comprise at least one activatable carboxylic acid function . it is preferable for this acylation to proceed before the reaction of the free carboxylic functions of the collagenic chain with the precursor of the mercaptoamino graft ( i ). having said this , it is not excluded for this acylation also to take place on the thiolated collagenic peptides obtained from step 1 and / or on the crosslinked collagenic peptides obtained from step 3 ( e . g . directly on a crosslinked film , with removal of the reagents by simple washing ). the acylation and coupling reactions of amine functions with carboxylic sites belonging to proteins are known to those skilled in the field of protein biochemistry . for further details in this respect , reference will be made in particular to the following books : “ techniques in protein chemistry ” r . l . lundblad chap . 10 - 14 . “ chemistry of protein conjugation and cross - linking ” s . s . wong , boca raton , crc press , 1993 , chap . 2 . it is interesting to note that the reagents used for the chemical modifications performed according to the processes in accordance with the invention are either convertible into nontoxic products or readily removable by nondegrading processes such as , for example , dialysis . moreover , the invention offers the very appreciable possibility of controlling the kinetics and the degree of crosslinking of the collagen . another appreciable advantage of the present invention is that it allows the mechanical and biodegradation properties to be modified by controlling the number of mercaptoamino residues introduced per unit of mass of the collagen . it is also interesting to be able to functionalize the crosslinked or noncrosslinked collagenic chains with hydrophilic functions , for example . finally , it is important to point out that the products according to the invention may be sterilized by the conventional methods for sterilizing biological polymers . finally , the very good solubility of the novel noncrosslinked collagenic peptides according to the invention in aqueous medium must be stressed , these peptides having the characteristic of containing sulfur - containing crosslinking functions borne exclusively by the carboxyls of the aspartic acids and glutamic acids . as a result , the crosslinkable products according to the invention find immediate applications firstly in human medicine and secondly in the field of biology . in human medicine , they may implants , for ophthalmological implants , prostheses ( for example bone prostheses ), dressings in the form of films or felts , artificial tissues ( epidermis , blood vessels , ligaments or bone ), bioencapsulation systems ( microspheres or microcapsules ) allowing the controlled release of active principles in vivo , biocompatibilizing coatings for implantable medical articles , or suture threads . the crosslinkable collagenic products according to the invention may also be used in surgery , as adhesives and / or as sealing materials ( cements ). in biology , the materials according to the invention constitute excellent supports for two - dimensional cell cultures ( films ) and three - dimensional cell cultures ( felts ). the crosslinked collagen according to the invention may be used alone or as a mixture , for example with modified or unmodified biological polymers or synthetic polymers . for each of the abovementioned biomedical applications , it is essential to have available a crosslinked collagen which has determined and specific physicochemical , mechanical or biological properties . consequently , it is necessary to control fully the chemical modifications of the collagen , so as to be able to produce a wide range of crosslinkable collagens and thus to satisfy most of the constraints appearing during the development of the specifications for a given application . it emerges from the above description that the invention fully satisfies this need . other advantages and variants of the present invention will emerge clearly from the implementation examples given below . synthesis of a collagenic peptide ( 2nd subfamily ) in which the carboxylic acids are substituted with cysteine ethyl ester ( degree of substitution representing 0 . 8 % of the amino acids ) 25 g of atelocollagen ( types i + iii , extracted from calf skins , 1 . 3 mmol of cooh / g ) are placed in 2 . 5 l of water and the temperature of the medium is raised to 50 ° c . with stirring . the 1 % w / v solution thus obtained is filtered through a 0 . 22 μm filter . once the temperature has fallen to 30 ° c ., 46 . 5 g of cystine diethyl ester are added and the ph is adjusted to 4 . 2 . 0 . 6 g of 1 -( 3 - dimethylaminopropyl )- 3 - ethylcarbodiimide hcl is then added and the reaction is left to proceed for 2 h at 30 ° c . with stirring . the reaction medium is concentrated to 5 % w / v and dialyzed against water to remove the excess reagents and the reaction byproducts . the product obtained is a stable synthetic intermediate . it is a collagenic peptide ( 1st subfamily ) a fraction of the aspartic acids and glutamic acids of which are substituted with cystine diethyl ester . the degree of substitution is measured by assaying with nstb ( 2 - nitro - 5 - thiosulfobenzoate ), a reagent for disulfide bridges . this assay is described in : thannhauser t . w . et al ., analysis of disulfide bonds in peptides and proteins . methods in enzymology . jacoby w . b . and griffith o . xl new - york : academic press , 1987 . vol . 