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referring again to fig1 there is shown an exercise bicycle which has a body portion 2 , a pair of pedals 4 , 5 , longitudinal base support 6 , a pair of transverse base supports 7 , 8 and a seat 12 which is supported by adjustable member 14 whose position is locked by locking means 16 of the present invention . adjustment member 14 is received within tubular member 15 which in turn cooperates with locking means 16 . adjustable member 21 is received within tubular member 20 having opening 22 and in turn cooperates with locking means 18 . locking means 18 secures adjustment member 21 in the desired angular position within opening 22 and locking means 24 secures handlebars 26 , 28 and housing 2a in the desired axial position on adjustable member 21 . the housing 21 which in the form shown is movable with handlebars 28 , 29 on adjustable member 21 and may contain electronics and display means to show speed , distance , calories used and the like . in this manner , by adjusting locking means 16 , 18 and 24 the elevation of seat 12 , the elevation of handlebars 26 , 28 and the rotational position of handlebars 26 , 28 may be established . referring to fig2 through 4 , a preferred embodiment of the present invention will be considered . a tubular portion 30 of the apparatus which will receive an adjustable member 56 is provided with an opening so that the locking means may be provided . the locking means in this embodiment consists of a frame - like member 32 which defines an opening 36 within which adjustable member 56 may be reciprocated when the locking means is in unlocked position . fixedly secured to the locking member 32 is a threaded stud 38 which projects through the opening in the tubular portion 30 and is threadedly engaged within hub portion 42 of knob 40 . it will be appreciated that as the knob is rotated in a first direction the framing member 32 will be urged responsively in a path oriented generally transversely with respect to the longitudinal axis of the adjustable member 56 . the apparatus is such that movement in a first direction will establish locking of the adjustable member 56 in a desired position and the rotation of the knob 40 in the other direction will unlock the adjustable member 56 . the adjustable member 56 will be received within the passageway 44 of the tubular member 30 . as is shown , the tubular portion 30 , in the preferred embodiment has a pair of generally opposed recesses 52 , 54 . in the locked position , such as is shown in fig3 the framing member 32 will be received in the recess 54 disposed adjacent to knob 40 . when it is desired to unlock the adjustable member for moving it to another position or rotating the same , the knob 40 is rotated in the opposite direction thereby causing translational movement of the framing member 32 in a path generally transverse to the longitudinal axis of adjustment member 56 and relieving the compressive restraint thereby permitting free movement of the adjustment member 56 . it will be appreciated that this device permits effective secure locking of the adjustable member which may directly or indirectly be secured to a seat , handlebars or other portions of exercise apparatus desired to be moved while permitting manual operation in an easy manner . while the embodiment of fig2 through 4 illustrate a generally rectangular frame member 32 associated with a generally rectangular tubular member 30 it will be appreciated that the members 30 , 32 may be of generally circular configuration or any other desired configurations . one advantage of having a non - circular configuration is that undesired rotation of the frame member 32 with respect to the tubular member 30 is resisted . referring further to fig5 through 7 a further embodiment of the invention will be considered . in this embodiment , a first tubular locking member 66 is provided with a pair of relieved surfaces 68 , 72 which define , respectively , recesses 70 , 74 . connecting means 78 are fixedly secured to the tubular element 66 and , in the form shown , are of generally u - shape having a pair of lateral walls 80 , 84 and a base wall 82 . a threaded stud 86 is fixedly secured to the base wall 82 and projects outwardly therefrom . in use , the tubular element 66 and the connecting member 78 would be disposed within a tubular portion such as portion 30 in fig2 with the stud 86 projecting through an opening in the tubular portion . a second tubular element 92 would also be positioned within the tubular portion 30 . this member also has a pair of surfaces 94 ( second surface not shown ) which define recesses 96 ( second recess not shown ). this structure has a closed end wall 98 having an aperture 100 through which stud 86 passes . knob 102 is threadedly secured to stud 86 . the four recesses ( two opposed pairs ) in the two tubular elements 66 , 92 are adapted , when in closed position and placed in compression to effect clamping engagement with the adjustable member 104 . fig6 shows the structure in compressed condition locking the adjustable member 104 and fig7 shows the structure in unlocked position which permits rotational and translational movement of adjustable member 104 . while the devices of the present invention may have locking components made of any suitable material , it is presently preferred to make them of a suitable metal or resinous plastic . while several preferred geometric configurations have been illustrated for purposes of clarity of disclosure , it will be appreciated that the invention is not so limited . a prime feature of the invention is that the construction be such that rotation of an externally disposed knob which is threadedly secured to a framing component results in the framing elements disposed within the tubular member being placed in compression so as to lock the adjustable member which has a path of movement generally transverse thereto in secure position . while for convenience of reference herein specific reference has been made to exercise bicycles it will be appreciated by those skilled in the art that the apparatus of the present invention may be employed in a wide variety of types of exercise equipment such as rowing machines , fitness treadmills and pogo sticks , for example . whereas particular embodiments of the invention have been described above for purposes of illustration , it will be appreciated by those skilled in the art that numerous variations of the details may be made without departing from the invention as described in the appended claims . | 8 |
the present invention will be described more fully hereinafter with reference to the accompanying drawings in which preferred embodiments of the invention are shown . fig2 illustrates a tolerant input buffer circuit according to an embodiment of the present invention . referring to fig2 the tolerant input buffer is one of signal transmission circuits implemented in a semiconductor integrated circuit and includes a first transmission circuit t 2 , a second transmission circuit t 3 , a first inverting circuit 17 , a first switching circuit 15 , and a second switching circuit t 4 . the tolerant input buffer may further include an electrostatic discharge ( esd ) protection circuit 13 and a second inverting circuit 19 . the esd protection circuit 13 protects an internal circuit of a semiconductor memory device from esd applied from outside of the semiconductor memory device and is installed in a pad of a chip in order to prevent discharge from an external pin from applied esd . when esd is applied to an input pin 11 , the esd protection circuit 13 causes a punch - through phenomenon , thereby sending high current caused by esd to the ground voltage vss and protecting the internal circuit of the memory device . that is , in a case where a very high voltage is induced to the drains of mos transistors t 12 , t 13 , and t 14 , punch - through occurs in the mos transistors t 12 , t 13 , or t 14 . the esd protection circuit 13 includes a plurality of transistors t 11 through t 15 . the source of the transistor t 11 is connected to a first supply voltage vdd 1 ( e . g ., 3 . 3v ), and the gate thereof is connected to a node a . the gate of the transistor t 12 is connected to the first supply voltage vdd 1 , the drain thereof is connected to the node a , and the source and substrate thereof are connected to the drain and substrate of the transistor t 11 . the source of the transistor t 13 is connected to the first supply voltage vdd 1 , and the substrate and gate thereof are connected to the source and substrate of the transistor t 12 , the substrate of the transistor t 4 and the substrate of the transistor t 3 , and the drain thereof is connected to the node a . the gate of the transistor t 14 is connected to the first supply voltage vdd 1 , the drain thereof is connected to the node a , and the substrate thereof is connected to the ground voltage vss . the gate , source , and substrate of the transistor t 15 are connected to the ground voltage vss , and the drain thereof is connected to the source of the transistor t 14 . a resistor r 2 connected between the node a and a node b , transmits an input signal in input to a pad 11 from the node a to the node b and restricts current flowing from the node a to the node b . preferably , in a case where the supply voltage of the semiconductor memory device is 3 . 3v or 2 . 5v , the tolerant input buffer tolerates the input signal in from 0v to 5v . preferably , in a case where the supply voltage of the semiconductor memory device is 1 . 8v , the tolerant input buffer tolerates an input signal in from 0v to 3 . 3v . the first transmission circuit t 2 transmits a signal of the node b to a node n 11 . the first transmission circuit t 2 is an nmos transistor . the gate of the nmos transistor is connected to the first supply voltage vdd 1 , the drain thereof is connected to the node b , and the source thereof is connected to the node n 11 , and a predetermined substrate voltage ( e . g ., negative voltage ) is supplied to the substrate thereof . the first supply voltage vdd 1 may be 3 . 3v , 2 . 5v , or 1 . 8v , but in the illustrative embodiment of fig2 the first supply voltage vdd 1 is 3 . 3v . that is , in a case where the voltage of the node b is greater than 3 . 3v , the maximum voltage transmitted to the node n 11 corresponds to a voltage drop from the first supply voltage vdd 1 of 3 . 3v to a threshold voltage ( hereinafter referred to as ‘ vth ’) of the first transmission circuit t 2 . for example , assuming that 3 . 3v is supplied to the gate of the first transmission circuit t 2 and the threshold voltage vth of the first transmission circuit t 2 is 0 . 7v , the maximum voltage transmitted to the node n 11 is 2 . 6v . however , considering a body effect of the first transmission circuit t 2 , the maximum voltage transmitted to the node n 11 may be smaller than 2 . 6v . the second transmission circuit t 3 transmits the signal of the node b to the 26 node n 11 . the second transmission circuit t 3 is a pmos transistor . the gate of the pmos transistor t 3 is connected to a node d , and the source thereof is connected to the node b , and the drain thereof is connected to the node n 11 , and a predetermined substrate voltage ( e . g ., positive voltage ) is supplied to the substrate thereof . the second transmission circuit t 3 transmits the signal of the node b to the node n 11 in response to the amplitude of the signal of the node b and the amplitude of the signal of the node d . that is , the second transmission circuit t 3 is turned on and transmits the signal of the node b to the node n 11 only if the signal of the node b is greater in amplitude than the signal of the node d and greater than the threshold voltage vth of the second transmission circuit t 3 . the first inverting circuit 17 inverts the signal of the node n 11 and outputs the inverted signal to a node c . a schmitt trigger is used as the first inverting circuit 17 . the first switching circuit 15 pulls down the node d in a case where the signal of the node c is logic ‘ high ’. the first switching circuit 15 includes nmos transistors t 5 and t 6 . the gate of the nmos transistor t 5 is connected to the first supply voltage vdd 1 , the drain thereof is connected to the node d , and the substrate thereof is connected to the ground voltage vss . the gate of the nmos transistor t 6 is connected to the node c , and the source and substrate thereof are connected to the ground voltage vss , and the drain thereof is connected to the source of the nmos transistor t 5 . however , the first switching circuit 15 may include only the transistor t 6 , the drain thereof being connected to the node d , the gate thereof being connected to the node c , and the source and substrate thereof being connected to the ground voltage vss . the second switching circuit t 4 transmits the signal of the node b to the node d . the second switching circuit t 4 is a pmos transistor . the gate of the pmos transistor is connected to a second supply voltage vdd 2 , the source thereof is connected to the node b , and the drain thereof is connected to the node d . here , in this illustrative embodiment , the second supply voltage vdd 2 is 2 . 5v . however , the second supply voltage vdd 2 may be a voltage other than 2 . 5v . preferably , the first supply voltage vdd 1 is greater than the second supply voltage vdd 2 . the second inverting circuit 19 inverts the signal of the node c and outputs an output signal out to a predetermined internal circuit ( not shown ). fig3 illustrates a tolerant input buffer circuit according to another embodiment of the present invention . referring to fig3 the tolerant input buffer , as one of signal transmission circuits , includes a first transmission circuit t 2 , a second transmission circuit t 3 , a first inverting circuit 17 , a first switching circuit 15 , a second switching circuit t 4 , a voltage generation circuit 23 , and a transition voltage control circuit 21 . the tolerant input buffer may further include an electrostatic discharge ( esd ) protection circuit 13 and a second inverting circuit 19 having the same structure as fig2 . the basic operation of the tolerant input buffer of fig3 is similar to the tolerant input buffer of fig2 . thus , detailed descriptions related to only the voltage generation circuit 23 and the transition voltage control circuit 21 are included as below . the transition voltage control circuit 21 is connected between the node n 11 and the first switching circuit 15 . the transition voltage control circuit 21 may include a voltage comparator . according to the state of the signal of the node n 11 , logic ‘ high ’ is transitioned to logic ‘ low ’, or logic ‘ low ’ is transitioned to logic ‘ high ’. that is , the transition voltage control circuit 21 may control an input logic low voltage ( vil ) or an input logic high voltage ( vih ) of the first switching circuit 15 . for example , the transition voltage control circuit 21 recognizes the case where the signal of the node n 11 is 3v , as the vih , thereby turning on the nmos transistor t 6 of the first switching circuit 15 . further , the transition voltage control circuit 21 recognized a case where the signal of the node n 11 is 2v , as the vih , thereby turning on the nmos transistor t 6 of the first switching circuit 15 . the voltage generation circuit 23 supplies a predetermined signal to the gate of the second switching circuit t 4 , thereby controlling the operation of the second switching circuit t 4 . that is , the second switching circuit t 4 transmits the signal of the node b to the node d in response to the output signal of the voltage generation circuit 23 supplied to the gate . for example , assuming that the output signal of the voltage generation circuit 23 is 2 . 5v , and the threshold voltage vth of the second switching circuit t 4 is 0 . 8v , the second switching circuit t 4 is turned on and transmits the signal of the node b to the node d in a case where a signal greater than 3 . 3v is input to the node b . further , assuming that the output signal of the voltage generation circuit 23 is 1 . 8v and the threshold voltage vth of the second switching circuit t 4 is 0 . 8v , the second switching circuit t 4 is turned on and transmits the signal of the node b to the node d in a case where a signal greater than 2 . 6v is input to the node b . in a case where the output signal of the voltage generation circuit 23 increases , the amplitude of the signal of the node b turning on the second switching circuit t 4 increases . however , in a case where the output signal of the voltage generation circuit 23 decreases , the amplitude of the signal of the node b turning on the second switching circuit t 4 decreases . since switching of the second switching circuit t 4 is controlled by the output signal of the voltage generation circuit 23 , switching of the second transmission circuit t 3 may be controlled . thus , a signal transmitted from the node b to the node n 11 may be controlled by switching of the second transmission circuit t 3 . fig4 illustrates the comparison of dc voltage characteristics of the conventional tolerant input buffer circuit with the tolerant input buffer circuit according to the embodiments of the present invention . referring to fig1 , and 4 , in denotes a signal input to a pad 1 or 11 , vn 1 denotes a dc voltage of a node n 1 , and vn 11 denotes a dc voltage of the node n 11 . in the conventional tolerant input buffer , in a case where the voltage of the input signal in is linearly increased to 2 . 2v , the voltage transmitted to the node n 1 is linearly increased . however , in a case where the voltage of the input signal in is greater than 2 . 2v , the first transmission circuit t 2 ( fig2 & amp ; 3 ) is cut off , and the voltage transmitted to the node n 1 is not linearly increased , and is gradually increased according to the leakage current of the first transmission circuit t 2 . however , in the tolerant input buffer according to the embodiments of the present invention , even if the input signal in is increased to 3 . 7v , the voltage transmitted to the node n 11 through the second transmission circuit t 3 is linearly increased . in a case where the input signal in is greater than 3 . 7v , the second transmission circuit t 3 is cut off and is gradually increased by leakage current of the first and second transmission circuits t 2 and t 3 . fig5 illustrates a comparison of ac voltage characteristics of the conventional tolerant input buffer circuit with the tolerant input buffer circuit according to the embodiments of the present invention . referring to fig1 , and 5 , in denotes a signal input to a pad 1 or 11 , vn 1 denotes an ac voltage of a node n 1 , and vn 11 denotes an ac voltage of the node n 11 . in a case where the input signal in of the tolerant input buffer according to the present invention is increased from 0v to 4v , the voltage of the node n 11 is linearly increased to 4v and is maintained at 4v . vn 11 shown in fig5 is higher than vn 11 shown in fig4 because of capacitance of the second transmission circuit t 3 . with reference to fig2 , and 5 , in a case where the first supply voltage vdd 1 is 3 . 3v , and the second supply voltage vdd 2 is 2 . 5v , if the input signal in of 0v is input to the input pad 11 , the first transmission circuit t 2 is turned on and transmits the signal of the node b of 0v to the node n 11 . the schmitt trigger 17 inverts the node n 11 and outputs ‘ high ’ to the node c . the nmos transistor t 6 is turned on in response to the ‘ high ’ level at node c , and thus , the node d is pulled down to the ground voltage vss . since the voltage of 0v is applied to the gate of the second transmission circuit t 3 in the state where 0v is input to the node b , the second transmission circuit t 3 is turned off . in such a case , the second switching circuit t 4 is turned off . next , if the input signal in increased to 1v is input to the input pad 11 , the first transmission circuit t 2 transmits the signal of 1v to the node n 11 . the first inverting circuit 17 is not transitioned to ‘ high ’ in response to the signal transmitted to the node n 11 , and thus , the output of the node c is maintained at ‘ high ’. accordingly , the first switching circuit 15 is turned on and pulls down the node d , and thus , 0v is applied to the gate of the second transmission circuit t 3 . accordingly , if a voltage higher than the threshold voltage vth of the second transmission circuit t 3 is input to the node b , that is , to the source of the second transmission circuit t 3 , and 0v is applied to the gate of the second transmission circuit t 3 , the second transmission circuit t 3 is turned on and transmits the input signal in of 1v to the node n 11 . the first transmission circuit t 2 is turned on , but the second switching circuit t 4 is turned off . further , if the input signal in , which is increased , e . g ., to 2 . 2v , is input to the input pad 11 , the threshold voltage vth of the first transmission circuit t 2 is increased due to a body effect of the first transmission circuit t 2 , and thus , the threshold voltage vth of the first transmission circuit t 2 is increased to a level greater than the voltage of the gate and source of the first transmission circuit t 2 , and the first transmission circuit t 2 is turned off . however , the first inverting circuit 17 is not transitioned from ‘ high ’ to ‘ low ’ and still outputs ‘ high ’ to the node c . thus , the node d is pulled down to the ground voltage vss , and the second transmission circuit t 3 is turned on . that is , the input signal in input to the source of the second transmission circuit t 3 is 2 . 2v , and a signal input to the gate of the second transmission circuit t 3 is 0v , and thus , the second transmission circuit t 3 is turned on and transmits the signal of the node b to the node n 11 . thus , the input signal in of 2 . 2v is transmitted to the node n 11 . in such a case , the second switching circuit t 4 is turned off . if the input signal in ( e . g ., greater than 2 . 2v ) is input to the input pad 11 , the inverting circuit 17 outputs ‘ low ’ to the node c in response to the signal of the node n 11 greater than the vih . thus , the nmos transistor t 6 of the first switching circuit 15 is turned off , and the node d is floated . at this time , the voltage of the node d increases , but the voltage of the node d is maintained at a predetermined voltage ( e . g ., about 1v ) due to leakage current of the nmos transistors t 5 and t 6 . thus , the second transmission circuit t 3 is still turned on and transmits the signal of the node b to the node n 11 . the second switching circuit t 4 is still turned off . in a case where the input signal in of 3 . 6v is input to the input pad 11 , and a signal corresponding to the input signal in is input to the node b , considering a body effect of the second switching circuit t 4 , the signal transmitted to the source ( node b ) of the second switching circuit t 4 is greater than the sum of the signal supplied to the gate of the second switching circuit t 4 and the threshold voltage vth of the second switching circuit t 4 , and thus , the second switching circuit t 4 is turned on . accordingly , the signal of the node b is transmitted to the node d , and thus , the second transmission circuit t 3 is turned off . further , if the input signal in greater than 3 . 6v is input to the input pad 11 , the first and second transmission circuits t 2 and t 3 are turned off . the tolerant input buffer is stable even if the input signal in greater than a tolerant voltage is transmitted to the node b . for example , the input signal in from 0v to 1v is transmitted to the node n 11 through the first transmission circuit t 2 , and the input signal in from 1v to 2 . 2v is transmitted to the node n 11 through the first and second transmission circuits t 2 and t 3 , and the input signal in from 2 . 2v to 3 . 6v is transmitted to the node n 11 through the second transmission circuit t 3 . the input signal in greater than 3 . 6v is not transmitted to the node n 11 because the first and second transmission circuits t 2 and t 3 are cut off . the numerical values are used only to illustrate the operation of the signal transmission circuit , for example , the tolerant input buffer according to the embodiments of the present invention . accordingly , the tolerant input buffer according to the present invention shows voltage linearity even for an input signal greater than the conventional tolerant input buffer , thereby facilitating design of circuits with stable dc voltage and improved delay characteristics . further , since voltage linearity is improved , the voltage linearity may be effectively used in an analog tolerant input buffer . while this invention has been particularly shown and described with reference to preferred embodiments thereof , it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims . | 6 |
an employer choosing to utilize the subject system ( s ) and / or method ( s ) must first adopt , or be maintaining , a plan which describes the participant &# 39 ; s retirement benefit in the form of an account balance . the employer must amend the plan documents and the attendant participant disclosures to allow the participants the ability to elect that all or a portion of the participants &# 39 ; account balances be paid as a lifetime stream of income . a retiring participant then elects , under the plan &# 39 ; s existing processes , the portion ( if any ) of the account to be paid out as a lifetime income stream . payments to the participant would be placed upon a payment schedule , and begin at the selected plan payment date . payments will be made to the participant either through the plan &# 39 ; s normal processes or ; if elected by either the plan employer or the plan participant , through a “ plan distributed annuity ” (“ pda ”) which is distributed by the plan to the participant . a pda is a type of annuity recognized by the internal revenue code as an “ in - kind ” distribution of an annuity contract from the plan . it may be an immediate annuity or it may be a deferred annuity . it may be a fixed annuity or it may be a variable annuity . the exact form of annuity may be chosen by the plan . to accommodate the pda , certain embodiments of the invention provide that a group annuity contract which is owned by the plan provides either separate investment accounts or a guaranteed lifetime stream of payments ( as described herein ), and may also issue individual pdas on behalf of the plan to plan participants . a participant &# 39 ; s account balance or promise of a lifetime income guarantee are transferred to the pda , then issued to the plan participant . these pdas are favored tax vehicles under which a plan participant receives the same beneficial treatment and protections under the internal revenue code as does participants who remain in a plan which fully integrates this feature into its ongoing processes . lifetime benefits would be computed in the same manner as benefits that remain integrated with the plan . the plan sponsor may have the ability to choose the underlying investment funds in the pda . the plan participants have all of the same benefits as earlier described above . however , under a pda , it is the insurance company which administers the program . throughout any access period elected by the participant , the participant will have full rights to the account balance in the plan , as otherwise described by the plan , including the right to withdraw funds or change investments . any such activity would result in recalculation of the participant &# 39 ; s lifetime stream of income . after any access period ceases , the participant may still be able to change the manner in which the underlying investments supporting the lifetime payouts are managed ( should this option be made available by the plan ). the ability to have lifetime , fixed payments made to plan participants through existing plan processes may also be provided . the subject systems and methods integrate the payment of a lifetime stream of income with a participant &# 39 ; s continued use and access to the participant &# 39 ; s account balance in a plan by utilizing that account balance in determining the amount upon which a lifetime stream of income is computed . in using the account , the plan rules governing that account are preserved during any access period required by a lifetime income program , including the right to direct the investment of the account , rollover deposits into the account , and make withdrawals from the account . the retention of the participants &# 39 ; rights to plan account balances is a feature which helps successfully integrate the subject system / method into the plan &# 39 ; s processes . retention of participant account balance rights is accomplished in one of two ways during any access period permitted by the lifetime income design . first , participants will continue to be allowed to remain invested in the same investment funds as other participants who have not elected lifetime income payments . second , electing participant account balances are deposited in separate accounts of a specially designed group annuity owned by the plan , which account balances are invested in the same or similar funds that are otherwise available to plan participants not electing lifetime income streams . in either case , an automated system / method is provided to use those balances in computing the amount of the periodic payment under the lifetime income stream . a common custodial arrangement may be provided to facilitate the plan &# 39 ; s trading practices between its investment funds . the ability to integrate with a participant &# 39 ; s account within the plan enables the plan to utilize its entire array of existing administrative functions to support the regulatory and customer service requirements demanded in providing the lifetime benefit in the same manner as it would for those participants not electing the lifetime benefit . for example , any participant statements , trade confirmations , plan financial statements , distribution tax reporting and withholding , internet access , and the like would all be handled through the plan &# 39 ; s existing processes . any features or investments of the plans which were changed through the plan &# 39 ; s normal processes would then flow through to the participants electing lifetime income streams . once any access period which may be permitted by the plan is exhausted , a participant &# 39 ; s account balance within the plan is transferred to a group annuity contract or , if applicable , out of the variable separate accounts of a group annuity contract . at that point , the insurance company , not the plan , guarantees a lifetime income stream on behalf of the plan to the plan participant . should the plan provide a stream of lifetime income which varies based upon underlying equity fund performance , such funds may be selected by the plan . continued payments from the annuity contract may be made through the plan &# 39 ; s existing administrative processes . fig1 - 3 are flow charts illustrating an illustrative embodiment of the subject system and method . the subject embodiment is intended to be exemplary and is not intended to be construed as limiting the scope of the invention in any manner . fig1 is a flow chart illustrating a portion of one embodiment of the subject system and method . the portion of the embodiment illustrated in fig1 relates to establishing a payout record . the first operation in the embodiment illustrated in fig1 involves amending an existing plan , as necessary , to allow for benefits to be distributed as a lifetime payout stream ( 10 ). to the extent a plan has such capability at its creation , such amendment will not be necessary . once a plan is established or properly amended to provide a lifetime payout stream , use of the system and method is initiated by a plan participant electing the lifetime payout stream as a plan benefit ( 11 ). this election by the plan participant is made using the existing processes established by the plan ( such as electronic , voice , or paper election methods ). the lifetime form of benefit payout is described in the plan materials , which include this benefit option along with other benefit distribution options . also included in this election is the choice of having the lifetime income stream paid through the plan &# 39 ; s process , or through an independent process such as through the use of a “ plan distributed annuity ” (“ pda ”). in certain embodiments , the election to be paid through a pda can be made even after an initial election had been made to have the payments paid through the plan . the plan administrator collects this data and enters it into the plan &# 39 ; s system . the first subprocess imports the plan participant data from the plan administrator &# 39 ; s system ( 12 ), which aligns and integrates the data used by the system and method with the data used by the plan administrator in the plan &# 39 ; s day - to - day operations . the subject invention is intended for use by a wide variety of plans with varying types of systems , and the use of data feeds from diverse plans is anticipated . next , the subject system and method creates a lifetime payout record ( 13 ) from the administrator &# 39 ; s data feed . the data is sorted and stored for use by the other subprocesses to determine the amount of the payout and the manner in which it will be distributed . the system and method then determines ( 14 ) if the next payment in the series of lifetime payouts will be made through an independent process under a pda . the reference to a “ pda ” throughout this description is a generic reference to the payment of the lifetime payout through the use of an annuity contract held outside of the plan ( typically owned by the former plan participant , but could also be the employer ). for example , under a 401 ( k ) plan , such an annuity would be a “ pda ” as that term is defined by the internal revenue code ; under a 403 ( b ) plan , the vehicle would be a “ 90 - 24 transfer ,” as that term is described under revenue ruling 90 - 24 ; under a 457 ( b ) payout the vehicle may simply be a non - qualified annuity . any such pda may either be a group or individual annuity . election of a pda may occur either initially , or through a change to an earlier election of lifetime payouts through the plan . this pda choice can also be made by plan sponsors at the time of plan termination or some other plan transition . this information is then stored in master storage ( 19 ). if a pda is not elected , the system and method inquires as to whether or not the type of lifetime payout which was elected provides participants the right to withdraw funds from the account from which the lifetime payouts will be made and , if so , for what period of time the participant will have this right ( 15 ). this period of time is referred to as an “ access period .” it is contemplated that there will only be a limited number of access periods , as chosen by the plan sponsor , investment manager or any party administering the plan . this information is then stored in master storage ( 19 ). the system and method then inquires as to whether or not this is an initial election or a change in a previously made election , stating it in terms of whether or not the action is a “ first payment ” ( 16 ) in an access period . the answer to this question determines whether or not the system and method needs to generate trading instructions for the plan &# 39 ; s administrators to properly move a participant &# 39 ; s investments to the funds from which lifetime payouts will be made . if this is not a first payment of an access period ( but instead , for example , merely a change to an access period ), this information is stored in master storage ( 19 ). if this is the first payment during an access period , the system and method determines whether the payment will be made from funds in existing plan investments . if the payment will be made from funds in which the participant is already invested , this information is stored and no trading instructions are generated . if the payments will be made from certain designated investments other than those in which the participant is already invested ( including , but not limited to , separate accounts of a group annuity contract ), the system and method generates a trading instruction to the plan &# 39 ; s administrator to move the participant &# 39 ; s funds to those designated investments ( 18 ). these instructions are then stored in master storage ( 19 ). fig2 is a flow chart illustrating a portion of one embodiment of the subject system and method . the portion of the embodiment illustrated in fig2 relates to establishing and modifying the lifetime payout amount . the portion of the system and method illustrated in fig2 is periodically activated by an automatic calendar , whereby data is drawn from the master storage according to a prearranged schedule ( such as monthly ) ( 21 ). this operation may also be manually initiated periodically , or at other non - periodic times . because the amount and form of the lifetime payout made through the plan &# 39 ; s processes may change from period to period ( such as , from month to month ), this subroutine is preferably run before any periodic payment is made . data is retrieved from master storage ( 19 ), and account balance is imported from the plan &# 39 ; s administrative system ( 22 ), which is then also stored ( 19 ). a determination is then made as to whether or not a pda has been elected ( 23 ). if a pda has been elected , this information is stored . if a pda has not been elected , an inquiry is made as to whether or not an access period was elected , and whether there is any time remaining in an access period ( 24 ). if the answer is no , or if there is no time remaining in the access period , the benefit is in the formal annuitization stage . this information is then relayed to a separate process which uses that information to compute the value of the annuitized periodic payout ( 210 ). in the annuitization stage , the benefit will be calculated from performance units , rather than from performance of the separate account . if there is an access period , an inquiry is made as to whether or not the plan or the distribution is subject to the joint and survivor annuity rules ( qjsa ) imposed by the internal revenue code and the employee retirement security act of 1974 ( erisa ) ( 25 ). if these rules are applicable , they will affect the form of , and thus the amount of , the payment and an inquiry is made as to how much time is remaining in that access period ( 26 ). the rule is that a participant must be notified between 30 and 90 days before the actual annuitization of the benefit which occurs after the end of an access period , and in which time the form of annuity benefit ( for example , single life annuity or term certain ) must be selected . spousal consent is required if the election is for something other than a 50 % joint and survivor annuity . a notice / consent form is generated which will also describe the other distribution options which may be available to the participant . if there are 90 days or more , or 30 days or less , remaining before the end of the access period , and no waiver has been received , that fact is transferred to an expert system ( 210 ), and the calculation of the amount of payout is triggered . if there are less than 90 days remaining ( 26 ) in the access period , an inquiry is made as to whether or not the required consent forms have been received ( 27 ). the notice and consent requirements will determine whether the benefit is payable as a 50 % joint and survivor annuity , or in a form otherwise chosen by the participant . if the consents have been received , the system / method determines whether a joint life payout has been elected ( 213 ). if not , this information is directed to the expert processes for calculating benefits ( 210 ), and the benefits will be determined accordingly . if a joint life payout has been elected , the system / method determines whether joint payee data has been provided ( 214 ). if yes , the system / method proceeds to calculate benefits ( 210 ) as previously discussed . if joint payee data has not been provided , the system / method stops payment and provides a notice of cessation ( 215 ). data relating to these operations is then stored ( 19 ). if the consents ( 27 ) have not been received , and the next scheduled payment is not the first annuity payment ( 28 ), then consents are requested by an independent , pre - existing process ( 29 ). if consents have not been received , and the next scheduled payment is the first annuity payment , the system / method determines whether the plan requires a cessation of payment ( 216 ). if yes , payment is stopped and a notice of cessation is generated ( 215 ), and this information is stored ( 19 ). if the plan does not require cessation of payment , the system / method determines whether a joint life payout has been elected ( 213 ). after this determination , the system / method proceeds as previously described ( 213 , 214 , 215 ). if appropriate this information is then directed to the expert processes for calculating benefits ( 210 ), and any such benefit will be calculated under the default form of benefit required under the plan or under law . this procedure applies until the first scheduled payment after the first annuity payment is made . input from operations 25 , 26 , 213 , 214 or 29 triggers 210 to perform a calculation of the next periodic payout , drawing data as necessary from 21 or 19 . an example of such a system used to determine periodic payments is described above . the system will also calculate any loads or expenses which may be related to the provision of the benefit , and the value of the survivor benefit if the plan participant is deceased . both the amount of the payout and the loads are stored and transferred to master storage ( 211 , 212 ). fig3 is a flow chart illustrating a portion of one embodiment of the subject system and method . the portion of the embodiment illustrated in fig3 relates to executing the lifetime payout . the portion of the embodiment illustrated in fig3 is triggered by storage of data through 212 . once triggered ( 31 ), the information needed to execute the payout is retrieved ( 32 ) from master storage 19 . an inquiry is made as to whether a pda has been elected ( 33 ). if so , instructions are generated to the plan administrator to withdraw the participant &# 39 ; s account balance , if any , up to the amount elected by the participant , and to purchase a pda ( 34 ). if a pda is elected , the plan participant &# 39 ; s lifetime records are removed from the system , and will no longer be held and processed with other lifetime payments within the plan ( 35 ). this information is then stored in master storage 19 . if a pda has not been elected , an inquiry is made as to whether or not the participant or joint payee is deceased ( 36 ). if so , a death claim is processed and the participant record is set to inactive ( 37 ). an instruction is generated to either pay out the death benefit as a lump sum or in installments or , if annuitized , transfer any amounts allocated to the account back to the insurance company account ( 38 ). if the participant / joint annuitant is alive , an inquiry is made as to whether an access period is in effect ( 39 ). if so , an instruction is generated for the plan administrator to withdraw the periodic benefit payment from the account within the plan ( or plan owned annuity contract , if applicable ) ( 310 ). if there is no access period , then payments are in an annuitization phase . payment during the annuitization phase requires the ability to continue to make payments to plan participants beyond their calculated life expectancies . therefore , the subject system / method is designed to direct payments from an insurance company &# 39 ; s assets , if necessary , in a way which is transparent to the plan administrator . a determination is made as to whether the assets allocated to a participant &# 39 ; s lifetime annuitization account have been exhausted ( 311 ). if not , an instruction is generated to withdraw the periodic payment from the account . if so , an instruction is generated to transfer a predetermined amount from the insurance company &# 39 ; s general account to the policy account supporting the periodic payments ( 312 ). all of the instructions generated by this sub - routine are stored ( 313 ) in master storage 19 . after all instructions are stored , a data feed is automatically generated to the plan &# 39 ; s administrator ( 314 ). this data feed orders a distribution from the plan under its normal distribution processes ; orders investment instructions under the plan &# 39 ; s normal administrative processes ; identifies a withdrawal to be paid as a premium for a pda ; orders a death benefit distribution ; and / or updates the administrator &# 39 ; s records . any applicable tax reporting and withholding will be handled through the plan &# 39 ; s existing administrative processes . although the present invention has been described with reference to a particular system / method , one skilled in the art can easily ascertain from the foregoing description the characteristics of the invention . various changes and modifications may be made to adapt the various uses and characteristics without departing from the spirit and scope of the invention . | 6 |
fig1 shows a drill collar propellant gun 10 within a drill collar 12 that is made up in a drill string that extends into a drilled wellbore . the drill collar propellant gun 10 has an orifice 22 from which a bullet - shaped data sensing apparatus emerges upon being fired from the drill collar propellant gun 10 . a deployed data sensing apparatus 24 is shown as having been deployed from the drill collar propellant gun 10 into the formation rock matrix 20 into a formation of interest . fig2 shows a cross - sectional view of the drill collar propellant gun 10 of the present invention . the barrel 32 is shown as being oriented substantially planar with cross - section of the wellbore that is generally perpendicular to the axis of the wellbore at that depth . those skilled in the art will appreciate that such lateral embedding of a data sensing apparatus radially outward away from the axis of the wellbore need not necessarily be perpendicular to the axis of the wellbore , but may be accomplished through numerous angles of attack into the desired formation of interest . the barrel 32 terminates at the orifice 22 in the wall of the drill collar 12 . the data sensing apparatus , upon deployment , passes through the orifice 22 as it exits the drill collar 12 . the hollow interior 38 of the barrel 32 is substantially uniform along its length and is sized to receive and temporarily store the data sensing apparatus 24 . the muzzle cap 34 isolates the hollow interior 38 of the barrel 32 from the drilling mud 26 ( or other fluid , such as completion fluid ) residing in the annular area between the drill string and the side wall of the wellbore . the muzzle cap 34 is designed to withstand any hydrostatic pressure exerted on the drill collar propellant gun 10 by the column of drilling mud ( or other fluid ) in the well , but to shatter upon impact by the accelerated data sensing apparatus 24 or the rapidly moving gas immediately preceding deployment of the data sensing apparatus 24 . a ceramic material such as alumina is presently preferred for this purpose . alternatively , the muzzle cap may be metallic so that it &# 39 ; s pierceable by egress of the data sensing apparatus , and “ peels away ,” with a minimal loss of energy . the burn chamber 42 is adapted to receive or store a propellant like those described in u . s . patent application ser . no . 09 / 458 , 764 now abandoned . the burn chamber 42 provides a space for disposing a propellant into intimate contact with an ignition assembly 52 having an igniter 58 disposed in the burn chamber 42 . the ignition assembly 52 ignites the propellant disposed into the burn chamber 42 thereby resulting in a substantially rapid expansion of gas within the burn chamber 42 reaching a pressure up to or exceeding 100 , 000 pounds per square inch . the pressure caused by ignition of the propellant provides the driving force for acceleration , ejection and deployment of the data sensing apparatus 24 . the accelerated data sensing apparatus 24 moves from the barrel 32 through the sacrificially shattering muzzle cap 34 and out the orifice 22 to be substantially embedded into the formation rock matrix 20 . in a preferred embodiment , the burn chamber 42 is isolated from the barrel 32 by a rupture disk 36 . the rupture disk 36 is an engineered pressure diaphragm that is designed to rupture and relieve pressure at a predetermined threshold pressure achieved during the expansion of gases resulting from ignition of the propellant . the rupture disk 36 affords improved deployment of the data sensing apparatus by delaying the onset of acceleration of the data sensing apparatus within the barrel 32 until the pressure in the burn chamber 42 reaches a threshold pressure sufficient to cause the rupture disk 36 to fail . the rupture disk 36 fails at a predetermined elevated pressure , thereby causing a more rapid pressurization of the portion of the barrel 32 between the rupture disk 36 and the data sensing apparatus 24 than would be achieved if the burn chamber 42 were initially in fluid communication with the barrel 32 . this more rapid pressurization results in a more rapid or instantaneous acceleration of the data sensing apparatus 24 within the hollow interior 38 of the barrel 32 , and a greater exit velocity of the data sensing apparatus 24 upon firing of the drill collar propellant gun 10 . other means , such as shear pins or sacrificial threads , for holding the data sensing apparatus until a desired pressure level is reached in the burn chamber , may also be used to advantage with the present invention . as shown in fig1 the drill collar propellant gun 10 is contained within a drill collar 12 that is made up in a drill string above the drill bit 14 . when drilling mud is circulated in the well , it must pass through the drill string and the drill bit 14 , and return to the surface through the annular area between the drill string and the wellbore . fig2 shows a channel 28 passing through the drill collar propellant gun 10 to provide drilling mud flow to the drill bit 14 to lubricate the drill bit 14 , suspend drill cuttings and carry them to the surface for removal . the channel 28 is isolated from the burn chamber 42 and the barrel 32 of the drill collar propellant gun 10 throughout the length of the drill collar 12 . fig3 shows a cross - sectional view of the preferred arrangement of the barrel 32 and the burn chamber 42 . assuming a standard 6 . 75 - inch outside diameter drill collar , the maximum length of the barrel 32 that can be accommodated horizontally within the drill collar is about 5 inches . even with larger diameter drill collars , the barrel length that can be accommodated within the drill collar 12 is still relatively small , in ballistic terms , as compared to the length of the data sensing apparatus ( 2 . 5 to 4 inches ). in conventional gun - type devices having a relatively long barrel portion , the burn chamber is generally aligned with the barrel . however , in short - barrel configurations such as that involved with data sensing apparatus deployment in the present invention , acceleration of the data sensing apparatus is best achieved with near adiabatic expansion of the high pressure gas provided by ignition of the propellant and from which force is transferred to the data sensing apparatus . it is desirable to have near adiabatic expansion to achieve maximum force transfer from the propellant gas to the data sensing apparatus 24 . this requires that the burn chamber 42 of the present invention be non - aligned with the barrel 32 as shown in fig2 and 3 in order to fit both the barrel 32 and the burn chamber 42 within the limited space in the drill collar 12 . fig3 shows that the burn chamber 42 of the drill collar propellant gun 10 of the present invention is substantially non - aligned with the barrel 32 enabling maximum length of the portion of the barrel 32 through which the data sensing apparatus 24 may be accelerated prior to its shattering the muzzle cap 34 and its ejection from the drill collar 12 through the orifice 22 . fig4 shows a quartered cross - sectional view of the ignition assembly 52 which may be sealably and interchangeably disposed into an ignition assembly port 50 formed in the wall of the drill collar 12 . the ignition assembly 52 is controlled through an electrical connection 54 which , when remotely activated , triggers igniter 58 that protrudes into the burn chamber 42 ( not shown in fig4 ). in the preferred embodiment , igniter 58 contains a small quantity of a high energy chemical charge that is activated by a heat source or mechanical impact / shock . the heat source ( as well as the mechanical impact ) can be triggered or generated by an electrical signal , such as that provided via electrical connection 54 . once the high energy chemical charge is activated , propellant burning commences and high pressure gas is generated . fig5 shows cross - sectional view of the pressure relief assembly 62 that may be sealably and interchangeably disposed into a pressure relief assembly port 60 formed in the drill collar 12 . one purpose of the pressure relief assembly 62 is to provide a means for relieving trapped pressure remaining in the burn chamber 42 after an unsuccessful deployment of a data sensing apparatus . in the event that the chemical propellant becomes wet or otherwise compromised , the pressure resulting from ignition of the propellant may not result in rupture of the rupture disk 36 . in this event , the pressure relief assembly 62 may be used to safely release the trapped pressure within the burn chamber 42 in a controlled manner . removal of the pressure relief assembly 62 and the ignition assembly 52 provide access to the burn chamber for cleaning and maintenance , or for disposing measured amounts of the chemical propellant . a preferred arrangement of pressure relief assembly 62 and ignition assembly 52 is shown in fig2 but the locations of the two assemblies may be switched if desirable . general ballistics principles help determine the essential projectile parameters for the data sensing apparatus drill collar propellant gun 10 . design considerations include the required speed and weight of the data sensing apparatus necessary to achieve sufficient penetration of a given rock , the length / cross - section ratio to ensure straight flight of the data sensing apparatus and nose shape of the data sensing apparatus for optimum penetration depth . the data sensing apparatus 24 is therefore substantially bullet - shaped and is elongated about its axis to partially satisfy the second constraint ( sufficient , straight penetration ) expressed above . the drill collar propellant gun 10 may be remotely controlled using a transmitter / receiver combination . a receiver within the drill collar propellant gun 10 may receive commands through radio frequency ( rf ) or other electromagnetic means , or through mud telemetry systems . these devices and methods for communicating data and commands to remotely controlled devices in a wellbore are known in the prior art . communication with a remote transmitter or receiver using rf signals requires that an antenna be part of the drill collar propellant gun 10 , and such an antenna used for control purposes must be protected against the burn chamber pressure and temperature and protected from all impact forces . the data sensing apparatus 24 includes a substantially bullet - shaped shell equipped with encapsulated data sensor for indicating one or more properties of a subsurface formation of interest . the data sensing apparatus includes a transmitter for transmitting a signal representative of the sensor - indicated property to a remote data receiver . the data sensing apparatus may include a receiver for receiving remotely transmitted signals used by the data sensing apparatus to determine the optimal transmission frequency for communicating formation data to the remote receiver . those skilled in the art will appreciate that the present invention also contemplates the deployment of intelligent sensor apparatus 24 from a wireline tool , even though the description herein refers to an apparatus for data sensing apparatus deployment from a drill collar propellant gun made up in a drill collar of a drill string . in contrast to present day operations , the present invention makes formation pressure and temperature data , as well as other formation evaluation data ( e . g ., resistivity , gamma ray , density , and neutron measurements ), intermittently or continuously available while drilling or producing fluids from the formation of interest . this advantage enables better decisions concerning drilling mud weight and composition at a much earlier time in the drilling process without necessitating costly tripping of the drill string for the purpose of running a conventional formation tester . once a data sensing apparatus is remotely deployed using the present invention , intermittent or continuous accurate formation data may be obtained while drilling , a feature that is not possible according to currently known drilling techniques . monitoring of pressure in penetrated formations may continue as long as communication with the data sensing apparatus is available . this feature is dependent of course on the nature of the communication link between the transmitter / receiver circuitry within the drill collar and any deployed intelligent remote sensors . it is contemplated by and within the scope of the present invention that the remote data sensing apparatuses , once deployed in the formation , will have the benefit of stored energy in the form of a battery , fuel cell or other energy source , and may provide a source of formation data for a substantial period of time . it is further contemplated that a replaceable or auxiliary source of stored energy may be adapted to be received by the deployed data sensing apparatus exposed to the wellbore for periodically restoring the energy source supporting continued data transmission from the data sensing apparatus . in view of the foregoing it is evident that the present invention is well adapted to attain all of the objects and features hereinabove set forth , together with other objects and features which are inherent in the apparatus disclosed herein . as will be readily apparent to those skilled in the art , the present invention may easily be produced in other specific forms without departing from its spirit or essential characteristics . the present embodiment is , therefore , to be considered as merely illustrative and not restrictive . the scope of the invention is indicated by the claims that follow rather than the foregoing description , and all changes which come within the meaning and range of equivalence of the claims are therefore intended to be embraced herein . | 4 |
while the making and using of various embodiments of the present invention are discussed in detail below , it should be appreciated that the present invention provides many applicable inventive concepts that may be embodied in a wide variety of specific contexts . to facilitate the understanding of this invention , a number of terms are defined below . terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention . terms such as “ a ”, “ an ” and “ the ” are not intended to refer to one a singular entity , but include the general class of which a specific example may be used for illustration . the terminology herein is used to describe specific embodiments of the invention , but their usage does not limit the invention , except as outlined in the claims . the term “ integrally formed spr sensor ” refers to a spr sensor in which at least a portion of the detector system is disposed within a sensor housing that is transparent to radiation produced by a desired radiation source . various radiation sources producing light detectable by photodetectors may be employed including for example light emitting diodes ( leds ), laser , incandescent lamp , filament or similar devices . where the light source produces unpolarized light , a polarizer may be included after the light source to provide polarized light . where the light source produces polarized light ( as with certain lasers producing highly linearly polarized beams ), polarizers may be eliminated . the light produced by the radiation source is able to pass through the housing and strikes an exterior surface of the housing on which a thin conducting layer is formed . alternatively , the thin conducting layer may be disposed on a glass slide , or the like , which is located adjacent an exterior surface of the housing and having an index matching fluid disposed between the slide and the housing . in alternate embodiments , radiation sources and polarizers are also contained within the housing . optionally , temperature sensors and other desired elements may be incorporated integrally or separately . the term “ e - field flow cell ” refers to a flow cell constructed to permit the establishment of an electrically biased field within a detector portion of the flow cell . the electrically biased field is generated by opposite electrodes placed on , or in proximity to , a portion of a flow cell interior surface . at least one of the electrodes may also functions as , or is in functional proximately to , an analyte specific substrate such that generation of an electrical bias will concentrate charged molecules on or near the analyte specific derivatized plasmon layer . the term “ m - field flow cell ” refers to a flow cell constructed to permit the establishment of a magnetic field within a detector portion of the flow cell . the magnetic field is generated by placement of at least one magnet or electromagnet on , or in proximity to , a portion of a flow cell interior surface . at least one surface able to serve as a magnet also functions as , or is in functional proximity to , an analyte specific substrate such that generation of magnetic field will concentrate charged molecules on or near the analyte specific derivatized spr layer . the following examples of possible embodiments are included for the sake of completeness of disclosure and to illustrate the methods and apparatus of the present invention . in no way are these examples intended to limit the scope or teaching of this disclosure . a description of the sensors employed herein may be found in , e . g ., u . s . pat . nos . 5 , 946 , 083 , 5 , 912 , 456 and 5 , 898 , 503 , relevant portions thereof are incorporated herein by reference . the advantages of the present invention are illustrated in fig1 through 5 . fig1 depicts a cross - sectional view of a portion of one embodiment of a flow cell 100 for regulating the interaction of molecules in accordance with the present invention . the flow cell 100 may be formed in one piece or may be formed of a sandwich of materials and may be composed of teflon fluorocarbon resin or other suitable inert material , including , for instance but without limitation , suitable metals , plastic and glass materials . the flow cell has at least one flow cell sample cavity 102 functioning as an analyte test or detection chamber . one or more surfaces of the flow cell sample cavity 102 may be derivativized and modified as suitable to form a sensor for measurement of a variety of molecules and interactions such as for example measurement of receptor - ligand interactions . the inflow conduit 104 functions as a channel through which one or more samples are guided into the flow cell sample cavity 102 and may be formed of suitable materials known in the art such as for instance those having the properties of plastic , nylon and / or metal tubing . flow cell sample cavity 102 may include a probe for monitoring conditions within the cavity , for example , a bead thermister 106 connected via thermister contact 108 to distal monitoring equipment for monitoring the temperature of the flow cell sample cavity 102 . in other embodiments , other conditions such as for example ph , pressure , etc . may be measured by providing one or more sensors ( not shown ) in fluid communication with the flow cell sample cavity 102 . in a sandwich - type construction such as the flow cell embodiment of fig1 a metal or similar rigid housing plate 110 secures a gasket 112 . gasket 112 has at least one channel that forms a flow cell sample cavity 102 . the gasket is placed between a teflon spacer 114 and an analyte reactive sensing surface 116 . in this embodiment of fig1 gasket 112 is composed of , e . g ., silicone and the channel may be laser - cut . the analyte reactive sensing surface 116 is , e . g ., a 50 nanometer thick gold (“ au ”) layer . thermistor 106 may reside directly in the channel forming the flow cell sample cavity 102 . in an embodiment of fig1 where the flow cell is used in conjunction with an spr sensor , the flow cell sample cavity 102 is positioned so that it overlays the active spr region . in accordance with the present invention , a capacitor for creating and controlling an electric field in a sample is created within flow cell sample cavity 102 by electrically coupling a first electrode connection 118 to the surface of the au analyte reactive sensing surface 116 . the first electrode connection 118 may comprise a thin strip of platinum placed in electrical contact with the gold surface and underneath the silicone gasket . by virtue of the electric coupling , the au surface may serve as a first electrode . a second electrode 120 is located in a position substantially opposite to the au analyte reactive sensing surface 116 . the liquids and biological buffers used for most biosensing assays serve as the dielectric . the second electrode 120 may include a sheet of platinum placed between the silicone gasket and the teflon block . as shown in fig1 the first and second electrodes or connections thereto may protrude from the flow cell . after measurement , the sample is evacuated from the flow cell sample cavity via outflow conduit 122 . flow cell 100 may include one or more liquid conduits directed appropriately for sampling to take place and one or more outlets that may be connected directly or though appropriate valving to a vacuum pump , e . g ., contained within a host or ancillary unit ( not shown ). a liquid sample may therefore be pulled into analyte detection chamber 102 of the flow cell 100 and guided across an analyte reactive sensing surface 116 . the analyte reactive sensing surface is most typically a derivatized surface plasmon layer in optic communication with an integrally formed surface plasmon resonance sensor . the surface plasmon layer may be derivatized in a number of ways for binding selective ligands to a metal layer . the derivatization process may be a single step or several step process in which a first organic layer is deposited followed by binding ( e . g ., covalently ) of selected ligands depending on the desired analyte to be detected . after measurement , rather than proceeding into the pump , the test sample is caught in one or more waste receptacles outside of the flow cell ( not shown ). other sensing system configurations according to the present invention may use one or more valves for dynamic sampling , including applying one or more reagents contained in one or more reservoirs . one or more reservoirs may also contain cleaning solutions or materials for calibration purposes . a sample delivery and sensing unit may additionally include a thermal heat generating device , such as a heating coil . the sample delivery and sensing unit may further include a thermal heat exchange device , such as fan , for example . thermal heat generating and / or thermal heat exchange devices may function to stabilize the temperature within the flow cell or between the flow cell and the surface plasmon sensor . in one embodiment , the electrodes are connected to a source measuring unit ( smu ) such as for example a keithley model 236 source measuring unit ( smu ). the smu is used to source voltage and measure current during the course of the assay . in a conventional direct binding spr assay , an analyte is typically bound to an immobilized ligand on the spr surface . the changes in local refractive index that occur during analyte binding describe the kinetics of interaction between the two molecules . for example , an antigen to which an antibody has been raised is attached to the surface of the spr sensor . a dilute solution of specific antibody , for example , a monoclonal antibody or fragment thereof , is allowed to flow across the sensor surface . binding of the antibody results in a change in refractive index . similarly , the characteristics of other receptor ligand interactions may be evaluated in this way to determine binding kinetics . ligand concentration can be measured by spr . one such ligand concentration measurement is performed using a competitive binding assay . in the case of an antigen - antibody competitive binding assay , the antibody is used as a large mass molecule whose binding is competitively prevented by free antigen or ligand in solution . when the antibody binds to the ligand bound to the gold spr surface a linear increase in refractive index is observed . samples of antibody containing ligand show a change in the rate of antibody adsorption and in the amount of antibody bound . in accordance with a feature of the present invention , the antibody may be conjugated to a negatively charged polystyrene bead . the bead serves to amplify the changes in refractive index that occur upon binding of the antibody to the sensor surface as a result of its large mass . in addition , negatively charged sulfate groups on the polystyrene bead may increase the rate at which the antibody binds to the ligand on the sensor surface when a positive bias is applied to the surface . antibody binding is typically limited by diffusion . the electric field in the e - field assisted assay helps to transport and concentrate the antibody over its immobilized binding partner to enhance the rate of binding . in one embodiment of a competitive binding assay , the sensor is first calibrated by introducing into the flow cell analyte detection chamber a volume of anti - ligand antibody conjugated to beads , for example , 0 . 5 micron polystyrene beads , in a surfactant containing buffer that reduces non - specific interactions ( e . g ., 50 mm glycine + 0 . 1 % triton x - 100 ). a positive bias is applied to the au surface containing the immobilized ligand to which the antibody is directed . a typical electrical bias may be , e . g ., a 1 - 10 volt pulse for 1 - 10 seconds . the electric field is subsequently reversed to repulse the non - specific binding of molecules whose affinity for the ligand is reduced . a typical reversal bias may be , e . g ., a 1 - 10 volt pulse for 1 - 10 seconds . a baseline is again obtained in 50 mm glycine + 0 . 1 % triton x - 100 . binding of anti - ligand antibody to the sensor surface is seen as a refractive index increase . the peak height for this “ reference sample ” ([ ligand ]= 0 ) describes the maximum amount of anti - ligand antibody expected to bind without interference . a reference may be evaluated periodically to verify that the regeneration process does not affect the ability of the ligand derivatized surface to bind anti - ligand antibody . the antibody may be stripped from the sensor and the surface regenerated using , e . g ., 0 . 1 % triton + 0 . 12 n naoh . antibody binding may be examined in the presence of a liquid sample containing , e . g ., 0 or 1 ppm of the ligand . the presence of ligand in the liquid sample reduces the amount of antibody binding to the sensor surface . samples are considered positive for ligand when the amount of antibody binding in the presence of the liquid sample is demonstrably and reproducibly less that obtained when antibody is bound in the buffer above ( e . g ., 50 mm glycine + 0 . 1 % triton x - 100 alone ). in one embodiment of the present invention , the flow cell is disposed such that the flow cell sample cavity 102 of fig1 is in fluidic contact with the sensing surface of an integrally formed surface plasmon resonance sensor . one embodiment of such an integrally formed surface plasmon resonance sensor 200 is depicted in fig2 . in the integrally formed surface plasmon resonance sensor 200 of fig2 a light source 202 ( e . g ., a light emitting diode ( led ), a laser diode or any other suitable source of radiation ), is disposed within a housing 204 . the housing 204 is made of a material that is transparent to the radiation from the source 202 ( e . g ., suitable plastics or epoxy ). a number of materials have been found suitable for construction of integrally formed sensor housings . in particular , an epoxy marketed under the trademark epocast 2013 parts a / b by furane products company has been found useful especially for radiation sources in the infrared range . other usable materials include , e . g ., emerson & amp ; cumming , stycast 1269a parts a / b , tracon trabond f114 , dexter hysol os1000 , norland 61 and 63 , dexter hysol mg18 or nitto 8510 - 1100 . a polarizing filter 206 is disposed in a position after the radiation source 202 to produce polarized light 208 . there are many suitable polarizers such as the plastic polarizing material ( e . g ., a polaroid hn7 linear polarizer ). because light source 202 acts like a point source of light , the light rays diverge from each other . likewise , the polarized light 208 has rays that are diverging from each other . the diverging polarized radiation reflects from a planar mirror 210 that is disposed so that the plane thereof is not normal to the direction to the polarized radiation 208 . the diverging polarized radiation , after being reflected from the mirror 210 , is directed toward a curved ( concave ) mirror 212 disposed on a curved exterior surface of the housing 204 . when the mirror 212 is concave , the shape of this mirror may be constructed so that the radiation reflecting therefrom converges at spr layer 214 . the surface plasmon resonance layer 214 includes a thin layer of a conductive material such as , for example , copper , silver , gold or other suitable materials exhibiting surface plasmon resonance . the layer 214 is generally planar although other configurations , such as convex or concave configurations , or featured with steps , periodic or non - periodic , may also be used . this layer 214 , in one embodiment of the invention , may include a film of gold approximately 500 angstroms thick . the thickness of a surface plasmon resonance layer may vary from about 200 to about 600 angstroms ( 20 to about 60 nanometers ) and still permit surface plasmon resonance to occur . the specific film thickness is determined by experimentation with respect to the frequency of the radiation for the source 202 and the properties of the conductive material used for layer 214 . when radiation strikes a thin conductive film at the interface of an insulator , the intensity of reflection therefrom is a function of the angle of incidence of the radiation onto the film and the refractive index of the material in contact with the other side of the film . hence , by determining the angle at which minimum reflectance occurs , it is possible to determine the index of refraction of the material on the side of the film opposite the side the radiation is reflected from . the configuration depicted in fig2 produces diverging radiation that is reflected from the thin surface plasmon resonance layer 214 . the diverging radiation passes through the housing 204 and is intercepted by a detector array 216 disposed at or near an external surface of the housing 204 . the housing 204 is disposed upon a lead frame 218 , which is in electrical connection with the light source 202 and the detector array 216 . in addition , any desired ancillary integral equipment such as for instance , reference light sources and / or temperature sensors would be placed in electrical communication with the lead frame 218 . for optical radiation , the detector array 216 may include an array of photodetectors . each detector in the array 216 produces a signal on an output pin with a voltage that is proportional to the intensity of the radiation striking the detector . by measuring the voltage at each detector and knowing the angle that the radiation striking that detector intercepted the surface plasmon resonance layer , a plot of reflected radiation intensity as a function of the angle is produced . that plot generally correlates to the index of refraction of the substance on the side of the surface plasmon resonance layer opposite the side that reflects the radiation . the physical location of the elements illustrated in fig2 may be moved or relocated while retaining the function described above . [ 0064 ] fig3 illustrates an alternative configuration of an integrally formed spr 300 . this alternative configuration includes a substrate 302 on which the sensor is constructed and on which a light transmissive housing 304 is coupled . a light source 306 is preferably located above or within the substrate 302 . disposed above the light source 306 is a physical aperture 308 through which light from the source 306 passes . in operation , a polarizer 310 is located near the aperture 308 to polarize the light passing through aperture 308 . the polarized light continues through the housing 304 and strikes a thin surface plasmon resonance layer 312 . the polarized light is reflected internally from layer 312 and continues through housing 304 and strikes a planar mirror 314 . the polarized light reflects from the mirror 314 and is directed through the housing 304 and onto a detector array 316 . as shown in fig3 the light source 306 , aperture 308 , polarizer 310 and detector array 316 are disposed within housing 304 . as with the housing 204 described in fig2 the housing 304 is made of a material that is transparent or substantially transparent to the light from light source 306 . housing 304 is formed in a geometric configuration so that light from the source 306 will reflect from the spr layer 312 , the mirror 314 and strike detector array 316 . any configuration accomplishing this is suitable , however , there are several considerations that need to be taken into account in designing sensors of the type illustrated in fig2 and 3 . it is desirable to have the radiation impinging on the detector array at angles as close as possible to 90 degrees . this is due to the fact that the sensitivity of the discrete detector elements used in the detector array are most sensitive to light impinging along its optical axis . light impinging from angles where the light rays are not parallel to the optical axis results in a lower output signal which may be preferred in some embodiments . by designing the structures of fig2 and 3 to have the light strike the detector array at an angle close to 90 degrees , a detector will have the maximum possible sensitivity . for most purposes , however , if the angle at which light strikes the detector array is between about 60 and 90 degrees , the “ off - axis ” falloff of each detector in the array is not considered to be a major problem . indeed , with calibration , the sensor of this invention may use light incidence angles of less than about 45 degrees and still be useful . it is to be further noted from fig2 and 3 that the surface plasmon resonance layer may be formed on a surface of the exterior of the housing . it is also possible to have the surface plasmon resonance layer ( a thin conductive film ) disposed on a glass slide , or the like , which is located adjacent an exterior surface of the housing and having an index matching fluid disposed between the slide and the housing . the mirror may even be formed on an exterior surface of the housing . this mirror will have sufficient mass so that the effect of surface plasmon resonance will not occur on the surface thereof . those of skill in the art will recognize that the elements of the integrally formed surface plasmon resonance sensors devices such as those depicted in fig2 and 3 may be relocated , rearranged or reoriented within the transparent housing while retaining equivalence in function according to the present invention . further alternative designs are possible . for example , it is possible to use a surface plasmon resonance layer disposed on a curved or featured exterior surface of the housing ( not illustrated ). likewise , the mirror may be constructed on a curved surface . it is also possible to have more than one mirror and / or spr surface disposed along the light path between the source and the detector array . it will also be clear that the light from the source may strike a mirror or a lens prior to striking the surface plasmon resonance layer . further variations in the radiation path and corresponding structure of the housing may be conceived while retaining the functionality of the sensor illustrated herein . the structures as illustrated in fig2 and 3 do not depict filters disposed within the housing . a filter may be disposed between the detector array and the mirror . for example , the filter may be placed adjacent the detector array . alternatively , the housing may be made of a material transparent to radiation at the frequencies produced by the source and opaque to other frequencies . in either configuration , radiation at frequencies other than those produced by the source will not form a significant portion of the output of the detector array . the integrally formed sensors may additionally include a temperature sensor disposed adjacent to the surface plasmon resonance ( spr ) layer and / or the surface of the housing . the temperature sensor produces an electrical signal indicative of the temperature of the spr layer during operation thereof . the temperature signal may be used to compensate for apparent changes in the measured index of refraction by the invention as a result of changes in the operating temperature of the device . the integrally formed sensors may additionally include a reference detector disposed proximately to the light source . such detector may be used to calibrate the invention over long periods of time since the intensity of a source may vary over time . the following example of one embodiment of the interaction regulated spr apparatus and method is included for the sake of completeness of disclosure and to illustrate one of may applications contemplated for the claimed technology . disposable gold - coated glass slides are used as the surface plasmon resonance ( spr )- active surfaces . other surfaces and coatings known to be compatible with spr may be alternatively employed . the slides are prepared by depositing 2 nanometers of chromium and 50 nanometers of gold ( au ) onto 0 . 008 - inch thick borosilicate glass ( erie scientific , erie , pa .) cut to fit over the sensor surface . both metal films are deposited by thermal evaporation ( varian model 3118 , base pressure less than 2 × 10 − 7 torr ). the gold deposition rate is 0 . 8 - 1 . 0 nanometers / sec , and the chromium deposition rate is 0 . 1 - 0 . 2 nanometers / sec . gold - coated slides are stored in fluoroware boxes in an uncontrolled laboratory ambient . prior to the attachment of bio - films , the gold spr surfaces may be routinely cleaned to enhance assay reproducibility . disposable slides are cleaned with 0 . 1 % triton x - 100 ( a non - ionic detergent ) and 0 . 12 n sodium hydroxide ( naoh ). slides are rinsed thoroughly with de - ionized water and dried with nitrogen . a tri - nitrotoluene ( tnt ) sensing bio - film is prepared on the disposable gold slides by spreading 0 . 5 microliters of tri - nitrobenzene bovine serum albumin (“ tnb - bsa ”— 20 micrograms / milliliter in phosphate buffered saline ph 7 . 4 ) across the surface of a cleaned gold - coated glass slide using a pipette tip . the slide is allowed to air dry and then placed into a 70 ° c . vacuum oven for 20 minutes . the tnb - bsa covered slide is rinsed in distilled or purified water and allowed to air dry before assembly on a spreeta - type spr sensor ( texas instruments , dallas , tex .). optical coupling of the tnb - bsa slide to the spreeta sensor is accomplished by applying approximately 0 . 2 microliters of index matching liquid (# 5040 , cargille incorporated , cedar groves , n . j .) onto the sensor surface and then placing the glass slide on top . a flow cell is used in these experiments to enable relatively small fluid volumes to be brought to and from the active portion of the spr sensing surface . the body of the flow cell used is a ¼ - inch thick teflon block with holes drilled to accept { fraction ( 1 / 16 )}- inch od teflon tubing . the flow cell is outfitted with a small glass bead thermistor . a silicone gasket , with a laser - cut channel is placed between the teflon block and sensor surface . the thermistor may reside directly in the flow cell channel . the channel is positioned so that it overlaps the active spr region . the flow cell is assembled and mounted above the tnb - bsa slide . in the e - field assisted assay , the flow cell is modified by the addition of two platinum electrodes in accordance with one embodiment of the present invention . a capacitor is created within the flow cell device by attaching a platinum electrode to the surface of the gold sensing layer and positioning a second platinum electrode above the flow cell channel . the liquids and biological buffers used for most biosensing assays serve as the dielectric . the electrodes are constructed using 0 . 003 ″ thick platinum foil ( electronic space products international , ashland , oreg .). the first electrode includes a thin strip of platinum placed on top of the gold slide and underneath the silicone gasket . the second electrode is a sheet of platinum placed between the silicone gasket and the teflon block . three holes are drilled in the sheet of platinum to accommodate the teflon tubing and the bead thermistor . the two electrodes are generally long enough to protrude from the flow cell . after assembly of the flow cell , the first electrode protrudes from the top of the sensor , while the second electrode protrudes from the bottom of the sensor . the electrodes are connected to a keithley model 236 source measuring unit (“ smu ”) ( keithley instruments incorporated , cleveland , ohio ) using a triaxial cable ( model 237 - alg - 2 , keithley instruments incorporated ). the smu is used to source voltage and measure current during the course of the assay . after assembling the spreeta type sensor and flow cell , the sensor is air initialized . liquids may be applied to the sensor surface using a simple peristaltic pump ( fisher brand variable flow peristaltic pump ) operating around 300 microliters / min . an spr curve is obtained in water . the baseline and other analysis parameters are set using this sample curve . the sensing surface is then washed with 0 . 1 % triton x - 100 and 0 . 12 n naoh to remove any loosely bound tnb - bsa or surface contaminants from the surface of the slide . following the washing procedure , a baseline is again obtained in 50 mm glycine + 0 . 1 % triton x - 100 . in a direct binding spr assay , the analyte is typically bound to an immobilized ligand on the spr surface . a high level summary of a competition assay format for the tnt assay according to one embodiment of the present invention is illustrated in fig4 . in the competition assay , a dilute solution of a monoclonal antibody to tnt is flowed across the sensor surface . the antibody is used as a large mass molecule whose binding is competitively prevented by free tnt in solution . when the antibody binds to the tnb - bsa groups on the gold surface , a linear increase in refractive index is observed . samples of antibody containing tnt cause a change in the rate of antibody adsorption and in the amount of antibody bound . in an e - field competition assay , the antibody is conjugated to a negatively charged polystyrene bead . the bead amplifies the changes in refractive index that occur upon binding of the antibody to the sensor surface as a result of its large mass . in addition , negatively charged sulfate groups on the polystyrene bead cause an increase in the rate at which the antibody binds to the tnb - bsa on the sensor surface when a positive bias is applied to the surface . the electric field in the e - field assisted assay helps to transport and concentrate the antibody over its immobilized binding partner and consequently enhances the rate of binding . to calibrate the spreeta sensor , 1 ml of anti - tnt antibody conjugated to 0 . 5 micron diameter beads in 50 mm glycine + 0 . 1 % triton x - 100 is introduced within the flow cell . a positive bias is applied to the gold (“ au ”) surface containing the immobilized tnb - bsa . a typical bias of 1 - 10 volts pulsed for 1 - 10 seconds is used . the electric field is subsequently reversed to repulse the non - specific binding of molecules whose affinity for the tnb - bsa is less than that of the anti - tnt antibodies . a typical bias of 1 - 10 volts per pulse of 1 - 10 seconds is used . a baseline is obtained in 50 mm glycine + 0 . 1 % triton x - 100 . binding of anti - tnt antibody to the sensor surface is measured as a refractive index increase . the peak height for this “ reference sample ” ([ tnt ]= 0 ) describes the maximum amount of anti - tnt antibody expected to bind without interference . a reference sample is run periodically to verify that the regeneration process does not affect the ability of the tnb - bsa surface to bind anti - tnt antibody . the antibody is stripped from the sensor and the surface regenerated using 0 . 1 % triton + 0 . 12 n naoh . antibody binding is examined in the presence of a liquid sample containing either 0 or 1 parts - per - million (“ ppm ”) tnt . the presence of tnt in the liquid sample reduces the amount of antibody binding to the sensor surface . in the example shown on fig5 samples are considered positive for tnt when the amount of antibody binding in the presence of the liquid sample is less than 54 % of that obtained when antibody is bound in 50 mm glycine + 0 . 1 % triton x - 100 alone . in contrast , in the tnt assay with the e - field , the same initial steps as above are conducted using antibodies conjugated with negatively charged beads . beaded antibodies are combined with a liquid sample ( that may or may not contain tnt ) and the solution is exposed to the sensor surface . a positive bias is placed on the sensor surface ( relative to a parallel plate counter electrode ) and the bias draws the beaded antibodies immediately toward the surface , resulting in an instantaneously high concentration of antibody at the surface . reactions are then able to take place in a concentrated local environment . the bias is removed and the beads move away from the surface and only those beads bound by their linked antibodies are expected to remain . after the bias is removed , buffer is again introduced for a new baseline and the difference between the new and old baselines reports the presence and quantity of tnt in the solution . furthermore , the charged beads not only bring the antibody down to the surface quickly and in high concentration , but they also amplify the spr signal on a molecule by molecule basis because they increase the size of the specifically bound molecule , thus , amplifying the effect on the surface plasmon resonance . in this example , bead derivatized antibodies are approximately 1 micron in diameter as opposed to the approximately 50 angstrom individual protein . while this invention has been described with reference to illustrative embodiments , this description is not intended to be construed in a limiting sense . upon reference to the description , it will be apparent to persons skilled in the art that various modifications and combinations of the illustrative embodiments as well as other embodiments of the invention can be made without departing from the spirit and scope of the invention . it is therefore intended that the appended claims encompass any such modifications or embodiments . | 6 |
this invention relates to an improved applicator for mascara . the improvement comprises employing a hollow core applicator head on a conventional rod - type mascara applicator . the applicator comprises handle means attached to one end of a shaft and the applicator head attached to the shaft &# 39 ; s other end . the applicator head has a hollow core and is typically of a circular or elliptical shape in cross - section . of course , the head may be of any desired cross - sectional shape . the head is provided with multiple slits or slots which extend less than completely through the longitudinal axis of head . the precise configuration , dimensions and spacing of the transverse slits along the axis of the head depend on the desired application properties . generally the slits are substantially parallel to one another to permit uniform application of mascara . the slits need not , but may , be perpendicular to the axis of the head . in order to minimize any possible wiping effect the slits desirably extend substantially completely through the applicator head . however , they cannot extend completely through the head since the structural integrity of the head requires that the segments formed by the slits be joined by some minimal reinforcing member or rod . referring to fig1 and 3 which depict the preferred embodiment of the invention , a shaft or rod 10 is attached at one end to handle means , in this case threaded cap 9 , while applicator head 8 is attached to the shaft &# 39 ; s opposite end . applicator head 8 is in the form of a helical spiral 5 . opening 7 is filled with mascara upon dipping into a mascara source , thus providing a reservoir of mascara in which the eyelash can be completely immersed . the mascara composition employed should be of a consistency which permits easy immersion of the lashes therein . on the other hand the mascara should have a viscosity or consistency high enough to be retained within the applicator head . this latter characteristic will be variable according to the size and configuration of the head employed . a mascara having a viscosity of 20 as measured on a brookfield helipath td at 4 rpm has been employed successfully with the invention . since the lashes are completely immersed in mascara when the applicator head of the invention is employed , a film of mascara is applied to the entire circumference thereof . the helical spiral in fig2 is the preferred embodiment of the invention in that it maximizes the area which serves as a reservoir for the mascara while minimizing any wiping action of the applicator head . the coil gauge , shape and number of turns per inch can be adjusted to achieve the desired application properties . fig4 and 5 depict an alternative embodiment of the invention . in this embodiment the applicator head is formed of axially spaced concentric parallel rings 11 mounted on rod 12 . a modification of this embodiment is shown in fig6 and 7 wherein the rings 13 have openings 14 positioned opposite the point 15 where they are mounted on rod 12 . the openings 14 facilitate immersion of the lashes in the reservoir of mascara which fills opening 16 . in this embodiment , the ring dimensions , shape and spacing can also be adjusted according to desired application properties . the applicator heads have been depicted as forming a straight line with the applicator shaft . however , if desired the head may be of a curved configuration . moreover , the head may taper toward the end opposite that attached to the shaft . for example , fig8 and 9 depict an applicator head which is the same as that depicted in fig4 and 5 except that rings 17 progressively diminish in circumference . such tapering or reduction in circumference of the applicator head can facilitate mascara application to the lashes in the corners of the eyes . brushes could also be attached to the end of the head to facilitate such application . fig1 and 11 depict an applicator head which is a modification of that shown in fig1 and 3 . in this embodiment , the applicator head is formed by two wires 18 and 19 which form a parallel helical spiral . opening 21 is in this case the reservoir . applicator heads of helical configuration may also be formed using more than two wires . typically mascara applicator heads in accordance with the invention will be between 0 . 25 and 0 . 90 inches long and between 0 . 10 and 0 . 375 inches in diameter . for acceptable mascara application the gauge of the rings or wire will typically be 0 . 015 to 0 . 035 inches and the slits will be 0 . 01 to 0 . 06 inches wide . specific embodiments of applicator heads which may be used in the invention have a length of 0 . 7 inch , a diameter of 0 . 175 inch , a wire gauge of 0 . 034 inch , 0 . 028 inch slits and about 16 turns or rings per inch . these dimensions , of course , are not intended to limit the invention ; rather mascara applicator heads of any conventional or suitable dimensions may be employed . it is to be understood that the applicator head of the invention can be formed of any material which provides at least the minimum rigidity required for application of mascara . materials such as relatively rigid plastics or metals are obviously acceptable possibilities . further , the rings or wire which form the applicator head may be round , elliptical , rectangular or of any other desired rounded or flat edged configuration . the surface of the material forming the head may be smooth . however , an increase in the amount of mascara which can be applied with the applicator of the invention might be achieved by employing a rough surfaced applicator head or a head wherein the coil or rings are made of or covered with small bristles . it is to be understood that the several embodiments shown are illustrative of the invention and that various changes and modifications can be made without departing from the scope of the invention as set forth in the claims . | 0 |
referring initially to fig1 , there is illustrated a system 10 constructed according to one preferred embodiment of the invention . according to this embodiment , the system 10 is installed in vertical wellbore 12 of a well , the wellbore 12 being lined with casing 14 . the system 10 includes a passive gas / liquid separation device 16 in the form of flow tube 18 which is located above the heel portion 20 of the well , which heel portion 20 connects the vertical wellbore 12 with a generally horizontal borehole 22 . the fluid flow 38 ( i . e ., liquid , gas slugs and water ) from horizontal borehole 22 reaches the heel 20 as shown , and rises upwardly in the vertical casing where it meets the flow tube 18 . at this location , the fluid enters the vertical flow tube 18 and proceeds upwardly along the spiral path defined by spiral baffle 24 . the system of fig1 includes one preferred form of gas / liquid separation device 16 in the form of spiral baffle , or auger 24 , positioned in flow tube 18 and defining a spiral path for the gas / liquid mix rising from the horizontal borehole 22 . the spiral shaped path of baffle 24 tends to separate the gas slugs 26 from the liquid medium by centrifugal forces imposed on the liquid , which forces cause the liquid portion to migrate radially outwardly from the center of baffle 24 , as the mix rises and increases in velocity . the lighter gas portion will remain closer to the center and enter central gas tube 28 via apertures 30 , to be directed into the annulus 32 defined between flow tube 18 and casing 14 . the gas portion in the center of baffle 24 may include a relatively lesser portion of liquid in the mix . as noted , as the gas / liquid mix rises up the spiral path of the gas / liquid separation baffle 24 , the heavier liquid portion migrates outwardly along the spiral path , and the gaseous portion enters apertures 30 in the center of the spiral baffle 24 and is directed into annulus 32 . annular packer 34 is provided with vent valve 36 , which is adapted to vent excess gas to the atmosphere in the event an excessive amount of gas is produced and accumulated in the annulus 32 to form a high pressure zone . in particular , as can be seen from the figures , liquid will enter the annulus 32 ; however a reduced flow rate due to a large “ settling area ” will allow the liquid and gas to separate by density differences . the separated liquid will be directed to the tubing , the gas will remain in the annulus , captured under the packer until reinjected into the tubing . it will be appreciated that the combination of the continuous rotational path of the fluids while traveling upwardly along the spiral path , and the progressively increasing velocity of the fluids as they rise upwardly , will cause radially outward migration of the heavier liquids ( i . e ., oil and water ) and retention of the most gaseous phase closer to the center as shown by arrow 23 . simultaneously , by the action of the spiral path , the gaseous slugs 26 will be broken up into smaller bubbles , which enter central gas flow tube 28 via inlet aperture ( s ) 30 . thereafter , as noted , the liquid phase of oil ( sometimes combined with water ) will proceed upwardly into production flow tube 18 , while the gaseous phase in the form of relatively smaller bubbles will migrate upwardly , or will be lifted by compressor 44 ( if required ) and then proceed to injection device 40 , which allows one - way flow of gas from annulus 32 into production flow tube 18 , preferably in a controlled manner , where the gases are mixed with the liquid phase in a dispersed and uniform manner . in the flow tube 18 , an optional electric submersible pump 42 can also be installed in flow tube 18 as shown in phantom lines in fig1 , to assist the production flow upward toward surface if required by the conditions prevailing in the well . annular packer 34 will contain the mostly gaseous medium formed by the dispersed slugs , if and until the pressure exceeds the pre - set pressure of relief valve 36 . should the pre - set pressure be exceeded , the relief valve 36 will permit the gaseous medium to escape into the annulus and rise to the surface as illustrated schematically by the arrow 35 shown in phantom lines . in fig1 , injection device 44 is positioned in the annulus 32 as shown , and arranged to communicate with the production flow tube 18 such that gas exiting central gas tube 28 can be directed into the annulus 32 , and then into the production flow tube 18 in a controlled manner and the form of relatively fine bubbles , at an elevated location immediately below packer 34 . thereafter , the merged fine gas bubbles and the production liquid mix is allowed to flow to elevated locations above packer 34 and proceed upwardly to the wellhead at the earth &# 39 ; s surface . as noted , depending upon the particular characteristics and conditions in the well , an optional compressor 44 can be positioned as shown in fig1 , in the annulus 32 to assist the upward movement of the predominantly gaseous medium exiting central gas tube 28 and entering annulus 32 via apertures 30 . compressor 44 comprises an artificial lift system that electrically drives multiple centrifugal stage impellers to increase the pressure and thereby lift the predominantly gaseous medium from annulus 32 . the compressor 44 may be powered by electric power provided from the surface . depending upon the circumstances and well completion conditions , the compressor can be in any of several forms . the steps of diffusing the gaseous slugs into predominantly fine gas particles , and then re - introducing them into the predominantly liquid phase of the production flow increases the flow rate of the produced fluid stream and maintains the continuous operational characteristics of the well . it is also noted that the assist provided by the optional compressor 44 promotes improved merging of the now dispersed gaseous medium with the predominantly liquid flow in the production flow tube 18 . as shown in fig1 , an electric submersible pump 42 can optionally be positioned in production flow tube 18 above compressor 44 to provide artificial lift to the predominantly liquid medium in flow tube 18 . in fig1 , the production flow tube 18 is open at the mouth 45 to receive fluids as depicted by arrows 46 . in fig1 , the fluid ( both liquid and gas ) at the mouth 45 of the flow tube 18 would generally be at a first pressure , designated as pgas / liquid . once the flow of liquid and gas slugs enters the flow tube 18 and gas / liquid separation device 16 as shown in fig1 , and the separation of the gas from the liquid takes place by the gas passing through the path of spiral baffle or auger 24 , the gas will rise in the wellbore annulus 32 and it will be ultimately trapped therewithin under an annular sealing device , such as packer 34 , or the like . since the pressure pgas of the gas in the annulus 32 , prior to re - entry into the flow tube 18 , by injection device 40 , is greater than the liquid pressure pliquid in the flow tube 18 , any relatively small amount of liquid in the annulus 32 will be redirected from the annulus 32 into the flow tube 18 , and then flow naturally within the flow tube 18 toward the surface in flow tube 18 along with the production flow . as the liquid rises in the flow tube 18 , the hydrostatic pressure will decrease primarily due to the change in height . as noted , the pressure of the liquid will be different at the various locations in the tubing string and an upper location will have a lower pressure than a deeper location as will be explained hereinbelow , using water as an example . referring again to fig1 , at a predetermined vertical distance above the mouth 44 of flow tube 18 , pgas will be greater than pliquid . at this location , the primarily gas flow in the annulus 32 below the packer 34 will be at a higher pressure than that of the medium in the flow tube 18 , which is comprised primarily of a liquid . the gas will then be directed via a controlled gas injection device 40 for injection into the liquid stream . as noted , the gas injection device 40 will control the rate of gas injection into the flow tube 18 , as shown schematically by arrows 46 in fig1 . the gas injection device 40 is a valve used in a gas lift system which controls the flow of lift gas into the production tubing conduit in a controlled manner . the gas injection device 40 , which can be in the form of an injection valve , is located in a gas lift mandrel 48 , which also provides communication with the gas supply in the tubing annulus 32 . gas lift mandrel 48 is a device installed in the tubing string and is shown schematically in fig1 . operation of the gas injection device 40 is determined by preset opening and closing pressures in the tubing of the annulus , depending upon the specific application . the gas lift injection device 40 or other suitable gas injection controlled metering device , or nozzle is preferably capable of providing specifically controlled metered gas flow into the liquid stream in the flow tube 18 in a manner to produce finely dispersed gas bubbles in the liquid stream . in particular , the gas injection device 40 allows one - way flow of gas from the high pressure zone of annulus 32 into flow tube 18 , as explained previously , due to the fact that pgas is greater than pliquid at such elevated location . any relatively small amount of liquid which is mixed with the gas in the annulus 32 will naturally flow back into the flow tube 18 through gas injection device 40 . injection device 40 preferably will be arranged to re - inject the gas into the tubing at the same rate that it is stripped out of the liquid / gas flow by the passive gas separation process of gas / liquid separation device 16 . a venting device such as vent valve 36 , is positioned preferably within the packer 34 to vent excess gas to the atmosphere in the event such an excessive amount of gas is produced and accumulated in the annulus 32 to form a high pressure zone . therefore , if the gas is not reinjected at the same rate that it is stripped , the gas will fill the annulus 32 until it reaches the stripped pressure . the passive gas / liquid separation system will no longer strip out the gas ; rather the gas will stay in solution with the liquid and will be injected into the tubing . referring now to fig2 - 3 , there is illustrated an alternative embodiment 100 of the inventive system , which includes passive gas / liquid separation device 102 in the form of flow tube 116 . wellbore 112 is lined with casing 114 in which flow tube 116 is positioned to form annulus 118 with casing 114 , as shown . in this embodiment , flow tube 116 is closed at its lowermost end by plug 120 . in principle , the operation of the embodiment of fig2 and 3 differs from the previous embodiment , but the objectives and results are similar . the tortuous apertures 124 in flow tube 116 receive and direct the liquid 126 containing gaseous slugs 128 into the flow tube 116 as shown , while the major portion of the gaseous medium is permitted to move upwardly into annulus 118 via apertures 124 . the flow tube 116 includes a central separator baffle 130 for further assistance and guidance of the liquid medium , the central baffle 130 being surrounded by circular baffle 132 as shown in fig2 and 3 . major portions of the gaseous slugs 128 are broken up while entering the flow tube 116 via tortuous apertures 124 , which are so configured as shown , as to encourage the liquid component to enter the circular baffle 132 , as shown schematically by arrows 134 . the gaseous medium is “ encouraged ” to move upwardly and outwardly toward annulus 118 as depicted schematically by arrows 136 , and the predominantly liquid flow is depicted by arrow 137 . fig3 is a cross - sectional view taken along lines 3 - 3 of fig2 , illustrating the escape of gaseous medium by arrows 136 which were previously in the form of gaseous slugs 128 , via tortuous apertures 124 and into annulus 118 . in particular , a controlled gas injection device 138 is positioned above compressor 140 and below packer 142 , which is provided with vent valve 144 as in the embodiment of fig1 and 2 . in all other respects , the uppermost structure and operation of the embodiment of fig2 and 3 are the same as the operation of the previous embodiments . referring now to fig4 , there is illustrated an enlarged cross - sectional view of a lowermost portion of yet another alternative embodiment 200 of the invention , in which the flow from a horizontal borehole of the well enters the tube 210 , which is closed at its lowermost end by integrally formed base plate 212 , the flow tube 210 including apertures 214 which create respective tortuous paths as depicted by arrows 216 , for separation of the gas from the liquid . this path causes the gas slugs to be broken up and to be stripped from the liquid while entering the annulus 218 formed between the flow tube 210 and the casing 220 . the gas is thus stripped from the liquid / gas mix and then permitted to accumulate in the annulus 218 , where it is reinjected into the flow tube 210 at the upper end ( not shown in fig4 ) in the same manner as described in connection with the previous embodiments . in all other respects , the operation and the remaining structure and function of the embodiment of fig4 , are the same as with the previous embodiments . referring now to fig5 , there is shown yet another alternative embodiment 300 of the invention , in which the passive gas / liquid separation device 324 is positioned in the horizontal borehole of the well . the system of fig5 is similar in most respects to the gas / liquid separation device system of fig1 and 2 , except that it is located in the horizontal borehole . the well completion system 300 is comprised of vertical borehole 310 provided with vertical casing 312 surrounding production flow tube 314 to form annulus 316 . horizontal borehole 322 is depicted schematically as being joined with vertical borehole 310 at heel 320 . located in horizontal borehole is a passive gas / liquid separation device 324 , which is structurally and functionally identical to the passive gas / liquid separation device shown in fig1 and 2 , including a spiral shaped baffle or auger 326 positioned and adapted to receive gaseous slug - laden fluids from the well through the horizontal borehole 322 , as depicted by arrows 328 and slugs 330 . the slug - laden fluids depicted by arrows 328 enter mouth 334 of the gas / liquid separation device 324 and proceed downstream to passively separate the gas components from the liquid components while breaking up the gaseous slugs into relatively smaller pluralities of bubbles . as in the system of fig1 and 2 , the gaseous slugs are broken up into smaller bubbles and exit flow tube 336 . thereafter the primarily gaseous medium is assisted by compressor 339 if needed , and then injected into vertical flow tube via controlled injection device 338 where it is mixed with the predominantly liquid medium passing through spiral shaped baffle or auger 326 as in the system disclosed in fig1 and 2 . the now homogeneous liquid / gas mixture flows with the assistance of electric submersible pump ( designated as “ esp ”) 340 and then to vertical flow tube 314 where it proceeds upwardly through surface as shown by arrow 342 . in all other respects , the operation of this embodiment is the same as the previous embodiments . referring now to fig6 , there is shown yet another alternative embodiment 400 of the invention , in which the passive gas / liquid separation device 410 is positioned in the horizontal borehole of the well . the passive gas / liquid separation device 410 of this system is similar to the system of fig2 and 6 . system 400 is comprised of a vertical borehole 412 provided with vertical casing 414 surrounding production flow tube 415 to form annulus 416 . horizontal borehole 422 is depicted schematically as being joined with vertical borehole 414 at heel 420 . located in horizontal borehole 422 is a passive gas / liquid separation device 410 which is structurally and functionally identical to the passive gas / liquid separation device shown in fig2 and 5 , including flow tube 426 containing central baffle 428 surrounded by circular baffle 430 . as described in connection with the embodiment of fig2 and 3 , the slug - laden fluids proceed from the well through horizontal borehole 422 as shown schematically by arrows 432 . as the fluids flow through the horizontal borehole 422 , the gaseous slugs 431 are made to pass through a series of tortuous paths where they are divided into a plurality of relatively smaller bubbles as the slugs are dispersed . the mostly gaseous medium then migrates toward annulus 434 and toward compressor 436 , and is then injected under controlled conditions by injection device 435 into the flow tube 426 where a homogeneous mix 438 of liquid and relatively smaller gas bubbles is produced . annulus packer seal 440 is positioned in the annulus and includes having a release vent valve 442 which permits release of the predominantly gaseous media in the event the pressure rises in annulus 434 exceeds a pre - set value . the resultant homogeneous mixture depicted by arrow 438 is then directed to surface . in all other respects , the passive gas / liquid separation system shown in fig6 is structurally and functionally the same as the corresponding system of fig2 and 3 . fig7 is a graph which illustrates the liquid and gas pressures in relation to the depth of the well , in feet , for the embodiments of fig1 - 6 . in particular , the liquid and gas conditions at two different depth locations identified respectively as “ upstream location 1 ” and “ downstream location 2 ” are shown in the graph . | 1 |