143 , 115 - 119 . [ s — s ]: 0 . 094 mmol / g of dry product ; i . e . 0 . 87 mol % of substituted amino acids . the product obtained may be isolated by lyophilization or may be reduced to give the corresponding thiol collagen . 7 . 6 g of glycine , 5 . 8 g of 1 , 4 - dithiothreitol and a sufficient amount of 4n naoh to reach a ph of 9 . 0 are added to the modified collagenic peptide dissolved at 5 % w / v in water , obtained in step i . the reaction medium is stirred for three hours at 35 ° c . at this stage , the solution is acidified to ph 2 with 6n hcl , dialyzed against 0 . 012n hcl to remove all trace of reagents and of reaction byproducts and then filtered through a 0 . 22 μm filter . the product thus purified is isolated by lyophilization . the degree of substitution is measured by an assay with 5 , 5 ′- dithiobis - 2 - nitrobenzoic acid ( dtnb ), a reagent which is specific for thiol functions . this assay is described in : “ ellman g . l ., tissue sulfhydryl groups , archives of biochemistry and biophysics , 1959 , 82 , 70 - 77 ”. [ sh ]: 0 . 091 mmol / g of dry product , i . e . 0 . 8 mol % of substituted amino acids . the entire synthesis may be performed aseptically so as to obtain in fine the product in the form of a sterile lyophilizate . synthesis of a collagenic peptide ( 2nd subfamily ) in which the carboxylic acids are substituted with cysteine ethyl ester ( degree of substitution representing 3 mol % of the amino acids ) example 1 is repeated , the only difference being that the amount of coupling agent is 2 . 9 g . [ sh ]: 0 . 347 mmol / g of dry product , i . e . 3 . 3 mol % of substituted amino acids . synthesis of a collagenic peptide ( 2nd subfamily ) in which the carboxylic acids are substituted with cysteine ethyl ester ( degree of substitution representing 7 mol % of the amino acids ) example 1 is repeated , the only difference being that the amount of coupling agent is 12 g . [ sh ]: 0 . 706 mmol / g of dry product , i . e . 7 mol % of substituted amino acids . synthesis of a gelatin ( 2nd subfamily ) in which the carboxylic acids are substituted with cysteine ethyl ester ( degree of substitution representing 5 mol % of the amino acids ) example 1 is repeated , replacing the atelocollagen with gelatin ( gelatin extracted from pig skins , 250 bloom , 1 mmol of cooh / g ). [ sh ]: 0 . 536 mmol / g of dry product , i . e . 5 . 2 mol % of substituted amino acids . synthesis of a collagenic peptide ( 2nd subfamily ) in which the carboxylic acids are substituted with cysteamine ( degree of substitution representing 3 mol % of the amino acids ) example 1 is repeated , replacing 46 . 5 g of cystine diethyl ester with 28 . 4 of cystamine . [ sh ]: 0 . 33 mmol / g of dry product , i . e . 3 . 0 mol % of substituted amino acids . synthesis of a collagenic peptide ( 2nd subfamily ) in which the amines are acetylated ( graft g ) and in which the carboxylic acids are substituted with cysteine ethyl ester ( degree of substitution representing 5 mol % of the amino acids ) 25 g of atelocollagen ( types i + iii , extracted from calf skins , 1 . 0 mmol of cooh / g ; 0 . 33 mol of ε - nh 2 / g ) are placed in 0 . 5 l of water and the temperature of the medium is raised to 50 ° c . with stirring . the 5 % w / v solution thus obtained is filtered through a 0 . 22 μm filter . after cooling the solution to 30 ° c ., 4 . 2 g of nahco 3 and a sufficient quantity of 4n naoh to adjust the ph to 8 . 5 are dissolved . 7 . 34 ml of acetic anhydride are then added slowly and sequentially , over 30 minutes with stirring at 30 ° c ., while maintaining the ph at 8 . 5 with 4n sodium hydroxide solution . the solution is then acidified slowly to ph 3 with 6n hcl and is dialyzed against water to remove the excess reagents . finally , the 1 % w / v medium is diluted with water and the synthesis is continued as described in example 1 ( coupling of cystine diethyl ester followed by reduction ). [ acetyl ] by assay of acetic acid ( boehringer kit ) after basic hydrolysis of the product : 0 . 30 mmol / g of dry product , i . e . 2 . 9 mol % of acetylated amino acids ( virtually total acetylation of the lysine residues ). [ sh ]: 0 . 53 mmol / g of product , i . e . 5 . 1 mol % of substituted amino acids . synthesis of a collagenic peptide ( 2nd subfamily ) in which the amines are substituted with peg ( graft g ) and in which the carboxylic acids are substituted with cysteine ethyl ester ( degree of substitution representing 5 mol % of the amino acids ) 10 g of atelocollagen ( types i + iii , extracted from calf skins , 1 . 3 mmol of cooh / g ; 0 . 33 mol of ε - nh 2 / g ) are placed in 0 . 5 l of water and the temperature of the medium is raised to 50 ° c . with stirring . the 2 % w / v solution thus obtained is filtered through a 0 . 22 μm filter . once the temperature has fallen to 30 ° c ., the ph is adjusted to 9 . 0 with 4n naoh . 5 g of methoxypolyethylene glycol propionic acid n - hydroxysuccinimidyl ester ( spa - peg ) of mw 5000 g / mol are then added and the reaction is left to proceed at 30 ° c . with stirring for 30 min , while maintaining the ph at 9 by adding 4n naoh . a further 5 g of spa - peg are added and the reaction medium is stirred for 30 min while maintaining the ph . the medium is then diluted to ½ with water to bring the collagen concentration to 1 % w / v . 