in the embodiment for a sedan ( e . g . four - door type , etc .) ( shown schematically in fig1 . 1 ), the paneling element 1 according to fig1 comprises a filling panel 2 which is surrounded by a u - shaped frame 3 . the latter is composed of rigidly interconnected frame segments 4 , of which one frame segment 4 . 1 is aligned transversely with respect to the longitudinal axis of the vehicle and is arranged between the a - pillars , while lateral frame segments 4 . 2 forming the “ limbs ” of the u - shaped frame 3 extend in the direction of travel and have downwardly directed projections 5 . 1 and 5 . 2 in each case in the region of the “ a ” and “ b ” pillars . the frame segments 4 form a generally stiff , supporting structure of the paneling element 1 while the relatively soft filling panel 2 is intended to determine , for example , the acoustic properties of the paneling element . the frame segment 4 . 1 which runs transversely is shown provided with accessory parts in the form of sun visors 6 and an inner rear view mirror 7 while the lateral frame segments 4 . 2 are shown equipped with grab handles 8 . the filling panel 2 has an illuminating console 9 . 1 . if a paneling element 1 is requested for a vehicle of the same product line but with an enlarged interior ( fig1 . 2 ), all of the components of the basic version can again be used . the enlarged dimensions of the vehicle interior are taken into account by the fact that the lateral frame segments 4 . 2 are extended in the longitudinal direction of the vehicle by frame segments 4 . 3 which are shown equipped with grab handles 8 for the occupants of a third row of seats . as shown in fig1 . 2 , the filling panel 2 is composed of a first segment 10 . 1 , such as used in the basic version , and of an extending , second segment 10 . 2 which is further shown to include an illuminating console 9 . 2 . if a sedan is manufactured with a side airbag 11 ( see fig1 . 3 and 2 . 1 ), the lateral frame segments 4 . 2 may be replaced with frame segments which contain the airbag , while the frame segments 4 . 1 and the filling panel 2 may remain the same . the supplier of the paneling element 1 can therefore react within a short time to requests made by the vehicle manufacturer and can prepare an adapted paneling element . corresponding adaptations are also possible in a variety of colors and paneling materials . in the embodiment shown according to fig2 . 1 , in addition to the projections 5 . 1 and 5 . 2 for the “ a ” and “ b ” pillars , projections 5 . 3 for the paneling of the “ c ” pillar are also shown integrally formed on the lateral frame segments 4 . 2 . moreover , the frame 3 is shown to surround the filling panel 2 around the circumference by the connection of a rear frame segment 4 . 4 which runs transversely , intended to provide a dimensionally stable component . if a vehicle of the same structural shape of the body with a glass roof is ordered , the frame according to fig2 . 1 , which is of essentially rectangular design , can be provided with an additional transverse strut 12 ( fig2 . 2 ). in this case , the area 13 . 1 formed by the transverse strut 12 , the lateral frame segments 4 . 2 and the rear frame segment 4 . 4 accommodates a reduced filling panel 2 which is surrounded around its circumference by the frame , while the front area 13 . 2 is not covered and permits a view or access to the glass roof panel . alternatively , the filling panel may be constructed from two segments 10 . 1 and 10 . 2 , of which the front segment 10 . 1 is displaceable in a gap between the rear segment 10 . 2 and the metal structure of the vehicle roof ( as shown in fig2 . 3 ). guide rails for this purpose can be integrally formed , for example , in the lateral frame segments 4 . 2 and can be covered in the basic version by the filling panel 2 , which is shown to fill the entire frame 3 as a single piece . according to an alternative embodiment , it is also conceivable to attach these rails as separate components to the lateral frame segments 4 . 2 . if a vehicle supplied in the basic version is to be provided at the factory or subsequently with improved equipment , such can be undertaken according to fig2 . 4 by inserting a transverse support element 14 between the lateral frame struts 4 . 2 , the transverse support element spanning the filling panel on the interior side and being equipped , for example , with a display 15 . fig2 . 5 shows the components of a paneling element designed in accordance with an embodiment of the present invention ( similar to fig2 . 4 ) in a perspective illustration . in fig3 , method steps for the manufacturing and the fitting of the paneling element 1 shown in fig1 . 1 are illustrated by way of example . the process as shown in fig3 . 1 begins with the production of the individual frame segments 4 . 1 and 4 . 2 which are preferably manufactured by injection molding of a plastic . alternatively , other manufacturing methods can be used , for example pressing or blow molding , etc . the filling panel may be cut from a semi - finished product and is provided with recesses 16 for the later accommodation of accessory parts . furthermore , an additional frame segment 4 . 5 , the use of which will be explained later , may be provided . as shown in fig3 . 2 , the frame segments 4 and the filling panel 2 are provided with accessory parts shown as the sun visors 6 , the rear view mirror 7 , the grab handles 8 and the illuminating console 9 . further equipment may be integrated in the frame segments , a non - exhaustive list including , for example , reading lamps , ventilation system components , storage compartments , displays for time , temperature and the like , sockets and also remote communication devices having gate drives . if a frame segment which runs transversely is to be arranged permanently in the rear region of the frame 3 , the frame segment could also accommodate a brake light . in addition to the illuminating console , the filling panel may also have , for example , recesses for sliding or glass roofs panels . the frame segments 4 . 1 and 4 . 2 are then hooked together in the outer region of their connecting points in such a manner that they form , in one installation position , a u - shaped frame 2 with spread - out “ limbs ” in which the filling panel 2 is placed ( as shown in fig3 . 3 ). the frame segments are then pivoted into their final position ( as shown in fig3 . 4 ), in which case the lateral frame segments 4 . 2 are connected at their end lying opposite the front frame segment 4 . 1 to the filling panel 2 by latching , screwing or bonding , for example . in addition , in this region the frame segment 4 . 5 is placed onto the ends of the lateral frame segments 4 . 2 , so that the paneling element 1 is stabilized by an encircling frame for further transportation and alignment in the vehicle interior . after the paneling element 1 has been fitted into the vehicle body , the frame segment 4 . 5 , which acts as an installation aid , can be detached again and re - used ( as shown in fig3 . 5 ). fig4 shows a connection between a first frame segment , for example a lateral frame segment 4 . 2 , and a frame segment which runs coaxially , for example the extending frame segment 4 . 3 which is illustrated in fig1 . 2 . correspondingly , however , angled connections or other connections between frame segments may also be formed . the frame segments 4 . 2 and 4 . 3 which are to be connected are provided on the end side with coupling elements 17 shown in the form of an electric plug 18 with an associated socket 19 , and a connection piece 20 with an associated plug - in opening 21 , the latter being used , for example , for supplying washing water to a rear - window washing device or to supply fresh air into the vehicle interior . the frame segments 4 . 2 and 4 . 3 can be connected to each other via connectors shown as latching lugs 22 which engage in corresponding latching openings 23 . the filling panel 2 can be pushed into a groove 24 which extends along the frame segments 4 . 2 . a further groove - like recess 25 , into which , for example , a lighting strip ( not illustrated ) can be placed , is shown to run in the frame segments 4 . 2 and 4 . 3 below the groove 24 . in order to avoid direct contact between the end surfaces of the frame segments 4 . 2 and 4 . 3 , which may result in “ creaking ” or “ squeaking ” noises during the driving operation of the vehicle , the end surfaces are spaced apart from one another in the connection ( as shown in fig5 ) by the insertion of a shaped part 26 consisting of a different material . the shaped part 26 is provided with recesses 27 , 28 in the region of the coupling elements 17 , so that it does not interrupt the connection . furthermore , latching lugs 22 . 1 may be integrally formed on the shaped part 26 on both sides and engage in corresponding latching openings 23 . 1 in the frame segments 4 . 2 and 4 . 3 . alternatively , a separate shaped piece 29 can be constructed having two latching lugs 22 . 2 , which can be inserted into the latching openings 23 . 2 , and penetrating the shaped part 26 in the region of a further recess 30 . fig6 illustrates an example of an angled connection between the frame segments 4 . 1 and 4 . 2 in the final position which is suitable , for example , to carry out the installation method described in relation to fig3 . in the installation position , the lateral frame segment 4 . 2 is placed at an angle shown as exceeding 90 ° with the latching openings 23 onto the latching lugs 22 , which are integrally formed on the frame segment 4 . 1 , and is subsequently pivoted into the position illustrated , to enclose the filling panel 2 . the latching lugs 22 are intended to secure the final position of the frame segments 4 in conjunction with an undercut 31 in the frame segment 4 . 2 , into which the frame segment 4 . 1 pivots . fig7 shows the possible formation of a filling panel 2 between the segments 10 . 1 and 10 . 2 . the filling panel is provided in the abutting region with a z - shaped transition 32 . the abutting surfaces 33 , which face the vehicle body and run orthogonally with the filling panel 2 , can be connected to each other via adhesive tapes 34 . alternatively , the connection can also be undertaken , for example , by a touch - and - close fastener , or the like . in the embodiment shown according to fig8 , the segments 10 . 1 and 10 . 2 are shown embedded in a form - fitting manner in a transverse strut 12 of the frame 2 , the strut having additional functionalities in the form of a lamp 35 or a ventilation opening 36 . fig9 illustrates an embodiment of a connection between the filling panel 2 and a frame segment 4 , in which the filling panel 2 can be pushed into a groove 24 of the frame segment 4 . below the groove 24 , lamps 35 are shown embedded in the frame segment 4 which is also shown to include a ventilation duct 37 that communicates with the vehicle interior via ventilation openings 36 . a projection 38 which is integrally formed on the frame segment 4 and protrudes into the interior of the vehicle covers the ventilation openings 36 in such a manner that they are no longer visible for the occupants . fig1 shows another embodiment of the connection between the filling panel 2 and frame segment 4 . the frame 2 is shown to comprise two u - shaped frame segments 4 . 6 and 4 . 7 which are fitted to each other by their limbs to form a rectangular frame 2 . the frame segments 4 . 6 , 4 . 7 are provided with an upwardly protruding , essentially encircling web 39 . the latter has a plurality of latching lugs 22 into which the filling panel 2 may be latched from above . fig1 illustrates connecting elements for installing the paneling element 1 in the vehicle body . in the illustrated embodiment , the filling panel 2 completely covers the frame 3 , which is shown with an s - shaped cross section . the fastening between the paneling element 1 and the support 40 of the vehicle body takes place via dowels 41 which are first placed into the filling panel 2 or are integrally formed thereon and are then pushed into holes 42 of the support 40 . insertion of a screw 43 causes the dowel 41 to be expanded on the end side and to be anchored in the vehicle body . undoing the screw 43 enables the paneling element 1 to be detached again from the vehicle . the order or sequence of any process or method steps may be varied or re - sequenced according to alternative embodiments . in the claims , any means - plus - function clause is intended to cover the structures described herein as performing the recited function and not only structural equivalents but also equivalent structures . other substitutions , modifications , changes and omissions may be made in the design , operating configuration and arrangement of the preferred and other exemplary embodiments without departing from the spirit of the present inventions as expressed in the appended claims . | 1 |
the actuator 1 according to the invention and schematically illustrated on fig1 is an electrical actuator , i . e . an actuator using an electric power for operating . such an actuator 1 is adapted for actuating ( that is moving ) a mechanical member , in particular a control surface of an aircraft , including of a transport airplane . according to the invention , such an actuator 1 is improved so as to be protected from being damaged as a result of an overheating . an electronic control module 2 receiving a control electric signal ( to be set forth below ) via a link 3 and converting this control electric signal into a ( speed ) set - point value i 0 for an electric motor 4 ; said electric motor 4 driving a hydraulic pump 5 , according to the speed set - point value i 0 received from said control module 2 ; said pump 5 being associated to this hydraulic block 6 further comprising an accumulator 7 and generating a hydraulic power according to the driving achieved by said electric motor 4 . this hydraulic power allows to move a hydraulic jack 8 ; and said hydraulic jack 8 comprising two chambers 9 and 10 able to be supplied by said pump 5 and separated by a piston 12 connected to a stem 13 . said hydraulic jack 8 is usually moved as a function of the difference of pressure existing in these two chambers 9 and 10 . moving said hydraulic jack 8 generates the effort produced by the actuator 1 on the mechanical member it operates , in particular , a control surface of an aircraft . said actuator 1 further comprises one or more current pressure relief valves 11 allowing the effort it generates to be limited . each pressure relief valve 11 is associated with an opening pressure representing a difference of pressure between the chambers 9 and 10 , for which the pressure relief valve 11 is automatically opened so as to implement its protection function . indeed , usually , a pressure relief valve is formed so as to automatically open under the effect of a predetermined pressure of fluids , to then evacuate a fluid flow rate so as to limit the pressure in the chambers and to close when normal service conditions have been restored . said actuator 1 being an electrical actuator could correspond to an electro - hydrostatic actuator of the eha (& lt ;& lt ; electro - hydrostatic actuator & gt ;& gt ;) type . it could then be an electrical backup hydraulic actuator of the ebha (& lt ;& lt ; electrical backup hydraulic actuator & gt ;& gt ;) type , when it operates in the electric mode . such an ebha actuator is a hybrid actuator comprising the characteristics both of a usual hydraulic servo - control and of an electro - hydrostatic actuator of the eha type . in a nominal situation ( failure free ), the ebha actuator operates as a usual servo - control . on the other hand , in the case of a failure affecting the hydraulic mode , this ebha actuator switches to an electric mode and operates as an eha actuator . although not exclusively , said actuator 1 can be used more particularly for actuating a control surface of an aircraft , including of a transport airplane , for instance a depth control surface , a direction control surface or a lateral control surface of an airplane . in such an application , said actuator 1 could be part of a control system 17 of a control surface further comprising , as shown on fig2 : a control means 14 allowing to generate the control electric signal being transmitted via the link 3 to the control module 2 of the actuator 1 . such a control means 14 could comprise usual manual means , for instance a handle or a control member , allowing an operator , in particular the pilot of the aircraft , to generate a control signal with a view to moving a control surface 15 . such a control means 14 could further comprise usual automatic means allowing to automatically generate , in particular , from measured values , a control electric signal ; and said control surface 15 , for instance a lateral , depth or direction control surface being moved by said actuator 1 ( or by a plurality of actuators 1 ), as illustrated by a link 16 in dash - dots on fig2 . according to the invention , for protecting such an actuator 1 from being damaged as a result of an overheating , the latter further comprises , as shown on fig3 : means 18 for implementing a monitoring so as to be able to detect an opening of said pressure relief valve 11 ; means 19 for calculating , upon the detection of an opening of a pressure relief valve 11 , an auxiliary set - point value iaux allowing , when being applied to the electric motor 4 , to limit the speed of the latter to a predetermined maximum speed ; and means 20 for applying ( via a link 21 ) to said electric motor 4 said auxiliary set - point value iaux ( received from means 19 via a link 22 ), instead of said set - point value i 0 , upon the detection of an opening of a pressure relief valve 11 . consequently , for being protected from being damaged as a result of an overheat , the electrical actuator 1 is provided with means 19 intended for calculating an auxiliary set - point value iaux that will be applied to the electric motor 4 , upon the detection ( by means 18 ) of an opening of said pressure relief valve 11 . this auxiliary set - point value laux is applied to the electric motor 4 so that it limits its speed and , hence , the action thereof upon the hydraulic pump 5 . its speed is then limited to said predetermined maximum speed , being lower than the tolerated maximum speed of the motor 4 . this predetermined maximum speed is defined so as to prevent an overheating of the actuator 1 able to damage it when it is applied to the motor 4 . this maximum speed is determined usually , in particular , by means of tests . a usual sensor 23 for measuring the current motor speed of the electric motor 4 ; a usual sensor 24 for measuring the current moving speed of the stem 13 of the hydraulic jack 8 ; and a processing unit 31 being connected by a link 32 to the means 19 and comprising , as shown on fig4 : an element 25 for calculating an estimated motor speed , from the current speed of said stem 13 being measured and received via a link 26 from the sensor 24 . the estimated motor speed represents the speed of the motor 4 allowing to generate said measured current speed for the stem 13 of the hydraulic jack 8 ; an element 27 for calculating the difference between said estimated motor speed ( received via a link 28 from the element 25 ) and said measured current motor speed ( received via a link 29 from the sensor 23 ); and an element 30 for comparing said difference to a predetermined maximum value , and for detecting an opening of a pressure relief valve 11 , for which the means 20 should apply said auxiliary set - point value to said electric motor 4 , when such difference is higher than said predetermined maximum value . indeed , when the pressure relief valve 11 is opened , a part of the flow generated by the pump 5 ( under the control of the motor 4 ) circulates thru the pressure relief valve 11 , instead of supplying one chamber of the hydraulic jack 8 . as this part of the flow could be significant , the speed of the stem 13 of the hydraulic jack 8 is no longer proportional to the speed of the motor 4 . preferably , said processing unit 31 further comprises an element 38 for filtering said difference ( received by a link 39 ) between the estimated motor speed and the current motor speed , before transmitting it to said element 30 ( via a link 40 ), so as not to take dynamic modifications of high frequencies into account . in a preferred embodiment , said element 25 comprises ( integrated ) means for calculating said estimated motor speed vest , by means of the following expression : s represents the surface of the cross - section of the piston 12 of the hydraulic jack ; vram is the current speed measured by the sensor 24 of the stem 13 of the hydraulic jack 8 : vram = dy / dt , y representing a move of the stem 13 ; and cyl represents the capacity of the pump 5 ( that is the volume of the fluid being moved when the pump 5 achieves one revolution ). means 34 for determining whether the control electric signal received via the link 3 has the effect ( if is applied as such to the actuator 1 ) to generate an increasing difference of pressure ( that is a difference of pressure increasing between the chambers 9 and 10 ) or a decreasing difference of pressure ( that is a difference of pressure dropping between the chambers 9 and 10 ) in the hydraulic jack 8 ; and means 35 being connected via a link 36 to said means 34 and being formed so as to inhibit the application , if appropriate , of said auxiliary set - point value iaux to said electric motor 4 , when said control electric signal being received has the effect of generating a decreasing difference of pressure in absolute value , that is a difference of pressure tending to decrease . to this end , said means 35 could act via a link 37 on said means 20 so that the latter transmit , via the link 21 , the control order ( that is said set - point value i 0 ) received via a link 42 , in case of an inhibition . in a preferred embodiment , said means 19 , 20 , 31 and 35 are part of a unit 33 being integrated into the electronic control module 2 . it allows to guarantee the stop load of the actuator 1 , specified by the flight qualities ; it allows for the opening of a pressure relief valve 11 , controlling the speed of the motor 4 of the actuator 1 so as to limit the overheat of the equipment ; and it does not use the measurement by a sensor of a difference of pressure between the chambers 9 and 10 of the actuator 1 , which could lack in accuracy , except for knowing the sign of this difference of pressure so as to be able to inhibit the protection function when the difference of pressure is decreasing . | 1 |
while the present invention is open to various modifications and alternative constructions , the preferred embodiments shown in the drawing will be described herein in detail . it is understood , however , that there is no intention to limit the invention to the particular forms disclosed . on the contrary , the intention is to cover all modifications , equivalent structures and methods , and alternative constructions falling within the spirit and scope of the invention as expressed in the appended claims . the simplicity and relative inexpensiveness of the inventive modular equipment enclosure system may be seen by reference to fig1 and 2 . there is shown a modular equipment enclosure system 10 of the present invention configures with two modules or segments . the enclosure system 10 includes two chambers 12 , 14 for electronic components situated side - by - side , and placed over two side - by - side battery compartments 16 , 18 . a pair of open front doors 20 , 22 are provided to help seal the chambers , and spanning the two chambers is a continuous roof cap or panel 24 . to each side of the chambers is a side panel 26 , 28 . also included are two rear doors 30 , 32 . an air conditioning system 34 for thermal management is attached to the rear door 30 . a pair of skids support each module , such as the first pair of skids 40 , 42 for the left side module and the second pair of skids 44 , 46 for the right side module . the various parts of the two segment modular enclosure system 10 are shown in more detail in fig3 and 4 . the skeleton of a segment or module is a frame unit 50 having a top portion or wall 52 and a bottom portion or wall 54 . between the top wall and the bottom wall are four vertical comer posts , two front comer posts 56 , 58 and two rear comer posts 60 , 62 . ( rear comer post 60 is shown in fig8 .) the comer posts form the front , rear and side portions of the frame unit . the top wall 52 and bottom wall 54 are secured to the four vertical comer posts such as by welding . the frame unit has a front opening 70 and a rear opening 72 . there are also a left side opening 74 and a right side opening 76 . the comer posts and top and bottom walls frame the front , rear and side openings , and the frame unit establishes the chamber for housing electronic equipment . to protect the equipment each of the openings are sealed against the environment and against tampering . the doors cover the front and rear openings and the side panels cover the side openings unless multiple frame units are aligned and attached to one another . in that case the adjoining side openings allow communication between chambers . the seal around each side opening abuts each other to close off the side openings as will be explained below . a second frame unit 78 is also shown and includes a top wall 80 , a bottom wall 82 and four vertical comer posts 84 , 86 , 88 and 90 . ( the comer post 90 is shown in fig7 .) the second frame unit 78 also includes a front opening 92 , a rear opening 94 , a left side opening 96 and a right side opening 98 . to facilitate attachment of the two frame units 50 , 78 ( and any additional frame units that may be needed ), there is a front bridge panel 100 , a rear bridge panel 102 and a top structural panel 104 . the front and rear bridge panels are dimensioned to align flush with the doors so as to enhance the appearance of the completed enclosure . for every additional frame unit , additional front and rear bridge panels and a structural panel are needed . each frame unit includes a plurality of horizontally disposed brackets extending from the two front comer posts of each frame unit to the two rear comer posts , such as the bracket 110 of the frame unit 50 and the bracket 112 of the frame unit 78 . a major advantage of the present invention is that the size of the frame unit allows for easy handling , transport and installation when compared to large size integral enclosures which are heavy and bulky . the large size enclosures typically require the services of a crane for installation thereby resulting in substantial costs . the modular enclosure system of the present invention obviates the need for a crane because of the smaller , much more manageable size modules or segments beginning with a frame unit . a segment , even when loaded with electronic equipment , can be passed through a standard thirty - six inch door , moved down a hallway and carried up stairs for rooftop installations . another important advantage is that the enclosure system 10 may be easily expanded when the need arises because the expansion , in the form of additional frame units and related elements , may be assembled on site quickly and economically . further , panel parts may be added or exchanged easily . all of this may be accomplished without disconnection of the electronic equipment housed within the enclosure system . because of the structure of the present invention , the enclosure may be assembled , disassembled and reassembled . to achieve a completely constructed enclosure system , it is essential that the electronic equipment chamber be sealed environmentally against seventy mph wind driven rain , salt fog , humidity , bugs and the like . this sealing must exist between frame units , between a frame unit and a set of doors and between a frame unit and a set of side panels . a major feature of the present invention is that each frame unit includes two sets of factory installed seals , and that these seals may act as primary or secondary seals as will be explained below . it is to be noted that caulking and liquid sealant are not required for assembly or for later expansion . the enclosure system can also be taken apart and reassembled and still maintain seal integrity . referring now to fig5 - 8 , there is illustrated a first type of seal 120 disposed along the front comer post 58 , but extending around the front opening 70 of the first frame unit 50 . the seal 120 , sometimes referred to as a “ push - on bulb seal ” is an elongated extrusion having an outer tubular portion 122 and a mounting portion of two parallel arms 124 , 125 . around the front opening 70 is a flange 126 . similar flanges 127 , 129 , 131 are formed around all of the openings as are shown and identified . the seal 120 is compression fitted or mounted to the flange in a manner well known to those skilled in the art . the first type of seal functions by having either another seal or a panel compress the tubular portion 122 so as to close off the region beyond the seal to moisture , dust and the like . an identical seal 130 surrounds the rear opening 72 . further , identical seals 132 , 134 surround the left side and right side openings 74 , 76 respectively . additional identical seals 136 , 138 and 140 surround the front , rear and left side openings 92 , 94 , 96 , respectively , of the frame unit 78 . another identical seal surrounds the right side opening 98 of the frame unit 98 but is not shown in fig7 . a second type of seal or gasket 146 is mounted vertically along the side of the front comer post 58 . the second type of seal has a generally rectangular cross section with an adhesive on one surface 145 and ribs 147 on the opposite surface . the adhesive allows the seal to be pressure sensitive and thereby applied to the frame units with ease . identical seals 148 , 150 , 152 are applied in the same manner to the comer posts 56 , 60 , 62 , respectively . identical seals 146 a , 152 a are applied to the comer posts 58 a , 62 a , respectively . identical seals 154 , 156 are also applied to comer posts 84 , 90 of the frame unit 78 . further identical seals are mounted horizontally about the side openings 74 , 98 . of course , the first and second type seals are applied identically to all corresponding features of the frame unit 78 . the designation “ a ” is used on the right side of fig8 because a modified embodiment is illustrated . instead of the frame unit 50 being connected to the frame unit 78 as is shown in fig1 , 7 , 9 , 10 , the right side opening 76 is closed by a side panel 26 a as it would be if only one module was being used . as can now be appreciated , the side panel 26 a can be easily removed and a second frame unit may be connected . the first type seals 120 , 136 and the second type seals 146 , 154 are primary seals while the first type seals 134 , 140 are secondary seals . in a like manner , the seals 120 , 130 , 148 , 150 are primary seals and the seal 132 is a secondary seal . the seals are available from vendors and may be acquired from schlegel corp . of rochester , new york . the front bridge panel 100 and the rear bridge panel 102 connect the two frame units 50 , 78 together in a manner that also compresses the two seals 134 , 140 . each of the bridge panels are connected to their respective vertical comer posts by fasteners , such as the two fasteners 160 , 162 near the front of the enclosure system and the two fasteners 164 , 166 near the rear of the enclosure system . as can be seen , a front wall 168 of the front bridge panel 100 and a front wall 170 of the rear bridge panel 102 align flush with the outer surfaces 172 , 173 of the front doors 20 , 22 , respectively , and the outer surfaces 176 , 178 of the rear doors 30 , 32 , respectively . the flush aligned look of the enclosure system enhances its aesthetic appeal . as shown in fig7 and also in fig9 and 10 when two cage frames are joined together , the seals make abutting contact such that the adjoining left and right side openings , such as the openings 76 , 96 , are entirely sealed or closed off . the front and rear seals 120 , 130 are engaged by the doors 20 , 32 , respectively , and these compress the seals when the doors are closed . in the case of the side seals 132 , 134 and the seals 146 , 146 a , 148 , 150 , 152 , 152 a , they are compressed by side panels 26 a , 28 as shown in fig8 the front and back bridge panels 100 , 102 and by the side seal 140 as shown in fig7 . using industry standard torque requirements , fasteners , such as the fasteners 200 , 202 may be used to attach the frame units 50 , 78 to the battery compartments 16 , 18 , respectively . referring back to fig1 , there is illustrated the upper portion of the attached frame units 50 , 78 and the two seals 134 , 140 , the seal 134 being part of the frame unit 50 and the seal 140 being part of the frame unit 78 . when the frame units are connected , the two seals compress one another . the top bridge panel 104 is arranged to cover the upper portions of the seals 134 , 140 and is attached to the two frame units 50 , 78 by fasteners 206 , 208 . the fasteners 200 , 202 , 206 , 208 may be sealed head insert types available from vendors , such as avk industrial products , a division of avi bank mfg . inc . of valencia , california . the advantage of the seals described here is that there is no need to apply caulking or liquid sealant to the frame units , to the panels or to the doors to ensure sealing worthiness and integrity . the seals disclosed here make installation , expansion and part replacement easy and quick as well as consistent . the chance of inconsistent sealing is much less with factory installed seals when compared to the field application of caulking or sealant . also , assembly is quick and easy using industry standard tools and torques . forming the various elements of the system uses standard metal forming tools and processes and assembly is well known by those skilled in the art . another important feature of the present invention is that the various parts are designed to limit the compression forces on the seals so as not to permanently distort them . because of this feature , the enclosure may be assembled , disassembled , expanded and reassembled numerous times . for example , to accommodate the rectangular seals 146 , 152 , 154 , 156 , which are about one - quarter inch thick , the front and rear bridge panels 100 , 102 are set back about one - eighth of an inch as shown in fig7 so that when attached , the seal will only be compressed about half of its thickness , well within its elastic limit . in a like manner , the dimensions of the bulb seals , the bridge panels and the flanges are designed to safely compress the bulb seals without permanent distortion and without seal failure . because the seals are protected , another important feature of the present invention is derived . the enclosures disclosed above are sealant and caulking free because the first and second types of seals are effective even after long term use or use after the seals have been compressed , released and compressed again . caulking and sealants may seal but they are not “ reuseable ”. if such a seal is broken because of disassembly , it is no longer effective . the battery compartments 16 , 18 are formed by housings 201 , 203 and include enclosed shelves 209 , 210 . front and back covers 212 , 214 , 216 and 218 , fig3 complete formation of the compartments . to prevent tampering , the covers cannot be removed unless the doors are opened . the shelves may be about 34 . 25 inches long , 34 . 13 inches wide and 14 . 29 inches high . the battery chamber may be about 33 . 75 inches by 31 . 5 inches by 13 . 75 inches . each frame unit is about 34 . 25 inches long , 34 . 13 inches wide and 57 . 75 inches high . the doors are each about 31 inches wide and 57 . 75 inches high . the wall thickness for most of the panels , the doors and the frame units is about 0 . 125 inches . mounted on the side panel 28 is a load center 220 , fig2 and mounted to the side panel 26 is an rf ground plate 222 , fig1 . also mounted on the side panel 26 is a cover plate 224 to close an opening for rf cables . if desired , a surge suppressor 226 may be mounted to the side panel 28 above the load center 220 . inside the frame unit is a consolidated receptacle box 228 , fig3 to power all 120 / 240 volt ac equipment mounted in the frame unit 50 and in all adjoining frame units . this feature allows easy field assembly and disassembly of the system thereby eliminating costs connected with adding conduit , wire and circuits . yet another feature may be seen by reference to fig3 . the roof cap 24 may be formed with rain gutters 230 , 232 in the form of “ j ” shaped elements . similar elements may be formed on the opposite side . the rain gutters direct rain water away from the front and rear openings of the frame units . the various parts of the enclosure are best seen in fig3 . the manufacture of these parts is relatively inexpensive because every frame unit , door , side panel , battery compartment housing and battery compartment cover are identical to every other part of the same description . an enclosure system may include one frame unit or a multiple number of frame units . each frame unit is designed to be handled by a single person using a standard two wheel , hand operated dolly . electronic equipment may also be installed in each frame unit of a multi - segment enclosure system at the factory . the equipment will be connected to community power at the site . if more than one frame unit is used to construct a particular enclosure system , each of the frame units may be limited in the amount of weight that it carries so as to assist in the ease of handling and installation . further , other modular pieces , such as thermal management systems may be easily bolted on to the enclosure system and may be moved or upgraded to accommodate system growth . as a subassembly , the door with the thermal management system can be removed by simply lifting the door off its hinges without the use of any tools . all modular systems now existing require the application of caulking of sealant which is time consuming and expensive as well as problem prone because such caulking or sealant is never completely uniform . also , caulking and sealants are one time seals . the present enclosure system eliminates caulking and sealant and requires nothing more than standard tools and torques both , for initial assembly or for expansion . the modular system of the present invention allows easy field assembly and disassembly thereby eliminating much of the costs usually affiliated with installation and the addition of conduit , wire and circuits . the doors are interchangeable and may be either left hand or right hand opening simply by manipulating the door one hundred eighty degrees before assembly . the specification describes in detail an embodiment of the present invention . other modifications and variations will , under the doctrine of equivalents , come within the scope of the appended claims . for example , different dimensions , opening geometries and sealing designs are considered equivalent structures . using one module or more than two modules are equivalent systems . thermal management devices may include air conditioning systems , heat exchangers or fans or any combination of these . further , the thermal management device may be attached to the doors or the side panels , or mounted above a frame unit or beneath . still other alternatives will also be equivalent as will many new technologies . there is no desire or intention here to limit in any way the application the doctrine of equivalents . | 7 |
graded index ( grin ) lenses are commonly used to couple light from one optical fiber to another through an optical element . lenses of this type are produced under the trade name &# 34 ; selfoc &# 34 ;; the mark is registered in japan and owned by the nippon sheet and glass co . ltd . when light propagating within an optical fiber is to be passed through a discrete optical element coupled to the optical fiber , the light must exit an end face of the fiber , be collimated , and the collimated beam must be directed towards the discrete optical element . in many instances , a grin lens capable of collimating diverging light rays exiting an optical fiber is disposed between the optical fiber and a discrete optical element . in such an instance where light is to pass from one optical fiber to another through an optical element , a pair of matched quarter pitch grin lenses can be placed within a gap between the two optical fiber end faces . thus , in operation light exits a first optical fiber , is collimated by a first quarter pitch grin lens , passes through a discrete optical element disposed between the pair of matched quarter pitched grin lenses , and is focused by the second quarter pitch grin lens of the pair into an end of a second optical fiber . since grin lenses are commonly available to meet a variety of specifications at a relatively low cost , and since these lenses are relatively compact , their use has become nearly ubiquitous in the field of opto - electronics . referring now to prior art fig1 first and second one quarter pitch grin lenses 12a and 12b are shown ; an outer end face of the first lens 12a ( on the left ) has input and output ports coupled to optical fibers ; an outer end face of the second lens 12b ( on the right ) has a single input port coupled to an optical fiber . focused light entering an end face of a 0 . 25 pitch grin lens 12a propagates through it and becomes collimated at an opposite end face of the lens . in this figure , an optical coupling is shown that includes a tap 16 disposed between the pair of matched quarter pitch grin lenses 12a and 12b . although in fig1 a 0 . 25 pitch grin lens is utilized , for a greater understanding of selfoc ® lenses the following explanation is provided . a one pitch lens describes the length of a grin lens required for light of a particular wavelength to execute one cycle or one sine wave . for example if an object is placed on one end face of the lens , an erect one - to - one magnification image is formed on the other end face of the lens . further , pitch p is directly proportional to the lens length ( z ) as shown in the equation below : ## equ1 ## where a ( λ ) is the index gradient constant , a coefficient that shapes the parabolic function or gradient profile of the lens . since the pitch of a lens is proportional to the length and its length is proportional to a predetermined wavelength of light that will be propagating though the lens , a quarter pitch collimating lens having predetermined length ( z ), collimates light of a predetermined wavelength . stated differently , for light to be collimated by a particular 0 . 25 pitch grin lens , its length ( z ) must be matched ( see equation ( 1 ) above ,) to the wavelength of the light it is capable of collimating . in operation , the arrangement of optical elements , serves to tap a predetermined portion of the input light into a single optical fiber and to pass a remaining portion of the input light . a beam of light is launched into an input port 14a of the first lens 12a and a portion is reflected back by the filter 16 to the output port on the same end face of the first lens 12a . the remaining portion of the input beam propagates through the filter 16 and is transmitted through second grin lens 12b ( on the right ), propagates and is focused at the output port 14c of the second grin lens 12b . although this device in some instances provides its intended function of providing a tap , it becomes increasingly limited in its application if other optical elements are included in the circuit . for example in fig3 an optical device is shown having the same elements of fig1 including an isolator 32 disposed between the splitter filter 16 and the second output grin lens 12b . one of the limitations of this device is that the tapped signal is extracted prior to the input optical signal propagating through the optical isolator 32 and thus does not provide accurate information relating to the output signal after having passed through the isolator . it would therefore be preferable to provide a tap at the output end of the device rather than at the input end . attempting to utilize a splitter filter 16 between the isolator 32 and the output lens 12b is not practicable . in such an embodiment , a considerable amount of space is required between the output lens and the isolator 32 to extract a tap signal from the device substantially increasing the overall length of the device . referring now to fig2 a grating is shown in the form of a holographic beam sampler ( hbs ) 25 for splitting a single beam optical input signal into two beams propagating in forward divergent directions . hbss are commercially available devices manufactured by gentec electrooptics of ste . foy quebec . the hbs is a diffraction grating that is capable of producing three useful pairs of transmitted orders symmetrically disposed with respect to a main beam ; wherein second and third order samples are respectively the square and the cube of the first order . an embodiment of a device in accordance with this invention used as a basic building block to achieve several other embodiments described hereafter , is shown in fig4 . a pair of grin lenses 12a and 12b are shown having their collimating ends back to back . disposed between the grin lenses 12a and 12b is a hbs positioned to receive light from the lens 12a and to transmit light to grin lens 12b in a first tapping mode of operation . light launched into port 14a at the focusing end of grin lens 12a is collimated by lens 12a and propagates into the hbs 25 where it is split in a predetermined ratio dependent upon the desired characteristics of the hbs 25 into two beams , a first of which propagates in its original forward direction with no change in angle , and a second of which propagates at an angle to the first beam in a forward direction . due to the properties of the grin lens , light along the optical axis is focused at a point on the axis at port 14b at an end face of lens 12b . the second beam off - angle from the optical axis of lens 12b is focused at port 14c offset from the optical axis . thus an input beam at 14a is directed to the ports 14b and 14c at lens 12b in a predetermined ratio providing a tap beam and a main beam . in a second coupling mode of operation , light that is launched into the two ports 14b and 14c enters the hbs 25 at two different angles and is combined into a single beam focused at port 14a . essentially , the tapping device described heretofore with reference to fig4 may be used in a backwards direction as a coupler . referring now to fig4 a , an embodiment similar to that of fig4 is shown , however , having 4 ports . in this embodiment a wdm filter 24a designed to pass light of wavelength λ1 and to reflect light of wavelength λ2 is disposed between the input grin lens 12a and the hbs 25 . thus when light comprising wavelengths λ1 and λ2 is launched into port 14a , light of wavelength λ2 is reflected back to port 14d while light of wavelength λ1 is passed to the hbs 25 . similarly , as with the previous embodiment , light irrespective of wavelength launched into the hbs 25 is split into two beams directed at different forward locations and as a consequence of being launched into the grin lens 12b , the two beams are ported to different ports 14b and 14c at the output of lens 12b . fig4 b is again similar to that of fig4 however , advantageously provides a means of tapping an isolated signal at the output end of the device . in fig4 b an optical isolator 24b is disposed between the input grin lens 12a and the hbs 25 . turning now to fig5 an embodiment of the invention is shown wherein two back to back input / output grin lenses 12a and 12b are disposed along a common optical axis and have a wavelength division multiplex / demultiplexing ( wdm ) filter 56 therebetween ; adjacent the focusing lens 12b is an isolator 32 optically coupled to and in - series with the collimating grin lens 12a . a hbs 25 is disposed between back to back input / output lenses 12a and 12b which are in series with the isolator 32 . advantageously , this arrangement of optical components allows light to be tapped from the output port after it has passed through the optical isolator 32 . in operation light comprising wavelengths λ1 and λ2 is launched into input port 14a ; the wdm filter 56 is designed to pass light of wavelength λ1 and reflect light of wavelength λ2 to port 14d . thus wavelength m is passed through the lens 12b the isolator 32 and the hbs 25 where conveniently the light is split into two beams in a predetermined ratio wherein 90 % of the light is routed to port 14b and 10 % of the light is routed to port 14c . a similar embodiment to fig5 is shown in fig6 however the beam passing through elements 56 , 32 , and 25 is collimated rather than being refocused prior to being launched into the isolator 32 . turning now to fig7 an amplifying circuit is shown having an amplifier 73 backwards pumped by a pump beam launched into port 14d of lens 12a . the pump beam of wavelength λ2 is reflected backwards by wdm 56 into port 14a and into an erbium doped amplifier edfa 73 . a signal of wavelength λ1 launched into the edfa 73 in a forward direction is amplified and passes through the wdm filter 56 , isolator 32 , hbs 25 and is focused at the two ports 14b and 14c . the invention in accordance with this embodiment amplifies , isolates and passes the amplified isolated signal to a main output port and a tap port 14b and 14c respectively . of course numerous other embodiments of this invention may be envisaged , without departing from the spirit and scope of this invention . | 6 |
an overall laminar panel assembly 2 embodying the present invention is depicted in plan view in fig1 the panel assembly consisting of upper and lower cover layers 4 and 6 and being especially suitable for use with a communications satellite and for contact with solar panels . the upper and lower cover layers 4 , 6 , probably best seen in fig3 are made of carbon fiber synthetic material , having crossing fiber directions . the panel assembly also includes a support core structure 8 which is in the form of an aluminum honeycomb core of low volumnmetric weight , for example 16 kg / m 3 , glued between cover layers 4 , 6 . at the outer edge of the panel 2 , the cover layers 4 , 6 are reinforced at the inner faces thereof which are turned inwardly toward each other by longitudinal straps having fiber direction orientation which is unidirectional in the longitudinal direction of the straps , as shown in fig1 in broken line form . the straps are provided with an edging 10 . as will be noted in the drawings , fiber direction is indicated in the various figures thereof by corresponding hatching or by arrows . the panel 2 includes four locations indicated at 12a , 12b , 12c and 12d spaced inwardly from the edges of the panel at which there are to be introduced into the panel 2 in a punctiform manner forces such as longitudinal forces , bending forces and particularly high transverse forces , which may be as high as 1700 n . these forces may be introduced with minimum losses during surface contact with solar cells . for this purpose , the panel assembly 2 is provided with force infeed elements 14 shown in fig2 - 4 which are glued into the panel assemblies 2 between the cover layers 4 and 6 at each of the force infeed points 12 . as shown most clearly in fig2 the force infeed element 14 consists of a central piece 16 of substantially square cross - sectional configuration , with each central piece 16 having four corner points from which a shear web 18 extends radially outwardly . the shear web 18 is bifurcated at branching points 20 into two web sections 22a and 22b which extend outwardly at an angle of about 45 ° relative to the longitudinal direction of the shear web 18 . all shear webs 18 including their web sections 22a and 22b are of generally identical design and configuration so that the outer web ends 24 of each of the web sections will lie at corner points of a regular octagon having the central piece 16 as its center . the force infeed element 14 is a unitary part which consists also of carbon fiber synthetic material but with a different arrangement in the various regions in accordance with localized loads . the central piece 16 comprises an inner fiber layer 26 . after bonding of the force infeed element 14 within the panel assembly 2 , a longitudinal bore 28 , as seen in fig4 is drilled through from the outside through the inner fiber layer 26 traversing also the cover layers 4 and 6 and extending perpendicularly to the surface extension thereof in order to receive in the bore 28 a force infeed bolt ( not shown ) or a titanium bushing pressed into the bore 28 . the inner fiber layer 26 has a fiber arrangement which is unidirectional in the axial direction of the central piece 16 or , respectively , the longitudinal bore 28 . it is surrounded by another fiber layer 30 in which the fibers extend in a circumferential direction of the central piece 16 ; that is , substantially in planes perpendicular to the fiber direction of the inner layer 26 , as is indicated by the arrows in fig2 and by the horizontal hatching shown in fig3 and 4 . the shear webs 18 , and 22a , 22b have a crossing fiber arrangement inclined at an angle of ± 45 ° to the longitudinal direction of the web . the web sections 22a , 22b each consist of a fiber ply 32a , 32b , with each ply converging at the branching point 20 and forming together the associated shear web 18 in such a manner that the web 18 will have a double wall thickness twice that of the web sections 22a , 22b and will then divide again at the associated corner point of the central piece 16 and then extend continuously , being bonded over a peripheral section of the central piece 16 , into the directly adjacent web 18 up to the outer end 24 of the web section 22a or , respectively , 22b starting therefrom , as is shown for the fiber ply 32a in the lower portion of fig2 . in order to reduce local longitudinal stresses in the cover layers 4 , 6 , circular reinforcement plates or so called doublers 33 , 34 are glued on to the top and bottom sides of the force infeed element 14 . the doublers 33 and 34 extend up to the branching points 20 as shown in broken line in fig2 and they are made from the same fiber composite material as the cover layers 4 , 6 so that they will also comprise a crossing fiber arrangement . the reinforcement plates 33 , 34 are inserted in corresponding recesses 36 , 38 formed in the force infeed element 14 . installation of the force infeed element 14 is effected in the manner explained in connection with fig3 simultaneously with production of the laminar panel 2 . first , the honeycomb core 8 is provided at the intended stage of installation of the element 14 with recesses 40 , 42 corresponding in size to the wall thickness of the doublers 33 , 34 and then the element 14 is placed on the honeycomb core 8 whereupon the core is slit at locations corresponding with the webs 18 , 22a , 22b and corresponding with the central piece 16 to form a slit 44 in the honeycomb core 8 . a portion of the core 8 corresponding to the central piece 16 is removed . element 14 is then inserted in the core 8 and any cells of the honeycomb core 8 which may have been pushed aside will be pressed against the side faces of the shear webs 18 , 22a , 22b and of the central body 16 . the doublers 33 , 34 are placed in the recesses 36 to 42 of the element 14 or of the core 8 , respectively . after application of the cover layers 4 , 6 the entire arrangement is bonded under the action of pressure and heat and a single operation to form an integral structure by providing the cover layers 4 and 6 as well as the doublers 33 and 34 at their inner faces toward the core 8 and element 14 , respectively , with a foil adhesive and by coating the force infeed element 14 at the side faces of the central piece 16 and of the webs 18 , 22a , 22b contiguous with the core 8 with a splicing adhesive which swells under the action of heat and firmly connects the contiguous cells of the honeycomb core 8 with the outer faces of element 14 as indicated in fig2 by the obliquely hatched areas at the interfaces between the core 8 and the element 14 . with the panel 2 thus formed , longitudinal bores 28 traversing the panel 2 in the region of the inner fiber layer 26 are drilled at the force infeed points 12a , 12b , 12c and 12d in the manner described above . the bores 28 are drilled substantially perpendicularly to the surface extension of the cover layers 4 , 6 and load infeed bushings ( not shown ) which may for instance be made of titanium are pressed into the bores 28 . the force infeed element in accordance with fig5 is essentially of the same fundamental construction as the embodiment depicted and described in fig1 - 4 and the corresponding parts in fig5 are identified by similar reference numerals increased by a factor of 100 . the element 114 shown in fig5 is , however , installed at the outer edge of a laminar panel assembly for punctiform introduction of forces and accordingly it is designed in a partially symmetrical arrangement , the sheer webs 118 , 122a , 122b extending over a planar sector defined by the outer edge of the laminar member . the central piece 116 is secured without interposition of a doubler directly between the reinforced longitudinal straps , shown in broken line form , of the upper and lower cover layers of the laminar panel while the upper and lower doublers also shown in broken lines , cover the inner web sections 118 outside of the central piece 116 up to the branching points 120 . the webs 118 will again have double the wall thickness of the webs 122 with fiber plies extending also in this embodiment continuously over the associated web 118 and a circumferential region of the central piece 116 into the adjacent shear web 118 . from the branching point 120 thereof they extend up to the outer web end 124 of the respective web sections 122a , 122b , as is shown for the fiber ply 132a embracing the central piece 116 on three sides thereof . the half - symmetrical web arrangement is achieved in that the web sections 122a starting from the webs 118 extending in a longitudinal direction of the straps at the branching points 120 continue in the longitudinal direction of the webs 118 and are not inclined at an angle of 45 ° to the longitudinal direction of the inner webs 118 , as was the case in the embodiment previously described . when arranged at a corner of the laminar panel , the web pattern is further modified in such a way that the webs 118 and 122a , 122b will be distributed only over a 90 ° sector . with regard to other considerations , the force infeed element 114 is produced and installed into the laminar panel assembly in the same manner as is the force infeed element 14 described with reference to fig1 - 4 . a force infeed element is shown in fig6 wherein the parts correspond to the parts described in connection with the first embodiment of fig1 - 4 , similar parts being identified with similar reference numerals increased by a factor of 200 . the force infeed element according to fig6 is again installed between the laminar cover layers and the honeycomb core in the manner described with reference to fig3 at a point away from the outer edge of the panel . this arrangement includes doublers shown in broken line but it comprises two central pieces 216a and 216b arranged juxtaposed each with a longitudinal bore 228a , 228b , respectively and connected together by a web 218 of double wall thickness . the web 218 again consists of two fiber plies each extending continuously over a portion of the outer circumference of the two central pieces 216a , 216b and the adjacent shear webs 222a , 222b . the web pattern according to fig6 essentially comprises a doubling of the web arrangement shown in fig5 with the exception that , as in the case of the embodiment first described with reference to fig1 - 4 , the webs 218 extend from the corner points of the central pieces 216a , 216b which are held spaced by a connecting web 218 . otherwise , the construction and installation of the force infeed 214 is essentially the same as that related to the embodiment described in connection with fig1 - 4 . while specific embodiments of the invention have been shown and described in detail to illustrate the application of the inventive principles , it will be understood that the invention may be embodied otherwise without departing from such principles . | 1 |
the following description of the preferred embodiment ( s ) is merely exemplary in nature and is in no way intended to limit the invention , its application , or uses . the present invention is a method of milling using a constant tool path algorithm ( or alternatively , “ milling algorithm ”) that can be used to produce holes in a consistent , repeatable process . further , the process can be used to parallel - process a plurality of milled holes simultaneously . as noted above , an algorithmic approach proves mildly successful , in that a desired shape is produced using a constant angular velocity and tool pitch . as also noted above , this process does not compensate for the spacing of exposure steps generated near the center of the hole . referring to fig1 , a constant angular velocity tool path ( tool path ) 100 includes an initial voltage at the outer contour ( v max ) 110 , a plurality of laser exposure steps 120 , and the spacing of tool pitch 130 . using this approach , a large number of exposure steps 120 are generated near the target center , which result in excessive ablation in this area . in the present example , approximately 10 , 000 laser exposure steps 120 are used to create the spiraling shape of tool path 100 . referring to fig2 , a simplified schematic of a laser drilling system 200 , includes a laser 205 , a beam 207 , a shutter 210 , an attenuator 215 , a beam expander 220 , a spinning half - wave plate 225 , a first mirror 208 , a second mirror 217 , a third mirror 221 , a fourth mirror 222 , a piezo electric transducer ( pzt ) scan mirror 230 , a diffractive optical element ( doe ) 235 , a plurality of sub - beams 237 , a scan lens 240 , a microfilter 245 , an image transfer lens 250 , and a workpiece 255 , arranged as shown . although the present invention uses a picosecond laser system , the present invention may be generalized for use with other laser systems , such as excimer , co 2 , and copper vapor laser systems . a brief description of the elements and operation of laser drilling system 200 is provided below . in alternate embodiments , changes in the elements of laser drilling system 200 may be required . the present invention is not limited to the current selection and arrangement of elements in laser drilling system 200 . in operation , picosecond laser 205 emits beam 207 along the optical path identified in fig2 . beam 207 propagates along the optical path , where it is incident upon first mirror 208 . first mirror 208 redirects beam 207 along the optical path , where it is incident upon shutter 210 . shutter 210 opens and closes to selectively illuminate the work piece material . beam 207 exits shutter 210 and propagates along the optical path to attenuator 215 . attenuator 215 filters the energy of picosecond laser 205 in order to precisely control ablation parameters beam 207 exits attenuator 215 and propagates along the optical path , where it is incident upon second mirror 217 . second mirror 217 redirects beam 207 along the optical path , where it is incident upon beam expander 220 . beam expander 220 increases the size of beam 207 to serve two purposes . first , it increases the beam size for the correct functioning of the doe 235 as beam splitter . for the doe 235 to function correctly , the beam size incident upon doe 235 needs to be big enough to cover several periods of doe 235 . second , it increases the beam size to match the scan lens pupil size . beam 207 exits beam expander 220 and propagates along the optical path , where it is incident upon third mirror 221 . third mirror 221 redirects beam 207 along the optical path , where it is incident upon fourth mirror 222 . fourth mirror 222 redirects beam 207 along the optical path , where it is incident upon spinning half - wave plate 225 . spinning half - wave plate 225 changes the polarization of beam 207 . upon exiting spinning half - wave plate 225 , beam 207 propagates along the optical path , where it is incident upon pzt scan mirror 230 . pzt scan mirror 230 moves in a pre - defined pattern using a milling algorithm ( not shown ) to drill the holes in workpiece 255 . pzt scan mirror 230 redirects beam 207 along the optical path , where it is incident upon doe 235 . doe 235 splits beam 207 into a plurality of sub - beams 237 , which allow parallel drilling of workpiece 255 . sub - beams 237 exit doe 235 and propagate along the optical path , where they are incident upon scan lens 240 . scan lens 240 determines the spot size of sub - beams 237 upon workpiece 255 . sub - beams 237 exit scan lens 240 and propagate along the optical path , where they are incident upon microfilter 245 . microfilter 245 equalizes the intensities of sub - beams 237 . sub - beams 237 exit microfilter 245 and propagate along the optical path , where they are incident upon image transfer lens 250 . image transfer lens 250 re - images the focal spots of sub - beams 237 onto workpiece 255 . sub - beams 237 ablate workpiece 255 in a pattern according to the pre - defined milling algorithm . referring to fig3 a , a constant arc speed tool path 300 a and includes an initial outer contour exposure voltage ( v max ) 310 , a plurality of exposure steps 320 having constant arc speed and spacing , and the spacing of tool pitch 330 . in operation , the desired tool path 300 a , in the present example , consists of many revolutions separated by a tool pitch 330 , which can be constant or variable depending on the desired final shape . utilizing this constant arc speed tool path provides a way to avoid manufacturing off - specification products and a way to produce repeatable results in milling . v max 310 determines the outer radius of the spiral in tool path 300 a . each revolution , as shown , has many discrete exposure steps 320 , which are specified by the software algorithm described in step 430 of method 400 below . in reference to fig2 and 3 , as laser 205 pulses at a fixed repetition rate , the uniform ablation is translated into a constant propagation speed of pzt scan mirror 230 to direct the laser strike point onto exposure steps 320 of workpiece 255 . the constant arc speed tool path depicted in fig3 a provides for a flat surface in workpiece 255 being ablated . maintaining this flat surface in workpiece 255 provides a laser drilling system tool path allowing for constant material removal . this constant arc speed tool path also provides a way to provide a laser drilling system tool path allowing for constant material removal . during the manufacturing process employing the present invention , milling is also performed outward as the second half of the milling process . when the laser milling reaches the end of the inward spiral at t = t , the laser strike point is directed moving in an outward spiral tool path 300 b as shown in fig3 b . after the laser strike point reaches the maximum radius for the next layer of milling at t = t ′, the next inward spiral begins . referring to fig4 , a method 400 of laser milling includes several steps . at step 410 , an operator or technician provides a control system ( not shown ), such as a computer , that is capable of running an algorithm via a software program . the control system is electronically connected to pzt scan mirror 230 to provide operational control signals for implementation of the algorithm . at step 420 , the operator or technician uses customer - specified information , such as cad files , and technical notes to determine the desired hole geometry , including taper angle , exit hole diameter , and entrance hole diameter . the operator or technician determines the voltage , v max 310 , by considering entrance hole diameter , laser spot size , and voltage response of pzt scan mirror 230 . the operator or technician also uses the spot size of laser 205 to determine the minimum allowable tool pitch 330 of tool path 300 a . for example , if the spot size is 10 microns , tool pitch 330 should be a maximum of 10 microns to prevent under - ablated ridges from forming along outer walls of the radial contours . a pitch size around two microns works well with the 10 - micron laser spot . a typical 40 - volt of bias on the pzt scan mirror 130 deflects beam 107 by about 45 microns on workpiece 255 . at step 430 , the operator or technician launches software code ( not shown ), which resides in the control system identified in step 410 above to calculate the radius and angular speed over the period of laser drilling , t , to manufacture the desired hole geometry . for example , the following formula , formula ( a ), describes the radius “ r ” along tool path 300 a at any given time “ t ” during the laser drilling : r ( t ) = r 0 2 - ( r 0 2 - r min 2 t ) t ( a ) similarly , the following formula , formula ( b ), describes the angular velocity “ ω ” along tool path 300 a at any given time “ t ” during the laser drilling to achieve constant arc speed : ω ( t ) = ω 0 r 0 r ( t ) ( b ) also , when the laser milling reaches the end of the inward spiral tool path 300 a at t = t , the laser strike point is directed moving in an outward spiral tool path 300 b determined by the following equations during t ≦ t ≦ t ′. formula ( c ), describes the radius “ r ” along tool path 300 a at any given time “ t ” during the laser drilling : r ′ ( t ) = 2 r min 2 - r 0 2 + ( r 0 2 - r min 2 t ) t ( c ) similarly , the following formula , formula ( d ), describes the angular velocity “ ω ” along tool path 300 b at any given time “ t ” during the laser drilling to achieve constant arc speed : ω ′ ( t ) = ω 0 r 0 r ′ ( t ) ( d ) these four formulas are used to formulate the tool paths for drilling conical shapes , which resides in algorithmic form in the software on the control system . this step provides guidelines to create tool path geometry . at step 440 , the control system transmits the results of the algorithm executed in step 430 to a tool path controller ( not shown ), such as a microprocessor , to initiate execution of the tool path and commence laser drilling . at step 450 , the controller identified in step 440 transmits voltages to pzt scan mirror 230 over time that correspond to the digital output of the algorithm executed in step 430 . the voltages are applied to pzt scan mirror 230 to translate its position in accordance with the calculated tool path and desired hole geometry in workpiece 255 . at step 460 , laser drilling system 200 mills workpiece 255 per the tool path algorithm , in a pattern illustrated in fig3 above . in the present invention , laser milling is performed using a layer - by - layer spiraling algorithm (“ tool path ”), thus , forming a tapered hole by decreasing v max 310 for successive spirals . as previously discussed , the present invention is not limited to the spiral shape ; in alternate embodiments , other tool path algorithms keeping uniform exposure for varied shapes can be used . also , v max can be decreased in various ways between successive layers to achieve a desired contour in a finished workpiece . the vertical cross section containing the axis of the hole determines how the v max ( i ) is progressed where i is the number of steps for reducing the v max . a linear function of v max ( i + 1 )= v max ( i )− δv max results in a constant taper with fixed taper angle . another function of v max ( i + 1 )= v max ( i ) −( δv max * i ) makes the taper angle less and less steep as radius is reduced . on the other hand , v max ( i + 1 )= v max ( i )−( δv max / i ) makes the taper angle progressively steeper . in general , the vmax ( i ) needs to be determined by the cross section ( or shape ) specification . at step 470 , the tool path algorithm identified in step 430 determines whether the desired hole geometry has been achieved . the hole geometry has been achieved when the tool path algorithm has completed the pre - calculated number of necessary spiral ablations . conventional measuring techniques such as use of confocal microscopy and optical profilometry can also be used to determine if the desired hole geometry has been reached . if yes , method 400 ends ; if no , method 400 returns to step 450 . a nozzle plate of an ink - jet head may be constructed with the laser drilling system of the present invention as further detailed below . as shown in fig5 , an ink - jet printer 500 has an ink - jet head 502 capable of recording on a recording medium 504 via a pressure generator . ink droplets emitted from the ink - jet head 502 are deposited on the recording medium 504 , such as a sheet of copy paper , so that recording can be performed on the recording medium 504 . the ink - jet head 502 is mounted on a carriage 506 capable of reciprocating movement along a carriage shaft 508 . more specifically , the ink - jet head 502 is structured such that it can reciprocate in a primary scanning direction x in parallel with the carriage shaft 508 . the recording medium 504 is timely conveyed by rollers 510 in a secondary scanning direction y . the ink - jet head 502 and the recording medium 504 are relatively moved by the rollers 510 . referring to fig6 , a pressure generator 600 is preferably a piezoelectric system , a thermal system , and / or equivalent system . in this embodiment , the pressure generator 600 corresponds to a piezoelectric system which comprises an upper electrode 602 , a piezoelectric element 604 , and an under electrode 606 . a nozzle plate 608 comprises a nozzle substrate 610 and a water repellent layer 612 . the nozzle substrate 610 is made of metal , resin , and / or equivalent material . the water repellant layer 612 is made , for example , of fluororesin or silicone resin . in this embodiment , the nozzle substrate 610 is made of stainless steel and has a thickness of 50 um , and the water repellent layer 612 is made of a fluororesin and has a thickness of 0 . 1 um . the ink - jet ink is filled in an ink supplying passage 614 , a pressure chamber 616 , an ink passage 618 , and a nozzle 620 . ink droplets are ejected from the nozzle 620 as the pressure generator 600 pushes the pressure chamber element 620 . as a result of the present invention , very good nozzles are formed without flash and foreign matter ( carbon etc ) in the nozzle plate . further , the accuracy of the nozzle outlet diameter is 20 um ± 1 . 5 um . the present invention has several advantages . a first advantage of the present invention is that it avoids manufacturing off - specification products with micromachining . a second advantage of the present invention is that it provides a way to produce consistent , repeatable results in milling . a third advantage of the present invention is that it provides a system and guidelines for creating tool path geometry . a fourth advantage of the present invention is that it maintains constant exposure of a laser source on a workpiece without active laser power control . a fifth advantage of the present invention is that it provides constant material removal . a sixth advantage of the present invention is that the spiraling milling effect provides a continuous , consistent , and seamless laser ablation of a workpiece . a seventh advantage of the present invention is that the spiraling milling provides a way to machine micro features with cylindrical symmetry using laser ablation . an eighth advantage of the present invention is that it provides uniform material removal with predictable ablation rate so that an arbitrary profile may be established . the present invention also has some disadvantages . one disadvantage of the present invention is that it is time intensive . however , any milling operation will require a similar amount of time to perform and thus is not a significant concern . a second disadvantage of the present invention is that it provides an increase in operational speed at the expense of control . however , the alternative closed loop system that provides additional control is too slow for cost effective mass manufacturing environment . another way to solve the same problem is to fire the laser at a faster rate when the hole radius is at the outer exposure steps . however , this approach requires additional process control that is difficult to synchronize and manage in the laser system . the description of the invention is merely exemplary in nature and , thus , variations that do not depart from the gist of the invention are intended to be within the scope of the invention . such variations are not to be regarded as a departure from the spirit and scope of the invention . | 1 |
in a first embodiment of the invention , a dispenser 100 is provided as illustrated in fig1 - 6 and 8 - 9 . dispenser 100 has a container 102 , a pivotable lid 104 , a handle 106 , and a dispensing mechanism 108 . container 102 has an open bottom 110 , which is covered by dispensing mechanism 108 . container 102 is intended to contain granular materials to be dispensed by dispenser 100 . granular materials include , for example , salt , pepper , sugar , other seasonings , grains , powders and colorants . dispensing mechanism 108 has a first member 112 , a second member 114 and a third member 116 . first member 112 is the member that is closest to container 102 . first , second and third members 112 , 114 and 116 have first , second and third member dispensing apertures 122 , 124 and 126 , selected ones of which are sometimes referred to as 122 c , m , 124 c , m and 126 c , m , respectively . second member 114 is rotatable about a pivot axis 128 relative to first and third members 112 and 116 . in practice , preferably , first and third members 112 and 116 rotate while second member 114 is stationary , but alternatively second member 114 could rotate while first and third members 112 and 116 are stationary or second member 114 could rotate in a direction opposite to first and third members 112 and 116 , for example . the first , second and third member dispensing apertures 122 , 124 and 126 typically have the same pattern of distribution in their respective members 112 , 114 and 116 so that the pattern of first member dispensing apertures 122 can be aligned with the pattern of second member dispensing apertures 124 and the pattern of third member dispensing apertures 126 can be aligned with the pattern of second member dispensing apertures 124 by rotation of the first and third members 112 and 116 relative to second member 114 around pivot axis 128 , respectively . the members are generally in the shape of flat circular discs , as shown and maintained in a stacked arrangement by a fastener 130 . fastener 130 is preferably removable to permit disassembly of dispensing mechanism 108 . preferably fastener 130 connects to a threaded pivot 132 . preferably , first and third members 112 and 116 are rotatable around pivot 132 and pivot axis 128 passes through fastener 130 and pivot 132 . threaded pivot 132 as shown is integral to member 112 , but it can be separate . pivot 132 also includes a key 134 . third member 116 has an opening 135 for pivot 132 . opening 135 includes a keyway 136 matching key 134 . second member 114 has an opening 138 through which pivot 132 and key 134 passes . opening 138 limits the rotation of pivot 132 and by extension the rotation of first and third members 112 and 116 , respectively , to second member 114 . the patterns of dispensing apertures 122 , 124 , and 126 form squares as illustrated , such that members 112 , 114 and 116 can be rotated so that the patterns on the first and second members 112 and 114 and the patterns on the second and third members 114 and 116 can be selectively aligned by rotation . in one embodiment , members 112 , 114 and 116 have at least one dispensing aperture 122 , 124 and 126 , respectively . the number of dispensing apertures per member can be as desired , ranging from one to eight or more , for example . as illustrated , the number of dispensing apertures per member is eight . dispensing apertures and openings can have raised rims as described below . in particular , as shown in fig5 and 9 , dispensing apertures 122 have rims 140 that are raised around part of the perimeter of the trailing portions during dispensing movement of corresponding dispensing apertures on side 142 of first member 112 facing container 102 . rims 140 are partially raised relative to side 142 . partially - raised rims 140 help fill apertures 122 during dispensing as described later . as illustrated , rim 140 typically is raised around about 33 % or more of the circumference of aperture 122 on side 142 , more typically at least about 50 % to about 60 % or 70 % around the trailing portions of member 112 . a typical height for rims 140 is about 0 . 4 mm . on side 144 of member 112 , opposed to side 142 , rims 146 are provided that are raised around the entire perimeter of apertures 122 relative to side 144 . member 114 has a side 148 facing container 102 and a side 150 facing away . rims 152 of second member dispensing apertures 124 on side 148 are not raised . rim 154 of opening 138 on side 148 is raised . rims 146 and 154 are raised by substantially the same amount , which in the illustrated embodiment is a height of about 0 . 4 mm . rim 154 is configured to allow free movement of the member 116 relative to member 114 . rims 146 provide strength to member 112 adjacent apertures 122 to reduce friction and wear . apertures 124 and opening 138 have rims 156 and 157 , respectively , on side 150 . rims 156 and 157 are raised by substantially the same amount . member 116 does have a raised rim 159 around its periphery to substantially match the height of rims 156 and 157 , which in the illustrated embodiment is a height of about 2 mm ( note the figure may not be to scale ). rims 156 and 157 provide uniform and level points on the same surface . elevated rims 156 and 157 prevent binding between surfaces by any granular material located on member 116 . the rims of apertures 126 are level with member 116 as are the rims for opening 135 . apertures 122 , 124 and 126 may be of different size and shape . apertures 122 and 124 are substantially circular or substantially cylindrical when taking into account the thickness of members 112 and 114 , respectively . typically , apertures 122 are circular and have the same or a slightly larger radius and circumference than circular apertures 124 . apertures 122 and 124 are laid out in the same pattern such that the area of apertures 124 are contained within the area of apertures 122 when viewed from above as can be seen in fig3 b . apertures 124 are sized to provide a desired amount of granular material with each dispense . typical diameter values for circular apertures 122 , 124 and 126 are 7 . 0 , 5 . 4 and 7 . 0 × 9 . 0 mm , respectively . apertures 126 can be substantially circular or substantially oval , for example . preferably aperture 126 is substantially oval , e . g . two semicircles of the same radius joined by a rectangle , with two axes of symmetry , a major and a minor . the oval has a major axis which is substantially tangential to pivot axis 128 and a minor axis which is substantially radial to pivot axis 128 . the minor axis is the same or larger than the diameter of apertures 124 such that granular materials being dispensed from apertures 124 are not impeded by the rim of apertures 126 . as illustrated , apertures 122 , 124 and 126 are laid out in a square or rectangle pattern with apertures substantially in the corner of the rectangle and apertures substantially in the middle of the side of the rectangle . the square or rectangle is sized such that corner apertures 122 c do not overlap middle apertures 124 m and middle apertures 122 m do not overlap corner apertures 124 c as member 112 is rotated relative to member 114 during a dispensing operation as shown in fig3 a and 4 b . similarly , corner apertures 126 c do not overlap middle apertures 124 m and middle apertures 126 m do not overlap corner apertures 124 c as member 116 is rotated relative to member 114 during a dispensing operation . third member 116 has a plurality of deflectors 158 for deflecting and spreading granular materials during dispensing . preferably , there is a deflector 158 associated with a separate one of each of apertures 126 . specifically corner apertures 126 c are associated with deflectors 158 c and middle apertures 126 m are associated with deflectors 158 m . as illustrated , deflectors 158 , sometimes referred to as 158 c and 158 m , attach to member 116 along a side of apertures 126 facing away from pivot 132 and extend beneath apertures 126 , but they could be attached on the side facing pivot 132 . corner deflectors 158 c are designed to deflect dispensed granular materials tangentially with respect to pivot axis 128 . middle deflectors 158 m are designed to deflect granular materials radially with respect to pivot axis 128 . middle deflectors 158 m as illustrated deflect granular materials inwardly , but they could be oriented to deflect granular materials outwardly . corner deflectors 158 c are narrow relative to middle deflectors 158 m to achieve the desired tangential deflections . the types and orientation of deflectors 158 can vary depending on the pattern of apertures 126 and on the area over which granular material is to be dispensed . by matching individual deflectors 158 to individual apertures 126 , it is possible to control the dispersion of dispensed granular materials to a greater degree than prior art dispensers which had a single deflector . in addition , individual deflectors 158 represent a significant savings in material costs relative to the prior art . the thickness of member 112 determines the portion of granular seasoning to be dispensed . replacement of this member 112 with a thicker or thinner member 112 allows the same dispenser to be modified to deliver greater or lesser amounts , respectively , of seasoning . in addition , larger or smaller apertures 122 , 124 and 126 , respectively , in members 112 , 114 and 116 , respectively , also allow greater or lesser amounts of seasoning to be dispensed . dispensing mechanism 108 may be attached to container 102 by any suitable structure . as illustrated dispensing mechanism 108 is part of a closure 160 ( for open bottom 110 ) having an outer body 161 . the upper half of outer body 161 tapers towards the middle to match a recessed taper 162 of container 102 . outer body 161 has two tabs 164 and 166 which attach dispensing mechanism 108 to container 102 by engaging two slots in container 102 . one of the two slots is not illustrated ; the other slot is slot 170 . as illustrated , second member 114 is integral to closure 160 . dispenser 100 also has baffles 171 . baffles 171 may be located in container 102 generally , within open bottom 110 more specifically , or within closure 160 . baffles 171 may be arranged in a spoke pattern and be connected to a support ring 169 . preferably the number of baffles 171 matches the number of apertures 122 . dispensing mechanism 108 is actuated by moving a lever 172 . lever 172 is removably connected to yoke 174 by hook 173 . yoke 174 has slots 175 and 176 . pivot 132 is received in slot 175 . member 116 has a pin 178 attached or integral to it . pin 178 is received in slot 176 . outer body 161 extends downwardly so that yoke 174 , pin 178 , and deflectors 158 are raised above a countertop or other support surface when dispenser 100 is placed upright on the countertop or support surface . outer body 161 has an opening 180 through which yoke 174 connects to a finger grip 186 . yoke 174 has a circular portion 182 . circular portion 182 is wider than opening 180 and the rest of yoke 174 to not deflect or minimize deflecting of dispensed granular materials and to limit the movement of yoke 174 outwardly . lever 172 rotates around removable pivot 184 in handle 106 . lever 172 has finger grip 186 which is an opening within the body 188 of lever 172 . lever body 188 is biased against or towards the body of container 102 by a biasing element 190 , which can be any suitable spring for pushing the lever body against or towards the body of container 102 . preferably , biasing element 190 pivots around pivot 184 at one end 192 . the opposite end 194 of biasing element 190 moves within a track 196 within handle 106 . biasing element 190 has a bend 198 of greater than 45 degrees ( π / 4 radians ), preferably greater than 60 degrees ( π / 3 radians ), and most preferably greater than about 75 degrees ( 5π / 12 radians ) when installed . bend 198 is located adjacent pin 200 of handle 106 . operation of the dispensing mechanism is described next . fig3 a , 3 b , 5 and 8 illustrate dispenser 100 with dispensing mechanism 108 in its “ rest ” position . in the rest position , apertures 122 and 124 are aligned permitting granular material to flow out of container 102 , through apertures 122 and into apertures 124 . in the rest position , granular materials cannot flow through apertures 124 to the exterior because of member 116 ; apertures 124 are not aligned with apertures 126 . adjacent apertures 122 are separated by baffles 171 when looking into container 102 . in other words , each aperture 122 is located between an adjacent pair of baffles 171 . as described below , baffles 171 and member 114 are stationary while members 112 and 116 rotate . however , it is conceivable that baffles 171 and member 114 rotate together about their axis during a dispensing operation while members 112 and 116 are stationary . referring to the figures generally and in particular to fig2 and 4 a and 4 b , a user of dispenser 100 initiates a dispensing operation by moving finger grip 186 in the direction indicated by the translation arrow a in fig4 a ( which can be done by a user squeezing together lever 172 and handle 106 with the user &# 39 ; s hand having the user &# 39 ; s fingers f inserted into finger grip 186 and the user &# 39 ; s palm p resting against handle 106 . the movement causes lever 172 to pivot around pivot 184 . pin 200 then pushes on spring biasing element 190 and causes it to bend more and end 194 to move upwardly within track 196 . the movement of lever 172 then causes hook 173 to pull yoke 174 outwardly . yoke 174 in turn pulls pin 178 , which follows yoke 174 while moving initially to the right within slot 176 . the movement of pin 178 causes the rotation of members 116 and 112 relative to member 114 and baffles 171 clockwise as shown by the rotation arrow b in fig4 b . as shown in fig9 , rims 140 are raised and have an outward ramp 202 on the leading portion of aperture 122 as member 112 rotates clockwise . the rotation of member 112 causes granular materials to be pushed up by raised rim 140 and ramp 202 . as the user further pulls on finger grip 186 , member 112 is further rotated which causes apertures 122 to pass under a baffle 171 . ramps 202 and baffles 171 then cooperate to push granular material in container 102 into apertures 122 and to prevent or help break up any clumps of granular material . for purposes of the invention , apertures 122 can pass under a baffle because first member 112 is stationary and baffles 171 rotate as a whole about an axis or because baffles 171 are stationary and first member 112 rotates about its axis , for example . when a user fully pulls on finger grip 186 , dispenser 100 dispenses granular material m as shown in fig1 . dispensing mechanism 108 , at this point in the dispensing operation , is illustrated in fig4 b and 6 . apertures 124 and 126 are aligned permitting granular materials m to drop out of aperture 124 , some of which will then strike and be directed by deflectors 158 , and thereby dispensing and distributing the granular materials over a controlled area . after the dispense , a user can complete the dispensing operation by releasing finger grip 186 . members 112 and 116 will then rotate back ( counterclockwise ) relative to member 114 to the positions illustrated in fig3 b , 5 and 8 . as member 112 rotates back , raised rims 140 tend to push granular materials into apertures 122 . the portion of raised rim 140 facing aperture 122 is preferably substantially vertical . another feature that assists with filling of apertures 122 and 124 is that adjacent apertures 122 are staggered radially from pivot axis 128 , such that adjacent apertures do not travel on the same path , which could result in inconsistent filling of apertures 122 and 124 . preferably adjacent apertures 122 are staggered such that their paths do not overlap during a dispense operation . at the rest position , apertures 122 and 124 are aligned permitting granular materials to drop from aperture 122 into aperture 124 . dispensing mechanism 108 , including handle 106 , lever 172 and finger grip 186 enables dispensing with minimal movement and maximum visibility of the food during dispensing . this enables better operation , more accurate dispensing of seasoning onto the intended food item or items and reduced operator fatigue . an important feature of this embodiment is a number of cooperating or multiple stop mechanisms . specifically , dispensing mechanism 108 limits or stops the rotation of members 112 and 116 relative to member 114 in several ways . first , movement of lever body 188 is limited by handle 106 and container 102 . second , rotation of key 134 is limited by opening 138 . third , the movement of yoke 174 is limited by pivot 132 in slot 175 . fourth , the rotation of member 116 is limited by pin 178 in slot 176 . fifth , movement of yoke 174 is limited by circular portion 182 and opening 180 . dispensing mechanism 108 can have a primary stop mechanism which can be any of the above mechanisms and combinations thereof with other mechanisms being redundant and coming into play only as the primary stop mechanism wears . having multiple stop mechanisms distributes the stopping forces over the multiple stop surfaces to provide for a more durable and longer lasting dispensing mechanism 108 . advantageously , one or more of the stop mechanisms makes a noise during ordinary use by impact when maximum movement is achieved which signifies to the user that finger grip 186 can be released or that dispenser 100 is ready to dispense again . a second version of dispenser 100 is illustrated in fig7 as dispenser 300 . in this embodiment , deflectors 158 are located inwardly of apertures 126 . deflectors 158 m then deflect granular materials outwardly . in addition , outer body 161 has legs 204 which keep the dispensing mechanism 108 off of countertops . in addition , legs 204 may be useful to maintain a minimum distance between the dispenser and foods to be seasoned , for example . both versions of dispenser 100 include openings 206 in outer body 161 , which permit granular materials between first and second members 112 and 114 to exit via openings 206 . openings 206 help prevent granular materials from accumulating between first and second members 112 and 114 and thereby binding dispensing mechanism 108 . although the components of dispenser 100 may be composed of any suitable material to facilitate their respective functions in accordance with the invention , dispenser 100 is substantially composed of a substantially rigid , food - safe material , such as a food - grade polymer , such as polycarbonate , nylon or various polymer blends as known in the art , the parts of which may be formed by any suitable manufacturing process , including , for example , injection molding . the food - safe material used is preferably translucent or clear , especially for container 102 , so that the level of granular seasoning material can be visually discerned through the side of container 102 . biasing element 190 is preferably composed of a food - grade metal suitable for springs such as stainless steel . in another aspect of the invention , a method for seasoning food is provided . the method includes holding container 100 or 300 containing granular seasoning , over a food item to be seasoned . next , the user squeezes a handle of the dispensing mechanism causing rotation of the second member relative to the first and third members and aligns the at least one third member aperture with the at least one second member aperture . the alignment causes seasoning to be dispensed from the at least one second member aperture . the dispensed seasoning is deflected and dispersed by the deflectors over the food item . a noise is generated by the dispenser responsive to the squeezing . the user then releases the handle and the biasing element causes the second member to rotate relative to the first and third members and aligns the at least one first member aperture with the at least one second member aperture causing seasoning to fill the at least one second member aperture . while the invention has been described with respect to certain preferred embodiments , as will be appreciated by those skilled in the art , it is to be understood that the invention is capable of numerous changes , modifications and rearrangements and such changes , modifications and rearrangements are intended to be covered by the following claims . | 0 |
broadly speaking we will describe techniques for estimating and regulating current on the secondary side of a transformer in a switched mode power supply ( smps ) using primary side sensing . this is dependent on accurate timing . we will describe techniques which enable the timing of the ‘ knee ’ point on the fly - back signal — that is the point when the current on the secondary side has reached zero — to be determined accurately despite using a knee - point detection method that is noisy . among other things , the techniques we describe produce an accurate estimate of the time when the secondary side is conducting by generating a timing signal from the rising edge of flyback signal to the last edge of the ‘ knee ’- point signal before the falling edge of the flyback signal . referring to fig1 a this shows a simplified block diagram of a single - switch flyback smps . a dc source 20 is connected to the primary winding of a transformer 21 in series with a primary side switch 31 and a current sensing resistor 30 . the secondary winding of the transformer 21 is connected to an output diode 22 in series with a capacitor 23 . a load 24 is connected across the output capacitor 23 . an auxiliary winding on the transformer 21 is connected between the negative terminal of the dc supply 20 and the timer 27 generating a voltage - sense ( vs ) signal . the primary current ip produces a voltage across resistor 30 , generating a primary winding current - sense ( cs ) signal . the driver 25 controls the on - times and the off - times of the switch 31 with the drive signal . the timer block 27 generates two timing signals , t 0 and t 1 , by sensing the drive , and vs or cs signals . t 0 represents the charge - time , i . e . the time when a current is flowing through the primary side of the transformer 21 . t 1 represents the discharge - time , i . e . the time when a current is flowing through the secondary side of the transformer 21 . the signals t 0 , t 1 and cs , are used in a current model ( cm ) block 28 to produce an error signal err . a ( constant ) output current target ( oct ) signal represents the target output current of the secondary winding . the err signal represents a difference between oct and an output current model ( ocm ) signal which estimates the output current of the smps ( an ocm signal may or may not be produced explicitly in the smps ). the err signal is used in the control block 26 to control the driver 25 in such a way that the error signal err converges towards zero ( so that the ocm signal converges towards oct ). one alternative way to sense the current is to put the current sensing resistor 31 in the return path , as shown in fig1 b . one alternative way to sense the voltage is to use a resistive divider ( resistors 32 and 33 ) on the primary , as shown in fig1 c , thus eliminating the auxiliary winding . fig2 shows one example implementation of the timer block 27 . in this example the signal drive is used directly for generating t 0 and the reflected secondary - side voltage sensed on the auxiliary ( or primary ) winding of transformer 21 is used to generate the discharge - time signal t 1 . it is preferable to employ primary - side sensing for the discharge time since it is desirable for only primary - side sensing to be employed . one way in which the discharge time may be determined uses an output voltage model ( ovm ) block 40 which has an output , ov , which approximates the output voltage of the smps and which can be compared with the sensed voltage signal vs by comparator 41 to generate signal t 1 . in general , an smps controller which incorporates primary - side sensing for output voltage regulation will already include some form of output voltage model . an alternative to the use of an output voltage model per se is simply to compare the sensed voltage waveform with a reference level in order to generate the discharge - time signal t 1 . however in order to improve the current regulation better techniques for the generation of the important timing signals t 0 and t 1 are desirable , as explained below . ocm = n & lt ; cs & gt ; & lt ; t 1 & gt ; & lt ; t 0 & gt ; equation 1 where & lt ; x & gt ; denotes the low - pass filtered ( average ) signal x . cs is the primary side current ( or a primary side current sense signal ), t 0 the time when the primary side of the transformer is conducting ( charge time ) or a signal dependent on this , t 1 the time when the secondary side of the transformer is conducting ( discharge time ) or a signal dependent on this , and n a constant depending on , for example , the transformer turns ratio and the value of resistor 30 . averages may be taken over one or more smps periods or instantaneous values t 1 and t 0 may be used instead of average values to estimate the output current . equation 1 may be used to implement an error function , the results of which can be used to control the output current of the smps . it can be seen from equation 1 that accurate estimation of the current on the secondary side of a transformer using primary side sensing is dependent on accurate timing . a block diagram of an improved timer module 27 , which enables improved output current regulation , is shown in fig3 a ; a variant implementation is shown in fig3 b . it is also helpful to refer to the waveforms of fig6 , which illustrate the operation of the timer in the context of the smps . timing signal t 0 should represent the time when the primary side switch is conducting current and charging the transformer . however because the turn - off of the switching device 31 is not instantaneous , especially when using a high - voltage bjt ( bipolar junction transistor ) as a switch , the drive signal is too short . to address this problem , in embodiments a comparator 50 is used to generate a signal hi when the voltage sense signal vs & gt ; 0 volts ( although an alternative reference voltage level may be employed ), and t 0 is then stretched until the rising edge of the hi signal . the implementations shown in fig3 use a latch 51 which is set by the rising edge of drive and reset by the rising edge of hi . the output of the latch 51 provides timing signal t 0 . alternatively comparator 50 may employ current sense signal cs , rather than voltage sense signal vs , to generate the rising edge of the hi signal . in the latter case t 0 is stretched until the falling edge of the cs signal . timing signal t 1 should represent the time when the secondary side is conducting and discharging the transformer . an accurate timing of the end of the discharge - time is provided by the “ knee - point ” of the vs signal . this signal can be obtained a decaying - peak detector ( dpd ) 53 . we have previously described a similar decaying or leaky - peak detector , albeit in a different context , in wo 2007 / 135452 ( u . s . ser . no . 11 / 445 , 473 ), which description is hereby incorporated by reference . the knee - detect output signal of the leaky - peak detector , knee , is a noisy signal as it detects all the “ knees ” on a noisy voltage sense ( vs ) signal . one could use knee directly to generate t 1 but some preferred implementations of the output current model block ( see below ) use an average value of t 1 and glitches on t 1 would cause the estimated output current ocm to be too low . therefore in preferred embodiments a more accurate measure of timing signal t 1 is generated from the difference of two intermediate signals , using t 1 = flybk − negt . referring again to fig6 , flybk is high from the falling edge of t 0 to the first falling edge of hi . a signal negt is generated which is high for an amount of time equal to the difference between the true transformer reset point ( at the “ knee point ” on the vs waveform ) and the zero - crossing point on the vs waveform . as can be seen in fig6 , in embodiments t 1 = flybk − negt is bipolar and its average value represents the length of time during which the secondary side of the transformer is conducting . the implementation shown in fig3 a uses a latch 52 to generate the flybk signal . the latch 52 is set by the falling edge of t 0 and reset by the falling edge of hi . a dual - slope integrator dsi 54 generates negt from flybk and knee , as explained in more detail below . broadly speaking , therefore the estimation of timing signal t 1 employs : i ) detection by some means of the end point of secondary side current conduction — the ‘ knee point ’— where those means can be susceptible to false early triggering due to noise , parasitic impedance - induced oscillations or other disturbances ; ii ) detection by some means of a later , less ambiguously detected , event in the sensed waveform , for example a first or other zero crossing or turning point in the oscillatory portion of that waveform , subsequent to the end of secondary side current conduction ; and then iii ) use of the elapsed time between the events detected in ( i ) and ( ii ) to determine an accurate , substantially noise - immune value for t 1 . fig3 b shows a preferred embodiment of a timing generation module . here the comparator 50 has been split into comparators 50 a and 50 b , each referenced to an individual voltage , va and vb respectively . this arrangement provides greater flexibility and accuracy in independently setting the trigger values of the sensed waveforms which will in turn determine the falling edges of t 0 and t 1 . broadly speaking the leading and trailing edges on t 0 and t 1 signals can be triggered by rising or falling edges of any suitable primary side signals , including the vs and cs waveforms , or by signals derived therefrom . for example , the falling edge of t 0 and / or the rising edge of t 1 can be determined by the time when the cs voltage returns to ground . further , the inputs to the latches 51 and 52 can be delayed by a fixed delay to accommodate for fixed delay in the system . fig4 shows an example implementation of the decaying peak detector ( dpd ) 53 of fig3 a and 3 b . the decaying peak detector has the sensed voltage signal as an input and vpd tracks the vs waveform except when the slope of vs exceeds a certain ( negative ) value , at which point the vs and vpd waveforms separate from each other . the knee signal from the dpd is active when the vpd signal is tracking the vs signal , that is when vs is increasing or “ updating ” vpd , going inactive on detection of a real or false knee in vs . in the example behavioural model shown in fig4 diode 61 and capacitor 62 together comprise a peak detector . preferably a voltage source 64 adds a small dc offset compensating for the forward voltage drop of diode 61 . current generator 63 ( here a current sink ) discharges the voltage on the capacitor 62 , defining the maximum negative slope of the decay on vpd , so that comparator 60 makes the knee signal active if the vs ( negative slope ) is greater than or equal to the voltage ( negative slope ) on capacitor 62 . in embodiments the rate of discharge of capacitor 62 by current sink 63 may be chosen according to the implementation to approximately follow the sensed secondary side voltage , providing an approximate tangent to this voltage prior to its oscillatory or resonant portion . optionally the dpd 53 may be reset , for example during t 0 , by opening a switch ( not shown ) in series with the vs input and closing a switch ( not shown ) across capacitor 62 . fig5 shows an example implementation of the dual slope integrator ( dsi ) 54 of fig3 a and 3 b . as mentioned above , a signal negt is generated which is high for an amount of time equal to the time from the last falling edge of knee to the falling edge of flybk . in the implementation we describe generation of negt is based on an analogue dual - slope integrator , but other techniques may also be employed . thus the dual slope integrator 54 of fig5 generates negt from knee and flybk . referring to fig5 , capacitor 14 acts as an integrator and is either ( i ) charged by current source 10 , ( ii ) discharged by current source 11 , or ( iii ) reset to gnd by the action of switches 12 and 13 . the waveforms can be found in fig6 . in embodiments current sources 10 and 11 are sourcing the substantially the same current so that the rate of charging and discharging is the substantially same . referring to fig5 and 6 , in operation flybk goes high and negt is forced low by blanking gate 16 . when knee goes low switch 12 connects capacitor 14 to current source 12 and negta ramps upwards . the initial glitches on knee cause inconsequential glitches on negta since negt is blanked by gate 16 . after some initial glitches , knee goes high again before the true knee point and negta is reset to ground . then knee goes low at the true knee point and negta is released and ramps upwards . when flybk finally goes low switch 13 connects capacitor 14 to current source 11 , negta starts ramping down and negt goes high . when negta reaches its starting value , here ground , negt goes low by the action of comparator 15 . since the charge rate and the discharge rate is the same , negt is high by the same amount of time as the time from the last falling edge of knee to the falling edge of flybk . we now give example implementations of current model ( cm ) block 28 . as illustrated this generates an error function signal err representing the difference between an estimated output current of the smps and a desired target output current . for details of example implementations reference may be made to the applicant &# 39 ; s patent applications gb2439997 and gb2439998 , hereby incorporated by reference . a first example implementation of such an error function is shown in fig7 a . the error function for the first implementation ( for simplicity disregarding n ) is : in this implementation , cs , t 0 , and t 1 are fed through respective low - pass filters 112 , 113 and 114 , to generate the averages of the three signals : & lt ; cs & gt ;, & lt ; t 1 & gt ;, and & lt ; t 0 & gt ;. the averaged signals are used in a multiplier / divider 111 to produce ocm . ocm is then compared to the output current target oct in subtracter 115 to produce the error signal err . as mentioned previously & lt ; t 1 & gt ; and & lt ; t 0 & gt ; may be replaced by non - averaged t 1 and t 0 and then low - pass filters 113 and 114 may be omitted , but where as described above a bipolar t 1 is employed averaging automatically “ corrects ” the value of t 1 for the time offset between the true knee point and the first zero - crossing afterwards . a second example implementation of such an error function is shown in fig7 b . by multiplying the right - hand side of equation 2 by & lt ; t 0 & gt ;/& lt ; t 1 & gt ; the error signal becomes : the difference in this implementation that & lt ; t 0 & gt ; and & lt ; t 1 & gt ; have been switched on the input of the multiplier / divider 111 . also oct and & lt ; cs & gt ; have been switched . in this implementation the signal path carrying oct is subtracted from & lt ; cs & gt ; in subtracter 115 . the err signal in this implementation will differ in magnitude to that of the first example implementation but this does not adversely affect the operation of the surrounding circuitry . again , & lt ; t 1 & gt ; and & lt ; t 0 & gt ; can be replaced by t 1 , and t 0 , but with the same comment as above . fig7 c , which is taken from gb2439997 , shows a further alternative implementation in which the cs signal is averaged during t 0 in the first low - pass filter 122 ( formed by a first resistor and capacitor ). note that the input of the first low - pass filter 122 is high impedance when t 0 is low by the action of the switch 121 . therefore cs is averaged only when t 0 is high , otherwise the voltage is held on the capacitor 122 . the output signal of the first low - pass filter 122 is buffered by 123 to produce the signal v 1 . v 1 is then multiplied by t 1 over t , the total smps cycle period ( t 1 effectively providing both t 1 and t ) by switching the second low - pass filter 126 ( formed by a second resistor and capacitor ) between ground and v 1 . the switches 124 and 125 are turned on by t 1 and the inverse of t 1 respectively . example embodiments of the controller 26 of fig1 a are shown in fig8 a and 8 b . in fig8 a the controller integrates the err signal ; in fig8 b the controller integrates the difference between the ocm and oct signals . in both cases the integration is performed by action of the resistor 70 , the capacitor 72 , and the amplifier 73 . together they form an inverting integrator . if the output current is too high , the error voltage err — or the difference ocm − oct — will be positive , and the signal cc will decrease which reduces the output power of the smps ( and vice versa for a too low output current ). in fig8 b the purpose of the buffer 74 is to reduce the load on the low - pass filter 126 in the current model 28 . the purpose of resistor 71 is to cancel the pole from the cm 28 by inserting a zero . this way the transfer function from oc to cc only has one dominant pole at zero frequency . the controller may be implemented without resistor 71 by replacing this with a wire . in this alternative implementation of the controller , the low - pass filter 114 in the current module cm 28 is no longer required . in effect , removing the low - pass filter 114 , i . e . letting the time constant t 3 go to zero , reduces the required value of the resistor 71 to zero . the driver 25 in fig1 a may comprise a pulse - width and / or pulse - frequency modulator that controls the drive signal . the drive signal turns on and off the primary side switch 31 . the width and frequency of the drive signal controls the power delivered to the secondary side of the transformer 21 . the input signal cc preferably controls the driver 25 such that the power delivered to the secondary side is dependent on ( increases monotonically with respect to ) the input signal cc . for further details reference may be made to the applicant &# 39 ; s co - pending applications pct / gb2005 / 050244 , pct / gb2005 / 050242 , gb 0526118 . 5 ( all of which applications are hereby incorporated by reference in their entirety ). broadly speaking we have described techniques for generating accurate representations of timing signals used for an output current model in a primary - side sensing controller . in embodiments t 0 is compensated for delays in the turn - on / off of the primary switch , and t 0 edges are generated from edges on the vs , cs and / or drive , with or without a fixed delay . in embodiments t 1 is generated directly or indirectly from a “ knee - detector ” which may be , for example , a leaky - peak detector or a comparator . more particularly in embodiments t 1 is generated from flybk and negt signals , where flybk is high from the vs signal going high from a time after the drive has been turned off till the zero - crossing point on the vs waveform , and where negt is high for an amount of time equal to the difference between the true transformer reset point ( at the “ knee point ” on the vs waveform ) and the zero - crossing point on the vs waveform . the position of negt in the switching period is unimportant however negt is high by substantially the same amount of time as the time from the last falling edge of knee to the falling edge of flybk . in embodiments generation of negt can be implemented with a dual - slope integrator , which may be either analogue or digital . embodiments of the smps we describe may also include an output voltage control loop , preferably a primary - side sensing voltage control loop . we have previously described a number of suitable techniques including , for example , that of in wo 2007 / 135452 ( u . s . ser . no . 11 / 445 , 473 ) which samples the output voltage at the knee in the reflected secondary side voltage waveform ( identified using a decaying peak detector to approximate a tangent to the decaying secondary side waveform ), at which point because substantially no current is flowing to the smps output the secondary side voltage accurately reflects the output voltage of the smps . we have described the operation of embodiments of the above - described output current estimation technique in the context of an example of an smps operating in a discontinuous conduction mode ( dcm ), but the techniques also work in critical conduction mode and in continuous conduction mode ( ccm ) since no particular shape is assumed for the waveforms involved ; instead the described signal processing employs the actual , sensed signal waveforms . no doubt many other effective alternatives will occur to the skilled person . for example although some embodiments of the timer circuit have been described which employ a voltage sense signal to generate timing signals t 0 and t 1 , the skilled person will appreciate that the current sense signal may alternatively be employed . it will be understood that the invention is not limited to the described embodiments and encompasses modifications apparent to those skilled in the art lying within the spirit and scope of the claims appended hereto . | 7 |
fig1 shows a first embodiment of the current invention where hydrocarbons such as untreated heavy low quality crude oil , vr ( vacuum reside ), asphaltin or coke , if available from upgrading process , is injected together with oxidation gas ( oxygen , air or enriched air ) to a combustion area of a high - pressure direct contact steam generator 51 . heat is released from the exothermic reaction . water is injected to the combustion area 51 to maintain the high temperature under control to prevent damage to the facility while achieving full oxidation reaction of the carbon in order to minimize the amount of unburned carbon solids . an additional amount of water is injected to produce steam . the amount of water is controlled to produce steam where all the liquids with the soluble materials become solids and all liquids evaporate or burn to gas and solid ash . additional chemical materials can be added to the reaction . as an example , limestone or magnesium oxide can be added to the water in a case where the fuel used is rich with sulfur . the gas and solids move to a high pressure solid separation block 52 where the solid phase is removed from the gas phase . this can done in a continues way or in intervals combined with pressure drops . the high pressure , high temperature gas is mixed and washed through water 53 to remove the remaining solids and to produce wet steam . the rejected water and solids from this block are injected back into the steam generator 51 . in the case where the water or the fuel includes a high percentage of impurities that react to produce unacceptable corrosive materials that can corrode the pipes and the well casing ( high chlorine , sulfur etc ), then an additional reaction block for corrosion control is added . the wet steam is injected to a high - pressure , high - temperature corrosive gas scrubber 54 where the water is circulated and re - generated at 56 to remove the remaining corrosive gases . this exact scrubbing and re - generation of the injected steam - gas mixture is chosen according to the impurities that appear in the water and the oil at the specific site . those units are commercially available . it is important to emphasize that the purification treatment at this stage is not designed to allow the release of the gases to the atmosphere ( which requires removal of most contaminates ) but only to maintain the corrosive product at an acceptable level relative to the facility design . as an example , in a case in which stainless steel is be used for piping and casing , then even with heavily polluted fuel and water feeds there will be no need for block 54 . the steam and gas mixture flows to a high pressure separator block 55 where the steam and reaction gases are separated from the liquids and readied for injection into the reservoir . the condensations are injected back to the steam generator 51 . fig2 shows steam production block 50 ( described in fig1 ) that includes a solid removal block and an acid gas removal block . the pressure of the steam and gas mixture is dropped in block 57 to the range as required for injecting into the formation . an additional block 58 of direct contact heat generation is used to raise the temperature to produce a superheated steam and gas mixture . the direct contact heat generator uses oxygen or enriched air and hydrocarbon gas to produce a clean reaction and avoid the creation of solids . the extra heat results in raised temperatures that will be designed to prevent condensation in the pipe prior to the injecting into the formation . condensation in the carbon dioxide rich environment will result in corrosion in the steam and gas pipes to the wells . the actual temperature of the superheated dry steam will be calculated to overcome the losses in the pipes to avoid condensation all the way through the entire length of the underground horizontal injection pipe . this block will be added only if the injection pressure is high enough such that dropping the pressure will not prevent the risk of condensation and corrosion . fig3 shows the combination and the connection between the high pressure direct contact steam generator 205 and an upgrader , where the upgrader is in a remote location from the direct contact steam production facility and the sagd . the solid fuel waste can be “ green ” coke from a delay coker or any other type of coke or asphaltin . the exact type of fuel depends on the upgrading processes used . a pipe system is used to send the solid fuel to the direct contact steam generator 205 . the solid fuel produced by the upgrader is ground to a grain size of less than six millimeters and mixed with recycled and process water in block 203 . the slurry mixture is then pumped through a pipeline to a separator 204 that separates more then 60 % of the water at the water separation station 204 , and sends it back through the pipeline system back to the pumping station at the upgrader 203 where it will be added to the ground fuel with the make - up water and recycled back . in the sagd location , after the excessive water is removed , the slurry is injected to the direct contact high pressure steam generator 205 , together with oxygen or enriched air . fig4 shows a system for supporting a sagd facility , where the system is combined with a standard prior art sagd water treatment facility . the system includes an air separation unit 103 , a co - generator facility 102 to produce energy and steam , and an air separation facility to produce oxygen or enriched air and direct contact steam generation . the water treatment facility in the sagd 101 provides high quality water to the co - generator 102 where energy and steam is produced . the energy produced in the co - generation is used to operate the air separation unit to produce oxygen or enriched air . the oxygen or enriched air is injected into the high - pressure direct contact steam generator 104 , together with water and fuel . the low - quality water contains residual bitumen emulsion with no further treatment . this prevents the need for expensive chemicals and facilities for the water purification emulsion separation . any available hydrocarbon or coke can be used as fuel in the manner of the sagd produced bitumen on - site or the solid carbons and / or heavy hydrocarbons shipped from an upgrader . the direct contact steam generator 104 produces mainly steam and carbon dioxide for downhole injection . fig5 is the combination of fig3 and fig4 . it shows a system , apparatus and method that incorporates a prior art existing and operating sagd facility and an upgrader facility as part of an expansion of an existing sagd and upgrader . the upgrader 111 receives the heavy oil product from an existing sagd . as part of an expansion , an additional direct contact steam generation facility 115 is added in close proximity to the sagd wells . this new facility consumes the reject water from the existing sagd facility , currently disposed of in a disposal well , as well as additional oily water , most probably with an oil emulsion that will be rejected and sent directly to the new steam generator instead of being treated with chemicals to separate the remaining oil . a co - generation 112 will produce steam and energy to support an air separation unit 113 . the air separation unit 113 will provide the oxygen or enriched air to the new steam generator 115 . most of the fuel for the new direct contact steam generator will be the upgrader by - product ( such as coke ) that will be sent in slurry form by using the pipe system . the remaining energy produced by the co - generator 112 will be used by the upgrader or the sagd utilities . the steam produced by the co - generator 112 will be sent to the existing sagd 114 . most of the thermal expansion capacity in the sagd portion will be due to the additional steam / co2 mixture produced by the new direct contact steam generator in block 115 . the waste from block 115 will be in a solid form that will prevent the need for disposal wells . the additional co2 released to the atmosphere due to expansion will be minimized because the high thermal efficiency and because most of it will be injected directly into the reservoir where some of it will permanently stay . fig6 shows a system and apparatus for supporting a new sagd facility , where all the steam required for the oil production is produced in a direct contact steam generator without the traditional water treatment and the otsg for generating the steam . water treatment is minimized as the direct contact process can use low quality water with organics such as oil . the product from the production well 321 flows to a separation process 322 where the oil is separated from the water to produce oil and gas 323 . the separation process requirements are simpler and consume less chemicals the acceptance of oil in the water reduces the complexity of the water treatment facility , the chemicals required to operate it and the operating costs when compared to the process used in the prior art otsg or boilers . the produced water 317 with the oil traces and additional low quality make - up water 316 are injected to the steam production facility 312 where it is mixed with the hot gases produced from the burning fuel to produce the steam . the produced oil and gas 323 separates the oil from the gas 324 . the gas is further separated in a gas separation unit 325 into hydrocarbon products and non - valuable gases , such as nitrogen , carbon dioxide and possibly sulfur dioxide . the hydrocarbons 326 are sent to an upgrader for further processing 327 . the non - valuable gases are treated to remove the sulfur and other contaminations 330 prior to release into the atmosphere . in option i , an air separation unit 331 is used for producing a minimum of 75 % oxygen enriched air 332 for injection into the pressurized combustion chamber . in option ii , air is compressed 333 and injected to the combustion chamber under pressure . in option iii , after the oil and gas separation , some produced crude oil 329 is sent to the combustion reactor 311 to produce flue gas and steam . in option iv , where upgrader products are available , then instead of using crude oil for the combustion , a vr ( vacuum residue ), extracted asphaltin or coke 328 will be used in the combustion chamber 311 for producing the steam and co2 mixture . in the combustion chamber , the fuels are mixed with the oxygen in an exothermic reaction . the produced water 317 is injected into the combustion chamber steam combustion section 312 together with make - up low quality water 316 . from the steam production , a dry superheated steam is produced together with the solids resulting from the crude oil combustion and the low quality water that is used . the solids are separated in a solids separation unit 313 . the solids are removed in a solid form or in a slurry form . the produced steam and flue gas is treated at 314 to control and reduce the corrosiveness of the steam / flue gas mixture for injecting it into the injection wells . the necessity and characteristics of this unit is a function of the fuel quality , the water quality and the underground reservoir conditions . the product is recovered , together with water and gas , in the production well 321 . in the case that air is used for the steam generation , or during the start - up / heat - up mode , then the flue gases are recovered through a separate well 320 or through a discharge pipe through the injection well itself to relief the underground pressure in the reservation . fig7 shows a system , an apparatus and a method for supporting and expanding a prior art sagd facility . the system is combined with a standard prior art operating sagd water treatment facility . in this prior art sagd facility , steam is produced in steam generator 436 . the steam for expansion will be produced using direct contact steam generators 411 and 412 where the steam is produced from water without treatment . this minimizes the investment in expanding the water treatment facility since the direct contact process can use low quality water with organics such as oil . the product from the production well 420 is separated in block 421 . this separation is simplified since there is no requirement to remove the oil from the water for the production of the steam or for the water disposal . the produced oily water will be used without any additional treatment in the direct contact steam generator unit 412 . the produced oil and gas is sent for further processing in the existing prior art facilities . the produced gas is treated to remove contaminations , especially sulfur gas , before being released into the atmosphere . this process is required when using air for the steam production in the direct contact steam generator since this will result in a significant amount of produced nitrogen . the produced de - oiled water is then used for producing steam in the existing prior - art sagd facility . the de - oiled water is pumped to the prior art lime softeners 424 , where most of the dissolved solids are removed as a sludge 426 . the soft water is pumped through filters 427 where a filter waste is produced at 430 . the filtered water is treated in an ion - exchange system 432 where additional waste is generated at 433 . the treated water is used for generating steam in a otsg or a co - generator 436 . typically , an 80 % steam is produced . this wet steam is separated in a steam separator 435 to produce 100 % steam for downhole injection . the liquid blow - down that was disposed using disposal wells is used without any additional treatment in the new direct contact steam generator 412 . the new direct contact steam generator can use heavy oil , vr , asphaltin or coke for the high pressure combustion . in addition , oxygen enriched air or air is injected for the combustion process 411 . the steam is produced by high - pressure , direct contact between the hot combustion gases and the injected water . the water for the process is the produced water , brackish water 416 sewage effluent 417 or any type of available water . from the steam production , a dry superheated steam is produced together with the solids resulting from the crude oil combustion and the low quality water that is used . the solids are separated in a separator 413 where the solids are removed . the steam / flue gas mixture 414 is injected into the reservoir with the steam produced in the prior art existing facility . for further understanding of the present invention , the following is an example of the usage of the present invention . an existing sagd facility located in alberta produces heavy oil from the tar - sand . the produced bitumen is transferred by pipelines to an upgrader . the sagd uses water from local water wells with a water treatment facility that is based on hot lime softeners or evaporators . the upgrader produces significant amounts of solid coke , currently with no commercial value . in addition there is approximately 10 % of low - quality water rejected at the sagd facility that is disposed back to an underground formation through a pipe system and disposal wells . there are waste water tanks and ponds that are used for holding process water , mostly water with fine clay particles that cannot be separated or re - used prior to long settling periods . the advantages in the use of the present invention for the sagd expansion over the existing technologies are as follows . first , there is a reduction of the co 2 emissions due to the high thermal efficiency and the fact that the co 2 is injected into the formation , the use of low quality waste water and the produced solid waste ( a “ zero ” liquid discharged system ) that can be easily discharged in local landfill , and the use of a low quality fuel , especially the use of coke as a fuel . this cost effective and environmentally - friendly expansion with the implementation of the current invention is as follows . first , a direct contact steam generator is located at the sagd area . this direct contact steam - generator will use oxygen or enriched air from an air separation unit to limit the amount of the uncondensed nitrogen gas injected to the underground formation . the feed for this system will be low - quality water , including untreated oily water from the existing sagd or any available source . the fuel can be any locally available produced bitumen produced by the sagd . the waste from the steam generation process will be in the form of solids . this makes it inexpensive to send to a landfill . the injected product will be a mixture of superheated steam , co2 and other gases in the temperature and pressure similar to the existing facility which is in the range of 250 ec and 2000 kpa . secondly , the addition of a co - generator provides the energy for the air separation unit . additional steam produced by the co - generator . the water to produce this steam is treated conventionally by expanding the existing water treatment facility in a traditional method which is hot / warm lime softeners or evaporators . the fuel will be the coke from the upgrader where the produced bitumen from the sagd facility is treated . because the coke material is located near the upgrader , and not near to the sagd facility , the coke will be grind and mixed with the waste water from the upgrading process , settlement ponds water or from any other source . the slurry mixture will be transported using pipes to the direct contact steam generator , where the slurry will be injected to react with the oxygen / enriched air to produce the steam . the present invention is a system and method for the production of steam for integration in a sagd facility to produce hot gas . mainly composed from steam , for downwell use from low grade fuel and water which minimizes the co2 emissions and produces a dry solid waste . this is done by direct contact production of steam from low quality hard and oily water and fuel that can be untreated heavy oil , vr or coke . the process is adiabatic such that the produced gases maintain most of their thermal energy in the form of their temperature and pressure throughout the process and up to the point where they are injected into the reservoir . the direct contact steam generation process creates solid waste as result of the low quality water and fuel used . the high temperature and pressure separation and removal of the solids is a key stage for continuous operation . the separation is done when all or most of the liquids have already transferred to the gas so that it is done mainly between the solids and the gas phase . it can be done continually or in intervals with pressure drop to increase the evaporation and reduce the moisture in the solids waste . the gas purification stages ( like scrubbing remaining solids and corrosive gases ) are done under high pressure and under pressure where additional water is converted into steam . to minimize the corrosive effects of the co2 in the injection gas and to minimize the requirement for special corrosion - resistant steel for deep high pressure wells , the gas mixture is further heated , preferably by a direct contact burner that heats the gas mixture to a temperature in which the steam is in “ dry ” super - heated state all the way to the underground formation through the horizontal perforated underground sagd injection pipe . the steam condensates in the formation , outside of the injection pipe . to minimize the amount of the nitrogen that is non - condensate gas with limited dissolvent in the reservoir , an air separation unit can be incorporated . the system can be integrated with prior art sagd units . the integration allows for the use of reject water . it also allows for the reduction in the requirement for the water - oil separation process in the existing prior art sagd since it allows rejection of the oily water emulsion that will be used as a water source for direct contact . the prior art sagd technologies require full separation of the residual oil from the water . both prior art water treatment technologies — the softening and the evaporating — require full removal of any residual oil . from the environmental perspective it is also impossible to release reject oily water to the environment or inject it to an underground water injection well . as a result , the water treatment process is expensive and requires expensive chemicals and filters . the ability to release a portion of the deeply emulsified oily water to another facility will be advantageous to the prior art sagd . the invention is intended to improve the advantages of the current processes used in sagd and to reduce their disadvantages , especially the water quality and fuel quality . the present invention minimizes as much as possible , the greenhouse gas emissions . this application can be combined with an existing sagd plant by using the low - quality rejected water and waste oil . the present invention is intended to work with commercially proven sagd technologies or similar designs and with the prior art for the use of steam and stimulating gases ( e . g ., co 2 ) to recover the bitumen . since the present invention does not deal directly with the subsurface formation , it can be further developed , engineered and tested remotely from the oil sand projects . the risk involved is decreased as the underground portion of the process is developed and proven . because of the present amount of activities and development in the oil sand area , the ability to build and test new technologies or to construct new testing facilities in the oil sand regions are very limited and the costs are extremely high in comparison to the same activities carried out somewhere else . the current application pilot plant facility can be developed and built where human resources are available and in much lower cost compared to the costs in north alberta where most of the oilsands deposits are located . the heat efficiency of the injection is maximized , compared to indirect steam generation methods . this is due to the fact that the heat transfer occurs through direct contact and , in addition , the combustion gases transfer most of the thermal energy to the formation as the formation acts as a heat exchanger to the combustion gases . this results in higher heat efficiency compared to the standard manner of steam production where the heat in the combusted gases are released into the atmosphere at a much higher temperature . the foregoing disclosure and description of the invention is illustrative and explanatory thereof . various changes in the details of the illustrated construction can be made within the scope of the appended claims without departing from the true spirit of the invention . the present invention should only be limited by the following claims and their legal equivalents . | 4 |
a milking system or milking station 1 for voluntary milking comprising cleaning means in accordance with the invention is illustrated in fig1 . an automatic milking machine ( not illustrated in detail ) is provided for milking animals , such as for example cows . the automatic milking machine comprises teat cups 2 connected to an end unit by means of milk lines ( only small portions of which attached to the teat cups are shown in the figure ). a milking robot or other automatic handling device 3 having a handling device , such as a robot arm 4 , equipped with a gripper device 5 in its far end is provided for automatically fetching the teat cups 2 of the milking machine from a rack 6 , in which the teat cups 2 are stored . the robot arm 4 moves the teat cups 2 toward the udder of the cow and attaches them to the teats of the cow . the teat cups 2 may be fetched , moved and attached one at a time or several at a time . the milking robot 3 is typically equipped with a camera system or other detecting device 7 for determining the exact positions of the teats to which the teat cups 2 are to be attached . the gripper device 5 is intended to grip , to hold and to release the teat cups 2 or other equipment , such as for example a teat - cleaning cup 11 . the milking station 1 may comprise other conventionally used devices , not shown or described in detail herein . for example , teat - treatment devices may be provided , identification members for identifying a cow etc . the milking station 1 further comprises a control unit 8 , which is responsible for controlling the milking station 1 . processing within the control unit 8 comprise , inter alia , initiation of various activities in connection with the milking such as opening and closing of gates , controlling of the automatic milking machine and the milking robot 3 . the control unit 8 typically comprise a microcomputer , suitable software and a database including information of each of the cows being milked by the automatic milking machine , such as for example when a specific cow was last milked or last fed , or her milk production , her health etc . in accordance with the invention , means are provided for enabling efficient cleaning of the gripper device 5 . in one embodiment of the invention , the means comprise a cleaning device 9 having a suitable cleaning member 10 . the cleaning member 10 may for example comprise spray means for spraying cleaning agents on the gripper device 5 , or blowing means for blowing air , preferably compressed air , onto the gripper device 5 and thereby cleaning it . other types of cleaning members are conceivable as well . in a particular embodiment the cleaning member 10 is a sponge or the like . the cleaning is then effectuated by removing dirt off the gripper device 5 by rubbing it against the sponge . the cleaning member 10 of the cleaning device 9 is then a suitable sponge . the use of a sponge provides a cost - efficient solution , with low energy consumption and low purchase costs . further , the sponge is easily replaced when need arises . the robot arm 4 comprising the gripper device 5 is moved towards the cleaning device 9 upon initiation of a gripper device cleaning procedure . the gripper device 5 of the robot arm 4 is thereby moved to a cleaning position ( indicated by dashed lines in the figure ) in which the cleaning can be performed . in case the cleaning member 10 is a sponge , the robot arm 4 is preferably arranged to move back and forth in front of the sponge a number of times in order to rub the gripper device 5 against it . upon finishing the cleaning of the gripper device 5 , the robot arm 4 is returned to a non - active or an idle position . the robot arm 4 is then ready for a subsequent operation , such as fetching teat cups 2 or the like . for ease of illustration , the cleaning device 9 is shown as a separate unit in the figure . however , the cleaning device 9 is preferably integrated with the milking station 1 in any suitable manner , for example constituting part of or being arranged on the enclosure of the milking station 1 . the cleaning device may be arranged on a part of the milking robot 3 . the only requirement is that the cleaning device 9 is placed so as to be within reach of the gripper device 5 of the robot arm 4 . the control unit 8 comprises software for effectuating the cleaning procedure in accordance with the invention . the cleaning procedure for cleaning the gripper device 5 may be programmed and customized to suit the needs of the specific farm in which it is utilized . the cleaning may , for example , be performed after each cow that has been milked , after every fifth or tenth milked cow , a certain number of times an hour or whatever frequency is most appropriate for the particular milking farm . the frequency may depend on various factors , such as the number of cows ( the environment may be more soiled the more cows are being kept ), the water quality , the sensitivity of the gripper device and so on . the frequency with which to cleanse the gripper device 5 can be set by the user and is easily changed should such need arise . the suitable cleaning frequency is programmed into the control unit 8 . there are means for transmitting signals from the control unit 8 to the milking robot 3 , for initiation of the gripper device cleaning procedure . that is , the control unit 8 comprises means , such as software , for initiating the gripper device cleaning procedure . however , the gripper device 5 may comprise means for transmitting signals to the control unit 8 as well . for example , the gripper device 5 may include sensing means for sensing if the surface of the gripper device 5 is too soiled to function properly and transmit an indication to the control unit 8 about this . such sensing of a soiled surface may be implemented by means of a camera and a laser source emitting laser light . the detecting device 7 described earlier may be utilised in this sensing of a soiled surface . the camera is provided to register laser light as reflected from the gripper device 5 and to thereby enable a determination of whether the surface of the gripper device 5 is soiled . the gripper device 5 may comprise an optical sensor for this end , which optical sensor presumably is as soiled as the gripper device surface in which it is arranged . alternatively , inductive sensors may be provided in the gripper device 5 for sensing a magnetic field or an inductance or a change thereof as caused by the gripper device surface being soiled . a video camera or ccd - camera may be utilised for the above sensing of a soiled surface . such camera may be fixedly arranged to take images of the gripper device 5 in the idle position , and the control unit 8 may then comprise means for processing the images or evaluating the need of cleansing in dependence on the amount of reflected light . the cleaning may also be initiated if the gripper device 5 fails to grip hold of a teat cup . sensing means for sensing such failure is then included within the gripper device 5 . such sensing means are disclosed in a patent application entitled “ detecting arrangement and method for a magnetic gripper device ”, filed on sep . 2 , 2005 , assigned to the same applicant as the present application . the control unit 8 may be programmed to initiate the cleaning procedure of the gripper device 5 in case of such teat attachment failure . further , the sensing means may also detect if the performance of the gripper device 5 is deteriorating , that is , the gripper device 5 may still be capable of holding a teat cup 2 but the grip is deteriorating . the gripper device 5 is then cleaned before a failure occurs . typically , when a teat attachment step fails , the control unit 8 of the milking machine starts a fault - localizing test . such fault - localizing tests require rather long periods of time in order to be performed , typically about 10 - 15 minutes , during which no milking can be done . in contrast , the cleaning step in accordance with the invention may be accomplished within about 5 - 10 s . therefore , should the teat attachment procedure fail , cleaning of the gripper device 5 is a fast way to eliminate the possibility of the gripper device 5 being too dirty as the cause to the failure , or a fast way to obtain a successful teat attachment in case the reason for the failure is indeed that the gripper device 5 is too dirty . the detecting device 7 , for example a camera , for determining the exact positions of the teats may need cleaning as well . the detecting device 7 is preferably cleansed regularly in order to not reduce its performance . the cleaning of the detecting device 7 may , for example , be performed by moving the robot arm 4 comprising the detecting device 7 to a cleaning position . in an embodiment of the invention , the same cleaning device is utilised for cleaning the gripper device 5 . since the cleaning of the gripper device 5 is performed in a similar manner or even by utilising the same cleaning means as is used for cleaning the detecting device 7 , a most cost - efficient cleaning of gripper devices is provided . in an embodiment of the invention , the cleaning of the gripper device 5 is performed each time cleaning of the detecting device 7 is effectuated . in particular , the cleaning device 9 may be adapted to accomplish simultaneous cleaning of the detecting device 7 and the gripper device 5 . the cleaning device 9 may comprise different cleaning members for the gripper device 5 and the detecting device 7 , respectively . the different cleaning members may then be arranged so as to allow simultaneous cleaning to be performed . the invention is also related to a corresponding method , illustrated in fig2 . the method 20 for cleaning the gripping device 5 arranged on the robot arm 4 of the milking station 1 is initiated in step 21 . the initiation may be triggered , for example , at completion of a milking occasion or at a detected failure to grip the teat cup 2 as described above . the initiation may be triggered by other means as well . in step 22 the robot arm 4 comprising the gripper device 5 is moved to a cleaning position . in the cleaning position , the robot arm 4 is in close proximity of the cleaning device 9 comprising the cleaning member 10 . finally , in step 23 , the cleaning of the gripper device 5 is carried out . the gripper device cleaning procedure may comprise any suitable ways of cleaning the gripper device 5 . for example , the gripper device cleaning procedure may comprise rubbing the gripper device 5 against a sponge , or spraying cleaning agents on the surface of the gripper device , or even a combination of the described different cleaning procedures . in the cleaning position , a detecting device 7 of the milking station 1 can also be cleaned . such step of cleaning the detecting device 7 can be effectuated before or after the cleaning of the gripper device 5 . upon completion of the gripper device cleaning procedure , the robot arm 4 may be moved to an idle position , in which the robot arm 4 is ready for a subsequent operation , such as a teat attachment procedure . the gripper device 5 is preferably an electromagnetic gripper device , but any other type of gripper device may benefit from the present invention . since electromagnetic gripper devices do not have any movable parts or open spaces wherein dirt may gather , they are particularly suitable for being cleansed by means of the invention . in the above description a milking station has been described in connection with an automatic milking system , and in particular a milking station for voluntary milking . however , the present invention may be utilised in other milking environments as well , for example in a not fully automated milking environment . for the purposes of the present invention , a milking station can be any area in which a milking animal is being milked , that is , an area arranged to house at least one animal for milking . the present invention can be implemented in any type of milking stall , for example a parallel stall arrangement or a rotary milking parlour . the term “ milking station ” is thus intended to encompass different types of milking stations . similarly , throughout the above description the term “ robot arm ” has been utilised . however , the term robot arm has been used in an illustrative embodiment of the invention , in which the term robot arm is generally used to denote a part of a milking robot . in the above description , the term “ robot arm ” could be exchanged to “ handling device ”. the handling device is intended to denote a handling device for handling teat cups and other milking related equipment . in accordance with the invention , such handling device may be the described robot arm of a milking robot , but it may alternatively be a supporting arm or service arm that can be moved in a computer - controlled manner , semi - manually or manually to a cleaning position . in summary , the present invention provides an efficient cleaning of gripper devices . the farmer is alleviated from the task of manually inspecting the gripper devices and wash them upon need . further , by regularly cleaning the gripper device the operation of the milking station is ensured and the gripper device provides at all times a firm and reliable grip of the teat cups . while the present invention has been described in various embodiments it shall be appreciated that the invention is not limited to the specific features and details set forth , but is defined only by the appended patent claims . | 0 |
as used in this application , terms such as “ front ,” “ rear ,” “ side ,” “ top ,” “ bottom ,” “ above ,” “ below ,” “ upwardly ” and “ downwardly ” are intended to facilitate the description of the electrical receptacle of the invention , and are not intended to limit the structure of the invention to any particular position or orientation . fig1 and 2 depict a jack that incorporates a first embodiment of a pcb and contact assembly according to the invention . the jack comprises a dielectric housing 10 similar to that disclosed in u . s . pat . no . 6 , 994 , 594 , which is incorporated herein by reference in its entirety . the housing has side walls 12 , a top wall 14 , a rear wall 15 , an extended bottom wall 16 and a front - opening plug - receiving cavity 18 . a wiring unit 20 is coupled to the housing 10 and includes a printed circuit board ( pcb ) 22 supported on bottom wall 16 , with its narrower front portion 23 extending through an opening in rear wall 15 into the jack interior below cavity 18 . eight wire terminals 24 are mounted on pbc 22 ( only four are visible in fig2 among posts 24 a ). wire terminals 24 are standard insulation displacement contacts ( idc ) to which standard wiring ( not shown ) can be connected and then secured under a snap - on cover 25 , which appears only in fig1 . these terminals are electrically connected via conductive traces or paths on the pcb 22 respectively to eight resilient terminal contacts 40 , which are held in place on the pcb in two offset rows of four contacts each by a dielectric contact cradle 30 secured to the pcb by adhesive or other suitable means . the preferred material for terminal contacts 40 is beryllium copper ( becu ). other suitable high - performance alloys may also be used . referring to fig3 and 4 , contact cradle 30 has a profile that matches the narrower front portion 23 of pcb 22 , and includes a semi - cylindrical post 32 on each side that mates with a corresponding semi - cylindrical recess 26 on each side of pcb 22 . contact cradle 30 has eight short openings or apertures 34 arranged in two offset rows of four apertures each . a terminal contact 40 extends from the circuit board through each aperture 34 , which is dimensioned to allow the terminal contact 40 to move freely during insertion and removal of a mating plug , i . e ., without touching the contact cradle . contact cradle 30 also has eight longer openings 36 arranged in two offset rows of four openings each . these openings are axially aligned with respective apertures 34 and overlie portions of respective terminal contacts 40 . thus , the terminal contacts 40 are arranged in two interdigitating rows of four contacts each . referring to fig5 - 7 , each terminal contact 40 has a substantially uniform thickness and three portions : a beam - like base portion 42 extending along the pcb ; a connecting portion 44 extending obliquely above the pcb through an aperture 34 for making electrical contact with the respective wire terminal of an inserted connector plug ; and a transition portion 46 interconnecting the base portion and the connecting portion . connecting portion 44 is distally curved to form a crest c and an obtuse angle , terminates in a slightly downwardly turned free end 48 , and tapers from a wider section adjacent transition portion 46 toward its narrower free end 48 . transition portion 46 is gently curved , forming an obtuse angle where it joins connecting portion 44 and base portion 42 . transition portion 46 also rests on a respective compensation coupling contact 28 of the pcb , where it is constrained against upward movement by an overlying web 38 of the contact cradle between opening 36 and aperture 34 . a majority of the length of the base portion 42 lies substantially parallel to the pcb 22 . the tail end 47 of the base portion is constrained by a shoulder 39 of the contact cradle at the end of opening 36 . constraining shoulder 39 can be configured to permit limited upward movement of tail end 47 during insertion of a mating plug , or alternatively configured to prevent any upward movement of tail end 47 . the base portion 42 makes electrical contact with a respective wire terminal 24 via the pcb conductive traces or paths in a known manner . see fig4 , which schematically shows a representative pcb trace 49 extending from one terminal contact 40 . alternatively , the transition portion 46 can communicate electrically with a respective wire terminal 24 via its respective compensation coupling contact 28 and an associated pcb trace 49 . compensation coupling contact 28 serves as a fulcrum about which the connecting portion 44 of the terminal contact pivots during connector plug insertion and removal . accordingly , during pivoting motion of the connecting portion 44 , the unconstrained section of the base portion 42 ( between web 38 and shoulder 39 ) flexes , thus distributing bending stresses throughout the length of the contact and minimizing stress concentrations . the non - uniform width of the terminal contact 40 , depicted in fig7 , results in controlled bending and also contributes to proper distribution of bending stresses . transition portion 46 , which is the widest and overlies fulcrum 28 , flexes the least . base portion 42 tapers substantially continuously from there to its tail end 47 , which is about half the width of transition portion 46 . connecting portion 44 tapers substantially continuously from transition portion 46 toward the even narrower free end 48 . relative stress levels during deflection are depicted in fig6 : lighter shading represents higher stress ; darker shading represents lower stress . this distribution of stresses allows for proper generation of normal contact force between the mating conductors , while reducing permanent contact set and the potential for contact failure . compensation ( e . g ., capacitive ) elements 50 on or in the pcb ( only one representative element 50 is schematically shown in fig4 ) communicate with respective compensation coupling contacts 28 . the electrical connection between the transition portion 44 and the compensation coupling contact 28 enables the application of a crosstalk compensation signal to the terminal contact 40 at its fulcrum point . this location is a very short distance — on the order of about 0 . 080 in .— from the crest c of the connecting portion 44 , where the electrical interface ( point of contact ) forms between the terminal contact 40 and the wire terminal of a fully inserted conductor plug . accordingly , the amount of compensation required to counteract objectionable crosstalk is minimized , resulting in improved electrical performance . the embodiment of fig8 - 10 incorporates a somewhat different contact anchoring system to achieve substantially the same improved electrical performance in a reliable jack connector . in this embodiment , the jack housing 10 is the same as that illustrated in fig2 ; the wiring unit 20 includes the same wire terminals 24 mounted on a pcb ; and the resilient terminal contacts are arranged in two interdigitating rows of four contacts each . however , the pcb 122 does not have a contact cradle attached to it . instead , the two rows of contacts 140 are fixed relative to the pcb by two elastomeric members 134 , 136 , which are fitted to the pcb ( e . g ., bonded ) in mating openings 124 , 126 substantially in the plane of the pcb . the entire length of the connecting portion 144 of each terminal contact is exposed above the pcb . the elastomeric members 134 , 136 preferably are made of neoprene ( poly - chloroprene ) having a durometer hardness of about 40 ( shore a ). other synthetic or natural rubber materials would also be suitable . as in the first embodiment , the connecting portion 144 of each terminal contact 140 tapers toward its free end 148 , is distally curved to form a crest c and an obtuse angle , and terminates in a slightly downwardly turned free end 148 . the straight base portion 142 is narrower than the transition portion 146 and is embedded in the elastomeric member 134 ( or 136 ). the transition portion 146 makes electrical contact with a respective wire terminal 24 via its respective compensation coupling contact 128 and an associated pcb conductive trace or path ( not shown ) in a known manner . the transition portion 146 of this embodiment has two gentle reverse bends forming obtuse angles . one bend overlies a respective compensation coupling contact 128 on the pcb , which also communicates with a respective compensation element 150 ( only one representative element 150 is schematically shown in fig9 ). as illustrated in fig1 , the terminal contacts 140 in their relaxed ( undeflected ) state are spaced from the compensation coupling contacts 128 , and make an electrical connection with those contacts only when the terminal contacts deflect upon insertion of a mating plug . it is also possible to configure the assembly such that the terminal contacts 140 always engage the compensation coupling contacts 128 . assembly of the jack of the second embodiment involves first embedding the terminal contacts 140 , in their proper parallel positions , in the elastomeric members 134 , 136 , leaving the connecting portions 144 exposed . the elastomeric members are then fitted to the pcb 122 in openings 124 , 126 . fitting of the elastomeric members may involve , for example , bonding the elastomeric members to the pcb and / or engaging mating structures ( e . g ., ribs and grooves ) on the elastomeric members and in the openings 124 , 126 . the assembled pcb is then installed in the jack housing 10 . the eight - position eight - contact ( 8p8c ) jacks of the above two embodiments have been chosen as examples that illustrate the principles of the invention . it should be understood by those skilled in the art that the invention can encompass jacks having a different number and / or arrangement of contacts , and that other changes and modifications may be made without departing from the scope of the invention as defined by the appended claims . | 8 |
in one embodiment of the invention , r 1 represents tert - butyl . in one embodiment of the invention , r 1 represents hydrogen , halogen ( e . g . f or cl ) or halogen - substituted phenyl ( e . g . f — c 6 h 4 —). in one embodiment of the invention , r 12 represents c 1 - 6 - fluoroalkyl . in a further embodiment of the invention , r 12 represents trifluoromethyl . in another embodiment of the invention , r 1 and r 2 together with the benzene ring , or , with the proviso that m is 0 , r 2 and r 3 together with the benzene ring or r 3 and r 4 together with the benzene ring form a 9 - 11 - membered bicyclic ring system which may be fully conjugated or partly saturated , and which may optionally be substituted with one or more substituents selected among halogen , hydroxy , nitro , cyano , c 1 - 6 alkyl , c 1 - 6 - alkenyl , c 1 - 6 alkynyl , c 3 - 8 cycloalkyl , c 4 - 8 cycloalkenyl , c 1 - 6 alkoxy , c 1 - 6 haloalkoxy and c 1 - 6 - haloalkyl . in a further embodiment of the invention , r 1 and r 2 together with the benzene ring form a naphthalene ring system . in a still further embodiment of the invention , r 2 represents halogen ( e . g . cl ). in yet another embodiment of the invention , m is 0 , and r 3 and r 4 together with the benzene ring form a tetrahydronaphthalene ring system . in another embodiment of the invention , m is 0 , and r 3 and r 4 together with the benzene ring form an indane ring system . in a further embodiment of the invention , m is 0 , and r 3 represents — sr 17 , — s ( o ) r 17 or — s ( o ) 2 r 17 ; in a further aspect of the latter embodiment of the invention , r 17 represents arylc 1 - 6 alkyl ( e . g . benzyl ). in yet another embodiment of the invention , m is 0 , and r 3 represents — sch 3 , — s ( o ) ch 3 or — s ( o ) 2 ch 3 . in a still further embodiment of the invention , m is 0 , and r 3 represents — or 17 . in another embodiment of the invention , m is 0 , and r 3 represents — nh 2 , — nh — cor 17 or — nh — s ( o ) 2 r 17 . in another embodiment of the invention , m is 0 , and r 3 represents chlorine or fluorine . in a further embodiment of the invention , m is 0 , and r 3 represents — s ( o ) 2 nr 17 r 18 ; in a further aspect of the latter embodiment of the invention , nr 17 r 18 represents morpholin - 4 - yl . in another embodiment of the invention , m is 0 , and r 3 represents optionally substituted aryl or heteroaryl . in a further embodiment of the invention , m is 0 , and r 3 represents optionally substituted aryl . in a still further embodiment of the invention , m is 0 , and r 3 represents optionally substituted phenyl . in one aspect of the latter embodiment , r 3 is phenyl substituted with one or more substituents selected among halogen , cyano , c 1 - 6 alkyl , c 1 - 6 haloalkyl , c 1 - 6 haloalkoxy , c 1 - 6 alkoxy , — s ( o ) p r 17 and — c ( o )— r 17 , wherein p and r 17 are as defined above . in another embodiment of the invention , r 4 represents halogen ( e . g . cl ) or hydroxy . in still another embodiment of the invention , r 1 represents tert - butyl , and r 4 represents c 1 - 6 alkyl . in yet another embodiment of the invention , one substituent among r 5 , r 6 and r 7 represents — s ( o ) 2 cf 3 , and one of the remaining substituents among r 5 , r 6 and r 7 represents chloro . in a further embodiment of the invention , one substituent among r 5 , r 6 and r 7 represents 4 - trifluoromethylsulfonyl , and one of the remaining substituents among r 5 , r 6 and r 7 represents 2 - chloro . in a further aspect of this latter embodiment , the single remaining substituent among r 5 , r 6 and r 7 represents hydrogen . specific , individual embodiments of compounds according to the present invention include each of the following compounds : 5 - tert - butyl - 3 ′, 5 ′- difluoro - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 4 - hydroxy - 2 - methyl - 4 ′- trifluoromethoxy - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 4 - hydroxy - 2 - methyl - 3 ′- trifluoromethyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 3 - bromo - 5 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - hydroxy - 2 - methyl - benzamide ; 5 - tert - butyl - 4 ′- fluoro - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 4 - hydroxy - 2 - methyl - 4 ′- methylsulfanyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 3 ′, 4 ′- difluoro - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 4 ′- cyano - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 3 - bromo - 5 - tert - butyl - n -( 3 - chloro - 4 - trifluoromethylsulfanyl - phenyl )- 6 - hydroxy - 2 - methyl - benzamide ; 5 - tert - butyl - 3 ′, 4 ′- difluoro - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 3 - chloro - 4 - trifluoromethylsulfanyl - phenyl )- amide ; 5 - tert - butyl - 3 ′- chloro - 4 ′- fluoro - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 4 ′- fluoro - 4 - hydroxy - 2 , 3 ′- dimethyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 3 - chloro - 5 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - hydroxy - 2 - methyl - benzamide ; 5 - tert - butyl - 4 - hydroxy - 4 ′- methanesulfonyl - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 3 ′, 4 ′- difluoro - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 3 - chloro - 4 - trifluoromethanesulfinyl - phenyl )- amide ; 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 3 - trifluoromethanesulfonyl - phenyl )- amide ; 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 3 - trifluoromethylsulfanyl - phenyl )- amide ; 2 - hydroxy - naphthalene - 1 - carboxylic acid ( 3 - trifluoromethanesulfonyl - phenyl )- amide ; 3 - hydroxy - naphthalene - 2 - carboxylic acid ( 3 - trifluoromethanesulfonyl - phenyl )- amide ; 1 - hydroxy - 5 , 6 , 7 , 8 - tetrahydro - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 1 - hydroxy - 5 , 6 , 7 , 8 - tetrahydro - naphthalene - 2 - carboxylic acid ( 4 - trifluoromethylsulfanyl - phenyl )- amide ; 4 - benzenesulfonyl - 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 4 - trifluoromethylsulfanyl - phenyl )- amide ; 4 - chloro - 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 4 - trifluoromethylsulfanyl - phenyl )- amide ; 3 - adamantan - 1 - yl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 5 - methyl - benzamide ; 4 - chloro - 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 5 - methyl - benzamide ; 4 - chloro - 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 3 - chloro - 4 - trifluoromethylsulfanyl - phenyl )- amide ; 3 - adamantan - 1 - yl - n -( 3 - chloro - 4 - trifluoromethylsulfanyl - phenyl )- 2 - hydroxy - 5 - methyl - benzamide ; 3 - adamantan - 1 - yl - n -( 3 - chloro - 4 - trifluoromethylsulfanyl - phenyl )- 2 - hydroxy - 5 - methyl - benzamide ; 6 - adamantan - 1 - yl - 5 - hydroxy - indan - 4 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 4 -( 4 - fluoro - phenylsulfanyl )- 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - adamantan - 1 - yl - 2 ′, 4 ′- difluoro - 4 - hydroxy - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 4 -( 4 - fluoro - benzenesulfinyl )- 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 2 ′, 4 ′- difluoro - 4 - hydroxy - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 2 ′, 4 ′- difluoro - 4 - hydroxy - 5 -( 1 - methyl - cyclohexyl )- biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 4 -( 4 - ethanesulfonyl - phenyl )- 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 1 - hydroxy - 4 -( 4 - methoxy - phenyl )- naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 4 -( 4 - fluoro - phenyl )- 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 1 - hydroxy - 4 - p - tolyl - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 4 -( 4 - cyano - phenyl )- 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 4 -( 3 , 5 - difluoro - phenyl )- 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 1 - hydroxy - 4 -( 3 - trifluoromethyl - phenyl )- naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 4 -( 4 - acetyl - phenyl )- 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 2 - hydroxy - 5 - methyl - 3 -( 1 , 1 , 2 , 2 - tetramethyl - propyl )- n -( 4 - trifluoromethanesulfonyl - phenyl )- benzamide ; 4 ′- bromo - 5 - tert - butyl - 4 - hydroxy - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 2 ′, 4 ′- difluoro - 4 - hydroxy - biphenyl - 3 - carboxylic acid ( 4 - trifluoromethanesulfonyl - phenyl )- amide ; 2 ′, 4 ′- difluoro - 4 - hydroxy - 5 -( 1 - methyl - cyclopentyl )- biphenyl - 3 - carboxylic acid ( 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 -( 1 , 1 - dimethyl - propyl )- 2 ′, 4 ′- difluoro - 4 - hydroxy - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 -( 1 - cyclopropyl - 1 - methyl - ethyl )- 2 ′, 4 ′- difluoro - 4 - hydroxy - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - chloro - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 3 -( 1 , 1 - dimethyl - propyl )- 2 - hydroxy - benzamide ; n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 5 - methanesulfonyl - 3 -( 1 , 1 , 2 , 2 - tetramethyl - propyl )- benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 5 - methanesulfonyl - 6 - methyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - ethyl - 2 - hydroxy - benzamide ; 3 , 5 - di - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - ethyl - 6 - hydroxy - benzamide ; 6 - tert - butyl - 5 - hydroxy - indan - 4 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 - methylsulfanyl - benzamide ; 3 - tert - butyl - 2 - hydroxy - 5 , 6 , 7 , 8 - tetrahydro - naphthalene - 1 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 5 - methanesulfinyl - 6 - methyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 5 - methoxy - benzamide 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - isopropyl - benzamide 5 - tert - butyl - 3 ′, 5 ′- difluoro - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 4 ′- fluoro - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 3 ′, 5 ′- difluoro - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 3 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 4 ′- fluoro - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 3 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 5 - fluoro - 2 - hydroxy - 6 - methyl - benzamide ; 3 - tert - butyl - 5 - chloro - n -( 3 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 5 - iodo - 6 - methyl - benzamide ; 3 - tert - butyl - 5 - chloro - 2 - hydroxy - 6 - methyl - n -( 4 - trifluoromethanesulfonyl - phenyl )- benzamide ; 5 - tert - butyl - 3 ′, 4 ′- difluoro - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 3 ′, 4 ′- difluoro - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid □( 3 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 4 - hydroxy - 4 ′- methoxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 5 -( 5 - cyano - thiophen - 2 - yl )- 2 - hydroxy - 6 - methyl - benzamide ; 5 - tert - butyl - 4 ′- dimethylsulfamoyl - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 4 - hydroxy - 2 - methyl - 4 ′-( morpholine - 4 - sulfonyl )- biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 3 - 1 , 3 - benzodioxol - 5 - yl - 5 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - hydroxy - 2 - methyl - benzamide ; 5 - tert - butyl - 4 - hydroxy - 3 ′- methoxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 4 -( 3 , 4 - difluorophenyl )- 1 - hydroxynaphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; 1 - hydroxy - 4 -( 4 - trifluoromethylphenyl ) naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; 1 - hydroxy - 4 -( 3 - methoxyphenyl ) naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; 4 - bromo - 1 - hydroxynaphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; 5 - bromo - 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxybenzamide ; 5 - tert - butyl - 3 ′, 4 ′- difluoro - 4 - hydroxybiphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; 5 - tert - butyl - 4 ′- fluoro - 4 - hydroxybiphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; 5 - tert - butyl - 3 ′, 5 ′- difluoro - 4 - hydroxybiphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; 3 , 5 - di - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxybenzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxy - 6 - methylbenzamide ; 1 - hydroxy - 3 - methylnaphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethane - sulfonylphenyl ) amide ; 4 - bromo - 1 - hydroxy - 3 - methylnaphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; 3 - bromo - 5 - tert - butyl - 6 - hydroxy - 2 - methyl - n -( 2 - nitro - 4 - trifluoromethanesulfonyl - phenyl )- benzamide ; 5 - tert - butyl - 3 ′- fluoro - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 ′- tert - butyl - 3 ′-( 2 - chloro - 4 - trifluoromethanesulfonyl - phenylcarbamoyl )- 4 ′- hydroxy - 2 ′- methyl - biphenyl - 3 - carboxylic acid methyl ester ; 3 - tert - butyl - n -( 3 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 5 - fluoro - 2 - hydroxy - 6 - methyl - benzamide ; 3 - tert - butyl - 5 - chloro - n -( 2 - dimethylamino - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - benzamide ; 3 - tert - butyl - 5 - chloro - n -( 2 - dipropylamino - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - benzamide ; 3 - tert - butyl -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 -( morpholine - 4 - sulfonyl )- benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 5 - dimethylsulfamoyl - 2 - hydroxy - 6 - methyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 5 - dimethylsulfamoyl - 2 - hydroxy - 6 - methyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - ethyl - 2 - hydroxy - 5 - methylsulfanyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - ethyl - 2 - hydroxy - 5 - methanesulfinyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - ethyl - 2 - hydroxy - 5 - methanesulfonyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - isopropyl - 5 - methylsulfanyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - isopropyl - 5 - methanesulfinyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - isopropyl - 5 - methanesulfonyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 -( 2 , 2 , 2 - trifluoro - ethylsulfanyl )- benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 5 - trifluoromethylsulfanyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 5 - isopropylsulfanyl - 6 - methyl - benzamide ; 5 - tert - butoxy - 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - ethyl - 2 - hydroxy - 5 - methoxy - benzamide ; n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 3 - isopropyl - 6 - methyl - 5 - methylsulfanyl - benzamide ; n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 3 - isopropyl - 5 - methanesulfinyl - 6 - methyl - benzamide ; n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 3 - isopropyl - 6 - methyl - 5 - methylsulfonyl - benzamide ; 3 - tert - butyl - n -( 2 - methoxy - 4 - trifluoromethanesulfonyl - phenyl )- 6 - methyl - 2 - hydroxy - 5 - methylsulfanyl - benzamide ; 3 - tert - butyl - n -( 2 - methoxy - 4 - trifluoromethanesulfonyl - phenyl )- 6 - methyl - 2 - hydroxy - 5 - methanesulfinyl - benzamide ; 3 - tert - butyl - n -( 2 - cyano - 4 - trifluoromethanesulfonyl - phenyl )- 6 - methyl - 2 - hydroxy - 5 - methanesulfonyl - benzamide ; 3 - tert - butyl - n -( 2 - cyano - 4 - trifluoromethanesulfonyl - phenyl )- 6 - methyl - 2 - hydroxy - 5 - fluoro - benzamide ; 3 - tert - butyl - n -( 2 - methyl - 4 - trifluoromethanesulfonyl - phenyl )- 6 - methyl - 2 - hydroxy - 5 - fluoro - benzamide ; 3 - tert - butyl - n -( 2 - methoxy - 4 - trifluoromethanesulfonyl - phenyl )- 6 - methyl - 2 - hydroxy - 5 - fluoro - benzamide ; 3 - tert - butyl - n -( 2 - cyano - 4 - trifluoromethanesulfonyl - phenyl )- 6 - methyl - 2 - hydroxy - 5 - chloro - benzamide ; 3 - tert - butyl - n -( 2 - methyl - 4 - trifluoromethanesulfonyl - phenyl )- 6 - methyl - 2 - hydroxy - 5 - chloro - benzamide ; 3 - tert - butyl - n -( 2 - methoxy - 4 - trifluoromethanesulfonyl - phenyl )- 6 - methyl - 2 - hydroxy - 5 - chloro - benzamide ; 3 - tert - butyl - n -( 2 - cyano - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 - methylsulfanyl - benzamide ; 3 - tert - butyl - 2 - hydroxy - 6 - methyl - 5 - methylsulfanyl - n -( 2 - methyl - 4 - trifluoromethanesulfonyl - phenyl )- benzamide ; n -( 2 - bromo - 4 - trifluoromethanesulfonyl - phenyl )- 3 - tert - butyl - 2 - hydroxy - 6 - methyl - 5 - methylsulfanyl - benzamide ; 3 - tert - butyl - n -( 2 - cyano - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 - methylsulfinyl - benzamide ; 3 - tert - butyl - 2 - hydroxy - 6 - methyl - 5 - methylsulfinyl - n -( 2 - methyl - 4 - trifluoromethanesulfonyl - phenyl )- benzamide ; n -( 2 - bromo - 4 - trifluoromethanesulfonyl - phenyl )- 3 - tert - butyl - 2 - hydroxy - 6 - methyl - 5 - methylsulfinyl - benzamide ; 3 - tert - butyl - n -( 2 - cyano - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 5 - methoxy - 6 - methyl - benzamide ; 3 - tert - butyl - 2 - hydroxy - 5 - methoxy - 6 - methyl - n -( 2 - methyl - 4 - trifluoromethanesulfonyl - phenyl )- benzamide ; n -( 2 - bromo - 4 - trifluoromethanesulfonyl - phenyl )- 3 - tert - butyl - 2 - hydroxy - 5 - methoxy - 6 - methyl - benzamide ; n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 3 - tert - butyl - 2 - hydroxy - 5 - methoxy - 6 - methyl - benzamide ; 1 - hydroxy - 3 - methyl - 4 - methylsulfanyl - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 1 - hydroxy - 4 - methanesulfinyl - 3 - methyl - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 1 - hydroxy - 4 - methanesulfonyl - 3 - methyl - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; and 4 - chloro - 1 - hydroxy - 3 - methyl - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide . further individual embodiments of compounds according to the present invention include each of the following compounds : 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methoxy - benzamide ; 6 - tert - butyl - 5 - hydroxy - 2 , 3 - dihydro - benzofuran - 4 - carboxylic acid ( 2 - chloro - 4 - trifluoromethane - sulfonyl - phenyl )- amide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 , 5 - dihydroxy - 6 - methyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 , 5 - dihydroxy - 6 - methoxy - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 , 6 - dihydroxy - 5 - methoxy - benzamide ; 3 , 5 - di - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 , 6 - dihydroxy - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 5 - cyano - 2 - hydroxy - 6 - methyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 -( 4 - methyl - piperazine - 1 - sulfonyl )- benzamide ; n -( 2 - bromo - 4 - trifluoromethanesulfonyl - phenyl )- 3 - tert - butyl - 5 - fluoro - 2 - hydroxy - 6 - methyl - benzamide ; 3 - acetyl - 5 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - hydroxy - 2 - methyl - benzamide ; 3 - acetyl - 5 - tert - butyl - 6 - hydroxy - n -( 2 - methoxy - 4 - trifluoromethanesulfonyl - phenyl )- 2 - methyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 - nitro - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 -( toluene - 4 - sulfonylamino )- benzamide ; 3 - amino - 5 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - hydroxy - 2 - methyl - benzamide ; 3 - acetylamino - 5 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - hydroxy - 2 - methyl - benzamide ; 1 - hydroxy - 4 -( 4 - methoxyphenyl ) naphthalene - 2 - carboxylic acid ( 2 - methyl - 4 - trifluoromethanesulfonylphenyl ) amide ; 4 -( 4 - fluorophenyl )- 1 - hydroxynaphthalene - 2 - carboxylic acid ( 4 - trifluoromethanesulfonylphenyl ) amide ; 4 -( 4 - fluorophenyl )- 1 - hydroxynaphthalene - 2 - carboxylic acid ( 2 - methyl - 4 - trifluoromethanesulfonylphenyl ) amide ; 1 - hydroxynaphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; 1 - hydroxy - 8 - methylnaphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl ) amide ; n -( 3 - chloro - 5 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - benzamide ; 3 - benzylsulfanyl - 5 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - hydroxy - 2 - methyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 - propylsulfanyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 -( propane - 1 - sulfinyl )- benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 - phenylmethanesulfinyl - benzamide ; 3 - tert - butyl - 5 - chloro - 2 - hydroxy - 6 - methyl - n -( 2 - propyl - 4 - trifluoromethanesulfonyl - phenyl )- benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 5 - isobutylsulfanyl - 6 - methyl - benzamide ; 3 - tert - butyl - 5 - chloro - n -( 2 - ethyl - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 - phenylmethanesulfonyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 -( propane - 1 - sulfonyl )- benzamide ; 5 - tert - butyl - 4 ′- cyano - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - methyl - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 4 ′- cyano - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - ethyl - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 5 - tert - butyl - 4 ′- cyano - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - cyano - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 -( propane - 2 - sulfonyl )- benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 -( propane - 2 - sulfinyl )- benzamide ; 5 - tert - butyl - 4 ′- cyano - 4 - hydroxy - 2 - methyl - biphenyl - 3 - carboxylic acid ( 2 - propyl - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 3 - tert - butyl - 5 - chloro - n -( 3 - cyano - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - benzamide ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 -( 2 - methyl - propane - 1 - sulfinyl )- benzamide ; n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxy - 3 - isopropyl - 6 - methylbenzamide ; n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxy - 6 - methylbenzamide ; 5 - chloro - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxybenzamide ; n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxy - 6 - isopropyl - 3 - methylbenzamide ; n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 5 - fluoro - 2 - hydroxybenzamide ; 3 - chloro - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 6 - hydroxy - 5 - isopropyl - 2 - methylbenzamide ; 3 - chloro - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 6 - hydroxy - 2 - methylbenzamide ; 3 , 5 - dichloro - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxy - 6 - methylbenzamide ; 3 - chloro - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 6 - hydroxy - 2 - isopropyl - 5 - methylbenzamide ; n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxy - 3 , 4 , 6 - trimethylbenzamide ; 4 - chloro - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxybenzamide ; 2 - hydroxybiphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 , 3 , 4 , 5 - tetrafluoro - 6 - hydroxybenzamide ; 5 - tert - butyl - 4 - hydroxy - 2 - methylbiphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 3 , 5 - difluoro - 2 - hydroxybenzamide ; 3 ′, 5 ′- difluoro - 4 - hydroxy - 2 - methylbiphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; 4 ′- cyano - 4 - hydroxy - 2 - methylbiphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 4 - fluoro - 2 - hydroxybenzamide ; 3 ′, 5 ′- difluoro - 4 - hydroxy - 5 - isopropyl - 2 - methylbiphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; 3 - tert - butyl - 6 - chloro - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxybenzamide ; 3 - tert - butyl - 6 - chloro - 2 - hydroxy - n -( 2 - methyl - 4 - trifluoromethanesulfonylphenyl ) benzamide ; 5 - chloro - 2 - hydroxy - 4 - methylbiphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; 5 - chloro - 4 ′- fluoro - 2 - hydroxy - 4 - methylbiphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ; n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - hydroxy - 2 , 4 - dimethyl - 3 - methylsulfanyl - benzamide ; n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - hydroxy - 3 - methanesulfinyl - 2 , 4 - dimethyl - benzamide ; 3 - tert - butyl - 5 - tert - butylsulfanyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - benzamide ; 3 - tert - butyl - 5 - tert - butylsulfinyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - benzamide ; 3 - tert - butyl - 5 - tert - butylsulfonyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - benzamide ; n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 , 3 - difluoro - 6 - hydroxy - 5 - methyl - benzamide ; 4 -( 4 - dimethylamino - phenyl )- 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ; 2 , 5 - di - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - hydroxy - 3 - methoxy - benzamide ; 6 - tert - butyl - 2 -[( 2 - chloro - 4 - trifluoromethanesulfonyl - phenylamino )- hydroxy - methyl ]- 3 , 4 - dimethoxy - phenol ; 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 , 6 - dihydroxy - benzamide ; and 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - isopropyl - 5 - methoxy - benzamide . compounds according to formula i may comprise chiral carbon atoms , chiral sulfur atoms or carbon - carbon double bonds which may give rise to stereoisomeric forms , e . g . enantiomers , diastereomers and / or geometric isomers . the present invention relates to all such isomers , either in pure form or as mixtures thereof . pure isomeric forms may either be prepared from intermediates which are pure isomers themselves , by purification of a mixture of isomers after the synthesis , or by a combination of the two methods . purification of isomeric forms is well known in the art , e . g . as described by jaques in enantiomers , racemates and resolution , wiley , 1981 . the compounds of the present invention are useful in the treatment of diseases or states that benefit from an increase in the mitochondrial respiration . the compounds of the present invention are believed to be particular well - suited for the treatment of obesity as such or preventing weight gain and for the treatment of conditions , diseases or disorders where obesity is involved in the etiology . in one embodiment , the invention thus provides a method of treating the metabolic syndrome , insulin resistance , dyslipidemia , hypertension , obesity , type 2 diabetes , type 1 diabetes , diabetic late complications including cardiovascular diseases , cardiovascular disorders , disorders of lipid metabolism , neurodegenerative and psychiatric disorders , dysregulation of intraocular pressure including glaucoma , atherosclerosis , hypertension , coronary heart disease , gallbladder disease , osteoarthritis or cancer . more specifically such conditions include the metabolic syndrome , type 2 diabetes ( especially in obese patients ), diabetes as a consequence of obesity , insulin resistance , hyperglycemia , prandial hyperglycemia , hyperinsulinemia , impaired glucose tolerance ( igt ), impaired fasting glucose ( ifg ), increased hepatic glucose production , type 1 diabetes , lada , pediatric diabetes , dyslipidemia ( especially in obese patients ), diabetic dyslipidemia , hyperlipidemia , hypertriglyceridemia , hyperlipoproteinemia , micro -/ macroalbuminuria , nephropathy , retinopathy , neuropathy , diabetic ulcers , cardiovascular diseases , arteriosclerosis , coronary artery disease , cardiac hypertrophy , myocardial ischemia , heart insufficiency , congestional heart failure , stroke , myocardial infarction , arrhythmia , decreased blood flow , erectile dysfunction ( male or female ), myopathy , loss of muscle tissue , muscle wasting , muscle catabolism , osteoporosis , decreased linear growth , neurodegenerative and psychiatric disorders , alzheimers disease , neuronal death , impaired cognitive function , depression , anxiety , eating disorders , appetite regulation , migraine , epilepsia , addiction to chemical substances , disorders of intraocular pressure , bacterial infections , mycobacterial infections . in the present context cancer is intended to include forms such as hematological cancer , e . g . leukemia , acute myeloid leukemia , chronic myeloid leukemia , chronic lymphatic leukemia , myelodysplasia , multiple myeloma , hodgkin &# 39 ; s disease , or solid tumor forms , such as fibrosarcom , small or non - small cell long carcinoma , gastric , intestinal or colorectal cancer , prostate , endometrial , ovarian or breast cancer , brain , head or neck cancer , cancer in the urinary tract , such as kidney or bladder cancer , malignant melanoma , liver cancer , uterine and pancreatic cancer . in another embodiment , the invention relates to the use of a chemical uncoupler compound according to the present invention for maintaining a weight loss . the use of compounds according to the present invention in the treatment of obesity may very likely reduce or eliminate side - effects such as irritation of the skin , glaucoma , etc ., that are known to occur in connection with treatment of obesity with dnp and other chemical uncouplers that have narrow safety windows . uncouplers may also reduce insulin release from β - cells , and may thus be useful in providing β - cell rest . inducing β - cell rest may be useful in connection with β - cell transplantation , and it has also been described that inducing β - cell rest may be useful in preventing diabetes . obesity drugs which regulate the appetite and reduce food intake often suffer from lack of long - term efficiency in terms of body weight loss because the body in response to the treatment lowers the rate of the metabolism . in contrast hereto , compounds of the present invention increase the metabolism , and they are therefore believed to be particularly suited for maintaining a weight loss . compounds of the present invention are also believed to be particularly well suited for the treatment of conditions , diseases or disorders where reactive oxygen species are involved in the etiology , and wherein a reduction in the amount of reactive oxygen species is beneficial . in one embodiment , the invention thus provides a method of treating , and in particular preventing , ageing and damage to the heart , endothelial cells and neuronal tissue , diabetic microvascular diseases in the retina , the renal glomerus and the peripheral nerve cells , the method comprising administering to a patient in need thereof a therapeutically effective amount of one or more compound of the present invention to a patient need thereof . the subject ( patient ) may be any mammal suffering from a condition benefiting from increased mitochondrial respiration . such mammals may include , for instance , horses , cows , sheep , pigs , mice , rats , dogs , cats , primates such as chimpanzees , gorillas and rhesus monkeys , and , in particular , humans . it is well - known that many compounds used to combat insects or parasites , i . e . insecticides or parasiticides , respectively , are chemical uncouplers . it is thus believed that chemical uncoupler compounds according to the present invention may be useful as insecticides or parasiticides . in methods of the present invention , a compound of the present invention may be administered alone or in combination with one or more other therapeutically active compounds , either concomitantly or sequentially , and in any suitable ratios . such other therapeutically active compounds may , for example , be selected from antidiabetic agents , antihyperlipidemic agents , antiobesity agents , antihypertensive agents and agents for the treatment of complications resulting from , or associated with , diabetes . suitable antidiabetic agents include insulin , glp - 1 ( glucagon like peptide - 1 ) derivatives such as those disclosed in wo 98 / 08871 ( novo nordisk a / s ), the contents of which are incorporated herein by reference , as well as orally active hypoglycemic agents . suitable orally active hypoglycemic agents include imidazolines , sulfonylureas , biguanides , meglitinides , oxadiazolidinediones , thiazolidinediones , insulin sensitizers , α - glucosidase inhibitors , agents acting on the atp - dependent potassium channel of the pancreatic 1 - cells , e . g . potassium channel openers such as those disclosed in wo 97 / 26265 , wo 99 / 03861 and wo 00 / 37474 ( novo nordisk a / s ), the contents of all of which are incorporated herein by reference , potassium channel openers such as ormitiglinide , potassium channel blockers such as nateglinide or bts - 67582 , glucagon antagonists such as those disclosed in wo 99 / 01423 and wo 00 / 39088 ( novo nordisk a / s and agouron pharmaceuticals , inc . ), the contents of both of which are incorporated herein by reference , glp - 1 agonists such as those disclosed in wo 00 / 42026 ( novo nordisk a / s and agouron pharmaceuticals , inc . ), the contents of which are incorporated herein by reference , dpp - iv ( dipeptidyl peptidase - iv ) inhibitors , ptpase ( protein tyrosine phosphatase ) inhibitors , glucokinase activators , such as those described in wo 02 / 08209 to hoffmann la roche , inhibitors of hepatic enzymes involved in stimulation of gluconeogenesis and / or glycogenolysis , glucose uptake modulators , gsk - 3 ( glycogen synthase kinase - 3 ) inhibitors , compounds modifying the lipid metabolism such as antihyperlipidemic agents and antilipidemic agents , compounds lowering food intake , and ppar ( peroxisome proliferator - activated receptor ) and rxr ( retinoid x receptor ) agonists such as alrt - 268 , lg - 1268 or lg - 1069 . in one embodiment of a method of the invention , a compound of the present invention may be administered in combination with insulin or an insulin analogue . in a further embodiment , a compound of the present invention may be administered in combination with a sulfonylurea , e . g . tolbutamide , chlorpropamide , tolazamide , glibenclamide , glipizide , glimepiride , glicazide or glyburide . in another embodiment , a compound of the present invention may be administered in combination with a biguanide , e . g . metformin . in yet another embodiment of a method of the present invention , a compound of the present invention may be administered in combination with a meglitianide , e . g . repaglinide or senaglinide / nateglinide . in a still further embodiment , a compound of the present invention may be administered in combination with a thiazolidinedione insulin sensitizer , e . g . troglitazone , ciglitazone , pioglitazone , rosiglitazone , isaglitazone , darglitazone , englitazone , cs - 011 / ci - 1037 or t 174 , or a compound disclosed in wo 97 / 41097 ( e . g . 5 -[[ 4 -[ 3 - methyl - 4 - oxo - 3 , 4 - dihydro - 2 - quinazolinyl ]- methoxy ] phenylmethyl ] thiazolidine - 2 , 4 - dione ), wo 97 / 41119 , wo 97 / 41120 , wo 00 / 41121 or wo 98 / 45292 , the contents of all of which are incorporated herein by reference . in another embodiment , a compound of the present may be administered in combination with an insulin sensitizer such as , e . g ., gi 262570 , ym - 440 , mcc - 555 , jtt - 501 , ar - h039242 , krp - 297 , gw - 409544 , cre - 16336 , ar - h049020 , ly510929 , mbx - 102 , clx - 0940 , gw - 501516 or a compound disclosed in wo 99 / 19313 ( nn622 / drf - 2725 ), wo 00 / 50414 , wo 00 / 63191 , wo 00 / 63192 , wo 00 / 63193 and wo 00 / 23425 , wo 00 / 23415 , wo 00 / 23451 , wo 00 / 23445 , wo 00 / 23417 , wo 00 / 23416 , wo 00 / 63153 , wo 00 / 63196 , wo 00 / 63209 , wo 00 / 63190 or wo 00 / 63189 , the contents of all of which are incorporated herein by reference . in one embodiment , a compound of the present invention may be administered in combination with an α - glucosidase inhibitor , e . g . voglibose , emiglitate , miglitol or acarbose . in a further embodiment , a compound of the present invention may be administered in combination with a glycogen phosphorylase inhibitor , e . g . a compound as described in wo 97 / 09040 . in another embodiment , a compound of the present invention may be administered in combination with a glucokinase activator . in one embodiment , a compound of the present invention may be administered in combination with an agent acting on the atp - dependent potassium channel of the pancreatic β - cells , e . g . tolbutamide , glibenclamide , glipizide , glicazide , bts - 67582 or repaglinide . in another embodiment , a compound of the present invention may be administered in combination with nateglinide . in one embodiment , a compound of the present invention may be administered in combination with an antihyperlipidemic agent or an antilipidemic agent , e . g . cholestyramine , colestipol , clofibrate , gemfibrozil , lovastatin , pravastatin , simvastatin , probucol or dextrothyroxine . in another embodiment , a compound of the present invention may be administered in combination with more than one of the above - mentioned compounds , e . g . in combination with : metformin and a sulfonylurea such as glyburide ; a sulfonylurea and acarbose ; nateglinide and metformin ; acarbose and metformin ; a sulfonylurea , metformin and troglitazone ; insulin and a sulfonylurea ; insulin and metformin ; insulin , metformin and a sulfonylurea ; insulin and troglitazone ; insulin and lovastatin ; etc . in one embodiment , a compound of the present invention may be administered in combination with one or more antiobesity agents or appetite regulating agents . such agents may be selected from the group consisting of cart ( cocaine amphetamine regulated transcript ) agonists , npy ( neuropeptide y ) antagonists , mc3 ( melanocortin 3 ) agonists , mc4 ( melanocortin 4 ) agonists , orexin antagonists , tnf ( tumor necrosis factor ) agonists , crf ( corticotropin releasing factor ) agonists , crf bp ( corticotropin releasing factor binding protein ) antagonists , urocortin agonists , β3 adrenergic agonists such as cl - 316243 , aj - 9677 , gw - 0604 , ly362884 , ly377267 or az - 40140 , msh ( melanocyte - stimulating hormone ) agonists , mch ( melanocyte - concentrating hormone ) antagonists , cck ( cholecystokinin ) agonists , serotonin reuptake inhibitors ( fluoxetine , seroxat or citalopram ), norepinephrine reuptake inhibitors ( e . g . sibutramine ), 5ht ( serotonin ) agonists , bombesin agonists , galanin antagonists , growth hormone , growth factors such as prolactin or placental lactogen , growth hormone releasing compounds , trh ( thyreotropin releasing hormone ) agonists , ucp 2 or 3 ( uncoupling protein 2 or 3 ) modulators , leptin agonists , da ( dopamine ) agonists ( bromocriptin , doprexin ), lipase / amylase inhibitors , ppar modulators , rxr modulators , tr β agonists , adrenergic cns stimulating agents , agrp ( agouti related protein ) inhibitors , h3 histamine antagonists such as those disclosed in wo 00 / 42023 , wo 00 / 63208 and wo 00 / 64884 , the contents of all of which are incorporated herein by reference , exendin - 4 , glp - 1 agonists and ciliary neurotrophic factor . further agents of relevance are bupropion ( antidepressant ), topiramate ( anticonvulsant ), ecopipam ( dopamine d1 / d5 antagonist ), naltrexone ( opioid antagonist ), and peptide yy 3 - 36 ( batterham et al , nature 418 , 650 - 654 ( 2002 )). in another embodiment , the antiobesity agent employed is a lipase inhibitor , e . g . orlistat . in a further embodiment , the antiobesity agent employed is an adrenergic cns - stimulating agent , e . g . dexamphetamine , amphetamine , phentermine , mazindol , phendimetrazine , diethylpropion , fenfluramine or dexfenfluramine . in another embodiment , a compound of the present invention may be administered in combination with one or more antihypertensive agents . examples of relevant antihypertensive agents are : β - blockers such as alprenolol , atenolol , timolol , pindolol , propranolol and metoprolol ; ace ( angiotensin converting enzyme ) inhibitors such as benazepril , captopril , enalapril , fosinopril , lisinopril , quinapril and ramipril ; calcium channel blockers such as nifedipine , felodipine , nicardipine , isradipine , nimodipine , diltiazem and verapamil ; and α - blockers such as doxazosin , urapidil , prazosin and terazosin . it should be understood that treatment of a subject in need thereof with any suitable combination of a compound according to the invention with diet and / or exercise and / or with one or more of the above - mentioned compounds , and optionally with one or more other active substances is considered to be within the scope of the present invention . the present invention also provides pharmaceutical compositions comprising as an active ingredient , at least one compound of the present invention , preferably in a therapeutically effective amount , suitable for use in any of the methods according to the present invention , together with one or more pharmaceutically acceptable carriers or excipients . such pharmaceutical compositions may further comprise any of the further therapeutically active compounds as indicated above . the pharmaceutical composition is preferably in unit dosage form , comprising from about 0 . 05 mg to about 1000 mg , preferably from about 0 . 1 mg to about 500 mg , and most preferably from about 0 . 5 mg to about 200 mg of a compound suitable for any of the methods described above . the compounds of the present invention may be administered alone or in combination with pharmaceutically acceptable carriers or excipients , in either single or multiple doses . the pharmaceutical compositions according to the invention may be formulated with pharmaceutically acceptable carriers or diluents as well as any other known adjuvants and excipients in accordance with conventional techniques such as those disclosed in remington : the science and practice of pharmacy , 20 th edition , gennaro , ed ., mack publishing co ., easton , pa ., 2000 . the pharmaceutical composition may be specifically formulated for administration by any suitable route , such as the oral , rectal , nasal , pulmonary , topical ( including buccal and sublingual ), transdermal , intracisternal , intraperitoneal , vaginal and parenteral ( including subcutaneous , intramuscular , intrathecal , intravenous and intradermal ) route , the oral route being preferred . it will be appreciated that the preferred route will depend on the general condition and age of the subject to be treated , the nature of the condition to be treated and the active ingredient chosen . pharmaceutical compositions for oral administration include solid dosage forms such as hard or soft capsules , tablets , troches , dragees , pills , lozenges , powders and granules . where appropriate , they can be prepared with coatings such as enteric coatings , or they can be formulated so as to provide controlled release of the active ingredient , such as sustained or prolonged release , according to methods well known in the art . liquid dosage forms for oral administration include solutions , emulsions , aqueous or oily suspensions , syrups and elixirs . pharmaceutical compositions for parenteral administration include sterile aqueous and non - aqueous injectable solutions , dispersions , suspensions or emulsions , as well as sterile powders to be reconstituted in sterile injectable solutions or dispersions prior to use . depot injectable formulations are also regarded as being within the scope of the present invention . other suitable administration forms include suppositories , sprays , ointments , crèmes , gels , inhalants , dermal patches , implants , etc . a typical oral dosage is in the range of from about 0 . 001 to about 100 mg / kg body weight per day , preferably from about 0 . 01 to about 50 mg / kg body weight per day , and more preferably from about 0 . 05 to about 10 mg / kg body weight per day , administered in one or more doses such as 1 - 3 doses . the exact dosage will depend upon the frequency and mode of administration , the sex , age , weight and general condition of the subject treated , the nature and severity of the condition treated and any concomitant diseases to be treated , and other factors evident to those skilled in the art . the formulations may conveniently be prepared in unit dosage form by methods known to those skilled in the art . a typical unit dosage form for oral administration one or more times per day , such as 1 - 3 times per day , may contain from 0 . 05 to about 1000 mg , preferably from about 0 . 1 to about 500 mg , and more preferably from about 0 . 5 mg to about 200 mg of a compound of the invention . for parenteral routes such as intravenous , intrathecal , intramuscular and similar administration , typical dosages are in the order of about half the dosage employed for oral administration . a compound for use according to the present invention is generally utilized as the free substance or as a pharmaceutically acceptable salt thereof . examples of the latter are : an acid addition salt of a compound having a free base functionality , and a base addition salt of a compound having a free acid functionality . the term “ pharmaceutically acceptable salt ” refers to a non - toxic salt of a compound for use according to the present invention , which salts are generally prepared by reacting a free base with a suitable organic or inorganic acid , or by reacting an acid with a suitable organic or inorganic base . when a compound for use according to the present invention contains a free base functionality , such salts are prepared in a conventional manner by treating a solution or suspension of the compound with a chemical equivalent of a pharmaceutically acceptable acid . when a compound for use according to the present invention contains a free acid functionality , such salts are prepared in a conventional manner by treating a solution or suspension of the compound with a chemical equivalent of a pharmaceutically acceptable base . physiologically acceptable salts of a compound with a hydroxy group include the anionic form of the compound in combination with a suitable cation , such as sodium or ammonium ion . other salts which are not pharmaceutically acceptable may be useful in the preparation of compounds of the invention , and these form a further aspect of the invention . for parenteral administration , solutions of compounds for use according to the present invention in sterile aqueous solution , in aqueous propylene glycol or in sesame or peanut oil may be employed . aqueous solutions should be suitably buffered where appropriate , and the liquid diluent rendered isotonic with , e . g ., sufficient saline or glucose . aqueous solutions are particularly suitable for intravenous , intramuscular , subcutaneous and intraperitoneal administration . the sterile aqueous media to be employed are all readily available by standard techniques known to those skilled in the art . suitable pharmaceutical carriers include inert solid diluents or fillers , sterile aqueous solutions and various organic solvents . examples of solid carriers are lactose , terra alba , sucrose , cyclodextrin , talc , gelatine , agar , pectin , acacia , magnesium stearate , stearic acid and lower alkyl ethers of cellulose . examples of liquid carriers are syrup , peanut oil , olive oil , phospholipids , fatty acids , fatty acid amines , polyoxyethylene and water . moreover , the carrier or diluent may include any sustained release material known in the art , such as glyceryl monostearate or glyceryl distearate , alone or mixed with a wax . the pharmaceutical compositions formed by combining the compounds for use according to the present invention and the pharmaceutically acceptable carriers are then readily administered in a variety of dosage forms suitable for the disclosed routes of administration . the formulations may conveniently be presented in unit dosage form by methods known in the art of pharmacy . formulations of the present invention suitable for oral administration may be presented as discrete units , such as capsules or tablets , which each contain a predetermined amount of the active ingredient , and which may include a suitable excipient . furthermore , the orally available formulations may be in the form of a powder or granules , a solution or suspension in an aqueous or non - aqueous liquid , or an oil - in - water or water - in - oil liquid emulsion . compositions intended for oral use may be prepared according to any known method , and such compositions may contain one or more agents selected from the group consisting of sweetening agents , flavouring agents , colouring agents and preserving agents in order to provide pharmaceutically elegant and palatable preparations . tablets may contain the active ingredient ( s ) in admixture with non - toxic pharmaceutically acceptable excipients which are suitable for the manufacture of tablets . these excipients may , for example , be : inert diluents , such as calcium carbonate , sodium carbonate , lactose , calcium phosphate or sodium phosphate ; granulating and disintegrating agents , for example corn starch or alginic acid ; binding agents , for example , starch , gelatine or acacia ; and lubricating agents , for example magnesium stearate , stearic acid or talc . the tablets may be uncoated or they may be coated by known techniques to delay disintegration and absorption in the gastrointestinal tract and thereby provide a sustained action over a longer period . for example , a time delay material such as glyceryl monostearate or glyceryl distearate may be employed . they may also be coated by the techniques described in u . s . pat . nos . 4 , 356 , 108 ; 4 , 166 , 452 ; and 4 , 265 , 874 , the contents of which are incorporated herein by reference , to form osmotic therapeutic tablets for controlled release . formulations for oral use may also be presented as hard gelatine capsules where the active ingredient is mixed with an inert solid diluent , for example , calcium carbonate , calcium phosphate or kaolin , or a soft gelatine capsules wherein the active ingredient is mixed with water or an oil medium , for example peanut oil , liquid paraffin , or olive oil . aqueous suspensions may contain the compound for use according to the present invention in admixture with excipients suitable for the manufacture of aqueous suspensions . such excipients are suspending agents , for example sodium carboxymethylcellulose , methylcellulose , hydroxypropylmethylcellulose , sodium alginate , polyvinylpyrrolidone , gum tragacanth and gum acacia ; dispersing or wetting agents may be a naturally - occurring phosphatide such as lecithin , or condensation products of an alkylene oxide with fatty acids , for example polyoxyethylene stearate , or condensation products of ethylene oxide with long chain aliphatic alcohols , for example , heptadecaethyl - eneoxycetanol , or condensation products of ethylene oxide with partial esters derived from fatty acids and a hexitol such as polyoxyethylene sorbitol monooleate , or condensation products of ethylene oxide with partial esters derived from fatty acids and hexitol anhydrides , for example polyethylene sorbitan monooleate . the aqueous suspensions may also contain one or more colouring agents , one or more flavouring agents , and one or more sweetening agents , such as sucrose or saccharin . oily suspensions may be formulated by suspending the active ingredient in a vegetable oil , for example arachis oil , olive oil , sesame oil or coconut oil , or in a mineral oil such as a liquid paraffin . the oily suspensions may contain a thickening agent , for example beeswax , hard paraffin or cetyl alcohol . sweetening agents such as those set forth above , and flavouring agents may be added to provide a palatable oral preparation . these compositions may be preserved by the addition of an anti - oxidant such as ascorbic acid . dispersible powders and granules suitable for preparation of an aqueous suspension by the addition of water provide the active compound in admixture with a dispersing or wetting agent , suspending agent and one or more preservatives . suitable dispersing or wetting agents and suspending agents are exemplified by those already mentioned above . additional excipients , for example , sweetening , flavouring , and colouring agents may also be present . the pharmaceutical compositions comprising compounds for use according to the present invention may also be in the form of oil - in - water emulsions . the oily phase may be a vegetable oil , for example , olive oil or arachis oil , or a mineral oil , for example a liquid paraffin , or a mixture thereof . suitable emulsifying agents may be naturally - occurring gums , for example gum acacia or gum tragacanth , naturally - occurring phosphatides , for example soy bean , lecithin , and esters or partial esters derived from fatty acids and hexitol anhydrides , for example sorbitan monooleate , and condensation products of said partial esters with ethylene oxide , for example polyoxyethylene sorbitan monooleate . the emulsions may also contain sweetening and flavouring agents . syrups and elixirs may be formulated with sweetening agents , for example glycerol , propylene glycol , sorbitol or sucrose . such formulations may also contain a demulcent , a preservative and flavouring and colouring agents . the pharmaceutical compositions may be in the form of a sterile injectable aqueous or oleaginous suspension . this suspension may be formulated according to the known methods using suitable dispersing or wetting agents and suspending agents described above . the sterile injectable preparation may also be a sterile injectable solution or suspension in a non - toxic parenterally - acceptable diluent or solvent , for example as a solution in 1 , 3 - butanediol . among the acceptable vehicles and solvents that may be employed are water , ringer &# 39 ; s solution , and isotonic sodium chloride solution . in addition , sterile , fixed oils are conveniently employed as solvent or suspending medium . for this purpose , any bland fixed oil may be employed using synthetic mono - or diglycerides . in addition , fatty acids such as oleic acid find use in the preparation of injectables . the compositions may also be in the form of suppositories for rectal administration of the compounds of the invention . these compositions can be prepared by mixing the drug with a suitable non - irritating excipient which is solid at ordinary temperatures but liquid at the rectal temperature and will thus melt in the rectum to release the drug . such materials include , for example , cocoa butter and polyethylene glycols . for topical use , creams , ointments , jellies , solutions of suspensions , etc ., containing the compounds of the invention may be employed . in the context of the present invention , formulations for topical application include mouth washes and gargles . compounds of the present invention may also be administered in the form of liposome delivery systems , such as small unilamellar vesicles , large unilamellar vesicles , and multilamellar vesicles . liposomes may be formed from a variety of phospholipids , such as cholesterol , stearylamine , or phosphatidylcholines . in addition , some compounds of the present invention may form solvates with water or common organic solvents . such solvates are also encompassed within the scope of the invention . thus , a further embodiment provides a pharmaceutical composition comprising a compound for use according to the present invention , or a pharmaceutically acceptable salt , solvate , or prodrug thereof , and one or more pharmaceutically acceptable carriers , excipients , or diluents . if a solid carrier is used for oral administration , the preparation may be tabletted , placed in a hard gelatine capsule in powder or pellet form , or may be in the form of a troche or lozenge . the amount of solid carrier will vary widely , but will usually be from about 25 mg to about 1 g . if a liquid carrier is used , the preparation may be in the form of a syrup , emulsion , soft gelatine capsule or sterile injectable liquid such as an aqueous or non - aqueous liquid suspension or solution . a typical tablet that may be prepared by conventional tabletting techniques may contain : if desired , the pharmaceutical composition comprising a compound according to the present invention may comprise a compound according to the present invention in combination with further active substances , such as those described in the foregoing . the present invention also provides methods for the preparation of compounds for use according to the present invention . the compounds can be prepared readily according to the following general procedures ( in which all variables are as defined before , unless so specified ) using readily available starting materials , reagents and conventional synthesis procedures . in these reactions , it is also possible to make use of variants which are themselves known to those of ordinary skill in this art , but which are not mentioned in greater detail . a hewlett packard series 1100 instrument is used . the hplc pump is connected to two eluent reservoirs containing : ( a ) 0 . 01 % tfa in water , ( b ) 0 . 01 % tfa in acetonitrile . gradient : 5 %- 100 % acetonitrile linear during 7 . 5 min at 1 . 5 ml / min . the analysis is performed at 40 ° c . by injecting an appropriate volume of the sample ( preferably 1 μl ) onto the column which is eluted with a gradient of acetonitrile . detection : 210 nm , analogue output from dad ( diode array detector ), els ( analogue output from els ), and ms ionisation mode api - es , scan 100 - 1000 amu step 0 . 1 amu . after the dad the flow is divided yielding approx 1 ml / min to the els and 0 . 5 ml / min to the ms . as method a , except that the gradient is : 5 %- 100 % acetonitrile linear during 4 min at 2 . 7 ml / min . an agilent series 1100 instrument is used . the hplc pump is connected to two eluent reservoirs containing : ( a ) 0 . 1 % tfa in water , ( b ) acetonitrile . gradient : 60 %- 95 % acetonitrile linear during 8 min at 10 ml / min . the analysis is performed at room temperature by injecting an appropriate volume of the sample onto the column ( luna 5μ c18 ( 2 ) 100 å , 250 × 10 mm ) which is eluted with a gradient of acetonitrile . detection : 210 nm , analogue output from dad ( diode array detector ), els ( analogue output from els ), and ms ionisation mode api - es , scan 150 - 700 amu step 0 . 1 amu . after the dad the flow is divided yielding approx 0 . 5 ml / min to the els and 0 . 5 ml / min to the ms . the mobile phase containing the desired molecular weight is automatically collected by the fraction collector . to a solution of the bromo - substituted phenol i ( 1 equivalent ) in water the appropriate substituted aryl boronic acid ii ( 1 . 1 equivalent ) is added . the appropriate palladium catalyst ( palladium acetate 0 . 005 to 0 . 01 equivalents ) is added together with the appropriate base ( sodium carbonate , 3 equivalents ). the reaction mixture is stirred at room temperature overnight or heated under reflux overnight . the reaction is followed by tlc or lc - ms . the reaction mixture is made acidic by addition of 1n hydrochloric acid solution , and the mixture is stirred at room temperature for 1 - 3 hours . the water phase is extracted with ethyl acetate . the organic phase is dried over sodium sulfate , and the solvent is evaporated . pure compounds iii are obtained by crystallization from an organic solvent or by column chromatography . the bromo - substituted phenols i are either commercially available or may be synthesized in one - step reactions from commercially available compounds by methods analogous to standard methods reported in the literature , e . g . huang ; yunsheng et al ; j . med . chem . 