18 . 5 g of cystine diethyl ester are added and the ph is adjusted to 4 . 2 . 2 . 2 g of 1 -( 3 - dimethylaminopropyl )- 3 - ethylcarbodiimide hcl are then added and the reaction is left to proceed for 2 h at 30 ° c . with stirring . the reaction medium is concentrated to 5 % w / v and dialyzed against water to remove the excess reagents and the reaction byproducts . 3 . 0 g of glycine , 2 . 3 g of 1 , 4 - dithiothreitol and a sufficient quantity of 4n naoh to reach a ph of 9 . 0 are added to the modified collagenic peptide dissolved at 5 % w / v in water . the reaction medium is stirred for 3 hours at 35 ° c . at this stage , the solution is acidified to ph 2 with 6n hcl , dialyzed against 0 . 012 n hcl to remove all trace of reagents and reaction byproducts and then filtered through a 0 . 22 μm filter . the product thus purified is isolated by lyophilization . the lyophilizate is extracted with 2 l of absolute ethanol , contracted with acetone and then dried under vacuum at 30 ° c . for 18 h . the absence of ungrafted polyethylene glycol is monitored by gel permeation chromatography , with refractometric detection . [ sh ]: 0 . 247 mmol / g of dry product , i . e . 4 . 5 mol % of substitution of the amino acids . [ peg ]: 0 . 8 mol % substitution of the amino acids , degree recalculated according to the amount of oh - proline assayed in the modified product / unmodified product . 250 mg of the collagenic peptide are placed in 5 g of water for injection and are stirred in a sealed flask for 15 min at 40 ° c . the ph measurements are carried out at 30 ° c . the ph adjustments are carried out using 1n naoh . a number of solubility examples are given in table 1 . 250 mg of lyophilizate are placed in 4 . 5 ml of 10 mm ph 7 . 4 phosphate - buffered saline ( pbs ) and the mixture is stirred in a sealed flask at 40 ° c . for 15 minutes . the ph is adjusted to 7 . 4 ± 0 . 1 with 1n naoh and the amount of pbs required to obtain a final collagenic peptide concentration of 50 g / l is added . the samples are placed at 37 ° c . 100 μl of a 1 % h 2 o 2 solution in pbs preheated to 37 ° c . are added to 900 μl of the collagenic peptide solution . the indications of table 2 show that the crosslinking by oxidation ( kinetics and degree ), under given conditions , depends on the modified collagenic peptide used . a solution containing 20 g / l of precursor collagenic peptide is prepared by dissolving lyophilizate in sterile water . in this example , 2 . 0 g of lyophilizate are dissolved in 98 g of sterile water . the mixture is stirred in a sealed container at 40 ° c . for 15 min in order to obtain complete dissolution . the ph of the solution is adjusted to 6 . 5 with 1n sodium hydroxide solution , at 25 ° c . the solution is stirred again at 40 ° c . for 10 min . the solution at 40 ° c . is filtered through membranes of porosity 0 . 45 μm and then membranes of porosity 0 . 2 μm . the final filtration is carried out over sterile molds ( polystyrene petri dishes may be used ). 40 . 0 g of filtered solution are run into two 12 × 12 cm 2 molds . the molds are closed . the solution is matured , which is reflected by a physical gelation , for 24 h at a temperature of 16 ° c .± 1 ° c . this temperature is necessarily less than the gel / sol transition temperature . the maturation is carried out in a chamber at controlled temperature , and the molds rest on a horizontal plate . after 24 h , the mold covers are removed and the gelled solutions are evaporated over 24 h , at the same temperature in a confined chamber , in the presence of desiccants ( typically sodium hydroxide pellets ). after 24 h , the films obtained are dry , clear and smooth . the dry films are crosslinked at 20 ° c ., by adding 30 g of 0 . 3 % hydrogen peroxide solution in an aqueous decimolar solution of ammonium acetate . the crosslinked film is removed and washed successively with 30 g of ph 7 . 4 phosphate buffer and 30 g of water . all the solutions used are sterile . the film is then left to dry under a laminar flow fume cupboard for 24 h . the dried films obtained contain a residual percentage of water of about 10 %. the films obtained are stable at room temperature . they remain stable and manipulable after 24 h in water or in a phosphate buffer . tensile mechanical properties of the films obtained according to example 10 the measurements of the mechanical properties of the films are carried out using a universal testing machine of dy34 type of the brand adamel lhomargy . the films are hydrated at ambient temperature in a phosphate buffered saline ( pbs , ph = 7 . 4 ) for 2 h . next , they are cut into 4 mm by 30 mm strips using a very sharp sample punch . the thickness is measured on the hydrated samples . the samples are mounted on a cardboard frame which helps to position them in the jaws . the sample of film is kept hydrated . the frame is cut just before the tensile test , which proceeds at a constant speed of 2 mm / min . the initial modulus and the breaking stress are calculated from the tensile curves using the sections of hydrated test pieces . the tensile properties of the films obtained according to the process described in example 10 depend on the modified collagenic peptide used , as shown in table 3 .
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