2001 , 44 ( 11 ), 1815 - 1826 , or mach ; robert h et al ; med . chem . res . 1999 , 9 ( 6 ) 355 - 373 . compound iii ( 1 equivalent ) is dissolved in xylene together with the appropriate substituted aniline iv ( 1 - 1 . 1 equivalent ). the reaction mixture is heated to reflux , and phosphorus trichloride , pcl 3 ( 0 . 33 equivalent ) is carefully added . the reaction mixture is heated under reflux for 1 - 2 days . the reaction mixture is allowed to cool to room temperature , and the product v is isolated by filtration and purified by recrystallization from an organic solvent , or by column chromatography . boron trichloride catalyzed ortho carbamoylation of phenols may be achieved by a method similar to that described by o . piccolo , l . filippini , l . tinucci , tetrahedron , 1986 , 42 ( 3 ), 885 - 892 , as follows : a solution of the phenol i ( 1 mmol ) in dichloromethane ( 5 ml ) is added to a stirred solution of boron trichloride ( 1m in dichloromethane , 1 - 1 . 1 mmol ) under nitrogen at − 10 ° c . after 5 minutes , a solution of the aryl isocyanate ii ( 1 - 1 . 1 mmol ) in dichloromethane ( 5 ml ) is added . the resulting mixture is stirred under reflux for 2 h , then at ˜ 40 ° c . overnight . the mixture is cooled to room temperature and stirred for 4 h after the addition of 4 m hcl ( 10 ml ), and diethyl ether ( 25 ml ) is then added . if a precipitate forms it is filtered off , rinsed with a small amount of diethyl ether and dried to give the anilide iii . if no well - defined precipitate forms , the organic layer is separated , dried , and the solvent is evaporated . the crude product may be purified by column chromatography . the starting phenols i are either commercially available or may be synthesized in one - step reactions from commercially available compounds by methods analogous to standard methods reported in the literature , e . g . c . d . braddock , s . c . tucker , j . m . brown , bull . soc . chim . fr . 1997 , 134 ( 3 - 4 ) 399 - 410 ; b . p . bandgar , l . s . uppalla , v . s . sadavarte , j . chem . research ( s ), 2000 , 582 - 583 ; k . menting , w . eichel , k . reimenschneider , h . l . k . schmand , p . boldt . j . org . chem . 1983 , 48 ( 17 ) 2814 - 2820 ; charpentier , bruno ; bernardon , jean - michel ; eustache , jacques ; millois , corinne ; martin , bernard ; et al . ; j . med . chem . 1995 , 38 ( 26 ) 4993 - 5006 . thus , the introduction of r 1 = tertiary alkyl or cycloalkyl may be accomplished starting from the appropriate phenol i with r 1 ═ h by alkylation procedures , e . g . by treatment of the phenol with an alkylating agent in the presence of an acid catalyst . suitable alkylating agents and catalysts are , e . g ., halides such as r 1 cland a lewis acid such as alcl 3 ; or tertiary alcohols r 1 oh in the presence of a strong acid such as h 2 so 4 or cf 3 so 3 h . aryl isocyanates ii may be prepared from the appropriate substituted anilines by treatment with phosgene or a phosgene equivalent as reported in the literature [ see , e . g ., k . kurita , t . matsumura , y . iwakura , j . org . chem . 1976 , 41 ( 11 ) 2070 - 2071 ]. in order to suppress the formation of side - products such as 1 , 3 - disubstituted urea and 1 , 3 , 5 - trisubstituted biuret , it may be feasible to use the hydrochloride of the aniline rather than the aniline itself . as for general procedure ( b ) except that the phenol i and the isocyanate ii are dissolved in dry toluene instead of dichloromethane , and that the reaction mixture after the addition of the isocyanate is heated at 100 - 120 ° c . overnight . as for general procedure ( a ) except that in step b , compound iii ( 1 mmol ) is added to thionyl chloride ( 1 - 5 ml ) and the mixture is stirred for 5 - 10 min . acetonitrile ( 1 - 5 ml ) is then added , followed by the appropriately substituted aniline iv ( 1 . 0 - 1 . 1 mmol ). the mixture is stirred at room temperature for 30 - 90 min and then evaporated to dryness . the residue is stirred in 1 n naoh ( 25 ml ) for 15 minutes and acidified by the addition of 1 m hcl . the product v is isolated by filtration , washed with water and purified by crystallization from an organic solvent , or by column chromatography . compound i ( 1 equivalent ) is added to excess thionyl chloride ( 2 - 20 equivalents ) and the mixture is stirred for 5 - 10 min . acetonitrile is added , followed by the appropriately substituted aniline ii ( 1 . 0 - 1 . 1 equivalent ). the mixture is stirred at room temperature for 30 - 90 min and then evaporated to dryness . the residue is either subjected to column chromatography to give compound iii or stirred in 1 n naoh ( 25 ml ) for 15 minutes and acidified by the addition of 1 m hcl . product iii is then isolated by filtration , washed with water and purified by crystallization from an organic solvent , or by column chromatography . a mixture of compound i ( 1 equivalent ) and the appropriately substituted aniline ii ( 1 . 0 - 1 . 1 equivalent ) in xylene is heated to reflux , and phosphorus trichloride ( pcl 3 ) ( 0 . 33 - 1 . 0 equivalent ) is carefully added . the reaction mixture is heated under reflux for 2 - 48 hours and allowed to cool to room temperature . the crude product is isolated by filtration or by evaporation to dryness , and pure compound iii is obtained by recrystallization from an organic solvent , or by column chromatography . as for general procedure ( a ) except that in step b a mixture of compound iii ( 1 mmol ) and the appropriately substituted aniline ( 1 . 0 - 1 . 1 mmol ) in acetonitrile ( 1 - 5 ml ) thionyl chloride ( 1 . 5 mmol ) is added . the mixture ( suspension or solution ) is stirred at room temperature for 5 - 10 hours . the compound is isolated by filtration and crystallization or by aqueous work - up : the residue is stirred in 1 n naoh ( 25 ml ) for 15 minutes and acidified by the addition of 1 m hcl . the product v is isolated by filtration or by extraction , washed with water , and purified by crystallization from an organic solvent , or by column chromatography . to a suspension of compound i ( 10 . 0 mmol ) in dichloromethane ( 20 ml ) is added disulfur dichloride ( 5 . 0 mmol ) dropwise . acetonitrile ( 10 ml ) is added , and a clear solution is formed . the reaction mixture is stirred overnight at room temperature . the separated compound ii is isolated by filtration and used in the next reaction step without further purification . to a solution of compound ii ( 4 . 23 mmol ) in methanol ( 45 ml ) is added the appropriate alkylation reagent ( 12 - 42 mmol ). sodium borohydride ( 60 . 0 mmol ) is added at a rate such that the temperature does not exceed 40 ° c . compound iii is purified by aqueous acid work up , followed by crystallization or column chromatography . this reaction is performed in a manner analogous to that in general procedure a ( step b ), general procedure d or general procedure e , starting from compound iii obtained in step b above and the appropriately substituted aniline iv , to give compound v . compound v is oxidised using an appropriate oxidising reagent , such as hydrogen peroxide in acetic acid ( stirring at room temperature for 2 - 12 hours ), or m - chloro - peroxybenzoic acid ( 1 equivalent ) in dichloromethane . compound vi thus obtained is purified by filtration and crystallization , or by aqueous work - up followed by crystallization or column chromatography . compound v is oxidised using an appropriate oxidising reagent , such as hydrogen peroxide in acetic acid ( heating at 100 ° c . for 6 - 12 hours ), or m - chloro - peroxybenzoic acid ( 2 equivalents ) in dichloromethane . compound vi thus obtained is purified by filtration and crystallization , or by aqueous work - up followed by crystallization or column chromatography . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ 1 . 40 ( s , 9h ) 2 . 18 ( s , 3h ) 6 . 99 - 7 . 07 ( m , 2h ) 7 . 12 ( s , 1h ) 7 . 19 - 7 . 27 ( m , 1h ) 8 . 20 ( d , j = 8 . 59 hz , 1h ) 8 . 24 ( s , 1h ) 8 . 64 ( d , j = 8 . 59 hz , 1h ) 9 . 16 ( s , 1h ) 10 . 61 ( s , 1h ); hplc - ms ( method b ): m / z = 528 , 530 ( m + 1 ); r t = 2 . 88 min . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ 1 . 40 ( s , 9h ) 2 . 17 ( s , 3h ) 7 . 11 ( s , 1h ) 7 . 39 - 7 . 46 ( m , 4h ) 8 . 20 ( d , j = 8 . 59 hz , 1h ) 8 . 25 ( d , j = 2 . 02 hz , 1h ) 8 . 65 ( d , 1h ) 9 . 09 ( s , 1h ) 10 . 65 ( s , 1h ); hplc - ms ( method b ): m / z = 2 . 97 ( m + 1 ); r t = 6 . 10 min . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ 1 . 41 ( s , 9h ) 2 . 17 ( s , 3h ) 7 . 13 ( s , 1h ) 7 . 58 - 7 . 77 ( m , 4h ) 8 . 21 ( d , j = 8 . 59 hz , 1h ) 8 . 25 ( s , 1h ) 8 . 65 ( d , j = 8 . 59 hz , 1h ) 9 . 14 ( s , 1h ) 10 . 62 ( s , 1h ); hplc - ms ( method b ): m / z = 594 ( m + 1 ); r t = 2 . 92 min . 1 h nmr ( dmso - d 6 ): δ 1 . 37 ( s , 9h ) 2 . 29 ( s , 3h ) 7 . 39 ( s , 1h ) 8 . 20 ( d , j = 8 . 59 hz , 1h ) 8 . 25 ( s , 1h ) 8 . 61 ( d , j = 8 . 59 hz , 1h ) 9 . 21 ( s , 1h ) 10 . 69 ( s , 1h ); hplc - ms ( method b ): m / z = 528 , 530 , 532 ( m + 1 ); r t = 2 . 78 min . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ 1 . 39 ( s , 9h ) 2 . 15 ( s , 3h ) 7 . 08 ( s , 1h ) 7 . 26 ( t , j = 8 . 84 hz , 2h ) 7 . 30 - 7 . 39 ( m , 2h ) 8 . 20 ( d , j = 9 . 10 hz , 1h ) 8 . 24 ( s , 1h ) 8 . 63 ( d , j = 8 . 59 hz , 1h ) 9 . 02 ( s , 1h ) 10 . 62 ( s , 1h ); hplc - ms ( method b ): m / z = 544 , 546 ( m + 1 ); r t = 2 . 90 min . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): 1 . 47 ( s , 9h ) 2 . 17 ( s , 3h ) 2 . 49 ( s , 3h ) 7 . 08 ( s , 1h ) 7 . 25 ( d , 2h ) 7 . 33 ( d , 2h ) 8 . 20 ( d , 1h ) 8 . 24 ( s , 1h ) 8 . 62 ( d , 1h ) 8 . 99 ( s , 1h ) 10 . 60 ( s , 1h ); hplc - ms ( method b ): m / z = 572 , 574 ( m + 1 ); r t = 2 . 90 min . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ 1 . 39 ( s , 9h ) 2 . 16 ( s , 3h ) 7 . 10 ( s , 1h ) 7 . 11 - 7 . 19 ( m , 1h ) 7 . 33 - 7 . 43 ( m , 1h ) 7 . 43 - 7 . 55 ( m , 1h ) 8 . 20 ( d , j = 9 . 04 hz , 1h ) 8 . 25 ( d , j = 1 . 88 hz , 1h ) 8 . 63 ( d , j = 8 . 29 hz , 1h ) 9 . 09 ( s , 1h ) 10 . 60 ( s , 1h ); hplc - ms ( method b ): m / z = 562 , 564 ( m + 1 ); r t = 2 . 92 min . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ ppm 1 . 40 ( s , 9h ) 2 . 17 ( s , 3h ) 7 . 11 ( s , 1h ) 7 . 53 ( d , j = 8 . 59 hz , 2h ) 7 . 90 ( d , j = 8 . 08 hz , 2h ) 8 . 20 ( d , j = 9 . 60 hz , 1h ) 8 . 24 ( s , 1h ) 8 . 64 ( d , j = 8 . 59 hz , 1h ) 9 . 19 ( s , 1h ) 10 . 65 ( s , 1h ); hplc - ms ( method b ): m / z = 551 , 553 ( m + 1 ); r t = 2 . 72 min . 1 h nmr ( dmso - d 6 ): δ 1 . 35 ( s , 9h ) 2 . 22 ( s , 3h ) 7 . 38 ( s , 1h ) 7 . 72 ( dd , j = 8 . 48 , 2 . 07 hz , 1h ) 7 . 87 ( d , j = 8 . 67 hz , 1h ) 8 . 23 ( d , j = 1 . 88 hz , 1h ) 9 . 12 ( s , 1h ) 10 . 94 ( s , 1h ); hplc - ms ( method b ): m / z = 496 , 498 , 500 ( m + 1 ); r t = 2 . 86 min . step b : from the product formed in step a and 3 - chloro - 4 - trifluoromethanesulfanyl aniline 1 h nmr ( dmso - d 6 ): δ 1 . 38 ( s , 9h ) 2 . 08 ( s , 3h ) 7 . 08 ( s , 1h ) 7 . 11 - 7 . 19 ( m , 1h ) 7 . 30 - 7 . 42 ( m , 1h ) 7 . 42 - 7 . 56 ( m , 1h ) 7 . 75 ( d , 1h ) 7 . 86 ( d , 1h ) 8 . 26 ( d , j = 1 . 88 hz , 1h ) 8 . 98 ( s , 1h ) 10 . 95 ( s , 1h ); hplc - ms ( method b ): m / z = 530 , 532 ( m + 1 ); r t = 3 . 00 min . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ 1 . 40 ( s , 9h ) 2 . 16 ( s , 3h ) 7 . 10 ( s , 1h ) 7 . 26 - 7 . 35 ( m , 1h ) 7 . 45 - 7 . 54 ( m , 2h ) 8 . 20 ( d , j = 8 . 67 hz , 1h ) 8 . 25 ( d , j = 1 . 88 hz , 1h ) 8 . 63 ( d , j = 8 . 29 hz , 1h ) 9 . 10 ( s , 1h ) 10 . 59 ( s , 1h ); hplc - ms ( method b ): m / z = 578 , 580 , 582 ( m + 1 ); r t = 2 . 99 min . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ 1 . 39 ( s , 9h ) 2 . 15 ( s , 3h ) 2 . 26 ( 3h ) 7 . 00 ( d , j = 8 . 67 hz , 1h ) 7 . 05 - 7 . 08 ( m , 1h ) 7 . 68 ( dd , j = 8 . 85 , 2 . 07 hz , 1h ) 7 . 79 ( d , j = 2 . 26 hz , 1h ) 8 . 19 ( dd , 1h ) 8 . 25 ( d , j = 2 . 26 hz , 1h ) 8 . 62 ( d , j = 8 . 29 hz , 1h ) 10 . 60 ( s , 1h ); hplc - ms ( method b ): m / z = 558 , 560 ( m + 1 ); r t = 2 . 98 min . 1 h nmr ( dmso - d 6 ): δ 1 . 36 ( s , 9h ) 2 . 27 ( s , 3h ) 7 . 24 ( s , 1h ) 8 . 20 ( d , j = 8 . 67 hz , 1 h ) 8 . 25 ( d , j = 1 . 88 hz , 1h ) 8 . 60 ( d , j = 8 . 67 hz , 1h ) 9 . 17 ( s , 1h ) 10 . 67 ( s , 1h ); hplc - ms ( method b ): m / z = 484 , 486 , 488 ( m + 1 ); r t = 2 . 74 min . to a solution of 5 - tert - butyl - 4 - hydroxy - 2 - methyl - 4 ′- methylsulfanyl - biphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ( 1 equivalent ) in dichloromethane 3 - chloro - peroxybenzoic acid ( 2 equivalents ) was added . the reaction mixture was stirred at room temperature overnight . the organic phase was washed with sodium carbonate solution and evaporated the title compound was purified by column chromatography . 1 h nmr ( cdcl 3 ): δ 1 . 37 ( s , 9h ) 2 . 37 ( s , 3h ) 7 . 20 ( s , 1h ) 7 . 45 ( d , j = 8 . 29 hz , 2h ) 7 . 96 ( d , j = 8 . 29 hz , 2h ) 8 . 04 ( d , j = 1 . 88 hz , 1h ) 8 . 46 ( s , 1h ) 8 . 97 ( d , j = 9 . 04 hz , 1h ) 9 . 51 ( s , 1h ); hplc - ms ( method b ): m / z = 626 , 628 ( m + 1 ); r t = 2 . 52 min . the compound was prepared by a method described in : tetrahedron letters , vol . 35 , no 28 , pp . 4955 - 4958 , 1994 . to a solution of 5 - tert - butyl - 3 ′, 4 ′- difluoro - 4 - hydroxy - 2 - methylbiphenyl - 3 - carboxylic acid ( 3 - chloro - 4 - trifluoromethylsulfanyl - phenyl )- amide ( 1 equivalent ) in a mixture of carbontetrachloride and acetonitril 1 : 1 sodium periodate ( 3 equivalents ) and ruthenium trichloride hydrate ( 0 . 05 equivalents ) were added . the reaction mixture was stirred at room temperature overnight . water and diethyl ether was added and the organic phase was separated . the organic phase was washed with sodium carbonate solution and evaporated . the title compound was purified by column chromatography . 1 h nmr ( cdcl 3 ): δ 1 . 37 ( s , 9h ) 2 . 37 ( s , 3h ) 7 . 20 ( s , 1h ) 7 . 45 ( d , j = 8 . 29 hz , 2h ) 7 . 96 ( d , j = 8 . 29 hz , 2h ) 8 . 04 ( d , j = 1 . 88 hz , 1h ) 8 . 46 ( s , 1h ) 8 . 97 ( d , j = 9 . 04 hz , 1h ) 9 . 51 ( s , 1h ); hplc - ms ( method b ): m / z = 626 , 628 ( m + 1 ); r t = 2 . 52 min . from 1 - hydroxy - 2 - naphthoic acid and 3 - trifluoromethanesulfonyl - aniline ; mp 194 - 195 ° c . ; 1 h nmr ( dmso - d 6 ): δ 13 . 47 ( s , 1h ), 10 . 95 ( s , 1h ), 8 . 62 ( s , 1h ), 8 . 46 - 8 . 41 ( m , 1h ), 8 . 33 ( d , j = 8 . 08 hz , 1h ), 8 . 11 ( d , j = 9 . 10 hz , 1h ), 7 . 97 - 7 . 87 ( m , 3h ), 7 . 73 - 7 . 67 ( m , 1h ), 7 . 64 - 7 . 58 ( m , 1h ), 7 . 52 ( d , j = 9 . 10 hz , 1h ); hplc - ms ( method a ): m / z : 396 ( m + h ), 418 ( m + na ) r t = 5 . 1 min . from 1 - hydroxy - 2 - naphthoic acid and 3 - trifluoromethanesulfanyl - aniline ; white crystals , mp 154 ° c . ; 1 h nmr ( dmso - d 6 ): δ 13 . 73 ( s , 1h ), 10 . 68 ( s , 1h ), 8 . 32 ( d , j = 8 . 08 hz , 1h ), 8 . 19 ( br s , 1h ), 8 . 12 ( d , j = 8 . 59 hz , 1h ), 8 . 04 - 8 . 00 ( m , 1h ), 7 . 93 ( d , j = 8 . 08 hz , 1h ), 7 . 72 - 7 . 66 ( m , 1h ), 7 . 63 - 7 . 52 ( m , 3h ), 7 . 50 ( d , 1h ); hplc - ms ( method a ): m / z : 364 ( m + 1 ), 386 ( m + na ), r t = 5 . 4 min . from 2 - hydroxy - 1 - naphthoic acid and 3 - trifluoromethanesulfonyl - aniline ; mp 179 - 180 ° c . ; 1 h nmr ( dmso - d 6 ): δ 8 . 74 ( s , 1h ), 8 . 18 ( d , j = 8 . 08 hz , 1h ), 7 . 91 - 7 . 71 ( m , 5h ), 7 . 51 - 7 . 43 ( m , 1h ), 7 . 36 - 7 . 29 ( m , 1h ), 7 . 19 ( d , j = 9 . 10 hz , 1h ); hplc - ms ( method a ): m / z : 396 ( m + h ), 418 ( m + na ); r t = 4 . 0 min . the title compound was prepared from 3 - methoxy - naphthalene - 2 - carboxylic acid , 3 - trifluoromethanesulfonyl - aniline and pcl 3 in xylene according to the general procedure ( a ) step b ; white crystals ; 1 h nmr ( cdcl 3 ): δ 10 . 23 ( s , 1h ), 8 . 87 ( s , 1h ), 8 . 38 - 8 . 34 ( br peak at 8 . 28 ppm , 1h ), 7 . 94 ( d , j = 8 . 08 hz , 1h ), 7 . 82 - 7 . 76 ( m , 2h ), 7 . 69 ( t , j = 8 . 08 hz , 1h ), 7 . 61 - 7 . 55 ( m , 1h ), 7 . 48 - 7 . 42 ( m , 1h ), 7 . 32 ( s , 1h ), 4 . 21 ( s , 3h ); hplc - ms ( method b ): m / z : 410 ( m + h ), 432 ( m + na ), 841 ( 2m + na ); r t = 2 . 39 min . boron tribromide ( 8 . 1 ml of a 0 . 1 m solution in dichloromethane ) was added to a stirred solution of 3 - methoxy - naphthalene - 2 - carboxylic acid ( 3 - trifluoromethanesulfonylphenyl )- amide ( 0 . 33 g , 0 . 8 mmol ) in dry dichloromethan ( 10 ml ) at − 70 ° c . under nitrogen . then the dry ice bath was removed and the mixture was allowed to warm up to room temperature . after 30 min . the mixture was extracted with saturated aqueous sodium bicarbonate ( 2 × 30 ml ). the organic phase was dried over mgso 4 , filtered and evaporated to give the title compound . yield 0 . 32 g ( 100 %); pale yellow crystals , mp 212 - 213 ° c . ; 1 h nmr ( dmso - d 6 ): δ 11 . 05 ( br s , 1h ), 8 . 76 - 8 . 73 ( br , peak at 8 . 75 ppm , 1h ), 8 . 42 ( br s , 1h ), 8 . 30 - 8 . 25 ( m , 1h ), 7 . 93 ( d , j = 8 . 08 hz , 1h ), 7 . 90 - 7 . 84 ( m , 2h ), 7 . 78 ( d , j = 8 . 08 hz , 1h ), 7 . 55 - 7 . 49 ( m , 1h ), 7 . 40 - 7 . 32 ( m , 2h ); hplc - ms ( method b ): m / z : 396 ( m + h ), 418 ( m + na ); r t = 2 . 29 min . from 1 , 2 , 3 , 4 - tetrahydro - 5 - naphthol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; white crystals , 1 h nmr ( cdcl 3 ): δ d 11 . 73 ( s , 1h ), 8 . 92 ( d , j = 9 . 09 hz , 1h ), 8 . 10 ( d , j = 2 . 02 hz , 1h ), 7 . 99 ( dd , 1h ), 7 . 30 ( d , j = 8 . 08 hz , 1h ), 6 . 72 ( d , j = 8 . 08 hz , 1h ), 2 . 82 ( m , 2h ), 2 . 75 - 2 . 69 ( m , 2h ), 1 . 88 - 1 . 75 ( m , 4h ); hplc - ms ( method b ): m / z : 434 ( m + h ), 436 ( m + 2 + h ), 456 ( m + na ), 458 ( m + 2 + na ), r t = 2 . 75 min . from 1 , 2 , 3 , 4 - tetrahydro - 5 - naphthol and 1 - isocyanato - 4 - trifluoromethanesulfanyl - benzene ; white crystals , mp 167 ° c . ; 1 h nmr ( cdcl 3 ): δ d 12 , 13 ( s , 1h ), 7 . 94 ( s , 1h ), 7 . 70 - 7 . 56 ( m , 4h ), 7 . 23 ( d , j = 8 . 08 hz , 1h ), 6 . 65 ( d , j = 8 . 08 hz , 1h ), 2 . 80 - 2 . 61 ( br peaks at 2 . 76 & amp ; 2 . 70 , 4h ), 1 . 86 - 1 . 69 ( br , 4h ); hplc - ms ( method a ): m / z : 368 ( m + h ), 390 ( m + na ), r t = 5 . 78 min . 4 - benzenesulfonyl - 1 - hydroxy - naphthalene - 2 - carboxylic acid phenyl ester ( 0 . 210 g , 0 . 52 mmol ) and 4 - trifluoromethylsulfanyl - aniline ( 0 . 075 ml , 1 equivalent ) was stirred in a round bottom flask together with dry toluene ( 1 ml ). the mixture was heated at 165 - 175 ° c . for 45 min ., allowing the toluene to evaporate . the residue was triturated with ether - pentane 1 : 1 ( 1 ml ) and the precipitate was filtered off , rinsed on the filter with the same solvent and dried . the crude product was extracted with dichloromethane ( 2 ml ) and the insoluble material was collected by filtration and dried to give the title compound as a white solid . yield 0 . 139 g , mp 271 - 272 ° c . 1 h nmr ( dmso - d 6 ): δ 11 . 50 ( s , 1h ), 9 . 14 ( s , 1h ), 8 . 45 - 8 . 40 ( br d - like , 2h ), 8 . 06 - 8 . 00 ( br d - like , 2h ), 7 . 98 - 7 . 91 ( br d - like , 2h ), 7 . 83 - 7 . 74 ( m , 3h ), 7 . 69 - 7 . 56 ( m , 5h ); hplc - ms ( method b ): m / z : 504 ( m + h ), 526 ( m + na ); r t = 2 . 86 min . from 4 - chloro - 1 - naphthol and 1 - isocyanato - 4 - trifluoromethanesulfanyl - benzene ; beige crystals , mp 172 - 175 ° c . ; 1 h nmr ( cdcl 3 ): δ d 13 . 27 ( s , 1h ), 8 . 51 ( d , 1h ), 8 . 20 ( d , 1h ), 7 . 94 ( br s , 1h ), 7 . 80 - 7 . 69 ( m , 5h ), 7 . 67 - 7 . 62 ( m , 1h ); hplc - ms ( method b ): m / z : 398 ( m + h ), 400 ( m + 2 + h ), r t = 2 . 98 min . from 2 -( 1 - adamantyl )- 4 - methylphenol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; pale yellow crystals , mp 203 - 204 ° c . and 209 - 211 ° c . ( from heptane - etoac ); 1 h nmr ( dmso - d 6 ): δ d 11 . 90 ( s , 1h ), 8 . 87 ( d , 1h ), 8 . 86 ( s , 1h ), 8 . 10 ( d , 1h ), 7 . 99 ( dd , j = 8 . 58 hz , 2 . 03 hz , 1h ), 7 . 28 ( s , 1h ), 7 . 18 ( s , 1h ), 2 . 35 ( s , 3h ), 2 . 18 - 2 . 13 ( br m , 6h ), 2 . 13 - 2 . 06 ( br s , 3h ), 1 . 83 - 1 . 74 ( br , 6h ); hplc - ms ( method b ): m / z : 528 ( m + h ), 530 ( m + 2 + h ), 550 ( m + na ), 552 ( m + 2 + na ); r t = 3 . 29 min . from 4 - chloro - 1 - naphthol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; white crystals , mp 234 ° c . ; hplc - ms ( method b ): m / z 432 ( m + h ), 434 ( m + 2 + h ), r = 2 . 98 ; 1 h nmr ( cdcl 3 ) j 12 . 01 ( s , 1h ), 8 . 76 ( d , j = 9 . 10 hz , 1h ), 8 . 50 ( br d , 1h ), 8 . 33 ( d , j = 2 . 02 hz , 1h ), 8 . 21 ( s , 1h ), 8 . 20 ( dd , 1h ), 8 . 16 ( br d , 1h ), 7 . 88 - 7 . 83 ( m , 1h ), 7 . 76 - 7 . 71 ( m , 1h ). from 2 - tert - butyl - 4 - methylphenol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; white crystals , mp 209 - 212 ° c . ; 1 h nmr ( cdcl 3 ): δ 11 . 87 ( s , 1h ), 8 . 89 ( d , j = 8 . 89 hz , 1h ), 8 . 86 ( br s , 1h ), 8 . 11 ( d , j = 2 . 02 hz , 1h ), 8 . 00 ( dd , 1h ), 7 . 34 ( br d , 1h ), 7 . 19 ( br , 1h ), 2 . 36 ( s , 3h ), 1 . 43 ( s , 9h ); hplc - ms ( method b ): m / z : 450 ( m + h ), 452 ( m + 2 + h ), r t = 3 . 00 min . from 4 - chloro - 1 - naphthol and 2 - chloro - 4 - isocyanato - 1 - trifluoromethylsulfanyl - benzene ; yellow crystals , mp 148 - 149 ° c . ; hplc - ms ( method b ): m / z 432 ( m + h ), 434 ( m + 2 + h ), r t = 2 . 98 ; 1 h nmr ( cdcl 3 ) δ 13 . 49 ( s , 1h ), 9 . 73 ( br s , 1h ), 8 . 52 - 8 . 46 ( br d , 1h ), 8 . 20 - 8 . 14 ( br d , 1h ), 8 . 10 ( br s , 1h ), 8 . 05 ( br s - like ( d )), 7 . 85 - 7 . 79 ( d - like br m , 1h ), 7 . 77 - 7 . 70 ( d - like br m , 2h ), 7 . 65 - 7 . 58 ( t - like br m , 1h ). from 2 -( 1 - adamantyl )- 4 - methylphenol and 2 - chloro - 4 - isocyanato - 1 - trifluoromethylsulfanyl - benzene ; hplc - ms : m / z : 496 ( m + h ), 498 ( m + 2 + h ), 518 ( m + na ), 520 ( m + 2 + na ), r t = 3 . 42 min . from 5 , 6 , 7 , 8 - tetrahydro - 2 - naphthol and adamantan - 1 - ol in h 2 so 4 / ch 2 cl 2 ; crystals with a purple tinge , mp 169 - 169 . 5 ° c . ( from 96 % etoh ); 1 h nmr ( dmso - d 6 ): δ 6 . 89 ( s , 1h ), 6 . 36 ( s , 1h ), 4 . 53 ( s , 1h , oh ), 2 . 71 - 2 . 62 ( m , 4h ), 2 . 15 - 2 . 03 ( br m , peaks at 2 . 10 and 2 . 06 , 6h + 3h ), 1 . 80 - 1 . 70 ( m , 6h + 4h ). from 3 - adamantan - 1 - yl - 5 , 6 , 7 , 8 - tetrahydro - naphthalen - 2 - ol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; cream - colored crystals , mp 205 - 206 ° c . ; hplc - ms ( method b ): m / z : 568 ( m + h ), 570 ( m + 2 + h ), 590 ( m + na ), 592 ( m + 2 + na ); r t = 3 . 24 min . ; 1 h nmr ( dmso - d 6 ): δ 9 . 41 ( s , 1h ), 9 . 01 ( d , j = 8 . 59 hz , 1h ), 8 . 48 ( br s , 1h ), 8 . 08 ( d , j = 2 . 02 hz , 1h ), 7 . 99 ( dd , 1h ), 7 . 09 ( s , 1h ), 2 . 95 - 2 . 89 ( m , 2h ), 2 . 81 - 2 . 74 ( m , 2h ), 2 . 16 - 2 . 04 ( m , peaks at 2 . 12 and 2 . 08 , 6h + 3h ), 1 . 87 - 1 . 71 ( m , 4h + 6h ). 6 - adamantan - 1 - yl - indan - 5 - ol from 5 - indanol and adamantan - 1 - ol in h 2 so 4 / ch 2 cl 2 ; beige solid , mp 169 - 171 ° c . ; 1 h nmr ( cdcl 3 ) δ 7 . 08 ( s , 1h ), 6 . 53 ( s , 1h ), 4 . 61 ( br s , 1h ), 2 . 85 - 2 . 78 ( m , 4h ), 2 . 14 - 2 . 09 ( m , 6h ), 2 . 09 - 2 . 00 ( m , 5h ), 1 . 79 - 1 . 73 ( m , 6h ). from 6 - adamantan - 1 - yl - indan - 5 - ol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene , cream - colored crystals , mp 218 - 219 ° c . ; hplc - ms ( method b ): m / z : 554 ( m + h ), 556 ( m + 2 + h ), 576 ( m + na ), 578 ( m + 2 + na ); r t = 3 . 46 min . ; 1 h nmr ( cdcl 3 ) δ 11 . 92 ( s , 1h ), 8 . 95 ( d , 1h ), 8 . 77 ( br s , 1h ), 8 . 09 ( d , 1h ), 7 . 99 ( dd , j = 8 . 59 , 2 . 02 hz , 1h ), 7 . 34 ( s , 1h ), 3 . 36 - 3 . 28 ( m , 2h ), 2 . 95 - 2 . 88 ( m , 2h ), 2 . 25 - 2 . 12 ( m , 2h + 6h ), 2 . 12 - 2 . 05 ( br , 3h ), 1 . 84 - 1 . 73 ( m , 6h ). from 4 -( 4 - fluoro - phenylsulfanyl )- naphthalen - 1 - ol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene , pale yellow voluminous crystals , mp 195 - 198 ° c . ; hplc - ms ( method b ): m / z : 556 ( m + h ), 558 ( m + 2 + h ), 578 ( m + na ), 580 (+ 2 + na ), r t = 2 . 93 min . ; 1 h nmr ( dmso - d 6 ): δ 13 . 10 ( s , 1h ), 8 . 91 ( d , j = 9 . 10 hz , 1h ), 8 . 78 ( br s , 1h ), 8 . 53 ( d , j = 7 . 58 hz , 1h ), 8 . 27 ( d , j = 8 . 08 hz , 1h ), 8 . 11 ( d , j = 2 . 02 hz , 1h ), 8 . 00 ( dd , j = 2 . 02 hz , 9 . 10 hz , 1h ), 7 . 74 - 7 . 68 ( m , 1h ), 7 . 66 - 7 . 60 ( m + s at 7 . 62 ppm , 2h ), 7 . 25 - 7 . 19 ( m , 2h ), 7 . 02 - 6 . 95 ( m , 2h ). the starting compound 4 -( 4 - fluoro - phenylsulfanyl )- naphthalen - 1 - ol was prepared by sulfenylation of naphthalen - 1 - ol with 4 - fluoro - phenylsulfenyl chloride by a procedure similar to the one reported in the u . s . pat . no . 3 , 622 , 328 . from 2 ′, 4 ′- difluoro - 4 - hydroxy - biphenyl and adamantan - 1 - ol in h 2 so 4 / hoac ; pale crystals , mp 146 - 148 ° c . ; tlc ( toluene - heptane 7 : 3 ) r = 0 . 37 ; 1 h nmr ( cdcl 3 ) δ 7 . 40 - 7 . 31 ( m , 2h ), 7 . 20 ( dt , j = 8 . 08 , 2 . 02 hz , 1h ), 6 . 94 - 6 . 84 ( m , 2h ), 4 . 86 ( s , 1h ), 2 . 18 - 2 . 13 ( m , 6h ), 2 . 12 - 2 . 06 ( br , 3h ), 1 . 81 - 1 . 75 ( m , 6h ). from 3 - adamantan - 1 - yl - 2 ′, 4 ′- difluoro - biphenyl - 4 - ol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene , pale crystals , mp 177 - 178 ° c . ; hplc - ms ( method b ): m / z : 626 ( m + h ), 628 ( m + 2 + h ), 648 ( m + na ), 650 ( m + 2 + na ); r t = 3 . 38 min . ; 1 h nmr ( cdcl 3 ) δ 12 . 12 ( s , 1h ), 8 . 92 ( s , 1h ), 8 . 88 ( d , 1h ), 8 . 11 ( br ( d ), 1h ), 8 . 01 ( br ( dd ), 1h ), 7 . 58 ( s , 1h ), 7 . 57 ( s , 1h ), 7 . 45 - 7 . 36 ( m , 1h ), 7 . 04 - 6 . 90 ( m , 2h ), 2 . 20 ( br s , 6h ), 2 . 12 ( br s , 3h ), 1 . 81 ( br s , 6h ). a solution of 77 % m - chloroperbenzoic acid ( 0 . 036 g , 0 . 16 mmol ) in dichloromethane ( 1 ml ) was added at room temperature to a solution of 4 -( 4 - fluorophenylsulfanyl )- 1 - hydroxy - naphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide . ( 0 . 081 g , 0 . 15 mmol ) in dichloromethane ( 4 ml ). the mixture was stirred overnight and the precipitate was collected by filtration , rinsed with dichloromethane and dried to give the title compound as a white solid . yield 0 . 071 g ( 86 %); mp 198 - 199 . 5 ° c . ; hplc - ms ( method b ): m / z : 572 ( m + h ), 574 ( m + 2 + h ), 594 ( m + na ), 596 ( m + 2 + na ); r t = 2 . 48 min . ; tlc ( etoacmeoh 9 : 1 ): r f = 0 . 32 ; 1 h - nmr ( dmso - d 6 ): δ 13 . 6 ( br , 1h ), 9 . 03 - 8 . 95 ( br m , 1h ), 8 . 61 - 8 . 56 ( br m , 1h ), 8 . 44 ( d , 1h ), 8 . 26 ( br s - like ( d ), 1h ), 8 . 17 - 8 . 12 ( br d - like , 1h ), 8 . 11 - 8 . 05 ( br dd , 1h ), 7 . 75 - 7 . 67 ( m , 2h ), 7 . 60 - 7 . 44 ( m , 2h ), 7 . 37 - 7 . 29 ( m , 2h ). from 2 ′, 4 ′- difluoro - biphenyl - 4 - ol and t - butanol in h 2 so 4 / hoac ; yellow oil ; tlc ( toluene - heptane 7 : 3 ) r f = 0 . 36 ; 1 h nmr ( cdcl 3 ) δ 7 . 40 - 7 . 32 ( m , 2h ), 7 . 21 ( dt , j = 8 . 08 , 2 . 02 hz , 1h ), 6 . 95 - 6 . 85 ( m , 2h ), 6 . 72 ( d , j = 8 . 08 hz , 1h ), 4 . 90 ( s , 1h ), 1 . 44 ( s , 9h ). from 3 - tert - butyl - 2 ′, 4 ′- difluoro - biphenyl - 4 - ol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; white crystals , mp 114 - 115 ° c . ; hplc - ms ( method b ): m / z : 588 ( m + h ), 590 ( m + 2 + h ), 610 ( m + na ), 612 ( m + 2 + na ); r t = 3 . 22 min . ; 1 h nmr ( cdcl 3 ) δ 12 . 09 ( s , 1h ), 8 . 92 ( s , 1h , nh ), 8 . 89 ( d , 1h ), 8 . 11 ( br ( d ), 1h ), 8 . 01 ( br ( dd ), 1h ), 7 . 63 ( s , 1h ), 7 . 59 ( s , 1h ), 7 . 45 - 7 . 36 ( m , 1h ), 7 . 05 - 6 . 91 ( m , 2h ), 1 . 48 ( s , 9h ). 2 ′, 4 ′- difluoro - 3 -( 1 - methyl - cyclohexyl )- biphenyl - 4 - ol from 2 ′, 4 ′- difluoro - 4 - hydroxy - biphenyl and 1 - methyl - cyclohexanol in cf 3 so 3 h / toluene ; pale crystals , mp 60 - 62 ° c . ; 1 h nmr ( cdcl 3 ) δ d 7 . 41 ( br , 1h ), 7 . 40 - 7 . 33 ( m , 1h ), 7 . 20 ( dt , j = 8 . 08 , 2 . 02 hz , 1h ), 6 . 95 - 6 . 85 ( m , 2h ), 6 . 72 ( d , j = 8 . 08 , 2 . 02 hz , 1h ), 2 . 23 - 2 . 14 ( m , 2h ), 1 . 76 - 1 . 67 ( m , 6h ), 1 . 36 ( s , 3h , ch 3 ). from 2 ′, 4 ′- difluoro - 3 -( 1 - methyl - cyclohexyl )- biphenyl - 4 - ol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; white crystals , mp 114 - 115 ° c . ; hplc - ms ( method b ): m / z : 588 ( m + h ), 590 ( m + 2 + h ), 610 ( m + na ), 612 ( m + 2 + na ); r t = 3 . 22 min . ; 1 h nmr ( cdcl 3 ) δ 12 . 12 ( s , 1h ), 8 . 92 ( s , 1h ), 8 . 89 ( d , j = 8 . 6 hz , 1h , h ), 8 . 11 ( br ( d ), 1h ), 8 . 01 ( br d ( dd ), j = 8 . 08 hz 1h ), 7 . 65 ( br s , 1h ), 7 . 59 ( br s1h ), 7 . 48 - 7 . 33 ( m , 1h ), 7 . 06 - 6 . 89 ( m , 2h ), 2 . 32 - 2 . 13 ( br m , 2h ), 1 . 88 - 1 . 71 ( br m , 2h ), 1 . 71 - 1 . 28 ( br m + s , 9h ; s at 1 . 41 , ch 3 ). 1 h nmr ( dmso - d 6 ): δ 8 . 43 ( d , j = 7 . 58 hz , 1h ) 8 . 03 ( m , 4h ) 7 . 77 ( m , 4h ) 3 . 4 ( q hidden under d2o , 2h ) 1 . 18 ( t , j = 7 . 33 hz , 3h ); hplc - ms ( method a ): m / z = 357 ( m + 1 ); r t = 3 . 95 min 1 h nmr ( dmso - d 6 ): δ 8 . 73 ( d , j = 8 . 59 hz , 1h ) 8 . 51 ( d , j = 8 . 08 hz , 1h ) 8 . 33 ( d , j = 2 . 02 hz , 1h ) 8 . 19 ( dd , j = 8 . 59 and 2 . 02 hz , 1h ) 8 . 04 ( m , 3h ) 7 . 80 ( m , 3h ) 7 . 67 ( m , 2h ) 3 . 4 ( q hidden under d20 , 2h ) 1 . 19 ( t , j = 7 . 58 hz , 3h ); hplc - ms ( method a ): m / z = 598 ( m + ); r t = 5 . 31 min . 1 h nmr ( dmso - d 6 ): δ 12 . 67 ( br s , 1h ) 8 . 39 ( d , j = 8 . 08 hz , 1h ) 7 . 79 ( d , j = 7 . 58 hz , 1h ) 7 . 65 ( m , 2h ) 7 . 61 ( s , 1h ) 7 . 38 ( d , j = 8 . 59 hz , 2h ) 7 . 08 ( d , j = 8 . 59 hz , 2h ) 3 . 84 ( s , 3h ); hplc - ms ( method b ): m / z = 295 ( m + 1 ); r t = 1 . 82 min . 1 h nmr ( dmso - d 6 ): δ 11 . 67 ( br s , 1h ) 8 . 66 ( d , 1h ) 8 . 47 ( d , 1h ) 8 . 35 ( s , 1h ) 8 . 22 ( d , 1h ) 7 . 99 ( s , 1h ) 7 . 81 ( d , 1h ) 7 . 67 ( m , 2h ) 7 . 42 ( d , 2h ) 7 . 12 ( d , 2h ) 3 . 85 ( s , 3h ); hplc - ms ( method b ): m / z = 537 ( m + 1 ); r t = 2 . 89 min . 1 h nmr ( dmso - d 6 ): δ 12 . 71 ( br s , 1h ) 8 . 41 ( d , j = 7 . 58 hz , 1h ) 7 . 70 ( m , 3h ) 7 . 62 ( s , 1h ) 7 . 50 ( dd , j = 8 . 59 and 5 . 56 hz , 2h ) 7 . 35 ( dd , j = 9 . 1 hz , 2h ); hplc - ms ( method b ): m / z = 283 ( m + 1 ); r t = 1 . 85 min . 1 h nmr ( dmso - d 6 ): δ 11 . 67 ( br s , 1h ) 8 . 65 ( d , 1h ) 8 . 48 ( d , 1h ) 8 . 36 ( s , 1h ) 8 . 22 ( d , 1h ) 8 . 02 ( s , 1h ) 7 . 76 ( d , 1h ) 7 . 68 ( m , 2h ) 7 . 54 ( m , 2h ) 7 . 39 ( m , 2h ); hplc - ms ( method b ): m / z = 524 ( m + ); r t = 2 . 87 min . 1 h nmr ( dmso - d 6 ): δ 12 . 65 ( br s , 1h ) 8 . 39 ( d , j = 8 . 08 hz , 1h ) 7 . 78 ( d , j = 8 . 08 hz , 1h ) 7 . 65 ( m , 2h ) 7 . 61 ( s , 1h ) 7 . 33 ( m , 4h ) 2 . 40 ( s , 3h ); hplc - ms ( method b ): m / z = 279 ( m + 1 ); r t = 1 . 96 min . 1 h nmr ( dmso - d 6 ): δ 11 . 69 ( br s , 1h ) 8 . 67 ( d , 1h ) 8 . 48 ( d , 1h ) 8 . 35 ( s , 1h ) 8 . 22 ( d , 1h ) 8 . 00 ( s , 1h ) 7 . 82 ( d , 1h ) 7 . 67 ( m , 2h ) 7 . 40 ( d , 2h ) 7 . 36 ( d , 2h ) 2 . 42 ( s , 3h ); 1 h nmr ( dmso - d 6 ): δ 12 . 85 ( br s , 1h ) 8 . 42 ( d , j = 7 . 58 hz , 1h ) 7 . 99 ( d , j = 8 . 08 hz , 2h ) 7 . 71 ( m , 6h ); hplc - ms ( method b ): m / z = 290 ( m + 1 ); r t = 2 . 03 min . hplc - ms ( method a ): m / z = 531 ( m + 1 ) and 553 ( m + 23 ); r t = 5 . 64 min . 1 h nmr ( dmso - d 6 ): δ 8 . 41 ( d , j = 7 . 07 hz , 1h ) 7 . 78 ( d , j = 8 . 08 hz , 1h ) 7 . 70 ( m , 3h ) 7 . 34 ( m , 1h ) 7 . 22 ( m , 2h ); hplc - ms ( method a ): m / z = 301 ( m + 1 ); r t = 4 . 48 min . 1 h nmr ( dmso - d 6 ): δ 11 . 88 ( br s , 1h ) 8 . 65 ( d , j = 8 . 59 hz , 1h ) 8 . 50 ( d , j = 8 . 08 hz , 1h ) 8 . 36 ( d , j = 2 . 02 hz , 1h ) 8 . 21 ( dd , j = 8 . 59 and 2 . 02 hz , 1h ) 8 . 05 ( s , 1h ) 7 . 82 ( d , j = 8 . 08 hz , 1h ) 7 . 69 ( m , 2h ) 7 . 37 ( m , 1h ) 7 . 27 ( m , 2h ); hplc - ms ( method a ): m / z = 542 ( m + 1 ); r t = 5 . 97 min . 1 h nmr ( dmso - d 6 ): δ 12 . 8 ( br s , 1h ) 8 . 42 ( d , j = 7 . 58 hz , 1h ) 8 . 86 - 7 . 64 ( m , 8h ); hplc - ms ( method b ): m / z = 333 ( m + 1 ); r t = 2 . 33 min . 1 h nmr ( dmso - d 6 ): δ 11 . 69 ( br s , 1h ) 8 . 63 ( d , 1h ) 8 . 52 ( d , 1h ) 8 . 36 ( s , 1h ) 8 . 22 ( d , 1h ) 8 . 06 ( s , 1h ) 7 . 83 ( m , 4h ) 7 . 69 ( m , 3h ); hplc - ms ( method b ): m / z = 574 ( m + 1 ); r t = 2 . 99 min . 1 h nmr ( dmso - d 6 ): δ 12 . 8 ( br s , 1h ) 8 . 42 ( d , j = 7 . 58 hz , 1h ) 8 . 11 ( d , j = 8 . 59 hz , 2h ) 7 . 78 ( d , j = 8 . 08 hz , 1h ) 7 . 69 ( m , 3h ) 7 . 63 ( d , j = 8 . 59 hz , 2h ) 2 . 66 ( s , 3h ); hplc - ms ( method b ): m / z = 307 ( m + 1 ); r t = 1 . 997 min . 1 h nmr ( dmso - d 6 ): δ 11 . 83 ( br s , 1h ) 8 . 68 ( d , j = 8 . 59 hz , 1h ) 8 . 51 ( m , 1h ) 8 . 35 ( d , j = 2 . 02 hz , 1h ) 8 . 21 ( dd , j = 8 . 59 and 2 . 02 hz , 1h ) 8 . 14 ( d , j = 8 . 59 hz , 2h ) 8 . 06 ( s , 1h ) 7 . 81 ( m , 1h ) 7 . 68 ( m , 4h ) 2 . 67 ( s , 3h ); hplc - ms ( method b ): m / z = 548 ( m + 1 ); r t = 2 . 76 min . prep . hplc - ms ( method c ): m / z = 548 ( m + 1 ); r t = 9 . 10 min . from 4 - methyl - phenol in h 2 so 4 / ch 2 cl 2 ; colourless oil from column chromatography on silica with toluene - heptane 7 : 3 as eluent . tlc ( toluene - heptane 7 : 3 ) r f = 0 . 4 ; 1 h nmr ( cdcl 3 ) δ 7 . 06 ( d , j = 2 . 02 hz , 1h ), 6 . 86 ( dd , j = 2 . 02 , 8 . 08 hz , 1h ), 6 . 55 ( d , j = 8 . 08 hz ), 4 . 62 ( s , 1h , oh ), 2 . 26 ( s , 3h , 1 . 46 ( s , 6h ), 0 . 91 ( s , 9h ). from 4 - methyl - 2 -( 1 , 1 , 2 , 2 - tetramethyl - propyl )- phenol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; 1 h nmr ( cdcl 3 ) δ 11 . 79 ( s , 1h , oh ), 8 . 88 ( s , 1h , nh ), 8 . 87 ( d , j = 9 . 10 hz , 1h ), 8 . 11 ( d , j = 2 . 02 hz , 1h ), 7 . 99 ( dd , j = 2 . 02 hz , 9 . 10 hz , 1h ), 7 . 38 ( s , 1h ), 7 . 22 ( s , 1h ), 2 . 36 ( s , 3h ), 1 . 49 ( s , 6h ), 0 . 92 ( s , 9h ); hplc - ms ( method b ): m / z : 492 ( m + h ), 494 ( m + 2 + h ); r t = 3 . 09 min . from 4 ′- bromo - biphenyl - 4 - ol in h 2 so 4 / hoac ; white crystals , from column chromatography on silica with toluene - heptane 7 : 3 as eluent . tlc ( toluene - heptane 7 : 3 ) r f = 0 . 29 ; 1 h nmr ( cdcl 3 ) δ 7 . 52 ( 2h ) and 7 . 40 ( 2h ) ( j ab - system , j = 8 . 59 hz ), 7 . 45 ( d , j = 2 . 02 hz 1h ), 7 . 25 ( dd , 1h ), 6 . 73 ( d , j = 8 . 08 hz , 1h ), 1 . 45 ( s , 9h ). from 4 ′- bromo - 3 - tert - butyl - biphenyl - 4 - ol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; 1 h nmr ( cdcl 3 ) δ 12 . 07 ( s , 1h , oh ), 8 . 93 ( br s , 1h , nh ), 8 . 89 ( d , j = 8 . 59 hz , 1h ), 8 . 12 ( d , j = 2 . 02 hz , 1h ), 8 . 02 ( dd , 1h ), 7 . 70 ( d , j = 1 . 52 hz , 1h ), 7 . 54 ( d , j = 1 . 52 hz , 1h ), 7 . 60 ( 2h ) and 7 . 40 ( 2h ) ( j ab - system ), 1 . 49 ( s , 9h ); hplc - ms ( method b ): m / z : 590 ( m + h ), 592 ( m + 2 + h ); r t = 3 . 13 min . from 2 - tert - butyl - 5 - ethyl - phenol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; voluminous white crystals , mp 126 - 127 ° c . ; 1 h nmr ( cdcl 3 ): δ 9 . 30 ( s , 1h ), 9 . 09 ( d , j = 9 . 09 hz , h6 ′), 8 . 45 ( br s , 1h ), 8 . 09 ( d , j = 2 . 02 hz , 1h ), 8 . 01 ( dd , 1h ), 7 . 37 ( d , j = 8 . 08 hz , 1h ), 6 . 84 ( d , j = 8 . 08 hz , 1h ), 2 . 91 ( q , j = 7 . 58 hz , 2h ), 1 . 42 ( s , 9h ), 1 . 32 ( t , 3h ) ppm ; hplc - ms ( method b ): m / z : 464 ( m + h ), 466 ( m + 2 + h ), 486 ( m + na ), 488 ( m + 2 + na ), r t = 2 . 68 min . from 2 , 4 - di - tert - butyl - 5 - ethyl - phenol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; white crystals ; mp 157 - 158 ° c . ; 1 h nmr ( cdcl 3 ) δ 9 . 01 ( br d - like , 1h ), 8 . 41 ( br s , 1h ), 8 . 09 ( d , j = 2 . 0 hz , 1h ), 8 . 01 ( br dd , 1h ), 7 . 47 ( s , 1h ), 7 . 12 ( s , 1h ), 3 . 13 ( q , j = 7 . 58 hz , 2h ), 1 . 44 ( s , 9h ), 1 . 42 ( s , 9h ), 1 . 16 ( t , 3h ) ppm ; hplc - ms ( method b ): m / z : 520 ( m + h ), 522 ( m + 2 + h ), 542 ( m + na ), 544 ( m + 2 + na ), 558 ( m + k ), 560 ( m + 2 + k ), r t = 2 . 86 min . from 6 - tert - butyl - indan - 5 - ol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; pale yellow crystals , mp 172 - 173 ° c . ; 1 h nmr ( cdcl 3 ) δ 11 . 91 ( s , 1h ), 8 . 96 ( d , j = 8 . 59 hz , 1h ), 8 . 78 ( s , 1h ), 8 . 10 ( d , j = 2 . 02 hz , 1h ), 8 . 00 ( dd , 1h ), 7 . 40 ( s , 1h ), 3 . 33 ( t , 2h ), 2 . 92 ( t , 2h ), 2 . 21 ( quintet , 2h ), 1 . 43 ( s , 9h ) ppm ; hplc - ms ( method b ): m / z : 476 ( m + h ), 478 ( m + 2 + h ), 498 ( m + na ), 500 ( m + 2 + na ), r t = 2 . 86 min . from 2 - tert - butyl - 5 - methyl - 4 - methylsulfanyl - phenol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; white crystals , mp 155 . 5 - 156 . 5 ° c . ; 1 h nmr ( cdcl 3 ) δ 9 . 39 ( s , 1h ), 9 . 01 ( d , j = 9 . 09 hz , 1h ), 8 . 45 ( br s , 1h ), 8 . 09 ( d , j = 1 . 52 hz , 1h ), 8 . 02 ( dd , 1h ), 7 . 46 ( s , 1h ), 2 . 67 ( s , 3h ), 2 . 45 ( s , 1h ), 1 . 42 ( s , 9h ); hplc - ms ( method b ): m / z : 496 ( m + h ), 498 ( m + 2 + h ), 518 ( m + na ), 520 ( m + 2 + na ), r t = 2 . 76 min . from 3 - tert - butyl - 5 , 6 , 7 , 8 - tetrahydro - naphthalen - 2 - ol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; white crystals , mp 151 ° c . ( from acetonitrile ); 1 h nmr ( cdcl 3 ) δ 9 . 45 ( s , 1h ), 9 . 01 ( d , 1h ), 8 . 49 ( s , 1h ), 8 . 08 ( d , j = 1 . 52 hz , 1h ), 8 . 00 ( dd , 1h ), 7 . 15 ( s , 1h ), 2 . 96 - 2 . 89 ( m , 2h ), 2 . 82 - 2 . 74 ( m , 2h ), 1 . 89 - 1 . 72 ( m , 4h ), 1 . 41 ( s , 9h ) ppm ; hplc - ms ( method b ): m / z : 490 ( m + h ), 492 ( m + 2 + h ), r t = 2 . 92 min . a solution of m - cpba ( 77 % purity , 0 . 050 g , 0 . 22 mmol ) in dichloromethane ( 3 ml ) was added dropwise at room temperature to a stirred solution of 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 - methylsulfanyl - benzamide ( 0 . 10 g , 0 . 2 mmol ) in dichloromethane ( 3 ml ) and the mixture was stirred overnight . the solvent was removed in vacuo and the residue was extracted with ether . the insoluble residue was collected by filtration and dried to give the title compound , white crystals , mp 218 - 219 ° c . ( decomp . ); 1 h nmr ( dmso - d 6 ) δ 10 . 72 ( br s , 1h ), 9 . 60 ( s , 1h ), 8 . 71 - 8 . 56 ( m , 1h ), 8 . 30 - 8 . 14 ( m , 2h ), 7 . 76 ( s , 1h ), 2 . 66 ( s , 3h ), 2 . 27 ( s , 3h ), 1 . 42 ( s , 9h ) ppm ; hplc - ms ( method b ): m / z : 512 ( m + h ), 514 ( m + 2 + h ), 534 ( m + na ), 536 ( m + 2 + na ) r t = 2 . 14 min . from 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 - methylsulfanyl - benzamide and two equivalents of m - cpba in dichloromethane ; pale crystals , mp 220 - 221 ° c . ; 1 h nmr ( dmso - d 6 ) δ 10 . 89 ( br s , 1h ), 10 . 11 ( s , 1h ), 8 . 72 - 8 . 62 ( m , 1h ), 8 . 29 - 8 . 16 ( m , 2h ), 7 . 87 ( s , 1h ), 3 . 19 ( s , 3h ), 2 . 56 ( s , 3h ), 1 . 40 ( s , 9h ) ppm ; hplc - ms ( method b ): m / z 528 ( m + h ), 530 ( m + 2 + h ), 550 ( m + na ), 552 ( m + 2 + na ), r t = 2 . 27 min . from 2 - tert - butyl - 4 - methoxy - phenol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; pale yellow voluminous crystals , mp 126 - 127 ° c . ( phase transition ), and 137 - 138 ° c . ; 1 h nmr ( cdcl 3 ) δ 11 . 56 ( s , 1h ), 8 . 88 ( d , j = 9 . 10 hz , 1h ), 8 . 81 ( br s , 1h ), 8 . 11 ( d , j = 2 . 02 hz 1h ), 8 . 00 ( dd , 1h ), 7 . 20 ( d , j = 3 . 03 hz , 1h ), 6 . 85 ( d , j = 3 . 03 hz , 1h ), 3 . 84 ( s , 3h ), 1 . 44 ( s , 9h ); hplc - ms ( method b ): m / z : 466 ( m + h ), 468 ( m + 2 + h ), r t = 2 . 81 min . from 2 - tert - butyl - 5 - isopropyl - phenol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; off - white crystals , mp 116 - 116 . 5 ° c . ; 1 h nmr ( cdcl 3 ): δ 9 . 02 ( d , j = 8 . 59 hz , h6 ′), 8 . 42 ( s , 1h ), 8 . 30 ( br s , 1h ), 8 . 09 ( d , j = 2 . 02 hz , 1h ), 8 . 02 ( dd , 1h ), 7 . 41 ( d , j = 8 . 08 hz , 1h ), 6 . 93 ( d , j = 8 . 59 hz , 1h ), 3 . 26 ( m , 1h ), 1 . 41 ( s , 9h ), 1 . 33 ( d , 6h ) ppm ; hplc - ms ( method b ): m / z : 478 ( m + h ), 480 ( m + 2 + h ), 500 ( m + na ), 502 ( m + 2 + na ), r t = 2 . 76 min . step b : from the product formed in step a and 4 -( trifluoromethylsulfonyl ) aniline ; 1 h nmr ( dmso - d 6 ): δ 1 . 39 ( s , 9h ) 2 . 11 ( s , 3h ) 7 . 00 - 7 . 06 ( m , 2h ) 7 . 11 ( s , 1h ) 7 . 23 ( tt , j = 9 . 42 , 2 . 26 hz , 1h ) 8 . 11 ( d , j = 9 . 04 hz , 2h ) 8 . 18 ( d , j = 9 . 04 hz , 2h ) 9 . 10 ( br . s ., 1h ) 11 . 23 ( br . s ., 1h ) ppm ; hplc - ms ( method b ): m / z : 528 ( m + h ), r t = 2 . 78 min . step b : from the product formed in step a and 4 -( trifluoromethylsulfonyl ) aniline ; 1 h nmr ( dmso - d 6 ): δ 1 . 39 ( s , 9h ) 2 . 08 ( s , 3h ) 7 . 08 ( s , 1h ) 7 . 22 - 7 . 37 ( m , 4h ) 8 . 11 ( d , j = 8 . 59 hz , 2h ) 8 . 19 ( d , j = 8 . 59 hz , 2h ) 8 . 96 ( s , 1h ) 11 . 22 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z : 510 ( m + h ), r t = 2 . 71 min . step b : from the product formed in step a and 3 - chloro - 4 -( trifluoromethylsulfonyl ) aniline ; 1 h nmr ( dmso - d 6 ): δ 1 . 39 ( s , 9h ) 2 . 10 ( s , 3h ) 6 . 98 - 7 . 07 ( m , 2h ) 7 . 12 ( s , 1h ) 7 . 23 ( ft , j = 9 . 42 , 2 . 26 hz , 1h ) 8 . 01 ( dd , j = 9 . 04 , 1 . 88 hz , 1h ) 8 . 24 ( d , j = 9 . 04 hz , 1h ) 8 . 33 ( d , j = 1 . 88 hz , 1h ) 9 . 14 ( br . s ., 1h ) 11 . 37 ( br . s ., 1h ) ppm ; hplc - ms ( method b ): m / z : 562 ( m + h ), r t = 2 . 8 min . step b : from the product formed in step a and 3 - chloro - 4 -( trifluoromethylsulfonyl ) aniline ; 1 h nmr ( dmso - d 6 ): δ 1 . 39 ( s , 9h ) 2 . 07 ( s , 3h ) 7 . 09 ( s , 1h ) 7 . 22 - 7 . 36 ( m , 4h ) 8 . 01 ( dd , j = 9 . 10 , 2 . 02 hz , 1h ) 8 . 24 ( d , j = 9 . 09 hz , 1h ) 8 . 33 ( d , j = 2 . 02 hz , 1h ) 9 . 01 ( br . s ., 1h ) 11 . 36 ( br . s ., 1h ) ppm ; hplc - ms ( method b ): m / z : 544 ( m + h ), r t = 2 . 81 min . from 2 - tert - butyl - 4 - fluoro - 5 - methylphenol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; 1 h nmr ( cdcl 3 ): δ 1 . 41 ( s , 9h ) 2 . 53 ( d , j = 2 . 53 hz , 3h ) 7 . 18 ( d , j = 11 . 62 hz , 1h ) 8 . 02 ( dd , j = 9 . 10 , 2 . 02 hz , 1h ) 8 . 10 ( d , j = 2 . 02 hz , 1h ) 8 . 48 ( br . s ., 1h ) 9 . 00 ( d , j = 9 . 10 hz , 1h ) 9 . 79 ( br . s ., 1h ) ppm ; hplc - ms ( method b ): m / z : 468 ( m + h ), r t = 2 . 64 min . 1 h nmr ( dmso - d 6 ): δ 1 . 36 ( s , 9h ) 2 . 20 ( s , 3h ) 7 . 25 ( s , 1h ) 7 . 98 ( dd , j = 8 . 85 , 1 . 70 hz , 1h ) 8 . 25 ( d , j = 9 . 04 hz , 1h ) 8 . 30 ( d , j = 1 . 88 hz , 1h ) 9 . 19 ( s , 1h ) 11 . 33 ( s , 1h ); hplc - ms ( method b ): m / z = 484 , 486 ( m + 1 ); r t = 2 . 64 min . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 34 ( s , 9h ) 2 . 32 ( s , 3h ) 7 . 62 ( s , 1h ) 8 . 20 ( d , j = 8 . 67 hz , 1h ) 8 . 24 ( s , 1h ) 8 . 61 ( d , j = 8 . 67 hz , 1h ) 9 . 19 ( s , 1h ) 10 . 67 ( s , 1h ); hplc - ms ( method b ): m / z = 576 , 578 ( m + 1 ); r t = 2 . 82 min . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 36 ( s , 9h ) 7 . 24 ( s , 1h ) 8 . 05 - 8 . 23 ( m , 4h ) 9 . 14 ( s , 1h ) 11 . 19 ( s , 1h ); hplc - ms ( method b ): m / z = 450 , 452 ( m + 1 ); r t = 2 . 55 min . step b : from the product formed in step a and 4 - trifluoromethanesulfonyl aniline . step b : from the product formed in step a and 3 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ ppm 1 . 39 ( s , 9h ) 2 . 09 ( s , 3h ) 7 . 02 - 7 . 19 ( m , 2h ) 7 . 30 - 7 . 58 ( m , 2h ) 8 . 02 ( d , 1h ) 8 . 23 ( d , j = 8 . 67 hz , 1h ) 8 . 32 ( s , 1h ) 9 . 08 ( s , 1h ) 11 . 37 ( s , 1h ); step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ ppm 1 . 39 ( s , 9h ) 2 . 16 ( s , 3h ) 3 . 79 ( s , 3h ) 6 . 99 ( d , j = 8 . 67 hz , 2h ) 7 . 07 ( s , 1h ) 7 . 22 ( d , j = 8 . 67 hz , 2h ) 8 . 19 ( d , j = 8 . 67 hz , 1h ) 8 . 24 ( s , 1h ) 8 . 62 ( d , j = 8 . 67 hz , 1h ) 8 . 92 ( s , 1h ) 10 . 59 ( s , 1h ); hplc - ms ( method b ): m / z = 556 , 558 ( m + 1 ); r t = 2 . 94 min . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( cdcl 3 ): δ ppm 1 . 43 ( s , 9h ) 2 . 56 ( s , 3h ) 7 . 02 ( dd , j = 3 . 77 , 1 . 88 hz , 1h ) 7 . 26 ( d , j = 1 . 88 hz , 1h ) 7 . 40 ( s , 1h ) 7 . 63 ( dd , j = 3 . 77 , 1 . 88 hz , 1h ) 8 . 04 ( d , j = 9 . 04 hz , 1h ) 8 . 11 ( s , 1h ) 8 . 50 ( s , 1h ) 9 . 02 ( d , j = 9 . 04 hz , 1h ) 9 . 70 ( s , 1h ); hplc - ms ( method b ): m / z = 557 , 559 ( m + 1 ); r t = 2 . 76 min . step a : from 3 - bromo - 5 - tert - butyl - 6 - hydroxy - 2 - methyl - benzoic acid and 4 - dimethylsulfamoyl - boronic acid ( synlett ( 5 ): 892 - 894 apr 3 2004 ). step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( cdcl 3 ): δ 1 . 45 ( s , 9h ) 2 . 44 ( s , 3h ) 2 . 80 ( s , 6h ) 7 . 29 ( s , 1h ) 7 . 48 ( d , j = 8 . 08 hz , 2h ) 7 . 86 ( d , j = 8 . 08 hz , 2h ) 8 . 03 ( dd , j = 8 . 59 , 2 . 02 hz , 1h ) 8 . 11 ( d , j = 2 . 02 hz , 1h ) 8 . 54 ( s , 1h ) 9 . 04 ( d , j = 8 . 59 hz , 1h ) 9 . 60 ( s , 1h ); hplc - ms ( method b ): m / z = 633 , 635 ( m + 1 ); r t = 2 . 73 min . step a : from 3 - bromo - 5 - tert - butyl - 6 - hydroxy - 2 - methyl - benzoic acid and 4 - morpholine - 4 - sulfonyl ) phenyl - boronic acid ( synlett ( 5 ): 892 - 894 apr 3 2004 ). step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 39 ( s , 9h ) 2 . 16 ( s , 3h ) 3 . 79 ( s , 3h ) 6 . 99 ( d , j = 8 . 67 hz , 2h ) 7 . 07 ( s , 1h ) 7 . 22 ( d , j = 8 . 67 hz , 2h ) 8 . 19 ( d , j = 8 . 67 hz , 1h ) 8 . 24 ( s , 1h ) 8 . 62 ( d , j = 8 . 67 hz , 1h ) 8 . 92 ( s , 1h ) 10 . 59 ( s , 1h ); hplc - ms ( method b ): m / z = 556 , 558 ( m + 1 ); r t = 2 . 94 step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 39 ( s , 9h ) 2 . 16 ( s , 3h ) 6 . 05 ( s , 2h ) 6 . 74 ( dd , j = 7 . 91 , 1 . 51 hz , 1h ) 6 . 85 ( d , j = 1 . 51 hz , 1h ) 6 . 97 ( d , j = 7 . 91 hz , 1h ) 7 . 07 ( s , 1h ) 8 . 19 ( d , j = 7 . 91 hz , 1h ) 8 . 24 ( s , 1h ) 8 . 61 ( d , 1h ) 8 . 95 ( s , 1h ) 10 . 59 ( s , 1h ); hplc - ms ( method b ): m / z = 570 , 572 ( m + 1 ); r t = 2 . 74 . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 40 ( s , 9h ), 2 . 17 ( s , 3h ) 3 . 77 ( s , 3h ) 6 . 82 ( s , 1h ) 6 . 87 ( d , j = 7 . 54 hz , 1h ) 6 . 92 ( dd , j = 7 . 91 , 2 . 26 hz , 1h ) 7 . 10 ( s , 1h ) 7 . 35 ( dd , 1h ) 8 . 19 ( dd , j = 8 . 67 , 2 . 26 hz , 1h ) 8 . 24 ( d , j = 2 . 26 hz , 1h ) 8 . 62 ( d , j = 8 . 67 hz , 1h ) 8 . 98 ( s , 1h ) 10 . 58 ( s , 1h ); hplc - ms ( method b ): m / z = 556 , 578 ( m + 1 ); r t = 2 . 96 . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ 7 . 35 ( m , 1h ) 7 . 57 - 7 . 72 ( m , 4h ) 7 . 79 ( dd , 1h ) 8 . 03 ( s , 1h ) 8 . 20 ( dd , 1h ) 8 . 35 ( d , 1h ) 8 . 47 ( dd , 1h ) 8 . 65 ( d , 1h ) 11 . 7 ( s , 1h ); hplc - ms ( method b ): m / z = 542 ( m + 1 ); r t = 2 . 93 min . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ 7 . 66 - 7 . 80 ( m , 5h ) 7 . 92 ( d , 2h ) 8 . 07 ( s , 1h ) 8 . 21 ( dd , 1h ) 8 . 35 ( d , 1h ) 8 . 51 ( dd , 1h ) 8 . 67 ( d , 1h ) 11 . 74 ( s , 1h ); hplc - ms ( method b ): m / z = 574 ( m + 1 ); r t = 3 . 02 min . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ 3 . 83 ( s , 3h ) 7 . 06 ( m , 3h ) 7 . 47 ( dd , 1h ) 7 . 67 ( m , 2h ) 7 . 84 ( dd , 1h ) 8 . 04 ( s , 1h ) 8 . 21 ( dd , 1h ) 8 . 37 ( d , 1h ) 8 . 47 ( dd , 1h ) 8 . 64 ( d , 1h ) 11 . 66 ( s , 1h ); hplc - ms ( method b ): m / z = 536 ( m + 1 ); r t = 2 . 83 min . 4 - bromo - 1 - hydroxynaphthalene - 2 - carboxylic acid and 2 - chloro - 4 - trifluoromethanesulfonyl aniline were reacted as described in the general procedure ( a ), step b . 1 h nmr ( dmso - d 6 ): δ 7 . 72 ( dd , 1h ) 7 . 85 ( dd , 1h ) 8 . 10 ( d , 1h ) 8 . 20 ( d , 1h ) 8 . 34 - 8 . 39 ( m , 2h ) 8 . 45 ( d , 1h ) 8 . 73 ( d , 1h ) 11 . 97 ( s , 1h ); hplc - ms ( method b ): m / z = 510 ( m + 1 ); r t = 2 . 73 min . step b : from 5 - bromo - 3 - tert - butyl - 2 - hydroxybenzoic acid and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( dmso - d 6 ): δ 1 . 38 ( s , 9h ), 7 . 53 ( s , 1h ), 8 . 10 - 8 . 23 ( m , 3h ), 8 . 37 ( s , 1h ), 11 . 01 ( s , 1h ), 12 . 62 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z : 514 / 516 ( m + h ), r t = 2 . 91 min . step b : from the product formed in step a and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( dmso - d 6 ): δ 1 . 45 ( s , 9h ), 7 . 51 - 7 . 61 ( m , 2h ), 7 . 72 ( s , 1h ), 7 . 80 - 7 . 90 ( m , 1h ), 8 . 08 - 8 . 15 ( m , 1h ), 8 . 21 - 8 . 27 ( m , 2h ), 8 . 40 ( s , 1h ), 11 . 01 ( s , 1h ), 12 . 71 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z : 548 ( m + h ), r t = 3 . 03 min . step b : from the product formed in step a and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( dmso - d 6 ): δ 1 . 45 ( s , 9h ), 7 . 32 ( t , j = 8 . 84 hz , 2h ), 7 . 70 ( s , 1h ), 7 . 76 ( m , 2h ), 8 . 08 - 8 . 16 ( m , 1h ), 8 . 19 - 8 . 27 ( m , 2h ), 8 . 39 ( s , 1h ), 11 . 01 ( s , 1h ), 12 . 65 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z : 530 ( m + h ), r t = 3 . 01 min . step b : from the product formed in step a and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( dmso - d 6 ): δ 1 . 45 ( s , 9h ), 7 . 22 ( m , 1h ), 7 . 53 ( d , j = 7 . 58 hz , 2h ), 7 . 77 ( s , 1h ), 8 . 07 - 8 . 44 ( m , 4h ), 11 . 02 ( s , 1h ), 12 . 80 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z : 548 ( m + h ), r t = 3 . 04 min . step b : from 3 , 5 - di - tert - butyl - 2 - hydroxybenzoic acid and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( dmso - d 6 ): δ 1 . 32 ( s , 9h ), 1 . 40 ( s , 9h ), 7 . 50 ( s , 1h ), 7 . 87 ( d , j = 2 . 53 hz , 1h ), 8 . 11 - 8 . 25 ( m , 2h ), 8 . 37 ( s , 1h ), 10 . 84 ( s , 1h ), 12 . 41 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z : 492 / 494 ( m + h ), r t = 3 . 15 min . step b : from 3 - tert - butyl - 2 - hydroxy - 6 - methylbenzoic acid and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( dmso - d 6 ): δ 1 . 37 ( s , 9h ), 2 . 31 ( s , 3h ), 6 . 73 ( s , 1h ), 7 . 16 ( d , j = 8 hz , 1h ), 8 . 10 - 8 . 32 ( m , 2h ), 8 . 58 ( d , j = 8 hz , 1h ), 9 . 01 ( s , 1h ), 10 . 44 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z : 450 / 452 ( m + h ), r t = 2 . 74 min . boron trichloride 1m in dichloromethane ( 0 . 63 ml , 0 . 63 mmol ) was added to a 0 ° c . dry flask under a nitrogen atmosphere , and 3 - methylnaphthalen - 1 - ol ( prepared according to the literature ; m watanabe et al ; chem . pharm . bull . 34 ( 7 ) 2810 - 2820 , 1986 ) ( 100 mg , 0 . 63 mmol ) dissolved in 3 ml of dry toluene was added . the reaction mixture was stirred for 10 minutes at 0 ° c ., and then 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonylbenzene ( 198 . 6 mg , 0 . 70 mmol ) dissolved in 3 ml of dry toluene was added . the reaction mixture was stirred at 0 ° for 5 minutes , and then heated to 1200 for 1½ hours . the solvent was evaporated , and the residue was stirred in 50 ml of dichloromethane and 50 ml of 1m hydrochloric acid for 12 hours . the organic layer was separated , and the aqueous layer was extracted with 2 × 50 ml of dichloromethane . the combined organic layers were dried with sodium sulfate , the solvent was evaporated , and the product was finally crystallized from 3 ml of acetonitrile to give 150 mg of the title compound . 1 h nmr ( dmso - d 6 ): δ 10 . 58 ( br . s , 1h ) 10 . 19 ( br . s , 1h ) 8 . 67 ( d , 1h ) 8 . 29 - 8 . 24 ( m , 2h ) 8 . 21 ( dd , 1h ) 7 . 80 ( d , 1h ) 7 . 54 ( dd , 1h ) 7 . 48 ( dd , 1h ) 7 . 33 ( s , 1h ) 2 . 46 ( s , 3h ); hplc - ms ( method b ): m / z = 444 ( m + 1 ); r t = 2 . 587 min . 1 - hydroxy - 3 - methylnaphthalene - 2 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide ( 50 mg , 0 . 113 mmol ) was dissolved in 3 ml of dichloromethane , and the solution was cooled to 0 °. bromine ( 0 . 006 ml , 0 . 113 mmol ) dissolved in 0 . 5 ml dichloromethane was added , and the mixture was stirred for 45 minutes at 0 ° and then at room temperature for 2 hours . the solvent was evaporated , and the residue was crystallized from 2 . 5 ml of acetonitrile to give 25 mg of the title compound . 1 h nmr ( dmso - d 6 ): δ 2 . 56 ( s , 3h ) 7 . 58 ( dd , 1h ) 7 . 72 ( dd , 1h ) 8 . 18 - 8 . 34 ( m , 4h ) 8 . 66 ( d , 1h ) 10 . 34 ( br . s , 1h ) 10 . 79 ( br . s , 1h ); hplc - ms ( method b ): m / z = 524 ( m + 2 ); r t = 2 . 65 min . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 35 ( s , 9h ) 2 . 33 ( s , 3h ) 7 . 42 ( s , 1h ) 8 . 28 ( d , j = 8 . 67 hz , 1h ) 8 . 50 ( d , j = 8 . 67 hz , 1h ) 8 . 58 ( d , j = 1 . 88 hz , 1h ) 9 . 24 ( s , 1h ) 11 . 46 ( s , 1h ); hplc - ms ( method b ): m / z = 561 , 563 ( m + 1 ); r t = 2 . 75 min . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 35 - 1 . 44 ( s , 9h ) 2 . 17 ( s , 3h ) 7 . 05 - 7 . 26 ( m , 3h ) 7 . 41 - 7 . 55 ( m , 1h ) 8 . 20 ( d , j = 8 . 67 hz , 1h ) 8 . 25 ( d , j = 1 . 88 hz , 1h ) 8 . 63 ( d , j = 8 . 67 hz , 1 h ) 9 . 08 ( s , 1h ) 10 . 62 ( s , 1h ); hplc - ms ( method b ): m / z = 544 , 546 ( m + 1 ); r t = 2 . 92 min . step b : from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . step a : sodium hydride ( 2 . 8 g , 60 % dispersion in oil ) was carefully washed twice with petroleum ether , suspended in dry thf ( 150 ml ), and the suspension was cooled to 0 ° c . under nitrogen . a solution of 2 - tert - butyl - 4 - fluoro - 5 - methylphenol ( 8 . 7 g , 47 . 7 mmol ) in dry thf ( 150 ml ) was then added dropwise , and the mixture was stirred at room temperature for 2 h . a solution of chloromethyl methyl ether ( 10 . 9 ml , 143 mmol ) in dry thf ( 150 ml ) was added dropwise , and the resulting suspension was stirred at room temperature for 1 h and evaporated to dryness . the residue was partitioned between diethyl ether ( 200 ml ) and 1 n naoh ( 200 ml ). the organic layer was washed with brine ( 50 ml ), dried over mgso 4 and concentrated in vacuo to give 10 . 68 g ( 99 %) of 1 - tert - butyl - 5 - fluoro - 2 - methoxymethoxy - 4 - methylbenzene as a yellow oil ; 1 h nmr ( cdcl 3 ) δ 1 . 36 ( s , 9h ) 2 . 21 ( d , j = 1 . 88 hz , 3h ) 3 . 49 ( s , 3h ) 5 . 17 ( s , 2h ) 6 . 91 ( d , j = 7 . 16 hz , 1h ) 6 . 93 ( d , j = 12 . 06 hz , 1h ) ppm . step b : a solution of 5 g of the product formed in step a in dry thf ( 25 ml ) was cooled to − 78 ° c . under nitrogen . n - butyllithium ( n - buli ) ( 15 . 2 ml , 1 . 6 m in hexane ) was added dropwise over 5 min , and the reaction mixture was stirred at 0 ° c . for 1 . 5 h . the mixture was then transferred to a flask containing powdered , solid carbon dioxide by cannulation over a period of 5 min . the solid which formed was triturated with petroleum ether followed by diethyl ether to give 5 . 13 g ( 84 %) of 3 - tert - butyl - 5 - fluoro - 2 - methoxymethoxy - 6 - methylbenzoic acid as the lithium salt ; hplc - ms ( method b ): m / z : 293 ( m + na ), r t = 2 . 08 . step c : a solution of 2 g of the product formed in step b in water ( 25 ml ) was acidified by the addition of 1 m hcl ( 20 ml ) and extracted with dichloromethane ( 3 × 25 ml ). the combined organic phase was dried over na 2 so 4 and evaporated to dryness . the resulting free acid was dissolved in anhydrous methanol ( 25 ml ), and a few drops of boron trifluoride - diethyl etherate were added . the solution was stirred at room temperature for 65 h and evaporated to dryness . the residue was triturated with petroleum ether to give 827 mg ( 50 %) of 3 - tert - butyl - 5 - fluoro - 2 - hydroxy - 6 - methylbenzoic acid ; 1 h nmr ( dmso - d 6 ) δ 1 . 35 ( s , 9h ), 2 . 34 ( d , j = 2 . 53 hz , 3h ), 7 . 15 ( d , j = 11 . 62 hz , 1h ), ca . 12 . 5 ( br . s ., 1h ) ppm , one proton is hidden under the water peak ; hplc - ms ( method b ): m / z : 227 ( m + h ), r t = 2 . 36 min . step d : from the product formed in step c and 3 - chloro - 4 -( trifluoromethylsulfonyl ) aniline by analogy with step b in general procedure d ; 1 h nmr ( dmso - d 6 ): δ 1 . 40 ( s , 9h ) 2 . 45 ( d , j = 2 . 02 hz , 3h ) 7 . 16 ( d , j = 11 . 62 hz , 1h ) 7 . 68 - 7 . 73 ( m , 2h ) 8 . 08 ( d , j = 2 . 02 hz , 1h ) 8 . 18 ( d , j = 8 . 59 hz , 1h ) 9 . 29 ( br . s ., 1h ) ppm ; hplc - ms ( method b ): m / z : 490 / 492 ( m + na ), 468 / 470 ( m + h ), r t = 2 . 69 min . from 3 - tert - butyl - 5 - chloro - 2 - hydroxy - 6 - methylbenzoic acid and n -{ 2 - amino - 5 -[( trifluoromethyl ) sulfonyl ] phenyl }- n , n - dimethylamine by analogy with step b in general procedure d , except that the mixture was stirred for 48 h ; 1 h nmr ( cdcl 3 ): δ 1 . 41 ( s , 9h ) 2 . 57 ( s , 3h ) 2 . 71 ( s , 6h ) 7 . 41 ( s , 1h ) 7 . 85 - 7 . 97 ( m , 2h ) 8 . 88 ( d , j = 8 . 67 hz , 1h ) 9 . 47 ( br . s ., 1h ) 9 . 88 ( br . s ., 1h ) ppm ; hplc - ms ( method b ): m / z : 493 / 495 ( m + h ), r t = 2 . 94 min . from 3 - tert - butyl - 5 - chloro - 2 - hydroxy - 6 - methylbenzoic acid and n -{ 2 - amino - 5 -[( trifluoromethyl ) sulfonyl ] phenyl }- n , n - dipropylamine by analogy with step b in general procedure d , except that the mixture was stirred for 48 h ; 1 h nmr ( cdcl 3 ): δ 0 . 79 ( t , j = 7 . 00 hz , 6h ) 1 . 28 - 1 . 39 ( m , 4h ) 1 . 40 ( s , 9h ) 2 . 55 ( s , 3h ) 2 . 81 - 2 . 89 ( m , 4h ) 7 . 39 ( s , 1h ) 7 . 83 ( d , j = 2 . 26 hz , 1h ) 7 . 90 ( dd , j = 8 . 67 , 2 . 00 hz , 1h ) 8 . 84 ( d , j = 8 . 67 hz , 1h ) 9 . 48 ( br . s ., 1h ) 9 . 69 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z : 550 / 552 ( m + h ), r t = 3 . 16 min . a suspension of 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxy - 6 - methylbenzamide ( 200 mg , 0 . 45 mmol ) in dichloromethane ( 5 ml ) was cooled to 0 ° c . chlorosulfonic acid ( 178 μl , 2 . 7 mmol ) was added , and the mixture was stirred at room temperature for 3 . 5 h . the mixture was poured into ice water , and the organic phase was isolated , dried over na 2 so 4 and filtered . to the resulting solution was added morpholine ( 100 μl , 1 . 1 mmol ), and the mixture was stirred overnight at room temperature . the mixture was concentrated in vacuo and subjected to column chromatography , giving 21 mg ( 8 %) of the title compound ; 1 h nmr ( dmso - d 6 ): δ 1 . 44 ( s , 9h ) 2 . 84 ( s , 3h ) 3 . 18 - 3 . 24 ( m , 4h ) 3 . 70 - 3 . 79 ( m , 4h ) 7 . 97 - 8 . 08 ( m , 2h ) 8 . 12 ( d , j = 2 . 26 hz , 1h ) 8 . 44 ( br . s ., 1h ) 8 . 99 ( d , j = 8 . 67 hz , 1h ) 9 . 54 ( br . s ., 1h ) ppm ; hplc - ms ( method b ): m / z : 621 / 623 ( m + 23 ), 599 / 601 ( m + h ), r t = 2 . 27 . step a : 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxy - 6 - methylbenzamide ( 500 mg , 1 . 10 mmol ) was added over 5 min in small portions to a solution of chlorosulfonic acid ( 443 μl , 6 . 64 mmol ) in dichloromethane ( 20 ml ) with stirring at 0 ° c . the mixture was stirred at room temperature for 4 h and poured into ice water . the organic phase was isolated , dried over na 2 so 4 and filtered . the sticky solid was triturated with water , isolated by filtration , and dried to give 439 mg ( 72 %) of beige crystals of crude 5 - tert - butyl - 3 -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenylcarbamoyl )- 4 - hydroxy - 2 - methyl - benzenesulfonyl chloride . step b : to a solution of the product formed in step a ( 200 mg , 0 . 36 mmol ) in dichloromethane ( 3 ml ) was added dimethylamine hydrochloride ( 74 mg , 0 . 91 mmol ) and triethylamine ( 127 μl , 0 . 91 mmol ), and the mixture was stirred for 1 h at room temperature . the mixture was then concentrated in vacuo and subjected to column chromatography , giving 85 mg ( 42 %) of the pure title compound ; 1 h nmr ( cdcl 3 ): δ 1 . 43 ( s , 9h ) 2 . 82 ( s , 3h ) 2 . 84 ( s , 6h ) 7 . 99 ( s , 1h ) 8 . 04 ( dd , j = 9 . 04 , 2 . 26 hz , 1h ) 8 . 11 ( d , j = 2 . 26 hz , 1h ) 8 . 43 ( br . s ., 1h ) 8 . 99 ( d , j = 9 . 04 hz , 1h ) 9 . 57 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z : 579 / 581 ( m + 23 ), 557 / 559 ( m + h ), r t = 2 . 39 min . to a solution of crude 5 - tert - butyl - 3 -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenylcarbamoyl )- 4 - hydroxy - 2 - methyl - benzenesulfonyl chloride ( 200 mg , 0 . 36 mmol ) in dichloromethane ( 3 ml ) was added ammonia ( 1 . 8 ml of a 0 . 5 m solution in dioxane ), and the mixture was stirred for 1 h at room temperature . the mixture was concentrated in vacuo and purified by column chromatography to give 34 mg ( 18 %) of the pure title compound ; 1 h nmr ( cdcl 3 ): δ 1 . 42 ( s , 9h ) 2 . 90 ( s , 3h ) 4 . 00 ( very br . s ., 2h ) 8 . 04 ( dd , j = 9 . 04 , 1 . 88 hz , 1h ) 8 . 11 ( d , j = 1 . 88 hz , 1h ) 8 . 15 ( s , 1h ) 8 . 45 ( br . s ., 1h ) 8 . 99 ( d , j = 8 . 67 hz , 1h ) 9 . 54 ( br . s ., 1h ) ppm ; hplc - ms ( method b ): m / z : 551 / 553 ( m + 23 ), 529 / 531 ( m + h ), r t = 2 . 14 min . step a : 3 - tert - butyl - 2 - hydroxy - 6 - methoxy - benzoic acid was prepared in a sulfuric acid catalyzed t - butylation of 2 - hydroxy - 6 - methoxy - benzoic acid with t - butanol in glacial acetic acid by standard methods ; 1 h nmr ( cdcl 3 ): δ 12 . 96 ( s , 1h ), 11 . 6 ( br , 1h ), 7 . 40 ( d , j = 8 . 6 hz , 1h ), 7 . 42 ( d , j = 8 . 6 hz , 1h ), 4 . 03 ( s , 3h ), 1 . 37 ( s , 9h ); hplc - ms ( method b ): m / z 207 ( m - oh ), 225 ( m + h ), 247 ( m + na ), r t 2 . 07 min . the crude product was practically pure and was used without purification . step b : ( general procedure ( e )). from the product formed in step a and 2 - chloro - 4 - trifluoromethanesulfonyl - aniline , mp 198 - 199 ° c . ; 1 h nmr ( cdcl 3 ): 613 . 71 ( s , 1h ), 11 . 50 ( s , 1h ), 8 . 98 ( d , j = 9 . 1 hz , 1h ), 8 . 09 ( d , j = 2 . 5 hz , 1h ), 7 . 97 ( dd , j = 2 . 0 and 8 . 6 hz , 1h ), 7 . 41 ( d , j = 8 . 6 hz , 1h ), 6 . 43 ( d , j = 9 . 1 hz , 1h ), 4 . 07 ( s , 3h ), 1 . 41 ( s , 9h ); hplc - ms ( method b ): m / z 466 / 468 ( m + h ), r t 3 . 05 min . step a : 2 - tert - butyl - 4 - methoxy - 5 - methyl - phenol was prepared in a sulfuric acid catalyzed t - butylation of 4 - methoxy - 3 - methyl - phenol with t - butanol in glacial acetic acid by standard methods ; yield 93 %; 1 h nmr ( cdcl 3 ): δ 6 . 78 ( s , 1h ), 6 . 47 ( s , 1h ), 4 . 47 ( br s , 1h ), 3 . 79 ( s , 3h ), 2 . 14 ( s , 3h ), 1 . 40 ( s , 9h ). the crude oily product was practically pure and was used without purification . step b : ( general procedure ( c )). from the product formed in step a and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; off - white crystals , mp 121 - 122 ° c . ; 1 h nmr ( cdcl 3 ): δ 9 . 08 ( s , 1h ), 9 . 02 ( d , j = 9 . 1 hz , 1h ), 8 . 48 ( s , 1h ), 8 . 08 ( d , j = 2 hz , 1h ), 8 . 00 ( dd , j = 9 . 1 and 2 hz , 1h ), 7 . 06 ( s , 1h ), 3 . 85 ( s , 3h ), 2 . 46 ( s , 3h ), 1 . 43 ( s , 9h ); hplc - ms ( method b ): m / z 480 / 482 ( m + h ), 502 / 504 ( m + na ), r t 2 . 82 min . from 6 - tert - butyl - 2 , 3 - dihydro - benzofuran - 5 - ol and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; mp 201 - 202 ° c . ; 1 h nmr ( cdcl 3 ): δ 11 . 58 ( s , 1h ), 8 . 95 ( d , j = 9 hz , 1h ), 8 . 65 ( s , 1h ), 8 . 11 ( d , j = 1 . 5 hz , 1h ), 8 . 01 ( dd , j = 9 and 1 . 5 hz , 1h ), 7 . 09 ( s , 1h ), 4 . 65 ( t like m , 2h ), 3 . 64 ( t like m , 2h ), 1 . 41 ( s , 9h ); hplc - ms ( method b ): m / z 478 / 480 ( m + h ); 500 / 502 ( m + na ), r t 2 . 84 min . a stirred solution of 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 5 - methoxy - 6 - methyl - benzamide ( 0 . 150 g , 0 . 31 mmol ) in dry dichloromethane ( 2 ml ) under nitrogen was cooled to 0 ° c . a 1 m solution of boron tribromide in dichloromethane ( 0 . 34 ml , 1 . 1 equivalent ) was added dropwise and the mixture was allowed to stand at room temperature overnight and then washed with saturated aqueous sodium bicarbonate ( 10 + 2 × 5 ml ) and water ( 10 ml ), dried over sodium sulfate and filtered , and the solvent was evaporated to give the title compound ; mp 163 - 166 ° c . ; 1 h nmr ( cdcl 3 ): δ 9 . 20 ( s , 1h ), 9 . 02 ( d , j = 9 . 1 hz , 1h ), 8 . 47 ( brs , 1h ), 8 . 10 ( d , j = 2 . 5 hz , 1h ), 8 . 02 ( dd , j = 9 . 1 and 2 hz , 1h ), 6 . 95 ( s , 1h ), 4 . 62 ( br s , 1h ), 2 . 50 ( s , 3h ), 1 . 41 ( s , 9h ); hplc - ms ( method b ): m / z 466 ( m + h ), 468 ( m + 2 + h ), 488 ( m + na ), 490 ( m + 2 + na ), r t 2 . 34 min . to a stirred solution of 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 5 - methoxy - benzamide ( 0 . 200 g , 0 . 43 mmol ) in acetonitrile ( 5 ml ) was added a solution of ammonium cerium ( iv ) nitrate ( 0 . 71 g , 1 . 3 mmol ) in water ( 1 ml ). a voluminous precipitate formed and to facilitate the stirring , more acetonitrile ( 5 ml ) was added . after 2 h water ( 20 ml ) was added and the mixture was filtered . the filter cake was rinsed with water and dried . yield 0 . 198 g of crude hydroquinone ( 5 - tert - butyl - 3 , 6 - dioxo - cyclohexa - 1 , 4 - dienecarboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- amide ) as an orange solid . the crude product ( 0 . 157 g ) was heated with boiling methanol ( 15 ml ) for some minutes and allowed to stand at room temperature overnight . a precipitate was filtered off and the solvent was removed from the filtrate in vacuo . the residue was dissolved in a 1 : 2 mixture of ethyl acetate — heptane ( 5 ml ) and filtered through a short column of silica gel . removal of the solvent from the filtrate gave the title compound as a yellow oil , which crystallized by trituration with pentane ; yellow crystals , mp 171 - 175 ° c . ; 1 h nmr ( dmso - d 6 ): δ 12 . 54 ( s , 1h ), 11 . 33 ( s , 1h ), 9 . 01 ( d , j = 9 . 10 hz , 1h ), 8 . 10 ( d , j = 2 . 02 hz , 1h ), 7 . 98 ( dd , j = 2 . 02 ; 9 . 10 hz , 1h ), 7 . 20 ( s , 1h ), 4 . 95 ( s , 1h ), 3 . 97 ( s , 3h ), 1 . 41 ( s , 9h ); 13 c nmr ( cdcl 3 ): δ 169 . 16 ( c ═ o ), 156 . 81 , 142 . 40 , 141 . 87 , 139 . 43 , 136 . 59 , 131 . 55 , 130 . 85 , 125 . 76 , 124 . 00 , 122 . 06 , 119 . 70 ( cf 3 , j = 325 . 68 hz ), 106 . 34 , 62 . 66 , 35 . 05 , 29 . 20 ; hplc - ms ( method b ): m / z 482 ( m + h ), 484 ( m + 2 + h ), 504 ( m + na ), 506 ( m + 2 + na ), r t 2 . 71 min . ; c — h correlation spectra ruled out isomeric structures . step a : 2 - tert - butyl - 4 , 5 - dimethoxy - phenol was prepared in a sulfuric acid catalyzed t - butylation of 3 , 4 - dimethoxy - phenol with t - butanol in glacial acetic acid by standard methods ; purification by preparative hplc gave a pure product as a yellow oil ; 1 h nmr ( cdcl 3 ): 6 . 83 ( s , 1h ), 6 . 32 ( s , 1h ), 4 . 72 ( s , 1h ), 3 . 84 ( s , 3h ), 3 . 79 ( s , 3h ), 1 . 39 ( s , 9h ). step b : ( general procedure ( c )). from the product formed in step a and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; in this case a selective demethylation α - cured , and only the dihydroxy - monomethoxy - derivative was isolated ; mp 170 - 171 ° c . ; 1 h nmr ( cdcl 3 ): δ 12 . 77 ( s , 1h ), 11 . 14 ( s , 1h , nh ), 8 . 97 ( d , j = 9 . 10 hz , 1h ), 8 . 09 ( d , j = 2 . 02 hz , 1h ), 7 . 97 ( dd , 1h ), 7 . 15 ( s , 1h ), 7 . 02 ( s , 1h ), 3 . 93 ( s , 3h ), 1 . 42 ( s , 9h ); 13 c nmr ( cdcl 3 ) δ 169 . 63 , 156 . 61 , 142 . 64 , 142 . 14 , 137 . 04 , 131 . 44 , 130 . 60 , 129 . 70 , 125 . 49 , 124 . 40 , 122 . 20 , 119 . 71 ( q , j = 326 hz ), 116 . 94 , 102 . 28 , 57 . 44 , 34 . 84 , 29 . 38 ; hplc - ms ( method b ): m / z 482 / 484 ( m + h ), r t 2 . 86 min . ; c — h correlation spectra ruled out isomeric structures . from 2 - isopropyl - 5 - methyl - 4 - methylsulfanyl - phenol and 2 - chloro - 4 - trifluoromethanesulfonyl - aniline , 1 h nmr ( cd 3 od ): δ 8 . 78 - 8 . 63 ( br m , 1h ), 8 . 17 ( d , j = 2 . 0 hz , 1h ), 8 . 06 ( br d , j = 9 . 1 hz , 1h ), 7 . 30 ( s , 1h ), 4 . 9 ( s , water , oh , nh ), 3 . 35 , 3 . 23 ( m , methanol + methin ch ), 2 . 43 ( s , 3h ), 2 . 38 ( s , 3h ), 1 . 25 ( d , j = 7 . 1 hz , 6h ); hplc - ms ( method b ): m / z 482 / 484 ( m + h ), 504 / 506 ( m + na ), r t 2 . 58 min . step a : 2 - tert - butyl - 5 - ethyl - 4 - methoxy - phenol was prepared in a sulfuric acid catalyzed t - butylation of 3 - ethyl - 4 - methoxy - phenol with t - butanol in glacial acetic acid by standard methods ; yield 98 %; 1 h nmr ( cdcl 3 ): δ 6 . 79 ( s , 1h ), 6 . 49 ( s , 1h ), 4 . 51 ( br s , 1h ), 3 . 79 ( s , 3h ), 2 . 55 ( q , j = 7 . 6 hz , 2h ), 1 . 40 ( s , 9h ), 1 . 16 ( t , j = 7 . 6 hz , 3h ). the crude oily product was practically pure and was used without purification . step b : ( general procedure ( c )). from the product formed in step a and 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ; 1 h nmr ( cdcl 3 ): δ 8 . 87 ( d , j = 9 . 1 hz , 1h ), 8 . 30 ( s , 1h ), 8 . 00 ( d , j = 2 . 02 hz , 1h ), 7 . 90 ( dd , j = 9 . 1 and 2 . 02 hz , 1h ), 6 . 94 ( s , 1h ), 3 . 76 ( s , 3h ), 2 . 72 ( q , 2h ), 1 . 34 ( s , 9h ), 1 . 19 ( t , 3h ); hplc - ms ( method b ): m / z 494 / 496 ( m + h ), 516 / 518 ( m + na ), r t 2 . 72 min . from 3 , 5 - di - tert - butyl - 2 , 6 - dihydroxy - benzoic acid and 2 - chloro - 4 - trifluoromethanesulfonyl - aniline , mp 149 - 150 ° c . ; 1 h nmr ( cdcl 3 ): δ 11 . 77 ( s , 1h ), 8 . 29 - 8 . 26 ( br , 1h ), 8 . 13 - 8 . 07 ( br d - like , 1h ), 7 . 87 - 7 . 80 ( br d - like , 1h ), 7 . 65 ( s , 1h ), 1 . 43 ( s , 18 h ); hplc - ms ( method b ): m / z 508 / 510 ( m + h ), r t 3 . 19 min . from 3 - tert - butyl - 5 - cyano - 2 - hydroxy - 6 - methyl - benzoic acid and 2 - chloro - 4 - trifluoromethanesulfonyl aniline ; 1 h nmr ( cdcl 3 ): δ 1 . 41 ( s , 9h ) 2 . 84 ( s , 3h ) 7 . 65 ( s , 1h ) 8 . 04 ( d , j = 8 . 59 hz , 1h ) 8 . 12 ( s , 1h ) 8 . 47 ( s , 1h ) 8 . 97 ( d , j = 8 . 59 hz , 1h ) 10 . 55 ( s , 1h ); hplc - ms ( method b ): m / z = 497 / 499 ( m + 23 ), 475 / 477 ( m + 1 ); r t = 2 . 42 min . to a suspension of 5 - tert - butyl - 3 -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenylcarbamoyl )- 4 - hydroxy - 2 - methyl - benzenesulfonyl chloride ( 200 mg , 0 . 36 mmol ) in dichloromethane ( 3 ml ) was added n - methylpiperazine ( 101 μl , 0 . 91 mmol ), and the mixture was stirred for 1 . 5 h at room temperature . the mixture was concentrated in vacuo and purified by column chromatography to give the pure title compound which was isolated as colourless crystals of the hydrochloride salt ; 1 h nmr ( meod ): δ 1 . 45 ( s , 9h ) 2 . 61 ( s , 3h ) 2 . 93 ( s , 3h ) 3 . 04 - 3 . 27 ( m , 4h ) 3 . 50 - 3 . 67 ( m , 2h ) 3 . 76 - 3 . 94 ( m , 2h ) 7 . 96 ( s , 1h ) 8 . 08 ( dd , j = 8 . 67 , 1 . 88 hz , 1h ) 8 . 19 ( d , j = 1 . 88 hz , 1h ) 8 . 74 ( d , j = 8 . 67 hz , 1h ); hplc - ms ( method b ): m / z = 612 / 614 ( m + 1 ); r t = 1 . 77 min . from 3 - tert - butyl - 5 - fluoro - 2 - hydroxy - 6 - methyl - benzoic acid and 2 - amino - 5 - trifluoromethanesulfonyl - benzonitrile ; 1 h nmr ( cdcl 3 ): δ 1 . 41 ( s , 9h ) 2 . 56 ( d , j = 2 . 02 hz , 3h ) 7 . 21 ( d , j = 11 . 62 hz , 1h ) 8 . 21 - 8 . 34 ( m , 2h ) 8 . 47 ( br . s ., 1h ) 9 . 08 ( d , j = 8 . 59 hz , 1h ) 9 . 61 ( s , 1h ); hplc - ms ( method b ): m / z = 481 ( m + 23 ), 459 ( m + 1 ); r t = 2 . 46 min . from 3 - tert - butyl - 5 - fluoro - 2 - hydroxy - 6 - methyl - benzoic acid and 2 - methoxy - 4 - trifluoromethanesulfonyl aniline ; 1 h nmr ( cdcl 3 ): δ 1 . 40 ( s , 9h ) 2 . 48 ( d , j = 2 . 53 hz , 3h ) 4 . 03 ( s , 3h ) 7 . 15 ( d , j = 11 . 62 hz , 1h ) 7 . 48 ( s , 1h ) 7 . 76 ( dd , j = 8 . 59 , 2 . 02 hz , 1h ) 8 . 59 ( br . s ., 1h ) 8 . 86 ( d , j = 8 . 59 hz , 1h ) 10 . 06 ( s , 1h ); hplc - ms ( method b ): m / z = 464 ( m + 1 ); r t = 2 . 63 min . from 3 - tert - butyl - 5 - fluoro - 2 - hydroxy - 6 - methyl - benzoic acid and 2 - methyl - 4 - trifluoromethanesulfonyl aniline ; 1 h nmr ( cdcl 3 ): δ 1 . 41 ( s , 9h ) 2 . 45 ( s , 3h ) 2 . 50 ( d , j = 2 . 53 hz , 3h ) 7 . 16 ( d , j = 11 . 62 hz , 1h ) 7 . 66 ( br . s ., 1h ) 7 . 89 ( d , j = 2 . 02 hz , 1h ) 7 . 97 ( dd , j = 8 . 59 , 2 . 02 hz , 1h ) 8 . 65 ( d , j = 8 . 59 hz , 1h ) 9 . 67 ( s , 1h ); hplc - ms ( method b ): m / z = 470 ( m + 23 ), 448 ( m + 1 ); r t = 2 . 58 min . from 3 - tert - butyl - 5 - fluoro - 2 - hydroxy - 6 - methyl - benzoic acid and 2 - bromo - 4 - trifluoromethanesulfonyl aniline ; 1 h nmr ( cdcl 3 ): δ 1 . 41 ( s , 9h ) 2 . 55 ( d , j = 2 . 53 hz , 3h ) 7 . 18 ( d , j = 11 . 62 hz , 1h ) 8 . 05 ( dd , j = 8 . 59 , 2 . 02 hz , 1h ) 8 . 25 ( d , j = 2 . 02 hz , 1h ) 8 . 48 ( br . s ., 1h ) 8 . 97 ( d , j = 8 . 59 hz , 1h ) 9 . 70 ( s , 1h ); hplc - ms ( method b ): m / z = 512 / 514 ( m + 1 ); r t = 2 . 64 min . from 5 - acetyl - 3 - tert - butyl - 2 - hydroxy - 6 - methyl - benzoic acid and 2 - chloro - 4 - trifluoromethanesulfonyl aniline ; 1 h nmr ( cdcl 3 ): δ 1 . 45 ( s , 9h ) 2 . 60 ( s , 3h ) 2 . 74 ( s , 3h ) 7 . 81 ( s , 1h ) 8 . 02 ( dd , j = 8 . 59 , 2 . 02 hz , 1h ) 8 . 10 ( d , j = 2 . 02 hz , 1h ) 8 . 48 ( br . s ., 1h ) 9 . 01 ( d , j = 8 . 59 hz , 1h ) 9 . 77 ( s , 1h ); hplc - ms ( method b ): m / z = 514 / 516 ( m + 23 ), 492 / 494 ( m + 1 ); r t = 2 . 36 min . from 5 - acetyl - 3 - tert - butyl - 2 - hydroxy - 6 - methyl - benzoic acid and 2 - methoxy - 4 - trifluoromethanesulfonyl aniline ; 1 h nmr ( cdcl 3 ): δ 1 . 44 ( s , 9h ) 2 . 60 ( s , 3h ) 2 . 68 ( s , 3h ) 4 . 02 ( s , 3h ) 7 . 47 ( s , 1h ) 7 . 71 - 7 . 85 ( m , 2h ) 8 . 57 ( br . s ., 1h ) 8 . 87 ( d , j = 8 . 59 hz , 1h ) 10 . 04 ( s , 1h ); hplc - ms ( method b ): m / z = 510 ( m + 23 ), 488 ( m + 1 ); r t = 2 . 49 min . from 3 - tert - butyl - 5 - chloro - 2 - hydroxy - 6 - methyl - benzoic acid and 2 - amino - 5 - trifluoromethanesulfonyl - benzonitrile ; 1 h nmr ( dmso - d 6 ): δ 1 . 38 ( s , 9h ) 2 . 13 ( s , 3h ) 7 . 30 ( s , 1h ) 8 . 05 ( d , j = 8 . 59 hz , 1h ) 8 . 42 ( dd , j = 8 . 59 , 2 . 02 hz , 1h ) 8 . 70 ( d , j = 2 . 02 hz , 1h ) 9 . 16 ( br . s ., 1h ) 13 . 09 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 497 / 499 ( m + 23 ), 474 / 476 ( m + 1 ); r t = 2 . 47 min . a solution of fuming nitric acid ( 0 . 26 ml , 6 . 2 mmol ) in acetic acid ( 2 ml ) was added dropwise to a solution of 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxy - 6 - methylbenzamide in acetic acid ( 50 ml ) and the mixture was stirred at room temperature for 2 h . the precipitate was isolated by filtration and washed with acetic acid and petroleum ether to give the pure title compound as yellow crystals ; 1 h nmr ( cdcl 3 ): δ 1 . 44 ( s , 9h ) 2 . 79 ( s , 3h ) 8 . 05 ( dd , j = 9 . 10 , 2 . 02 hz , 1h ) 8 . 09 ( s , 1h ) 8 . 13 ( d , j = 2 . 02 hz , 1h ) 8 . 47 ( br . s ., 1h ) 8 . 99 ( d , j = 9 . 10 hz , 1h ) 10 . 05 ( s , 1h ); hplc - ms ( method b ): m / z = 517 / 519 ( m + 23 ), 495 / 497 ( m + 1 ); r t = 2 . 48 min . from 3 - tert - butyl - 5 - chloro - 2 - hydroxy - 6 - methyl - benzoic acid 2 - methyl - 4 - trifluoromethanesulfonyl aniline ; 1 h nmr ( cdcl 3 ): δ 1 . 40 ( s , 9h ) 2 . 44 ( s , 3h ) 2 . 59 ( s , 3h ) 7 . 41 ( s , 1h ) 7 . 60 ( br . s ., 1h ) 7 . 89 ( d , j = 2 . 02 hz , 1h ) 7 . 89 ( dd , j = 8 . 59 , 2 . 02 hz , 1 hz ) 8 . 67 ( d , j = 8 . 59 hz , 1h ) 9 . 37 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 486 / 488 ( m + 23 ), 464 / 466 ( m + 1 ); r t = 2 . 61 min . tosyl chloride ( 63 mg , 0 . 33 mmol ) was added to a solution of 3 - amino - 5 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - hydroxy - 2 - methyl - benzamide ( 139 mg , 0 . 3 mmol ) in pyridine ( 1 ml ) with stirring at 0 ° c . under nitrogen . the mixture was stirred for 2 h and evaporated to dryness . the residue was triturated with 1 m hydrochloric acid ( 3 ml ), and the crude product was isolated by filtration and recrystallized from heptane / ethyl acetate to yield 104 mg ( 56 %) of the pure title compound ; 1 h nmr ( cdcl 3 ): δ 1 . 21 ( s , 9h ) 2 . 44 ( s , 3h ) 2 . 53 ( s , 3h ) 6 . 71 ( s , 1h ) 7 . 29 ( d , j = 8 . 59 hz , 2h ) 8 . 01 ( dd , j = 8 . 59 , 2 . 02 hz , 1h ) 8 . 10 ( d , j = 2 . 02 hz , 1h ) 8 . 97 ( d , j = 8 . 59 hz , 1h ) 9 . 97 ( s , 1h ); hplc - ms ( method b ): m / z = 641 / 643 ( m + 23 ), 619 / 621 ( m + 1 ); r t = 2 . 51 min . from 3 - tert - butyl - 5 - chloro - 2 - hydroxy - 6 - methyl - benzoic acid 2 - methoxy - 4 - trifluoromethanesulfonyl aniline ; 1 h nmr ( cdcl 3 ): δ 1 . 40 ( s , 9h ) 2 . 57 ( s , 3h ) 4 . 02 ( s , 3h ) 7 . 40 ( s , 1h ) 7 . 48 ( s , 1h ) 7 . 77 ( dd , j = 8 . 59 , 2 . 02 hz , 1h ) 8 . 50 ( br . s ., 1h ) 8 . 86 ( d , j = 8 . 59 hz , 1h ) 9 . 71 ( s , 1h ); hplc - ms ( method b ): m / z = 480 ( m + 1 ); r t = 2 . 73 min . zinc powder ( 6 . 5 g ) was added in several portions over a period of 2 days to a vigorously stirred suspension of 3 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 2 - hydroxy - 6 - methyl - 5 - nitro - benzamide ( 887 mg , 1 . 8 mmol ) in acetic acid ( 50 ml ). the mixture was filtered , and the filtrate was evaporated to dryness . the resulting oil was triturated with water ( 10 ml ), and the crude product was filtered off , washed with water and dried to give 0 . 79 g ( 95 %) of the pure title compound ; 1 h nmr ( cdcl 3 ): δ 1 . 40 ( s , 9h ) 2 . 38 ( s , 3h ) ca . 3 . 8 ( very br s , 2h ) 6 . 87 ( s , 1h ) 8 . 00 ( dd , j = 8 . 59 , 2 . 02 hz , 1h ) 8 . 08 ( d , j = 2 . 02 hz , 1h ) 8 . 38 ( br . s ., 1h ) ca . 8 . 6 ( very br . s ., 1h ) 9 . 03 ( d , j = 8 . 59 hz , 1h ); hplc - ms ( method b ): m / z = 465 / 467 ( m + 1 ), r t = 1 . 76 min . acetic anhydride ( 22 μl , 0 . 23 mmol ) was added to a solution of 3 - amino - 5 - tert - butyl - n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - hydroxy - 2 - methyl - benzamide in acetic acid ( 2 ml ). the vessel was sealed and the solution was heated at 150 ° c . for 30 min using microwave irradiation . the cooled solution was poured into water ( 25 ml ), and the resulting precipitate was filtered off and washed with water and petroleum ether to give the crude product , which was purified by column chromatography to give 52 mg ( 47 %) of the pure title compound ; 1 h nmr ( cdcl 3 ): δ 1 . 40 ( s , 9h ) 2 . 23 ( s , 3h ) 2 . 47 ( s , 3h ) 6 . 97 ( br . s ., 1h ) 7 . 30 ( s , 1h ) 8 . 01 ( dd , j = 8 . 59 , 2 . 02 hz , 1h ) 8 . 09 ( d , j = 2 . 02 hz , 1h ) 8 . 54 ( br . s ., 1h ) 9 . 00 ( d , j = 8 . 59 hz , 1h ) 9 . 75 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 507 / 509 ( m + 1 ); r t = 2 . 22 min . step b : from the product formed in step a and 2 - methyl - 4 - trifluoromethanesulfonyl aniline 1 h nmr ( dmso - d 6 ): δ 2 . 49 ( s , 3h ) 3 . 91 ( s , 3h ) 7 . 06 ( d , j = 8 . 59 hz , 2h ) 7 . 29 ( s , 1h ) 7 . 04 ( d , j = 8 . 59 hz , 2h ) 7 . 61 ( m , 2h ) 7 . 81 ( m , 1h ) 7 . 90 ( d , j = 2 . 02 hz , 1h ) 7 . 96 ( dd , j = 2 . 02 and 8 . 59 hz , 1h ) 8 . 12 ( br . s , 1h ) 8 . 55 ( m , 2h ) 13 . 10 ( br . s , 1h ); hplc - ms ( method b ): m / z = 516 ( m + 1 ); r t = 2 . 845 min . step b : from the product formed in step a and 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( dmso - d 6 ): δ 7 . 40 ( dd , j = 8 . 34 and 8 . 34 hz , 2h ) 7 . 57 ( dd , j = 7 . 58 and 7 . 58 hz , 2h ) 7 . 64 - 7 . 74 ( m , 3h ) 8 . 10 ( s , 1h ) 8 . 18 ( d , j = 8 . 59 hz , 2h ) 8 . 25 ( d , j = 8 . 59 hz , 2h ) 8 . 45 ( d , j = 8 . 08 hz , 1h ) 11 . 09 ( br . s , 1h ) 13 . 49 ( br . s , 1h ); hplc - ms ( method b ): m / z = 490 ( m + 1 ); r t = 2 . 937 min . step b : from the product formed in step a and 2 - methyl - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( dmso - d 6 ): δ 2 . 48 ( s , 3h ) 7 . 40 ( dd , j = 8 . 84 and 8 . 84 hz , 2h ) 7 . 57 ( dd , j = 8 . 59 and 8 . 59 hz , 2h ) 7 . 64 - 7 . 71 ( m , 2h ) 7 . 77 ( d , j = 7 . 58 hz , 1h ) 8 . 04 - 8 . 12 ( m , 4h ) 8 . 45 ( d , j = 7 . 58 hz , 1h ) 10 . 93 ( br . s , 1h ); hplc - ms ( method b ): m / z = 504 ( m + 1 ); r t = 2 . 876 min . 1 h nmr ( dmso - d 6 ): δ 7 . 57 ( d , j = 9 . 1 hz , 1h ) 7 . 63 ( dd , j = 8 . 59 and 8 . 59 hz , 1h ) 7 . 70 ( dd , j = 8 . 59 and 8 . 59 hz , 1h ) 7 . 96 ( d , j = 8 . 08 hz , 1h ) 8 . 09 ( d , j = 9 . 09 hz , 1h ) 8 . 21 ( dd , j = 2 . 27 and 8 . 84 hz , 1h ) 8 . 36 ( d , j = 2 . 53 hz , 1h ) 8 . 40 ( d , j = 8 . 59 hz , 1h ) 8 . 77 ( d , j = 8 . 59 hz , 1h ) 11 . 54 ( br . s , 1h ); hplc - ms ( method b ): m / z = 430 ( m + 1 ); r t = 1 . 524 min . 8 - methyl - naphthalen - 1 - ol ( 142 mg , 0 . 898 mmol ) ( w . cocker et al ., j . chem . soc . 1960 , 2230 ) was dissolved in 5 ml of dry toluene under a nitrogen atmosphere , and the solution was cooled to 0 ° c . boron trichloride ( 1m in dichloromethane ) ( 0 . 98 ml , 0 . 98 mmol ) was added and the reaction mixture was stirred for 10 min at 0 ° c . 2 - chloro - 1 - isocyanato - 4 - trifluoromethanesulfonyl - benzene ( 256 . 3 mg , 0 . 898 mmol ) was dissolved in 10 ml dry toluene and added to the reaction mixture . after 5 min at 0 ° c . the mixture was heated at 120 ° c . for 1 . 5 h . the reaction mixture was suspended in methanol and filtered , and the isolated product was then recrystallized from 15 ml of acetonitrile to afford 118 mg ( 30 %) of the title compound as a yellow solid . 1 h nmr ( cdcl 3 ): δ 3 . 01 ( s , 3h ) 7 . 32 ( m , 2h ) 7 . 44 ( d , j = 9 . 1 , 1h ) 7 . 49 ( d , j = 7 . 58 and 7 . 58 hz , 1h ) 7 . 62 ( d , j = 8 . 08 hz , 1h ) 8 . 02 ( dd , j = 2 . 02 and 8 . 59 hz , 1h ) 8 . 13 ( d , j = 2 . 02 hz , 1h ) 8 . 95 ( d , j = 9 . 1 hz , 1h ) 13 . 49 ( br . s , 1h ); hplc - ms ( method b ): m / z = 444 ( m + 1 ); r t = 2 . 82 min . 1 h nmr ( dmso - d 6 ): δ 6 . 98 - 7 . 14 ( m , 2h ) 7 . 44 - 7 . 57 ( m , 1h ) 8 . 06 ( dd , j = 7 . 91 , 1 . 88 hz , 1h ) 8 . 18 ( dd , j = 9 . 04 , 2 . 26 hz , 1h ) 8 . 31 ( d , j = 2 . 26 hz , 1h ) 9 . 05 ( d , j = 8 . 67 hz , 1h ) 11 . 59 ( br . s ., 1h ) 12 . 26 ( br . s ., 1h ). step b : from the product formed in step a , benzyl bromide and sodium borohydride . step c : from the product formed in step b and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 26 ( s , 9h ) 2 . 34 ( s , 3h ) 3 . 99 ( s , 2h ) 7 . 05 ( s , 1h ) 7 . 18 - 7 . 34 ( m , 5h ) 8 . 17 ( d , 1h ) 8 . 24 ( d , 1h ) 8 . 59 ( dd , 1h ) 9 . 04 ( s , 1h ) 10 . 54 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 572 , 574 ( m + 1 ); r t = 2 . 97 min . step b : from the product formed in step a , 2 - iodopropane and sodium borohydride . step c : from the product formed in step b and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 21 ( d , j = 7 . 07 hz , 6h ) 1 . 36 ( s , 9h ) 2 . 38 ( s , 3h ) 3 . 09 - 3 . 24 ( m , 1h ) 7 . 34 ( s , 1h ) 8 . 18 ( d , 1h ) 8 . 24 ( s , 1h ) 8 . 59 ( d , 1h ) 9 . 12 ( s , 1h ) 10 . 64 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 524 , 526 ( m + 1 ); r t = 2 . 96 min . step b : from the product formed in step a , 1 - iodopropane and sodium borohydride . step c : from the product formed in step b and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( dmso - d 6 ): δ ppm 0 . 97 ( t , j = 7 . 35 hz , 3h ) 1 . 37 ( s , 9h ) 1 . 47 - 1 . 62 ( m , 2h ) 2 . 34 ( s , 3h ) 2 . 78 ( t , j = 7 . 16 hz , 2h ) 7 . 30 ( s , 1h ) 8 . 19 ( d , j = 9 . 42 hz , 1h ) 8 . 24 ( s , 1h ) 8 . 59 ( d , j = 8 . 67 hz , 1h ) 9 . 01 ( s , 1h ) 10 . 61 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 524 , 526 ( m + 1 ); r t = 2 . 93 min . step b : from the product formed in step a , 1 - iodopropane and sodium borohydride . step c : from the product formed in step b and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . step d : from the product formed in step c and 3 - chloroperoxybenzoic acid ( 1 . 0 equivalent ), in dichloromethane at room temperature . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 01 ( t , j = 7 . 35 hz , 3h ) 1 . 40 ( s , 9h ) 1 . 51 - 1 . 79 ( m , 2h ) 2 . 27 ( s , 3h ) 2 . 58 - 2 . 70 ( m , 1h ) 2 . 71 - 2 . 89 ( m , 1h ) 7 . 68 ( s , 1h ) 8 . 18 ( d , 1h ) 8 . 25 ( s , 1h ) 8 . 62 ( d , 1h ) 9 . 59 ( s , 1h ) 10 . 72 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 541 , 543 ( m + 1 ); r t = 2 . 33 min . step b : from the product formed in step a , benzyl bromide and sodium borohydride . step c : from the product formed in step b and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . step d : from the product formed in step c and hydrogen peroxide in acetic acid at room temperature . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 26 ( s , 9h ) 2 . 24 ( s , 3h ) 3 . 91 ( d , j = 13 . 14 hz , 1h ) 4 . 19 ( d , j = 12 . 13 hz , 1h ) 7 . 00 ( d , j = 7 . 07 hz , 2h ) 7 . 15 ( s , 1h ) 7 . 21 - 7 . 34 ( m , 3h ) 8 . 20 ( d , 1h ) 8 . 26 ( s , 1h ) 8 . 61 ( d , 1h ) 9 . 55 ( s , 1h ) 10 . 61 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 588 , 590 ( m + 1 ); r t = 2 . 53 min . 1 h nmr ( dmso - d 6 ): δ 0 . 91 ( t , j = 7 . 33 hz , 3h ) 1 . 37 ( s , 9h ) 1 . 53 - 1 . 65 ( m , 2h ) 2 . 27 ( s , 3h ) 2 . 76 - 2 . 86 ( m , 2h ) 7 . 23 ( s , 1h ) 7 . 93 ( s , 1h ) 8 . 02 ( d , j = 8 . 08 hz , 1h ) 8 . 42 ( d , j = 8 . 08 hz , 1h ) 9 . 03 ( s , 1h ) 10 . 32 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 492 , 494 ( m + 1 ); r t = 2 . 81 min . step b : from the product formed in step a , 1 - iodo - 2 - methylpropane and sodium borohydride . step c : from the product formed in step b and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( dmso - d 6 ): δ ppm 0 . 99 ( d , j = 6 . 78 hz , 6h ) 1 . 37 ( s , 9h ) 1 . 66 - 1 . 80 ( m , 1h ) 2 . 34 ( s , 3h ) 2 . 69 ( d , j = 6 . 41 hz , 2h ) 7 . 29 ( s , 1h ) 8 . 19 ( d , j = 8 . 67 hz , 1h ) 8 . 24 ( s , 1h ) 8 . 59 ( d , j = 8 . 29 hz , 1h ) 9 . 00 ( s , 1h ) 10 . 60 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 538 , 540 ( m + 1 ); r t = 2 . 94 min . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 19 ( t , j = 7 . 35 hz , 3h ) 1 . 37 ( s , 9h ) 2 . 27 ( s , 3h ) 2 . 84 ( q , j = 7 . 28 hz , 2h ) 7 . 23 ( s , 1h ) 7 . 93 ( s , 1h ) 8 . 03 ( d , j = 9 . 04 hz , 1h ) 8 . 40 ( d , j = 8 . 67 hz , 1h ) 9 . 04 ( s , 1h ) 10 . 37 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 478 , 480 ( m + 1 ); r t = 2 . 67 min . step b : from the product formed in step a , benzylbromide and sodium borohydride . step c : from the product formed in step b and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . step e : from the product formed in step c and hydrogen peroxide in acetic acid at 100 ° c . 1 h nmr ( dmso - d 6 ): δ d ppm 1 . 25 ( s , 9h ) 2 . 50 ( s , 3h ) 4 . 54 ( s , 2h ) 7 . 14 ( d , j = 6 . 57 hz , 2h ) 7 . 26 - 7 . 40 ( m , 4h ) 8 . 22 ( d , 1h ) 8 . 26 ( s , 1h ) 8 . 64 ( d , 1h ) 10 . 08 ( s , 1h ) 10 . 81 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 604 , 606 ( m + 1 ); r t = 2 . 53 min . step b : from the product formed in step a , 1 - iodopropane and sodium borohydride . step c : from the product formed in step b and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . step e : from the product formed in step c and hydrogen peroxide in acetic acid at 100 ° c . 1 h nmr ( dmso - d 6 ): δ 0 . 96 ( t , j = 7 . 35 hz , 3h ) 1 . 39 ( s , 9h ) 1 . 54 - 1 . 71 ( m , 2h ) 2 . 52 ( s , 3h ) 3 . 14 - 3 . 27 ( m , 2h ) 7 . 81 ( s , 1h ) 8 . 22 ( d , j = 8 . 67 hz , 1h ) 8 . 26 ( s , 1h ) 8 . 65 ( d , j = 8 . 67 hz , 1h ) 10 . 11 ( s , 1h ) 10 . 86 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 556 , 558 ( m + 1 ); r t = 2 . 48 min . step b : from the product formed in step a and 2 - methyl - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 40 ( s , 9h ) 2 . 18 ( s , 3h ) 2 . 46 ( s , 3h ) 7 . 10 ( s , 1h ) 7 . 53 ( d , j = 8 . 59 hz , 2h ) 7 . 91 ( d , j = 8 . 08 hz , 2h ) 8 . 01 ( d , 1h ) 8 . 00 ( s , 1h ) 8 . 39 ( d , j = 8 . 08 hz , 1h ) 9 . 11 ( s , 1h ) 10 . 39 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 531 ( m + 1 ); r t = 2 . 79 min . step b : from the product formed in step a and 2 - ethyl - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 09 ( t , j = 6 . 82 hz , 3h ) 1 . 40 ( s , 9h ) 2 . 18 ( s , 3h ) 2 . 87 ( q , j = 7 . 58 hz , 2h ) 7 . 10 ( s , 1h ) 7 . 54 ( d , j = 8 . 08 hz , 2h ) 7 . 90 ( d , 2h ) 7 . 91 ( s , 1h ) 8 . 02 ( d , j = 8 . 59 hz , 1h ) 8 . 44 ( d , j = 8 . 59 hz , 1h ) 9 . 05 ( s , 1h ) 10 . 41 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 545 ( m + 1 ); r t = 2 . 77 min . step b : from the product formed in step a and 2 - cyano - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 38 ( s , 9h ) 2 . 19 ( s , 3h ) 7 . 13 ( s , 1h ) 7 . 53 ( d , j = 8 . 08 hz , 2h ) 7 . 91 ( d , j = 8 . 08 hz , 2h ) 8 . 41 ( d , 1h ) 8 . 47 ( d , 1h ) 8 . 71 ( s , 1h ) 9 . 26 ( s , 1h ) 11 . 50 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 542 ( m + 1 ); r t = 2 . 62 min . step b : from the product formed in step a , 2 - iodopropane and sodium borohydride . step c : from the product formed in step b and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . step e : from the product formed in step c and hydrogen peroxide in acetic acid at 100 ° c . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 18 ( d , j = 7 . 07 hz , 6h ) 1 . 39 ( s , 9h ) 2 . 28 ( s , 3h ) 3 . 36 - 3 . 43 ( m , 1h ) 7 . 77 ( s , 1h ) 8 . 22 ( d , j = 8 . 59 hz , 1h ) 8 . 26 ( s , 1h ) 8 . 65 ( d , j = 9 . 10 hz , 1h ) 10 . 14 ( s , 1h ) 10 . 87 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 556 , 558 ( m + 1 ); r t = 2 . 40 min . step b : from the product formed in step a , 2 - iodopropane and sodium borohydride . step c : from the product formed in step b and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . step d : from the product formed in step c and hydrogen peroxide in acetic acid at room temperature . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 01 ( d , j = 6 . 57 hz , 3h ) 1 . 21 ( d , j = 7 . 07 hz , 3h ) 1 . 40 ( s , 9h ) 2 . 28 ( s , 3h ) 2 . 77 - 2 . 91 ( m , 1h ) 7 . 60 ( s , 1h ) 8 . 20 ( d , j = 9 . 10 hz , 1h ) 8 . 25 ( s , 1h ) 8 . 63 ( d , j = 8 . 59 hz , 1h ) 9 . 61 ( s , 1h ) 10 . 74 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 540 , 542 ( m + 1 ); r t = 2 . 45 min . step b : from the product formed in step a and 2 - propyl - 4 - trifluoromethanesulfonyl aniline . 1 h nmr ( cdcl 3 ): δ ppm 1 . 03 ( t , j = 7 . 33 hz , 3h ) 1 . 43 ( s , 9h ) 1 . 65 - 1 . 79 ( m , 2h ) 2 . 39 ( s , 3h ) 2 . 68 ( t , j = 7 . 83 hz , 2h ) 7 . 25 ( d , 2h ) 7 . 42 ( d , j = 8 . 59 hz , 2h ) 7 . 73 ( s , 1h ) 7 . 75 ( s , 1h ) 7 . 89 ( s , 1h ) 7 . 97 ( dd , j = 8 . 84 , 2 . 27 hz , 1h ) 8 . 62 ( d , j = 8 . 59 hz , 1h ) 9 . 34 ( s , 1h ); hplc - ms ( method b ): m / z = 559 ( m + 1 ); r t = 2 . 83 min . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 36 ( s , 9h ) 2 . 22 ( s , 3h ) 7 . 26 ( s , 1h ) 8 . 32 ( dd , 1h ) 8 . 39 ( d , 1h ) 8 . 58 ( d , j = 2 . 02 hz , 1h ) 9 . 30 ( s , 1h ) 11 . 59 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 475 , 477 ( m + 1 ); r t = 2 . 58 min . step b : from the product formed in step a , 1 - iodo - 2 - methylpropane and sodium borohydride . step c : from the product formed in step b and 2 - chloro - 4 - trifluoromethanesulfonyl aniline . step d : from the product formed in step c and 3 - chloroperoxybenzoic acid ( 1 . 0 equivalent ) in dichloromethane at room temperature . 1 h nmr ( dmso - d 6 ): δ ppm 1 . 02 ( d , j = 6 . 41 hz , 3h ) 1 . 11 ( d , j = 6 . 78 hz , 3h ) 2 . 05 - 2 . 19 ( m , 1h ) 2 . 26 ( s , 3h ) 2 . 56 - 2 . 63 ( m , 2h ) 7 . 71 ( s , 1h ) 8 . 22 ( d , 1h ) 8 . 25 ( s , 1h ) 8 . 61 ( d , 1h ) 9 . 58 ( s , 1h ) 10 . 69 ( br . s ., 1h ); hplc - ms ( method b ): m / z = 554 , 556 ( m + 1 ); r t = 2 . 41 min . from 2 - hydroxy - 3 - isopropyl - 6 - methylbenzoic acid and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 400 mhz , dmso - d 6 ): δ 1 . 16 ( d , j = 6 . 57 hz , 6h ), 2 . 28 ( s , 3h ), 3 . 28 ( m , j = 6 . 6 hz , 1h ), 6 . 78 ( d , j = 8 . 08 hz , 1h ), 7 . 16 ( d , j = 8 . 08 hz , 1h ), 8 . 17 ( d , j = 8 . 59 hz , 1h ), 8 . 25 ( s , 1h ), 8 . 54 ( d , j = 8 . 59 hz , 1h ), 8 . 95 ( s , 1h ), 10 . 44 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z = 436 / 438 ( m + h ), r t = 2 . 66 min . from 2 - hydroxy - 6 - methylbenzoic acid and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 400 mhz , dmso - d 6 ): δ 2 . 34 ( s , 3h ), 6 . 76 ( d , j = 7 . 58 hz , 1h ), 6 . 80 ( d , j = 8 . 08 hz , 1h ), 7 . 20 ( t , j = 7 . 83 hz , 1h ), 8 . 16 ( dd , j = 8 . 59 , 2 . 02 hz , 1h ), 8 . 26 ( d , j = 2 . 02 hz , 1h ), 8 . 62 ( d , j = 8 . 59 hz , 1h ), 10 . 35 ( s , 1h ), 10 . 46 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z = 394 / 396 ( m + h ), r t = 2 . 30 min . from 5 - chloro - 2 - hydroxybenzoic acid and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 7 . 11 ( d , j = 8 . 67 hz , 1h ), 7 . 56 ( dd , j = 8 . 85 , 2 . 83 hz , 1h ), 7 . 98 ( d , j = 3 . 01 hz , 1h ), 8 . 19 ( dd , j = 8 . 85 , 2 . 07 hz , 1h ), 8 . 32 ( d , j = 2 . 26 hz , 1h ), 9 . 01 ( d , j = 9 . 04 hz , 1h ), 11 . 52 ( s , 1h ), 12 . 63 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 414 / 416 / 418 ( m + h ), r t = 2 . 48 min . from 2 - hydroxy - 6 - isopropyl - 3 - methylbenzoic acid and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 1 . 19 ( d , j = 6 . 78 hz , 6h ), 2 . 18 ( s , 3h ), 2 . 97 ( m , j = 6 . 8 hz , 1h ), 6 . 81 ( d , j = 7 . 91 hz , 1h ), 7 . 14 ( d , j = 7 . 54 hz , 1h ), 8 . 16 ( dd , j = 8 . 29 , 2 . 26 hz , 1h ), 8 . 24 ( d , j = 2 . 26 hz , 1h ), 8 . 50 ( d , j = 8 . 29 hz , 1h ), 8 . 84 ( s ( br ), 1h ), 10 . 55 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 436 / 438 ( m + h ), r t = 2 . 50 min . from 5 - fluoro - 2 - hydroxybenzoic acid and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 7 . 10 ( dd , j = 9 . 04 , 4 . 52 hz , 1h ), 7 . 40 ( dt , j = 8 . 38 , 3 . 20 hz , 1h ), 7 . 74 ( dd , j = 9 . 42 , 3 . 39 hz , 1h ), 8 . 19 ( dd , j = 8 . 85 , 2 . 07 hz , 1h ), 8 . 32 ( d , j = 2 . 26 hz , 1h ), 9 . 02 ( d , j = 9 . 04 hz , 1h ), 11 . 59 ( s ( br ), 1h ), 12 . 35 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 398 / 400 ( m + h ), r t = 2 . 22 min . from 3 - chloro - 6 - hydroxy - 5 - isopropyl - 2 - methylbenzoic acid ( obtainable by chlorination of 2 - hydroxy - 3 - isopropyl - 6 - methylbenzoic acid by the procedure described in ind . j . chem ., sect b 2004 , 43 , 1335 - 1338 ) and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ1 . 17 ( d , j = 6 . 78 hz , 6h ), 2 . 25 ( s , 3h ), 3 . 28 ( m , j = 6 . 8 hz , 1h ), 7 . 26 ( s , 1h ), 8 . 19 ( d , j = 8 . 67 hz , 1h ), 8 . 26 ( d , j = 1 . 88 hz , 1h ), 8 . 53 ( d , j = 8 . 67 hz , 1h ), 9 . 13 ( s , 1h ), 10 . 61 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z = 470 / 472 / 474 ( m + h ), r t = 2 . 56 min . from 3 - chloro - 6 - hydroxy - 2 - methylbenzoic acid ( obtainable by chlorination of 2 - hydroxy - 6 - methylbenzoic acid by the procedure described in ind . j . chem ., sect b 2004 , 43 , 1335 - 1338 ) and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 2 . 29 ( s , 3h ), 6 . 80 ( d , j = 8 . 67 hz , 1h ), 7 . 33 ( d , j = 8 . 67 hz , 1h ), 8 . 17 ( d , j = 8 . 67 hz , 1h ), 8 . 26 ( d , j = 1 . 88 hz , 1h ), 8 . 51 ( d , j = 8 . 67 hz , 1h ), 10 . 23 ( s ( br ), 1h ), 10 . 58 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 428 / 430 / 432 ( m + h ), r t = 2 . 24 min . from 3 , 5 - dichloro - 2 - hydroxy - 6 - methylbenzoic acid ( obtainable by dichlorination of 2 - hydroxy - 6 - methylbenzoic acid by the procedure described in ind . j . chem ., sect b 2004 , 43 , 1335 - 1338 ) and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , cdcl 3 ): δ 2 . 42 ( s , 3h ), 6 . 65 ( s , 1h ), 7 . 46 ( s , 1h ), 7 . 94 ( d , j = 9 . 04 hz , 1h ), 8 . 02 ( s , 1h ), 8 . 42 ( s , 1h ), 8 . 92 ( d , j = 8 . 67 hz , 1h ) ppm ; hplc - ms ( method b ): m / z = 462 / 464 / 466 ( m + h ), r t = 2 . 26 min . obtainable by chlorination of n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxy - 6 - isopropyl - 3 - methylbenzamide by the procedure described in ind . j . chem ., sect . b 2004 , 43 , 1335 - 1338 ; 1 h nmr ( 400 mhz , dmso - d 6 ): δ 1 . 34 ( d , j = 7 . 58 hz , 6h ), 2 . 18 ( s , 3h ), 3 . 17 ( m , 1h ), 7 . 22 ( s , 1h ), 8 . 18 ( dd , j = 8 . 59 , 2 . 02 hz , 1h ), 8 . 25 ( d , j = 2 . 02 hz , 1h ), 8 . 49 ( d , j = 8 . 59 hz , 1h ), 9 . 10 ( s , 1h ), 10 . 61 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z = 470 / 472 ( m + h ), r t = 2 . 58 min . from 2 , 3 , 5 - trimethylphenol and 2 - chloro - 1 - isocyanato - 4 -( trifluoromethanesulfonyl ) benzene ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 2 . 10 ( s , 3h ), 2 . 21 ( s , 3h ), 2 . 28 ( s , 3h ), 6 . 65 ( s , 1h ), 8 . 16 ( dd , j = 8 . 67 , 1 . 88 hz , 1h ), 8 . 25 ( d , j = 1 . 88 hz , 1h ), 8 . 62 ( d , j = 8 . 67 hz , 1h ), 9 . 09 ( s ( br ), 1h ), 10 . 39 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 422 / 424 ( m + h ), r t = 2 . 49 min . from 4 - chloro - 2 - hydroxybenzoic acid and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 7 . 10 ( s ( br ), 1h ), 7 . 12 ( dd , j = 9 , 1 . 8 hz , 1h ), 8 . 06 ( d , j = 8 . 67 hz , 1h ), 8 . 19 ( dd , j = 9 . 04 , 2 . 26 hz , 1h ), 8 . 32 ( d , j = 2 . 26 hz , 1h ), 9 . 02 ( d , j = 9 . 04 hz , 1h ), 11 . 47 ( s ( br ), 1h ), 12 . 82 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 414 / 416 / 418 ( m + h ), r t = 2 . 39 min . from 2 - hydroxybiphenyl - 3 - carboxylic acid and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 7 . 17 ( t , j = 7 . 72 hz , 1h ), 7 . 40 ( m , 1h ), 7 . 48 ( t , j = 7 . 54 hz , 2h ), 7 . 52 - 7 . 59 ( m , 3h ), 8 . 10 ( dd , j = 7 . 7 , 1 . 5 hz , 1h ), 8 . 21 ( dd , j = 8 . 85 , 2 . 07 hz , 1h ), 8 . 33 ( d , j = 2 . 26 hz , 1h ), 8 . 68 ( d , j = 9 . 04 hz , 1h ), 11 . 55 ( s ( br ), 1h ), 11 . 63 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 456 / 458 ( m + h ), r t = 2 . 62 min . from 2 , 3 , 4 , 5 - tetrafluoro - 6 - hydroxybenzoic acid and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 400 mhz , cdcl 3 ): δ 8 . 03 ( dd , j = 9 . 10 , 2 . 02 hz , 1h ), 8 . 15 ( d , j = 2 . 02 hz , 1h ), 8 . 88 ( d , j = 9 . 10 hz , 1h ), 9 . 56 ( d , j = 21 . 73 hz , 1h ), 12 . 44 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z = 452 / 454 ( m + h ), r t = 2 . 31 min . step b : from the product formed in step a , 5 - tert - butyl - 4 - hydroxy - 2 - methylbiphenyl - 3 - carboxylic acid , and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 1 . 40 ( s , 9h ), 2 . 16 ( s , 3h ), 7 . 10 ( s , 1h ), 7 . 26 - 7 . 33 ( m , 2h ), 7 . 33 - 7 . 39 ( m , 1h ), 7 . 39 - 7 . 50 ( m , 2h ), 8 . 20 ( d , j = 8 . 67 hz , 1h ), 8 . 24 ( s ( br ), 1h ), 8 . 63 ( d , j = 8 . 67 hz , 1h ), 9 . 00 ( s , 1h ), 10 . 64 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z = 426 / 428 ( m + h ), r t = 2 . 94 min . from 3 , 5 - difluoro - 2 - hydroxybenzoic acid ( cf . synth . comm . 1996 , 26 , 2775 - 2781 ) and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 7 . 53 - 7 . 74 ( m , 2h ), 8 . 20 ( d ( br ), j = 9 . 04 hz , 1h ), 8 . 32 ( s ( br ), 1h ), 8 . 98 ( d , j = 9 . 04 hz , 1h ), 11 . 64 ( s ( br ), 1h ), 12 . 65 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 416 / 418 ( m + h ), r t = 2 . 40 min . step a : from 3 - bromo - 6 - hydroxy - 2 - methylbenzoic acid ( obtainable by bromination of 2 - hydroxy - 6 - methylbenzoic acid according to the procedure described in j . org . chem . 1997 , 62 , 4504 - 4506 ) and 3 , 5 - difluorophenylboronic acid . step b : from the product formed in step a , 3 ′, 5 ′- difluoro - 4 - hydroxy - 2 - methylbiphenyl - 3 - carboxylic acid , and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 2 . 21 ( s , 3h ), 6 . 87 ( d , j = 8 . 29 hz , 1h ), 6 . 97 - 7 . 09 ( m , 2h ), 7 . 19 ( d , j = 8 . 29 hz , 1h ), 7 . 24 ( m , 1h ), 8 . 17 ( d ( br ), j = 8 . 67 hz , 1h ), 8 . 26 ( s ( br ), 1h ), 8 . 54 ( d ( br ), j = 8 . 67 hz , 1h ), 10 . 24 ( s ( br ), 1h ), 10 . 52 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 506 / 508 ( m + h ), r t = 2 . 56 min . step a : from 3 - bromo - 6 - hydroxy - 2 - methylbenzoic acid ( obtainable by bromination of 2 - hydroxy - 6 - methylbenzoic acid according to the procedure described in j . org . chem . 1997 , 62 , 4504 - 4506 ) and 4 - cyanophenylboronic acid . step b : from the product formed in step a , 4 ′- cyano - 4 - hydroxy - 2 - methylbiphenyl - 3 - carboxylic acid , and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 2 . 19 ( s , 3h ), 6 . 89 ( d , j = 8 . 29 hz , 1h ), 7 . 18 ( d , j = 8 . 29 hz , 1h ), 7 . 51 ( d , j = 7 . 73 hz , 2h ), 7 . 90 ( d , j = 7 . 73 hz , 2h ), 8 . 17 ( d ( br ), j = 8 . 67 hz , 1h ), 8 . 25 ( s ( br ), 1h ), 8 . 54 ( d , j = 8 . 67 hz , 1h ), 10 . 24 ( s ( br ), 1h ), 10 . 52 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 495 / 497 ( m + h ), r t = 2 . 40 min . from 4 - fluoro - 2 - hydroxybenzoic acid and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 6 . 84 ( dd , j = 10 . 55 , 2 . 36 hz , 1h ), 6 . 91 ( dt , j = 8 . 57 , 2 . 36 hz , 1h ), 8 . 12 ( dd , j = 9 . 04 , 7 . 16 hz , 1h ), 8 . 18 ( dd , j = 8 . 67 , 1 . 88 hz , 1h ), 8 . 31 ( d , j = 1 . 88 hz , 1h ), 9 . 02 ( d , j = 8 . 67 hz , 1h ), 11 . 40 ( s , 1h ), 12 . 85 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 398 / 400 ( m + h ), r t = 2 . 34 min . step a : from 3 - bromo - 6 - hydroxy - 5 - isopropyl - 2 - methylbenzoic acid ( obtainable by treatment of 2 - hydroxy - 3 - isopropyl - 6 - methylbenzoic acid with bromine ( 1 . 05 equiv .) in acetic acid for 18 hours at 20 ° c .) and 3 , 5 - difluorophenylboronic acid . step b : from the product formed in step a , 3 ′, 5 ′- difluoro - 4 - hydroxy - 5 - isopropyl - 2 - methylbiphenyl - 3 - carboxylic acid , and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 1 . 19 ( d , j = 6 . 78 hz , 6h ), 2 . 17 ( s , 3h ), 3 . 33 ( m , j = 6 . 78 hz , 1h ), 7 . 04 ( m , 2h ), 7 . 12 ( s , 1h ), 7 . 24 ( tt , j = 9 . 5 , 2 hz , 1h ), 8 . 19 ( d ( br ), j = 8 . 67 hz , 1h ), 8 . 26 ( s ( br ), 1h ), 8 . 55 ( d ( br ), j = 8 . 67 hz , 1h ), 9 . 11 ( s , 1h ), 10 . 56 ( s , 1h ) ppm ; hplc - ms ( method b ): m / z = 548 / 550 ( m + h ), r t = 2 . 80 min . from 3 - tert - butyl - 6 - chloro - 2 - hydroxybenzoic acid and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 400 mhz , dmso - d 6 ): δ 1 . 37 ( s , 9h ), 6 . 96 ( d , j = 8 . 59 hz , 1h ), 7 . 27 ( d , j = 8 . 59 hz , 1h ), 8 . 20 ( d ( br ), j = 8 . 62 hz , 1h ), 8 . 24 ( s ( br ), 1h ), 8 . 61 ( d ( br ), j = 8 . 62 hz , 1h ), 9 . 59 ( s , 1h ), 10 . 80 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 470 / 472 ( m + h ), r t = 2 . 95 min . 3 - tert - butyl - 6 - chloro - 2 - hydroxybenzoic acid may be synthesized from 2 - tert - butyl - 5 - chlorophenol ( obtainable by tert - butylation of 3 - chlorophenol according to general procedure ( b )) by a modification of the procedure described in ber . 1921 , 54 , 1213 - 1220 . 2 - tert - butyl - 5 - chlorophenol is treated with oxalyl chloride ( 0 . 1 m 5 - chlorophenol ) for 72 hours at 50 ° c . concentration furnishes chloro ( oxo ) acetic acid 2 - tert - butyl - 5 - chlorophenyl ester as an oil , which is then dissolved in dichloromethane ( concentration 0 . 33 m ). the resulting solution is added to a suspension of aluminum chloride ( 3 equiv .) in dichloromethane ( 0 . 17 m final concentration ) at 0 ° c . stirring is continued for 20 minutes . extractive aqueous work - up with ethyl acetate yields 7 - tert - butyl - 4 - chlorobenzofuran - 2 , 3 - dione as a solid . the solid is then dissolved ( concentration 0 . 12 m ) in 1 m aqueous sodium hydroxide , and the mixture is cooled in an ice - water bath . 35 % aqueous hydrogen peroxide ( 22 equiv .) is added dropwise over 5 minutes . the cooling bath is removed , and the stirring is continued at room temperature for another 2 hours . the reaction mixture is poured slowly into 1 . 0 m aqueous hcl , resulting in formation of a solid . filtration and washing with water furnishes 3 - tert - butyl - 6 - chloro - 2 - hydroxybenzoic acid as a solid . the crude product may be recrystallized from water - ethanol . from 3 - tert - butyl - 6 - chloro - 2 - hydroxybenzoic acid ( the synthesis of which is described under the preparation of 3 - tert - butyl - 6 - chloro - n -( 2 - chloro - 4 - trifluoromethanesulfonylphenyl )- 2 - hydroxybenzamide ) and 2 - methyl - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 400 mhz , dmso - d 6 ): δ 1 . 37 ( s , 9h ), 2 . 45 ( s , 3h ), 6 . 97 ( d , j = 8 . 51 hz , 1h ), 7 . 26 ( d , j = 8 . 51 hz , 1h ), 8 . 00 ( s ( br ), 1h ), 8 . 02 ( d ( br ), j = 7 . 58 hz , 1h ), 8 . 33 ( d ( br ), j = 7 . 58 hz , 1h ), 9 . 54 ( s ( br ), 1h ), 10 . 51 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 450 / 452 ( m + h ), r t = 2 . 77 min . step 1 ( analogous to general procedure ( a ), step a ): from 3 - bromo - 5 - chloro - 2 - hydroxy - 6 - methylbenzoic acid and phenylboronic acid . step 2 ( analogous to general procedure ( a ), step b ): from the product formed in step 1 , 5 - chloro - 2 - hydroxy - 4 - methylbiphenyl - 3 - carboxylic acid , and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 2 . 33 ( s , 3h ), 7 . 37 ( s , 1h ), 7 . 38 ( t , j = 7 . 4 hz , 1h ), 7 . 46 ( t , j = 7 . 4 hz , 2h ), 7 . 53 ( d , j = 7 . 4 hz , 2h ), 8 . 19 ( d ( br ), j = 8 . 63 hz , 1h ), 8 . 26 ( s ( br ), 1h ), 8 . 58 ( d , j = 8 . 63 hz , 1h ), 9 . 31 ( s , 1h ), 10 . 70 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 504 / 506 / 508 ( m + h ), r t = 2 . 65 min . 3 - bromo - 5 - chloro - 2 - hydroxy - 6 - methylbenzoic acid may be synthesized from 3 - tert - butyl - 5 - chloro - 2 - hydroxy - 6 - methylbenzoic acid , which upon treatment with concentrated sulfuric acid for 1 hour at room temperature yields 3 - chloro - 6 - hydroxy - 2 - methylbenzoic acid . conversion with bromine ( 1 . 15 equiv .) in acetic acid for 3 hours at 20 ° c . yields 3 - bromo - 5 - chloro - 2 - hydroxy - 6 - methylbenzoic acid . step 1 ( analogous to general procedure ( a ), step a ): from 3 - bromo - 5 - chloro - 2 - hydroxy - 6 - methylbenzoic acid ( the synthesis of which is described under the preparation of 5 - chloro - 2 - hydroxy - 4 - methylbiphenyl - 3 - carboxylic acid ( 2 - chloro - 4 - trifluoromethanesulfonylphenyl ) amide )) and 4 - fluorophenylboronic acid . step 2 ( analogous to general procedure ( a ), step b ): from the product formed in step 1 , 5 - chloro - 4 ′- fluoro - 2 - hydroxy - 4 - methylbiphenyl - 3 - carboxylic acid , and 2 - chloro - 4 -( trifluoromethanesulfonyl ) aniline ; 1 h nmr ( 300 mhz , dmso - d 6 ): δ 2 . 33 ( s , 3h ), 7 . 28 ( t , j = 8 . 85 hz , 2h ), 7 . 38 ( s , 1h ), 7 . 56 ( dd , j = 8 . 48 , 5 . 46 hz , 2h ), 8 . 19 ( d ( br ), j = 8 . 86 hz , 1h ), 8 . 26 ( s ( br ), 1h ), 8 . 57 ( d , j = 8 . 86 hz , 1h ), 9 . 35 ( s , 1h ), 10 . 70 ( s ( br ), 1h ) ppm ; hplc - ms ( method b ): m / z = 522 / 524 / 526 ( m + h ), r t = 2 . 66 min . from 3 , 5 - dimethyl - 4 - methylsulfanyl - phenol and 2 - chloro - 4 - trifluoromethanesulfonyl - aniline ; mp 201 - 202 ° c . ; 1 h nmr ( cdcl 3 ): δ 9 . 00 ( d , j = 9 . 10 hz , 1h ), 8 . 97 ( s , 1h ), 8 . 54 ( br s , 1h ), 8 . 09 ( d , j = 2 . 02 hz , 1h ), 8 . 00 ( dd , j = 8 . 59 and 2 . 02 hz , 1h ), 6 . 83 ( s , 1h ), 2 . 89 ( s , 3h ), 2 . 58 ( s , 3h ), 2 . 22 ( s , 3h ); hplc - ms ( method b ): m / z 454 / 456 ( m + h ), 476 / 478 ( m + na ), r t 2 . 48 min . from n -( 2 - chloro - 4 - trifluoromethanesulfonyl - phenyl )- 6 - hydroxy - 2 , 4 - dimethyl - 3 - methylsulfanyl - benzamide ; white crystals , mp 205 - 206 ° c . ; hplc - ms ( method b ): m / z 470 / 472 ( m + h ), 492 / 494 ( m + na ), r t 1 . 73 min . assay ( i ): glucose utilisation in a human epithelia cell line ( fsk - 4 cells ) the assay measures indirectly the activity of the respiratory chain in fsk - 4 cells by using d -( 6 - 3h ( n ))- glucose . the 3 h - proton will first be released in the tca cyclus and transported to the respiratory chain where it will be incorporated into water . the water is thereafter separated from the d -( 6 - 3 h ( n ))- glucose by evaporation . finally , the radioactivity in the water is determined using a topcounter . fsk - 4 cells obtained from atcc ( maryland , usa ), are cultured in growth medium ( mccoy &# 39 ; s medium with the following addition 100 units / ml penicillin and streptomycin and 10 % fcs ( fetal calf serum )) at 37 ° c . and 5 % co 2 . all media are obtained by gibco ( life technologies , maryland , usa ) where not otherwise mentioned . at day zero the cells are harvested using trypsin - edta and washed in assay medium ( mem medium with the following addition 1 × non - essential amino acids ( m7145 , 2 mm glutamin , 100 units / ml penicillin and streptomycin , 0 . 0075 % sodium bicarbonate , 1 mm sodium pyrovate and 2 % horse serum ) using centrifugation . the cells are plated into single stripplates wells ( corning b . v . life sciences , the netherlands ) that are placed into 24 - well plates ( corning b . v . life sciences , the netherlands ) with a concentration of 1 , 5 × 10 4 cells / 100 μl assay medium / well . the cells are then incubated at 37 ° c . and 5 % co 2 overnight . the next day the compounds to be tested are diluted to different concentrations in dmso ( sigma , mo ., usa ) to 100 times final concentration . they are then diluted to a final concentration in assay medium containing 10 μci / ml d -( 6 - 3 h ( n ))- glucose ( perkinelmer life sciences inc ., boston , usa ). the medium is removed from the cells and 200 μl of the compound dilutions are added in duplicates . the cells are then incubated for another 24 hours at 37 ° c . and 5 % co 2 . finally the cells are lysed by adding 50 μl 10 % tca ( trichloroacetate ). 300 μl of sterile water is then added to the 24 - wells that surrounds the stripplate wells . the plate is sealed with top - seal - tape ( packard , perkinelmer life sciences inc ., boston , usa ) and the plate is incubated in a heating cupboard at 50 ° c . to equilibrium the radioactive water formed in the respiratory chain into the water in the 24 - well plate by evaporate . the plates incubate for 8 hours where the heating cupboard is turned off . the top seal is removed when the samples have reached room temperature . one ml scintillation liquid ( packard microscient , perkinelmer life sciences inc ., boston , usa ) is added to all the samples and the radioactivity is determined using a topcounter ( packard , perkinelmer life sciences inc ., boston , usa ). non - specific activity is determined by evaporating 200 μl of the dilution medium containing the d -( 6 - 3 h ( n ))- glucose into 300 μl sterile water , and total radioactivity is determined by counting 5 μl assay medium with 10 μci / ml d -( 6 - 3h ( n ))- glucose . the half maximal concentration ( ec 50 ) and maximal efficacy ( e max ) are calculated using the hill equation in graphpad prism 3 . 0 ( graphpad software , inc .). in studies where the linear slope is determined the following concentration of the compound is used ; 5 ×, 3 ×, 2 ×, 1 , 5 ×, 1 , 25 ×, 1 ×, 0 . 85 ×, 0 . 7 ×, 0 . 5 ×, 0 . 3 ×, 0 . 2 × and 0 × ec 50 . from the percentage increase in glucose utilisation the linear slope is calculated using the michaelis - menten equation . assay ( ii ): the effect of chemical uncouplers on mitochondrial respiration using isolated mitochondria . this assay is used to investigate if the increase in glucose utilisation caused by the test compounds observed in the glucose utilisation assay is due to an increase in the respiration of the mitochondria . this is done by measuring oxygen consumption in isolated rat liver mitochondria . a clark oxygen electrode is used to determine the oxygen consumption . the isolated mitochondria are added to assay medium ( d - mannitol 220 mm , magnesiumcloride 5 mm , hepes 2 mm and potassiumphosphate 5 mm , ph = 7 , 4 ) containing rotenone ( an inhibitor of clomplex 1 ) and oligomyocin ( an inhibitor of the atp - synthase ) and the rate of oxygen consumptions is measured , when stabilized nutrient ( e . g . succinate ) is added and an increase in the rate of oxygen consumption is measured . when the rate of oxygen consumption again has stabilized the test compound is added and the oxygen consumption is measured . if the test compound stimulates the rate of oxygen consumption , it is regarded as a chemical uncoupler . assay ( iii ): identification of chemical uncouplers that increase energy expenditure in vivo the effect of the chemical uncouplers on energy expenditure ( oxygen consumption ) in vivo is determined by indirect calorimetry . briefly , animals are placed in airtight chambers . air is continuously led to and from the chambers . the gas concentrations of oxygen ( o 2 ) and carbondioxide ( co 2 ) in the air led to and from the chambers ( inlet and outlet air ) are recorded and the consumption of o 2 and the production of co 2 are calculated . based on the amount of o 2 consumed and co 2 produced , energy expenditure is calculated . compounds which at a given dose increase whole body energy expenditure without obvious deleterious effects are deemed to be chemical uncouplers that increase energy expenditure . | 2 |
in one aspect , the present invention is directed to improve highly visible architecturally pleasing photoluminescent exit signs . this non - electrical exit sign &# 39 ; s purpose is to guide people to exits in both normal and emergency conditions . the use of a photoluminescent back panel enables the sign to be seen when loss of power occurs . fig1 - 3 illustrate one embodiment of a photoluminescent exit sign 10 in accordance with the present invention , which generally includes two component parts . photoluminescent exit sign 10 may include a faceplate 20 with a plurality of cutouts having beveled edges or angled surface openings defining the word “ exit ” and optional chevrons , and a photoluminescent backplate 50 ( best shown in fig2 and 3 ). for example , faceplate 20 may be a planar member such as an elongated planer member , e . g ., a rectangular planar member , having a front side 22 ( fig2 and 3 ), a rear side 24 ( fig2 and 3 ), a top edge 26 , a bottom edge 27 , a right side edge 28 , and a left side edge 29 . faceplate 20 may be formed from a metallic material such as an aluminum plate in which the cutouts are milled or formed with a plurality of peripherally - extending angled or beveled edges 30 ( fig1 and 3 ) that exposes the bright natural or bare metallic material around the edge of the letters . faceplate 20 may further include a colored coating 40 such as a dark solid color coating disposed on front surface 22 . the solid colored surface may be a red or black polymer or anodized coating . the contrast between the front coated surface of the faceplate and the cutouts is best illustrated in fig4 which shows a portion of the faceplate having a dark black color which surrounds the right chevron cutouts through which light may be emitted therethrough from the photoluminescent backplate 50 . as best shown in fig1 and 2 , in faceplate 20 , the periphery of each of the openings defining the letters and each of the directional chevrons may be defined by a beveled edge 30 . for example , beveled edges 30 may extend around the entire periphery of each of the letters and each of the directional chevrons . in addition , the beveled edges may extend from front surface 22 to rear surface 24 . the beveled edges may further be disposed on an angle of about 45 - degree relative to front surface 22 of faceplate 20 . for example , faceplate 20 may have a thickness of about 1 / 16 - inch . the cutouts or openings may be formed with a machining tool that produces a beveled edge of about 45 - degrees relative to the front surface and extending from the front surface to the rear surface resulting in an exposed beveled surface about 1 . 5 mm wide . backplate 50 may comprise a photoluminescent impregnated polymer sheet such as a photoluminescent impregnated thermoplastic polymer sheet , e . g ., a photoluminescent impregnated polymer pvc ( polyvinylchloride ) sheet . backplate 50 includes a front surface 52 and a rear surface 54 , and may have a length and width which corresponds to the length and width of the faceplate . front surface 52 of backplate 50 is abutted and disposed tightly against rear surface 54 of faceplate 20 so that lowermost edges 32 ( fig2 ) of beveled edges 30 rests on the front surface of backplate 50 . for example , front surface 52 may be adhesively bonded to rear surface 24 of faceplate 20 . the photoluminescent impregnated polymer sheet desirably has a luminance of at least about 50 mcd / m2 at 60 minutes after exposure to 1000 lux xenon arc lamp for 5 minutes . a suitable photoluminescent impregnated polymer sheet is available from jalite usa of milford , pa ., model number jlume . the rear surface of the backplate is typically disposed against a wall or other surface such as above a door or doorway . for example , when photoluminescent exit sign 10 is installed in a desired location , an installer may attach the rear surface to the wall using a suitable adhesive or bonding agent which is applied between the rear surface of the backplate and the wall . alternatively , one or more adhesive materials may be disposed on the rear surface of the backplate . for example , as shown in fig3 , one or more adhesive strips 70 having a release sheet 75 may be disposed on the rear surface of the backplate . alternatively , an optional frame may be used to secure the photoluminescent exit sign to the wall or the exit sign may be operably supported to hang from the ceiling . fig5 - 7 illustrate another embodiment of a photoluminescent exit sign 100 in accordance with the present invention , which generally includes three component parts . photoluminescent exit sign 100 may include a faceplate 120 with a plurality of cutouts having beveled edges or angled surface openings defining the word “ exit ” and optional chevron ( s ), a backplate 150 , and a photoluminescent layer 160 ( best shown in fig6 and 7 ). for example , faceplate 120 may be a planar member such as an elongated planer member , e . g ., a rectangular planar member , having a front side 122 ( fig6 and 7 ), a rear side 124 ( fig2 and 3 ), a top edge 126 , a bottom edge 127 , a right side edge 128 , and a left side edge 129 . faceplate 120 may be formed from a metallic material such as an aluminum plate in which the cutouts are milled or formed with a plurality of peripherally - extending angled or beveled edges 130 ( fig5 and 6 ) that expose the bright natural or bare metallic material around the edge of the letters . faceplate 120 may further include a colored coating 140 such as a dark solid color coating disposed on front surface 122 . for example , the solid colored surface may be a suitable red or black polymer or anodized coating . the contrast between the front coated surface of the faceplate and the cutouts is best illustrated in fig8 which is shows a portion of the faceplate having a dark black color which surrounds the right chevron cutout through which light may be emitted therethrough from the photoluminescent layer 160 . as best shown in fig5 and 6 , in faceplate 120 , the periphery of each of the openings defining the letters and each of the directional chevrons may be defined by beveled edge 130 . for example , beveled edges 130 may extend around the entire periphery of each of the letters and each of the directional chevrons . in addition , the beveled edges may extend from front surface 122 to rear surface 124 . the beveled edges may further be disposed on an angle of about 45 - degree relative to front surface 122 of faceplate 120 . for example , faceplate 120 may have a thickness of about 1 / 16 - inch . the cutouts or openings may be formed with a machining tool that produces a beveled edge of about 45 - degrees relative to the front surface and extending from the front surface to the rear surface resulting in an exposed beveled surface about 1 . 5 mm wide . backplate 150 may comprise a metal or plastic planar layer such as formed from a pvc plastic or aluminum material . photoluminescent layer 160 may be a sheet of photoluminescent material or a photoluminescent coating . for example , backplate 150 and photoluminescent layer 160 may be a photoluminescent lacquer - coated aluminum plate . backplate 150 includes a front surface 152 and a rear surface 154 , and may have a length and width which corresponds to the length and width of the faceplate . photoluminescent layer 160 is disposed on backplate 150 . a front surface of photoluminescent layer 160 is abutted and disposed tightly against rear surface 124 of faceplate 120 so that lowermost edges 132 ( fig6 ) of beveled edges 130 rests on the front surface of photoluminescent layer 160 . for example , rear surface of the faceplate may be adhesively bonded to front surface of photoluminescent layer 160 . photoluminescent layer 160 desirably has a luminance of at least about 50 mcd / m2 at 60 minutes after exposure to 1000 lux xenon arc lamp for 5 minutes . a suitable photoluminescent impregnated polymer sheet is available from jalite usa of milford , pa ., model number jlume . the rear surface of the backplate is typically disposed against a wall or other surface such as above a door or doorway . for example , when photoluminescent exit sign 100 is installed in a desired location , an installer may attach the rear surface to the wall using a suitable adhesive or bonding agent which is applied between the rear surface of the backplate and the mounting surface . alternatively , one or more adhesive materials may be disposed on the rear surface of the backplate . for example , as shown in fig7 , one or more adhesive strips 170 having a release sheet 175 may be disposed on the rear surface of the backplate . fig9 - 11 illustrate another embodiment of a photoluminescent exit sign 200 in accordance with the present invention , which generally includes two component parts . photoluminescent exit sign 200 may include a faceplate 220 with a plurality of beveled cutouts or angled surface openings defining the word “ exit ” and optional chevrons , and a backplate 250 of photoluminescent material . for example , faceplate 220 may be a planar member such as an elongated planer member , e . g ., a rectangular planar member , having a front side 222 , a rear side 224 ( fig1 and 11 ), a top edge 226 , a bottom edge 227 , a right side edge 228 , and a left side edge 229 . faceplate 220 may be formed from a metallic material such as an aluminum plate in which the cutouts are milled or formed with a peripherally - extending angled or beveled edge that exposes the bright natural metallic material around the edge of the letters and optional chevrons . faceplate 220 may further include a colored coating 240 such as a dark solid color coating disposed on front surface 222 . the solid colored surface may be a red or black polymer or anodized coating . the contrast between the front coated surface of the faceplate and the cutouts may be similar to that shown in fig4 and 8 . as best shown in fig9 and 10 , in faceplate 220 , the periphery of each of the openings defining the letters and each of the directional chevrons may be defined by a beveled edge 230 . for example , beveled edges 230 may extend around the entire periphery of each of the letters and each of the directional chevrons . in addition , the beveled edges may extend between front surface 222 and rear surface 224 . the beveled edges may further be disposed on an angle of about 45 - degree relative to front surface 222 of faceplate 220 . for example , faceplate 220 may be about ⅛ - inch in thickness . the cutouts or openings may be formed with a machining tool that produces a beveled edge of 45 - degrees relative to the front surface and extending from the front surface to about the middle of the faceplate , e . g ., half of the cut ( 1 / 16 - inch depth ). a straight or normal edge 235 disposed at 90 - degrees relative to the front or rear surface of the faceplate extends from the beveled edge to the rear surface for the remaining half of the cut ( 1 / 16 - inch depth ). backplate 250 may comprise a photoluminescent impregnated polymer sheet such as a photoluminescent impregnated thermoplastic polymer sheet , e . g ., a photoluminescent impregnated polymer pvc ( polyvinylchloride ) sheet . backplate 250 includes a front surface 252 and a rear surface 254 , and may have a length and width which corresponds to the length and width of the faceplate . front surface 252 of backing plate 250 is abutted and disposed tightly against rear surface 224 of faceplate 220 so that lowermost edges 232 ( fig1 ) of normal edges 235 rests on the front surface of backplate 250 . for example , front surface 252 may be adhesively bonded to rear surface 224 of faceplate 250 . the photoluminescent impregnated polymer sheet desirably has a luminance of at least about 50 mcd / m2 at 60 minutes after exposure to 1000 lux xenon arc lamp for 5 minutes . a suitable photoluminescent impregnated polymer sheet is available from jalite usa of milford , pa ., model number jlume . the rear surface of the backplate is typically disposed against a wall or other surface such as above a door or doorway . for example , when photoluminescent exit sign 200 is installed in a desired location , an installer may attach the rear surface to the wall using a suitable adhesive or bonding agent which is applied between the rear surface of the backplate . alternatively , one or more adhesive materials may be disposed on the rear surface of the backplate . for example , as shown in fig1 , one or more adhesive strips 270 having a release sheet 275 may be disposed on the rear surface of the backplate . alternatively , an optional frame may be used to secure the photoluminescent exit sign to the wall or the exit sign may be operably supported to hang from the ceiling . fig1 - 14 illustrate another embodiment of a photoluminescent exit sign 300 in accordance with the present invention , which generally includes three component parts . photoluminescent exit sign 300 may include a faceplate 320 with a plurality of cutouts having beveled edges or angled surface openings defining the word “ exit ” and optional chevrons , and a backplate 350 and photoluminescent layer 360 ( best shown in fig1 and 14 ). for example , faceplate 320 may be a planar member such as an elongated planer member , e . g ., a rectangular planar member , having a front side 322 ( fig1 and 14 ), a rear side 324 ( fig1 and 14 ), a top edge 326 , a bottom edge 327 , a right side edge 328 , and a left side edge 329 . faceplate 320 may be formed from a metallic material such as an aluminum plate in which the cutouts are milled or formed with a plurality of peripherally - extending angled or beveled edges 330 ( fig5 and 6 ) that exposes the bright natural or bare metallic material around the edge of the letters . faceplate 320 may be formed from a metallic material such as an aluminum plate in which the cutouts are milled or formed with a peripherally - extending angled or beveled edge that exposes the bright natural metallic material around the edge of the letters and optional chevrons . faceplate 320 may further include a colored coating 340 such as a dark solid color coating disposed on front surface 322 . for example , the solid colored surface may be a suitable red or black polymer or anodized coating . the contrast between the front coated surface of the faceplate and the cutouts may be similar to that shown in fig4 and 8 . as best shown in fig1 , in faceplate 320 , the periphery of each of the openings defining the letters and each of the directional chevrons may be defined by beveled edge 330 . for example , beveled edges 330 may extend around the entire periphery of each of the letters and each of the directional chevrons . in addition , the beveled edges may extend between front surface 322 and rear surface 324 . the beveled edges may further be disposed on an angle of about 45 - degree from front surface 322 of faceplate 320 . for example , faceplate 320 may be about ⅛ - inch in thickness . the cutouts or openings may be formed with a machining tool that produces beveled edge 330 of 45 - degrees relative to the front surface and extending from the top surface to about the middle of the faceplate , e . g ., half of the cut ( 1 / 16 - inch depth ). a straight or normal edge 335 disposed at 90 - degrees relative to the front or rear surface of the faceplate extends from the beveled edge to the rear surface for the remaining half of the cut ( 1 / 16 - inch depth ). backplate 350 may comprise a metal or plastic planar layer such as formed from a pvc plastic or aluminum material . photoluminescent layer 360 may be a sheet of photoluminescent material or a photoluminescent coating . for example , backplate 350 and photoluminescent layer 360 may be a photoluminescent lacquer - coated aluminum plate . backplate 350 includes a front surface 352 and a rear surface 354 , and may have a length and width which corresponds to the length and width of the faceplate . photoluminescent layer 360 is disposed on backplate 350 . a front surface of photoluminescent layer 360 is abutted and disposed tightly against rear surface 324 of faceplate 320 so that lowermost edges 332 ( fig1 ) of edge 335 rests on the front surface of photoluminescent layer 360 . for example , rear surface of the faceplate may be adhesively bonded to front surface of photoluminescent layer 360 . photoluminescent layer 360 desirably has a luminance of at least about 50 mcd / m2 at 60 minutes after exposure to 1000 lux xenon arc lamp for 5 minutes . a suitable photoluminescent impregnated polymer sheet is available from jalite usa of milford , pa ., model number jlume . the rear surface of the backplate is typically disposed against a wall or other surface such as above a door or doorway . for example , when photoluminescent exit sign 300 is installed in a desired location , an installer may attach the rear surface to the wall using a suitable adhesive or bonding agent which is applied between the rear surface of the backplate . alternatively , one or more adhesive materials may be disposed on the rear surface of the backplate . for example , as shown in fig1 , one or more adhesive strips 370 having a release sheet 375 may be disposed on the rear surface of the backplate . alternatively , an optional frame may be used to secure the photoluminescent exit sign to the wall or the exit sign may be operably supported to hang from the ceiling . the exposed metallic material around the peripheral edges of the cutout letters defining the word “ exit ” and optional chevrons creates contrast between the design and the anodized black or red color of the faceplate as well as heightened contrast between the photoluminescent material and the faceplate increasing visibility and conspicuity under normal lighting . in visibility tests of the embodiment described with reference to fig1 - 4 , the photoluminescent exit sign , performed by underwriter &# 39 ; s laboratory ( ul ), the beveled natural aluminum edge of the sign functioned to increase the visibility of the exit sign &# 39 ; s directional chevron indicator . in the completely dark test conditions stipulated by ul , the exit sign &# 39 ; s beveled metal edge reflected the luminance of the photoluminescent material and the test participants could easily describe the indicated direction of travel indicated by the exit sign &# 39 ; s chevron at the required 40 feet viewing distance . chevrons made from material having the same luminance properties as the exit sign &# 39 ; s photoluminescent backing plate and having similar and even slightly larger sizes , were not able to have their direction differentiated by the test participants at the required 40 feet viewing distance when a beveled edge faceplate was not used . thus , the aesthetic design enhancement of the beveled edge gives an attractive depth dimension to a photoluminescent exit sign in light conditions , and has also become a distinctive technical differentiator , giving the exit sign higher visibility in dark conditions . from the present description , photoluminescent exit signs in accordance with the present invention may have one , two , or no directional chevrons resulting in four different designs , e . g ., exit signs with right pointing chevron , exit signs with left pointing chevron , exit signs with both left and right pointing chevrons , and exit signs with no chevrons . the 1 / 16 - inch and ⅛ - inch thick architectural grade aluminum material also exhibits a significantly improved aesthetic design when compared to other existing photoluminescent exit signs giving it greater appeal for use by those designing the interior space of high - end buildings . in addition , the exit signs may be readily attached to a wall such as above a door with adhesive , suitable fasteners or optional frame . while the above description of the invention is directed to exit signs , it will be appreciated that signs having other words , letters , indicia , or designs , may incorporate the techniques of the present invention . thus , while various embodiments of the present invention have been illustrated and described , it will be appreciated to those skilled in the art that many changes and modifications may be made thereunto without departing from the spirit and scope of the invention . | 6 |
referring to fig1 an aircraft ejection seat is shown generally at 11 . seat 11 , for purposes of illustration , is shown without many life support and operational attachments which are conventionally attached thereto . in its upper extremity , a parachute pack 12 is secured . the riser assembly for parachute 12 is held to seat 11 by a conventional mechanism , not shown , and terminates in shoulder straps 13 which pass through riser rollers shown at 14 and are secured beneath seat back 16 . referring to fig2 the riser assembly according to the invention is shown separated from the seat for greater clarity . shoulder straps 13 are connected to a main riser 17 . additional restraint straps 18 are firmly attached to the back of the seat at a point not shown . upon deployment of the parachute 12 , retaining straps 18 are severed by an automatic guillotine knife , not shown , which forms a part of aircraft seat 11 . a lanyard 19 has an end formed in a loop and is held to main riser 17 by means of a web sheath 21 . web sheath 21 is sewn along part of its length to main riser 17 , but is attached for the remainder thereof by two marginal strips 22 of pressure - releasable hook and pile fabric material . a variety of such hook and pile fabric materials are known and may be used following normal engineering trade - offs , however , that marketed under the trade name of velcro has proven satisfactory in developmental models . main riser 17 splits into a rear riser or riser strap 23 and a front riser or riser strap 24 at a junction point 25 . such a construction arrangement is conventional in parachute harness manufacture . rear riser 23 and front riser 24 are held together with lateral strips of pressure attachment material 22 in a similar fashion to web sheath 21 . rear riser straps 23 and front riser straps 24 are attached to the parachute shrouds 26 by conventional links 27 . the control or operating line 28 operates the control mechanism which may be a conventional four line release or a four line extender such as shown in u . s . pat . nos . 3 , 779 , 489 and 3 , 958 , 780 issued to matsuo on dec . 18 , 1973 and may 25 , 1976 respectively . control line 28 is terminated by a speed link 29 which attaches to lanyard 19 permitting the parachute canopy 12 to be selectively removed from front and rear risers 23 and 24 . referring to fig2 a and 3 , the placing of lanyard 19 between rear riser 23 and front riser 24 is illustrated . although exaggerated for the purposes of clarity , fig3 illustrates the flat configuration possible permitting the combined riser assembly to pass through the riser yoke rollers 14 without danger of snagging or malfunction . referring to fig4 the parachute pack 12 is seen to comprise a molded plastic case 31 and a tight - fitting lid 32 . lid 32 and case 31 are contoured at the point of closure to permit links 27 to extend therefrom such that rear riser 23 and front riser 24 may be conveniently attached thereto . control line 28 is thus positioned to extend between the risers , placing ring 29 in position to engage with lanyard 19 . in operation , when parachute 12 deploys , risers 23 and 24 are withdrawn from behind seat back 16 . the opening of the canopy also separates front riser 24 from rear riser 23 as shown in fig2 b , freeing lanyard 19 from that portion of its encasement . the aircrew member may reach up and grasp lanyard 19 and pull it downward to effect line release and lengthening . as lanyard 19 is drawn downward , speed link 29 comes to the forward or upper end of sheath 21 . the pressure fastening material 22 separates to allow ring 29 to be drawn downward without interference or binding . this opening feature prevents binding or jamming by speed link 29 and facilitates the conversion of the parachute from the hemispherical to the gliding configuration , well understood in the art . the foregoing description , taken together with the appended claims and drawings , constitutes a disclosure sufficient to enable one versed in the parachute manufacturing arts , having the benefit of the teachings thereof , to make and use the invention . | 1 |
fig1 shows an electromagnetically operated valve as a first embodiment of an injection valve for fuel injection systems of internal combustion engines powered by a compressed and externally ignited fuel mixture according to the present invention . the fuel injection valve has a tubular nozzle body 1 with a spray orifice 2 can be used for direct high - pressure injection of fuel . spray orifice 2 of the fuel injection valve ( which is inserted into a cylinder of an internal combustion engine ) is sealed with respect to the outside by ring gasket 3 . nozzle body 1 has a longitudinal axial bore 4 which accommodates a valve needle 5 . upstream from spray orifice 2 , a valve seat face 6 is formed on nozzle body 1 and cooperates with a truncated conical valve closing body 7 of valve needle 5 to yield a tight seating . upstream from valve closing body 7 , valve needle 5 has a cylindrical section 8 with one or more spiral swirl grooves 9 provided on a lateral surface of the cylindrical section 8 . swirl grooves 9 are closed in the radial direction by nozzle body 1 surrounding cylindrical section 8 . the swirl grooves 9 extend from a fuel chamber 10 ( being within the longitudinal axial bore 4 in nozzle body 1 ) to a feed point 11 in the area of valve seat face 6 . a swirl flow that promotes turbulence in the fuel is created with swirl grooves 9 . due to the small cross - sectional area of swirl grooves 9 , the flow of fuel through swirl grooves 9 creates an unwanted force acting against the x direction of the coordinate system ( shown in fig1 ), i . e ., a force component in the closing direction of valve needle 5 . this force component is caused by friction , shock losses and pressure drop generated by the fuel as it flows through swirl grooves 9 . since the force component described here counteracts the opening of valve needle 5 , it can have a negative effect on valve performance . fuel chamber 10 is bordered on the upstream end by guide section 12 and is connected through outlet orifices 13 to a hollow axial bore 14 passing through the upper area of valve needle 5 . on the end opposite to valve closing body 7 , valve needle 5 is connected to an armature 15 . armature 15 operates with a magnetic coil 16 for closing and opening the fuel valve . a coil body 17 that is stepped in the radial direction encloses the winding of magnetic coil 16 . stepped coil body 17 partially overlaps core 18 , and with a step of a larger diameter it also axially overlaps intermediate part 19 at least in part . armature 15 , core 18 and housing 20 are composed of a ferromagnetic material . a closed magnetic circuit is formed by core 18 , armature 15 and housing 20 , where armature 15 is pulled in the direction of core 18 when magnetic coil 16 is electrically energized . this causes valve needle 5 to be raised in the x direction against the restoring force of restoring spring 21 , which in turn causes the fuel injection valve to open . restoring spring 21 is supported on supporting plate 25 . power supply cable 22 supplies electric power to magnetic coil 16 and is connected to housing 20 by plug connection 23 . mounting elements 24 are used to assemble housing 20 . when the fuel injection valve is opened , armature 15 with its armature stop face 33 strikes the face of core 18 facing spray orifice 2 . as an improvement on the first embodiment according to the present invention , the force component acting against the x direction , which is transmitted to valve needle 5 as the fuel flows through swirl grooves 9 ( which act as a throttling constriction ) is reduced , compensated or ( if necessary ) even overcompensated by a force component acting on valve needle 5 in the x direction . to obtain this result , the fuel is directed through a second throttling constriction with a flow component directed away from spray orifice 2 . the opposite force component is exerted on valve needle 5 as the fuel passes through this second throttling constriction . in the first embodiment according to the present invention , the fuel flows through a connection 26 to a fuel inlet chamber 27 . the fuel flows from an area between fuel inlet chamber 27 and armature stop face 33 and through an annular clearance 28 ( which is between armature 15 and surrounding housing 20 ). annular clearance 28 is relatively narrow to permit loss - free crossing of the magnetic field lines between housing 20 and armature 15 . therefore , annular clearance 28 forms a second throttling constriction , so that as fuel flows through annular clearance 28 , a force component is exerted on armature 15 in the x direction and thus also on valve needle 5 that is connected to armature 15 . this force component counteracts the force component that is exerted on valve needle 5 opposite the x direction as fuel flows through swirl grooves 9 forming a first throttling constriction . therefore , the force component acting on valve needle 5 in the closing direction because of the flow of fuel through swirl grooves 9 can be compensated ( or at least greatly reduced ) by suitable sizing the width of annular clearance 28 . if necessary , it is also possible for the force acting in the closing direction to be overcompensated and thus to accelerate the opening of the fuel valve . thus , the switching performance of the fuel injection valve is greatly improved by the fuel injection valve according to the present invention . after flowing through annular clearance 28 , the fuel flows radially in the direction of the junction of hollow bore 14 provided in valve needle 5 in the area of armature stop face 33 . the fuel flows through outlet orifices 13 and hollow bore 14 ( from fuel chamber 27 ) and then flows through swirl grooves 9 to feed point 11 . the fuel is substantially prevented from flowing directly from fuel inlet chamber 27 to fuel chamber 10 ( bypassing annular clearance 28 ) via a narrow guide clearance between guide section 12 and nozzle body 1 . the compensating force can be adjusted by varying the diameter of armature 15 . fig2 shows a top view of armature 15 with armature stop face 33 . according to this embodiment of the present invention , radial grooves 29 may be provided on the armature stop face 33 of the armature 15 facing the core 18 to promote the flow of fuel from annular clearance 28 surrounding lateral surface 30 to central hollow bore 14 of valve needle 5 in this area . fig3 shows a side view of an improved armature 15 illustrated in fig2 . axially aligned grooves 31 are provided on lateral surface 30 . the cross - sectional area of the throttling constriction can be varied through the amount , width , and depth of grooves 31 without affecting the guide clearance between armature 15 and housing 20 . thus , the compensating force exerted on armature 15 due to the throttling constriction on lateral surface 30 can be adjusted according to the intended reduction , compensation or even overcompensation of the force component exerted on valve needle 5 at swirl grooves 9 . fig3 also shows radially aligned grooves 29 on armature stop face 33 . fig4 shows a top view of a second embodiment of armature 15 according to the present invention . the throttling constriction here is formed by longitudinal axial bores 32 , the amount and diameter of which determine the effective flow cross section . the second compensating throttling constriction may be designed in a number of ways within the scope of the present invention . the throttling constriction may also be provided directly in the area of valve needle 5 . for example , the throttling constriction may also be designed in the form of bores provided in the wall surrounding hollow bore 14 so they open into hollow bore 14 and have an axial directional component . it is important for the present invention for an area to be provided in the fuel feed where the fuel flow has a flow component directed away from spray orifice 2 , with the fuel flow being throttled and force being transferred to valve needle 5 in this area . according to another embodiment of the present invention , flow forces of different types can be compensated , regardless of whether they are caused by swirl grooves , swirl bores or other throttling flow channels . | 5 |
referring to fig1 reference number 1 indicates a blank of flexible base material from which the sheet comprising the present invention may be fabricated . suitable materials include woven textiles and disposable materials such as nonwoven webs , plastic film reinforced paper , and various types of plastic film . an especially suitable material is a nonwoven polypropylene web such as that marketed by kimberly - clark corporation under the trademark &# 34 ; evolution &# 34 ;. the invention is not limited to the specific type of material . the sheet comprises a rectangular central portion 3 , a pair of opposed side panels 5 , and a pair of opposed end panels 7 . each side panel is bounded by an exterior edge 9 and an interior edge 11 . each end panel is bounded by an exterior edge 13 and an interior edge 15 . the central portion is intended to cover the top portion of a mattress , and the side and end panels are intended to cover respective sides and ends of the mattress . to form corner pockets , each side panel is folded over along interior edge 11 so the side panels attain facing contact with respective common face portions of the underlying central portion , as shown in fig2 . each side panel is attached to at least one end panel when the sheet is to be used as a top sheet ; if the sheet is to be used as a bottom sheet , each side panel is attached to both end panels . attachment occurs along diagonal lines 17 which extend from the intersections of edges 9 and 13 to the points where edges 11 coincide with edges 15 . the drawings show the attachment lines to be positioned at a 45 ° angle to edges 13 , but the attachment lines may be positioned at angles from about 30 ° to 60 ° without detracting from the utility of the corner pockets . the nature of attachment lines 17 may differ according to the type of sheet material . for example , a sheet made from a woven textile may be sewn . sheets formed from a thermoplastic nonwoven web such as fibrous polyproylene may be suitably attached by the application of heat and pressure . a base material of plastic film is preferably attached with hot melt adhesives . if the sheet is to be fabricated from material which is attachable to itself by sewing or heat sealing , the side panels are folded over onto the central portion and end panels prior to attachment , as described above . if the sheet is made from a material which requires an adhesive , a modified procedure is required . lines of adhesive are applied to at least one pair of corners of the unfolded blank of fig1 as indicated by lines 19 . the adhesive lines extend diagonally from the corners to the intersection of edges 11 and 15 . alternatively , adhesive may be applied along lines 21 extending from the intersection of edges 11 and 15 toward edge 13 in mirror images of lines 19 . side panels 5 are subsequently folded over along edge 11 , and the panels are firmly pressed onto the underlying end panels along the adhesive lines to create permanent bonds . pairs of elastic bands 23 for aiding in maintaining proper fit of the pockets are fastened to the folded - over and attached side panels in cooperation with the attachment lines . in the embodiment shown in fig2 two pairs of bands are employed for a bottom sheet . the material comprising the bands and the method of fastening them to the sheet may vary with the sheet material . sheet materials , such as polyethylene film , that are compatible with adhesives may employ bands of natural rubber fastened with a hot melt adhesive . a heat sealable base material such as a polypropylene web may use bands which are heat sealable ; an illustrative heat sealable band material is a polymer sold under the trademark &# 34 ; tuftane &# 34 ;. bands used with woven textile sheets may be fastened by sewing . the bands are fastened in a stretched condition , preferably adjacent the edges 9 , as shown in fig2 inner end 25 of each band is fastened between the interior and exterior edges of the associated end panel with the preferred fastening point located coincident with the attachement line 17 . outer end 27 of each band is fastened to the same side panel as end 25 at a distance from edge 13 greater than the width of end panel 7 . it will be appreciated that the distance between ends 25 and 27 is less when the sheet is operatively placed over the mattress , as shown in fig3 than when the sheet is in the flat state during the manufacturing process , fig2 . to function properly , the bands 23 must be stretched sufficiently during manufacture to allow a residual tension when the sheet is in use . the relative tension between the initial and operative states depends on the properties of the elastic material and the length of the bands . to minimize the initial tension while permitting sufficient residual tension , it is desirable to employ bands that are as long as practical and to use a &# 34 ; stretchy &# 34 ; material , i . e ., material with a high elongation per unit length . the choice of elastic material may be restricted by compatibility with the sheet material ; if so , the length of the bands takes on added importance . the limiting fastening point for ends 27 is the mid - point of edges 9 . to keep the cost of the completed sheet to a minimum , shorter bands are preferred . to cover the mattress , the sheet is placed on the mattress with the folded side panels underlying the central portion 3 . in this condition the elastic bands are in a relaxed state , and the end panels 7 are also folded under the central portion . an elastic band is pulled downward along the corner of the mattress and then tucked diagonally under the mattress corner . simultaneously , the folded - under side and end panels adjacent the corner will unfold so as to cover the sides and ends of the mattress in the region of that corner . the other bands are similarly positioned under the respective mattress corners . the fitted sheet thus assumes a position of utility in which it is restrained securely in place . as shown in fig2 and 3 , the construction of the fitted sheet by means of attachment lines 17 results in the formation of a triangular flap 29 of excess material at each corner . if considered objectionable , the flaps may be easily removed by cutting the sheet along lines parallel to the attachment lines 17 but displaced therefrom a small distance toward the intersection of edges 11 and 13 . under some conditions , as for example with a heat sealable base material , flaps 29 may be removed simultaneously with the forming of the attachment lines by use of suitable hot knives of conventional construction . the result is a fitted sheet possessing an especially neat appearance . the fitted sheet may be advantageously manufactured in a continuous manner . flexible base material may be supplied as a continuous web 31 from a supply roll 33 by means of feed rolls 35 , as shown schematically in fig4 . the method of forming the corner pockets will vary with the type of sheet material . for a material most suitably attached to itself with adhesive , pairs of lines of adhesive are applied to the web at predetermined spaced intervals corresponding to the length of a mattress plus twice its depth . the adhesive lines are shaped as v &# 39 ; s of predetermined height , as represented by reference numerals 49 of fig5 with the points of v &# 39 ; s lying on the exterior edges 34 of the web . the height of the v &# 39 ; s 49 corresponds to the depth of the mattress . alternatively , adhesive may be deposited as v &# 39 ; s 51 which point toward the center of the web in mirror images of v &# 39 ; s 49 . adhesive may be applied by a pair of applicators 37 which reciprocate normal to the direction of web motion , as indicated by arrows 39 , fig5 . the relative longitudinal motion of the web and transverse motion of the applicator result in the formation of lines 49 and 51 . it will be appreciated by those skilled in the art that other apparatus for applying adhesive , such as print rolls , may be employed . after the adhesive is deposited , a conventional folding horn 47 is used to fold over the edges of the web onto the underlying portion so the fold lines pass through the tops of the v &# 39 ; s 49 or 51 . the folded - over edges are then pressed firmly to the web as by a pressure nip formed by rolls 52 , thus forming attachment lines 57 . if the base material is not compatible with adhesives , a different procedure than the foregoing may be followed . the continuous web 31 is first folded over using a conventional folding horn 47 along fold lines 53 which are parallel to outer edges 34 . the folded edges are then attached to the underlying web along attachment lines shaped as pairs of v &# 39 ; s 57 with the points of the v &# 39 ; s located at the fold lines 53 . in the case of sheets made from woven textiles , attachment may occur by sewing . a polypropylene web preferably has the attachment lines created by applying heat and pressure in a manner more fully explained hereinafter . subsequently , stretched elastic bands 23 are fastened to the folded and attached edges . each band is preferably fastened adjacent an edge 34 . the outer ends are fastened to points 59 which are symmetrically located about the points of attachment v &# 39 ; s 57 . the span between the two outside ends is greater than the width of the v and less than the length of the sheet , as shown in fig6 . the bands are also fastened at two intermediate points 61 located symmetrically about the points of the v &# 39 ; s with a span less than the width of the v . preferably , the intermediate points 61 coincide with the respective legs of attachment lines 57 . apparatus for fastening the bands depends on the sheet and band materials . for materials compatible with adhesives , apparatus similar to that described in u . s . pat . no . 4 , 227 , 952 and schematically illustrated in fig4 may be used . adhesive is deposited from nozzles 58 onto two stretched elastic ribbons 60 which are supplied from supply rolls ( not shown ). chain 62 carries a plurality of web support plates 64 which are arranged and spaced so as to form a substantially continuous supporting surface for the web , with small gaps 66 between them . as chain 62 traverses sprockets 68 , the support plates 64 spread and form larger gaps 70 . chain 72 carries a plurality of tucker bars 74 which register with gaps 70 to push web 31 into gaps 70 to form folds 76 in the sheet material . the portions of the web which are folded into gaps 70 correspond with the portions between the outer fastening points 59 . hold - down belt 78 with pressure plate 81 firmly presses the elastic ribbons 60 to the web and maintains contact until the adhesive has set . cut - off knife 83 is timed to sever the ribbons within the small gaps 70 , but not the web . draw rolls 84 withdraw the composite web and superimposed bands from the fastening apparatus , and the folds in the web are removed as the slack is taken out . different fastening apparatus is required for sheet and band materials that are not compatible with adhesives . for example , it is contemplated that bands used with a woven textile web would be most advantageously fastened by sewing at a sewing station . apparatus for fastening the bands to a web of heat sealable material such as non - woven polypropylene may be of the form shown schematically in fig7 . chains 62 and 72 , together with web support plates 64 and tucker bars 74 , may be employed as previously described . two stretched elastic ribbons 60 and folded web 31 pass between support plates 64 and traveling heaters 85 carried by chain 89 . heaters 85 are spaced so as to coincide with fastening points 59 and 61 on the web . thus , as the web and ribbons advance between the traveling heaters and support plates , the ribbons are fastened to the web at locations 59 and 61 . the ribbons are subsequently cut by knife 83 , and the combination of the web and bands is withdrawn by draw rolls 84 . the final step in the continuous method of manufacture is to cut the web and bands into individual sheets 73 , which are shown schematically in the flat state . the cuts are made along transverse lines 63 connecting the points of v &# 39 ; s 57 , as shown in fig6 . the cutting of the web into individual sheets may be accomplished by flying knives 69 mounted on rolls 71 , as schematically illustrated in fig4 . it may be desirable to remove triangular sections 65 of excess material that are created at each corner . this is readily accomplished by cutting along lines 67 , which are parallel to v &# 39 ; s 57 but slightly displaced therefrom toward the fold lines . cutting lines 67 may be performed simultaneously with cutting lines 63 by properly modifying the configuration of flying knives 69 . a web composed of a heat sealable material lends itself to a very efficient method of simultaneously forming attachment lines 57 , removing triangular pieces 65 , and severing the web and bands along lines 63 . a hot knife 75 may be mounted to the periphery of a rotary drum 77 , as diagrammatically illustrated in fig7 . the hot knife is constructed in a configuration corresponding to lines 57 , 63 , and 67 . as the web and ribbons pass between drum 77 and back - up roll 79 , the attachment lines are formed and the web is cut along lines 63 and 67 concurrently without the necessity of separate attaching and cutting operations . the finished sheets produced from the above continuous method are suitable for use as bottom sheets . the method can easily be modified to manufacture top sheets which include only two fitted corners with cooperating elastic bands per sheet . this is accomplished by doubling the space between the attachment v &# 39 ; s 57 with the respective bands 23 while maintaining the spacing of the transverse cuts 63 . thus , it is apparent that there has been provided , in accordance with the invention , an elasticized fitted mattress covering and method that fully satisfy the objects , aims and advantages set forth above . while the invention has been described in conjunction with specific embodiments thereof , it is evident that many alternatives , modifications , and variations will be apparent to those skilled in the art in light of the foregoing description . accordingly , it is intended to embrace all such alternatives , modifications , and variations as fall within the spirit and broad scope of the appended claims . | 0 |
[ 0014 ] fig1 illustrates in schematic form the process and apparatus 10 of the present invention . the apparatus is composed fundamentally of two mated embossing rolls 15 and 16 , multiple glue metering / application rolls 11 - 14 , a pressure roll 17 , a strip - off roll 18 , and a chilled s - wrap 19 . the embossing rolls are steel , with a matched embossing pattern etched into them which interlocks to emboss a web of sheet material passed therebetween . the roll with pockets and raised lands is referred to as the female embossing roll 15 , while the roll with raised nubs and recessed lands is referred to as the male embossing roll 16 . the female embossing roll preferably has a release coating applied to its surface . the glue application / metering rolls 11 - 14 typically alternate between being plain steel or rubber - coated steel . the glue application roll 14 ( the last roll in the glue system ) is always rubber coated steel . the pressure roll 17 and strip off roll 18 are also rubber coated steel . the chilled s - wrap is composed of hollow steel rolls 19 with a release coating on their outside surfaces and coolant flowing through the rolls . the direction of roll rotation is shown in fig1 with arrows . more specifically , with reference to fig1 an adhesive ( such as a hot melt pressure sensitive adhesive ) 40 is extruded onto the surface of the first rotating roll 11 via a heated slot die 9 . the slot die is supplied by a hot melt supply system ( with a heated hopper and variable speed gear pump , not shown ) through a heated hose . the surface speed of the first of the glue metering rolls 11 is considerably slower than the nominal tangential line speed of the web of sheet material 50 to be embossed and adhesive - coated . the metering nips are shown in fig1 as stations 1 , 2 , and 3 . the remaining glue metering rolls 12 - 14 rotate progressively faster so that the glue application nip , station 4 , is surface speed matched . the glue 40 is transferred from the glue application roll 14 to the female embossing roll 15 at station 4 . the glue 40 travels with the female embossing roll surface to station 5 , where it is combined with the polymer web 50 which is carried into station 5 via male embossing roll 16 . at station 5 , the polymer web 50 is embossed and combined with the glue 40 simultaneously to form an adhesive coated web 60 . the web 60 , glued to the surface of roll 15 , travels with the roll surface to station 6 , where a rubber coated pressure roll 17 applies pressure to the glued portion of the web . the web 60 , still glued to the female embossing roll 15 , travels to station 7 , where it is stripped off the female embossing roll 15 via strip - off roll 18 . the finished adhesive - coated web 60 then travels to the chilled s - wrap 19 at station 8 , where it is cooled to increase its strength . the adhesive ( or glue ) 40 is applied to the land areas of the female embossing roll 15 only . this is accomplished by carefully controlling the female embossing roll to glue application roll clearance and runout at station 4 . the gap between these rolls is controlled such that the glue covered rubber roll 14 applies glue to the lands only , without pressing the glue into the recesses or pockets between lands . the glue application roll 14 is a rubber coated steel roll . the rubber coating is ground in a special process to achieve approximately 0 . 001 inches tir runout tolerance . the nip is controlled in the machine with precision wedge blocks . a rubber coating is utilized to ( 1 ) protect the coating on the female embossing roll 15 from damage due to metal - to - metal contact and ( 2 ) to allow the glue application roll to be very lightly pressed against the female embossing roll , so that the deflection of the rubber compensates for the actual runout of the embossing roll and glue application roll , allowing glue to be applied everywhere evenly on the female embossing roll lands . the glue application roll 14 is lightly pressed against the female embossing roll 15 such that the deflection of the rubber surface compensates for embossing roll and glue application roll runout , but the deflection is not so high as to press glue into the pockets in the surface of the female embossing roll 15 . deposition of glue exclusively onto the lands of the female embossing roll 15 is essential to prevent glue from being transferred onto the tops of the embossments in the web . adhesive present on the tops of the embossments would cause them to exhibit adhesive properties prior to activation of the web via crushing of the embossments . the adhesive or glue utilized is highly elastic in nature , and a transition from a stationary slot die 9 to full tangential line speed can result in the glue being extended and fractured , or in non - adhesion to the first metering roll . to reduce the extension rate of the glue , it is applied first to a slow moving roll and then through a series of metering gaps ( stations 1 , 2 , and 3 ) it is milled down to a very thin glue film and accelerated at the desired tangential line speed . the glue rolls must be ground to exacting tolerances for diameter and runout to maintain the precise inter - roll gap dimensions required for glue metering and acceleration . typical runout tolerance is 0 . 00005 inches tir . the glue rolls must be heated uniformly circumferentially and across the machine direction to avoid thermally - induced crown or runout of the rolls . it has been found that , in the case of electrically heated rolls , a single heater failure can create enough runout to prevent uniform glue printing onto the web . in such a case , ammeters are used to indicate heater failures . heat loss through bearings and roll shafts can create roll crown , which also prevents uniform glue printing . often the roll &# 39 ; s bearing blocks must be heated to prevent temperature gradients in the cross machine direction . the female embossing roll 15 preferably includes a release coating applied to both the land surfaces and to the surfaces of the pockets or recesses therebetween . the release coating and the glue properties must be carefully balanced to provide the best combination of adhesion and release . the coating must allow the very hot ( typically 300 - 350 ° f .) glue to transfer to the female embossing roll and yet allow the adhesive - coated polymer film web to release at the embossing roll temperature ( typically 160 - 180 ° f .). if the release coating promotes too little adhesion , the glue will not transfer from the glue application roll to the female embossing roll , while if the release coating promotes too much adhesion , the final adhesive - coated web cannot be removed from the surface of the female embossing roll without tearing or stretching the polymer film . the film should be embossed at the highest possible embossing temperature to promote crisp , high - caliper embossments and allow the glued film web to release from the female embossing roll with lower strip - off force . however , the temperature of the embossing rolls must be kept below the softening point of the film web so that the final adhesively - coated web will have sufficient tensile strength to be removed from the female embossing roll . a balance between release temperature and film softening temperature has been found to be a critical parameter in defining successful operating conditions for operating at high speeds . the strip - off roll assists in removing the final product from the female embossing roll without damaging the film . since the product ( film web ) is glued to the surface of the female embossing roll , very high forces can be developed at the strip - off point . the strip off roll localizes these high forces to a very short length of web , resulting in less distortion of the web and more control over the strip - off angle . preventing distortion of the final product is essential to provide consistent film properties and prevent the film from having regions which are prematurely activated to exhibit adhesive properties . the amount or degree of engagement between the male and female embossing rolls must be carefully controlled to prevent damage to the rolls or to the film web . the outside surfaces of the embossing rolls are ground to a 0 . 00005 inch tir runout tolerance . the engagement is controlled in the machine with precision wedge blocks . the engagement of the embossing rolls governs the final caliper of the film ( i . e ., the final height of the embossments ). another important criteria is the fit or correspondence between the male and female embossing rolls . one useful technique is to form one roll via a photoetching process and utilize this roll as a “ master ” to form the other roll as a negative image . the equipment must also be designed so as to maintain precise synchronization of the mating embossing rolls . the embossing and glue rolls are all individually heated and controlled to allow precise control of glue transfer temperatures and embossing roll release temperature . the use of mating male and female embossing rolls of complementary pattern shapes fully supports the thin film web during the embossing and adhesive process step to ensure that the forces are properly distributed within the film material . full support of the web , as opposed to thermoforming or vacuum forming a film with an open support structure such as an apertured belt or drum wherein the portion of the web being deformed into the apertures or recesses is unsupported , is believed to allow an increase in the rate at which strains are imparted to the web without damage to the web and thus allow for higher production speeds . the simultaneous application of the adhesive to the film during the embossing step provides precise registration of the adhesive on the undeformed portions of the web between embossments . precise control over the adhesive , particularly the thickness and uniformity of the adhesive layer applied to the female embossing roll , is an important factor in producing a high quality product at high speed . especially in the case of very low add - on levels of adhesive , even slight variations in the thickness of the adhesive during transfers from roll to roll can result in coverage gaps by the time the adhesive is applied to the embossing roll . at the same time , such variations can lead to excess adhesive in certain regions of the embossing roll which could either contaminate the recesses in the roll or result in incomplete adhesive transfer to the web and a buildup of adhesive on the embossing roll . [ 0031 ] fig3 and 4 show a pattern 20 created using an algorithm described in greater detail in commonly - assigned , concurrently - filed , co - pending u . s . patent application ser . no . ______ , in the name of kenneth s . mcguire , entitled “ method of seaming and expanding amorphous patterns ”, the disclosure of which is hereby incorporated herein by reference . it is obvious from fig3 and 4 that there is no appearance of a seam at the borders of the tiles 20 when they are brought into close proximity . likewise , if opposite edges of a single pattern or tile were brought together , such as by wrapping the pattern around a belt or roll , the seam would likewise not be readily visually discernible . as utilized herein , the term “ amorphous ” refers to a pattern which exhibits no readily perceptible organization , regularity , or orientation of constituent elements . this definition of the term “ amorphous ” is generally in accordance with the ordinary meaning of the term as evidenced by the corresponding definition in webster &# 39 ; s ninth new collegiate dictionary . in such a pattern , the orientation and arrangement of one element with regard to a neighboring element bear no predictable relationship to that of the next succeeding element ( s ) beyond . by way of contrast , the term “ array ” is utilized herein to refer to patterns of constituent elements which exhibit a regular , ordered grouping or arrangement . this definition of the term “ array ” is likewise generally in accordance with the ordinary meaning of the term as evidenced by the corresponding definition in webster &# 39 ; s ninth new collegiate dictionary . in such an array pattern , the orientation and arrangement of one element with regard to a neighboring element bear a predictable relationship to that of the next succeeding element ( s ) beyond . the degree to which order is present in an array pattern of three - dimensional protrusions bears a direct relationship to the degree of nestability exhibited by the web . for example , in a highly - ordered array pattern of uniformly - sized and shaped hollow protrusions in a close - packed hexagonal array , each protrusion is literally a repeat of any other protrusion . nesting of regions of such a web , if not in fact the entire web , can be achieved with a web alignment shift between superimposed webs or web portions of no more than one protrusion - spacing in any given direction . lesser degrees of order may demonstrate less nesting tendency , although any degree of order is believed to provide some degree of nestability . accordingly , an amorphous , non - ordered pattern of protrusions would therefore exhibit the greatest possible degree of nesting - resistance . three - dimensional sheet materials having a two - dimensional pattern of three - dimensional protrusions which is substantially amorphous in nature are also believed to exhibit “ isomorphism ” as utilized herein , the terms “ isomorphism ” and its root “ isomorphic ” are utilized to refer to substantial uniformity in geometrical and structural properties for a given circumscribed area wherever such an area is delineated within the pattern . this definition of the term “ isomorphic ” is generally in accordance with the ordinary meaning of the term as evidenced by the corresponding definition in webster &# 39 ; s ninth new collegiate dictionary . by way of example , a prescribed area comprising a statistically - significant number of protrusions with regard to the entire amorphous pattern would yield statistically substantially equivalent values for such web properties as protrusion area , number density of protrusions , total protrusion wall length , etc . such a correlation is believed desirable with respect to physical , structural web properties when uniformity is desired across the web surface , and particularly so with regard to web properties measured normal to the plane of the web such as crush - resistance of protrusions , etc . utilization of an amorphous pattern of three - dimensional protrusions has other advantages as well . for example , it has been observed that three - dimensional sheet materials formed from a material which is initially isotropic within the plane of the material remain generally isotropic with respect to physical web properties in directions within the plane of the material . as utilized herein , the term “ isotropic ” is utilized to refer to web properties which are exhibited to substantially equal degrees in all directions within the plane of the material . this definition of the term “ isotropic ” is likewise generally in accordance with the ordinary meaning of the term as evidenced by the corresponding definition in webster &# 39 ; s ninth new collegiate dictionary . without wishing to be bound by theory , this is presently believed to be due to the non - ordered , non - oriented arrangement of the three - dimensional protrusions within the amorphous pattern . conversely , directional web materials exhibiting web properties which vary by web direction will typically exhibit such properties in similar fashion following the introduction of the amorphous pattern upon the material . by way of example , such a sheet of material could exhibit substantially uniform tensile properties in any direction within the plane of the material if the starting material was isotropic in tensile properties . such an amorphous pattern in the physical sense translates into a statistically equivalent number of protrusions per unit length measure encountered by a line drawn in any given direction outwardly as a ray from any given point within the pattern . other statistically equivalent parameters could include number of protrusion walls , average protrusion area , average total space between protrusions , etc . statistical equivalence in terms of structural geometrical features with regard to directions in the plane of the web is believed to translate into statistical equivalence in terms of directional web properties . revisiting the array concept to highlight the distinction between arrays and amorphous patterns , since an array is by definition “ ordered ” in the physical sense it would exhibit some regularity in the size , shape , spacing , and / or orientation of protrusions . accordingly , a line or ray drawn from a given point in the pattern would yield statistically different values depending upon the direction in which the ray extends for such parameters as number of protrusion walls , average protrusion area , average total space between protrusions , etc . with a corresponding variation in directional web properties . within the preferred amorphous pattern , protrusions will preferably be non - uniform with regard to their size , shape , orientation with respect to the web , and spacing between adjacent protrusion centers . without wishing to be bound by theory , differences in center - to - center spacing of adjacent protrusions are believed to play an important role in reducing the likelihood of nesting occurring in the face - to - back nesting scenario . differences in center - to - center spacing of protrusions in the pattern result in the physical sense in the spaces between protrusions being located in different spatial locations with respect to the overall web . accordingly , the likelihood of a “ match ” occurring between superimposed portions of one or more webs in terms of protrusions / space locations is quite low . further , the likelihood of a “ match ” occurring between a plurality of adjacent protrusions / spaces on superimposed webs or web portions is even lower due to the amorphous nature of the protrusion pattern . in a completely amorphous pattern , as would be presently preferred , the center - to - center spacing is random , at least within a designer - specified bounded range , such that there is an equal likelihood of the nearest neighbor to a given protrusion occurring at any given angular position within the plane of the web . other physical geometrical characteristics of the web are also preferably random , or at least non - uniform , within the boundary conditions of the pattern , such as the number of sides of the protrusions , angles included within each protrusion , size of the protrusions , etc . however , while it is possible and in some circumstances desirable to have the spacing between adjacent protrusions be non - uniform and / or random , the selection of polygon shapes which are capable of interlocking together makes a uniform spacing between adjacent protrusions possible . this is particularly useful for some applications of the three - dimensional , nesting - resistant sheet materials of the present invention , as will be discussed hereafter . as used herein , the term “ polygon ” ( and the adjective form “ polygonal ”) is utilized to refer to a two - dimensional geometrical figure with three or more sides , since a polygon with one or two sides would define a line . accordingly , triangles , quadrilaterals , pentagons , hexagons , etc . are included within the term “ polygon ”, as would curvilinear shapes such as circles , ellipses , etc . which would have an infinite number of sides . when describing properties of two - dimensional structures of non - uniform , particularly non - circular , shapes and non - uniform spacing , it is often useful to utilize “ average ” quantities and / or “ equivalent ” quantities . for example , in terms of characterizing linear distance relationships between objects in a two - dimensional pattern , where spacings on a center - to - center basis or on an individual spacing basis , an “ average ” spacing term may be useful to characterize the resulting structure . other quantities that could be described in terms of averages would include the proportion of surface area occupied by objects , object area , object circumference , object diameter , etc . for other dimensions such as object circumference and object diameter , an approximation can be made for objects which are non - circular by constructing a hypothetical equivalent diameter as is often done in hydraulic contexts . a totally random pattern of three - dimensional hollow protrusions in a web would , in theory , never exhibit face - to - back nesting since the shape and alignment of each frustum would be unique . however , the design of such a totally random pattern would be very time - consuming and complex proposition , as would be the method of manufacturing a suitable forming structure . in accordance with the present invention , the non - nesting attributes may be obtained by designing patterns or structures where the relationship of adjacent cells or structures to one another is specified , as is the overall geometrical character of the cells or structures , but wherein the precise size , shape , and orientation of the cells or structures is non - uniform and non - repeating . the term “ non - repeating ”, as utilized herein , is intended to refer to patterns or structures where an identical structure or shape is not present at any two locations within a defined area of interest . while there may be more than one protrusion of a given size and shape within the pattern or area of interest , the presence of other protrusions around them of non - uniform size and shape virtually eliminates the possibility of an identical grouping of protrusions being present at multiple locations . said differently , the pattern of protrusions is non - uniform throughout the area of interest such that no grouping of protrusions within the overall pattern will be the same as any other like grouping of protrusions . the beam strength of the three - dimensional sheet material will prevent significant nesting of any region of material surrounding a given protrusion even in the event that that protrusion finds itself superimposed over a single matching depression since the protrusions surrounding the single protrusion of interest will differ in size , shape , and resultant center - to - center spacing from those surrounding the other protrusion / depression . professor davies of the university of manchester has been studying porous cellular ceramic membranes and , more particularly , has been generating analytical models of such membranes to permit mathematical modeling to simulate real - world performance . this work was described in greater detail in a publication entitled “ porous cellular ceramic membranes : a stochastic model to describe the structure of an anodic oxide membrane ”, authored by j . broughton and g . a . davies , which appeared in the journal of membrane science , vol . 106 ( 1995 ), at pp . 89 - 101 , the disclosure of which is hereby incorporated herein by reference . other related mathematical modeling techniques are described in greater detail in “ computing the n - dimensional delaunay tessellation with application to voronoi polytopes ”, authored by d . f . watson , which appeared in the computer journal , vol . 24 , no . 2 ( 1981 ), at pp . 167 - 172 , and “ statistical models to describe the structure of porous ceramic membranes ”, authored by j . f . f . lim , x . jia , r . jafferali , and g . a . davies , which appeared in separation science and technology , 28 ( 1 - 3 ) ( 1993 ) at pp . 821 - 854 , the disclosures of both of which are hereby incorporated herein by reference . as part of this work , professor davies developed a two - dimensional polygonal pattern based upon a constrained voronoi tessellation of 2 - space . in such a method , again with reference to the above - identified publication , nucleation points are placed in random positions in a bounded ( pre - determined ) plane which are equal in number to the number of polygons desired in the finished pattern . a computer program “ grows ” each point as a circle simultaneously and radially from each nucleation point at equal rates . as growth fronts from neighboring nucleation points meet , growth stops and a boundary line is formed . these boundary lines each form the edge of a polygon , with vertices formed by intersections of boundary lines . while this theoretical background is useful in understanding how such patterns may be generated and the properties of such patterns , there remains the issue of performing the above numerical repetitions step - wise to propagate the nucleation points outwardly throughout the desired field of interest to completion . accordingly , to expeditiously carry out this process a computer program is preferably written to perform these calculations given the appropriate boundary conditions and input parameters and deliver the desired output . the first step in generating a pattern useful in accordance with the present invention is to establish the dimensions of the desired pattern . for example , if it is desired to construct a pattern 10 inches wide and 10 inches long , for optionally forming into a drum or belt as well as a plate , then an x - y coordinate system is established with the maximum x dimension ( x max ) being 10 inches and the maximum y dimension ( y max ) being 10 inches ( or vice - versa ). after the coordinate system and maximum dimensions are specified , the next step is to determine the number of “ nucleation points ” which will become polygons desired within the defined boundaries of the pattern . this number is an integer between 0 and infinity , and should be selected with regard to the average size and spacing of the polygons desired in the finished pattern . larger numbers correspond to smaller polygons , and vice - versa . a useful approach to determining the appropriate number of nucleation points or polygons is to compute the number of polygons of an artificial , hypothetical , uniform size and shape that would be required to fill the desired forming structure . if this artificial pattern is an array of regular hexagons 30 ( see fig5 ), with d being the edge - to - edge dimension and m being the spacing between the hexagons , then the number density of hexagons , n , is : n = 2 3 3 ( d + m ) 2 it has been found that using this equation to calculate a nucleation density for the amorphous patterns generated as described herein will give polygons with average size closely approximating the size of the hypothetical hexagons ( d ). once the nucleation density is known , the total number of nucleation points to be used in the pattern can be calculated by multiplying by the area of the pattern ( 80 in 2 in the case of this example ). a random number generator is required for the next step . any suitable random number generator known to those skilled in the art may be utilized , including those requiring a “ seed number ” or utilizing an objectively determined starting value such as chronological time . many random number generators operate to provide a number between zero and one ( 0 - 1 ), and the discussion hereafter assumes the use of such a generator . a generator with differing output may also be utilized if the result is converted to some number between zero and one or if appropriate conversion factors are utilized . a computer program is written to run the random number generator the desired number of iterations to generate as many random numbers as is required to equal twice the desired number of “ nucleation points ” calculated above . as the numbers are generated , alternate numbers are multiplied by either the maximum x dimension or the maximum y dimension to generate random pairs of x and y coordinates all having x values between zero and the maximum x dimension and y values between zero and the maximum y dimension . these values are then stored as pairs of ( x , y ) coordinates equal in number to the number of “ nucleation points ”. it is at this point , that the invention described herein differs from the pattern generation algorithm described in the previous mcguire et al . application . assuming that it is desired to have the left and right edge of the pattern “ mesh ”, i . e ., be capable of being “ tiled ” together , a border of width b is added to the right side of the 10 ″ square ( see fig6 ). the size of the required border is dependent upon the nucleation density ; the higher the nucleation density , the smaller is the required border size . a convenient method of computing the border width , b , is to refer again to the hypothetical regular hexagon array described above and shown in fig5 . in general , at least three columns of hypothetical hexagons should be incorporated into the border , so the border width can be calculated as : now , any nucleation point p with coordinates ( x , y ) where x & lt ; b will be copied into the border as another nucleation point , p ′, with a new coordinate ( x max + x , y ). if the method described in the preceding paragraphs is utilized to generate a resulting pattern , the pattern will be truly random . this truly random pattern will , by its nature , have a large distribution of polygon sizes and shapes which may be undesirable in some instances . in order to provide some degree of control over the degree of randomness associated with the generation of “ nucleation point ” locations , a control factor or “ constraint ” is chosen and referred to hereafter as β ( beta ). the constraint limits the proximity of neighboring nucleation point locations through the introduction of an exclusion distance , e , which represents the minimum distance between any two adjacent nucleation points . the exclusion distance e is computed as follows : where λ ( lambda ) is the number density of points ( points per unit area ) and β ranges from 0 to 1 . to implement the control of the “ degree of randomness ”, the first nucleation point is placed as described above . β is then selected , and e is calculated from the above equation . note that β , and thus e , will remain constant throughout the placement of nucleation points . for every subsequent nucleation point ( x , y ) coordinate that is generated , the distance from this point is computed to every other nucleation point that has already been placed . if this distance is less than e for any point , the newly - generated ( x , y ) coordinates are deleted and a new set is generated . this process is repeated until all n points have been successfully placed . note that in the tiling algorithm useful in accordance with the present invention , for all points ( x , y ) where x & lt ; b , both the original point p and the copied point p ′ must be checked against all other points . if either p or p ′ is closer to any other point than e , then both p and p ′ are deleted , and a new set of random ( x , y ) coordinates is generated . if β = 0 , then the exclusion distance is zero , and the pattern will be truly random . if β = 1 , the exclusion distance is equal to the nearest neighbor distance for a hexagonally close - packed array . selecting β between 0 and 1 allows control over the “ degree of randomness ” between these two extremes . in order to make the pattern a tile in which both the left and right edges tile properly and the top and bottom edges tile properly , borders will have to be used in both the x and y directions . once the complete set of nucleation points are computed and stored , a delaunay triangulation is performed as the precursor step to generating the finished polygonal pattern . the use of a delaunay triangulation in this process constitutes a simpler but mathematically equivalent alternative to iteratively “ growing ” the polygons from the nucleation points simultaneously as circles , as described in the theoretical model above . the theme behind performing the triangulation is to generate sets of three nucleation points forming triangles , such that a circle constructed to pass through those three points will not include any other nucleation points within the circle . to perform the delaunay triangulation , a computer program is written to assemble every possible combination of three nucleation points , with each nucleation point being assigned a unique number ( integer ) merely for identification purposes . the radius and center point coordinates are then calculated for a circle passing through each set of three triangularly - arranged points . the coordinate locations of each nucleation point not used to define the particular triangle are then compared with the coordinates of the circle ( radius and center point ) to determine whether any of the other nucleation points fall within the circle of the three points of interest . if the constructed circle for those three points passes the test ( no other nucleation points falling within the circle ), then the three point numbers , their x and y coordinates , the radius of the circle , and the x and y coordinates of the circle center are stored . if the constructed circle for those three points fails the test , no results are saved and the calculation progresses to the next set of three points . once the delaunay triangulation has been completed , a voronoi tessellation of 2 - space is then performed to generate the finished polygons . to accomplish the tessellation , each nucleation point saved as being a vertex of a delaunay triangle forms the center of a polygon . the outline of the polygon is then constructed by sequentially connecting the center points of the circumscribed circles of each of the delaunay triangles , which include that vertex , sequentially in clockwise fashion . saving these circle center points in a repetitive order such as clockwise enables the coordinates of the vertices of each polygon to be stored sequentially throughout the field of nucleation points . in generating the polygons , a comparison is made such that any triangle vertices at the boundaries of the pattern are omitted from the calculation since they will not define a complete polygon . if it is desired for ease of tiling multiple copies of the same pattern together to form a larger pattern , the polygons generated as a result of nucleation points copied into the computational border may be retained as part of the pattern and overlapped with identical polygons in an adjacent pattern to aid in matching polygon spacing and registry . alternatively , as shown in fig3 and 4 , the polygons generated as a result of nucleation points copied into the computational border may be deleted after the triangulation and tessellation are performed such that adjacent patterns may be abutted with suitable polygon spacing . once a finished pattern of interlocking polygonal two - dimensional shapes is generated , in accordance with the present invention such a network of interlocking shapes is utilized as the design for one web surface of a web of material with the pattern defining the shapes of the bases of the three - dimensional , hollow protrusions formed from the initially planar web of starting material . in order to accomplish this formation of protrusions from an initially planar web of starting material , a suitable forming structure comprising a negative of the desired finished three - dimensional structure is created which the starting material is caused to conform to by exerting suitable forces sufficient to permanently deform the starting material . from the completed data file of polygon vertex coordinates , a physical output such as a line drawing may be made of the finished pattern of polygons . this pattern may be utilized in conventional fashion as the input pattern for a metal screen etching process to form a three - dimensional forming structure . if a greater spacing between the polygons is desired , a computer program can be written to add one or more parallel lines to each polygon side to increase their width ( and hence decrease the size of the polygons a corresponding amount ). while particular embodiments of the present invention have been illustrated and described , it will be obvious to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention , and it is intended to cover in the appended claims all such modifications that are within the scope of the invention . | 1 |
fig1 shows the configuration of an interferometer system 10 in which flat surfaces 1 and 2 of flats a and b , respectively , define the particular configuration of cavity 4 for which the opd measurements ( at each pixel ) constituting the cavity shape are made , the cavity shape being the distance between flat a and b at each pixel . interferometer system 10 can be the assignee &# 39 ; s commercially available wyko 6000 fizeau phase shifting interferometer , which includes light source 12 producing beam 14 through beamsplitter 13 into lens 16 . collimated light from lens 16 passes as beam 17 through an anti - reflective coating on the rear surface of flat b , which is shown in fig1 as the reference surface of cavity 4 , which in the wyko 6000 interferometer can be shifted along the optical axis by pzt ( piezoelectric transducer ) 25 . numeral 26 designates the physical connection of flat b to pzt 25 . some of that light is reflected by front surface 2 back through lens 16 , and is reflected by beam splitter 13 as beam 20 , which is focused by lens 21 onto the detector array of ccd camera 22 , wherein each element of such detector array corresponds to a pixel in the field of view of the interferometer . the rest of beam 17 passes to surface 1 of flat a , which in the wyko 6000 corresponds to the test surface supported by a physical connection 27 to a stationary support 28 , and is reflected as beam 18 back through lens 16 , interfering with beam 19 , and being reflected by beamsplitter 13 into the ccd detector array of camera 22 , which senses the resulting interference pattern . the output of ccd camera 23 is input to computer 24 , which may be a dell model 466 . appendix 1 attached hereto is an object code printout of a program which is written in the language c to be executed on computer 24 of the wyko 6000 interferometer for solving equations ( 11 )-( 15 ) to obtain the absolute profiles of flats a , b and c . fig5 a shows the six cavity measurement configurations of three flats a , b , and c for which relative surface topography measurements must be made by means of interferometer system 10 of fig1 the topography being the height of each pixel of the entire surface or an area thereof relative to a reference plane . the profile of the surface is the height of each pixel along a line , such as a diameter or a polar coordinate circle , relative to a reference plane . fig6 shows front and rear views of flats a , b , and c and their front surfaces 1 , 2 , and 3 , respectively . their x , y coordinate axes are superimposed on their respective front surfaces 1 , 2 and 3 . the rear views in fig6 all are &# 34 ; flipped in the x direction &# 34 ;. the meaning of this is explained subsequently . such relative surface topography measurements produce the opd at each pixel of the image in cavity 4 for each of the six measurement configurations . in each configuration , the upper flat in the diagram of fig5 a is of a front view , and the lower flat is &# 34 ; flipped in the x direction &# 34 ; and is of a rear view of that flat . in some configurations , the upper flat is rotated 180 °, 90 °, or 45 ° with respect to the lower flat . in fig5 a , m1 represents the set of optical path distance ( opd ) interferometer measurements at all pixels in the interferometer &# 34 ; field of view &# 34 ; between the facing surfaces 1 and 2 of flat a and flat b , respectively , with flat b being flipped in the x direction ( i . e ., about the y axis ). m2 represents the opd measurements for all pixels between the facing surfaces of flat a and flat b with flat a rotated counterclockwise 180 ° and flat b flipped in the x direction . m3 represents the opd measurements for all pixels between facing surfaces of flat a and flat b with flat b flipped in the x direction and flat a rotated counterclockwise 90 ° ( from its initial angle ). m4 represents the opd measurements for every pixel with flat b flipped in the x direction and flat a rotated 45 ° counterclockwise . m5 represents the cavity shape between flat a in its original orientation and flat c flipped in the x direction . m6 represents the cavity shape between flat b and flat c flipped in the x direction . in accordance with the present invention , it is recognized that a cartesian coordinate system , a function f ( x , y ), which represents the surface topography of an optical flat can be expressed as the sum of an even -- even part f ee ( x , y ), an odd -- odd part f oo ( x , y ), an odd - even part f oe ( x , y ), and an even - odd part f eo ( x , y ) as indicated in the equation where the subscripts indicate the symmetry of the function in the x direction and in the y direction , respectively . because the flats such as a and b in fig1 are facing each other , one flat , for example b , is &# 34 ; flipped &# 34 ; relative to the other so that the test surface and the reference surface face each other to define the cavity 4 defined by surfaces 1 and 2 of flats a and b in fig1 . at this point , it may be conceptually helpful to refer to fig2 for an explanation of what is meant by &# 34 ; even &# 34 ; and &# 34 ; odd &# 34 ; functions . it is known that a one - dimensional mathematical function f ( x ) can be expressed as the sum of an even function and a corresponding odd function , for example f e ( x ) is an &# 34 ; even &# 34 ; function and f o ( x ) is an &# 34 ; odd &# 34 ; function ; that is , f e ( x ) is an &# 34 ; even &# 34 ; function because f e ( x )= f e (- x ), and f o ( x ) is an &# 34 ; odd &# 34 ; function because f o ( x )=- f o (- x ). that is , f e ( x ) is an &# 34 ; even &# 34 ; function because it has left - right symmetry with respect to its values in the left and right cartesian coordinate half planes , and similarly , f o ( x ) is an &# 34 ; odd &# 34 ; function because it has left - right anti - symmetry with respect to its values in the left and right half planes . similarly , an &# 34 ; even &# 34 ; function of y has symmetry with respect to its values in the top and bottom cartesian coordinate half planes , and an &# 34 ; odd &# 34 ; function of y has anti - symmetry with respect to its values in the top and bottom half planes . in fig2 curve 30 illustrates how the function f ( x ) is equal to the sum of its corresponding even component f e ( x ), indicated by numerals 31 and 32 , and its corresponding odd function f o ( x ), indicated by numerals 33 and 34 . the adding of f e ( x ) and f o ( x ) yields f ( x ) because parts 31 and 33 add to produce portion 30 of f ( x ) for x greater than zero , and opposite polarity portions 32 and 34 cancel for negative values of x . from curve 31 , 32 in fig2 it can be seen that if even function f e ( x ) is &# 34 ; flipped &# 34 ; along the x axis to produce f e (- x ), the magnitude and polarity of the &# 34 ; flipped &# 34 ; function is unchanged . however , if odd function f o ( x ) is flipped about the x axis to produce f o (- x ), the magnitude is unchanged , but its polarity is opposite . the one - dimensional function of equation 1a is similar to the function of equation ( 1 ) above , except that equation ( 1 ) is two - dimensional ( in the x and y directions ). for a two - dimensional cartesian coordinate system , an example is shown in fig3 to illustrate the f ee ( x , y ) and f oo ( x , y ) terms of equation ( 1 ). in fig3 numerals 35 , 36 , 37 , 38 , 39 and 42 with adjacent solid dots represent triangular pyramid shapes extending upward out of the two - dimensional x , y plane of the paper toward the reader . numerals 40 and 41 with adjacent hollow circles 45 designate identical triangular pyramids extending downward below the x , y plane of the paper away from the reader . fig3 illustrates that that is , f ee ( x , y ) has a left - right symmetry and a top - bottom symmetry . f oo ( x , y ) has a left - right antisymmetry and a top - bottom antisymmetry . thus , a function f ( x , y ) in a cartesian coordinate system can be expressed as the sum of an even - odd , an odd - even , an even -- even , and an odd -- odd function as follows . if two flats are defined by f ( x , y ) and g ( x , y ), respectively , and if g ( x , y ) is &# 34 ; flipped &# 34 ; in the x direction , then the measured optical path difference ( opd ) is equal to for convenience , an operator ! x , meaning &# 34 ; flip the flat in the x direction &# 34 ; and an operator !. sup . θ , meaning &# 34 ; rotate the flat in the θ direction &# 34 ;, are defined f ( x , y )!. sup . θ = f ( x cos θ - y sin θ , x sin θ + y cos θ ). ( 4b ) from equations 5 , when the flat is rotated or flipped , some of the four components change sign . this fact is used to solve for the four components of equation 1 . using these expressions , it is relatively easy to solve for the first three of the foregoing terms f oe ( x , y ), f ee ( x , y ), and f eo ( x , y ), as follows : m 1 , m 2 , and m 5 from fig5 a can be written as ## equ5 ## therefore , all the odd - even and the even - odd parts of the three flats can be obtained easily as ## equ6 ## to cancel all the odd - even and the even - odd parts from m 1 , m 5 , and m 6 , one can &# 34 ; rotate the data 180 °&# 34 ; using the rotation operation defined in equations 5 . m 1 , m 5 , and m 6 are defined as ## equ7 ## it should be noted that m 1 , m 5 , and m 6 include only even -- even and odd -- odd functions . from equation 5c all the even -- even parts can be derived easily as given below : ## equ8 ## the following discussion is directed to solving for f oo ( x , y ). a fourier series is used to explain the symmetry properties when a flat is rotated . in a polar coordinate system , the profile of a flat surface on a circle centered at the origin is a function of θ and has a &# 34 ; period &# 34 ; of 360 °. it can be shown that for x 2 + y 2 = constant , the equation of a circle , f oe ( x , y ), f ee ( x , y ), f eo ( x , y ), and f oo ( x , y ) can be expressed as σf m cos ( mθ ), σf n cos ( nθ ), σf m sin ( mθ ), and σf n sin ( nθ ), respectively , where m is an odd integer and n is an even integer . what is meant by the profile around a polar coordinate circle for the function sin 2θ is illustrated in fig4 a , wherein the (+) and (-) symbols in each of the four quadrants indicate a &# 34 ; period &# 34 ; of 2 around the periphery of polar coordinate circle 42 by indicating the quadrants of polar coordinate circle 42 in which the function sin 2θ is positive and negative . fig4 b illustrates the same information for the odd -- odd function sin 4θ which has a period of 4 around the periphery of polar coordinate circle 42 , wherein the (+) and (-) symbols appearing in 45 ° increments around the periphery of polar coordinate circle 42 show the period is 4 . for an odd -- odd function , the profile of a flat surface along a polar coordinate circle can be defined using only fourier sine terms . the odd -- odd function f oo , 2θ does not have a perfect solution , but for the purposes of the present invention it can be sufficiently accurately defined by the first few terms of the fourier series expansion . fig4 a and 4b thus are useful in understanding how a fourier series expansion of the f oo ( x , y ) function is formed as a sum of odd -- odd terms of different angular frequencies . the fundamental frequency of σf n sin ( nθ ) is 2 , corresponding to a period of 180 °, where n is an even integer . to emphasize this , a subscript 2θ is added to the term f oo ( x , y ). thus , f oo ( x , y ) can be expressed as a fourier sine series as where ## equ9 ## where f 2m are coefficients of the 2mth terms of the fourier series . similarly , f oo , 4θ is divided into two groups , and defines the 4oddθ term as in equations 6 - 8 . hence , it should be noted that each term includes a very broad spectrum of the fourier sine series . for example , f oo , 2oddθ includes the components of sin ( 2θ ) , sin ( 6θ ) , sin ( 10θ ) , sin ( 14θ ), etc . for a smooth flat surface , the odd -- odd part f 00 , 2θ can be accurately represented by the first two terms of equation 9 . using the above - described rotation operator , it can be shown that comparing equation 10 with equation 6 , one can see that the sign of f oo , 2oddθ is opposite , as is the sign of f oo , 4oddθ . thus , the 2oddθ and 4oddθ terms can be solved by rotating the flat 90 ° and 45 °, respectively . in theory , the higher order terms can be derived by rotating the flat at a smaller angle . for example , the 8oddθ term can be determined by rotating 22 . 5 °. therefore , the terms of all frequencies of the odd -- odd part f 00 , 2θ of a flat can be obtained . it should be noted , however , that no fourier expansion is actually used for deriving the entire absolute topography of the flat in accordance with the present invention . the fourier series are given here merely to provide insight into the limitations of this method . the equations of the cavity shape measurements of the six measurement configurations of the pairs of flats a - b , a - c , and b - c shown in fig5 a are ## equ10 ## it can be shown that the odd -- odd part of equation 1 can not be solved exactly . the fact that the signs of some terms change after a rotation is used to solve for the odd - even , the even - odd , and the even -- even parts of a flat first , and then the odd -- odd part is solved . if the odd -- odd parts of the surfaces can be approximated by 2oddθ and 4oddθ terms , the topographies of the three flats a , b and c can be approximated by the equations the various even and odd components of equations 11 - 13 are defined as given below : ## equ11 ## where ## equ12 ## in theory , as long as the odd -- odd parts of the surfaces of flats a , b and c can be approximated by 2oddθ and 4oddθ terms , the surfaces of such flats can be determined by taking the opd measurements for the six configurations of fig5 a and inserting the data from such measurements into equations 11 - 15 to calculate the surface topographies of flats a , b and c . in practice , the rotation operation ! 45 ° in equations 14 and 15 requires interpolation to obtain the heights of points not on the nodes of a square grid array , and such interpolation may introduce small errors . the interpolation for the height of a point is accomplished by weighting the heights of the three or four surrounding grid nodes linearly proportionally to the distances from this point to each of the nodes . see j . grzanna and g . schulz , &# 34 ; absolute testing of flatness standards at square - grid points &# 34 ;, opt . commun . 77 , 107 - 112 ( 1990 ). &# 34 ; decentering &# 34 ; of the flats which may occur as a result of the rotation operations and the flip operations also may introduce small errors . from our experiments , we find that the measurement reproducibility error is the major limiting factor of the accuracy of this method . for the three flats a , b and c there are four basic configurations . the above described embodiment of the invention uses six measurement configurations as shown in fig5 a , which permits use of an iteration method to reduce the measurement reproducibility error , which occurs when the flats are removed and replaced back to the mount between the various measurements . in summary , the absolute topography of a flat can be calculated using simple arithmetic and without fourier series , least squares , or zernike polynomial fitting . with the six measurements of fig5 a , the profiles along the four diameters of the three flats in the 0 °, 45 °, 90 °, and 135 ° directions are exact . the relationship among the profiles along these diameters is also defined exactly . because the flat a is approximated by the sum of the odd - even , even - odd , and even -- even functions and the known components of the odd -- odd function , the area between two adjacent diameters is missing sin ( 8nθ ) components , where n = 1 , 2 , 3 . . . . these higher order terms can be derived by rotating the various flats at smaller angles . equations 11 - 13 represent the absolute entire surface topographies of the three flats or wafers a , b , and c expressed as sums of the even -- even , odd - even , even - odd , and odd -- odd functions described above , the first three terms being easily solved as indicated above in the references c . ai and j . c . wyant , &# 34 ; absolute testing of flats decomposed to even and odd functions &# 34 ;, spie proceeding 1776 , 73 - 83 ( 1992 ), and c . ai and j . c . wyant , &# 34 ; absolute testing of flats by using even and odd functions &# 34 ;, appl . opt . 32 , ( to appear in 1993 ), the odd -- odd function being expressed by the first two terms of the fourier series expansion as indicated above . equations 14 and 15 give the values of the various terms in equations 11 - 13 as a function of the interferometer - measure cavity shape measurements m1 - m6 as shown in fig5 a . use of the above described technique and equations to obtain absolute measurements of the topographies of optical flats a , b , and c in accordance with equations 11 , 12 , and 13 using interferometer 10 of fig1 is outlined in the flow chart of fig7 . as indicated in block 50 of fig7 flats a and b are attached by means of suitable mounts to interferometer 10 in the configuration indicated by block m 1 of fig5 a . interferometer 10 then is operated to perform phase - shifting measurements to obtain opds at each pixel in the field of view of interferometer 10 for the cavity 4 defined by the present configuration of flats a and b . this set of opds constitutes the cavity shape m 1 indicated in fig5 a . cavity shape m 1 then is stored in computer 24 of interferometer 10 . next , in accordance with block 51 of fig7 flat a is rotated 180 ° counterclockwise relative to its initial orientation . interferometer 10 then is operated to generate and store the cavity shape m 2 . in accordance with block 52 , flat a then is rotated to an orientation that is 90 ° counterclockwise from its initial orientation . interferometer 10 then is operated to compute and store the cavity shape m 3 corresponding to the configuration shown in the m 3 block of fig5 a . in accordance with block 53 , flat a is rotated to an orientation 45 ° counterclockwise from its original orientation . interferometer 10 then is operated to generate and store the cavity shape m 4 indicated in fig5 a . in accordance with block 54 , flat b is removed , and flat c is mounted in its place on interferometer 10 in the configuration indicated in the m 5 block of fig5 a , that is , flipped in the x direction . interferometer 10 then is operated to compute and store the cavity shape m 5 . finally , in accordance with block 55 of fig7 flat a is removed from interferometer 10 and replaced by flat b , oriented as indicated in the m 6 block of fig5 a . interferometer 10 then computes and stores the cavity shape m 6 . then , as indicated in block 56 , appropriate ones of equations 14 and 15 are solved using the program of appendix 1 to obtain values of the even -- even , even - odd , and odd - even terms of equations 11 , 12 , and 13 . next , in accordance with block 57 of fig7 the various terms obtained according to block 56 are subtracted from m 1 , and m 3 , and m 6 to obtain m 1 &# 39 ;, m 3 &# 39 ;, and m 6 &# 39 ; of equations 15 . next , according to block 58 , the various terms in equations 14 and 15 are solved using the program of appendix 1 to obtain values for the terms a oo , 2oddθ , b oo , 2oddθ , and c oo , 2oddθ . finally , other expressions of equations 14 and 15 are solved to obtain values of a oo , 4oddθ , b oo , 4oddθ , and c oo , 4oddθ . next , in accordance with block 58a of fig7 the various terms obtained according to blocks 56 and 58 are subtracted from m 1 , m 4 , and m 6 to obtain m 1 &# 34 ;, m 4 &# 34 ;, and m 6 &# 34 ; of equations 15 . the terms obtained in block 56 , 58 , and 59 of fig7 then are combined in accordance with equations 11 , 12 , and 13 to obtain the absolute topographies of the entire surfaces of flats a , b , and c . the above technique was derived by recognizing that some of the even -- even , even - odd , etc . terms include functions that undergo polarity changes when rotated by a particular number of degrees so as to result in additional equations and so as to result in cancellation of various terms when the equations are solved mathematically . by experimentation and intuition , it was found that such cancellations occur in such a way as to greatly reduce the number of measurements needed . fig5 b shows eight measurement configurations of flats a , b , and c , rather than six as in fig5 a . the methodology according to fig5 b is similar to the methodology corresponding to fig5 a , but the equations are different , and are given below . in each configuration in fig5 b , the flat is of a front view , and the lower one is flipped in x and is of a rear view . in various configurations shown in fig5 b , one flat is rotated 180 °, 90 °, or 45 ° with respect to another flat . the equations of the eight configurations are ## equ13 ## using equations 2b and 2c , m 1 , m 2 , and m 5 can be written as ## equ14 ## which are similar to equations 5a . therefore , all of the odd - even and the even - odd parts of the three flats can be obtained easily according to ## equ15 ## which are similar to equations 5b . to cancel all of the odd - even and the even - odd parts from m 1 , m 5 , and m 6 , one can &# 34 ; rotate the data by 180 °&# 34 ; using the rotation operation defined in equations 5 . m 1 , m 5 , and m 6 are defined as ## equ16 ## which are identical to equations 5c . it should be noted that m 1 , m 5 , and m 6 include only even -- even and odd -- odd functions . all of the even -- even parts can also be obtained easily as ## equ17 ## which are identical to equations 5d . because all of the even -- even , even - odd , and odd - even parts of each flat are obtained , they can be subtracted from m 1 , m 5 , m 6 , and m 7 , respectively . the difference includes only the odd -- odd part a oo , 2θ , b oo , 2θ and c oo , 2θ . m &# 39 ; 1 , m &# 39 ; 3 , m &# 39 ; 6 , and m &# 39 ; 7 are defined as ## equ18 ## all of the 2oddθ parts of the three flats are obtained as ## equ19 ## the 2evenθ term of equation 6 can be divided into two halves , namely the 4evenθ and 4oddθ terms . the 4oddθ term can be obtained by rotating one flat 45 ° instead of 90 °. using a similar procedure for deriving equations 21 and 22 , m &# 34 ; 1 , m &# 34 ; 4 m &# 34 ; 6 and m &# 34 ; 8 are defined as ## equ20 ## then , all of the 4oddθ terms can be obtained as ## equ21 ## in summary , the sum of one half of the fourier sine series ( i . e ., 2oddθ term ) is obtained from the 90 ° rotation group . the other half is further divided into two halves , and one of them ( i . e ., 4oddθ term ) is obtained from the 45 ° rotation group . thus , after each rotation , one half of the unknown components of the fourier sine series of the odd -- odd function is obtained . the higher order terms can be derived by rotating the flat at a smaller angle . for example , the 8oddθ term is determined by rotating 22 . 5 °. if the odd -- odd component of the flat can be approximated by the first terms as are those in equation 9 , the three flats can be approximated by equations 11 - 13 . it has been recognized that the flat topographies can be calculated using either four or six of the measurement configurations of fig5 a because m 3 and m 2 can be expressed in terms of m 4 and m 1 . see l - z shao , r . e . parks and c . ai , &# 34 ; absolute testing of flats using four data sets &# 34 ;, spie proceeding 1776 , 94 - 97 ( 1992 ). using the operators of equations 4a and 4b , it can be shown easily that m 3 and m 2 can be expressed in terms of m 4 and m 1 , that is , ## equ22 ## therefore , both m 2 and m 3 in all the equations 14 and 15 can be substituted with equations 25 and 26 . then only four measurements m 1 , m 4 , m 5 , and m 6 of the six - measurement procedure are needed . it is shown above that a oo , 2oddθ , b oo , 2oddθ , and c oo , 2oddθ are derived from two nonrotational measurements m 1 and m 6 and a 90 ° measurement m 3 , and a oo , 4oddθ , b oo , 4oddθ , and c oo , 4oddθ are derived from two nonrotational measurements m 1 and m 6 and a 45 ° measurement m 4 . similarly , it can be shown easily that a oo , 8oddθ , b oo , 8oddθ , and c oo , 8oddθ can be derived by two nonrotational measurements m 1 and m 6 and a 22 . 5 ° measurement . here m 7 is defined as a 22 . 5 ° measurement which is similar to m 4 , except that flat a is rotated 22 . 5 °, rather than 45 °, i . e ., using the same procedure for deriving a oo , 4oddθ , b oo , 4oddθ , and c oo , 4oddθ of equations 14 , one can obtain ## equ23 ## where m 1 r , m 6 r , and m 7 r are the differences after subtracting the known parts of flat a and flat b from m 1 , m 6 , and m 7 , respectively , i . e ., ## equ24 ## where a &# 39 ;, b &# 39 ;, and c &# 39 ; are defined as below : ## equ25 ## all of the components of the 2oddθ , 4oddθ , and 8oddθ terms are obtained by rotating the flat 90 ° ( m 3 ), 45 ° ( m 4 ), and 22 . 5 ° ( m 7 ), respectively . similarly to equations 27 - 30 , the components of the 16oddθ , 32oddθ , and higher order terms with a smaller rotation angle , can be derived . in the derivation of equations 25 and 26 , the 180 ° measurement m 2 is expressed in terms of the 90 ° measurement m 3 , which is also expressed in terms of a 45 ° measurement m 4 . using the same procedure , the 45 ° measurement m 4 can be expressed in terms of the 22 . 5 ° measurement m 7 . therefore , from equations 25 , 26 , and 31 , m 2 m 3 , and m 4 can be expressed in terms of m 1 and m 7 . hence , only four measurements m 1 , m 5 , m 6 , and m 7 are needed . the four parts can be derived in different sequence and different combinations . because only four measurements are needed , we redefine the equations of the four configurations and express the equations for all components explicitly in terms of these four measurements . here , we use n 1 to represent the measurements in order to distinguish them from the measurements m 1 . the four measurements n 1 , n 2 , n 3 , and n 4 correspond to m 1 , m 5 , m 6 , and m 4 , respectively , as follows : ## equ26 ## using the previous procedures , we derive the components of even -- even and even - odd first : ## equ27 ## the even -- even components are easily solved for , as previously described for the six - measurement and eight - measurement embodiments of the invention . next , we derive the odd - even components of each flat . to make the error analysis easy , we manipulate the expressions such that the right - hand side of the equation always has the same number of measurements for each flat . therefore ## equ28 ## where in summary , if the odd -- odd parts of the surfaces can be approximated by 2oddθ and 4oddθ terms , the flats can be derived with this four - measurement algorithm . each flat can be calculated from the sum of the corresponding terms in equations 33 , 34 , 36 , and 37 . while the invention has been described with reference to several particular embodiments thereof , those skilled in the art will be able to make the various modifications to the described embodiments of the invention without departing from the true spirit and scope of the invention . it is intended that all combinations of elements and steps which perform substantially the same function in substantially the same way to achieve the same result are within the scope of the invention . ## spc1 ## | 6 |
a cell culture model for chronic myelogenous leukemia ( cml ) acquired chemoresistance and related methods are provided herein . compounds for treating cml and methods for the discovery of those compounds are also provided . the following definitions are to assist with review of the present disclosure and are meant to encompass any equivalents . “ agonist ” refers to a ligand that interacts with or binds to its receptor to up - regulate , accelerate , or activate the activity of a compound , receptor , gene , or protein . “ antagonist ” refers to a ligand that interacts with or binds to its receptor to downregulate , suppress , or inhibit the activity of a compound , receptor , gene , or protein . “ antisense molecule ” refers to a nucleic acid molecule that hybridizes to all or a portion of a target gene or all or a portion of an mrna encoded by a target gene . hybridization of an antisense molecule to a target gene or a portion thereof may inhibit expression of the target gene by inhibiting transcription of the gene sequence , while hybridization of an antisense molecule to a transcript encoded by a target gene may inhibit expression of the target gene by inhibiting translation of the transcript into a polypeptide sequence . “ chemotherapeutic agent ” refers to any chemical compound or treatment method that induces cell damage , results in cell death , or both . specific chemotherapeutic agents include but are not limited to kinase inhibitors such as tyrosine kinase inhibitors ( tki ), which include , imatinib , gefitinib , erlotinib , lapatinib , ci - 1033 , pki - 166 , gw - 2016 , as well as others that will be known to one of ordinary skill in the art . other chemotherapeutic agents include imatiactinomycin - d , adriamycin , androgens , asparagine , azathioprine , bcg , bleomycin , camptothecin , cisplatin , epirubicin , etopside , gemcitabine , hydroxyurea , interferon alpha , interferon beta , interferon gamma , mitomycin c , paclitaxel , thioguanine , 5 - fluorouracil , 6 - mercaptopurine , or other drugs . in addition , “ chemotherapeutic agent ” may refer to radiation and waves , such as electroemissions , gamma radiation , microwaves , uv - irradiation , or x - rays . other chemotherapeutic agents may include natural or synthetic antibodies , tyrosine kinase inhibitors , enzymatic inhibitors , growth factor inhibitors , metastases - inhibiting compounds , or oncogenic protein inhibitors , such as compounds that inhibit ras , protein kinase , or dna topoisomerase . “ sirt1 inhibitor ” refers to one or more compound that inhibits sirt1 activity . such inhibition includes direct as well as indirect inhibition of sirt1 activity . exemplary sirt1 inhibitors include , but are not limited to , one or more agent or compound which results in inhibition of sirt1 function , inhibition of expression of sirt1 protein , inhibition of transcription or translation of the sirt1 gene , or both . for example , a sirt1 inhibitor includes sirtinol as well as its derivatives and other small molecule compounds able to reduce or inhibit sirt1 activity . sirt1 inhibitors include sirtinol , a sirtinol analogue or derivative , splitomicin , a splitomicin analogue , napthol , a napthol derivative , an indole , an indole derivative , sirna , shrna , antisense rna , or any combination thereof . “ duration ” refers to the amount of time a desired gene is expressed , and may be measured , for example , in months , weeks , days , hours , minutes and / or seconds . “ inhibit ” with regards to an activity means to suppress the activity , either by decreasing the level or rate of the activity , blocking or preventing the activity entirely , or preventing an increase in the activity under conditions in which the activity would normally be increased . “ in combination with ” refers to two or more substances being administered simultaneously or in series close enough in time to bring about a therapeutically effective result . “ leukemic disorder ” refers to a cancerous disorder of blood forming tissues ( e . g ., spleen , bone marrow , lymphatics , liver ) characterized by excessive leukocyte production . the term encompasses myeloid leukemias such as , for example , acute myeloid leukemia ( aml ), chronic myeloid leukemia ( cml ), and various subtypes thereof , and lymphocytic leukemias such as , for example , acute lymphocytic leukemia ( all ), chronic lymphocytic leukemia ( cll ), hairy cell leukemia ( hcl ), and various subtypes thereof . “ pharmaceutically acceptable carrier ” refers to a pharmaceutically acceptable material , composition , or vehicle that is involved in carrying or transporting a compound of interest from one tissue , organ , or portion of the body to another tissue , organ , or portion of the body . for example , the carrier may be a liquid or solid filler , diluent , excipient , solvent , or encapsulating material , or some combination thereof . each component of the carrier must be “ pharmaceutically acceptable ” in that it must be compatible with the other ingredients of the formulation . it also must be suitable for contact with any tissue , organ , or portion of the body that it may encounter , meaning that it must not carry a risk of toxicity , irritation , allergic response , immunogenicity , or any other complication that excessively outweighs its therapeutic benefits . “ polynucleotide ” refers to any polyribonucleotide , polydeoxyribonucleotide , or hybrid polyribo - polydeoxyribonucleotide , including naturally occurring polynucleotides , synthetic polynucleotides , or any chemically , enzymatically , or metabolically modified forms of naturally occurring polynucleotides . the term encompasses both single - and double - stranded molecules , including dna - dna , dna - rna , or rna - rna duplexes , as well as molecules that are a mixture of single - and double - stranded regions . “ polynucleotide ” also refers to triple - stranded molecules comprising dna , rna , or both dna and rna . polynucleotides may contain any of the standard pyrimidine or purine bases ( i . e ., adenine , guanine , cytosine , thymine , uracil ), as well as any modified or uncommon bases such as tritylated bases or inosine . in addition , the backbone of a polynucleotide may be modified for stability or for other reasons . “ polynucleotides ” also refers to relatively short polynucleotides , often referred to as oligonucleotides , and to peptide nucleic acids ( pnas ) formed by conjugating bases to a peptide backbone . “ prodrug ” as used herein refers to a derivative of a pharmaceutically or therapeutically active drug that is transformed into the active drug by an enzymatic or chemical process . prodrugs may be developed to alter the metabolic stability or transport characteristics of a drug , to mask side effects or toxicity of a drug , or to improve or alter other characteristics of the drug . see , for example , notari , r . e . 1985 . theory and practice of prodrug kinetics . methods enzymol 112 : 309 - 323 ; bodor , n . 1981 . novel approaches in prodrug design . drugs of the future 6 : 165 - 182 ; bundgaard , h . 1985 , “ design of prodrugs : bioreversible derivatives for various functional groups and chemical entities ,” chap . 1 in design of prodrugs , h . bundgaard , ed ., elsevier , n . y ., 1985 . “ rna interference ” ( rnai ) refers to a post - transcriptional gene silencing ( pgsr ) process whereby one or more exogenous small interfering rna ( sirna ) molecules are used to silence expression of a target gene . “ sirnas ” ( short interfering rnas ) are double - stranded rna molecules , generally around 15 - 30 nucleotides in length , that are complementary to the sequence of the mrna molecule transcribed from a target gene . following introduction into a cell , the sirna molecule associates with one or more cellular proteins to form a sirna / protein complex ( risc ), which then binds to the mrna transcript of the target gene . risc binding results in degradation of the mrna molecule , thereby preventing translation . “ shrnas ” ( small hairpin rnas ) are short “ hairpin - turned ” rna sequences that may be used to inhibit or suppress gene expression . “ subject ” refers to any animal , including a human , having a cell that may be treated by the methods or products discovered or tested by the methods of this disclosure . “ route of administration ” may refer to any administration pathway known in the art , including but not limited to aerosol , enteral , nasal , ophthalmic , oral , parenteral , rectal , transdermal ( e . g ., topical cream or ointment , patch ), or vaginal . “ transdermal ” administration may be accomplished using a topical cream or ointment or by means of a transdermal patch . “ parenteral ” refers to a route of administration that is generally associated with injection , including infraorbital , infusion , intraarterial , intracapsular , intracardiac , intradermal , intramuscular , intraperitoneal , intrapulmonary , intraspinal , intrasternal , intrathecal , intrauterine , intravenous , subarachnoid , subcapsular , subcutaneous , transmucosal , or transtracheal . “ therapeutically effective amount ,” “ therapeutically effective concentration ” or “ therapeutically effective dose ” is an amount of a compound that produces a desired therapeutic effect in a subject , such as preventing or treating a target condition , alleviating symptoms associated with the condition , or producing a desired physiological effect . a population of cells may be contacted with a therapeutically effective amount of a compound to study its effect in vitro or to produce a desired therapeutic effect ex vivo or in vitro . the precise therapeutically effective amount is an amount of the composition that will yield the most effective results in terms of efficacy of treatment in a given subject . this amount will vary depending upon a variety of factors , including but not limited to the characteristics of the therapeutic compound ( including activity , pharmacokinetics , pharmacodynamics , and bioavailability ), the physiological condition of the subject ( including age , sex , disease type and stage , general physical condition , responsiveness to a given dosage , and type of medication ), the nature of the pharmaceutically acceptable carrier or carriers in the formulation , and the route of administration . one skilled in the clinical and pharmacological arts will be able to determine a therapeutically effective amount through routine experimentation , namely by monitoring a subject &# 39 ; s response to administration of a compound and adjusting the dosage accordingly . for additional guidance , see remington : the science and practice of pharmacy 21 st edition , univ . of sciences in philadelphia ( usip ), lippincott williams & amp ; wilkins , philadelphia , pa ., 2005 . “ treating ” or “ treatment ” of a condition may refer to preventing the condition , slowing the onset or rate of development of the condition , reducing the risk of developing the condition , preventing or delaying the development of symptoms associated with the condition , reducing or ending symptoms associated with the condition , generating a complete or partial regression of the condition , or some combination thereof . according to embodiments of the disclosure and as discussed in detail in example 1 below , a cell culture model for chronic myelogenous leukemia ( cml ) acquired chemoresistance and related methods for generating such a model is provided . in some embodiments , the cell culture model is generated by utilizing a naïve blast crisis cml cell line treated with a cytotoxic agent and allowed to relapse and acquire bcr - abl mutations . in some embodiments , the naïve blast crisis cml cell line is a kcl - 22 cell line . blast crisis cml cell line kcl - 22 is insensitive to treatment with 1 μm imatinib ( deininger et al . 1997 ). treating kcl - 22 cells with mutation - inducing doses of imatinib , induced apoptosis of the kcl - 22 cells , however , relapse occurred within two weeks of the development of t315i bcr - abl mutation . a “ mutation - inducing dose ,” “ mutation - inducing concentration ” or “ mutation - inducing amount ” is an amount of a compound that , when exposed to a cell , stimulates a nucleic acid mutation in the cell . in some embodiments , a mutation - inducing dose is about 2 . 5 μm , about 5 μm , about 10 μm , about 2 . 5 μm or higher , or between about 2 . 5 μm and about 10 μm . in some embodiments , a mutation - inducing dose is a concentration that may have a therapeutic effect when administered to a subject . following the initial apoptosis upon sti - 571 treatment with dosages that are equivalent or nearly equivalent to therapeutically effective doses found in human plasma , the kcl - 22 cells developed the t315i mutation of the bcr - abl kinase domain at high frequency in two weeks . however , when small molecule inhibitors of sirt1 were used in combination with sti - 571 , the bcr - abl mutation was prevented and cml cells were eliminated without relapse . these results demonstrate t315i mutation can be rapidly induced by imatinib treatment but is preventable . therefore , the culture system developed provides , among other things , an in vitro system to study mechanisms of bcr - abl mutagenesis in the natural molecular and cellular contexts of cml . the methods and system provided herein can be used to develop strategies to treat and prevent formation of such a mutation . the discovery that sirt1 inhibitors can block t315i mutation and completely eliminate cml cells when administered with imatinib also provides a novel treatment modality for cml patients . in addition , the t315i mutant cells generated from this system also provide invaluable tools for studying mechanisms of resistance after mutation and strategies to eradicate these highly resistant cells . in contrast to previous cell line models that are involved with gene amplification , altered bcr - abl expression , and / or additional chromosomal rearrangements ( mahon et al . 2000 ; rosenhahn et al . 2007 ; tipping et al . 2003 ), genetic mutations of bcr - abl primarily account for resistance in the model . development of bcr - abl mutations in this model is highly reproducible and occurs in 2 weeks with a single dose of imatinib treatment . t315i mutation has been shown in cml cell line kbm5 after several months of treatment with gradually increasing concentrations of imatinib ( ricci et al . 2002 ), but the mutation induction time in kcl - 22 cells is much shorter . although a relatively short period of time ( 3 - 6 weeks ) is also reported for developing bcr - abl mutations in primary cml cells cultured in vitro ( koptyra et al . 2006 ; jiang et al . 2007 ), the model described herein is simpler and more advantageous , because , for example , it utilizes a commercially available cell line and routine culture conditions . therefore , this model is valuable for studying mechanisms of acquired resistance and developing strategies to prevent relapse . finding that bcr - abl mutations are dependent on bcr - abl gene expression is in line with the previous finding that bcr - abl can promote self - mutagenesis ( koptyra et al . 2006 ), which indicates that genome instability caused by bcr - abl transformation is perhaps the driving force for its mutations . consistent with this notion , we observe that clonal cells can derive mutations without pre - existing mutations from the original patient and that these clonal cells can develop distinct bcr - abl mutations as well as resistance without mutations . development of resistant bcr - abl mutations may resemble adaptive mutations promoting survival and growth in bacteria under stressful conditions , which involves multiple dna repair pathways ( rosenberg 2001 ; karpinets et al . 2006 ). bcr - abl transformation alters regulation of multiple dna repair pathways causing genome instability ( melo & amp ; barnes 2007 ). it would be interesting to determine how altered dna repair may influence mutations with this model in the future . although bcr - abl cdna has been widely used to study its mutagenesis , comparison between the mutagenesis potential of randomly integrated bcr - abl cdna versus the native bcr - abl locus has not been shown before . based on the studies discussed above , the bcr - abl translocation locus itself may play a role in promoting mutations , as mutagenesis on the locus is far more efficient than on randomly integrated bcr - abl cdna in the same cells . this locus - dependent influence is validated by showing that hprt mutation rate is relatively constant although the bcr - abl mutation rate is more dynamic . further , distinct clonal mutations resulted from the cell cloning process , which affects the mutagenesis process . this indicates that there is a dynamic process for bcr - abl mutagenesis on its native locus . such bcr - abl mutations may be influenced by the epigenome structure of the translocation locus , and the environmental change or cloning process can result in subtle alteration of the local epigenome producing altered mutation hot spots . the specific inhibition of bcr - abl kinase activity in kcl - 22 cells is a complex process . cellular phosphorylation in kcl - 22 cells is not affected by overexpression of k1176r kinase - inactive bcr - abl or by efficient delivery of bcr - abl antibody . mutation phenotype in mutant bcr - abl - overexpressing cells does not change with 2 . 5 μm imatinib treatment , but mutant bcr - abl blocks mutations at 5 μm imatinib . the precise mechanism for this difference is not yet clear . because cells harboring mature tetramer bcr - abl protein ( smith et al . 2003 ; mcwhirter et al . 1993 ) wholly from mutant monomers may not be able to grow in culture , most cells for analysis should carry hybrid bcr - abl protein with wild type and mutant monomers . the e13a2 bcr - abl , expressed in kcl - 22 cells , is known to have high tyrosine kinase activity ( lucas et al . 2009 ). the hybrid bcr - abl may retain normal phosphorylation ability on most substrates but may affect certain substrates regulating bcr - abl mutations , and its effect would not be shown unless strong selection is applied . alternatively , the mutant bcr - abl may affect mutations independent of its kinase activity . k1176r bcr - abl retains certain functions , such as the intact cellular localization and adhesion regulation ( wertheim et al . 2002 ), and may continue recruiting proteins necessary for mutagenesis but in a less efficient way . although ros production was previously found to promote bcr - abl mutations ( koptyra et al . 2006 ), inhibition of ros by high concentrations of anti - oxidants was unable to prevent bcr - abl mutations and relapse as discussed above . however , these two studies use quite different cell culture systems . kcl - 22 cells have a basal level of ros , compared with high levels of ros in blast crisis cml cells previously studied , although low levels of ros are also noticed in a subpopulation of cml cells ( koptyra et al . 2006 ). in addition , primary cml cell culture uses growth factor - supplemented medium ( koptyra et al . 2006 ; jiang et al . 2007 ), whereas kcl - 22 cells are growth factor - independent . given that abl kinase domain mutations can be detected even in normal human progenitor cells cultured in the growth factor medium ( jiang et al . 2007 ), growth factor culture may affect ros production and mutations . according to some embodiments the present disclosure also includes novel mechanisms for acquired resistance through active induction of genetic mutations of oncogenic tyrosine kinases in human cancer . as discussed above , hic1 suppresses tumorigenesis is through regulation of stress and dna damage responsive gene , sirt . sirt1 is a key gene for controlling active induction of genetic mutations on tyrosine kinases through altering dna damage pathways . hic1 directly regulates sirt1 transcription as shown in fig2 . inhibitors of sirt1 will inhibit acquired resistance through prevention of genetic mutations , and thus are especially useful in the clinical setting where a combination of cancer therapeutics is applicable or utilized . the present disclosure , however , is not limited to cml . rather , as is understood by a person of ordinary skill in the art , the mechanisms of acquired resistance and functions of sirt1 and its inhibitors described herein can also be applied to treatment of acquired resistance in other cancers . in addition , the mechanisms of acquired resistance and functions of other genes and their inhibitors can be applied to the treatment of acquired resistance in cancer . clonal cells derived from parental kcl - 22 cells also predominantly develop resistance to imatinib by bcr - abl mutations including the t315i , e255k and y253h mutations . the mutations exhibited by the clonal cells encompass the most frequently observed mutations in cml patients ( shah et al . 2002 ; soverini et al . 2006 ). furthermore , the rapid relapse is similar to that seen in blast crisis patients . the ability to form bcr - abl mutations in clonal cells indicates that pre - existing rare mutant cells from the original patient are not required for development of resistance . the bcr - abl mutation frequency varies among clones while hp rt ( hypoxanthine phosphoribosyl transferase ) mutation frequency remains relatively constant . unlike the broad mutation spectrum of hprt observed in parental or clonal cells , bcr - abl mutations may be limited to one mutation in a parental cell or a clone . additionally , while the spontaneous mutation frequency of hprt remains relatively constant throughout cell passages , frequency of bcr - abl mutation declines in later passages . see , for example , fig2 . the data provided herein indicate that bcr - abl mutations upon imatinib treatment are not always derived from random dna replication error during clonal expansion or cell propagation , but are actively induced by imatinib treatment . the disclosure includes a novel model system for testing and identifying therapeutic modalities and compounds for treating cml . the disclosure includes systems , methods and cell lines based on the discovery that the targeting of a tyrosine kinase ( as an anti - cancer treatment ) may in itself be mutagenic and thereby induce dna mutations thereby directly or indirectly contributing to clinical acquired chemoresistance . sirt1 activation is essential for efficient bcr - abl oncogenic transformation and development of a cml - like myeloproliferative disorder . further , sirt1 activation by bcr - abl is more selective to hematopoietic stem / progenitor cells , which produce massive expansion of granulocyte - macrophage lineage , and sirt1 knockout inhibits such biased differentiation and myeloproliferative disorder . this is consistent with the role of bcr - abl in promoting proliferation of myeloid progenitor cells ( jamieson et al . 2004 ). although activated by bcr - abl , inhibition of sirt1 overcomes cml cell resistance to imatinib and has a synergistic effect with bcr - abl inhibition to induce apoptosis , indicating that sirt1 - regulated pathways including ku70 may confer a survival advantage for cml progenitor cells in addition to those classic survival pathways ( fig3 e ). sirt1 is also an important intermediate factor for bcr - abl functions in cml to deacetylate and activate ku70 , thereby promoting cml genome instability through increasing infidelity dna repair ( fig3 e ). it was also found that high levels sirt1 promote de novo genetic mutations in prostate cancer cells upon dna damage . because sirt1 is overexpressed in a variety of cancers , sirt1 likely plays an important role in tumorigenesis to promote cancer genome instability . this in turn facilitates cancer cells to rapidly evolve and develop mutations for acquired resistance . the studies described herein improve the understanding of sirt1 and its roles in tumorigenesis . further , the studies provide a strong rationale for developing inhibitors of sirt1 activity or expression to overcome cml resistance to bcr - abl inhibitors . although the current application is directed to developing cancer treatments directed to sirt1 inhibitors , other cancer treatments may be developed as well . sirt1 activation is a novel mechanism for cml stem / progenitor cell proliferation and survival and to promote cancer genome instability resulting mutations for acquired resistance . accordingly , sirt1 targeting is a valuable cancer treatment pathway . the novel tissue culture method provided herein closely simulates in vivo cml relapse on imatinib treatment using kcl - 22 cells . by direct exposure of cells to imatinib with concentrations pertinent to those in patient plasma , the t315i mutation of bcr - abl can be induced rapidly with high frequency . the resultant t315i mutant cells differ from parental kcl - 22 cells in size , morphology and cell cycle , and they are highly resistant to various treatments . streptococcus faecalis ( sf ) medium or supplying insulin in serum medium will also provide cml cells resistance to imatinib treatment . finally , the combination of imatinib with sirt1 inhibitors will prevent cml relapse and abolish growth - factor - induced resistance . thus , the methods outlined herein provide a platform for studying strategies for preventing formation of drug resistance and screening for small molecule inhibitors for blocking cml relapse . the present discoveries may be used for methods for treating or preventing cancer cell growth , treating or preventing resistance of a cancer cell to chemotherapy , or treating or preventing the relapse growth of one or more cancer cell . using the culture model described above , key features of clinical resistance such as rapid relapse through bcr - abl mutations after imatinib treatment can be replicated . this model may serve as a system for designing , testing , screening and identifying new therapeutic strategies for treating cml . for example , the resistance model can be used to screen modulators of enzymatic activity or small molecule inhibitors such as those which inhibit sirt1 , chemotherapeutics , compounds , or anti - cancer modalities having therapeutic efficacy or those able to inhibit bcr - abl mutation based resistance . the resistance model may also be used for further studies of resistance mechanisms , which will allow for the design of new therapeutic strategies , such as use of small molecule inhibitors to prevent the induction of those mutations that accompany a cancer drug treatment . according to one embodiment , a method for screening for a candidate sirt1 inhibitor for reducing chemoresistance or relapse in a cancer cell culture can be broadly applied and has the following steps . first , a base level of chemoresistance or relapse is established in a cancer cell culture , such as a cancer cell line , after administration of one or more chemotherapeutic agents by treating the cancer cell culture with the chemotherapeutic agent under conditions which induce chemoresistance or relapse in the cell culture . then , the candidate sirt1 inhibitor is administered to previously untreated cells of the cell culture before , during , and / or after administering the one or more chemotherapeutic agents . finally , the level of chemoresistant or relapsed cells after treatment with the candidate sirt1 inhibitor and the chemotherapeutic drug is measured . a reduction or absence of chemoresistant or relapsed cells as compared to base level of chemoresistance or relapse established at the outset of the model indicates that the compound is a sirt1 inhibitor . according to another embodiment , a sirt1 inhibitor compound for preventing chemoresistance or treating cml and a method for developing such a sirt1 inhibitor for treating cancer is provided . in some embodiments , such a method may include the following steps . first , a pharmacophore model of sirt1 inhibitors of a sirt1 substrate binding pocket is generated . then , one or more sirt1 inhibitor test compounds are identified . next , the one or more sirt1 inhibitor test compounds are administered to a cml acquired resistant culture model , such as the model described herein . next , an effective test dosage for the one or more sirt1 inhibitor test compounds that block cml cell relapse is determined and compared to an effective sirtinol dosage . an effective sirtinol dosage is an amount of sirtinol that , is able to prevent , in whole or in part , chemoresistance related to bcr - abl mutation , relapse after treatment with a tyrosine kinase inhibitor , or elicits another desirable effect in a cml cell , including , but not limited to inhibition of cell growth or induce cell death . finally , one or more of the sirt1 inhibitor test compounds is selected as a sirt1 inhibitor lead compound when the effective test dosage is lower than the effective sirtinol dosage . as described below , a computational ( pharmacophore ) model of sirt1 inhibitors for blocking substrate binding is provided . in one embodiment , 3d pharmacophore search from ncl chemical library of 250 , 253 compounds was performed , followed by two rounds of the cell - based screening . as described below , a group of one or more lead compounds that inhibited cml acquired resistance at 1 - 5 μm and blocked sirt1 deacetylase activity was identified . according to one embodiment , the one or more lead compounds are water soluble and have better inhibitory effect than other known sirt1 inhibitors . in some embodiments , the lead compounds have two distinct sirt1 binding moieties : one to block substrate binding and the other to block nad binding . a computational docking study confirmed that these compounds can be docked into both substrate and nad binding pockets . blocking both substrate binding and nad binding pocket individually has synergistic effect on sirt1 inhibition . in one embodiment , a nitrogen - bond linker structure was identified that enhances specific hydrophilic interaction between the lead compounds and sirt1 and also increases the water solubility of the lead compounds . the cancer or cancer cell is usually a hematologic disorder or a solid tumor . commonly , the hematologic disorder is chronic myelogenous leukemia ( cml ). an exemplary cancer cell associated with a solid tumor is non - small cell lung carcinoma ( nsclc ). a therapeutically effective amount of a sirt1 modulator or a combination of multiple sirt1 modulators is administered to a subject in need thereof . frequently , a therapeutically effective amount of a modulator such as a sirt1 inhibitor is administered . a sirt1 inhibitor includes one or more inhibitors of sirtuins ( class iii histone / protein deacetylases ), such as sirtinol or its analogue , which is administered in combination with the chemotherapeutic agent . generally , the sirt1 modulator is administered at or about the same time as the chemotherapeutic agent , but can also , if desired , be administered prior to or subsequent to the administration of the chemotherapeutic agent . the sirt1 modulator may either be an agonist or antagonist of sirt1 and may be any molecule , compound or agent that acts to modulate sirt1 . such modulators include , but are not limited to , derivatives , analogues , small molecules , decoy molecules , drugs or prodrugs , polynucleotides , particularly antisense molecules and rna interference using sirna , shrna , polypeptides , antibodies , including chimeric antibodies , or any other substance that acts on sirt1 in an intended manner . if the sirt1 modulator is a sirt1 antagonist , acting to inhibit sirt1 , the inhibitor is preferably a napthol compound ( for example , sirtinol or splitomicin ), ex - 527 , an indole or its derivative , sirna , shrna , or any combination thereof . drug resistance or cancer cell relapse may be caused by administration of a chemotherapeutic agent such as imatinib , gefitinib , nilotinib , dasatinib , or another cancer - treating drug . imatinib is a tyrosine kinase inhibitor . it interferes with bcr - abl protein function . gefinitib inhibits egfr kinase . bcr - abl drug resistance may be caused by administration of a chemotherapeutic agent such as imatinib , nilotinib , dasatinib , vx - 680 ( a dual aurora kinase and bcr - abl inhibitor ) or another cancer - treating drug . alternatively , resistance may be caused by another drug or compound administered to the patient , environmental factors , or may be a naturally occurring resistance . relapse in chronic myeloid leukemia patients treated with imatinib , such as sti - 571 , is an example of one form of clinical chemoresistance associated with a point mutation or amplification of the bcr - abl gene . thus , the sirt1 modulator may also be administered in conjunction with a tyrosine kinase inhibitor . both the sirt1 modulator and the chemotherapeutic agent are to be applied in therapeutically effective amounts and for any duration necessary to treat the cancer or prevent relapse of the cancer . a clinician can gauge the dosages for each required by the subject using known methods of optimizing drug performance and delivery by taking into account clinical data regarding tolerances , age , gender , severity of the disease , health of the subject , and the like . preferably , the sirt1 modulator is an inhibitor that is administered to the subject in a pharmaceutically acceptable carrier . the route of administration may be any route effective to carry the therapeutic sirt1 modulator to the cancer cells in the subject , including any of the routes discussed above . in addition , the sirt1 modulator may also be used treat or prevent insulin and transferrin - induced resistance as well as egfr ( epidermal growth factor receptor ) associated resistance . a method of preventing chemoresistance in cml cells comprising administering a therapeutic drug or combination of therapeutic drugs that prevent formation of a t315i mutation and other bcr - abl mutations is also provided . these bcr - abl mutations in cancer cells , particularly , cml cells are responsible for anti - apoptotic activity and , as such , prevent the cancerous cells from responding to traditional chemotherapy , radiotherapy , or other cytotoxic agents . preferably , the therapeutic drug is comprises a sirt1 antagonist , such as sirtinol , a sirtinol analogue , splitomicin , an indole , sirna , shrna , aurora kinase inhibitor , or any combination thereof . another embodiment improves the efficacy of a cytotoxic agent directed to cml cells , in a subject , by administering to the subject at least one cytotoxic agent directed to cml cells , and administering to the subject a sirt1 inhibitor in a therapeutically effective amount , so that the sirt1 inhibitor enhances the efficacy of the cytotoxic agent relative to the effect of the cytotoxic agent in the absence of the sirt1 inhibitor . the cytotoxic agent may be a bcr - abl inhibitor , such as sti - 571 , imatinib , nilotinib , or dasatinib , or any combination thereof and the sirt1 inhibitor is sirna , a napthol compound , sirtinol , splitomicin , an indole , or any combination thereof . this method also treats or prevents insulin and transferrin - induced resistance . the methods of the present disclosure may be performed on any animal with cancer or cml , but are preferably for humans . having described the invention with reference to the embodiments and illustrative examples , those in the art may appreciate modifications to the invention as described and illustrated that do not depart from the spirit and scope of the invention as disclosed in the specification . the examples are set forth to aid in understanding the invention but are not intended to , and should not be construed to limit its scope in any way . the examples do not include detailed descriptions of conventional methods . such methods are well known to those of ordinary skill in the art and are described in numerous publications . further , all references cited above and in the examples below are hereby incorporated by reference in their entirety , as if fully set forth herein . cell lines and culture and drugs . cml cell lines kcl - 22 and k562 were purchased from german collection of cell cultures , braunschweig , germany , and grown in rpmi 1640 medium with 10 % fetal bovine serum ( hyclone ). sti - 571 was provided by novartis , basel , switzerland . 6 - thioguanine ( 6 - tg ) was purchased from sigma and 2 . 5 μg / ml final concentration was used for selection . sirtinol , splitomicin , nicotinamide , trichostatin a 5 - aza - 2 - deoxycytidine and hat were also purchased from sigma . for serum - free culture , basic supplements ( its i - 1884 ), egf and hdl were purchased from sigma and insulin from roche . resistance assay . 5 × 10 5 kcl - 22 or k562 cells in 1 ml medium per well in 24 - well plates , and treated with various combinations of drugs . cells were maintained in these cultures without changing medium . aliquots of cells at specified time points were removed and cell numbers were counted on a hematocytometer . cell viability was assessed by trypan blue exclusion whenever necessary . typically , after three to five weeks in culture when their medium volume significantly decreased , fresh drug - free medium was supplied to the cells . isolation of nucleic acids . total rna and dna are isolated using standard protocols . for sequencing the egfr kinase domain , the egfr kinase domain is amplified by rt - pcr of total rna or by pcr of genomic dna with a high fidelity dna polymerase ( strategene ) using primers previously described ( pao et al ., 2004 ). pcr products are cloned into the pcr2 . 1 vector using topo ta cloning kit ( invitrogen ). at least ten clones for each treatment are sequenced . for mutant - enriched pcr sequencing of t790m mutation , the egfr exon 20 is amplified using primers described ( inukai et al ., 2006 ). after digestion of the first round pcr product with bstui ( neb ), the second round nested pcr is performed and the pcr products are sequenced directly . soft agar colony formation assay . a standard two - layer soft agar culture was performed with a bottom layer of 0 . 7 % agarose and top layer of 0 . 35 % agarose . five hundred cells per well in 6 - well plates were seeded with warm top agar and were incubated for three weeks . plates were then stained with 0 . 005 % crystal violet for 1 hour , and colonies were scored with aid of microscope . for resistance assay in soft agar , one million cells were added per well and imatinib ( sti - 571 ) or 6 - tg added to both top and bottom agar to their final concentrations . to clone or recover soft agar colonies for further analysis , individual colonies were plucked and expanded in liquid culture . cell cycle , cell proliferation and apoptosis analysis . cell cycle was analyzed by fixing cells with 70 % ethanol at − 20 ° c . overnight . after washing , cells were resuspended in phosphate - buffered saline containing 1 mg / ml rnase a , incubated for 30 min at 37 ° c ., and then stained with propidine iodine ( 50 μg / ml ) for 30 min at room temperature before flow cytometry analysis . cell proliferation was analyzed using a xtt cell proliferation kit ( roche applied science ), and apoptosis was analyzed with annexin v kit ( bd pharmingen ) as per the manufacturer &# 39 ; s instruction . spectral kayotyping and fluorescent in situ hybridization ( fish ) analysis . for spectral karyotyping analysis , 10 mitotic cells of each sample were analyzed , 5 by gtg - band analysis and 5 by 24 - color karyotyping . triple - color fish was performed with lsi abl1 / aass ( 9q34 . 1 )/ bcr ( 22q11 . 2 ) probes ( vysis , inc .) ( huntly et al . 2003 ), and 200 cells of each sample were evaluated . these assays were done by city of hope cytogenetics core laboratory . sequencing abl kinase domain and hprt ( hypoxanthine phosphoribosyl transferase ). the abl kinase domain ( abl - k ) was amplified by rt - pcr of total rna or by pcr of genomic dna with a high fidelity dna polymerase ( strategene ) using the primers for the 579 bp kinase domain using cdna templates shown below as previously described ( gorre et al ., 2001 ). to confirm mutations , the abl kinase domain was also amplified by pcr using genomic dna as templates with the intron primers below which span abl exon 6 for t315i mutation ( t3151 ), and intron primers below , which span abl exon 5 for e255k and y253h mutations ( e255k / y253h ). pcr products were cloned into the pcr2 . 1 vector using topo ta cloning kit ( invitrogen ). at least ten clones for each treatment were sequenced by sequencing facility of beckman research institute . for analysis of genomic dna mutations pcr products were directly sequenced without subcloning . for hprt sequencing , the codon sequence was amplified by rt - pcr using primers previously described ( osterholm et al . 1995 ). pcr products were purified with a pcr product clean - up kit ( qiagen ) and sequenced directly . reverse transcription - pcr for sequencing bcr - abl oligomerization and src homology 3 / 2 ( sh3 / 2 ) domains was also performed . for sequencing the bcr - abl sh3 / 2 domain , primers described previously ( ray et al . 2007 ) were used . for the oligomerization domain , the following primers ( bcr - abl - oligo ) were used . for sequencing hp rt , the codon sequence was amplified by reverse transcription - pcr using the primers below : other primers . primers described above and elsewhere in the specification are as follows : cell cloning by limiting dilution . cells were counted and diluted to 5 cells per ml , and seeded onto 96 - well plate with 100 μl ( or 0 . 5 cell ) per well . individual cell seeding was then confirmed by microscopy , and single cell clones were grown and expanded for further analysis . immunoprecipitation . bcr - abl expression and phosphorylation were directly analyzed by western blot using anti - c - abl monoclonal antibody ( bd pharmingen , 554148 ) and anti phospho - tyrosine antibody ( upstate biotechnology , inc ., 05 - 321 ). to validate bcr - abl phosphorylation , bcr - abl from 500 μg of total cell lysate of kcl - 22 cells was isolated with 2 μg of anti - c - abl and 100 μl of 50 % slurry of protein a - agarose beads ( upstate biotechnology , inc .). alternatively , protein g - agarose beads or a mixture or protein a and g - agarose beads may be used for isolating bcr - abl . western blot . for protein analysis by western blot , the following antibodies are used : rabbit monoclonal anti - sirt1 ( 1 : 5000 , epitomics ), and anti - gapdh ( 1 : 5000 , trevigen ). apoptosis analysis was performed using a tmr - red in situ cell death detection kit ( roche ) as per manufacturer &# 39 ; s protocol . normal human lung lysate are purchased from prosci . analysis of reactive oxygen species ( ros ) and dna damage . ros was analyzed using redox - sensitive fluorochrome 2 ′. 7 ′- dichlorofluorescein diacetate ( sigma ) as described previously ( koptyra et al . 2006 ). when coupled with the apoptosis analysis , cells were labeled with annexin v first and then 2 ′. 7 ′- dichlorofluorescein diacetate . an h2ax phosphorylation assay kit ( millipore , 17 - 344 ) was used to analyze dna damage by flow cytometry as per the manufacturer &# 39 ; s suggestions . gene expression analysis . total cellular rna with trizol ( invitrogen ) using a standard protocol . first strand dna was synthesized and hic1 expression by quantitative real - time rt - pcr using a kit with sybr green label ( invitrogen ) as per the manufacture &# 39 ; s instruction on a biorad machine opticon . the following are the hic1 primers ( spanning introns ), 5 ′- ggacggaccagcaggaca - 3 ′( exon 1a ) and 5 ′- gcgctggttgttgagctg - 3 ′ ( exon 2 ). [& gt ; ref | nt — 010718 . 15 | hs17 — 10875 : 1561637 - 1565694 homo sapiens chromosome 17 genomic contig , reference assembly ] sirt1 expression was analyzed by western blot using 1 : 5000 diluted rabbit monoclonal sirt1 antibody ( epitomics ). controls used were gapdh or actin as loading controls with rabbit anti - gapdh ( trevigen ) or anti - actin ( sigma ) at 1 : 5000 dilution . gapdh [& gt ; ref | nt — 009759 . 15 | hs12 — 9916 : 6497433 - 6502281 homo sapiens chromosome 12 genomic contig , reference assembly ] primers used are as follows : production of lentiviral vectors . for production of lentiviral vectors , four million 293t cells are co - transfected with 15 μg of the vector , 15 μg of gag - pol , 5 μg of vsv - g , and 5 μg of rev plasmids by the method of calcium phosphate co - precipitation ( kowolik , c . m ., p . yam , y . yu , and j . k . yee . 2003 . hiv vector production mediated by rev protein transduction . mol ther 8 : 324 - 331 ). the supernatant is collected at 24 hours and 36 hours after transfection . the supernatants are pooled and passed through a 0 . 45 um filter , concentrated by ultracentrifugation . to determine vector titer , 1 × 10 5 293t cells are seeded in a six - well plate in the presence of 4 mg / ml polybrene , and cells are transduced for 5 hours and analyzed by facs for gfp expression within 24 hours . shrna lentiviral vectors and gene knockdown . oligonucleotides for abl shrna ( gttggttcatcatcattca ) ( seq id no : 29 ) were synthesized and cloned into the psicor vector ( ventura et al . 2004 ) that contains a selection cassette for puromysin by a standard protocol . a scrambled shrna was subcloned into the vector as a mock control the vsv - g ( g - protein of vesicular stomatitis virus ) pseudotyped lentiviral vectors were produced using a four - plasmid transfection system as described previously ( kowolik et al . 2003 ). high titer lentiviral stocks , typically 1 to 3 × 10 7 infectious units / ml , were used for the studies with multiplicity of infection ( moi ) around 5 . for sirt1 knockdown in transformed cd34 + cells , sirt1 shrna sequences were cloned into the hiv7 - sf - rfp lentiviral vector . mig210 or migr1 ( gfp ) and shrna ( rfp ) double transduced cells were sorted by flow cytometry for cd34 + gfp + rfp + for in vitro apoptosis and proliferation study described above . for bcr - abl knockdown , one millions cells were infected overnight with recombinant lentivirus by multiplicity of infection of 3 each in the presence of 8 μg / ml polybrene . under this condition , the transduction rate in these cells was typically about 99 %. dna damage assay . the assay was performed as described ( xiao et al ., 2003 ). kcl - 22 cells were pre - selected for four days in hat medium to remove pre - existing hprt mutations . the efficiency of hat selection was confirmed by plating these cells on soft agar with 2 . 5 μg / ml 6 - thioguanine , which produced zero colony . hat - selected cells were then treated with 0 . 5 μm cpt for 1 hour and used for soft agar clonogenic assay with 6 - thioguanine . the rest of hat - selected cells were cultured in medium without selection . soft agar colonies were scored after three weeks as described ( yuan et al ., 2008 ). bcr - abl overexpression analysis . amphotropic retroviral vectors for wild type p210 bcr - abl , k1176r p210 mutant and the empty vector mig r1 were produced using phoenix - ampho packaging cells ( atcc ) and the transduction was carried out as previously described ( ramaraj et al ., 2004 ; pear et al ., 1998 ). briefly , kcl - 22 cells were transduced with the aforementioned vectors at a multiplicity of infection of around 6 . cells were spin - infected by centrifugation at 1000 × g for 90 min and then returned to the incubator and cultured overnight . after removing viruses , cells were expanded in culture for 5 days , and green fluorescent protein ( gfp )- expressing cells were isolated by fluorescent - activated cell sorting ( facs ). for second round transduction , facs - enriched cells were re - infected with the above vectors using the same conditions . genomic dna sequencing analysis of imatinib - resistant soft agar colonies was performed using the intron primers for the t315i mutation on the endogenous bcr - abl locus and exon primers for 579 - bp transduced bcr - abl cdna as described above . to increase pcr efficiency on the transduced bcr - abl cdna , another reverse primer ( 5 ′- tagtccaggaggttcccgtag ) ( seq id no : 21 ) was used to pair with the same exon forward primer used for 579 - bp cdna , which produced a 321 - bp pcr product . real - time pcr for gene amplification and expression analysis . quantitative real - time pcr was performed with superscript iii platinum two - step qrt - pcr kit with sybr green ( invitrogen ) as per the manufacturer &# 39 ; s instruction on the biorad machine opticon . for bcr - abl rna analysis , we extracted total cellular rna with trizol ( invitrogen ) using a standard protocol . the primer pairs for abl genomic dna analysis were 5 ′- gcctgtctctgtgggctgaag - 3 ′ ( seq id no : 6 ) and 5 ′- caaggcgtctgctggcatta - 3 ′ ( seq id no : 13 ); primers for bcr - abl rna analysis were 5 ′- cgtgcagagtggagggagaac - 3 ′ ( seq id no : 30 ) and 5 ′- gcatctgactttgagcctcagg - 3 ′ ( seq id no : 31 ). pcr cycling conditions were : 94 ° c . 5 min followed by 94 ° c . 30s , 60 ° c . 30s , 55 ° c . 30s for 40 cycles . fluorescent allele - specific oligonucleotide - polymerase chain reaction ( aso - pcr ) assay . a fluorescent aso - pcr was carried out as previously described , with modifications . purified t315i - positive rna from t315i bcr - abl cells was diluted with t315i - negative rna to 1 : 10 , 1 : 100 and 1 : 1000 , and all rnas were reverse transcribed using random hexamers and superscript iii kit ( invitrogen ). pcr was carried out with 1 μl of rt reaction each with optimal conditions of 45 cycles and 60 ° c . annealing temperature . the primers for aso - pcr are as follows : forward outer primer 5 ′- cgtgaagaccttgaaggaggacaccatg - 3 ′ ( seq id no : 32 ), reverse outer primer 5 ′- fam - ttctccaggtactccatggctgacgaga - 3 ′ ( seq id no : 33 ), reverse t3151 mutation primer 5 ′- fam - tccaggaggttcccgtaggtcatgaactaaa - 3 ′ ( seq id no : 34 ), forward primer 5 ′- cccgggagcccccgttctatatcataac - 3 ′ ( seq id no : 35 ). pcr products were diluted and run on abi 3100 genetic analyzer ( applied biosystems ). care was taken to avoid contamination by performing pcr reactions in a separate room from that for nucleic acid extraction and pcr product electrophoresis , and personal return to pcr reaction room in the same day is prohibited after he handles nuclei acid extraction and electrophoresis . bidirectional pyrophosphorolysis - activated polymerization allele - specific amplification ( bi - pap ). bi - pap assay was performed as previously described 2 with the primer pairs ( t3151 - f *: 5 ′- ggagcccccgttctatatcatcaddt - 3 ′; seq id no : 36 ) and t3151 - r *: 5 ′- aggttcccgtaggt - catgaactcadda - 3 ′; seq id no : 37 ) and papase ( all purchased from biovision usa ). the pcr cycling conditions were : 1 cycle of 95 ° c . 60 s , 60 ° c . 30 s , 62 ° c . 30 s , 68 ° c . 45 s and 72 ° c . 45 s followed by 40 or 50 cycles of 95 ° c . 30 s , 60 ° c . 30 s , 62 ° c . 30 s , 68 ° c . 40 s and 72 ° c . 5 min . similar to aso - pcr , bi - pap reactions were performed in a separate room from that for nucleic acid extraction and pcr product analysis . treatment of kcl - 22 cells with 2 . 5 um sti - 571 or higher leads to relapse and formation of kcl - 22m cells having a t315i mutation . in contrast to the in vivo resistance observed in blast crisis cml patients treated with sti - 571 , cml cell lines derived from blast crisis patients are sensitive to sti - 571 treatment . sti - 571 at 1 μm selectively kills cml cells in bcr - abl dependent manner with the exception of kcl - 22 cells , whereas 10 μm sti - 571 can result in non - specific cell killing . in chronic phase cml patients , sti - 571 is given at 400 mg / day that produces the average peak plasma concentration at 4 . 4 μm and trough concentration at 2 . 0 μm . for blast crisis patients , sti - 571 dosage is increased to 600 mg / day . therefore , effects of imatinib concentrations at 1 , 2 . 5 , 5 and 10 μm were examined on the survival of kcl - 22 cells during prolonged culture . 5 × 10 5 kcl - 22 or k562 cells were seeded in 1 ml medium per well in 24 - well plates , and treated with various combinations of drugs . cells were maintained in these cultures without changing medium . aliquots of cells were taken out at specified time points and cell numbers counted using a hematocytometer . cell viability was accessed by trypan blue exclusion where necessary . typically , after three to five weeks in culture when medium volume significantly decreased , fresh drug - free medium was supplied to the cells to restore the wells to the original volume for prolonged culture . it was found that kcl - 22 cells were insensitive to 1 μm sti - 571 treatment as they continued to grow but at a lower rate than in the absence of the drug . sti - 571 at 2 . 5 μm and above effectively suppressed cell growth and induced partial cell death over time ( fig3 a ). small clusters of cells formed after about 10 days in treatment groups with 2 . 5 μm and above of sti - 571 and these cells appeared visibly larger with frequent bizarre shapes ( fig3 b ). after two weeks they repopulated the culture , indicating the relapse on the drug treatment . these emerging cells , named kcl - 22m , grew equally well as kcl - 22 cells , and no longer responded to presence of imatinib in the medium ( fig3 c ). they formed fewer and smaller soft agar colonies ( fig3 d ). the abnormal size and shape of kcl - 22m cells were confirmed by flow cytometric analysis , showing increase on both forward scatter ( for size ) and side scatter ( for complexity ) ( fig3 e ). kcl - 22m cells also exhibited different cell cycle status from kcl - 22 cells by increasing s / g2 population ( fig3 f ). molecular characterization of kcl - 22m cells was also performed . the kcl - 22 cells were resistant to imatinib treatment . by spectral karyotyping and fish analyses , it was found that kcl - 22m cells maintained the same cytogenetic profile as kcl - 22 cells , i . e ., 51 , x , del ( x )( p11 . 2p22 . 3 ), + der ( 1 ; 10 )( q10 ; p10 ), + 6 ,+ 8 ,+ 8 , t ( 9 ; 22 ) ( q34 . 1 ; q11 . 2 ), der ( 17 ; 19 )( q10 ; q10 ),+ 19 , i ( 21 )( q10 ), + der ( 22 ) t ( 9 ; 22 ), and carried two philadelphia chromosomes in all cells examined ( fig2 ). this cytogenetic data was in line with previously reported karyotype for kcl - 22 cells ( kubonishi et al ., 1983 ; rosenhahn , et al . 2007 ). in contrast to another kcl - 22 cell - derived imatinib - resistant cell line ( kcl - 22r ) that had additional translocations ( rosenhahn , et al . 2007 ), no novel chromosomal rearrangements were shown in kcl - 22m cells . using real time pcr , the abl dna content and bcr - abl rna level in kcl - 22m cells remained the same as in kcl - 22 cells ( fig4 ). imatinib effectively inhibited tyrosine phosphorylation by direct western blot analysis of total cell lysate or immunoprecipitation of bcr - abl protein ( fig4 a ). tyrosine phosphorylation was not altered by imatinib treatment in kcl - 22m cells ( fig4 a ). since genetic mutations are predominant mechanisms for in vivo resistance of sti - 571 , it was examined whether mutations occurred in the kcl - 22m cells . both cdna and genomic dna were sequenced for bcr - abl kinase domain using the strategies described by gorre et al ( 2001 ). see , for example , fig1 - 19 . in the 579 - bp cdna region of bcr - abl kinase domain covering the atp - binding pocket and activation loop , a single mutation ( c to t nucleotide change that resulted in amino acid t315i mutation at abl ) was found in kcl - 22m but not parental kcl - 22 cells ( fig4 b ). this is the same mutation as identified in patients . the mutant clones represented 40 % for 2 . 5 μm sti - 571 or 30 % for 5 μm sti - 571 treatment in all clones sequenced respectively . given that kcl - 22 cells have a normal copy of abl gene , which is also be amplified during rt - pcr , half of clones are expected to be wild type . therefore , the results show that at least 60 to 80 % of kcl - 22m clones may carry t315i mutation . sequencing of genomic dna further confirmed such a mutation . to search for mutations on other bcr - abl domains important for its kinase activity , oligomerization and sh3 / 2 domains were sequenced ( zhao et al ., 2002 ; smith et al ., 2003 ), but no additional mutations were identified . even when the sh3 / 2 sequencing fragment was extended through most of the 579 - bp kinase domain , only the t315i mutation was found . because the t315i mutation is one of the most powerful mutations generated upon relapse in response to sti - 571 treatment , this model encompasses the bcr - abl mutagenesis observed in clinical relapse . to determine whether the kcl - 22m cells were a mixture of t315i mutants and non - mutants , a limiting dilution was performed to obtain individual mutant cells from kcl - 22m relapsed on 2 . 5 and 5 μm imatinib , respectively . ten clones for each bcr - abl mutation were sequenced using genomic templates . it was found that 20 clones carried the t315i mutation ( fig4 b ). clonal resistant cells were separately derived by plating kcl - 22 cells on soft agar with 2 . 5 or 5 μm imatinib and cell colonies were grown . after three weeks , resistance cell colonies were randomly picked and expanded for dna sequence analysis . twenty clones ( 10 from each concentration of imatinib ) carried the t315i mutation ( fig4 b ). kcl - 22 cells at various passages relapsed on imatinib and all recurrent cells had the t315i mutation . kcl - 22 cells were also found to relapse in similar time courses with repeated doses as with a single dose ( fig4 ). these results indicate that kcl - 22 cells develop acquired resistance predominantly through the t315i bcr - abl mutation . t315i mutation rate . the t315i mutation rate was measured by plating kcl - 22 cells on soft agar with imatinib . a standard two - layer soft agar culture was performed with bottom layer of 0 . 7 % agarose and top layer of 0 . 35 % agarose . one million cells per well in 6 - well plates on warm top agar with imatinib in both top and bottom agar layers to their final concentrations were incubated for three weeks . plates were then stained with 0 . 005 % crystal violet for 1 hour , and colonies were scored with aid of microscope . the mutation rate with 5 and 10 μm imatinib was around 3 × 10 − 5 , and 5 . 7 × 10 − 5 with 2 . 5 μm imatinib ( fig4 c ). the mutation rate in liquid culture was also measured by serial two - fold dilutions of kcl - 22 cells followed by treatment with 5 μm imatinib . the lowest number of cells that consistently relapsed on imatinib was determined . the medium t315i mutation rate was about 1 / 12 , 500 or 8 × 10 − 5 . this is in general agreement with the rate observed in soft agar analysis given that the plating efficiency for kcl - 22 cells in soft agar was about 25 %. these results indicate that imatinib treatment of kcl - 22 cells results in acquired resistance through rare t315i mutation . this model encompasses a key bcr - abl mutagenesis process that occurs in clinical relapse . this is the first cml resistance model through bcr - abl mutations that can be rapidly reproduced within two weeks after exposing cells to in vivo effective concentrations of imatinib . to determine whether there is a pre - existing t315i mutation in kcl - 22 , two sensitive methods were used to detect t315i mutations in cdna ( by allele - specific oligonucleotide - pcr ) or genomic dna ( by bidirectional pyrophosphorolysis activated polymerization allele - specific amplification ) from untreated kcl - 22 cells : ( 1 ) a modified fluorescent allele - specific oligonucleotide - pcr assay ( willis et al ., 2005 ) and ( 2 ) a bidirectional pyrophosphorolysis - activated polymerization allele - specific amplification assay ( shi et al ., 2007 ). both methods reliably detected at least 1 % mutant allele , but no t315i mutation was found in kcl - 22 cells ( fig4 ). the sensitivity of these methods could not be further increased without sacrificing specificity , and therefore such methods should not be used to completely rule out the existence of rare mutant cells in kcl - 22 cells . however , after continuous culture of kcl - 22 cells in a refractory dose of imatinib ( 1 μm ) for 2 weeks , t315i mutation became readily detectable by conventional dna sequencing ( fig2 ). because t315i is the most resistant mutation for bcr - abl inhibitors ( weisberg et al ., 2005 ; von bubnoff et al ., 2006 ; shah et al ., 2004 ), this model encompasses one key bcr - abl mutagenesis process in clinical relapse . however , directly exposing cells to mutation - inducing concentrations of imatinib did not work for cml cell lines k562 and ku812 that underwent rapid apoptosis as previously reported ( deininger et al ., 1997 ). this is likely because the cells underwent apoptosis before bcr - abl mutations could be fully developed . this method may be applied to other cml cell lines . compared with the standard approach that requires the cells to be exposed to multiple rounds of gradually increasing concentrations of the drug for a period of several months , the culture model described herein offers a unique advantage in that bcr - abl mutations can be rapidly produced within 2 weeks after a single exposure of cells to concentrations of imatinib that are effective in vivo . in vivo , most bcr - abl mutations are found in relapsed cml patients although pre - existing t315i mutation is detected in some cml patients before imatinib treatment ( shah et al ., 2002 ; soverini et al ., 2006 ; roche - lestienne et al ., 2002 ). whether the pre - existing bcr - abl mutant cells originating in the patient is a requirement for development of resistance was investigated . individual kcl - 22 cell clones were isolated by limiting dilution or soft agar plating without drug treatment . eleven liquid culture clones ( l1 - l11 ) and thirteen soft agar clones ( ag1 - ag13 ) were expanded for analysis ( table 1 , below ). most of the clones failed to relapse , but four relapsed in two weeks with high frequency at different concentrations of imatinib . these were clones l1 , l7 , ag3 and ag11 ( table 1 and fig5 a ). after sequence analysis of relapsed cells , it was determined that clone l1 relapsed on 2 . 5 and 5 μm with e255k bcr - abl mutation ; clone l7 relapsed on all doses of the drug with y253h bcr - abl mutation ; clone ag3 relapsed without bcr - abl kinase domain mutations on 2 . 5 and 5 μm imatinib , but with t315i mutation on 10 μm imatinib ; clone ag 11 relapsed with t315i mutation on 2 . 5 μm imatinib which is similar to parental cells ( table 1 ). in table 1 , no mutations have been detected in clones l1 , l7 , ag3 and ag11 before sti treatment . nd was not done . the asterisk indicates that there was relapse after 50 days and remaining sensitivity to 2 . 50 sti 571 . these mutations conferred resistance of clonal cells to imatinib with t3151 having the greatest protective effect against proliferation inhibition by high concentrations of the drug ( fig5 b ). compared to parental cells , more bcr - abl mutations emerged from these clones . the ability of these clones to develop resistance through bcr - abl kinase domain mutations indicates that a pre - existing mutant cell originating from a patient is not required for resistance . the effects of imatinib treatment on ros and dna damage was examined in the culture method system described above were examined . following imatinib treatment , the bulk ros level was reduced in the nonapoptotic fraction of kcl - 22 cells while ros increased in the apoptotic fractions ( fig2 a and 23b ). accordingly , the bulk dna damage analyzed by γh2ax staining decreased in the nonapoptotic fraction of cells ( fig2 c ). in previous experiments , 200 μm of the anti - oxidant vitamin e or n - acetylcysteine is able to reduce ros and bcr - abl mutations . however , in the studies described herein , even a 100 × higher concentration of nac ( 25 mm ) or a 40 × higher vitamin e ( 8 mm ) failed to prevent imatinib - induced bcr - abl mutations and relapse ( fig2 d ). these data reveal that bcr - abl mutations in kcl - 22 cells cannot be explained simply due to a change in ros . it was then determined whether bcr - abl gene expression is required for its own mutations . kcl - 22 cells express a e13a2 bcr - abl fusion transcript , and the junction region sequence does not meet optimal shrna design criteria ( reynolds et al ., 2004 ). as previously reported ( li et al ., 2003 ), shrna that targets this region produced poor gene knockdown . therefore a shrna that targeted the abl sequence was used ( zhelev et al ., 2004 ) to knock down bcr - abl . it was found that bcr - abl knockdown rapidly inhibited proliferation and induced apoptosis of both kcl - 22 and kcl - 22m cells ( fig2 a ), showing continued dependence of bcr - abl for proliferation and survival of bcr - abl mutant cml cells . a lower apoptosis rate was observed in kcl - 22m cells ( fig2 a ), indicating that cells acquire additional survival advantage during development of resistance . in contrast , a bcr - abl - negative leukemia cell line hl - 60 proliferation was not inhibited nor was apoptosis induced when abl was knocked down , showing that effects in cml cells are bcr - abl - specific . both kcl - 22 and kcl - 22m cells with bcr - abl knockdown re - grew after 2 weeks . bcr - abl expression was partially restored in re - grown knockdown kcl - 22 cells but remained at a lower level than in mock knockdown cells ( fig2 b ). when treated with imatinib , re - grown bcr - abl knockdown kcl - 22 cells failed to relapse in liquid culture or form imatinib - resistant colonies on soft agar ( fig2 b and 24c ). similarly , bcr - abl knockdown immediately followed by imatinib treatment also blocked relapse in kcl - 22 cells but failed to prevent kcl - 22m cells from regrowing ( fig2 d ). although the shrna knocks down both abl and bcr - abl , loss of the dna repair protein abl would have been expected to further increase genetic mutation , which would contradict the above findings . therefore , these unexpected results show that formation of bcr - abl mutations is dependent on bcr - abl gene expression and that combination of bcr - abl knockdown and imatinib can block acquired resistance of kcl - 22 cells on the drug . to determine roles of bcr - abl kinase activity for its mutation , wild type p210 bcr - abl cdna and k1176r p210 bcr - abl mutant cdna were overexpressed in kcl - 22 cells . the mutant bcr - abl has an abolished kinase activity ( ramaraj et al ., 2004 ; wertheim et al ., 2002 ) or controls empty mig retroviral vectors ( pear et al ., 1998 ). the transduced cells were isolated by facs for gfp expression . overexpression of wild type bcr - abl increased cellular phosphorylation , but overexpression of the mutant bcr - abl did not reduce cellular phosphorylation ( fig2 a ), indicating that k1176r bcr - abl is not a dominant negative mutant in these cells . neither wild type nor mutant bcr - abl expression changed cell growth or soft agar cloning efficiency ( fig4 ). when treated with 2 . 5 μm imatinib , wild type bcr - abl - overexpressing cells developed significantly higher numbers of imatinib - resistant colonies than empty vector or mutant bcr - abl - transduced cells , and the majority of resistant colonies ( 8 out of 10 ) from wild type bcr - abl - overexpressing cells did not harbor the t315i mutation of the endogenous bcr - abl ( fig2 b ). this indicated that the transduced bcr - abl cdna may function as bcr - abl gene amplification for resistance . in contrast , all resistant colonies in the empty vector or mutant bcr - abl - transduced cells harbored t315i mutation of the endogenous bcr - abl ( fig2 b ). when treated with 5 μm imatinib , resistance provided by wild type bcr - abl cdna was largely diminished , and the majority of resistant colonies ( 7 out of 10 ) from wild type bcr - abl - overexpressing cells harbored t315i mutation of the endogenous bcr - abl ( fig2 b ). unexpectedly , under these conditions , mutant bcr - abl completely blocked imatinib - resistant colony formation ( fig2 b ). similar results were obtained when a second round of transduction was carried out using these vectors on the first round of gfp - enriched cells , aiming to further increase cdna expression . these results indicate a role of bcr - abl kinase activity for its mutation when cells are under treatment with a high concentration of imatinib . however , overexpression of mutant bcr - abl did not enhance reduction of total cellular or a bcr - abl substrate crkl protein phosphorylation upon imatinib treatment ( fig2 a ). therefore , functionally intact bcr - abl may be important for generating mutations , but kinase activity may not be absolutely required . bcr - abl cdna has been previously expressed in non - cml cells to generate random bcr - abl mutations ( 5 - 7 , 10 - 15 ) and is presumed to have similar mutagenesis capability . mutations on the transduced wild type bcr - abl cdna were examined in kcl - 22 cells . the transduced gene was distinguished from the endogenous bcr - abl by using exon primers that span multiple introns for genomic dna pcr and sequencing . all 20 imatinib - resistant clones from 2 . 5 and 5 μm drug treatment had visible gfp expression , indicating that they all carried functional transduced bcr - abl cdna . clones that did not harbor t315i mutation of the endogenous bcr - abl tended to have a higher yield of pcr products , revealing a higher copy number of the transduced bcr - abl in these clones for resistance ( fig2 c ). only one clone developed a bcr - abl kinase domain mutation ( t315i ) on the transduced bcr - abl among all 20 clones sequenced ( fig2 c ). therefore , although the transduced bcr - abl cdna was capable of mutagenesis in kcl - 22 cells , the mutation efficiency was significantly lower than that of the endogenous bcr - abl ( 9 of 20 clones , p = 0 . 008 ). this difference is not a result of experimental artifacts for the following reasons . first , wild type bcr - abl cdna was transduced into kcl - 22 cells using retroviral virions and would readily integrate into the genome of replicating kcl - 22 cells . nonintegrated viral dna would have been lost during the lengthy procedure for expanding transduced cells before and after facs sorting , colony formation of imatinib - resistant cells on soft agar , followed by expanding clonal cells in liquid culture for assay . the stable integration of the cdna was also evidenced by nearly homogeneous gfp expression of the expanded clonal cells in liquid culture . second , mutations were analyzed within the clonal population of wild type bcr - abl - transduced cells , and both endogenous and transduced alleles for each clone were analyzed and compared . this is an internally controlled comparison , and therefore mutation efficiency is not affected by external factors such as retroviral transduction efficiency . third , although kcl - 22 cells have two translocation chromosomes , the lower mutation rate of transduced bcr - abl cdna is unlikely a result of lower copy number of the transduced bcr - abl cdna . the cdna copy number may vary from clone to clone , but at least one copy of the cdna is expected for each of 10 clones ( clones 1 , 2 , 4 , 5 , 7 , 8 , and 10 under 5 μm and clones 1 , 5 , and 7 under 2 . 5 μm ) that did not efficiently amplify the longer cdna template ( 579 bp , fig2 c ), whereas the other 10 clones would have higher copy numbers . however , the single clone that developed bcr - abl cdna mutation ( clone 5 under 2 . 5 μm ) carried a low copy number of cdna . accordingly , increasing cdna copy number did not increase its mutation frequency . together , these results show that the native bcr - abl translocation locus in kcl - 22 cells has inherently high mutagenesis potential , and expression of functional bcr - abl from the locus promotes acquisition of bcr - abl mutations . because blast crisis cml cells are genetically unstable , overexpression of bcr - abl alters the fidelity of dna double - strand break repair ( slupianek et al ., 2006 ) and increases expression and activity of error - prone dna polymerase which increases dna replication error ( canitrot et al ., 1999 ). whether dna replication error is a cause of rare mutations in clonal or parental cells during clonal expansion and cell propagation was assessed . bcr - abl mutation rates versus spontaneous mutation rates introduced by dna replication error were determined . the latter was measured by spontaneous mutations on the hprt ( hypoxanthine phosphoribosyl transferase ) gene that resulted in cells resistant to 6 - thioguanine ( 6 - tg ). as shown in fig6 a , bcr - abl mutation rate was compared side by side with hprt mutation rate in four relapse - prone clones ( l1 , l7 , ag3 and ag11 ) and two never - relapse clones ( l3 and ag6 ). hp rt showed relatively constant mutation rate ( 0 . 8 to 2 . 5 × 10 − 5 ) among all clones regardless of their ability to relapse , whereas bcr - abl mutation rate was highly clone - dependent , from none ( clone l3 and ag6 ) to 7 × 10 − 5 . the stable hprt mutation rate among clones reflects the nature of random mutations introduced by dna replication error in these clones during clonal expansion , which appears different from bcr - abl mutations that are highly clone - dependent . treatment of cml cell lines k562 and bv173 with low doses of imatinib for a short time will specifically induce dna damage in these cells , but has no effect on non - bcr - abl expressing leukemic or normal cells ( czechowska et al ., 2005 ). whether imatinib treatment increases hprt mutation rate through elevating overall dna damage level was determined . since naïve cml cells cannot survive the prolonged culture required for a clonogenic assay , recurrent cells derived from parental and clonal cells were used for treatment with 6 - tg and 2 . 5 μm . as shown in fig6 b , imatinib treatment did not alter overall dna damage levels among these cells . hprt mutation types in 6 - tg resistant cells were also examined . loss of function for human hprt has been well characterized with a broad mutation spectrum including large truncation , deletion , insertion and point mutations on codons ( burkhart - schultz et al ., 1996 ; podlutsky et al ., 1998 ). from dna sequencing analysis of 6 - tg resistant soft agar colonies derived from clones ag11 , l1 and parental kcl - 22 cells , numerous hprt truncation , deletion , insertion and point mutations were identified in all these colonies ( fig6 c ). this is consistent with previous observations ( burkhart - schultz et al ., 1996 ; podlutsky et al ., 1998 ). the broad spectrum of hprt mutations differs from the single mutations seen for the above - described parental cells and clones indicating the possibility of a different mutagenesis pathway for bcr - abl on imatinib . the t315i mutation frequency in parental kcl - 22 cells was stable in early passages ( p8 and p16 ) but declined significantly in the late passage ( p36 ) ( fig6 d ). thus , the relapse of late - passage kcl - 22 cells was delayed , although the recurrent cells still harbored t315i mutation . in contrast , hprt mutation rates remained relatively constant even in the late passages of kcl - 22 cells . this indicates that bcr - abl mutations are actively induced by imatinib treatment . the development of different mutations from clonal cells was examined using the model system of the present disclosure . it was verified that the clonal cells did develop different mutations . l1 and ag11 cells were plated on soft agar with 2 . 5 μm imatinib and ten imatinib - resistant colonies were isolated after three weeks . all resistant l1 colonies carried the e255k mutation only and all resistant ag11 colonies carried the t315i mutation only ( fig5 c ), indicating clone - specific mutation patterns exist for resistance . whether the parental mutation type ( t3151 ) could be restored in clonal cells when re - supplied with a culture environment with the mixture of clonal cells was determined . clones l1 , l7 or ag3 , respectively , were mixed with an equal number of cells from a pool consisting of eight never - relapse clones ( n - pool ). identical mutation phenotypes were maintained for relapsed l1 , l7 and ag3 even after treatment with 2 . 5 or 5 μm imatinib ( fig5 d ). whether t315i mutation dominates over other mutations for resistance development was also determined . equal numbers of cells from clones l1 , l7 , ag3 and ag11 were mixed together and treated with imatinib . in recurrent cells from liquid culture , both e255k and t315i mutations were readily detected ( fig5 d ), which was consistent with the fact that l1 and ag 11 were fast relapse clones whereas l7 and ag3 had slower relapse time courses ( fig5 a ), indicating that t315i is not superior to e255k for imatinib resistance . together , these data indicate a certain plasticity of mutagenesis process in cml cells that may allow induction of different mutations in clonal cells . this plasticity is particularly evident in clone ag3 which exhibits concentration - dependent induction of t315i mutation at 10 μm imatinib . mutation phenotypes of some clonal cells are distinguished from that of parental cells and become clone - dependent . such results evidence that each clone adapts to a stable resistance mechanism . the limitation of bcr - abl mutations to certain clonal cells prompted further examination into whether the ability to form bcr - abl mutations is restricted to a rare subpopulation of cells such as stably formed mutant cells or “ premutant ” cells that are not yet mutated but destined to form mutations . cell pool analysis was performed by evenly dividing ( by volume ) 1 × 10 5 kcl - 22 cells ( calculated 25 mutants under 5 μm imatinib ) into 24 wells , with an average of calculated 1 mutant cell per well , and the cells grew for 10 days in the absence of imatinib . if mutant cells were fully derived from a fixed mutant subpopulation , they would have been randomly seeded into wells according to poisson distribution . therefore , at least one mutant or pre - mutant cell would have been expect to be in each of the 15 wells . after 10 days , cells in all wells exhibited similar growth and reached an average of 1 . 8 × 10 6 cells per well . all cells in each individual well were then analyzed for imatinib - resistant clones by clonogenic assay with 5 μm imatinib . only 3 of the 15 wells produced resistant colonies ( p = 0 . 0008 ) ( table 2 ). even if it was assumed that all mutants or pre - mutants happened to be seeded into these three wells ( an unlikely event ), enrichment of mutant or pre - mutant cells should have been seen in these three wells . however , an increased mutation frequency was not observed ( table 2 ). a the assumed mutant frequency under 5 μm imatinib was 2 . 5 × 10 − 4 as described in the text or 25 cells in 1 × 10 5 kcl - 22 cells . p value was calculated with two - tailed fisher exact test . to validate this finding , another cell pool assay was performed by evenly dividing 1 × 10 5 kcl - 22 cells ( calculated 48 mutants under 2 . 5 μm imatinib ) into 40 wells in the presence of 2 . 5 μm imatinib , an average of 1 . 2 mutant cell per well . similarly , 20 kcl - 22m cells were evenly divided into 20 wells in the presence of 2 . 5 μm imatinib . by poisson distribution , 28 wells should have received mutant or pre - mutant cells for kcl - 22 plating , and 12 wells should have received cells for kcl - 22m plating . however , only one well of kcl - 22 cells relapsed and re - grew . in contrast , five wells of kcl - 22m cells re - grew ( p = 0 . 006 ) ( table 3 ). these data indicate that most bcr - abl mutant cells found in kcl - 22 cells upon imatinib treatment are unlikely to have been derived from a fixed mutant or pre - mutant subpopulation , although the presence of a small portion of pre - existing mutant cells can not be completely ruled out . together with the cell cloning analysis , these results indicate that the emergence of bcr - abl mutations may be a dynamic process influenced by culture and environmental conditions . isolation and retroviral transduction of human cd34 ÷ cells . study of human samples was approved by the institutional review board . cd34 + cells were isolated from frozen bone marrow samples and transduced by retroviral vector mig210 bcr - abl or empty vector migr1 as previously described ( ramaraj et al ., 2004 ). cells were harvested 48 hours later and labeled with anti cd34 - apc . cd34 + gfp + cells were collected by flow cytometry . after cells were expanded in culture for seven days , total rna and protein lysate were prepared using standard protocols . sirt1 promoter assay . cml cells were seeded at 4 × 10 4 / well in 96 well plates and co - transfected with sirt1 promoter - luciferase reporters ( 2 . 8 kb and 90 bp promoter fragments ) ( nemoto et al ., 2004 ) and a control plasmid pmaxgfp ( lonza ). feofection reagent ( genovis ) was used to transfect 0 . 18 μg reporter and 0 . 02 μg pmaxgfp each well per the manufacturer &# 39 ; s instruction . six hours after transfection , cells were treated with imatinib and harvested after another 30 hs . luciferase activity was measured using dual - luciferase assay system ( promega ), and normalized to gfp reading in each lysate . rna and protein analyses . rna was extracted with trizol ( invitrogen ), synthesized the first strand dna with superscript iii kit ( invitrogen ), and analyzed gene expression using sybr greener qpcr supermix kit ( invitrogen ). for western blots , rabbit monoclonal anti - human sirt1 ( epitomics ), rabbit anti - mouse sirt1 ( upstate biotech ), mouse monoclonal anti - c - abl ( bd pharmingen ), mouse monoclonal anti - ku70 ( neomarker ), rabbit polyclonal anti - acetylated p53 ( cell signaling ) and rabbit polyclonal anti - acetylated foxo1 ( santa cruz biotech ) were used . to analyze ku70 acetylation , ku70 was pulled down from total cell lysate with anti - ku70 and protein a - agarose beads ( upstate biotech ) followed by acetylation detection with rabbit anti - acetyl lysine antibody ( cell signaling ). statistical analysis . for animal studies , kaplan - meier survival analysis was performed and statistical significance was calculated using log - rank test . for other data analysis , t - test was performed . two - tailed analysis was used in all cases and p & lt ; 0 . 05 is considered statistically significant . the effects of sirt1 stable knockdown on blockage of cml relapse by sirt1 inhibitors were determined . sirt1 shrnas were designed as described previously ( reynolds et al ., 2004 ). the first sirt1 shrna , sh1 , was subcloned into a lentiviral vector psicor ( ventura et al ., 2004 ) which contains an expression cassette for green fluorescent protein ( gfp ) ( fig1 a ). a scrambled shrna was subcloned into the vector as a mock control . the vsv - g ( g protein of vesicular stomatitis virus ) pseudotyped lentiviral vectors were produced using a four - plasmid transfection system as described ( kowolik et al ., 2003 ). these vectors transduced kcl - 22 and k562 cells with high efficiency and significant sirt1 knockdown was observed in both cell lines ( fig1 a ). mock or sirt1 knockdown cells were enriched by fluorescent activated cell sorting ( facs ) for gfp expression . no significant growth inhibition by sirt1 knockdown on cml cells was observed . treatment with imatinib resulted in relapse of the mock knockdown kcl - 22 cells after two weeks . the sirt1 knockdown showed significantly delayed or abolished relapse with relapse ranging from complete blockage during the two - month culture to delay by 27 days ( fig1 b ). sirt1 expression in the relapsed sirt1 knockdown cells was restored to the same level as that in the mock knockdown cells indicating that relapse in the sirt1 sh1 knockdown cells is mediated by those cells which contain little sirt1 knockdown in the original knockdown pool ( fig1 c ). sirt1 shrnas were based on homo sapiens sirtuin type 1 ( sirt1 ) mrna , complete cds ( accession no . af083106 ), and are as follows : the heterogeneity of sirt1 knockdown in the pooled population was confirmed using limiting dilution to clone individual sirt1 knockdown and mock knockdown cells . about one - third of sirt1 knockdown clones did not have significant sirt1 knockdown ( fig1 d ) while sirt1 level in mock knockdown clones remained unchanged . additional sirt1 knockdown was also generated using different shrna targets . sh2 was cloned into a vector similar to psicor cmv - gfp with a pkg - puro expression cassette instead of cmv - gfp cassette ( fig1 a ). this allows for enrichment of transduced cells using puromycin selection . sirt1 sh2 exhibited a higher knockdown efficiency than sh1 ( fig1 a ). the mock knockdown kcl - 22 cells relapsed after two weeks but sirt1 sh2 knockdown completely blocked the relapse for two months ( fig1 e ). whether the vector sequence affects shrna function was also assessed . sirt1 sh1 was subcloned into psicor pgk - puro vector and found to function similarly to sh1 in psicor cmv - gfp vector — only able to delay the relapse . this indicates that it is the level of knockdown but not the type of vector used that affects resistance . sirt1 knockdown using both sh1 and sh2 resulted in a further decreased sirt1 level ( fig1 a ), completely blocking relapse of kcl - 22 cells for two months ( fig1 f ). this indicates that sirt1 is a gene that regulates cml acquired resistance by promoting bcr - abl mutagenesis during imatinib treatment . to determine the consequence of sirt1 activation , kcl - 22 and k562 cells were treated with a small molecule inhibitor of sirt1 , sirtinol , with or without imatinib . sirtinol alone inhibited the growth and induced apoptosis of both cell lines , and the combination of sirtinol with imatinib further enhanced their inhibitory effects and apoptosis induction ( fig8 a - b and fig5 a - b ). sirtinol and imatinib both affected cell cycle of cml cells , reducing s / g2 / m and increasing sub - g1 population in kcl - 22 cells while rapidly increased sub - g1 and apoptotic fraction in k562 cells ( fig5 c - d ). since the level of sirt1 knockdown affected the cml resistance , to further determine specific roles of sirt1 on cml cells , sirt1 was knocked down using a third and most potent set of lentiviral shrna ( shsirt1 - 3 ) ( fig2 a and 33a ). it was found that the knockdown suppressed proliferation of kcl - 22 and k562 cells ( fig2 b ), and had synergistic effects with imatinib on induction of apoptosis in these cells ( fig2 c ). further , it was found that overexpression of sirt1 failed to protect cml cells from apoptosis induced by imatinib or bcr - abl knockdown ( fig3 a and 37b ), although sirt1 overexpression protected cml cells from oxidative stress ( fig3 c ), which is consistent with the fact that bcr - abl expression activates multiple survival pathways ( melo et al ., 2007 ). next , sirt1 knockdown was found to significantly inhibit soft agar colony formation of cml cells ( fig2 d ). to examine tumor growth in vivo , cml cells were transduced overnight with sirt1 shrna and transplanted the cells into non - obese diabetic severe combined immunodeficiency ( nod - scid ) mice . sirt1 knockdown significantly delayed the tumor growth of xenografted cml cells and prolonged the survival of mice ( p & lt ; 0 . 0001 , fig2 e ). further , to determine the effect of sirt1 inhibition for bcr - abl transformation in primary cd34 + cells , we co - infected the cells with mig210 and sirt1 shrna . sirt1 knockdown increased apoptosis of bcr - abl transduced cd34 + cells but had minimal effect on normal cd34 + cells ( fig4 a ). sirt1 knockdown suppressed proliferation and colony forming cell ( cfc ) formation of the transduced cd34 + cells ( fig4 b ). sirt1 knockdown induced foxo1 and p53 acetylation in bcr - abl transduced cd34 + cells ( fig4 c ). together , these results indicate that sirt1 knockdown suppresses growth and transformation of human cml cells . using lentiviral shrna to knock down sirt1 , it was found that the ability for kcl - 22 cells to form bcr - abl mutations was dependent on the residual amount of sirt1 left , and the shsirt1 - 3 vector that resulted in the most robust knockdown completely inhibited bcr - abl mutations ( fig3 a ). accordingly , the relapse of kcl - 22 cells on imatinib was delayed more with better sirt1 knockdown , with complete block of relapse by shsirt1 - 3 ( fig3 b ). to determine if sirt1 deacetylase activity is required for bcr - abl mutagenesis , wild type or h363y dominant - negative deacetylase - deficient sirt1 ( vaziri et al ., 2001 ) was overexpressed in kcl - 22 cells . expression of either wild type or h363y sirt1 did not affect cell growth or induce apoptosis ; however , h363y sirt1 expression significantly reduced bcr - abl mutations ( fig3 c ). together , these results reveal that high levels of sirt1 in cml cells promote bcr - abl mutations for acquired resistance , a process that is dependent on sirt1 deacetylase function . the potential downstream targets of sirt1 that are involved in controlling the cml cell resistance are determined . p53 is a key downstream target of sirt1 for apoptotic control in solid tumors . however , p53 is mutated in both kcl - 22 and k562 cells , indicating that other sirt1 targets might be involved . involvement of another sirt1 target , peroxisome proliferator - activated receptor - gamma coactivator 1 alpha ( pgc - 1α ), for induction of bcr - abl mutations through regulating reactive oxygen species ( ros ) is examined . the ros production is dramatically increased in blast crisis cml , which results in accumulation of dna damage product 7 , 8 - dihydro - 8 - oxo - 2 ′- deoxyguanosine ( 8 - oxog ). overexpression of bcr - abl in murine cells induces ros production , dna damage and bcr - abl mutations . however , cellular abl plays an important role in cellular dna damage repair and treatment with sti - 571 will also inhibit abl and inactivate cellular dna repair system . most of the cellular ros is produced by electron transport chain of active mitochondrial metabolism . pgc - 1α is a master activator for mitochondrial biogenesis and respiration that promotes ros production . sirt1 plays a critical role in this regulation by deacetylating pgc - 1α and thus activating its function . sti - 571 treatment inhibits bcr - abl function and cell growth but simultaneously reduces ability of cellular dna damage repair and results in t315i mutation , unless sirt1 is inactivated by sirtinol or pgc - 1α is inactivated . ku70 is an important downstream target of sirt1 for acquired resistance of cml cells . a search for essential sirt1 pathways involved in regulating both cml cell survival and dna damage responses was performed . among known sirt1 substrates , p53 is mutated in both kcl - 22 and k562 cells . another target , ku70 , is an important downstream effecter for sirt1 - mediated cell survival ( cohen et al ., 2004 ), and is also an important component of error - prone , non - homologous end joining ( nhej ) dna repair machinery ( khanna et al ., 2001 ). as shown in fig3 a , the acetylation levels of endogenous ku70 in cml cells are increased in proportion to the levels of sirt1 knockdown . when ku70 is knocked down ( fig3 b ), the combination of ku70 shrna with imatinib resulted in more apoptosis of kcl - 22 cells than each individual agent ( fig3 c ). however , the combination of ku70 knockdown with imatinib did not result in a synergistic induction of apoptosis that was seen with the combination of sirt1 knockdown and imatinib treatment ( fig2 c ), indicating that ku70 contributes in part to sirt1 - mediated cml cell survival . ku70 knockdown completely blocked bcr - abl mutations and kcl - 22 cell relapse on imatinib ( fig3 d ), indicating that ku70 is an important downstream target of sirt1 for promoting bcr - abl mutations and acquired resistance . therefore , high levels of sirt1 in cancer cells may activate ku70 by deacetylation to promote error - prone dna damage repair , which results in mutations for acquired resistance . to further determine the role of sirt1 in dna damage repair , stable kcl - 22 cell clones bearing a nhej reporter construct ej5 - gfp were generated . for comparison with homologous recombination ( hr ) repair , kcl - 22 cell clones carrying a hr reporter dr - gfp were also generated . after introducing dna damage on these reporters using endonuclease i - scel , it was found that nhej was much more efficient than hr for dna damage repair in kcl - 22 cells , and that sirt1 knockdown suppressed both hr and nhej activity with more prominent effect on nhej ( fig4 ), consistent with sirt1 regulation of ku70 functions as described above . in addition to modulating ku70 , sirt1 deacetylates hr repair factor nijmegen breakage syndrome - 1 ( nbs1 ; a component of mrn ( mre11 - rad50 - nbs1 ) complex ) and regulates recruitment of nbs1 and rad51 to dna damage foci for repair . it was found that both nbs1 and rad51 knockdown also suppressed bcr - abl mutations and cml cell relapse on imatinib ( fig5 ). this result was surprising because hr repair was not efficient in kcl - 22 cells . in addition , bcr - abl expression also compromises the fidelity of hr repair ( nowicki et al . 2004 ). thus , high levels of sirt1 in cml cells may alter functions of cellular repair machineries , in particular , error - prone dna damage repair , which promotes mutations for acquired resistance . aurora kinases are evolutionarily conserved family of serine / threonine kinases , with three homologous genes aurora a , b , and c in mammals . aurora a is essential for bipolar spindle assembly during mitosis and aurora b ensures proper chromosome attachment to the mitotic spindle , while aurora c is involved in regulation of cilia and flagella . aurora a is overexpressed in various types of human cancer and its gene amplification overrides the mitotic spindle assembly checkpoint , results in defective spindle formation and multinucleation , and increases cellular resistance to chemotherapeutic agent paclitaxel . selective inhibitors of aurora kinases have been developed for treatment of various cancers . the increase of g2 / m cell number , enlarged cell size and bizarre morphology of kcl - 22m cells show potential defects in cell mitosis , which will deregulate aurora kinases in these cells . using western blot , it was found that the overall level of aurora b in kcl - 22 and kcl - 22m cells are similar , but aurora a was abnormally stabilized in kcl - 22m cells that might account for morphological and cell cycle changes in these cells ( fig1 ). it has been found that the aurora kinase inhibitor , vx - 680 , potently inhibits t315i bcr - abl through a different structural mechanism from sti - 571 . three cml patients with t315i mutation responded to vx - 680 treatment , indicating that clinical responses of cml patients with t315i can be enhanced with inhibition of aurora kinases , mutant bcr - abl , or both . aurora kinase plays a role in the resistance of t315i mutation in cml cells . vx - 680 is a useful approach for eradicating mutant cells . aurora a is abnormally stabilized in kcl - 22m cells that have been treated with sti - 571 , but is degraded by treatment with sirt1 inhibitor sirtinol ( fig1 b ). abnormal stabilization of aurora a can be caused by mutations of its dna sequences for destruction boxes a and d ( fig1 a ) due to the pressure imposed by sti - 571 treatment . where inhibition of bcr - abl alone is insufficient to eradicate t315i bcr - abl mutant cells , combination treatment with sirt1 inhibitors along with a dual bcr - abl and aurora inhibitor such as vx - 680 is useful for eradicating the resistant cells . whether stabilization of aurora a in kcl - 22m cells might be due to alterations of its destruction signals is determined . aurora a is destructed after mitotic exit through ubiquibin ligase , which is regulated by two conserved short amino acid sequences , an n - terminal a box and a c - terminal d box ( fig1 a ), and mutations of these sequences stabilize aurora a . besides , phosphorylation of serine s51 in the a box of human aurora a or s53 in xenopus also inhibits its destruction . there is structural similarity of kinase domains of bcr - abl and aurora , and cross reactivity of their inhibitors . these results show that aurora a is involved in resistance of kcl - 22m cells . the effects of aurora a knockdown for kcl - 22m cells was also determined . aurora a shrnas was designed and tested . the knockdown of aurora a was confirmed by western blot . whether this knockdown reduces g2 / m cell population and restores normal cell morphology in kcl - 22m cells by flow cytometry , and whether it promotes apoptosis or inhibits growth of kcl - 22m cells is also assessed . to determine the role of aurora a overexpression in cml chemoresistance , aurora a is expressed with an exogenous promoter in kcl - 22 cells to examine whether it accelerated resistance , and in sti - 571 sensitive k562 cells to examine whether it helped these cells to develop resistance . wild type and / or mutant aurora a is used depending on the sequencing results from the first experiment . full length cdna of aurora a was pcr - amplified and subcloned into an expression cassette with simian virus 40 ( sv40 ) promoter in a lentiviral vector carrying cmv - gfp , which is similar to the vector used for shrna packaging . when a mutant is needed , site - directed mutagenesis is performed in the subcloned aurora a vector . recombinant viruses are then produced and used to infect kcl - 22 or k - 562 cells , and overexpression of aurora a is verified by western blot . infected cells are isolated by facs sorting for gfp expression , and if necessary , cloning of individual cells . resistance in these cells was measured by rate of mutation , time for relapse , and concentrations of sti571 needed to repress cell growth and induce apoptosis . knockdown of bcr - abl has a greater impact on kcl - 22 cells than kcl - 22m cells , and other gene changes such as aurora a also have important roles in resistance of kcl - 22m cells . overexpression of aurora a can render kcl - 22 cells more resistant to sti - 571 treatment and may develop resistant cells even without genetic mutations , and persistent aurora a may also render k - 562 cells resistant to 1 μm sti - 571 treatment . simultaneous knockdown of bcr - abl and aurora a can have a more significant impact than individual knockdown on cell growth and apoptosis of kcl - 22m cells . treatment with vx - 680 kills kcl - 22m and kcl - 22 cells efficiently as it inhibits both aurora kinases and wild type or t315i bcr - abl . sirt1 is required for sti - 571 resistance in mouse models and in primary human cml cells . it is examined whether the mechanisms that sirt1 inhibition enhances cml apoptosis and prevents relapse on sti - 571 in vitro applies to in vivo treatment . first , a xenograft model of human cml cells was used in non - obese diabetic severe combined immunodeficient ( nod - scid ) mice and examined whether the combined treatment with sirtinol and sti - 571 eliminates kcl - 22 cells in recipient mice and prolongs their survival without relapse . also examined was another cml cell line ku - 812 for xenograft study . ku - 812 is very sensitive to sti - 571 in vitro , but in vivo one third of mice with ku - 812 xenograft relapse on sti - 571 treatment after 48 to 60 days . it is determined whether the combination of sti - 571 and sirtinol blocks this relapse . second , murine bone marrow retroviral transduction and transplantation model was used to define specific roles of sirt1 in vivo for bcr - abl transformation and sti - 571 resistance with sirt1 knockout mice . many hallmarks of human cml are faithfully reproduced in balb / c mouse models employing retroviral transduction of bone marrow cells with p210 bcr - abl followed by transplantation to syngeneic recipients . mice develop cml - like myeloproliferative disease characterized by massive extramedullary hematopoiesis in spleen , liver and bone marrow with striking peripheral blood granulocytosis , and die within 3 - 4 weeks after transplantation . treatment with sti - 571 prolongs survival in 80 % of mice , while the rest exhibit primary resistance and no mice can be cured by the treatment . it is examined whether homozygous sirt1 knockout inhibits development of myeloproliferative disease in this model or significantly enhances the effects of sti - 571 treatment to inhibit resistance and even cure the disease , and whether combination of sirtinol and sti - 571 will significantly improve treatment of the disease generated with wild type mouse bone marrow . in vitro colony - forming - unit ( cfu ) assay is used to determine whether combination of sirtinol with sti - 571 will suppress blast - forming unit - erythroid ( bfu - e ) and cfu - granulocyte - monocyte ( cfu - gm ) colonies from late phase cml patients more efficiently than sti - 571 itself . since no animal studies have been conducted with sirtinol before , the pharmacokinetics of the compound was first determined . female nod - scid mice 6 to 8 weeks of age were given a single dose of sirtinol intraperitoneally ( i . p .) and at seven time points , namely 0 . 5 , 1 , 2 , 4 , 6 , 8 , and 24 hours , mice are sacrificed and blood , bone marrow and liver are collected for hplc - ms analysis . second , the effects of the combination of sirtinol and sti - 571 for treatment of xenografted cml cells were determined . induction of tumors by kcl - 22 cells in nod - scid mice was tested . mice were irradiated with 270 rads , and 4 to 6 hours later , transplanted with 3 million cells in phosphate - buffered saline each through tail vein . of 12 recipients , one died within one week likely due to infection and the other 11 recipients developed tumors between 3 to 5 weeks . most of mice exhibited visible tumors on neck , eye , and abdomen . necropsy and histopathological examination revealed that these solid tumors were derived from lymph nodes throughout the body , with the highest frequency in axillary , pancreatic and renal nodes , and tumors frequently infiltrated kidney , eye and muscle ( fig1 ). a significant number of human cells were not detected in peripheral blood by flow cytometric analysis of cd45 + cells in all 11 mice before they were sacrificed for tumor burden . microscopically visible tumors were not found in the spleen , liver and lung . to facilitate non - invasive assessment of in vivo anti - tumor activity of drugs , kcl - 22 cells stably expressing firefly luciferase were generated . cells were examined for their responses for sti - 571 and sirtinol treatment to ensure that luciferase expression does not alter effects of drugs . luciferase - expressing kcl - 22 cells are transplanted into nod - scid mice . mice with established tumors ( by luciferase imaging ) are divided into 4 groups with 5 mice each : group 1 , vehicle control ; group 2 , oral administration of sti - 571 twice daily with a morning dose of 50 mg / kg and an evening dose of 100 mg / kg ; group 3 , single i . p . injection of sirtinol with a dose producing stable plasma concentration of at least 50 μm ; group 4 , combination of sti - 571 and sirtinol . mice were imaged 5 to 7 days after treatment , and total body bioluminescence was collected to quantify the changes of tumor progression and regression . the ability of sirtinol and imatinib to block resistance related to bcr - abl mutations and non - mutants was determined in acute lymphocytic leukemia ( all ) cells . in humans , adult bcr - abl bearing ( all ) is highly chemoresistant and treatments are rarely successful , resulting in a poor survival rate ranging from & lt ; 10 % to 20 % ( bassan et al ., 2004 ). similar to kcl - 22 cells , the all cell line , sd1 is resistant to sti - 571 treatment ( deininger et al ., 1997 ). here , it was observed that prolonged treatment of sd1 cells with sti - 571 induced partial cell death , with cells relapsing after ten days without bcr - abl mutations ( fig1 c ). sirt1 inhibitor sirtinol alone or in combination with sti - 571 could eliminated these cells during prolonged cell culture ( fig1 c ) indicating again , that sirt1 controls key molecular pathways for chemoresistance of bcr - abl positive leukemia . suppression of sirt1 along with bcr - abl is an effective therapeutic approach . in combination with the materials and methods described in examples 1 and 2 above , the following additional materials and methods were used . animal studies . the use of animals was approved by the institutional animal care and use committee . for cml tumor xenograft assay , three million virally transduced cells were inoculated subcutaneously into the right flank of nod - scid mice conditioned by 270 rad irradiation . tumor length ( l ), height ( h ) and width ( w ) were measured weekly with a caliper . tumor volume is estimated from the formula , v = π ( l × h × w / 6 ). mice were euthanized when the tumor volume reached 1000 mm 3 . for bone marrow transduction / transplantation studies , sirt1 +/− mice were backcrossed to balb / c background for eight generations . retroviral transduction of bone marrow cells and transplantation were performed as described previously ( pear et al ., 1998 ). pe - labeled lineage ( gr - 1 , mac - 1 , b220 , ter119 and cd3e ) antibodies ( bd pharmingen ), and apc - labeled cd150 antibody ( biolegend ) were used for cell analysis or sorting . for the in vivo drug treatment study , imatinib was prepared freshly in pure h 2 o and tenovin - 6 was prepared in 20 % cyclodextrin ( w / v ) ( sigma , # c0926 ) and 10 % dmso ( v / v ) as described ( lain et al . 2008 ), and both were filtered sterile . at day 10 post transplantation , drugs were administrated continuously for 10 days . imatinib was administrated by oral gavage with 75 mg / kg in the morning and 125 mg / kg in the afternoon . tenovin - 6 was given by intraperitoneal injection at 50 mg / kg in the morning . vehicle control animals were treated with solution containing 20 % cyclodextrin and 10 % dmso . sirt1 knockout inhibits development of a cml - like disease in a mouse model . to further understand roles of sirt1 in cml , the impact of sirt1 knockout on cml disease development in a mouse bone marrow transduction / transplantation model ( pear et al ., 1998 ) was examined . many hallmarks of human cml are reproduced in this model and recipient mice develop a cml - like myeloproliferative disease and die within 2 - 4 weeks after transplantation . since the efficiency for generating the cml - like disease in this model is about 100 % in babl / c strain , sirt1 knockout mice ( cheng et al ., 2003 ) were backcrossed to the balb / c strain for at least eight generations . a portion of sirt1 −/− mice survived through adulthood with relatively normal development , although smaller body stature and closed eye lids were noticed in some mice as previously described ( cheng et al ., 2003 ). consistent with a previous report ( narala et al ., 2008 ), no significant difference in blood lineage differentiation and hematopoietic stem cell frequency were found in sirt1 −/− mice compared to wild type littermates ( fig5 a - c ). bone marrow cells from 3 - month old sirt1 −/− and sirt1 +/+ mice were transduced with bcr - abl ( mig210 ) or control vector ( mig r1 ), both bearing green fluorescent protein as a marker , and transplanted 2 . 5 × 10 5 or 1 × 10 5 transduced cells into lethally irradiated balb / c recipients ( fig2 a ). it was found that the transduction and engraftment efficiency for both wild type and knockout cells were similar ( fig3 ), and mice receiving 2 . 5 × 10 5 bcr - abl transformed sirt1 +/+ bone marrow cells developed the cml - like disease within three to four weeks with signature characteristics of the disease : markedly elevated white blood cell ( wbc ) counts predominated by granulocytes , splenomegaly , and multiple organ involvement ( fig2 a - b ) ( pear et al ., 1998 ). mice receiving bcr - abl transformed sirt1 −/− cells showed significantly delayed disease development with markedly lower peripheral blood wbc counts ( p & lt ; 0 . 0001 ) ( fig2 b ). in contrast to mice receiving transformed sirt1 −/− cells ( 10 % b220 + gfp + in all gfp + population ), bone marrow exhibited dramatic expansion of the gr - 1 / mac - 1 lineage in mice receiving transformed si rt1 +/+ cells , and occurred at the expense of b220 lineage differentiation ( 0 . 24 % b220 + gfp + in all gfp + population ) ( fig2 c ). as a consequence , mice receiving transformed sirt1 −/− cells survived much longer than mice receiving transformed sirt1 +/+ cells ( p & lt ; 0 . 0001 ) ( fig2 a ). no significant difference was observed with empty vector transformation ( fig2 a and 29b ). it was found that sirt1 expression was dramatically upregulated in bone marrow cells from mice receiving bcr - abl transformed sirt1 +/+ cells ( fig2 d ). to determine cell populations with sirt1 expression change , bone marrow cells were sorted for expression of hematopoietic stem / progenitor cell marker cd150 ( kiel et al ., 2005 ) and green fluorescent protein ( gfp ) marker from the retroviral vector for transformation . it was found that sirt1 activation occurred specifically in gfp + cd150 + transformed progenitor cells , but not in gfp + cd150 − cells or non - transformed cells ( fig2 e ), similar to that seen for human cd34 + progenitor cells ( fig2 b and 26c ). to further validate this finding , cml progenitor cells were sorted using classic lin - sca1 + ckit + ( lsk ) markers , and found that sirt1 rna was significantly elevated in cml progenitor cells ( fig4 a ). next , it was determined whether treatment of cml mice with a sirt1 inhibitor would deter the disease . due to the solubility , an effective concentration of sirtinol was not obtainable in vivo . therefore , a more potent and water soluble inhibitor tenovin - 6 that inhibits sirt1 and sirt2 was tested . treatment with tenovin - 6 at 5 μm and higher concentrations sensitized cml cells to imatinib - induced apoptosis ( fig5 a ). it was found that tenovin - 6 , administrated at 50 mg / kg / day , significantly extended cml mouse survival ( fig4 b ). no noticeable toxicity was detected with tenovin - 6 alone or in combination with imatinib ( fig4 c ). some mice with the combination treatment were the longest survivors ( fig5 ). these results show that sirt1 activation is required for efficient bcr - abl transformation of hematopoietic stem / progenitor cells and cml disease development . in combination with the materials and methods described in examples 1 , 2 and 3 above , the following additional materials and methods were used . cell lines and culture . h3255 cell line is obtained from national cancer institute and h1650 cell line from american type culture collection ( atcc ). gefitinib is obtained from astrazeneca or purchased from euroasia pharmaceuticals , and sirtinol is purchased from sigma . for resistance assay , 2 . 5 × 10 5 h3255 or h1650 cells are seeded per well in 6 - well plates overnight , and treat with drugs in 3 ml culture medium each . cells are maintained in culture without medium changes . relative cell numbers are analyzed over time in triplicate wells . cells are fixed with 4 % formaldehyde , stained with 0 . 1 % crystal violet and quantified by using odyssey infrared imaging system ( li - cor biosciences ). when relapse occurs , emerging cells reach confluence rapidly and are expanded into larger culture dishes . if the h3255 cells are unable to survive the applied dosage of gefitinib , then a lower therapeutic dose is used such as 0 . 4 μm , or the lowest therapeutically effective dose . using the above procedures , resistance models may be reproduced for h1650 cells . in addition , a faster relapse for h3255 cells with t790m mutation may be obtained ( e . g . in two weeks ). inhibition of sirt1 by sirtinol or by shrna may have a synergistic or additive effect with gefitinib for inducing apoptosis and suppressing growth . the relapse normally obtained through mutation or non - mutation mechanisms will be blocked or delayed . the resistance models may be also reproduced for other cancer cell lines , such as for example , another nsclc cell line pc - 9 that also relapses on gefitinib treatment . dna damage induction by camptothecin and de novo mutation analysis . cells were pre - selected for four days in hat medium to remove pre - existing hprt mutations . the efficiency of hat selection was confirmed by plating these cells on soft agar with 2 . 5 μg / ml 6 - thioguanine , which produced zero colony . hat - selected cells were then treated with 0 . 5 μm cpt for 1 hour , and then cultured for 10 days before used for soft agar clonogenic assay with 6 - thioguanine selection . the rest of hat - selected cells were cultured in medium without selection . the change of γh2ax was analyzed with γh2ax assay kit ( upstate biotech ). dna damage repair assay . five million kcl - 22 cells were transfected with 15 μg linearized repair reporter construct dr - gfp or ej5 - gfp by electroporation , and cells were selected for puromycin resistance . individual clones were plucked from soft agar and expanded to screen for clones carrying an intact copy of the reporter constructs by southern blotting as described previously ( bennardo et al . 2008 ; weinstock et a1 . 2006 ). clonal kcl - 22 cells with an intact copy of reporters were transduced by shsirt1 , shrad51 or shnbs1 for 24 h followed by electroporation with 50 μg i - scel encoding plasmid plus 10 μg ds - red . after another 48 h culture , the cells were analyzed by flow cytometry for gfp and ds - red expression to determine the repair efficiency . gfp + cells were the successfully repaired cells , and repair rate was normalized to ds - red transfection efficiency . dna methylation analysis . bisulfite genomic dna sequencing was performed as previously described ( frommer et al ., 1992 ; herman et al ., 1996 ). briefly , 1 μg of genomic dna is treated with sodium bisulfite for 16 hours , and the dna is then recovered using wizard dna clean - up system ( promega ). pcr products are cloned into pcr2 . 1 vector with topo ta cloning kit ( invitrogen ). at least ten clones each were sequenced for dna methylation analysis . for quantitative hic1 promoter methylation analysis , the massarray dna methylation analysis system ( sequenom ) was used as per the manufacturer &# 39 ; s protocol at city of hope functional genomic core . the methylation for individual or aggregate cpg sites was analyzed with epityper software v1 . 0 ( sequenom ). chip assay . this assay was performed as described previously 69 . we used stat5a or 5b antibody ( cell signaling ) for immunoprecipitation and used anti - flag antibody ( santa cruz ) as a control . the following primers were used for chip pcr analysis : for stat5a binding site , 5 ′- gcatctctgacctctcagca - 3 ′ ( sense ) ( seq id no : 38 ) and 5 ′- cagaaacaaaattcccagcttt - 3 ′( antisense ) ( seq id no : 39 ); for stat5b binding site , 5 ′- gggattggtatgaaggaacg - 3 ′ ( seq id no : 40 ) and 5 ′- agcgaaactccgtctcaaaa - 3 ′ ( antisense ) ( seq id no : 41 ); for gapdh , 5 ′- tctggggactaggggaagga - 3 ′ ( sense ) ( seq id no : 42 ) and 5 ′- ccgcaaggagagctcaaggt - 3 ′ ( antisense ) ( seq id no : 43 ). sirt1 mrna stability . kcl - 22 cells were seeded at 5 × 10 6 / ml in 12 - well plate with 2 . 5 μm imatinib or dmso as mock control . twelve hours later , actinomycin d ( 2 μg / ml ) was added and at 0 , 1 , 2 , 4 and 8 hours after actinomycin treatment , total rna was extracted . first strand cdna was reverse transcribed from 1 . 0 μg of total rna using superscript iii kit ( invitrogen ). one microliter of the first strand cdna synthesis reaction mixture was used for pcr amplification in a total volume of 50 μl . gapdh was amplified with 25 cycles and sirt1 was amplified with 30 cycles . the primer sequences used were : sirt1 promotes de novo genetic mutations of cancer cells upon dna damage . the role of sirt1 in regulating de novo dna damage in cml cells was investigated . sirt1 and mock knockdown kcl - 22 cells were treated with hypoxanthine aminopterin thymidine ( hat ) to remove preexisting hprt mutation , followed by treatment with camptothecin ( cpt ) to induce dna damage . cells were then analyzed for survival / proliferation and hprt mutations . sirt1 sh1 knockdown cells exhibited two fold less survival over time than mock cells ( fig1 b ). hprt mutation rate in sirt1 knockdown cells was decreased by 64 fold ( fig1 c ). similar results were obtained by both sirt1 sh1 and sirt1 sh2 knockdown ( fig3 d ). additionally , sirt1 knockdown reduced spontaneous hprt mutations when these cells were maintained for one month in culture ( fig3 d ). furthermore , sirt1 knockdown robustly suppressed cpt - induced de novo hprt mutations in prostate cancer cells ( fig3 ), indicating that sirt1 - mediated mutagenesis is independent of cancer cell types . these results indicate that sirt1 is a key protein promoting genetic instability and the evolution of oncogenes to resist and survive drug therapy and overcome dna damage ( fig1 d ). these findings are surprising given that sirt1 is shown to promote dna damage repair ( oberdoerffer et al ., 2008 ; wang et al ., 2008 ). it was also found that sirt1 knockdown inhibited dna damage responses by reduction of γh2ax staining ( fig3 e ). sirt1 inhibitors did not increase γh2ax expression in cml cells in the presence or absence of imatinib , in contrast to hdac inhibitor trichostatin a ( tsa ) that elicited robust γh2ax induction ( fig4 ). these results indicate that although a high level of sirt1 may enhance dna damage responses in cancer cells , it can also increase de novo genetic mutations . such paradoxical functions of sirt1 may be a result of altered dna damage repair mechanisms in cancer as further described below . sirt1 is activated by bcr - abl transformation in human hematopoietic stem / progenitor cells . promoter hypermethylation of hic1 increases progressively towards late phases of cml ( issa et al ., 1997 ). we initially hypothesized that upregulated sirt1 upon hic1 gene silencing may be important for cml chemoresistance . indeed , we found that sirt1 expression levels increased in blast crisis cml cell lines kcl - 22 and k562 ( fig2 a ), correlated with hic1 promoter hypermethylation and silencing in these cells ( fig3 and fig5 ). to examine sirt1 expression in primary human cml , we isolated cd34 + cml progenitor cells . it was found that sirt1 protein levels were tightly correlated with bcr - abl expression levels from chronic to blast crisis phase patients ( fig2 a ). noticeably , more advanced - phase samples showed high bcr - abl levels along with high sirt1 expression . this finding prompted the determination of the source of the change in sirt1 expression during bcr - abl transformation . normal cd34 + cells were isolated from healthy donors , and transduced with bcr - abl retroviral vector mig210 ( pear et al ., 1998 ). sirt1 protein was hardly detectable in normal cd34 + cells by western blot , but was dramatically upregulated by bcr - abl transduction ( fig2 b ). sirt1 rna level was also significantly upregulated by bcr - abl ( fig2 c ). bcr - abl transduction did not increase sirt1 expression in normal human fibroblasts w138 cells ( fig2 b ), mouse fibroblast nih3t3 cells , human renal cancer cell line 293 , and myeloid leukemia cell tf1 , nor did it further increase sirt1 levels in blast crisis cml cells ( fig3 a ). accordingly , bcr - abl transduction selectively activates sirt1 expression in normal human hematopoietic progenitor cells . to further examine regulation of sirt1 expression in cml , kcl - 22 and k562 cells were treated with the bcr - abl kinase inhibitor imatinib . sirt1 protein levels decreased in a drug concentration - dependent manner . in contrast , the treatment did not change sirt1 expression in kcl - 22m cells that express the imatinib - resistant t315i kinase domain mutant bcr - abl or in a prostate cancer cell line ( fig2 d ). to determine specificity of imatinib effect on sirt1 , bcr - abl was knocked down using lentiviral shrna . as a result , it was found that sirt1 protein levels decreased upon bcr - abl knockdown in kcl - 22 , kcl - 22m and k562 cells ( fig2 e ). these data further support that bcr - abl regulates sirt1 expression in cml cells . since sirt1 expression is subjected to multiple levels of regulation including protein phosphorylation ( ford et al ., 2008 ), mrna stability ( abdelmohsen et al ., 2007 ) and transcription ( nemoto et al ., 2004 ; chen et al ., 2005 ), it was determined how bcr - abl activates sirt1 expression . it was found that bcr - abl knockdown only affected endogenous sirt1 protein expression but not the exogenously introduced sirt1 ( fig3 b ), indicating that bcr - abl does not affect sirt1 protein stability per se . after blocking transcription by actinomycin d , imatinib treatment did not alter the half life of sirt1 mrna and thus its stability ( fig3 c ). to examine if bcr - abl expression activates sirt1 promoter , reporter constructs of the sirt1 promoter were transfected into kcl - 22 and k562 cells followed by imatinib treatment . imatinib treatment significantly inhibited sirt1 promoter activity ( fig2 f ). together , this data indicates that bcr - abl transformation of human hematopoietic progenitors selectively activates sirt1 promoter and transcription . as shown in fig2 a , sirt1 expression was found to be tightly correlated with bcr - abl levels in cd34 + hematopoietic progenitors from human cml patients ( fig2 a ). sirt1 expression was hard to detect in normal cd34 + progenitors , but expression of bcr - abl dramatically increased sirt1 protein and rna levels ( fig2 b and 26c ). bcr - abl expression in normal fibroblast w138 cells and several solid tumor cell lines did not increase sirt1 expression , indicating a relatively specific activation mechanism in hematopoietic progenitor cells . conversely , inhibition of bcr - abl by shrna knockdown or imatinib in blast crisis cml cells reduced sirt1 expression ( fig2 e ). as shown in fig2 f , bcr - abl expression activated sirt1 promoter , with a major responsive element located between − 1 . 48 kb and − 2 . 8 kb ( fig2 a ). the binding of stat5 ( signal transducer and activator of transcription 5 ) in this region was identified as a novel mechanism for sirt1 activation in hematopoietic cells ( fig2 b and 27c ). the rvista program ( loots & amp ; ocharenko 2004 ) was used to search for potential transcriptional factors binding at this region that are related to bcr - abl functions . two putative binding sites for signal transducer and activator of transcription 5 ( stat5a and 5b ) located at − 1838 and − 2235 ( fig5 ) were identified . no other stat members were found in this region . stat5 is a key signal transducer of bcr - abl in cml ( maria et al ., 1996 ), and is also activated in aml and acute lymphoid leukemia ( all ) ( van etten , 2007 ). stat5 knockout suppresses bcr - abl transformation and development of cml - like disease in mice ( ye et al ., 2006 ; hoelbl et al ., 2006 ). therefore , it may serve as a common activator of sirt1 in leukemia . to validate the role of stat5 , a stat5 knockdown was performed using shrna in cml cells . it was found that sirt1 expression was decreased accordingly ( fig2 c ). using chromatin immunoprecipitation ( chlp ) assay , it was found that both stat5a and 5b were associated with the sirt1 promoter ( fig2 b ). together , these results indicate that bcr - abl activates sirt1 transcription in human cd34 + progenitor cells for which stat5 is a key mediator . as shown in fig8 a and 28c ( top ), sirt1 inhibition by small molecule inhibitors or shrna knockdown sensitized cml cells to imatinib for growth suppression and induction of apoptosis . sirt1 knockdown inhibited soft agar colony formation and growth of xenografted cml cells in immunodeficient mice ( fig2 e ). to further examine sirt1 functions in cml , a mouse model employing retroviral bcr - abl transduction of mouse bone marrow cells was used , followed by transplantation of these cells to syngeneic recipients ( pear et al ., 1998 ). many hallmarks of human cml are reproduced in this model and recipient mice develop a cml - myeloproliferative disease and die in 3 - 4 weeks . sirt1 knockout mice were backcrossed to balb / c background . the sirt1 knockout did not affect normal hematopoiesis , stem cell frequency or engraftment , but the knockout inhibited bcr - abl transformation and development of the myeloproliferative disease ( fig2 a ). as in human progenitor cells , sirt1 expression was activated by bcr - abl in mouse hsc . sirt1 knockout significantly reduced the number of mouse cml stem cells ( fig3 ), identified as ckit + cd34 − side population in babl / c strain ( hu et al ., 2006 ). it has shown that sirt1 knockdown or inhibition resulted in increased p53 acetylation ( fig3 c and 32e ) and enhanced imatinib - mediated apoptosis in human cml cd34 + cells but not in normal ( cord blood ) cd34 + cells ( fig3 b and 32d ). similarly , aml cd34 + cells showed increased sirt1 expression and increased apoptosis on sirt1 inhibitor treatment ( fig3 f and 32g ). the results of the studies described herein indicate that sirt1 activation is required for efficient bcr - abl transformation . sirt1 inhibition suppresses disease development and induces apoptosis in leukemic but not normal stem cells . imatinib is the frontline treatment for cml ; however , acquired resistance develops frequently due to secondary bcr - abl mutations . a novel cell culture model in which a blast crisis human cml cell line kcl - 22 , following initial response to imatinib ( or nilotinib and dasatinib ), relapses in two weeks with acquisition of t315i mutation ( yuan et al ., 2010 ) has been developed as described above . acquisition of bcr - abl mutations is dependent on expression of functionally intact bcr - abl ( yuan et al ., 2010 ). inhibition of sirt1 by small molecules , nicotinamide , tenovin - 6 , sirtinol or splitomicin , blocks relapse of cml cells upon imatinib ( or nilotinib and dasatinib ) treatment regardless if they can enhance apoptosis ( fig1 a - b and fig4 a ). tenovin - 6 and nicotinamide blocked the relapse with a dose as low as 1 μm , below the concentrations to increase imatinib - mediated cell killing ( fig1 b , 47 c and 55 a ). in contrast , hdac inhibitor trichostatin a ( tsa ) fails to block relapse ( fig1 a and fig1 b ). it was found that treatment with the potent second generation bcr - abl inhibitors nilotinib and dasatinib also resulted in relapse and acquisition of t3151 mutation in kcl - 22 cells , but the combination with tenovin - 6 or sirtinol effectively blocked the recurrence ( fig4 b - c ). four kcl - 22 cell clones were generated , three of which can acquire different bcr - abl mutations upon imatinib treatment , i . e . e255k ( clone l1 ), y253h ( clone l7 ) and t315i ( clone ag11 ), whereas clone ag3 develops resistance without bcr - abl mutations . the combination of sirtinol with imatinib blocked relapse of all clonal kcl - 22 cells on imatinib . in contrast , tsa failed to block relapse of these clonal cells ( fig4 d ). these results indicate that combination of sirt1 inhibition with bcr - abl inhibition is a powerful approach to overcome acquired resistance through bcr - abl mutations . by gene knockdown , it was found that the ability for kcl - 22 cells to form bcr - abl mutations or to relapse was proportional to the residual level of sirt1 protein left after sirt1 knockdown ( fig3 a - b ). further , the shsirt1 - 2 vector moderately reduced sirt1 level and was insufficient to increase significant apoptosis ( fig5 b ) also reduced bcr - abl mutations ( fig3 a ). this is in line with the effect of tenovin - 6 described herein and indicates that bcr - abl mutation is more sensitive to sirt1 function than apoptosis induction . to further validate that sirt1 deacetylase activity is required for bcr - abl mutagenesis , wild type or h363y deacytylase - deficient sirt1 was overexpressed in kcl - 22 cells . the expression of either wild type or h363y sirt did not affect cell growth ( fig5 c ), but h363y sirt1 expression significantly reduced bcr - abl mutations ( fig3 c ). together , these results show that high levels of sirt1 in cml cells promote bcr - abl mutations for acquired resistance , a process that is dependent on sirt1 deacetylase function . the ability of sirt1 to promote mutations is not restricted to bcr - abl in cml cells , as sirt1 knockdown in prostate cancer cells also dramatically suppressed mutations on the hprt induced by dna damaging agent camptothecin ( fig3 ). it was further shown that an important mechanism for sirt1 in bcr - abl mutagenesis and cml cell survival was through deacetylation and activation of ku70 ( fig3 a ), an essential factor for error - prone non - homologous end joining dna repair ( khanna et al ., 2001 ) and a regulator of bax - mediated apoptosis ( cohen et al ., 2004 ). knockdown of ku70 completely blocked bcr - abl mutations and cml cell relapse on imatinib treatment ( fig3 d , right ). together , these studies indicate that sirt1 plays an important role in molecular pathogenesis of cml and development of acquired resistance by promoting genetic mutations and cancer genome instability . sirt1 may play a similar role in other leukemia and solid tumors where it is aberrantly activated . sirt1 inhibitor sirtinol synergizes with sti - 571 for apoptosis induction in cml cells . expression of hic1 in cml cell lines kcl - 22 and k562 was examined by quantitative real - time rt - pcr for the major hic1 transcript from its promoter 1a . the gene was silenced or down regulated in both cell lines compared to full hic1 expression in wi - 38 cells and silencing in mcf - 7 cells ( fig7 a ). this is a consequence of promoter hypermethylation ( chen et al ., 2003 ; issa et al ., 1997 ). western blot analysis showed that sirt1 was overexpressed in both cell lines after hic1 gene silencing ( fig7 b ). total cellular rna was extracted with trizol ( invitrogen ) using a standard protocol . the first strand dna was synthesized and hic1 expression was analyzed by quantitative real - time rt - pcr using a kit with sybr green label ( invitrogen ) as per the manufacture &# 39 ; s instruction on biorad machine opticon . hic1 primers were used spanning introns , 5 ′- ggacggaccagcaggaca - 3 ′ ( exon 1a ) ( seq id no : 14 ) and 5 ′- gcgctggttgttgagctg - 3 ′ ( exon 2 ) ( seq id no : 15 ). sirt1 expression was analyzed by western blot using 1 : 5000 diluted rabbit monoclonal sirt1 antibody ( epitomics ). gapdh was analyzed as a loading control with a rabbit antibody ( trevigen ) at 1 : 5000 dilution . sirtinol inhibits sirt1 and other sirtuin deacetylases with an ic 50 about 50 to 130 μm ( grozinger et al ., 2001 ; mai et al ., 2005 ; ota et al ., 2005 ). sti - 571 treatment alone induced rapid apoptosis in k562 cells with ic 50 of about 0 . 5 μm while it had a mild effect on kcl - 22 cells ( fig8 ) ( mahon et al ., 2000 ). treatment with 50 μm sirtinol alone inhibited the growth of both cell lines , and the combination of two drugs synergized their inhibitory effects ( fig8 a and 8c ). sirtinol alone significantly induced annexin v positive apoptotic cells in both lines and when combined with sti - 571 , it induced more dramatic apoptosis than each individual drug ( fig8 b and 8d ). sirtinol and sti - 571 both affected cell cycle of cml cells by reducing s / g2 and increasing sub - g1 population in kcl - 22 cells ( fig9 a ) while they rapidly increased sub - g1 and apoptotic fraction in k562 cells ( fig9 b ). cell cycle was analyzed by fixing cells with 70 % ethanol and then stained with propidine iodine ( 50 μg / ml ) for 30 min at room temperature . cell apoptosis was analyzed with annexin v kit ( bd pharminggen ) as per the manufacturer &# 39 ; s instruction . using the cml acquired resistance model as described herein , prevention of cml relapse on sti - 571 was examined . inhibition of sirt1 with small molecule inhibitors prevented cml relapse on sti - 571 . kcl - 22 cells were treated with sti - 571 at 1 , 2 . 5 and 5 μm in combination with various concentrations of sirtinol . at 50 μm and above , sirtinol effectively eliminated kcl - 22 cells in two to three weeks and blocked relapse of kcl - 22 cells on all three concentration of sti - 571 in culture for two to three months and no viable cells were visible under microscope ( fig1 a ). as with sti - 571 , treatment with sirtinol alone resulted in relapse after two weeks ( fig1 a ). the combination of sirtinol and sti - 571 is a powerful therapeutic approach for inhibiting acquired resistance of cml . another sirtuin specific inhibitor , splitomicin ( bedalov et al ., 2001 ; hirao et al ., 2003 ), was also tested for its ability to block relapse . splitomicin is also a naphthol compound and structurally similar to sirtinol . nicotinamide is a natural inhibitor of sirt1 ( avalos et al ., 2005 ; bitterman et al ., 2002 ). at 300 μm splitomicin and 15 mm nicotinamide , relapse of kcl - 22 cells on 5 μm sti - 571 was effectively blocked during prolonged culture as shown in fig1 b . in contrast to sirtinol , splitomicin and nicotinamide did not , by themselves , induce significant cell death and did not dramatically enhance cell killing by sti - 571 during the first two weeks ( fig1 b ). these results indicate that prevention of relapse does not require enhanced cell killing . the t315i mutation is resistant to treatment with nilotinib ( weisberg et al ., 2005 ) as well as dasatinib ( shah et al ., 2004 ). in murine cells transduced with wild type bcr - abl , the t315i mutation is also commonly induced by these drugs ( von bubnoff et al ., 2006 ; von bubnoff et al ., 2005 ). using the kcl - 22m cell line , combined treatment with sirtinol and sti - 571 was able to inhibit cell growth ( fig1 c ). effects of inhibitors of deacetylases and dna methyltransferases ( dnmt ) on chemoresistance of bcr - abl positive leukemia . in vitro , enhanced killing of cml cells occurs when imatinib is combined with dnmt inhibitor 5 - aza - 2 - deoxycytidine ( aza ) ( la rosee et al ., 2004 ) or with hdac inhibitors ( kawano et al ., 2004 ; yu et al ., 2003 ). whether these inhibitors prevent cml relapse on sti - 571 was examined . tsa ( an hadc inhibitor ) at 1 μm alone had little toxicity on kcl - 22 cells , but when combined with sti - 571 , massive apoptosis and dramatic cell killing was observed on all dosages of sti - 571 ( fig1 a ). after ten days , cells on all dosages of sti - 571 relapsed ( fig1 a ). these results indicate that an initial rapid and massive cell killing does not necessarily prevent relapse of cml on imatinib treatment . however , the combination of aza with sti - 571 while killing cells more slowly than tsa , did successfully block relapse on 2 . 5 and 5 μm ( fig1 b ). when aza , tsa , and sti - 571 were all combined , initial rapid cell death occurred due to the presence of tsa and relapse was blocked on 2 . 5 and 5 μm of imatinib due to the presence of aza ( fig1 c ). tsa and aza alone or in combination could not reactivate hic1 expression or reduce sirt1 level despite their effects on kcl - 22 cells . this is in contrast to hic1 reactivation by these drugs in carcinoma cells ( narayan et al ., 2003 ; rathi et al ., 2003 ), indicating that hypermethylated hic1 promoter is more difficult to reactivate in cml cells . for kcl - 22m cells , tsa had no effect on cell growth , whereas 1 μm aza inhibited its growth but did not promote significant cell death . the combination of 1 μm aza with 50 μm sirtinol induced partial cell death ( fig1 d ). using the acquired resistance model described herein , the effects of sirtinol and tsa was further investigated using clonal cells . these clones of kcl - 22 cells develop acquired resistance to imatinib through different mutations in three clones ( e255k for clone l1 , y253h for clone l7 and t315i for clone ag11 ) and non - mutation mechanism in clone ag3 ( fig3 ) ( yuan et al ., 2008 ). as shown in fig1 a and 12b , the combination of sirtinol with 2 . 5 μm imatinib blocked relapse in all four clones ; in contrast , all clones relapsed on the combination of tsa with imatinib . clone ag3 , developed resistance through non - bcr - abl mutation mechanism by 2 . 5 μm imatinib alone , but developed resistance through t315i mutation upon the combined imatinib and tsa treatment . these data indicate that hdac inhibitors transiently provide enhancement of cell killing , but promote genetic mutations of bcr - abl and acquired resistance . with the exception of kcl - 22 cells , no other cml cell lines are known to survive 1 μm sti - 571 treatment in serum containing culture . whether serum - free medium supplied with select growth factors provides a better culture environment for developing cml chemoresistance was determined . serum - free ( sf ) medium with insulin , transferring , epidermal growth factor ( egf ) and high density lipoprotein ( hdl ) was used . sf medium with the basic supplements ( 5 μg / ml insulin and 5 μg / ml transferring ) was sufficient to support growth of both k562 cells ( fig1 a ) and kcl - 22 cells . pre - incubation of k562 cells in sf medium with basic supplements for two days made k562 cells as refractory as kcl - 22 cells for treatment with 1 μm sti - 571 ( fig1 b , c ). sirtinol alone or in combination with sti - 571 resulted in rapid killing of both k562 and kcl - 22 cells ( fig1 c ) and no relapse over prolonged culture . sirtinol is able to overcome cml resistance in sf culture . addition of basic supplements to routine serum media also provided k562 cells transient resistance to treatment with 1 μm sti - 571 ( fig1 d ), which lasted up to two days . again , treatment with 50 μm sirtinol abolished this transient resistance ( fig1 e ). transient resistance conferred by insulin and transferrin supplement is of interest as insulin receptor is overexpressed in about 90 % primary cml cells . the key insulin downstream target phosphatidylinositol - 3 kinase ( pi3k ) is required for bcr - abl mediated transformation and inhibition of pi3k - akt - mtor pathway has been explored to overcome cml chemoresistance . sirt1 is a key gene for regulating insulin secretion and directly regulates akt downstream target foxo proteins through deacetylation . therefore , the effect of insulin itself for transient resistance to imatinib and the response of sirtinol treatment were examined . the addition of a broad range of concentrations of insulin , from 1 ng / ml to 5 μg / ml , provided about equal transient resistance of k562 to the treatment with 1 μm sti - 571 ; and again , sirtinol alone or in combination with sti - 571 abolished this transient resistance ( fig1 f ). together , these data show that activation of insulin pathway is sufficient to render cml cells transient resistance in vitro , and it can be inhibited by sirt1 inhibition . molecular basis of differential effects of sirtinol and tsa on cml chemoresistance . sirtinol inhibits nad - dependent class iii histone deacetylases ( sirtuin family ) while tsa inhibits class i and ii histone deacetylases ( hdacs ). the sirtuin family deacetylases are structurally unrelated to hdacs . both sirt1 and hdacs are involved in regulating gene transcription and post - translational deacetylation of numerous proteins . however , two inhibitors exhibit sharply different outcomes on blocking kcl - 22 relapse on sti - 571 . gene expression microarray approach was used to search for differential transcriptional regulation and to use a proteomic approach to search for differential protein acetylation profiles . the effects of these inhibitors on global gene transcription and global protein acetylation are analyzed . total rna is extracted from four groups of kcl - 22 cells : untreated , treated with sti - 571 alone , treated with sti - 571 and sirtinol , and treated with sti - 571 and tsa at three time points ( 2 , 4 and 8 days ) before relapse occurs . each sample is collected in triplicate . samples are then analyzed using affymetrix expression arrays followed by statistical analyses of gene expression changes among different groups . relevant genes are identified and rt - pcr or western blot is used to confirm their expression . the functional significance of new genes / targets in cml chemoresistance is further studied by knockdown in kcl - 22 cells similar to that described for sirt1 . total cell lysate is extracted from the four groups of kcl - 22 cells at three time points as described for the expression array . lysates are immunoprecipitated with anti - acetylated lysine antibody and bound proteins are eluted for gel electrophoresis . the gel is stained with coomassie and differential bands are sliced for mass - spectrum analysis . once key acetylation targets are identified , they are verified individually by immunoprecipitation and western blot . the following antibodies for protein analysis by western blot are used : rabbit monoclonal anti - sirt1 ( 1 : 5000 , epitomics ), rabbit polyclonal anti - pgc - 1a ( 1 : 1000 , chemicon ) and anti - gapdh ( 1 : 5000 , trevigen ). acquired resistance through secondary mutations on the targeted oncogenes are also predominant in other cancers , such as c - kit receptor and the platelet - derived growth factor receptor ( pdgfr ) in gastrointestinal stromal tumors , and epidermal growth factor receptor ( egfr ) in non - small cell lung cancer ( nsclc ). sirt1 in nsclc resistance with and without secondary mutations would be assessed in cell lines h3255 and h1650 . the h3255 line carries activating mutation l858r and the h1650 cells carry activating deletion ( e746 - a750 ) on the egfr kinase domain , which render these cells sensitive to treatment with egfr inhibitors gefitinib and erlotinib . both cell lines can relapse upon gefitinib treatment , and h3255 cells develop resistance with the secondary t790m mutation ( engelman et al ., 2006 . allelic dilution obscures detection of a biologically significant resistance mutation in egfr - amplified lung cancer . j clin invest 116 : 2695 - 2706 ) whereas h1650 cells develop resistance through mechanisms other than secondary mutations ( kwak et al ., 2005 . irreversible inhibitors of the egf receptor may circumvent acquired resistance to gefitinib . proc natl acad sci usa 102 : 7665 - 7670 .) a previous h1650 resistance model was derived by exposing cells directly to 20 μm gefitinib and a h3255 model was derived by exposing cells to gradually increasing concentrations of gefitinib ( starting with 40 nm ) for a few months . for patients receiving gefitinib 250 mg / d , the mean steady - state plasma concentration of the drug ranges from 0 . 4 to 1 . 4 μm , and higher concentrations of gefitinib result in off - target effects and toxicity ( cohen et al ., 2004 . united states food and drug administration drug approval summary : gefitinib ( zd1839 ; iressa ) tablets . clin cancer res 10 : 1212 - 1218 ; baselga et al ., 2002 . phase i safety , pharmacokinetic , and pharmacodynamic trial of zd1839 , a selective oral epidermal growth factor receptor tyrosine kinase inhibitor , in patients with five selected solid tumor types . j clin oncol 20 : 4292 - 4302 .). these previous methods did not use therapeutically effective concentrations of gefitinib . the nsclc model provided herein employs approaches as those used in the described cml model studies . 2 . 5 × 10 5 cells of h3255 or h1650 per well are seeded in 6 - well plates . multiple wells of each cell line are plated to allow sampling of cells at different time points . after overnight seeding , cells are treated with 1 μm gefitinib , or a therapeutically effective dose . the drug is maintained in the culture until cells relapse and re - grow as described for the cml studies . fresh medium is supplied to restore the original volume during the prolonged culture as needed . relative cell numbers are measured at various time points by staining cells with crystal violet and quantifying cell mass with infrared imaging system . the relapsed cells are expanded and tested for their resistance to gefitinib as compared to parental cells . total rna is extracted for synthesis of cdna and sequencing of egfr kinase domain ( exons 18 - 24 ), and genomic dna is extracted for direct sequencing to verify mutations detected by cdna sequencing using primers described previously ( pao et al ., pnas 101 : 13306 - 13311 , 2004 ). because h3255 harbors more than 40 copies of egfr that results in allelic dilution of the t790m mutation , a mutant - enriched pcr sequencing assay is used to detect the mutation . ( inukai et al ., cancer res 66 : 7854 - 7858 , 2006 ). briefly , after round one of amplification of both wild type and mutant alleles , the wild type pcr products are selectively cleaved by restriction enzyme bstui , which allows second round preferential amplification of the mutant allele for sequencing . the mutant - enriched pcr sequencing assay can detect one mutant allele among 1000 copies of wild type alleles , and thus is sensitive enough for analysis of t790m mutation in h3255 cells . using the above described method , genetic mutants in the nsclc acquired resistant cells are identified . sirt1 expression levels in lung cancer cells are assessed . sirt1 protein level was previously found increased in lung cancer cell lines h460 and h209 that bear wild type egfr . sirt1 expression in h3255 and h1650 cells before and after relapse , as compared to normal human lung lysates , is analyzed by western blot . combination treatment of sirtinol at various concentrations with 1 μm gefitinib may enhance apoptosis and inhibit growth of h3255 and h1650 cells . the apoptosis is analyzed by tunel staining and growth inhibition analyzed by crystal violet staining described above . the combination of the two drugs to block relapse of these two cell lines are examined for the prolonged culture up to two months . third , mock and sirt1 knockdown are generated in h3255 and h1650 nsclc cells using lentiviral shrna vectors developed for cml resistance studies as described above . the knockdown of sirt1 is confirmed by western blotting . whether sirt1 knockdown delays or blocks relapse of nsclc cells upon gefitinib treatment is examined . to develop a potent sirt1 inhibitor , a pharmacophore model of sirt1 inhibitors for the substrate binding pocket of sirt1 ( fig4 a ) was developed based on a sirtuin ligand database having 233 compounds specific to all sirtuin pockets . these highly conserved sirtuin pockets are based on small sirtuin protein crystal structures that show three pockets in each sirtuin protein for zinc ( zn ), nicotinamide adenine dinucleotide ( nad ) and a substrate . sirt1 is about twice larger than other sirtuins and there is no crystal structure currently available . the pharmacophore model was validated by selective identification of effective inhibitors for the sirt1 substrate binding pockets after query of the ligand database . using this pharmacophore model a search of a ncl library that included 250 , 253 compounds via unity ( sybyl ) 3d flexible database was performed . this search , coupled with active compound references , leadlikeness and diverse structure representation , led to the identification of a top hit list of 23 inhibitor compounds . using the culture model for cml acquired resistance described above , these inhibitor compounds were tested to determine their ability to block cml cell relapse . four of the identified compounds tested ( ncl compounds # 163580 , 261408 , 628445 , and 687305 ), were more effective in preventing cml cell relapse upon imatinib treatment than an effective dose of sirtinol . the effective dose of sirtinol that was used in this study was 50 μm . compounds 628445 and 163580 were chosen as models to search for similar compounds against the ncl database because the structure of compound 687305 could not be confirmed by mass spectrum analysis and the compound 261408 was found too toxic to cells . compounds derived from the 628445 search did not exhibit improvement of inhibitory activity . a similarity search for compound 163580 resulted in 17 potential ncl compounds , 12 of which were available for testing ( fig5 ). nine of these 12 compounds derived from the similarity search of compound 163580 showed a significantly improved ability to block cml relapse with working concentrations as low as 1 μm ( fig4 b ). most of them were water soluble and had a structural feature distinct from other known sirt1 inhibitors , as described further below . as shown in fig5 , eight of these nine improved compounds exhibited two structural moieties in common : naphthol (# 22 ) at one end and isonicotinamide (# 24 ) or a similar structure at the other end . these two moieties were connected through a hydrophilic linker containing two - nitrogen bond . consistently , the other four compounds lacking the isonicotinamide - like moiety did not exhibit an improved inhibitory activity (# 27 , 39 , 40 ) or exhibited only moderate improvement (# 28 ). the compounds also showed sirt1 inhibitory effects . for example , compounds # 22 [ n ′-(( 2 - hydroxyl - 1 - naphthyl ) methylene ) isonicotinohydrazide ] and # 24 [ n ′-( 1 -( 1 - hydroxy - 2 - naphthyl ) ethylidene ) isonicotinohydrazide ] outperformed sirtinol and tenovin - 6 as analyzed by a fret ( fluorescent energy transfer )- based biochemical assay ( fig4 c ) and cell - based analysis of acetylation of foxo1 , a cellular substrate of sirt1 ( fig4 d ). in sum , the addition of isonicotinamide or a similar structure to the naphthol structural base would likely increase the inhibitory activity . further , isonicotinamide was shown to antagonize the effect of nicotinamide by blocking base - exchange step of sirtuin deacetylation reaction in mm concentration ( sauve et al . 2005 ). however , it is noted that isonicotinamide is not a per se requirement as it only exists in compounds # 22 and # 24 . therefore , it is likely the isonicotinamide - like structure feature that is important for the compounds . in addition , a sirt1 catalytic core structure was constructed by homology modeling based on human sirt2 structure ( pdb id 1j8f ), and docking the compounds to the sirt1 homology model indicated that these inhibitors bound at the substrate binding pocket ( fig4 e ). surprisingly , these compounds could also be docked into the nad + binding pocket ( fig5 ). however , docking into the nad binding is consistent with the presence of the moiety of isonicotinamide - like structure in these compounds , showing that this moiety may block nad + binding , nad + usage , or interfere with base - exchange and deacetylation steps through the nad + binding pocket . given that inhibitors from individual binding pockets are generally weak , simultaneous blocking substrate and nad + binding may have a synergistic effect on sirt1 inhibition . optimization of lead compounds into a potent sirt1 inhibitor as a candidate anticancer drug . optimization of lead compounds is carried out by two complimentary approaches : improvement of the pharmacophore and isothermal titration calorimetry . optimization by improving pharmacophore . structure - activity relationship ( sar ) analysis is carried out on the lead ncl compounds identified through preliminary screens , as well as on compounds collected from literature . the pharmacophore model is optimized . a focused compound library consisting of 30 to 40 compounds is designed based on the sar study and the improved pharmacophore model . all compounds are synthesized by the city of hope synthetic chemistry core . synthesized compounds are first screened for their effective concentrations to block development of the bcr - abl t315i mutation using the cml kcl - 22 cell culture model described above ( yuan et al ., 2010 ). kcl - 22 cells in liquid culture are treated with 2 . 5 μm imatinib and various concentrations of sirt1 inhibitors alone and in combination . cells are monitored for cell death and relapse , and the lowest concentrations of compounds that block relapse on imatinib in two to three weeks are identified , and confirmed with prolonged culture . the ability of the compounds to block other bcr - abl mutations is similarly performed using three kcl - 22 clonal cell lines previously developed ( yuan et al ., 2010 ). inhibition of recombinant sirt1 deacetylase activity is performed using a fret - based sirt1 activity assay ( cayman chemicals and cisbio ) that does not produce altered substrate - sirt1 interaction , and ic 50 of each compound is determined . to further validate non - isotopic biochemical assay , 3 h labeled acetylated histone peptide ( millipore ) is used as a substrate for sirt1 deacetylation assay . the released 3 h labeled acetate after the reaction is exacted and quantified by scintillation . sirt1 inhibitor - induced acetylation of cellular sirt1 substrates , ku70 and foxo proteins , are determined by immunoprecipitation of these proteins followed by western blot analysis for acetyl lysine . acetylation of foxo1 is also directly examined by flow cytometry - based analysis as done in fig4 d . next , cross reactivity of an inhibitor to hdacs and other sirtuins is examined using commercially available deacetylase assay kits ( biomol and millipore ). a second round of optimization is optionally performed . a further refined pharmacophore model may be deduced on the basis of the above studies of the designed compounds . the 3d pharmacophore search may be used to query an 80 , 000 - diverse compound library purchased by city of hope and the ucsf zinc 13 million purchasable compound library to identify similar compounds for lead optimization . about 30 - 50 compounds with predicted favorable admet properties are synthesized and biological tests are carried out as described above . three - dimensional quantitative structure activity relationship ( 3d qsar ) models are built for compounds whose ic 50 for sirt1 is determined . the predictive power of the qsar correlation is used to estimate the bioactivity for new compounds and to guide the modification and refinement of existing structures to obtain optimal activity . optimization by isothermal titration calorimetry ( itc ). itc is an emerging technique for drug discovery . itc determines the enthalpy change associated with binding and provides a complete thermodynamic profile of the interaction , including binding affinity , number of binding sites , entropy change , and gibbs energy of binding ( ladbury et al .). this approach offers an advantage for lead compound optimization in the absence of sirt1 crystal structure . itc study of the compounds is carried out at the city of hope x - ray crystallography core using ta instruments nano itc low volume . for these measurements , the sirt1 ( 200 μl ) is titrated ( 25 injections ; 2 . 5 μl each ) with each inhibitor . the concentrations of the ligand and receptor are optimized to ensure accurate fitting ( e . g ., a clear sigmoidal curve ). in addition , the ligand is titrated into the buffer to account for heat of dilution and subtracted from the ligand - receptor titration . the data is processed using the ta software package . the thermodynamic profiles obtained from these compounds guide modification to obtain a high affinity and specific sirt1 inhibitor , i . e . compounds optimized for a more favorable ( negative ) enthalpy change or a more favorable ( positive ) entropy change to improve affinity and selectivity for sirt1 . new compounds are then synthesized for further itc measurements , followed by cell - based analyses as described in the above section . alternative methods . an all - around docking algorithm has been designed to perform docking of the designed compound library cross - validated by qsar and itc analysis results into the predicted binding sites on the sirt1 structure model . the protein - ligand binding free energies may be generated from charmm molecular dynamic ( md ) simulation by implementing enhanced - sampling algorithms ( li et al ., 2007 ; li et al ., 2006 ). the best predicted ligand binding mode then leads the optimization of improving binding affinity and the specificity . drug specificity and inhibition mechanisms may be studied structurally and biologically as follows : ligand binding mode . ligand binding mode shows how the inhibitor interacts with the protein . a homology model of sirt1 has been built based on the structure of sirt2 that shares more than 70 % sequence homology for the substrate binding pocket . the lead compounds are examined by docking analysis with the sirt1 homology model using sybyl ( tripos ) and glide ( schrodinger ) software , followed by molecular dynamic simulation . the docking and free energy component analysis will reveal amino acids of sirt1 that interact with the compounds . as shown above in fig4 e , docking of compound # 22 results in hydrogen bonding with residues ser370 , lys408 , glu416 , and asn417 of sirt1 were identified , and energetically favorable hydrophilic interactions were predicted between the compound and the substrate binding pocket . the conserved amino acids of sirt1 that interact with most compounds docking into the substrate binding pocket are identified . the predicted ligand binding pocket and binding mode are validated by mutant sirt1 proteins generated by site - directed mutagenesis , the itc studies described above , and biacore analyses . biacore is another quantitative assay for specific interaction between a ligand and a protein immobilized on a sensor surface . biacore analysis is performed at the city of hope high throughput screen core . the ligand binding pocket and the binding mode are further validated once the structure for sirt1 catalytic core domain or a larger fragment is obtained . the ligand binding mode also guides the lead optimization to improve binding affinity and selectivity as described above . crystallography study of sirt1 inhibition . the structures of several si rt1 homologous proteins are available ; however , the crystal structure of sirt1 , either catalytic core or full length , has not been solved . sirt1 is the largest sirtuin protein with very long n - and c - termini that are flexible and difficult to be crystallized . accordingly , additional structural information for sirt1 enhances understanding of precise drug inhibition mechanism and efforts to determine specificity of sirt1 inhibitors . first , different constructs are expressed by creating a his - tagged smt3 - sirt1 fusion . the n - terminal smt3 typically improves expression and permits highly specific cleavage of the tag by the smt3 specific protease , ulp1 , as previously described ( mossessova et al ., 2000 ; sun et al ., 2009 ; ahmed et al ., 2010 ). initially , a fragment that spans the catalytic core ( residues 220 - 494 based on blast searches of sirt1 and the pdb ) and full - length protein are generated . recombinant sirt1 is expressed in bacteria and purified using standard chromatographic methods . briefly , the clarified lysate is passed over a ni - nta column , washed extensively , and eluted with imidazole , and the smt3 tag is cleaved with histag - ulp1 and dialyzed . a second ni - nta column removes the smt3 and ulp1 . the cleaved sirt1 protein is concentrated and passed over a size exclusion column ( superdex g75 ). progress is monitored by sds - page . an ion - exchange column is used if additional steps are required . approximately 5 to 100 mgs of protein are typically generated using this system . in addition , limited proteolysis techniques are used on the full length protein to experimentally define the molecular boundaries of a stable construct . briefly , the purified full length sirt1 is exposed to papain and subtilisin at different concentrations for a defined period . sds - page is used identify stable fragments . these fragments are excised from the gel and subjected to n - terminal protein sequencing and mass spectrometry . new constructs are generated , expressed and purified based on this information . deacetylase activity of truncated sirt1 is validated by biochemical assays as described above . next , a generate crystal structure of the stable si rt1 fragments are generated in the presence and absence of an inhibitor or an acetylated p53 peptide . crystallization and structure determination are performed at the city of hope x - ray crystallography core . specifically , a mosquito crystallization robot is used to generate 200 ml drops for each condition . each screen ( 4 are initially tested ) consists of 96 different crystallization conditions . crystallization trials are monitored robotically using the formulatrix rock imager at 4 ° c . and 22 ° c . ( in total , 768 conditions are initially tested per sample ). promising leads are optimized and the diffraction properties of each lead are tested . the data is collected and analyzed . the apo structure , acetylated peptide bound and inhibitor bound structures are analyzed , and compared to known sirt2 , sirt3 and sirt5 structures . common and unique features of sirt1 crystal structures for substrate and inhibitor binding are identified . successful determination of the structure will point to residues that are important for ligand and inhibitor binding . this structural information is used to improve the sirt1 homology . residues that are important for inhibitor binding are confirmed by site - directed mutagenesis . deacetylase activity of mutant proteins is measured as described above , and interaction of mutant proteins with compounds is characterized by itc as described above . mechanisms of target inhibition in lsc . next , the effects of in vitro inhibitor treatment on acetylation of sirt1 targets in human cd34 + cml cells are examined . human cd34 + cml cells are isolated and cultured in vitro using a protocol previously described ( bhatia et al ., 2003 ; holtz et al ., 2002 ). acetylation of p53 and foxo proteins upon inhibitor treatment is analyzed by western blotting , or by flow cytometry based assay as described above . the ability of inhibitors to selectively alter gene expression associated with sirt1 signaling is evaluated by microarray analysis . affymetrix genechip human genome u133 plus 2 . 0 arrays were used to analyze gene expression changes in lsc upon imatinib and hdac inhibitor treatment ( zhang et al ., 2010 ). sirt1 related gene expression patterns are determined by analysis of expression changes in cd34 + cml cells following sirt1 shrna knockdown . gene set enrichment analysis ( gsea ) is used to determine pathways significantly altered by sirt1 expression . connectivity map ( cmap ) ( lamb et al ., 2006 ) is used for the gene signatures derived above to explore the functional connection of genetic perturbation and drug activities . signaling pathways affected by specific sirt1 inhibitors should significantly overlap with those by sirt1 shrna knockdown , but should be distinct from those affected by hdac inhibitors ( zhang et al ., 2010 ). in vivo target inhibition specificity is examined as described below . alternative methods . another approach that may be used is to mutate surface residues with high entropy ( e . g . predicts residues 235 - 238 within the catalytic core should be mutated to alanines — http :// nihserver . mbi . ucla . edu / ser /). in addition , the sirt2 and other sirtuin homologues may be used to identify productive crystal contacts ( n . b ., the human sirt2 homologue diffracted to 1 . 7 å ). in both cases , site directed mutagenesis is used to modify these residues and the assays described above are used to ensure that these mutations do not affect the activity . functional constructs are subjected to similar crystallization trials . determination of the efficacy for eradicating leukemia stem cells ( lsc ) in a mouse model of cml . in vivo drug treatment . the protocol for bone marrow transduction and transplantation is performed as previously described ( pear et al ., 1998 ). briefly , donor mice were primed by 5 - fluorouracil 3 days before harvest . bone marrow cells were transduced with retroviral vectors by co - sedimentation . typically , 2 . 5 × 10 6 transduced mononuclear cells are transplanted to each recipient . a typical study consists of four groups of mice : vehicle , imatinib , sirt1 inhibitor , and imatinib plus sirt1 inhibitor , with 12 mice per group . drugs are given for 10 consecutive days , beginning on day 10 after transplantation as described ( wolff et al ., 2001 ). imatinib is administered orally 50 mg / kg in the morning and 100 mg / kg in the afternoon with 8 hours apart . two of the lead compounds discussed above are used to set up assays initially . pharmacokinetics is performed as described below to determine the optimal drug doses and delivery routes before they are used for treatment . two doses ( or routes ) each inhibitor are examined . after 10 day treatment , peripheral blood is collected and analyzed by differential blood cell counts using hemavet ( drew scientific ) to determine the effects of the drug treatment . mice are monitored for up to six months , and kaplan - meier survival analysis is performed with log - rank test used for calculating statistical significance . eradication of leukemia stem cells . cml stem cells are identified as a fraction of side population ( gfp + ckit + cd34 − hoe − ) in babl / c background ( hu et al ., 2006 ). to determine if sirt1 inhibitor treatment eradicates lsc , bone marrow of the above described cml mice in different treatment groups is harvested . lineage positive cells are depleted using immunomagnetic beads ( easysep , stem cell technology ). the enriched cells will then be labeled with hoechst 33342 , cd34 and c - kit for lsc analysis as shown in the preliminary studies . to further examine the eradication of cml stem cells , serial bone marrow transplantation is performed by transplanting 5 × 10 6 bone marrow cells from mock and drug treated groups into lethally irradiated secondary recipients . the disease development and lsc is examined similarly as in primary recipients . the same regimen of drug treatment is tested in normal mice to determine impact of drugs on normal hsc . mechanisms of in vivo drug treatment . the effect of drug treatment on cell cycle and apoptosis of lsc is examined . lsc is labeled with pyronin y and hoechst 33342 to identify g0 and 01 population . apoptosis of lsc is monitored by annexin v staining . to determine the in vivo target specificity of a sirt1 inhibitor in mouse lsc , microarray - based gene expression analysis is carried out by the city of hope functional genomics core and division of biostatistics . mock and bcr - abl transformed hsc is isolated from sirt1 +/+ and sirt1 −/− mice to identify the altered signaling pathways by sirt1 knockout using affymetrix mouse 430 2 . 0 arrays coupled with a molecular amplification technique developed in the core for analyzing small number of cells . since lsc in sirt1 −/− mice are few , lsc may be harvested from bone marrow and spleen , and pool lsc from 5 to 10 mice for the assay if necessary . gene expression profiling will then be performed on lsc derived from wild type cml mice immediately after 10 - day treatment with sirt1 inhibitors or vehicle , 8 mice each . sirt1 inhibitor - induced signaling pathway alteration is compared with sirt1 knockout to determine if the inhibitor selectively inhibits sirt1 signaling in vivo . determination of the efficacy for killing human leukemia stem cells in vitro and in vivo . in vitro assays . cd34 + cells are isolated from samples from cml patients who have not received imatinib and normal healthy controls using immunomagnetic columns ( miltenyi ). cd34 + cd38 − and cd34 + cd38 + cells are selected using flow cytometry sorting . cells are cultured in medium supplemented with low concentrations of growth factors , with the following treatments : ( i ) no treatment , ( ii ) sirt1 inhibitor alone , ( iii ) imatinib alone , and ( iv ) sirt1 inhibitor combined with imatinib . cell proliferation is examined by 5 -( and 6 -) cfse labeling and apoptosis by annexin - v labeling . a proliferation index ( pi ) is calculated based on the cfse fluorescence profile as described previously ( bhatia et al ., 2003 ; holtz et al ., 2002 ). the percentage of annexin v + cells for total as well as dividing and non - dividing cells ( cfse low and high respectively ) is calculated . colony forming cells ( cfc ) assays are performed by plating cells in methylcellulose progenitor culture for 14 - 18 days . a similar approach is used to study the efficacy of the drug on aml stem cells using samples from newly diagnosed untreated aml patients . in vivo studies . to analyze the effect of drug treatment on cml and normal human hsc capable of initiating multilineage engraftment in nod / scid mice [ scid - repopulating cell ( src )], the nod / scid - il2rγ chain ko ( nsg ) model that supports improved engraftment of human hematopoietic cells is used . although larger numbers of cml cells are required to establish engraftment in nsg mice compared to normal cells , it has been found that engraftment with bcr - abl + cells is consistently observed and can be reproducibly measured . this assay has been used to demonstrate targeting of cml src by hdac inhibitor and imatinib combination ( zhang et al ., 2010 ). cml and normal human cd34 + cells ( cml 1 × 10 6 per mouse , normal 2 × 10 5 cells / mouse ) are exposed in vitro to a sirt1 inhibitor , imatinib or the combination of the two agents are followed by injection into sublethally irradiated ( 300 cgy ) 8 week nsg mice via tail vein injection . blood samples are obtained to monitor human cell engraftment 4 weeks after injection ( by flow cytometry for human cd45 + cells ). at 8 - 12 weeks animals are euthanized and marrow content of femurs and tibiae , spleen cells and blood obtained . human cell engraftment is analyzed by flow cytometry after labeling with anti - human cd45 antibody . specific human cell subsets are detected with antibodies to human cd34 , cd38 , cd14 , cd11b , cd33 , glycophorin a , cd19 and cd3 . the proportion of bcr - abl + human cells is evaluated by q - pcr analysis of cells engrafted in mouse tissue for bcr - abl and bcr ( human ) levels . a similar approach is used to analyze the effects of drug treatment on aml stem cells . four lead compounds from each round of optimization discussed above are tested for pk and toxicity . determination of the maximum tolerated dose ( mtd ) and toxicity . the initial dose will start with the equivalent to ic 50 dose of sirt1 inhibitors in vitro via intravenous ( iv ) injection . all animals are monitored for 4 hr immediately following administration of the inhibitor and will continue to be monitored for 1 week to observe for signs of delayed toxicity , which includes loss of appetite , changes in waste elimination , hunched posture , coat ruffling , eye crustiness , and changes in activity level . the mice will also be weighed 24 hr post - treatment , and animals that lose 20 % or more of its body weight are euthanized . dose escalation ( by 1 . 5 fold increase ) or reduction ( by ⅓ ) is carried out until the mtd is reached or until solubility limits the procedure . once single dose mtd is identified , multi - dose studies are carried out accordingly . pk determination . a three - phase single - dose pk study is performed in mice at the mtd following intravenous ( iv ) or oral administration to determine the half - life ( t 112 ) of the sirt1 inhibitors . blood samples are collected at different time points ( 0 . 25 - 48 hours ) for lc - ms analysis of drug concentrations . once the t 1 / 2 is determined , phase 2 pk studies are conducted to characterize the dose - dependent pks , volume of distribution ( vd ), clearance ( cl ), maximal drug concentration ( c max ), and the systemic bioavailability following both iv and oral single - dose administrations . phase 3 pk studies will collect normal tissues for an assessment of drug distribution . alternative methods . a sirt1 inhibitor for in vivo use must also consider factors such as stability , clearance , toxicity and solubility , so metrics such as formulation , pk , toxicity , and efficacy data are used to guide further chemical modifications to optimize inhibitors and to choose additional backup inhibitors . the references listed below , and all references cited in the specification above , are hereby incorporated by reference in their entirety , as if fully set forth herein . american cancer society , cancer facts . 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referring to fig1 and 2 , there is shown waste gated turbocharger apparatus 1 comprising a turbine housing 4 with a control rod 5 in a bush 8 , and a spring 7 between the bush 8 and a control lever 10 . the bush 8 has a first end 8 a and a second end 8 b . as can be seen , the bush 8 comprises a solid cylindrical portion . and a bore which extends through the solid cylindrical portion and which is defined by an inner surface of the solid cylindrical portion . the inner surface being in direct contact with the control rod 5 . also shown are wear washers 21 and 26 and waste gate 31 . fig2 also shows an actuator control 28 , a turbine 40 , an exhaust exit chamber 52 , and second inlet 53 . when exhaust gas enters through the second inlet 53 into the volute in the turbine housing 4 , the exhaust gases rotate the turbine wheel 40 . the turbine wheel speed is controlled by opening the waste gate 31 . this is done by rotating the control rod 5 by movement from control lever 10 . the exhaust gases then bypass the turbine 40 . the gases that have passed through the turbine wheel 40 and the waste gate 31 enter into the exit chamber 52 where they are forced into the exhaust system . the sealing system prevents exhaust gases from leaking from the turbocharger apparatus and has been designed so exhaust gases do not leak past the bush 8 so all of the exhaust gases may be treated by the exhaust after - treatment system . it must be remembered that the temperature of the turbine housing 4 can be over 1000 ° c and so the design has to work when the parts have expanded due to high temperature , and prevent gas leakage , and control the wear of moving parts . this has been done by pulling a spring load between the control rod 5 and the bush 8 the second end 8 b of the bush 8 and control rod 5 may be sealed . the spring 7 is mounted on the outside of the turbocharger apparatus 1 in order to prevent heat soak to spring 7 . where washers 21 , 26 have been positioned between the control rod 5 and bush 8 . these wear washers may be made of a material which can withstand very high temperature , and have low wear rates and corrosion resistance , such as ceramics . one problem with these materials is that the expansion rates are sometimes different from the materials that are used within other parts of the turbocharger , and so the design has to allow for different expansion rates in order to prevent gas leakage . the wear washers should be prevented from rotation on the parts that they are mounted on . in order to solve this problem , a square hole may be used in the bore of the wear washers . this locates on a square section of the bush 8 and on the control rod 5 . the spring 7 compensates for wear and different expansion rates in the system , as well as preventing exhaust gas leakage . in fig3 , the wear washers 21 , 26 also prevent wear on a fork 70 and a bush 8 . in fig4 the wear washers 21 , 26 also prevent wear on a lever 23 and the bush 8 . when the control rod 5 rotates , the control rod only has to rotate up to about 20 ° so when a coil spring is used this movement is taken up in the coil of the spring so the spring does not rotate . referring now to fig3 - 8 , there is shown in fig3 a variable turbocharger apparatus 2 of a sliding piston design whereby the piston ( not shown ) slides over the turbine wheel 40 in order to control the speed of the turbine wheel 40 . a fork 70 may be used to move the piston . fig3 shows that the same type of sealing system as in fig1 may be used with this type of variable turbocharger design . fig4 shows vnt type variable turbocharger apparatus 3 whereby exhaust gases are prevented from leaking from the turbocharger apparatus . fig4 shows vnt type turbocharger apparatus 3 with a first inlet 39 , an outlet 36 in a compressor housing 91 , a bearing assembly 82 , a oil inlet 78 , and an oil outlet 79 . also shown are a turbine housing 4 , a turbine 40 , a control lever 10 , a control rod 5 , bush 8 , a spring 7 , and an inner control lever 23 , with control ring 55 , and vanes 58 , with volute 96 , and a sealing plate 18 . when the exhaust gases pass through the volute 96 of the turbine housing 4 of the vnt turbocharger apparatus 3 , the gases pass over the vanes 58 that are mounted within the turbine housing 4 . these vanes 58 rotate to control the gas flow to the turbine 40 . this in turn controls the speed of the turbine 40 . the control of the vanes is by movement of the control lever 10 . this rotates the control rod 5 in the bush 8 to position the inner control lever 23 . the inner control level 23 is mounted in a slot in the control ring 55 which rotates when movement is applied to the inner control lever 23 . this in turn moves a lever ( not shown ) that is mounted on the end of the vane shaft 42 . this rotates the vanes 58 . the volute chamber 96 is sealed in order to try and prevent gas leakage from the turbocharger apparatus as can be seen with seal plate 18 . however , one of the problems with the vnt type turbocharger apparatus is exhaust gas leakage past the vanes along the vane shaft 42 into chamber 19 . this allows exhaust gas leakage from the turbocharger apparatus . in order to prevent this leakage , the same type of seal design as shown in the turbocharger apparatus of fig1 and the turbocharger apparatus 2 of fig3 may be used . fig5 shows vnt type turbocharger apparatus as shown in fig4 , with the same numbers as shown in fig4 . except where the turbocharger apparatus in fig4 uses a coil - type spring 7 , the spring in fig5 is a disc spring 15 . this type of spring helps prevent leakage . more specifically , the disc spring 15 has an inner concave area which , when the disc spring 15 is put under load , enables exhaust gas sealing at the first end 8 a of the bush 8 by preventing exhaust gas leakage past the inner concave area . this inner concave area is shown in fig5 . the disc spring 15 abuts against abutment means 17 which provides a continuous uninterrupted surface through which the exhaust gases cannot pass under all working conditions of the turbocharger apparatus 3 . fig6 shows a sealing system using the disc spring 15 . fig7 shows two different alternative designs for the wear washers 21 and 26 . these may be used in the sealing system . the square hole in one design and the slot in the other design are set into the bore of the wear washers so to prevent rotation of the wear washers when they are mounted on the control rod 5 and / or the bush 8 . fig8 shows a third design for the wear washers 21 , 26 where the wear washer is located in a slot to prevent rotation . referring to fig9 and 10 , there are shown two wear washers 100 , 102 . the wear washer 102 has a reduced diameter portion 104 . the reduced diameter portion 104 engages the wear washer 100 and gives less friction between the two wear washers 100 , 102 than would be the case if the entire adjacent surface of the wear washer 102 engaged the adjacent surface of the wear washer 100 . fig1 and 12 show two wear washers 106 , 108 in which the wear washer 106 is provided with a chamfered portion 110 . the wear washer 108 is provided with a complementary portion 112 which may be a chamfer or radius . contact between the two portions 110 , 112 may give a reduced frictional contact area than would be the case if the two wear washers 106 , 108 engaged each other over their entire adjacent surfaces . in fig1 - 12 , a turbocharger sealing systems are shown for preventing exhaust gas leakage from turbocharger apparatus that can work under extreme temperature conditions , and the turbocharger sealing system is able to adjust for wear within the turbocharger apparatus . it is to be appreciated that the embodiments of the invention described above with reference to the accompanying drawings have been given by way of example only and that modifications may be effected . thus , for example , due to the location of the sealing system on the vnt turbocharger apparatus , where the sealing system is better protected from heat , the wear washers may be of a different design , e . g . only one wear washer may be used or the sealing may be done without wear washers . | 5 |
referring to fig1 to 8 , the palm wrench the of the present invention comprises a c - shaped body 10 , a driving head 30 , two pivots 40 , two first resilient members 50 , a first bead 60 and a second resilient member 61 . the body 10 includes an inner periphery 13 and an outer periphery 14 , and has an opening 15 . a dent 17 is defined in the inner periphery 13 of the body 10 . two apertures 11 are respectively and diametrically defined in the inner periphery 13 of the body 10 . each aperture 11 communicates with a sink hole 12 defined in the outer periphery 14 of the body 10 . a line between the center of the opening 15 and the center of the dent 17 is perpendicular to the line between two respective centers of the two apertures 11 . multiple notches 16 are defined in the outer periphery 14 of the body 10 so that the user can easily grape the body 10 . the gap 21 is defined as the distance between the two outer ends of the two apertures 11 . the outer diameter 23 of the body 10 is between 45 mm to 75 mm . the distance of the gap 21 is larger than the inner diameter 22 of the inner periphery 13 of the body 10 , but is less than the outer diameter 23 of the outer periphery 14 of the body 10 . the ratio between the width 24 of the opening 15 and the inner diameter 22 of the inner periphery 13 of the body 10 is 0 . 5 : 1 to 0 . 9 : 1 , preferably , 0 . 6 : 1 to 0 . 8 : 1 . the best ratio is 0 . 7 : 1 . the driving head 30 has two pivotal holes 31 defined diametrically therein . the diameter of the pivotal holes 31 is the same as that of the apertures 11 . the outer diameter of the driving head 30 is smaller than the inner diameter 22 of the inner periphery 13 of the case 10 . each pivotal hole 31 co - axially communicates with a passage 32 which has inner threads 33 defined therein . the driving head 30 has a first function end 34 and a second function end 341 on two ends thereof . the first function end 34 and the second function end 341 each are rectangular protrusions of different sizes so as to be connected with a socket , an adapter or an extension rod . the driving head 30 has at least one first hole 35 defined in the outer periphery thereof and the at least one first hole 35 is located corresponding to the dent 17 . the two pivots 40 each have a head 44 , a stem 41 extending from the head 44 and a shank 42 extending from the stem 41 . the stem 41 has outer threads 43 defined in the outer periphery thereof . each pivot 40 extends through the aperture 11 with the stem 41 loosely extending through the aperture 11 . the shank 42 extends through the pivotal hole 31 and the passage 32 . the outer threads 43 are threadedly connected to the inner threads 33 . the head 44 is accommodated in the sink hole 12 . the driving head 30 is rotatable about the two pivots 40 relative to the body 10 . the two first resilient members 50 such as springs , are respectively located in the two apertures 11 of the body 10 and the pivotal hole 31 of the driving head 30 . the two first resilient members 50 are respectively mounted to the two shanks 42 of the two pivots 40 so as to be biased between the inner end of the pivotal hole 31 and the stem 41 . the two first resilient members 50 and the two pivots 40 are located symmetrically to the center of the driving head 30 . the first bead 60 and the second resilient member 61 are located in the at least one first hole 35 . the first bead 60 is biased by the second resilient member 61 so as to be engaged with the dent 17 to position the driving head 30 relative to the body 10 . as shown in fig8 , the driving head 30 is rotated about the two pivots 40 so as to be positioned to make the axis of the driving head 30 and the axis of the body 10 be perpendicular to each other , and the second function end 341 is located corresponding to the opening 15 . as shown in fig9 , the driving head 30 comprises a casing 301 , a rotational member 302 , a pawl 303 , a third resilient member 304 , a disk 305 , a clip 306 , a second bead 307 and a fourth resilient member 308 . the casing 301 is a ring like member and has ratchet teeth 3010 defined in the inner periphery thereof . the pivotal holes 31 , the passages 32 , and the at least one first holes 35 are located on the outer periphery of the casing 301 . the rotational member 302 is rotatably located in the casing 301 , wherein the first and second function ends 34 , 341 are respectively formed on the rotational member 302 . the first function end 34 has a groove 340 and the second function end 341 has a second hole 3410 . a semi - circular recess 3020 is defined in the rotational member 302 . the pawl 303 is located in the recess 3020 and within the casing 301 . the pawl 303 has engaging teeth 3030 defined in one side thereof so as to be engaged with the ratchet teeth 3010 . the pawl 303 has an insertion hole 3031 defined in the top thereof . the third resilient member 304 is a heart - shaped member which has a tip end 3040 and an insertion end which is formed by two ends of the third resilient member 304 . the third resilient member 304 is mounted to the first function end 34 and the insertion end is inserted into the insertion hole 3031 of the pawl 303 . the disk 305 is connected to the casing 301 and has a central hole 3050 through which the first function end 34 extends . the disk 305 has multiple ribs 3051 on the top thereof , and the tip end 3040 of the third resilient member 304 engaged with one of the ribs 3051 . the clip 306 is engaged with the groove 340 . the second bead 307 and the fourth resilient member 308 are located in the second hole 3410 . the second bead 307 is biased by the fourth resilient member 308 which is a spring . the disk 305 is rotatable about the rotational member 302 so as to drive the third resilient member 304 to move the pawl 303 within the recess 3020 , therefore , the driving head 30 is controlled to be rotated in clockwise or counter clockwise . as shown in fig1 , the driving head 30 has two first holes 35 , when the driving head 30 is rotated relative to the apertures 11 . each first hole 35 receives a first bead 60 and a second resilient member 61 therein . one of the first holes 35 is located corresponding to the opening 15 and the other one of the first holes 35 is located corresponding to the dent 17 . the pivots 40 do not have the stem 41 . fig1 to 13 show that the second function end 341 is a hexagonal recess . the pivots 40 do not have the stem 41 . as shown in fig1 , there is no dent 17 , the first hole 35 , the first bead 60 and the second resilient member 61 . the driving head 30 cannot be position when the driving head 30 is rotatable relative to the body 10 . as shown in fig1 , the first function end 34 is a polygonal recess . the driving head 30 has a handle 36 which is located in the opening 15 . the driving head 30 can be operated at any angle relative to the body 10 . when the driving head 30 is rotated at an 90 degree position relative to the body 10 , the second function end 341 faces the opening 15 , the outer periphery 14 and the outer periphery of the driving head 30 are normal to each other so that the user can easily operate the wrench . the pivots 40 each have a stem 41 and a shank 42 , the stem 41 is located in the aperture 11 , and the shank 42 is located in the passage 32 , so that the pivots 40 are well positioned . the driving head 30 can be positioned by engaging the first bead 60 with the dent 17 . in one embodiment , there are two first holes 35 and each first hole 35 has a first bead 60 and a second resilient member 61 , so that the driving head 30 can be positioned relative to the body 10 in two directions . the first and second function ends 34 , 341 allow different tools to be connected with the palm wrench of the present invention . furthermore , the opening 15 can accommodate the handle 36 of the driving head 30 or an h - shaped driving head . while we have shown and described the embodiment in accordance with the present invention , it should be clear to those skilled in the art that further embodiments may be made without departing from the scope of the present invention . | 1 |
throughout this specification , color names beginning with a small letter signify that the name of that color , as used in common speech is aptly descriptive . color names beginning with a capital letter designate values based upon the r . h . s . colour chart published by the royal horticultural society , london , england . the descriptive matter which follows pertains to 4 year old ‘ supechseventeen ’ plants on nemared ( unpatented ) rootstock , grown in the vicinity of wasco , kern county , calif ., during 2009 , and is believed to apply to plants of the variety grown under similar conditions of soil and climate elsewhere . general .— ( measurements taken on 4 year old tree unless otherwise noted .) size : medium . normal for most peach varieties . reaches a height of approximately 3 meters with normal pruning . spread : normal for most peach varieties . approximately 3 meters . vigor : moderately vigorous ; growth of about 1 . 8 to about 2 meters high during the first growing season . growth : semi - upright . productivity : productive . fruit set is usually two or more times desired amount for marketable size fruit ; thinning and spacing of fruit is necessary . form : vase formed . bearer : regular . fertility : self - fertile . canopy density : dense . hardiness : hardy in all fruit growing areas of california ; winter chilling requirement is approximately 350 hours at or below 7 . 2 c . disease resistance / susceptibility : no specific testing for relative plant disease resistance / susceptibility has been undertaken . under close observation in kern county , california , no particular plant / fruit disease resistance / susceptibility has been observed . trunk .— ( measurements at approximately 30 cm above soil line .) diameter : approximately 17 cm , varies with soil type , fertility , climatic conditions and cultural practices . texture : medium shaggy , increases with age of tree . trunk color : outer bark about light greyed - green 197d to about dark greyed - green 197a ; inner bark about dark greyed - orange 177a to about medium greyed - orange 174b . branches .— ( measurements at approximately 90 cm above soil line .) size : diameter ranges from approximately 9 cm . texture : medium shaggy ; increasing with tree age . color : branches vary from about light greyed - green 197d to about medium greyed - orange 166d . number of lenticels : medium . lenticels density : approximately 2 - 4 per cm 2 . lenticels color : about medium greyed - orange 166d . lenticels size : medium . lenticels length : approximately 3 mm . lenticels width : approximately 1 . 5 mm . flowering shoots .— ( data taken in july at midpoint of previous season shoots .) size : average diameter approximately 5 mm . color : topside : about dark greyed - orange 166b . underside : about light yellow - green 144c . internode length : medium ; approximately 11 - 16 cm . midway on flowering shoot . flowering shoot lenticels : sparse . color : about light greyed - green 196a . diameter : approximately 0 . 3 mm . flowering shoot leaf buds : shape : elliptic to conical . width : approximately 3 mm . length : approximately 4 mm . color : about medium greyed - green 197c . flowering shoot flower buds : shape : conical . width : approximately 25 mm . length : approximately 4 mm . color : about medium greyed - green 197c . number of buds per node : usually 2 . density of buds : medium . flower bud distribution : generally isolated in groups of 2 on one year old shoots . ratio of wood ( leaf ) buds to flowering shoots : 1 / 2 . leaves .— size : medium . average length : medium ; approximately 12 - 16 cm . average width : medium ; approximately 3 - 4 cm . thickness : medium . color : upper surface : about dark yellow - green 146b . lower surface : about medium yellow - green 146c . form : lanceolate . tip : cuspidate . base : v - shaped . margin : crenate . venation : pinately veined . vein color : about light yellow - green 144c to about medium greyed - orange 176d . surface texture : smooth . leaf blade ( ratio of length to width ): medium ; about 4 / 1 . shape in the cross section : concave . profile : up folded . leaf blade tip : curved downwardly . undulation of margin : slight . petiole .— average length : medium ; approximately 13 mm . average diameter : approximately 2 mm . color : about medium yellow - green 144a . stipules .— number / leaf bud : approximately 2 . typical length : approximately 7 mm . color : about dark greyed - orange 176a when dry . persistence : falls off . leaf glands .— form : reniform . average number : between about 0 and 6 ; usually between about 2 and 4 . position : on both leaf base and petiole , alternate . average size : medium ; approximately 1 by 1 . 5 mm . color : about medium yellow - green 144b . general .— flower blooming period : first bloom : approximately feb . 12 , 2009 . full bloom : approximately feb . 17 , 2009 . time of bloom : early . duration of bloom : medium ; approximately 12 days . diameter of fully opened flower : medium , approximately 40 mm . flower aroma : slight aroma . shape : rosaceous . peduncle .— length : medium ; approximately 4 mm . diameter : slender ; approximately 1 . 5 mm . color : about medium yellow - green 144a . pubescence : absent . petals .— number : 5 . arrangement : slightly overlapping . length : approximately 15 mm . diameter : approximately 9 mm . shape : oval . apex shape : rounded . base shape : narrows , cuneate . color : about light red - purple 62c , becoming darker over time . surface texture : smooth . margins : slightly undulating . claw length : short . margin waviness : weak . base angle : medium . division of upper margin : entire . pubescence of inner surface : absent . pubescence of outer surface : absent . sepals .— number : 5 . length : approximately 5 mm . diameter : approximately 3 mm . shape : triangular . color : about medium red - purple 64b outside surface . surface texture : smooth . margins : entire . positioning : touching petals when opened . pubescence of inner surface : absent . pubescence of outer surface : absent . stamens .— number : many ; usually 38 - 48 . average length : approximately 12 mm . filament color : about light red - purple 62c , darkening to medium red - purple 64b as flower ages . anther color : about medium red - purple 61b . flower pollen color : about dark yellow - orange 22a when dried . position : perigynous . pistil .— number : usually one . average length : approximately 18 mm . ovary diameter : approximately 1 . 5 mm . pubescence : none . stigma extension in comparison to anthers : usually with and above . frequency of supplementary pistils : few . receptacle .— depth : medium pubescence of inner surface : absent . pubescence of outer surface : absent . ovary .— pubescence : slight . density of hairs : dense . general .— ( description taken at the sun world research and development center near wasco , kern county , calif .) harvest : date of first pick : approximately may 4 , 2009 . date of last pick : approximately may 12 , 2009 . maturity when described .— firm - mature . season ripening .— very early . position of maximum diameter .— towards the middle . symmetry about the suture .— somewhat symmetric . size .— length ( stem end to apex ): approximately 66 mm . diameter in line with suture plane : approximately 65 mm . diameter perpendicular to suture plane : approximately 65 mm . average weight : approximately 135 gm . form .— viewed from apex : rounded , nearly symmetrical . viewed from side , facing suture : rounded , nearly symmetrical . viewed from side , perpendicular to suture : rounded , nearly symmetrical . apex shape .— rounded . fruit stem cavity .— shape : rounded . depth : medium ; approximately 0 . 8 cm . breadth : approximately 1 . 5 cm . width : medium . fruit stem .— length : approximately 9 mm . diameter : approximately 2 . 5 mm . color : about medium greyed - orange 164b . adherence to stone : medium . fruit skin .— thickness : medium . adherence to flesh : strong . surface texture : medium . pubescence : none . bloom : slight . ground color : about dark yellow - orange 17d when mature . overcolor : about medium red 47b . taste : neutral . reticulation : absent . roughness : absent . tenacity : tenacious to flesh . tendency to crack : slight , in wet season . flesh .— ripens : evenly . texture : firm , melting . fibers : few . flavor : mild . brix : approximately 12 °. juice : moderate . aroma : slight . color : about medium yellow - orange 15c when mature . acidity : medium . eating quality : good . stone / flesh ratio : about 1 / 4 . firmness : firm . pit cavity size .— length ( diameter in line with suture plane ): approximately 29 - 33 mm . diameter perpendicular to suture plane : approximately 19 mm . color : about medium yellow - orange 15c . fruit use .— fresh market . fruit shipping and keeping quality .— good , holds well in cold storage and maintains good firmness and eating quality ; minimal bruising and scarring in packing and shipping trials . suture line .— inconspicuous . stone .— ( measurements taken on dried stones .) stone freeness : clings over entire surface . degree of adherence to flesh : medium . stone size : size compared to fruit : medium . length ( diameter in line with suture plane ): approximately 29 - 33 mm . diameter perpendicular to suture plane : approximately 19 mm . width of stalk end : medium ; approximately 3 mm . angle of stalk end : right angle . hilum : oval . stone form viewed from side : oval . viewed from ventral side : flattened . viewed from stem end : oval , nearly symmetrical . stone shape : base shape : nearly straight . apex shape : pointed . stone surface : pitted throughout . stone halves : nearly symmetric . stone ridges : rounded continuous . stone outgrowing keel : partially developed . stone tendency to split : slight in wet season . stone color : about medium greyed - orange 166c when dried . position of maximum : toward middle . ventrical edge : medium . dorsal edge : narrow grooves , interrupted . | 0 |
a capped syringe s that has been labeled and filled according to one embodiment of this invention is shown in fig1 . a cap c covers and protects the sterility of the dispensing luer tip ( concealed from view in fig1 by the cap c ). since the barrel b of the syringe s is full in fig1 , the plunger p is extended longitudinally . a flap or substrate 10 for a label 12 is provided by two strips of adhesive tape 14 , 16 , both of which are wrapped around and adhered to respectively opposite sides of the barrel b and adhered to each other in face - to - face relation in extensions 18 , 20 of the adhesive tape 14 , 16 that extend in diametrically opposite directions from the barrel b . it is preferred , but not necessary , that at least one of the adhesive tapes 14 , 16 be transparent so that the graduation marks g that are on most conventional syringes as well as the plunger piston ( not shown ) in fig1 ) can be seen through the adhesive tape . in the embodiment shown in fig1 , the label 12 is a printed sheet that has been adhered to the panel extension 20 of the substrate 10 . however , the label could also be provided in other ways according to this invention . for example , but not for limitation , the printed information could be printed directly on one or both of the adhesive tapes 14 , 16 . such printing , if placed on a transparent tape 14 , 16 would preferably not be enough to mask the graduation marks g . another option could be to make one of the tapes , such as tape 14 opaque , perhaps with label information on it , but make the other tape 16 transparent so as not to mask or hide the graduation marks g . for another possibility , a sheet label similar to label 12 could be sandwiched between the two adhesive tapes 14 , 16 . as mentioned above , a significant feature of this invention is having a plurality of sterile , capped syringes s mounted in spaced apart relation to each other in a band or belt 30 , as shown in fig2 , for handling the syringes s in automated preparation operations . for example , belt 30 may be employed for pulling the syringes s into and preferably at least partially through a labeling and / or filling apparatus and process , as will be described in more detail below . the band or belt 30 can be made with the two elongated adhesive tapes 14 , 16 that were described above and which can be cut to separate the syringes s into individual syringes s with the label substrate 10 as shown in fig1 and as will be described in more detail below . before proceeding , reference is now made to fig1 a – 12 c and fig1 a – 13 c which illustrate alternate embodiments of caps c employable with syringes s of the type shown in fig1 and 2 . as shown , the caps c of the two embodiments each include a cylindrical outer member 500 for matingly engaging the outer flange provided at the dispensing end of the barrel b of the syringe s . in the fig1 a – 12 c embodiment , a cylindrical inner member 502 is also provided for matingly receiving the fluid port provided at the dispensing end of barrel b of syringe s . in the case of the embodiment shown in fig1 a – 13 c a central pin - like inner member 504 is provided for mating insertion into the fluid port provided at the dispensing end of the barrel b of syringe s . of further note , internal locating legs 506 are provided in the embodiment of fig1 a – 13 c for retentively engaging the fluid port of barrel b . as may be appreciated , the embodiments of fig1 a – 12 c and fig1 a – 13 c both provide for isolation of the contents of syringe s . there are many ways by which the plurality of syringes s can be mounted in the band or belt 30 shown in fig2 , and this invention is not limited to any one of such ways of doing so . however , for purposes of example , but not for limitation , one method and apparatus for mounting multiple syringes s into a band or belt 30 is shown in fig3 . as one tape strip , e . g ., tape strip 16 , is unwound from a roll 32 , as indicated by arrows 34 , 36 , it is threaded around the periphery 38 of a syringe mounting wheel 40 , which rotates as indicated by arrow 42 . a pair of rims ( only one rim 44 of the pair can be seen in the elevation view of fig2 ) extend radially outward beyond each side of the periphery 38 , and each of the rims 44 has a plurality of notches 46 in equal , angularly spaced relation to each other around the periphery 38 . as the wheel 40 rotates , preferably capped , empty syringes s are placed serially into the notches 46 , as indicated by arrows 48 , where they contact the adhesive side of the tape strip 16 . as the wheel 40 rotates , as indicated by the arrow 42 , it carries the syringes s in the notches 46 and in contact with the tape strip 16 to a position where the syringes s come into contact with the adhesive side of the other tape strip 14 , which is simultaneously being unwound from a roll 50 as indicated by arrows 52 , 54 , 56 . an idler wheel 58 positions the tape strip 14 in relation to the wheel 40 so that it contacts the syringes s mounted in the notches 46 . therefore , the tapes strips 14 , 16 get adhered to diametrically opposite sides of the syringes s . in this regard , a contact plate 67 may also be provided to insure engagement between tape strip 14 and syringes . as the syringes s , which are adhered to tape strips 14 , 16 emerge from the wheel 40 , they are captured by notches 60 in a press wheel 62 that rotates , as indicated by arrow 64 , to press the tape strips 14 , 16 to each other between the syringes s . press wheel 62 may be provided for driven rotation , wherein such driven rotation effects rotation of the tape rolls 32 and 50 , as well as rotation of syringe mounting wheel 40 as the tape strips 14 , 16 are pulled around press wheel 62 with syringes s secured therebetween . a rotatable pressing block 63 is juxtaposed to the press wheel 62 so that the tape strips 14 , 16 run between the press wheel 62 and the rotatable pressing block 63 . the pressing block 63 may be configured to present a plurality of semicircular surfaces that are spaced to be in opposing relation to notches 60 . thus , the press wheel 62 and the pressing block 63 cooperate to press and adhere the tape strips 14 , 16 tightly together and around the circumference of each syringe s . the pressing block 63 is preferably yieldably biased by a spring - loaded pivot arm 65 or some other bias system to press the pressing block 63 toward the press wheel 62 . after disengaging from press wheel 62 , the belt 30 with the syringes s mounted therein are fed as indicated by arrow 66 into a bin or bag 68 . alternatively , the belt 30 with syringes s could be fed directly into a labeling and / or filling apparatus , which will be described below . in general , the syringes s are positioned in the band or belt 30 in a common orientation , i . e ., with luers of all the syringes s on the same side of the band 30 . the notches 46 in the wheel 40 are spaced uniformly around the rim 44 , so the syringes s in the resulting band 30 are spaced equidistantly apart . the caps c can be placed on the syringes s either before , while , or after the syringes s are mounted in the band 30 . the band 30 of syringes s can then be fan folded or rolled and placed in the plastic bag 68 , which can be closed and / or sealed to protect sterility . the package or bag 68 of banded syringes 30 can then be sterilized by any of a variety of standard sterilization processes , for example by gamma radiation . the sterilized packages 68 of sterilized , banded syringes s , usually in quantities of about 200 to 1 , 000 syringes s per package 68 , are shipped to users , such as hospitals or other health care institutions , who will label and / or fill and re - cap the syringes s for use within an acceptable time after filling . fig4 illustrates another method and apparatus embodiment for mounting multiple syringes s into a band or belt 30 . in this embodiment a syringe feed - wheel 203 is driven synchronously with tape feed wheels 240 and 262 to form a band 30 of interconnected syringes s . more particularly , tape feed wheels 240 and 262 are driven to pull adhesive tapes 16 and 14 about idler wheels 215 and 258 from tape rolls 232 and 250 , respectively . tensioning devices 211 and 213 are provided to establish a desired amount of tension along tape strips 16 and 14 as they are fed to tape feed wheels 240 and 262 , respectively . as shown by fig4 , a vibrating track 201 is provided to advance syringes s for sequential loading into notches 205 of the syringe feed wheel 203 . in turn , the syringe feed - wheel 203 is located immediately adjacent to the tape feed - wheel 240 so that notches 246 of the tape feed - wheel and notches 205 of the syringe feed - wheel 203 are disposed in opposing relation . as such , it can be seen that tape 16 will be pressed into notches 246 on one side of syringes s to achieve conformal interconnection therewith . further in this regard , a pneumatic position and tension control device 207 is provided to enhance the interconnection between syringes s and tape 16 . device 207 includes a mount lever arm 207 a interconnected to the syringe feed - wheel 203 , and a pneumatic cylinder 207 b for locating the arm 207 a and syringe feed - wheel 203 as appropriate so that syringes s apply a predetermined , desired amount of force against tape 16 . after interconnection of one side of syringes s to adhesive tape 16 , the fig4 embodiment provides for the interconnection of adhesive tape 14 to the other side of syringes s . more particularly , tape feed - wheel 262 is driven synchronously with and positioned relative to tape feed - wheel 240 so that notches 260 are in aligned relation with notches 246 to capture syringes s between adhesive tape strips 14 and 16 . concomitantly , tape 14 is pressed about the syringes s to complete band 30 . as further shown in fig4 , a pneumatic position and tension control device 209 is provided at the tape feed - wheel 262 . device 209 includes a mount lever arm 209 a and a pneumatic cylinder 209 b for locating the tape feed - wheel 262 as appropriate to establish the desired amount of force applied by syringes s to tape strip 16 . referring now to the diagrammatic elevation view of the labeling and filling apparatus 70 in fig5 , a band 30 of syringes s is pulled from the bag 68 by a sprocket wheel or drum 72 and rotated to positions where the band 30 is cut to form the label substrates 10 ( see fig1 ), and , if the substrates are not already labeled , to attach labels 12 to the substrates 10 , and to remove the caps c , fill the syringes s with the desired medication , and replace the caps c . in fig5 , if the bands 30 do not already have labels , the user will prepare a quantity of labels 12 and mount them to feed into a labeling station 80 . the labels can be prepared in any suitable manner , for example , using a standard computer label printer , and the quantity of labels 12 prepared can correspond to the number of syringes s to be filled with medication that matches the labels 12 . the user also prepares the liquid medication 91 in a container 92 , which the user connects to a suitable fluid control system , such as conventional peristaltic pump 93 or other suitable syringe filling , fluid metering , or handling system . the medication will be conveyed via a suitable tube 94 or other conduit to the syringe filling station 90 , which will be explained in more detail below . the volume of medication to be pumped into each syringe s can be set and controlled in any of a variety of ways . for example , the pump 93 can be actuated to initiate a fill and deactuated when the syringe has been filled with the desired volume of medication , as will be described in more detail below . with continuing reference primarily to fig5 , the sprocket drum 72 has a plurality of notches 74 in equal , angularly - spaced relation to each other around the circumference of the drum 72 . the notches 74 are large enough to receive and retain a syringe s , and they are spaced apart from each other the same distance as the spacing between the syringes s in the band 30 . therefore , when at least one of the syringes s in the band 30 is positioned in an appropriate notch 74 , rotation of the drum 72 , as indicated by arrow 75 , will cause the band 30 to pull successive syringes s in the band 30 out of the bag 68 and into the labeling and filling apparatus 70 . suitable guides , for example , guides 76 , 77 , 78 , can be used to hold the syringes s in the notches 74 as the drum 72 rotates and carries the syringes s through the cutting station 100 , labeling station 80 , and filling station 90 . it is appropriate to mention at this point that the sequential order of cutting , labeling , and filling is not critical to the invention , and these operations can be performed in any sequential order or even simultaneously , depending on how one wishes to mount the appropriate equipment , as would be within the capabilities of persons skilled in the art once the principles of this invention are understood . however , the convenient sequence of cutting , labeling , and filling will be used for purposes of this description of the invention . the drum 72 can be driven to rotate , as indicated by arrow 75 , and to stop with syringes s positioned appropriately for the cutting , labeling , and filling operations at the respective stations 100 , 80 , 90 by any appropriate drive and control system as is well within the capability of persons skilled in the art , such as , for example , with a stepper motor ( not shown ) connected to appropriate motor control devices ( not shown ). a control panel ( not shown ) connected to the stepper motor can be set up for use by an operator to either jog the drum 72 through incremental steps and / or jog the cutting station 100 , labeling station 80 , or filling station 90 through their respective operations or to initiate continuous automatic operation . at the cutting station 100 , an actuator 101 drives a knife blade 102 as indicated by arrow 103 to cut and sever the band 30 to disconnect the syringes s from each other and to leave the resulting band segments or flaps connected to each syringe s to form individual label substrates 10 for each syringe s . the knife blade 102 is preferably serrated and a slot 104 in the drum in alignment with the knife blade 102 facilitate sure , complete cuts . any suitable actuator 101 can be used , such as a rotary drive motor , solenoid , or the like . a sheath ( not shown ) can be provided to cover the blade 102 when it is not cutting . an optical or other sensor ( not shown ) can be positioned adjacent the drum 72 where the syringes s are first engaged by notches 74 to detect whether any syringes s have missing caps . a signal from the sensor in response to a missing cap could actuate and alarm and / or shut down the apparatus to prevent an uncapped syringe s from being labeled and filled . for the syringe s that has advanced to the labeling station 80 , a labeler device 81 , moving as indicated by arrow 82 , affixes a label 12 to the substrate 10 . the labeler device 81 can be any of a variety of known label apparatus that transfer labels 12 from a strip 83 to an object , or it could be some other device , such as printer apparatus that prints the label directly onto the flap substrate 10 , or some combination of such apparatus , as would be within the capabilities of persons skilled in the art once they understand the principles of this invention . an optical sensor ( not shown ) is used to detect whether a label has been affixed to the substrate 10 at the label station 80 . a microprocessor ( not shown ) can be used to keep count of labels properly affixed and / or activate an alarm and / or shut down the apparatus 70 if a label is not detected on a substrate where a label is supposed to be affixed . for a syringe s that has advanced to the fill station 90 , the cap c ( not shown in fig5 ) is removed by a cap handling apparatus 110 , then a liquid dispensing apparatus 120 is connected to the luer l ( not shown in fig5 ) of the syringe s to dispense liquid medication into the syringe s , and the pump 93 ( or other suitable liquid metering or control apparatus ) is actuated to move the medication 91 from the container 92 into the syringe s . when the syringe s is filled with the desired volume of fluid , as sensed , for example , by a proximity sensor that senses the corresponding desired position of the plunger p ( not shown in fig4 ) of the syringe s , the pump 93 ( or other suitable liquid metering or control apparatus ) is deactuated . then , the liquid dispensing apparatus 120 is disconnected from the syringe s , and the cap handling apparatus 110 is moved into position to replace the cap c ( not shown in fig5 ) onto the luer ( not shown in fig4 ) of the syringe s . the cap handling apparatus 110 and the liquid dispensing apparatus 120 are mounted on a cammed shuttle 130 , which moves laterally in two axes , as indicated by arrow 131 in the plane of the paper and by arrow 132 perpendicular to the plane of the paper , to accomplish the cap removal , fill , and cap replacement functions described above . while these functions could be performed by myriad other devices and combinations of devices , as would be within the capabilities of persons skilled in the art once they understand the principles of this invention , an example cammed shuttle 130 , cap handling apparatus 110 , and liquid dispensing apparatus 120 shown diagrammatically in fig4 will be described in more detail below . after the syringes s leave the fill station 90 , they are allowed to drop individually out of the sprocket drum 72 and , for example , into a basket 115 or other receptacle . at this stage , the syringes s are labeled , filled , and ready for use , as shown in fig1 . referring now to fig6 a , 6 b , 6 c , 6 d , and 6 e in combination with fig5 , the cammed shuttle 130 is driven by a motor , such as a stepper motor 133 , which rotates a slotted cam lever or crank arm 134 mounted on the drive shaft 135 of the motor 133 . a driver block 136 has a slide pin or a cam roll ( concealed from view ) extending in one direction into the slotted race groove 137 of the cam lever or crank arm 134 and another cam follow pin or cam roll 138 extending in the opposite direction into a u - shaped cam slot 139 in a stationary cam block 140 . therefore , as the stepper motor 133 rotates , for example as shown by arrow 141 in fig6 b and 6 c , the cam lever 134 causes the cam follower pin or cam roll 138 extending from the driver block 136 to follow the u - shaped path of the cam slot 139 , which moves the two slide shafts 142 , 143 extending laterally from driver block 136 as well as the connecting block 144 at the distal ends of slide shafts 142 , 143 to move simultaneously in the same u - shaped motion pattern . the two slide shafts 142 , 143 extend slidably through two holes 145 , 146 in a pillow block 147 , which is mounted slidably on two support rods 148 , 149 . the support rods 148 , 149 are mounted in two stationary anchor blocks 150 , 151 and extend slidably through two holes 152 , 153 in pillow block 147 , which are perpendicular to , but vertically offset from , holes 145 , 146 . thus , as the stepper motor 133 drives the driver block 136 through the u - shaped pattern of cam slot 139 , the pillow block 147 slides laterally on support rods 148 , 149 as indicated by arrow 154 , while the slide shafts 142 , 143 slide longitudinally in pillow block 147 as indicated by arrow 155 . as a result , the connector block 144 and cammed shuttle 130 also move both laterally and longitudinally as indicated by arrows 131 , 132 in the same u - shape pattern as the u - shaped cam slot 139 to remove the cap c from the syringe s , connect the syringe s to a nozzle 121 in the liquid dispensing apparatus 120 to fill the syringe s , disconnect the nozzle 121 , and replace the cap c , as will be described in more detail below . suitable bushing or bearings can be used to enhance the sliding movement of the shafts 142 , 143 and support rods 148 , 149 in the pillow block 147 . referring now to fig6 a in combination with fig4 , the drum 72 has moved a syringe s to the filling station 90 , where it stops for the cap removal , fill , and cap replacement operation . the syringe s is shown in fig6 a positioned in a notch 74 with a label 12 affixed to the substrate 10 . as the drum 72 moved the syringe s to the position shown in fig6 a , the cap c was moved into a set of jaws 160 , which is aligned longitudinally with the syringe s when the slotted cam lever 134 is stopped in the position shown in fig6 a and the drum 72 stops the syringe s in the filling station 90 . a cap gripper 161 , such as resilient spring steel , presses against the cap c in jaws 160 to capture and retain the cap c in the jaws 160 . again , optical sensors ( not shown ) or other suitable sensors and / or control devices or methods can be used to stop the drum 72 when the syringe s is positioned with the cap c captured in the jaws 160 as would be understood by persons skilled in the art once they understand the principles of this invention . then , the motor 133 is actuated to rotate the slotted cam lever 134 as indicated by arrow 141 in fig6 b , which extends the slide shafts 142 , 143 , as indicated by arrow 156 , as the pillow block 147 slides to the right on support rods 148 , 149 , as indicated by arrow 157 . as a result , the cammed shuttle 130 moves the jaws 160 with the cap c away from the syringe s , thereby removing the cap c from the syringe s and leaving the luer l of the syringe s exposed and open , as shown in fig6 b . again , the gripper 161 described above retains the cap c in the jaws 160 when the cap c is removed from the luer l . continued rotation of the cam lever 134 as indicated by the arrow 141 in fig6 c translates the pillow block 147 still farther to the right on support rods 148 , 149 , as indicated by arrow 157 in fig6 c , until the longitudinal axis 122 of the fill connector or nozzle 121 aligns with the longitudinal axis 123 of syringe s , then retracts the slide shafts 142 , 143 , as indicated by arrow 158 , to position the nozzle 121 on luer l of the syringe s . at that position of the cammed shuttle 130 , the motor 133 is deactuated , so the nozzle 121 stays on the luer l while the pump 93 ( fig5 ) is actuated to pump liquid medication 91 from the container 92 to fill the syringe s . the fill connector or nozzle 121 is preferably mounted on the cammed shuttle 130 by a spring - loaded slide ( not shown ) or similar yieldable , resilient mounting to apply an appropriate , uniform force to the nozzle 121 as it is being forced by the cammed shuttle 130 onto the luer l of the syringe s . this motion to remove the cap c and place the fill connector or nozzle 121 on the syringe s can be accomplished in approximately 250 milliseconds with this mechanism . the u - shaped cam slot 139 provides a straight , longitudinal pull of the cap c in alignment with the longitudinal axis 123 of the syringe s and a corresponding straight , longitudinal push to attach the nozzle 121 to the luer l . as best seen in fig6 d , the plunger p of the syringe s is pushed outwardly by the liquid medication that is pumped into the syringe s . when the syringe s has been filled with the desired volume of liquid medication , the flow of liquid medication into the syringe s is stopped . the flow can be measured and stopped in a variety of ways , such as flow meters , valves , known pump displacement , and the like , as would be within the knowledge and capabilities of persons skilled in the art once they understand the principles of this invention . however , a particularly novel and innovative way of controlling the fill volume according to this invention is to use a sensor 124 to detect when the plunger p has been pushed out to a predetermined extent that corresponds to the fill volume desired , as illustrated in fig6 d . a myriad of sensors could be used for this function , such as a capacitive proximity sensor , optical sensor , microswitch , and the like . upon sensing the desired extension of the plunger p , a signal from the sensor 124 can be used to shut off the flow of liquid medication into the syringe s . a suitable signal control circuit , for example , a microprocessor and / or relay , ( not shown ) to shut off the pump 93 or to close some control valve ( not shown ) is well within the capabilities of persons skilled in the art once they understand the principles of this invention . as shown in fig6 d , the sensor 124 can be mounted on an adjustable base 125 with a scale 126 and pointer 127 to correlate adjustable physical position of the sensor with the desired fill volume . when the desired fill volume has been reached and detected , as explained above , a signal from the sensor 124 is used to deactuate the pump 93 . a preferred , albeit not essential , pump 93 is a peristaltic pump , such as , for example , a model 099 repeater pump , manufactured by baxa corporation , of englewood , colo ., which can be reversed momentarily to take the fluid pressure off the tubing 94 and syringe s to minimize , if not prevent , dripping of the liquid medication when the nozzle 121 is detached from the luer l . then , the motor 133 is actuated to rotate the cam lever 134 in the opposite direction , as indicated by the arrow 159 in fig6 e , to detach the nozzle 121 from the luer l of the syringe s and move the jaws 160 and cap c back into longitudinal alignment with the axis 123 of the syringe s for replacing the cap c on the syringe s . specifically , as the cam lever 134 rotates , as shown by arrow 159 , the cammed shuttle 130 moves back through the u - shaped pattern defined by the u - shaped cam slot 139 . first , the slide shafts 142 , 143 are extended as indicated by arrow 171 to detach the nozzle 121 from the luer l of syringe s . then the cammed shuttle is moved in an arc as indicated by arrow 172 to align the cap c in jaws 160 with the longitudinal axis 123 of the syringe s . finally , the slide shafts 142 , 143 are retracted again , as indicated by arrow 173 , to push the cap c back onto the syringe s . the cap handling apparatus 110 can be mounted by a spring - loaded slide ( not shown ) or some other yieldable , resilient structure , if desired , to ensure a uniform pressure application to the cap c as it is being pushed by the cammed shuttle 130 back onto the syringe s . at this position , shown in fig6 e , the fill is completed , and the drum 72 can be rotated again to move the cap c out of the jaws 160 and to move the next syringe s in the sequence into the jaws 160 for a repeat of the cap removal , fill , and cap replacement sequence described above on the next syringe s in the drum 72 . at the next position after the filling station 90 , a sensor ( not shown ), such as an optical sensor , is used to determine if the cap c is placed correctly back on the syringe s . if it is not placed correctly , the apparatus is stopped and / or an alarm is sounded in response to a signal from the sensor indicating that the cap c is not replaced . after that cap - check position , the drum moves the syringe to a point where hold down or guide tracks end , thereby freeing the syringe s to drop out of the drum 72 and into a chute ( not shown ) that guides the labeled , filled , and recapped syringe s into the holding basket 115 . the control system ( not shown ) can utilize signals from the sensors to record number of syringes s filled , program the number of doses desired and automatically stop when that number of syringes s are filled , record the number of doses actually pumped , record the number of doses or syringes in the basket 115 and keep track of rejected labels or syringes . other functions can also be provided . referring now to fig7 a and 7 b , the labeling and filling apparatus embodiment of fig5 and fig6 a – 6 e is further illustrated in a production implementation . of note , the labeling and filling apparatus 70 is shown in a compact table top arrangement that may be readily positioned in a sterile environment , e . g . within a sterile area having an appropriate exhaust hood . as will be recognized , the apparatus 70 includes a cutting station 100 , labeling station 80 and filling station 90 . the drum 72 may be driven in a clockwise direction by a step motor 301 , wherein syringes s are positioned into the notches 74 for sequential feeding to the work stations 80 , 90 and 100 . at cutting station 100 , an actuator 101 in the form of a stepper motor may be utilized . in particular , the actuator 101 may be controlled to turn a crank 303 having a cam follower 305 that is located in a slot 307 on a mount block 309 for cutting blade 102 . the block 309 is supported on rails 313 , wherein driven rotation of the crank 303 effects linear travel of the cutting blade 102 towards and away from the drum 72 and a belt 30 with syringes s carried thereby . the operation of actuator 101 may be timed in relation to the stepped movement of drum 72 so that belt 30 is cut into belt segments 10 of a consistent width by cutting blade 102 . at labeling station 80 , the labeling device 81 may include a stepper motor ( not illustrated ) to which a shaft ( not illustrated ) is interconnected for driven eccentric motion . that is , upon actuation stepper motor may drive shaft through an arc from a first position to a second position . by way of example , the first position may be as illustrated in fig7 a and 7 b , wherein the labeling device 81 is located in a down position for label placement . upon eccentric motion of the shaft to a second position , shaft will engage the labeling device 81 causing the cantilevered end thereof to cock upwards about a stationary shaft ( not illustrated ). as may be appreciated , the operation of stepper motor is timed in relation to the stepped movement of drum 72 to affect label placement on the belt segments 10 between adjacent syringes s . referring now to fig8 a – 8 d , operation of the filling station 80 shown in fig7 a and 7 b will be further described . in fig8 a a syringe s has advanced to the filling station 90 with a cap c inserted into cap handling apparatus 110 . as illustrated , syringe s has an interconnected belt segment on flap 10 with a label 12 adhered thereto . as next shown in fig8 b , it can be seen that filling station 90 has retracted away from drum 72 so as to remove cap c from the dispensing end of the syringe s . as previously noted , such retraction is achieved by activating stepper motor 133 to rotate cam lever 134 , thereby causing driver block 136 , slide shafts 142 , 143 , connecting block 144 and shuttle 130 to move along a first straight leg portion of u - shaped motion pattern . in the later regard , fig8 c shows the filling station 90 immediately after cam lever 134 has moved through the curved portion of the u - shaped motion pattern . in this position it can be seen that the nozzle 121 of the liquid dispensing apparatus 120 is aligned with the dispensing end of the syringe s . as such , and as seen in fig8 d , further movement of the filling station 90 along the second straight leg portion of the u - shaped motion pattern causes the liquid dispensing apparatus 120 to linearly advance towards syringe s , wherein the nozzle 121 engages and fluidly interconnects with the dispensing end of the syringe s . upon reaching the fig8 d position , filling station 90 may be controlled so that fluid is injected through nozzle 121 into the syringe s . as further shown in fig8 d , fluid has filled the syringe s to displace the plunger p into contact with the sensor 124 . at this point , a sensor signal is transmitted to terminate the filling of syringe s . thereafter , stepper motor 133 may again rotate cam lever 134 through the u - shaped motion pattern to reposition cap c back onto the dispensing end of the syringe s . as noted above , the filling and labeling apparatus 70 is only one embodiment of the present invention . numerous other embodiments will be apparent to those skilled in the art . by way of example , reference is now made to fig9 , 10 and 11 a – 11 f , which illustrate an alternate embodiment . in this embodiment a drum 472 is driven in a counter - clock wise direction , wherein a band 430 of syringes s pulled in series into the notches 474 for preparation operations . in the later regard , the band 430 is suspended from the drum 472 to facilitate aligned , side - by - side positioning of the syringes s in notches 474 . as schematically shown in fig9 , the syringes s are sequentially advanced through filling station 490 , labeling station 480 and cutting station 400 . thereafter , the separated syringes s may be directed into a container ( not shown ) via a chute 451 . the operation of labeling station 480 and cutting station 400 may be analogous to the operations of the labeling station 80 and cutting station 100 described above in relation to fig5 and fig6 a – 6 b . in contrast to that embodiment , however , the embodiment shown in fig9 , 10 and 11 a – 11 h may implement a different approach at filling station 490 . in the modified operation shown in fig9 , a syringe is first positioned at location i for cap removal , then located at a second position ii for filling , followed by location back at work location i for cap replacement . to facilitate an understanding of such approach , the labeling station 480 and cutting station 400 are not presented in fig1 . as best shown by fig1 , filling station 490 includes a cap handling apparatus 410 and liquid dispensing apparatus 420 . as will be appreciated , liquid dispensing apparatus 420 is interconnectable to a reservoir ( not shown ) containing a fluid for filling syringes s . of note , both the cap handling apparatus 410 and liquid dispensing apparatus 420 are mounted on a common support member 431 . support member 431 may be interconnected to a stepper motor ( not shown ) acutatable to affect linear travel of the cap handling apparatus 410 and liquid dispensing apparatus 420 towards and away from the drum 472 . such linear travel , together with the rotation of drum 472 are the only required motions for cap removal , filling and cap replacement . such operations will now be further described with reference to fig1 a – 11 h . fig1 a – 11 h are flat , diagrammatic views of filling station 490 from a rearward perspective relative to the isometric front view shown in fig1 . before proceeding , it should be noted that the filling station 490 shown in fig1 a – 11 h further includes a syringe flange retention track 492 and a plunger flange retention member 494 . as will be further described , the plunger flange retention number 494 is selectively retractable relative to retention track 492 so that fluid may be drawn from liquid dispensing apparatus 420 to fill syringes s . in this regard , liquid dispensing apparatus 420 may include a valve to control the passage / stoppage of fluid therethrough . by way of example , such valve may comprise an actuatable roller . with particular reference to fig1 a , a syringe s is shown in the first location i shown in fig9 wherein cap c has been inserted in the cap handling apparatus 410 for retention thereby . concomitantly , a flange on syringe s has been inserted and advanced within the retention track 492 . next , and as shown in fig1 b , cap handling apparatus 410 has been retracted from the syringe s with cap c retained thereby . as will be appreciated , such retraction may be affected via linear driven travel of the support member 431 shown in fig1 . fig1 c shows the syringe s moved to the location ii shown in fig9 . more particularly , drum 472 may be rotated clockwise to affect such positioning , wherein the liquid dispensing apparatus 420 is aligned with the dispensing end of the syringe s . then , liquid dispensing apparatus 420 may be advanced into engagement with the dispensing end of syringe s as shown in fig1 d . again , such linear travel may be affected via movement of support member 431 . of note , both fig1 c and lid show the plunger p being positioned in the retention member 494 . in this regard , and referring now to fig1 e , retention member 494 may be provided for driven retraction away from syringe s ( e . g . via an unshown stepper motor ), with the valve of liquid dispensing apparatus 420 opened so as to draw fluid through liquid dispensing apparatus 420 into the syringe s . as may be appreciated , the amount , or length , of retraction of retention member 494 may be precisely controlled to achieve a preset filling volume . when the desired volume has been reached , the valve of liquid dispensing apparatus 420 may be closed . where an actuatable roller is utilized , the roller may be positioned to pinch off a fluid conduit to back up the fluid a desired amount , thereby bringing the fluid pressure slightly below atmospheric pressure . after filling , the liquid dispensing apparatus 420 may be withdrawn from the dispensing end of the syringe s as shown in fig1 f . again , such linear travel may be affected by controlled retraction of the support member 431 . thereafter , syringe s may return to location i via counter - clockwise rotation of drum 472 , as shown in fig1 g . finally , cap c may be replaced onto the dispensing end of the syringe s via advancement of the cap handling apparatus 410 on support member 431 . the syringe s may then be advanced for further operations at the labeling station 480 and cutting station 400 shown in fig9 . the foregoing description is considered as illustrative only of the principles of the invention . furthermore , since numerous modifications and changes will readily occur to those skilled in the art , it is not desired limit the invention to the exact construction and process shown and described above . accordingly , resort may be made to all suitable modifications and equivalents that fall within a scope of the invention as defined by the claims which follow . the words “ comprise ,” “ comprises ,” “ comprising ,” “ include ,” “ including ,” and “ includes ” when used in this specification are intended to specify the presence of stated features , integers , components , or steps , but they do not preclude the presence or addition of one or more other features , integers , components , steps , or groups thereof . | 0 |
the preferred embodiments of the present invention are now explained with reference to fig1 - 6 . in the embodiments , the present invention is applied to a mask to be used when a thin film head for a magnetic disk drive is manufactured by using a reduction projection type exposure device . fig1 shows a simplified construction of major portions of a reduction projection type exposure device in which a mask of the present embodiment is used . in fig1 numeral 1 denotes a mask , numeral 2 denotes a projection optical system and numeral 3 denotes a wafer as a photosensitive substrate . a pattern of the mask 1 mounted on a reticle holder 5 is transferred to each shot area of the wafer 3 at a predetermined reduction factor ( for example 1 / 5 ) through the projection optical system 2 . an alignment microscope 4 is fixed above an area beyond a pattern area of the mask 1 . numeral 6 denotes a wafer alignment optical system arranged on a bottom surface of the reticle holder 5 . the alignment light from the wafer alignment optical system 6 is irradiated to the wafer 3 through a mirror 7 and the projection optical system 2 . the position of the wafer 3 can be detected by sensing a reflected light from the wafer 3 by the wafer alignment optical system 6 through the projection optical system 2 and the mirror 7 . numeral 8 denotes a focus detection and transmission system , and numeral 9 denotes a focus detection and reception system . a focus detection probe pattern is projected onto the wafer 3 obliquely to an optical axis of the projection optical system 2 by the focus detection and transmission system 8 . a light obliquely reflected from the image of the probe pattern on the wafer 3 is sensed by the focus detection and reception system 9 , which produces a focus signal representing the position of the wafer 3 along the optical axis of the projection optical system 2 . the wafer 3 is mounted on a wafer holder 13 which in turn is mounted on a wafer stage 14 . a mirror 11 and a reference mark 12 are mounted in the vicinity of the wafer holder 13 on a top surface of the wafer stage 14 , and a laser beam from a laser interferometer 10 is reflected by the mirror 11 . the wafer stage 14 is connected to a drive motor 16 through a lead screw 15 . a predetermined shot area of the wafer 3 can be sequentially moved into an image field of the projection optical system 2 by driving the drive motor 16 to move the top surface of the wafer stage 14 perpendicularly to the optical axis of the projection optical system 2 in a two - dimensional plane . in this case , the position of the wafer stage 14 is measured by the laser interferometer 10 . a z - stage is built in the wafer stage 14 to move the wafer 3 along the optical axis of the projection optical system 2 . in this case , an alignment mark is formed in the vicinity of the pattern area of the mask 1 , and the mask 1 is illuminated by an illumination light il emitted from an illumination optical system , not shown , while the reference mark 12 on the wafer stage 14 is arranged in the image field of the projection optical system 2 . the relative positioning of the reference mark 12 and the mask 1 is effected by sensing the reflected light from the alignment mark of the mask 1 and the reference mark 12 by the alignment microscope 4 . a light emissive mark may be used as the reference mark 12 . the position of the wafer 3 is detected by the wafer alignment optical system 6 arranged near the bottom surface of the mask 1 . in this case , the relative position of the wafer alignment optical system 6 to the reference mark 12 can be determined by previously detecting the reference mark 12 by the wafer alignment optical system 6 . in the exposure mode , the wafer 3 is sequentially driven at a predetermined pitch by the movement of the wafer stage 14 , and the image of the pattern of the pattern area of the mask 1 is exposed to the entire area of each shot area of the wafer 3 . in this case , since the wafer is not perfectly flat and the depth of focus of the projection optical system 2 is shallow , it is necessary to detect the level ( z - direction ) of the wafer 3 for each exposure shot and adjust the level to the focal plane of the projection optical system 2 . in the present embodiment , the focus detection is effected by the focus detection and transmission system 8 and the focus detection and reception system 9 . various examples of pattern arrangement of the mask 1 to be used in the reduction projection type exposure device of fig1 are now explained . fig2 shows a mask 1 in the first embodiment . in fig2 numeral 17 denotes a pattern area . an exposure light is irradiated to the entire area of the pattern area 17 . a non - pattern area 18 is formed in a portion of the pattern area 17 , and a pattern of a thin film head is formed in the entire area of the pattern area 17 other than the non - pattern area 18 . the non - pattern area 18 may be either a light screening area , a light transmitting area or a transluscent area . fig3 shows a shot area on the wafer on which the pattern of mask 1 of fig2 is transferred . the image of the pattern area 17 of fig2 is transferred to the shot area 17i of fig3 and the image of the non - pattern area 18 of fig2 is transferred to the area 18i of fig3 . numeral 19 denotes a probe pattern projected into the shot area 17i of fig3 from the focus detection and transmission system 8 of fig1 . in the present embodiment , the size of the area 18i on which the non - pattern area 18 is transferred is larger than the probe pattern 19 . in the semiconductor manufacturing process , the lithography process is repeated many times , but when the mask 1 having the non - pattern area 18 as shown in fig2 formed therein is used in each step , the area in which the focus detection probe pattern 19 is projected is always kept flat . thus , the focus detection is not affected by the unevenness of the pattern . assuming that the area 18i is at a lower level than the area 17i ( particularly the projection of the pattern ) in fig3 the level ( z - coordinate ) of the area 18i is detected by projecting the probe pattern 19 . when it is required to align the focal plane of the projection optical system to the projection of the pattern on the wafer 3 , the wafer 3 is displaced to a level equal to a sum of the z coordinate detected by the area 18i corresponding to the non - pattern area 18 and an offset corresponding to the height of the projection of the pattern . in this case , the offset value is determined by previously measuring the level difference between the wafer and the pattern . fig4 shows a mask 1 in a second embodiment of the present invention . in fig4 the pattern area of the mask 1 is divided into 9 × 9 sub - areas of the same size . each sub - area represents a minimum unit of the pattern such as a thin film head and the same device pattern 20 is formed in each sub - area . the device pattern 20 corresponds to the projection 26 shown in fig8 . a center sub - area of the 9 × 9 sub - areas is a non - pattern area 18 . the size of the non - pattern area 18 is equal to the size of one device pattern 20 . like in the first embodiment , the size of the area on the wafer corresponding to the non - pattern area 18 is larger than the size of the focus detection probe pattern . the size of the non - pattern area 18 may be as large as the area of several device patterns 20 instead of one device pattern 20 . for example , when the pattern depicted on the mask is the repetition of a cell which is sufficiently small relative to the entire area of the mask and several tens to several hundreds patterns of the same device are to be formed and when the size of the probe pattern corresponds to the size of one to several projected images of the device pattern , the size of the non - pattern area 18 may be adjusted to the size of one to several repetitive device patterns 20 so that the non - pattern area 18 may be formed without imparting a load to the design of the mask pattern . accordingly , the mask design and the arrangement of the repetitive device patterns 20 are smoothly effected . an economic photo - repeater may be used instead of by an electron beam in the manufacture of the mask . fig5 shows a mask 1 in a third embodiment of the present invention . in fig5 the like elements to those of fig4 are designated by the like numerals and the detailed explanation thereof is omitted . in fig5 numeral 18 denotes a non - pattern area which is of the same size as that of one repetitive device pattern 20 . a cross - shaped wafer alignment mark 21 is provided in the non - pattern area 18 . no alignment mark is provided on the mask 1 other than the wafer alignment mark 21 . the wafer alignment mark 21 is cross - shaped to conduct the alignment in the x - direction and the y - direction . the wafer alignment mark 21 is formed by a transparent member or a light screening member depending on whether the non - pattern area 18 is a light screen area or a transparent area . the projected image of the wafer alignment mark 21 is made sufficiently smaller than the probe pattern 19 of fig3 so that the focus detection is not affected thereby . the alignment mark may be formed without causing significant unevenness on the wafer ( for example , within the range of the depth of focus 10 of the projection optical system ), and in the process which creates large unevenness , the mask having no alignment mark formed thereon as shown in fig4 may be used . by setting a detection wavelength of the wafer alignment optical system 6 of fig1 outside of the range of photosensing wavelength of the photosensitive material , the same alignment mark can be used over a number of steps . in the third embodiment , since it is not necessary to put the alignment mark in the device pattern 20 , the size of one device pattern 20 can be somewhat reduced . where there are several tens to several hundreds device patterns in the mask , a substantial area may be saved as a whole . where the alignment marks are not put in all device patterns but they are put in only specified device patterns , other arrangement may be disturbed if the device pattern is larger than other device patterns . in practice , therefore , all device patterns should be of the same size , and the saving of area is not attained . where the shape of the alignment mark is to be changed by the change of the construction of the alignment optical system , the device pattern need not be changed and only the wafer alignment mark in the non - pattern area need be changed . accordingly , the design of the mask is facilitated . where the photo - repeater is used in the manufacture of the mask , the mask of the device pattern which has been previously used may be used as it is . a fourth embodiment is a modification of the wafer alignment mark 21 of fig5 . fig6 shows the transfer of a pattern of a mask of the present embodiment to a shot area on the wafer . in fig6 an area 18i corresponds to the projected image of the non - pattern area 18 of the mask 1 of fig5 . in this case , a cross - shaped alignment mark 23i is formed at a center of the area 18i and a framing area 22i is formed around the mark 23i . where the non - pattern area 18 of the mask 1 is a light screening area , a wafer alignment mark of a cross - shaped light screening area sandwiching a transparent framing area is formed therein . on the other hand , where the non - pattern area 18 of the mask 1 is a transparent area , a wafer alignment mark of a cross - shaped transparent area sandwiching a light screening framing area is formed therein . in fig6 a slit pattern 24 which is larger than the image 22i of the framing area of the image of the wafer alignment mark is projected as a probe pattern . in fig6 since the area of the image 23i of the wafer alignment mark is a flat area at the same level as other areas of the area 18i , the focus detection is effected more exactly and the detection of the wafer alignment mark formed on the wafer is facilitated . in the present embodiment , the non - pattern area is formed only at the center in the pattern area on the mask although it is not limitive . for example , at least three non - pattern areas may be provided in the periphery of the pattern area 17 shown in fig2 . the positions of the non - pattern areas in the pattern area 17 transferred onto the wafer are detected , and the inclination of the pattern area 17i on the wafer may be determined based on the detection results to adjust the inclination . the present invention is not limited to the above embodiments but various modifications thereof may be made without departing from the gist of the invention . | 6 |
the invention will be hereinafter explained in details with reference to an embodiment mode . fig1 a is a testing circuit according to an embodiment mode of the invention . the testing circuit is structured by a nand circuit 101 having two input portions connected in series . an input portion of the nand circuit is connected to a data signal line s 1 , s 2 , . . . , sn , one - by - one . a nand circuit to which a power source voltage vdd is inputted is referred to as the head , another nand circuit whose output portion is connected to a testing terminal is referred to as the tail for convenience . explanation is made on a testing method . the testing circuit as shown in fig1 a is formed on a substrate . each of the data signal lines s 1 , s 2 , . . . , sn is connected to a pixel portion one - by - one . a potential of a testing pulse is outputted to each data signal line and an output signal out is observed to conduct a test . fig1 b is a timing chart of testing pulses v 1 , v 2 , . . . , vn , a latch signal , and an output signal out . the testing pulses v 1 , v 2 , . . . , vn are outputted to the data signal line simultaneously with the input of the latch signal , therefore , the output signal out is inverted when the latch signal is inputted . in present testing method , a high signal is inputted as to all the testing pulses v 1 , v 2 , . . . , vn in an initial state of the test ( period 0 ). in inputting a first latch signal , the output signal out is low when the number of data signal lines is odd , and high when the number of data signal lines is even . during the next period ( a first state , period 1 ), a low signal is inputted only to the testing pulse v 1 inputted to the head nand circuit . during the following periods ( period 1 . . . period ( n )), the testing pulses are changed from high to low sequentially toward the tail nand circuit with every input of the latch signal . finally , the latch signal is inputted n + 1 times in all . in such a manner , the output signal out is switched between high and low with every input of the latch signal as shown in fig1 b . if the output signal out is not inverted when a latch signal is inputted , a defect can be detected in a latch circuit including a data signal corresponding to the pulse changed to low . a method of detecting a defect is explained in detail with reference to fig4 a and 4b . the testing pulses v 1 , v 2 , . . . , vn are inputted to respective input portions of the testing circuit at the timing of the latch signal through respective data signal lines s 1 , s 2 , . . . , sn as shown in fig4 a . each output of the nand circuits in the testing circuit is o 1 , o 2 , . . . , on , and the output of the tail nand circuit on corresponds to the output signal out . the state of these signals is shown in fig4 b ( 1 and 0 denote a high signal and a low signal , respectively ). states 401 to 406 in fig4 b show potential levels in a normal state after the input of the latch signal . a high signal is inputted to all the testing pulses v 1 , v 2 , . . . , vn , and n is an odd number , therefore , a testing output on is low in state 401 , for example . states 501 to 506 in fig5 a show potential levels in the case of a broken wiring in a fourth data signal line ( only low level ). in an initial state of the test 501 , a defect is located in an even - numbered data signal line , therefore , the potential level in the testing output on is the same as that in the normal state 401 in fig4 b . however , as the potential level in the testing output on is not changed in a first state 502 and a second state 503 , a defect can be detected . the change of the potential level in the testing output on can be observed from a fifth state 506 , and by observing this change , the location of broken wiring can be detected . states 507 to 512 in fig5 b show potential levels in the case where the fourth data signal line is short circuited to a power source voltage ( only high level ). in a fourth state 511 , since a defect is located in an even - numbered data signal line , the potential level in the testing output on is different from that in the normal state of fig4 b . as the change of the potential level can be observed from a sixth state 513 , the location of broken wiring can be detected by observing this change of the potential level . the above - mentioned testing circuit is characterized in that all the data signal lines are inputted simultaneously . therefore , the change from high to low is not occurred when the preceding data is left in the latch circuit due to a defect , and the potential level in the testing output on is not changed , thus the location of the defect can be detected . explanation will be hereinafter made on an embodiment of the invention . fig3 a shows an embodiment of the invention . an image display device includes a substrate 301 , a source driver circuit 302 , a gate driver circuit 303 , a pixel 304 , a data signal line 305 , a scanning line 306 , a video signal line 307 , and a testing circuit 308 . these circuits may be formed with thin film transistors . the thin film transistors may be manufactured by the methods disclosed in u . s . patent application publication no . 2001 / 0035526 filed by yamazaki et al . on apr . 24 , 2001 although not limited thereto . the entire disclosure of the u . s . patent application publication no . 2001 / 0035526 is incorporated herein by reference . the testing circuit 308 is placed opposite to the source driver circuit 302 , each data signal line 305 is connected to respective input potions of nand circuits with two input portions , and each nand circuit is connected in series . a power source voltage vdd is inputted to the head nand circuit and an output portion of the tail nand circuit is connected to a testing terminal . in the present invention of this embodiment , video signals are sequentially taken into a first latch circuit and then , inputted to a second latch circuit . after all the video signals are taken into the second latch circuit , they are inputted to the data signal line 305 in accordance with a latch signal . accordingly , the data signal line is tested by inputting testing pulses v 1 , v 2 , . . . , vn and the latch signal and observing the output signal out . the testing pulses are inputted to each video signal line 307 , and a high signal is inputted to all the data signal lines 305 in an initial state of the test . the output signal is changed depending on the number of data signal lines : a low signal is outputted when the number is odd and a high signal is outputted when the number is even . the testing pulses are inputted to the testing circuit simultaneously with the input of the latch signal , therefore , the testing pulses are changed from high to low toward the tail nand circuit with each input of the latch signal to conduct the test . a square wave signal is outputted at this time . defects such as a broken wiring and a short circuit can be detected when the output signal out is maintained high ( or low ) after inverting from the initial state and a square wave signal is observed in the state after the defective point . switching of the square wave signal between high and low is conducted simultaneously with the input of the latch signal . fig3 b shows an output signal out in the case of detecting a defect in a latch circuit . in fig3 b , a high signal is outputted with the input of a first latch signal ( an initial state of the test ), therefore , the number of data signal lines is confirmed as even ( if the number is odd , it means there is a defect ). the output signal out is inverted in inputting the next latch signal , it is found that there is no defect such as a broken wiring and a short circuit . in fig3 b , however , the output signal out is not changed to low in a third state and normal square wave signals reappear from a fourth state . in such a case , it can be confirmed that there is a defect in the latch circuit . normally , the signal changed from high to low has to be inputted to the third data signal line in the third state , but the signal is not completely changed to low in this case , therefore , a low signal is not supplied to the output signal out . seeing that a normal output signal out is detected from a fourth state , it is confirmed that a latch circuit connected to the third data signal line operates normally in the fourth state ( as a low signal is inputted to the third data signal line in the fourth state , the signal is completely changed to low in a second input ). when taking in ( writing in ) a data inputted from a video signal line , the data needs to be maintained before the timing of taking in the data ( setup time ), and the data needs to be maintained for a certain amount of time after the timing of taking in the data ( hold time ). in the case of increasing the driving frequency of the shift register , the time for taking in the data needs to be shortened . whether a data is taken in accurately or not can be tested by using the testing circuit of the invention . in this embodiment , examples of electronic devices mounting the semiconductor device which is applied to the testing circuit of the present invention are described with reference to fig6 a to 6e . fig6 a is a laptop personal computer manufactured according to the present invention . the laptop personal computer includes a main body 3001 , a casing 3002 , a display portion 3003 , a keyboard 3004 , and the like . fig6 b is a portable information terminal ( pda ) manufactured according to the present invention . the portable information terminal includes a main body 3021 , a display portion 3023 , an external interface 3025 , operation keys 3024 , and the like . as an attachment for operation , a stylus pen 3022 can be used . fig6 c is a video camera manufactured according to the present invention . the video camera includes a main body 3031 , a display portion 3032 , an audio input section 3033 , operation keys 3034 , a battery 3035 , an image receiving section 3036 , and the like . fig6 d is a cellular phone manufactured according to the present invention . the cellular phone includes a main body 3041 , a display portion 3044 , an audio output section 3042 , an audio input section 3043 , operation keys 3045 , an antenna 3046 , and the like . fig6 e is a digital camera manufactured according to the present invention . the digital camera includes a main body 3051 , a display portion a 3057 , an eye piece portion 3053 , operation keys 3054 , a display portion b 3055 , a battery 3056 , and the like . | 6 |
keeping in mind the basic philosophy of sacrificing learning time of speed at run - time , the learning system approach for a neural network implemented by the present invention is to update one weight at a time by slightly changing the weight and measuring the effect that the change has on the output . the weight is then permanently updated based on that change . if the output values approach the target values , the weight is updated in the direction of the slight change . if no change is noted in the output , or if the output is at the target , the weight is left at its original value . if the output diverges from the target , the weight is updated in the opposite direction or the small change . several different rules for updating the weight based on the output and target values are possible . while the learning efficiency of this algorithm is poorer than that of the prior art backpropagation approach , it has several profound advantages over traditional algorithms . first , it is easily amenable to a hardware implementation , as will be described hereinafter . this results from the fact that the learning circuitry is separate from the data access circuitry ; indeed , the data access scheme is irrelevant as far as the learning circuitry is concerned . second , because of the independence of the data access scheme , feedback ( recurrent ) neural network architectures can be implemented . learning algorithms such as backpropagation require strictly feedforward architectures ( i . e . no feed back in the data retrieval phase ). they are called single - attractor systems because outputs vary more or less continuously as inputs are varied continuously . multiple - attractor systems , on the other hand , embody stable output states , such that the output tends to remain at one of these equilibrium points until the input varies enough to push the system to another stable state . such stable states are created by the feedback connections of recurrent networks . multiple - attractor systems are important in applications such as pattern recognition . to have the type of implementation of the neural network itself limited by the requirements of the circuitry needed to teach the network is a case of the tail wagging the dog . the approach of this invention does not suffer from imposing such needless constraints on system design . as will be seen , it is a unique learning system that is amenable to hardware implementation ; and , its architecture can be programmed to implement either feedforward or recurrent networks . the hardware to implement a recurrent / feedforward learning network according to the present invention consists of two systems -- a data retrieval network and a learning network . a block diagram of the data retrieval network is shown in fig1 where it is generally indicated as 10 . the data retrieval network 10 is a modification of a standard hopfield neural network configuration and consists of an array of processing elements called neurons 12 that are connected together by a two - dimensional array of programmable conductance elements called synapses 14 . there are three kinds of neurons 12 : input neurons 12a , hidden neurons 12b , and output neurons 12c . input neurons 12a serve to inject the prompt information into the network 10 . output neurons 12c serve to transmit results calculated by the network 10 . all the other neurons 12b are called &# 34 ; hidden &# 34 ; because it is not possible to ascertain their state from an examination of the system &# 39 ; s inputs and outputs . note that it is possible for one neuron to be in input as well as an output neuron , and that the structure of the three neuron types may be different . in the most general case , synapses 14 connect all output neurons 12c to all input neurons 12a via the synaptic array . in this case , an n neuron system requires n 2 synapses . each synapse 14 allows the transmission of a percentage of the signal at the input of the synapse 14 to pass to the output of the synapse 14 . if no information is transmitted , the synapse 14 is defined to be &# 34 ; off &# 34 ;. if the synapse array is described by the conductance between input and output , where an off neuron 12 has a conductance of zero , then it can be seen that a single - attractor , feedforward network is implemented by making the synapse matrix lower triangular , with zero diagonal . in this case , no feedback is allowed in the system ; all weights transmit information in a direction from input to output . this is equivalent to the feedforward configuration of the backpropagation algorithm . if the matrix is not lower - triangular , then the system has feedback elements that can generate additional attractors . the structure of the neurons 12 employed in the present invention is standard . a summing amplifier combines the individual weighted signals from all synapses 14 , and an activation function circuit is used to translate this signal . not all neurons 12 necessarily use the activation function . for most learning algorithms to work , hidden neurons 12b ( and possibly others ) must have an activation function that is continuous and non - decreasing . the synapses 14 may be implemented in a number of ways , including , for example , the programmable analog resistive devices presently under development at the jet propulsion laboratory in pasadena , california , digitally controlled quantized digital to analog conductance converters , or cooled capacitors combined with multipliers . a block diagram of the learning network of the present invention is shown in fig2 where it is generally indicated as 16 . each synapse 14 has a third terminal 18 for modifying its weight . this programming terminal 18 is enabled by closure of the switch 20 connecting the synapse 14 to the update line 22 . the learning controller 24 consists of circuitry to update each synapse 14 in turn by enabling its programming switch 20 ( via the row and column select lines 26 , 28 , respectively ), changing the conductance value of the synapse slightly , and evaluating the effect of that slight change on the output 30 . a learning rule as also implemented within the learning controller 24 is then applied to determine the final change in that synapse &# 39 ; s conductance . it should be noted at this point that the manner and method of implementing the foregoing functional aspects of the learning controller 24 and the synapses 14 can be according to any of several well known to those skilled in the art without undue experimentation and , accordingly , in the interest of simplicity and the avoidance of redundancy , the particulars thereof are not addressed herein . a number of possible learning rules can be used by the learning controller 24 to perform the final synapse update . a rule that has been used successfully in simulations by the inventor herein is : ## equ2 ## where η is the learning rate , o + and o - are the i th output neuron results before and after the temporary synapse modification , t is the i th target value , and &# 34 ; sign &# 34 ; is the direction in which the i th output changes with respect to the i th target . this particular learning algorithm is quite simple and can be readily implemented in vlsi hardware . note that the system is based on a &# 34 ; trial and error &# 34 ; paradigm -- weights are updated to the extent that a slight change in weight ( the trial ) causes a useful change ( error reduction ) in the output . thus , errors and malfunctions in the data retrieval network 10 are taken into account in calculating weight update values . it should also be noted that although a single - channel learning circuit is described herein , it is possible to use correlation techniques to update several synapses 14 in parallel . this can be done , for example , by applying a small amount of noise to perform the initial synapse variation , and correlating the noise with the output variation . a possible configuration for the learning controller 24 is shown in fig3 . connected to receive the results of each output neuron 12c is a learning rule processor 32 which determines the component of error reduction or increase due to that neuron &# 39 ; s variation ( i . e . the calculation following the summation in the above equation , for example ). individual error components are summed in the summing amplifier 34 and the result is scaled by the learning rate at 36 . the update generator 38 is used to generate the actual signals required to change the weight of the synapses ; the actual circuitry depending , of course , on the specific synaptic device used . the overall procedure for performing learning is under the control of a digital events sequencer 40 which is repeatedly sequenced through its steps of operation as described herein by a clock input as indicated . after new training data is available at the network and target inputs , the sequencer 40 iteratively selects a synapse 14 ( via row and column enable signals on lines 26 , 28 ), and controls the initial and final weight change operations . a block diagram of a learning rule processor 32 that implements the learning rule given in the equation above is shown in fig4 . the component blocks thereof can be implemented readily in custom analog cmos vlsi chips . the absolute value of the change in neuron output is calculated using a sample - and - hold capacitor 42 and switch 44 , and an absolute value differencing circuit 46 . the absolute value of the difference between target and output is calculated by a subtraction circuit 48 and an absolute value circuit 50 . the latter subtraction result is also integrated and thresholded at 52 to determine the direction of change of the neuron output ( i . e . toward or away from the target ). multiplier circuits 54 are used to perform the actual multiplications . in conclusion , neural networks that learn will play an important role in future systems that perform ill - defined functions such as pattern recognition and decision - making based on sketchy or noisy input data . many applications will require real - time data retrieval , which can only be achieved with a fully - parallel hardware implementation of the neural network systems ; yet wherein , the time required for learning often is not a critical factor . the learning system of this invention as described hereinbefore and in the drawing figures which accompany it may be used to implement a wide variety of applications that require either single - attractor or multiple - attractor neural network system ; and , is eminently suitable for implementation in analog vlsi . | 6 |
with reference now to the figures , and in particular to fig1 , there is depicted a diagram of software infrastructure utilized in an exemplary embodiment of the present invention to create an optimized call flow with needed data for handling the call . a call 100 is received by an interactive voice response ( ivr ) host 102 , which includes an ivr application 104 that communicates with a business connector 106 . note that ivr host 102 is part of a presentation layer 108 , and communicates with a business layer 110 , which includes a pre - cache mechanism 112 ( which is further defined and described below ). when the ivr host 102 receives the call 100 , connector 106 presents a query , along with call information , to a business object 120 in pre - cache mechanism 112 . the query is for data needed by a service representative to assist the customer that placed the call . the query is based on call information , which may be any call parameters defined by the architect of the system , including automatic number identification ( ani ), dialed number identification service ( dnis ), caller entered information ( cei ), etc . the ani is a service that provides ivr host 102 with the telephone number of the system that sent call 100 . dnis is a telephone service that identifies , for ivr host 102 , the number that call 100 was placed ( dialed ) to ( assuming that ivr host 102 is able to intake calls to different numbers ). thus , if ivr host 102 handles calls to toll - free numbers that are sponsored by different enterprises / entities , dnis can identify which toll - free number was called , thereby providing useful information for accessing business data as described below . note also that the call parameter may be the cei , such as voice responses to pre - recorded questions posed by ivr host 102 ( e . g ., the name of the department or service being requested , the caller &# 39 ; s social security number , the caller &# 39 ; s name , etc .). alternatively , the cei may be inputs into a telephone keypad that are entered by the caller in response to prompts for information such as an account number , a social security number , an employee identifier , etc . as indicated by step 1 in fig1 , this call information is presented to business object 120 as a query for any business data that is relevant to the call information . for example , if the call information is an account number of the caller , then the business object 120 may retrieve an account history of charges and payments for that account . when business object 120 receives the call information , it generates and assigns a key to that call information . for example , assume that the call information includes the caller &# 39 ; s name , the caller &# 39 ; s account number , and the year for which the caller is asking for information about his account . business object 120 then builds a lookup table 124 , which assigns “ key 1 ” with “ data 1 ” ( data that is related to the caller &# 39 ; s name ), “ key 2 ” with “ data 2 ” ( data that is related to the caller &# 39 ; s account number ), and “ key 3 ” with “ data 3 ” ( data that causes the retrieval of account data only for a particular year ). at this point , business object 120 begins two operations simultaneously . the first operation is to send back to connector 106 the names of the ( one or more ) keys that have been assigned to the call 100 based on the call parameters . ( note that if none of the call parameters match a data descriptor located in lookup table 124 , an error is returned to ivr host 102 , indicating that there is no relevant information for that call parameter available to populate a screen - pop as described below .) these key ( s ) are then appended to call 100 , such as to a header that describes features of the call 100 . included then in the header are not only keys that identify the call parameters described above , but also the destination address ( i . e ., the agent desktop 114 ) for the call . thus , when the call 100 is sent to agent desktop 114 , the key ( s ) are appended to the call itself , as indicated by step 3 . while business object 120 is sending the above described key ( s ) to ivr host 102 , business object 120 is also obtaining and pre - fetching business data from a business data layer / legacy application ( bdlla ) 122 . bdlla 122 is a legacy database belonging to one of the enterprises that utilizes ivr host 102 to direct incoming calls to the appropriate agent desktop . data in bdlla 122 is used to populate a screen - pop , which appears on a monitor of the agent desktop 114 with pertinent information related to call 100 . as described at step 2 . 1 , business object 120 queries bdlla 122 using input parameters ( call parameters ; call information ) presented by ivr host 102 for the call 100 under consideration . as indicated by step 2 . 2 , appropriate business data is returned from bdlla 122 to business object 120 , where it is contained / cached against the data key ( s ) that were returned to ivr application 104 in step 2 . business object now has the business data readily cached and cross - referenced to the key ( s ) that are attached to call 100 ( after being sent from ivr host 102 to agent desktop 114 ). note that business object 120 , bdlla 122 and lookup table 124 are all part of a pre - cache mechanism 112 , and pre - cache mechanism 112 and agent desktop 114 are all part of a business layer 110 . note further that agent desktop 114 includes a desktop client 116 , which includes access to and control of applications 118 , one of which may be a screen - pop application . referring now to step 4 , when desktop client 116 receives call 100 with the appended key ( s ), desktop client 116 sends a query to business object 120 for any cached business data whose cache address in business object 120 is associated with the call - appended keys 1 , 2 and 3 . in the example above , desktop client 116 would send a request to business object for any business data identified in lookup table 124 for information related to the caller &# 39 ; s name ( key 1 ), the caller &# 39 ; s account number ( key 2 ), and the year that the caller is asking about ( key 3 ). business object 120 then sends this business data ( which was previously retrieved from bdlla 122 and cached in business object 120 ) to desktop client 116 , which uses this business data to populate the screen - pop application for use by the servicing agent . reference is now made to fig2 , which describes exemplary steps taken by the present invention , and correlating with the steps described in fig1 . after initiator block 202 in fig2 , an ivr application in the presentation layer presents a query , using call parameters , to a business object in the business layer ( block 204 ). if the business object does not recognize the caller information ( call parameters sent by the ivr application ), as described in query block 206 , then the business object returns an error message to the ivr application ( block 208 ), and the process ends ( terminator block 222 ). however , if the business object does recognize the caller information , then the business object returns one or more data keys to the ivr application ( block 210 ). the ivr application then attaches the data key ( s ) to the call ( block 212 ), and then routes the call with the attached key to the appropriate agent desktop ( block 214 ). concurrently , the business object queries the business layer , using input parameters presented by the ivr for the call under consideration ( block 216 ). data that is returned by the business layer to the business object is contained / cached within the business object against the data key ( s ) that was returned to the ivr application ( block 218 ). since the destination agent desktop has the data key ( obtained from the routed call ), the destination agent desktop can then use that data key to retrieve the business data that was cached by the business object ( block 220 ), which then deletes the business data from the business object &# 39 ; s cache , and the process ends ( terminator block 222 ). with reference now to fig3 , there is depicted a block diagram of an exemplary client computer 302 , whose architecture may be used by ivr host 102 , agent desktop 114 , and pre - cache mechanism 112 ( that is , host 102 , agent desktop 114 , and pre - cache mechanism 114 are physically distinct systems that use similar architecture as described in fig3 ). client computer 302 includes a processor unit 304 that is coupled to a system bus 306 . a video adapter 308 , which drives / supports a display 310 , is also coupled to system bus 306 . system bus 306 is coupled via a bus bridge 312 to an input / output ( i / o ) bus 314 . an i / o interface 316 is coupled to i / o bus 314 . i / o interface 316 affords communication with various i / o devices , including a keyboard 318 , a mouse 320 , a compact disk - read only memory ( cd - rom ) drive 322 , a floppy disk drive 324 , and a flash drive memory 326 . the format of the ports connected to i / o interface 316 may be any known to those skilled in the art of computer architecture , including but not limited to universal serial bus ( usb ) ports . client computer 302 is able to communicate with a software deploying server 402 via a network 328 using a network interface 330 , which is coupled to system bus 306 . network 328 may be an external network such as the internet , or an internal network such as an ethernet or a virtual private network ( vpn ). a hard drive interface 332 is also coupled to system bus 306 . hard drive interface 332 interfaces with a hard drive 334 . in a preferred embodiment , hard drive 334 populates a system memory 336 , which is also coupled to system bus 306 . data that populates system memory 336 includes client computer 302 &# 39 ; s operating system ( os ) 338 and application programs 344 . os 338 includes a shell 340 , for providing transparent user access to resources such as application programs 344 . generally , shell 340 is a program that provides an interpreter and an interface between the user and the operating system . more specifically , shell 340 executes commands that are entered into a command line user interface or from a file . thus , shell 340 ( as it is called in unix ®), also called a command processor in windows ®, is generally the highest level of the operating system software hierarchy and serves as a command interpreter . the shell provides a system prompt , interprets commands entered by keyboard , mouse , or other user input media , and sends the interpreted command ( s ) to the appropriate lower levels of the operating system ( e . g ., a kernel 342 ) for processing . note that while shell 340 is a text - based , line - oriented user interface , the present invention will equally well support other user interface modes , such as graphical , voice , gestural , etc . as depicted , os 338 also includes kernel 342 , which includes lower levels of functionality for os 338 , including providing essential services required by other parts of os 338 and application programs 344 , including memory management , process and task management , disk management , and mouse and keyboard management . application programs 344 include a browser 346 . browser 346 includes program modules and instructions enabling a world wide web ( www ) client ( i . e ., client computer 302 ) to send and receive network messages to the internet using hypertext transfer protocol ( http ) messaging , thus enabling communication with software deploying server 402 . application programs 344 in client computer 302 &# 39 ; s system memory also include a data retrieval optimizer ( dro ) 348 . dro 348 includes code for implementing the processes described in fig1 - 2 . in one embodiment , client computer 302 is able to download dro 348 from software deploying server 402 . the hardware elements depicted in client computer 302 are not intended to be exhaustive , but rather are representative to highlight essential components required by the present invention . for instance , client computer 302 may include alternate memory storage devices such as magnetic cassettes , digital versatile disks ( dvds ), bernoulli cartridges , and the like . these and other variations are intended to be within the spirit and scope of the present invention . as noted above , dro 348 can be downloaded to client computer 302 from software deploying server 402 , shown in exemplary form in fig4 . software deploying server 402 includes a processor unit 404 that is coupled to a system bus 406 . a video adapter 408 is also coupled to system bus 406 . video adapter 408 drives / supports a display 410 . system bus 406 is coupled via a bus bridge 412 to an input / output ( i / o ) bus 414 . an i / o interface 416 is coupled to i / o bus 414 . i / o interface 416 affords communication with various i / o devices , including a keyboard 418 , a mouse 420 , a compact disk - read only memory ( cd - rom ) drive 422 , a floppy disk drive 424 , and a flash drive memory 426 . the format of the ports connected to i / o interface 416 may be any known to those skilled in the art of computer architecture , including but not limited to universal serial bus ( usb ) ports . software deploying server 402 is able to communicate with client computer 302 via network 328 using a network interface 430 , which is coupled to system bus 406 . access to network 328 allows software deploying server 402 to deploy dro 348 to client computer 302 . system bus 406 is also coupled to a hard drive interface 432 , which interfaces with a hard drive 434 . in a preferred embodiment , hard drive 434 populates a system memory 436 , which is also coupled to system bus 406 . data that populates system memory 436 includes software deploying server 402 &# 39 ; s operating system 438 , which includes a shell 440 and a kernel 442 . shell 440 is incorporated in a higher level operating system layer and utilized for providing transparent user access to resources such as application programs 444 , which include a browser 446 , and a copy of dro 348 described above , which can be deployed to client computer 302 . the hardware elements depicted in software deploying server 402 are not intended to be exhaustive , but rather are representative to highlight essential components required by the present invention . for instance , software deploying server 402 may include alternate memory storage devices such as flash drives , magnetic cassettes , digital versatile disks ( dvds ), bernoulli cartridges , and the like . these and other variations are intended to be within the spirit and scope of the present invention . note further that , in a preferred embodiment of the present invention , software deploying server 402 performs all of the functions associated with the present invention ( including execution of dro 348 ), thus freeing client computer 302 from having to use its own internal computing resources to execute dro 348 . it should be understood that at least some aspects of the present invention may alternatively be implemented in a computer - useable medium that contains a program product . programs defining functions on the present invention can be delivered to a data storage system or a computer system via a variety of signal - bearing media , which include , without limitation , non - writable storage media ( e . g ., cd - rom ), writable storage media ( e . g ., hard disk drive , read / write cd rom , optical media ), system memory such as but not limited to random access memory ( ram ), and communication media , such as computer and telephone networks including ethernet , the internet , wireless networks , and like network systems . it should be understood , therefore , that such signal - bearing media when carrying or encoding computer readable instructions that direct method functions in the present invention , represent alternative embodiments of the present invention . further , it is understood that the present invention may be implemented by a system having means in the form of hardware , software , or a combination of software and hardware as described herein or their equivalent . thus , the method described herein , and in particular as shown and described in fig1 - 2 , can be deployed as a process software from software deploying server 402 ( shown in fig4 ) to client computer 302 ( shown in fig3 ). referring then to fig5 , step 500 begins the deployment of the process software . the first thing is to determine if there are any programs that will reside on a server or servers when the process software is executed ( query block 502 ). if this is the case , then the servers that will contain the executables are identified ( block 504 ). the process software for the server or servers is transferred directly to the servers &# 39 ; storage via file transfer protocol ( ftp ) or some other protocol or by copying though the use of a shared file system ( block 506 ). the process software is then installed on the servers ( block 508 ). next , a determination is made on whether the process software is to be deployed by having users access the process software on a server or servers ( query block 510 ). if the users are to access the process software on servers , then the server addresses that will store the process software are identified ( block 512 ). a determination is made if a proxy server is to be built ( query block 514 ) to store the process software . a proxy server is a server that sits between a client application , such as a web browser , and a real server . it intercepts all requests to the real server to see if it can fulfill the requests itself . if not , it forwards the request to the real server . the two primary benefits of a proxy server are to improve performance and to filter requests . if a proxy server is required , then the proxy server is installed ( block 516 ). the process software is sent to the servers either via a protocol such as ftp or it is copied directly from the source files to the server files via file sharing ( block 518 ). another embodiment would be to send a transaction to the servers that contained the process software and have the server process the transaction , then receive and copy the process software to the server &# 39 ; s file system . once the process software is stored at the servers , the users , via their client computers , then access the process software on the servers and copy to their client computers file systems ( block 520 ). another embodiment is to have the servers automatically copy the process software to each client and then run the installation program for the process software at each client computer . the user executes the program that installs the process software on his client computer ( i . e ., client computer 302 ) ( block 522 ) then exits the process ( terminator block 524 ). in query step 526 , a determination is made whether the process software is to be deployed by sending the process software to users via e - mail . the set of users where the process software will be deployed are identified together with the addresses of the user client computers ( block 528 ). the process software is sent via e - mail to each of the users &# 39 ; client computers ( block 530 ). the users then receive the e - mail ( block 532 ) and then detach the process software from the e - mail to a directory on their client computers ( block 534 ). the user executes the program that installs the process software on his client computer ( block 522 ) then exits the process ( terminator block 524 ). lastly a determination is made on whether to the process software will be sent directly to user directories on their client computers ( query block 536 ). if so , the user directories are identified ( block 538 ). the process software is transferred directly to the user &# 39 ; s client computer directory ( block 540 ). this can be done in several ways such as , but not limited to , sharing of the file system directories and then copying from the sender &# 39 ; s file system to the recipient user &# 39 ; s file system or alternatively using a transfer protocol such as file transfer protocol ( ftp ). the users access the directories on their client file systems in preparation for installing the process software ( block 542 ). the user executes the program that installs the process software on his client computer ( block 522 ) and then exits the process ( terminator block 524 ). the present software can be deployed to third parties as part of a service wherein a third party vpn service is offered as a secure deployment vehicle or wherein a vpn is built on - demand as required for a specific deployment . a virtual private network ( vpn ) is any combination of technologies that can be used to secure a connection through an otherwise unsecured or untrusted network . vpns improve security and reduce operational costs . the vpn makes use of a public network , usually the internet , to connect remote sites or users together . instead of using a dedicated , real - world connection such as leased line , the vpn uses “ virtual ” connections routed through the internet from the company &# 39 ; s private network to the remote site or employee . access to the software via a vpn can be provided as a service by specifically constructing the vpn for purposes of delivery or execution of the process software ( i . e . the software resides elsewhere ) wherein the lifetime of the vpn is limited to a given period of time or a given number of deployments based on an amount paid . the process software may be deployed , accessed and executed through either a remote - access or a site - to - site vpn . when using the remote - access vpns the process software is deployed , accessed and executed via the secure , encrypted connections between a company &# 39 ; s private network and remote users through a third - party service provider . the enterprise service provider ( esp ) sets a network access server ( nas ) and provides the remote users with desktop client software for their computers . the telecommuters can then dial a toll - bee number or attach directly via a cable or dsl modem to reach the nas and use their vpn client software to access the corporate network and to access , download and execute the process software . when using the site - to - site vpn , the process software is deployed , accessed and executed through the use of dedicated equipment and large - scale encryption that are used to connect a company &# 39 ; s multiple fixed sites over a public network such as the internet . the process software is transported over the vpn via tunneling which is the process of placing an entire packet within another packet and sending it over a network . the protocol of the outer packet is understood by the network and both points , called tunnel interfaces , where the packet enters and exits the network . the process for such vpn deployment is described in fig6 . initiator block 602 begins the virtual private network ( vpn ) process . a determination is made to see if a vpn for remote access is required ( query block 604 ). if it is not required , then proceed to query block 606 . if it is required , then determine if the remote access vpn exists ( query block 608 ). if a vpn does exist , then proceed to block 610 . otherwise identify a third party provider that will provide the secure , encrypted connections between the company &# 39 ; s private network and the company &# 39 ; s remote users ( block 612 ). the company &# 39 ; s remote users are identified ( block 614 ). the third party provider then sets up a network access server ( nas ) ( block 616 ) that allows the remote users to dial a toll free number or attach directly via a broadband modem to access , download and install the desktop client software for the remote - access vpn ( block 618 ). after the remote access vpn has been built or if it has been previously installed , the remote users can access the process software by dialing into the nas or attaching directly via a cable or dsl modem into the nas ( block 610 ). this allows entry into the corporate network where the process software is accessed ( block 620 ). the process software is transported to the remote user &# 39 ; s desktop over the network via tunneling . that is , the process software is divided into packets and each packet including the data and protocol is placed within another packet ( block 622 ). when the process software arrives at the remote user &# 39 ; s desktop , it is removed from the packets , reconstituted and then is executed on the remote user &# 39 ; s desktop ( block 624 ). a determination is then made to see if a vpn for site to site access is required ( query block 606 ). if it is not required , then proceed to exit the process ( terminator block 626 ). otherwise , determine if the site to site vpn exists ( query block 628 ). if it does exist , then proceed to block 630 . otherwise , install the dedicated equipment required to establish a site to site vpn ( block 638 ). then build the large scale encryption into the vpn ( block 640 ). after the site to site vpn has been built or if it had been previously established , the users access the process software via the vpn ( block 630 ). the process software is transported to the site users over the network via tunneling ( block 632 ). that is the process software is divided into packets and each packet including the data and protocol is placed within another packet ( block 634 ). when the process software arrives at the remote user &# 39 ; s desktop , it is removed from the packets , reconstituted and is executed on the site user &# 39 ; s desktop ( block 636 ). the process then ends at terminator block 626 . the process software which consists of code for implementing the process described herein may be integrated into a client , server and network environment by providing for the process software to coexist with applications , operating systems and network operating systems software and then installing the process software on the clients and servers in the environment where the process software will function . the first step is to identify any software on the clients and servers including the network operating system where the process software will be deployed that are required by the process software or that work in conjunction with the process software . this includes the network operating system that is software that enhances a basic operating system by adding networking features . next , the software applications and version numbers will be identified and compared to the list of software applications and version numbers that have been tested to work with the process software . those software applications that are missing or that do not match the correct version will be upgraded with the correct version numbers . program instructions that pass parameters from the process software to the software applications will be checked to ensure the parameter lists matches the parameter lists required by the process software . conversely parameters passed by the software applications to the process software will be checked to ensure the parameters match the parameters required by the process software . the client and server operating systems including the network operating systems will be identified and compared to the list of operating systems , version numbers and network software that have been tested to work with the process software . those operating systems , version numbers and network software that do not match the list of tested operating systems and version numbers will be upgraded on the clients and servers to the required level . after ensuring that the software , where the process software is to be deployed , is at the correct version level that has been tested to work with the process software , the integration is completed by installing the process software on the clients and servers . for a high - level description of this process , reference is now made to fig7 . initiator block 702 begins the integration of the process software . the first tiling is to determine if there are any process software programs that will execute on a server or servers ( block 704 ). if this is not the case , then integration proceeds to query block 706 . if this is the case , then the server addresses are identified ( block 708 ). the servers are checked to see if they contain software that includes the operating system ( os ), applications , and network operating systems ( nos ), together with their version numbers , which have been tested with the process software ( block 710 ). the servers are also checked to determine if there is any missing software that is required by the process software in block 710 . a determination is made if the version numbers match the version numbers of os , applications and nos that have been tested with the process software ( block 712 ). if all of the versions match and there is no missing required software the integration continues in query block 706 . if one or more of the version numbers do not match , then the unmatched versions are updated on the server or servers with the correct versions ( block 714 ). additionally , if there is missing required software , then it is updated on the server or servers in the step shown in block 714 . the server integration is completed by installing the process software ( block 716 ). the step shown in query block 706 , which follows either the steps shown in block 704 , 712 or 716 determines if there are any programs of the process software that will execute on the clients . if no process software programs execute on the clients the integration proceeds to terminator block 718 and exits . if this not the case , then the client addresses are identified as shown in block 720 . the clients are checked to see if they contain software that includes the operating system ( os ), applications , and network operating systems ( nos ), together with their version numbers , which have been tested with the process software ( block 722 ). the clients are also checked to determine if there is any missing software that is required by the process software in the step described by block 722 . a determination is made is the version numbers match the version numbers of os , applications and nos that have been tested with the process software ( query block 724 ). if all of the versions match and there is no missing required software , then the integration proceeds to terminator block 718 and exits . if one or more of the version numbers do not match , then the unmatched versions are updated on the clients with the correct versions ( block 726 ). in addition , if there is missing required software then it is updated on the clients ( also block 726 ). the client integration is completed by installing the process software on the clients ( block 728 ). the integration proceeds to terminator block 718 and exits . the process software is shared , simultaneously serving multiple customers in a flexible , automated fashion . it is standardized , requiring little customization and it is scalable , providing capacity on demand in a pay - as - you - go model . the process software can be stored on a shared file system accessible from one or more servers . the process software is executed via transactions that contain data and server processing requests that use cpu units on the accessed server . cpu units are units of time such as minutes , seconds , hours on the central processor of the server . additionally the assessed server may make requests of other servers that require cpu units . cpu units are an example that represents but one measurement of use . other measurements of use include but are not limited to network bandwidth , memory usage , storage usage , packet transfers , complete transactions etc . when multiple customers use the same process software application , their transactions are differentiated by the parameters included in the transactions that identify the unique customer and the type of service for that customer . all of the cpu units and other measurements of use that are used for the services for each customer are recorded . when the number of transactions to any one server reaches a number that begins to affect the performance of that server , other servers are accessed to increase the capacity and to share the workload . likewise when other measurements of use such as network bandwidth , memory usage , storage usage , etc . approach a capacity so as to affect performance , additional network bandwidth , memory usage , storage etc . are added to share the workload . the measurements of use used for each service and customer are sent to a collecting server that sums the measurements of use for each customer for each service that was processed anywhere in the network of servers that provide the shared execution of the process software . the summed measurements of use units are periodically multiplied by unit costs and the resulting total process software application service costs are alternatively sent to the customer and or indicated on a web site accessed by the customer which then remits payment to the service provider . in another embodiment , the service provider requests payment directly from a customer account at a banking or financial institution . in another embodiment , if the service provider is also a customer of the customer that uses the process software application , the payment owed to the service provider is reconciled to the payment owed by the service provider to minimize the transfer of payments . with reference now to fig8 , initiator block 802 begins the on demand process . a transaction is created than contains the unique customer identification , the requested service type and any service parameters that further , specify the type of service ( block 804 ). the transaction is then sent to the main server ( block 806 ). in an on demand environment the main server can initially be the only server , then as capacity is consumed other servers are added to the on demand environment . the server central processing unit ( cpu ) capacities in the on demand environment are queried ( block 808 ). the cpu requirement of the transaction is estimated , then the servers available cpu capacity in the on demand environment are compared to the transaction cpu requirement to see if there is sufficient cpu available capacity in any server to process the transaction ( query block 810 ). if there is not sufficient server cpu available capacity , then additional server cpu capacity is allocated to process the transaction ( block 812 ). if there was already sufficient available cpu capacity then the transaction is sent to a selected server ( block 814 ). before executing the transaction , a check is made of the remaining on demand environment to determine if the environment has sufficient available capacity for processing the transaction . this environment capacity consists of such things as but not limited to network bandwidth , processor memory , storage etc . ( block 816 ). if there is not sufficient available capacity , then capacity will be added to the on demand environment ( block 818 ). next the required software to process the transaction is accessed , loaded into memory , then the transaction is executed ( block 820 ). the usage measurements are recorded ( block 822 ). the usage measurements consist of the portions of those functions in the on demand environment that are used to process the transaction . the usage of such functions as , but not limited to , network bandwidth , processor memory , storage and cpu cycles are what is recorded . the usage measurements are summed , multiplied by unit costs and then recorded as a charge to the requesting customer ( block 824 ). if the customer has requested that the on demand costs be posted to a web site ( query block 826 ), then they are posted ( block 828 ). if the customer has requested that the on demand costs be sent via e - mail to a customer address ( query block 830 ), then these costs are sent to the customer ( block 832 ). if the customer has requested that the on demand costs be paid directly from a customer account ( query block 834 ), then payment is received directly from the customer account ( block 836 ). the on demand process is then exited at terminator block 838 . while the present invention has been particularly shown and 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 . furthermore , as used in the specification and the appended claims , the term “ computer ” or “ system ” or “ computer system ” or “ computing device ” includes any data processing system including , but not limited to , personal computers , servers , workstations , network computers , main frame computers , routers , switches , personal digital assistants ( pda &# 39 ; s ), telephones , and any other system capable of processing , transmitting , receiving , capturing and / or storing data . | 7 |
the weld metal of the invention contains a predetermined amount of each of c , si , mn , cr , mo , v , nb , n , and o , with the remainder consisting of fe and inevitable impurities . the weld metal may further contain one or both of a predetermined amount of cu and a predetermined amount of ni , and furthermore may contain a predetermined amount of b . the weld metal may further contain a predetermined amount of one or more of w , al , and ti . in the weld metal , an a value satisfies 200 or more , the a value being obtained by the weld metal composition according to a formula in addition , a z value is 0 . 05 or more , the z value being obtained according to a formula where n is number density ( particles / μm ) of carbide particles per unit grain boundary , the carbide particles existing in a prior austenite grain boundary of a stress - relief annealed weld metal , and [ insol . v ] is concentration of compound - type v determined by an extraction residue of the stress - relief annealed weld metal . c is an essential element for the weld metal to have strength . for the c content of less than 0 . 05 mass %, the weld metal does not have predetermined strength . in addition , the weld metal does not contain a sufficient amount of mc carbide , leading to degradation in creep rupture properties . for the c content of more than 0 . 15 mass %, carbide particles are coarsened , causing degradation in toughness . consequently , the c content is 0 . 05 to 0 . 15 mass %. a preferred lower limit of the c content is 0 . 07 mass %, and a preferred upper limit thereof is 0 . 13 mass %. si is an element to be contained in light of welding workability . for the si content of less than 0 . 10 mass %, welding workability becomes bad . for the si content of more than 0 . 50 mass %, the weld metal has excessively high strength or is increased in amount of hard phases such as martensite , leading to degradation in toughness . consequently , the si content is 0 . 10 to 0 . 50 mass %. a preferred lower limit of the si content is 0 . 15 mass %, and a preferred upper limit thereof is 0 . 40 mass %. mn is an element necessary for the weld metal to have strength . for the mn content of less than 0 . 60 mass %, the weld metal has a low strength at room temperature , and is less likely to have sr crack resistance . for the mn content of more than 1 . 30 mass %, an impurity promptly segregates into a prior y grain boundary , leading to degradation in temper embrittlement resistances . consequently , the mn content is 0 . 60 to 1 . 30 mass %. a lower limit of the mn content is preferably 0 . 70 mass %, and more preferably 0 . 75 mass %. an upper limit thereof is preferably 1 . 20 mass %, and more preferably 1 . 15 mass %. cr is an element effective in improving sr crack resistance . for the cr content of less than 1 . 80 mass %, film - like coarse cementite is precipitated in a prior y grain boundary , and sr crack resistance is degraded . for the cr content of more than 3 . 00 mass %, carbide particles are coarsened , causing degradation in toughness . consequently , the cr content is 1 . 80 to 3 . 00 mass %. a lower limit of the cr content is preferably 1 . 90 mass %, and more preferably 2 . 00 mass %. an upper limit thereof is preferably 2 . 80 mass %, and more preferably 2 . 60 mass %. mo is an element necessary for the weld metal to have strength . for the mo content of less than 0 . 80 mass %, the weld metal does not have predetermined strength . for the mo content of more than 1 . 20 mass %, the weld metal has excessively high strength , leading to degradation in toughness . in addition , the amount of dissolved mo is increased after sr annealing , and thus fine mo 2 c particles are precipitated during step cooling , leading to degradation in temper embrittlement resistance . consequently , the mo content is 0 . 80 to 1 . 20 mass %. a lower limit of the mo content is preferably 0 . 90 mass %. an upper limit thereof is preferably 1 . 15 mass %, and more preferably 1 . 10 mass %. v is an element that contributes to improving creep rupture properties and temper embrittlement resistance through formation of mc carbide and formation of v carbide in a grain boundary . for the v content of less than 0 . 25 mass %, the weld metal does not have the predetermined properties . for the v content of more than 0 . 50 mass %, the weld metal has excessively high strength , leading to degradation in toughness . consequently , the v content is 0 . 25 to 0 . 50 mass %. a lower limit of the v content is preferably 0 . 27 mass %, and more preferably 0 . 30 mass %. an upper limit thereof is preferably 0 . 45 mass %, and more preferably 0 . 40 mass %. nb is an element that contributes to improving creep rupture properties through formation of mc carbide . for the nb content of less than 0 . 010 mass %, the weld metal does not have predetermined strength . for the nb content of more than 0 . 050 mass %, the weld metal has excessively high strength , leading to degradation in toughness . consequently , the nb content is 0 . 010 to 0 . 050 mass %. a lower limit of the nb content is preferably 0 . 012 mass %. an upper limit thereof is preferably 0 . 040 mass %, and more preferably 0 . 035 mass %. n is an element to be inevitably contained during welding , and is industrially difficult to be decreased to 0 %. for the n content of more than 0 . 025 mass %, the weld metal has excessively high strength and therefore cannot have sufficient toughness . consequently , the n content is 0 . 025 mass % or less . the n content is preferably 0 . 020 mass % or less , and more preferably 0 . 018 mass % or less . o is an element that contributes to microstructure refinement through formation of oxide , and improves toughness . for the o content of less than 0 . 020 mass %, the effect of improving toughness is not exhibited . for the o content of more than 0 . 060 mass %, coarse oxide particles increase and act as initiation site of cracks , leading to degradation in toughness . hence , the o content is 0 . 020 to 0 . 060 mass %. a lower limit of the o content is preferably 0 . 025 mass %. an upper limit thereof is preferably 0 . 050 mass %, and more preferably 0 . 045 mass %. & lt ; cu : 1 . 00 mass % or less ( not including 0 mass %), ni : 1 . 00 mass % or less ( not including 0 mass %)& gt ; cu and ni are each an element effective in improving toughness through microstructure refinement . for each of the cu content and the ni content of more than 1 . 00 mass %, the weld metal has excessively high strength , leading to degradation in toughness . consequently , the cu content and the ni content are each 1 . 00 mass % or less . a lower limit of each of the cu content and the ni content is preferably 0 . 05 mass %, and more preferably 0 . 10 mass %. an upper limit thereof is preferably 0 . 80 mass %, and more preferably 0 . 50 mass %. the total content of cu and ni is preferably 0 . 05 to 1 . 50 mass %. b is an element that suppresses ferrite formation at a grain boundary , and thereby increases strength . the b content of more than 0 . 0050 mass % degrades sr crack resistance . consequently , the b content is 0 . 0050 mass % or less . the b content is preferably 0 . 0040 mass % or less , and more preferably 0 . 0025 mass % or less . a preferred lower limit of the b content is 0 . 0005 mass % or less . w is an element effective in increasing strength . the w content of more than 0 . 50 mass % coarsens carbide particles precipitated in a grain boundary , leading to bad influence on toughness . consequently , the w content is 0 . 50 mass % or less . a preferred lower limit of the w content is 0 . 08 mass %. a preferred upper limit thereof is 0 . 30 mass %. al is a deoxidizing element . the al content of more than 0 . 030 mass % coarsens oxide particles , leading to bad influence on toughness . consequently , the al content is 0 . 030 mass % or less . the al content is preferably 0 . 020 mass % or less , and more preferably 0 . 015 mass % or less . a preferred lower limit of the al content is 0 . 010 mass %. ti is an element effective in increasing strength . for the ti content of more than 0 . 020 mass %, precipitation strengthening by mc carbide is accelerated and thus inner - granular strength is extremely increased , resulting in degradation in sr crack resistance . consequently , the ti content is 0 . 020 mass % or less . a preferred lower limit of the ti content is 0 . 008 mass %. a preferred upper limit thereof is 0 . 015 mass %. the remainder of the weld metal consists of fe and inevitable impurities . examples of the inevitable impurities may include , but not limited to , p : 0 . 020 mass % or less , sn : 0 . 010 mass % or less , and as : 0 . 010 mass % or less . the a value is a parameter for controlling the number of mc particles contributing to improvement in creep rupture properties . specifically , the mc particles act as a barrier to dislocation migration during a creep rupture test , and thereby improves the creep rupture properties . although such an action is enhanced with an increase in the number of mc particles , the number of mc particles is decreased by ostwald ripening during the creep rupture test ; hence , how to maintain the number of mc particles during the creep rupture test is a point for improving the creep rupture properties . the inventors therefore have investigated a technique for maintaining the number of mc particles during the creep rupture test . in addition , the inventors have found that the creep rupture properties are improved by suppressing ostwald ripening , i . e ., a decrease in number of mc particles , during the creep rupture test while a sufficient number of mc particles are prepared before the creep rupture test . from such two viewpoints , the inventors have discovered the a value as a parameter for controlling the number of mc particles during the creep rupture test . to further improve the creep rupture properties , while it is effective to maintain the number of mc particles during the creep rupture test through controlling the a value , it is also effective to suppress grain boundary sliding during creep rupture test . in addition , it is necessary to make p segregation into a prior austenite grain boundary to be harmless , the p segregation causing temper embrittlement , in order to improve temper embrittlement resistance . the inventors therefore have investigated a measure satisfying the two , and have found that creep rupture properties and temper embrittlement resistance are each further improved by precipitating v carbide in a grain boundary . here , “ grain boundary ” refers to large angle grain boundary that includes not only a ferrite grain boundary but also a prior austenite grain boundary , a block boundary , a packet boundary , and the like . the carbide precipitated in the grain boundary ( hereinafter , referred to as “ carbide at grain boundary ”) acts as a resistance against grain boundary sliding during a creep rupture test . the number of the carbide particles at the grain boundary is in general decreased by ostwald ripening during the creep rupture test , and thus the carbide particles gradually lose a function of suppressing the grain boundary sliding . hence , it is effective in improving the creep rupture properties to suppress growth of the carbide at the grain boundary during the creep rupture test . the inventors have found that it is possible to suppress growth of the carbide at the grain boundary during the creep rupture test by precipitating v carbide in the grain boundary while the a value is satisfied . in addition , the inventors have found that the v carbide precipitated in the grain boundary incorporates p and thereby allows the p segregation into the prior austenite grain boundary to be harmless , the p segregation causing temper embrittlement , and finally have completed the invention . specifically , a plurality of types of carbide , such as v carbide , cr carbide , and mo carbide , exist in the prior austenite grain boundary . the inventors have investigated interaction between a type of the carbide at the grain boundary and segregated p with a physical analyzer that can three - dimensionally determine positions of individual atoms constituting a metal , i . e ., three - dimensional atom probe , and have found that v carbide has a function of incorporating the segregated p , and have found that temper embrittlement can be suppressed by precipitating the v carbide in the grain boundary . other types of carbide such as cr carbide do not incorporate segregated p . p migrates into a boundary between the cr carbide and a matrix , and thereby the boundary is weakened , so that temper embrittlement is not suppressed . this finding can be applied not only to weld metal but also to general steel materials . the steel materials are promisingly improved in toughness and suppressed in temper embrittlement through precipitation of v carbide into a grain boundary . the a value is a parameter for controlling the number of mc carbide particles and the number of the carbide particles at the grain boundary during the creep rupture test . for the a value of less than 200 , the number of mc particles is small before the creep rupture test . alternatively , ostwald ripening of the mc particles and of the carbide particles at the grain boundary progresses during the creep rupture test . this decreases number density of mc particles and of the carbide particles at the grain boundary , leading to degradation in creep rupture properties . hence , the a value is 200 or more . a lower limit of the a value is preferably 202 , and more preferably 205 . an upper limit of the a value is preferably 270 , and more preferably 250 . the z value is a parameter for determining the amount of v carbide at a grain boundary . a larger z value means a larger number of v carbide particles in a grain boundary , leading to further improvement in creep rupture properties and in temper embrittlement resistance . for the z value of lower than 0 . 05 , one or both of creep rupture properties and temper embrittlement resistance does not satisfy a predetermined value . consequently , the z value is 0 . 05 or more . a lower limit of the z value is preferably 0 . 07 , and more preferably 1 . 00 . an upper limit of the z value is preferably 0 . 20 , and more preferably 0 . 18 . & lt ; determination of number density n ( particles / μm ) of carbide particles at grain boundary & gt ; an exemplary determination process of the number density n ( particles / μm ) of the carbide particles at the grain boundary is now described with reference to fig1 and 2 . in fig1 and 2 , a circle drawn by a dot line has a circle - equivalent diameter of 0 . 4 μm , and corresponds to scale . a carbide particle having a circle - equivalent diameter of 0 . 40 μm or more is indicated by a black dot , and a carbide particle having a circle - equivalent diameter of less than 0 . 40 μm is indicated by a hatched dot . first , a test specimen for replica tem observation is obtained from the center of the final pass of weld metal subjected to sr annealing of 705 ° c .× 8 hr . subsequently , two images each having a visual field of 13 . 3 × 15 . 7 μm are photographed at 7500 magnifications (( a ) of fig1 ). the images are subjected to carbide form analysis with image analysis software ( image - pro plus , from media cybernetics ) according to the following procedure . ( 1 ) straight lines ai ( i = 1 , 2 , 3 , . . . , n ; n is the total of straight lines ) 6 μm in length are selected , each straight line intersecting with at least three carbide particles each having a circle - equivalent diameter of 0 . 40 μm or more (( b ) of fig1 ). for example , in ( b ) of fig1 , a straight line a 1 intersects with three carbide particles 1 , 2 , and 3 , each having a circle - equivalent diameter of 0 . 40 μm or more , indicated by black dots . similarly , a straight line a 2 intersects with carbide particles 2 , 3 , and 4 ; a straight line a 3 intersects with carbide particles 3 , 4 , and 5 ; a straight line a 4 intersects with carbide particles 4 , 5 , and 6 ; a straight line a 5 intersects with carbide particles 5 , 8 , and 9 ; a straight line a 6 intersects with carbide particles 8 , 9 , and 10 ; a straight line a 7 intersects with carbide particles 9 , 10 , and 11 ; and a straight line a 8 intersects with carbide particles 8 , 6 , and 7 . the straight lines ai include the straight lines a 1 to a 8 . ( 2 ) carbide particles each having a circle - equivalent diameter of 0 . 40 μm or more are selected , each carbide particle intersecting with one of the straight lines ai (( a ) of fig2 ). ( 3 ) the centers of circumscribed quadrangles of carbide particles adjacent to one another on each of the straight lines ai are connected to one another by straight lines bi ( i = 1 , 2 , 3 , . . . , m ; m is the total of straight lines ), and the total length of the straight lines b 1 to bm is defined as grain boundary length l ( μm ) (( b ) of fig2 ). ( 4 ) the quotient of the number of carbide particles divided by l ( μm ), each carbide particle having a circle - equivalent diameter of 0 . 40 μm or more and intersecting with one of the straight lines bi , is defined as number density n ( particles / μm ) of the carbide particles at the grain boundary . first , the thickness center of the weld metal subjected to sr annealing of 705 ° c .− 8 hr is electrolytically extracted with a 10 vol % acetylacetone - 1 vol % tetramethylammonium chloride - methanol solution . subsequently , such an extract is filtrated by a filter having a pore size 0 . 1 μm and a residue is collected , and then the residue is subjected to icp emission spectrometry to determine the concentration of compound - type v . a preferred mode for achieving the weld metal of the invention is now described . each of a welding material and a welding condition must be controlled to be within a predetermined range in order to achieve the weld metal . a welding material composition is naturally restricted by a required weld metal composition . furthermore , each of a welding condition and a welding material composition must be appropriately controlled in order to produce a predetermined carbide form . although any arc welding process can be used as a welding method for achieving the weld metal without limitation , preferred welding conditions of shielded metal arc welding ( smaw ) and submerge arc welding ( saw ) are as follows . & lt ; welding heat input 2 . 3 to 3 . 5 kj / mm , interpass and preheating temperature 190 to 250 ° c .& gt ; if heat input is below 2 . 3 kj / mm , or if interpass and preheating temperature is below 190 ° c ., cooling rate in welding is high , and a sufficient amount of carbide is not formed during cooling . the z value therefore does not satisfy the predetermined range . if heat input is above 3 . 5 kj / mm , or if interpass and preheating temperature is above 250 ° c ., cooling rate in welding is low , and cementite formation is accelerated in a final stage of cooling , leading to a decrease in production of v carbide in a grain boundary . the z value therefore does not satisfy the predetermined range . to produce the predetermined weld metal under such a preferred welding condition , welding rods are preferably manufactured while the following conditions are satisfied . & lt ; mo concentration in core wire : 1 . 20 mass % or less ( preferably 1 . 10 mass % or less ), cr concentration in core wire : 2 . 30 mass % or less ( preferably 2 . 28 mass % or less , more preferably 2 . 26 mass % or less ), si / sio 2 ratio in coating flux : 1 . 0 or more ( preferably 1 . 1 or more , more preferably 1 . 2 or more ), v concentration in coating flux : 0 . 85 mass % or more ( preferably 1 . 00 mass % or more ), zro 2 concentration in coating flux : 1 . 0 mass % or more ( preferably 1 . 1 mass % or more )& gt ; these are determined to control the z value . if the above - described parameter is deviated from the predetermined range , cr carbide , mo carbide , and cementite are nucleated on an austenite grain boundary during cooling in welding . consequently , the amount of v carbide is decreased during sr annealing , so that the z value is not allowed to be maintained to be within the predetermined range . in particular , during cooling after welding , cementite is easily precipitated in a grain boundary since it is formed without diffusion of an alloy element . hence , such precipitation of cementite and others are importantly suppressed . dissolved si is known to be effective in suppressing precipitation of cementite . to allow the weld metal to contain a certain amount of dissolved si , it is necessary to control the si / sio 2 ratio to be high and to allow a certain amount of zr as a strong oxidizing element to be contained . & lt ; welding heat input 2 . 2 to 5 . 0 kj / mm , interpass and preheating temperature during welding 190 to 250 ° c .& gt ; if heat input is below 2 . 5 kj / mm , or if interpass and preheating temperature is below 190 ° c ., cooling rate in welding is high , and a sufficient amount of carbide is not formed during cooling . the z value therefore does not satisfy the predetermined range . if heat input is above 5 . 0 kj / mm , or if interpass and preheating temperature is above 250 ° c ., cooling rate in welding is low , and cementite formation is accelerated in a final stage of cooling , leading to a decrease in production of v carbide in a grain boundary . the z value therefore does not satisfy the predetermined range . to produce the predetermined weld metal under such a preferred welding condition , the composition of the welding material is preferably controlled as follows . & lt ; si concentration in wire : 0 . 11 mass % or more ( preferably 0 . 15 mass % or more ), v /( cr + mo ) ratio in wire : 0 . 11 or more ( preferably 0 . 12 or more ), si / sio 2 ratio in flux : 0 . 050 or more ( preferably 0 . 060 or more )& gt ; these are determined to control the z value . if the above - described parameter is deviated from the predetermined range , cr carbide , mo carbide , and cementite are nucleated on an austenite grain boundary during cooling in welding . consequently , the amount of v carbide is decreased during sr annealing , so that the z value is not allowed to be maintained to be within the predetermined range . the welded structure of the invention includes one of the described weld metals . for example , when a boiler or a chemical reaction container is manufactured , the predetermined member is welded into a welded structure under the above - described condition , thereby the welded structure includes the weld metal of the invention . since the welded structure includes one of the weld metals of the invention , a weld bead stably has temper embrittlement resistance , creep rupture properties , strength , toughness , and sr crack resistance . this leads to improvement in reliability and durability of equipment used under environment of high temperature and pressure , such as a boiler and a chemical reaction container . to describe the effects of the invention , an example within the scope of the invention is now described in comparison with comparative examples out of the scope of the invention . weld metals were prepared using a base plate having a composition shown in table 1 under welding conditions described later , and were evaluated in properties . table 5 welding material wire composition ( mass % ( but “ v /( cr + mo )” is in ratio ) remainder : fe and inevitable impurities no . c si mn cr mo v nb n o cu ni b w al ti v /( cr + mo ) w1 0 . 135 0 . 20 1 . 2 2 . 1 1 . 03 0 . 38 0 . 021 0 . 006 0 . 015 — — — — — — 0 . 12 w2 0 . 135 0 . 20 1 . 2 2 . 1 1 . 03 0 . 40 0 . 022 0 . 006 0 . 015 — — — — — — 0 . 13 w3 0 . 125 0 . 25 1 . 3 2 . 3 1 . 06 0 . 42 0 . 022 0 . 006 0 . 015 0 . 11 — — — — — 0 . 12 w4 0 . 135 0 . 20 1 . 2 2 . 3 1 . 03 0 . 38 0 . 022 0 . 006 0 . 015 0 . 12 — 0 . 0012 — — — 0 . 11 w5 0 . 135 0 . 21 1 . 0 2 . 1 1 . 00 0 . 41 0 . 025 0 . 006 0 . 015 0 . 12 — 0 . 0018 — — — 0 . 13 w6 0 . 140 0 . 21 1 . 1 2 . 1 1 . 06 0 . 39 0 . 025 0 . 006 0 . 015 — 0 . 20 0 . 0012 — — — 0 . 12 w7 0 . 140 0 . 21 1 . 2 2 . 1 1 . 06 0 . 37 0 . 024 0 . 006 0 . 015 0 . 05 0 . 22 0 . 0012 0 . 16 — — 0 . 12 w8 0 . 140 0 . 21 1 . 3 2 . 5 1 . 04 0 . 39 0 . 023 0 . 006 0 . 015 0 . 06 0 . 20 0 . 0025 — — — 0 . 11 w9 0 . 090 0 . 20 1 . 0 2 . 3 1 . 06 0 . 38 0 . 031 0 . 006 0 . 015 0 . 12 — 0 . 0025 — — — 0 . 11 w10 0 . 170 0 . 20 1 . 2 2 . 5 1 . 06 0 . 44 0 . 038 0 . 006 0 . 015 0 . 11 — 0 . 0012 — — — 0 . 12 w11 0 . 136 0 . 13 0 . 8 2 . 4 1 . 02 0 . 39 0 . 024 0 . 006 0 . 015 0 . 11 — 0 . 0032 — — — 0 . 11 w12 0 . 115 0 . 82 1 . 3 2 . 0 0 . 95 0 . 33 0 . 025 0 . 006 0 . 015 0 . 12 — 0 . 0012 — — — 0 . 11 w13 0 . 135 0 . 29 1 . 4 2 . 5 0 . 98 0 . 41 0 . 022 0 . 006 0 . 015 0 . 11 0 . 75 0 . 0015 — — — 0 . 12 w14 0 . 135 0 . 28 1 . 1 1 . 9 1 . 05 0 . 38 0 . 025 0 . 006 0 . 015 0 . 11 — 0 . 0010 0 . 40 — — 0 . 13 w15 0 . 135 0 . 28 1 . 0 3 . 0 0 . 93 0 . 45 0 . 058 0 . 006 0 . 015 0 . 11 — 0 . 0012 — — — 0 . 11 w16 0 . 135 0 . 35 1 . 0 2 . 1 1 . 24 0 . 45 0 . 024 0 . 006 0 . 015 0 . 12 0 . 34 0 . 0018 — — — 0 . 13 w17 0 . 125 0 . 25 1 . 1 2 . 2 1 . 05 0 . 50 0 . 026 0 . 005 0 . 015 0 . 11 0 . 26 0 . 0012 — — — 0 . 15 w18 0 . 145 0 . 26 1 . 0 2 . 5 1 . 00 0 . 39 0 . 060 0 . 006 0 . 015 0 . 11 — 0 . 0015 0 . 26 — — 0 . 11 w19 0 . 135 0 . 38 1 . 0 2 . 9 0 . 98 0 . 43 0 . 040 0 . 027 0 . 015 0 . 11 0 . 22 0 . 0012 — 0 . 03 — 0 . 11 w20 0 . 135 0 . 38 1 . 2 2 . 3 1 . 10 0 . 45 0 . 012 0 . 006 0 . 026 0 . 11 0 . 06 0 . 0012 — — 0 . 02 0 . 13 w21 0 . 135 0 . 29 0 . 8 2 . 4 1 . 05 0 . 38 0 . 024 0 . 013 0 . 015 0 . 11 — 0 . 0018 — — 0 . 03 0 . 11 w22 0 . 135 0 . 40 1 . 2 2 . 1 0 . 96 0 . 37 0 . 033 0 . 006 0 . 015 0 . 11 0 . 98 — — — — 0 . 12 w23 0 . 135 0 . 21 1 . 2 2 . 3 0 . 83 0 . 37 0 . 038 0 . 006 0 . 013 0 . 11 — 0 . 0012 — 0 . 05 — 0 . 12 w24 0 . 135 0 . 20 1 . 2 2 . 1 1 . 03 0 . 35 0 . 021 0 . 006 0 . 015 — — — — — — 0 . 11 w25 0 . 135 0 . 20 1 . 1 2 . 2 1 . 03 0 . 36 0 . 021 0 . 006 0 . 015 — — — — — — 0 . 11 w26 0 . 135 0 . 20 1 . 1 2 . 1 1 . 04 0 . 38 0 . 021 0 . 006 0 . 015 — — 0 . 0015 — — — 0 . 12 w27 0 . 135 0 . 20 1 . 2 2 . 1 1 . 06 0 . 38 0 . 021 0 . 006 0 . 015 — — 0 . 0015 — — — 0 . 12 w28 0 . 135 0 . 20 1 . 0 2 . 2 1 . 06 0 . 38 0 . 021 0 . 006 0 . 015 — — 0 . 0012 — — — 0 . 12 w29 0 . 140 0 . 22 1 . 2 2 . 6 1 . 04 0 . 41 0 . 023 0 . 006 0 . 015 0 . 06 0 . 18 0 . 0025 — — — 0 . 11 w30 0 . 060 0 . 26 1 . 0 2 . 5 1 . 12 0 . 41 0 . 020 0 . 006 0 . 015 0 . 11 — 0 . 0012 — — — 0 . 11 w31 0 . 185 0 . 27 1 . 1 1 . 9 0 . 96 0 . 37 0 . 023 0 . 006 0 . 015 0 . 11 — — — — — 0 . 13 w32 0 . 135 0 . 69 0 . 6 2 . 3 1 . 07 0 . 39 0 . 022 0 . 006 0 . 015 0 . 11 — 0 . 0015 — — — 0 . 12 w33 0 . 135 0 . 28 1 . 5 2 . 3 1 . 05 0 . 40 0 . 024 0 . 006 0 . 015 0 . 11 — 0 . 0012 — — — 0 . 12 w34 0 . 140 0 . 26 1 . 1 3 . 3 1 . 36 0 . 46 0 . 031 0 . 006 0 . 015 1 . 20 — 0 . 0012 —- — — 0 . 10 w35 0 . 135 0 . 29 1 . 3 2 . 5 0 . 79 0 . 45 0 . 023 0 . 006 0 . 015 0 . 11 — 0 . 0012 — 0 . 08 — 0 . 14 w36 0 . 135 0 . 30 1 . 2 2 . 1 0 . 85 0 . 27 0 . 038 0 . 006 0 . 015 0 . 11 — 0 . 0065 — — — 0 . 09 w37 0 . 135 0 . 36 1 . 2 2 . 3 0 . 96 0 . 56 0 . 020 0 . 006 0 . 015 0 . 11 — — 0 . 55 — — 0 . 17 w38 0 . 135 0 . 27 1 . 1 2 . 5 1 . 03 0 . 39 0 . 072 0 . 006 0 . 015 0 . 11 — — — — 0 . 6 0 . 11 w39 0 . 140 0 . 43 1 . 2 2 . 7 1 . 09 0 . 39 0 . 010 0 . 006 0 . 012 0 . 11 — — — 0 . 05 — 0 . 10 w40 0 . 135 0 . 10 1 . 1 2 . 1 1 . 02 0 . 38 0 . 021 0 . 006 0 . 015 — — — — — — 0 . 12 w41 0 . 135 0 . 26 1 . 1 2 . 4 0 . 94 0 . 34 0 . 019 0 . 006 0 . 015 0 . 11 — 0 . 0010 — — — 0 . 10 w42 0 . 135 0 . 20 1 . 2 2 . 3 1 . 05 0 . 38 0 . 022 0 . 006 0 . 015 0 . 12 — — — — — 0 . 11 w43 0 . 090 0 . 20 1 . 0 2 . 29 1 . 10 0 . 38 0 . 031 0 . 006 0 . 015 0 . 12 — 0 . 0025 — — — 0 . 11 w44 0 . 135 0 . 20 1 . 2 2 . 1 1 . 03 0 . 38 0 . 020 0 . 030 0 . 015 — — — — — — 0 . 12 w45 0 . 135 0 . 20 1 . 2 2 . 1 1 . 03 0 . 38 0 . 021 0 . 006 0 . 03 — — — — — — 0 . 12 w46 0 . 135 0 . 20 1 . 2 2 . 1 1 . 03 0 . 38 0 . 020 0 . 006 0 . 015 — 1 . 2 — — — — 0 . 12 subsequently , each welded test sample was subjected to heat treatment of 705 ° c .× 8 hr as the stress relief annealing treatment ( sr treatment ). in the sr treatment , the test sample was heated up to a temperature of 705 ° c . while a heating condition was adjusted such that the heating rate was 55 ° c ./ h or less above the test sample temperature of more than 300 ° c . the test sample was then held for eight hours at 705 ° c ., and then cooled down to a temperature of 300 ° c . or lower at a cooling rate of 55 ° c ./ h or less . in the sr treatment , the heating rate and the cooling rate are each not regulated in a temperature range of the test sample of 300 ° c . or lower . subsequently , the sr - treated test sample was subjected to step cooling as an embrittlement accelerating treatment . fig3 shows a graph with a vertical axis as temperature and a horizontal axis as time , the graph explaining the treatment condition of the step cooling . as illustrated in fig3 , in the step cooling , while a heating condition was adjusted such that the heating rate was 50 ° c ./ h or less at the test sample temperature of more than 300 ° c ., the test sample was heated up to a temperature of 593 ° c . the test sample was then held for one hour at 593 ° c ., and was then cooled down to 538 ° c . at a cooling rate of 5 . 6 ° c ./ h and held for 15 hours at 538 ° c ., and was then cooled down to 524 ° c . at the same cooling rate and held for 24 hours at 524 ° c ., and was then cooled down to 496 ° c . at the same cooling rate and held for 60 hours at 496 ° c . subsequently , the test sample was cooled down to 468 ° c . at a cooling rate of 2 . 8 ° c ./ h and held for 100 hours at 468 ° c . subsequently , the test sample was cooled to a temperature of 300 ° c . or lower at a cooling rate of 28 ° c ./ h or less . in the step cooling , as with the sr treatment , the heating rate and the cooling rate are each not regulated in a temperature range of the test sample of 300 ° c . or lower . a sample for determination of a chemical composition was prepared as follows : a central portion of a weld metal formed in a groove was cut from the sr - treated test sample , and was subjected to chemical composition analysis by absorption photometry ( for b ), a combustion - infrared absorption method ( for c ), an inert gas fusion - thermal conductivity method ( for n , o ), and an inductively coupled plasma atomic emission spectrophotometry ( for other elements ). the determined chemical compositions are shown in tables 6 and 8 . & lt ; determination of number density n ( particles / μm ) of carbide particles at grain boundary & gt ; a determination procedure of the number density n ( particles / μm ) of the carbide particles at the grain boundary is now described with reference to fig1 and 2 . first , a test specimen for replica tem observation was obtained from the center of the final pass of the weld metal subjected to sr annealing of 705 ° c .× 8 hr . subsequently , two images each having a visual field of 13 . 3 × 15 . 7 μm were photographed at 7500 magnifications (( a ) of fig1 ). the images were subjected to carbide form analysis with image analysis software ( image - pro plus from media cybernetics ) according to the following procedure . ( 1 ) straight lines ai ( i = 1 , 2 , 3 , . . . , n ; n is the total of straight lines ) 6 μm in length were selected , each straight line intersecting with at least three carbide particles each having a circle - equivalent diameter of 0 . 40 μm or more (( b ) of fig1 ). ( 2 ) carbide particles each having a circle - equivalent diameter of 0 . 40 μm or more were selected , each carbide particle intersecting with one of the straight lines ai (( a ) of fig2 ). ( 3 ) the centers of circumscribed quadrangles of carbide particles adjacent to one another on each of the straight lines ai were connected to one another by straight lines bi ( i = 1 , 2 , 3 , . . . , m ; m is the total of straight lines ), and the total length of the straight lines b 1 to bm was defined as grain boundary length l ( μm ) (( b ) of fig2 ). ( 4 ) the quotient of the number of carbide particles divided by l ( μm ), each carbide particle having a circle - equivalent diameter of 0 . 40 μm or more and intersecting with one of the straight lines bi , was defined as number density n ( particles / μm ) of the carbide particles at the grain boundary . first , the thickness center of the weld metal subjected to sr annealing of 705 ° c .× 8 hr was electrolytically extracted with a 10 vol % acetylacetone - 1 vol % tetramethylammonium chloride - methanol solution . subsequently , such an extract was filtrated by a filter having a pore size 0 . 1 μm and a residue was collected , and then the residue was subjected to icp emission spectrometry to determine the concentration of compound - type v . the creep rupture properties were evaluated after the as - welded weld metal was subjected to sr annealing of 705 ° c .× 32 hr . the specific procedure was as follows . a creep test specimen , having a diameter of 6 . 0 mm and a gage length of 30 mm , was taken in a welding line direction illustrated in ( a ) of fig4 from the thickness center of the weld metal subjected to the sr annealing of 705 ° c .× 32 hr . the test specimen was subjected to a creep test under a condition of 540 ° c . and 210 mpa . a weld metal showing a rupture time of more than 1000 hr was evaluated to be good in creep rupture properties . strength was evaluated after the as - welded weld metal was subjected to sr annealing of 705 ° c .× 32 hr . the specific procedure was as follows . a tensile test specimen ( jis z3111 a2 ) was taken in a welding line direction illustrated in ( b ) of fig4 at a depth position of 10 mm from the thickness surface of the weld metal subjected to the sr annealing of 705 ° c .× 32 hr . the test specimen was determined in tensile strength ( ts ) according to the procedure of jis z 2241 . a weld metal showing ts of more than 600 mpa was evaluated to be good in strength . toughness was first evaluated after the as - welded weld metal was subjected to sr annealing of 705 ° c .× 8 hr , and second evaluated after the as - welded weld metal was subjected to sr annealing of 705 ° c .× 8 hr and successively subjected to step cooling . the specific procedure was as follows . a charpy impact test specimen ( jis z 31114 v - notch test specimen ) was taken perpendicularly to a welding line direction illustrated in ( c ) of fig4 from the thickness center of the weld metal subjected to the sr annealing of 705 ° c .× 8 hr . the test specimen was subjected to a charpy impact test according to the procedure of jis z 2242 . specifically , the temperature vtr 54 at which absorbed energy was 54 j was determined as an average of three measurements . for the weld metal subjected to step cooling after the sr annealing of 705 ° c .× 8 hr , the temperature vtr ′ 54 at which absorbed energy was 54 j was determined according to a similar procedure . a weld metal of which the vtr 54 and vtr ′ 54 were each − 50 ° c . or lower was evaluated to be good in toughness . the temper embrittlement resistance was evaluated after the as - welded weld metal was subjected to sr annealing of 705 ° c .× 8 hr and successively subjected to step cooling . the specific procedure was as follows . a weld metal satisfying “ δvtr 54 = vtr ′ 54 − vtr 54 ”≦ 5 ° c . was evaluated to be good in temper embrittlement resistance . a δvtr 54 having a negative value was represented as “ 0 ° c .”. such a value of δvtr 54 shows a good weld metal with substantially no temper embrittlement . the sr crack resistance was evaluated after the as - welded weld metal was subjected to sr annealing of 625 ° c .× 10 hr . the specific procedure was as follows . a ring crack test specimen having a slit width of 0 . 5 mm was taken from a final pass ( as - welded zone ) of the weld metal such that a neighborhood of a u notch corresponded to the as - welded zone illustrated in ( a ) of fig5 . the test was performed two times . the shape of the test specimen is shown in ( b ) of fig5 . as illustrated in ( c ) of fig5 , the 0 . 5 mm slit was forcedly contracted into a slit width of 0 . 05 mm , and then the contracted slit was closed by tig welding , so that tensile residual stress was applied to a notch bottom . the tig - welded test specimen was subjected to sr annealing of 625 ° c .× 10 hr , and then , as illustrated in ( d ) of fig5 , the test specimen was divided into three equal parts , and the section ( near the notch bottom ) of each part was observed by a light microscope to observe sr crack occurrence . a weld metal , of which all the six test specimens (= three observation surfaces by two tests ) showed no crack occurrence in the neighborhood of the notch , was evaluated to be good in sr crack resistance . tables 6 to 9 show results of such evaluations . tables 6 and 7 show the results for the shielded metal arc welding ( smaw ), and tables 8 and 9 show the results for the submerge arc welding ( saw ). an underlined numerical value does not satisfy the scope or the criterion of the invention . nos . 23 to 28 each had the z value that was below the lower limit , and were each bad in temper embrittlement resistance and / or creep rupture properties . no . 29 had the a value that was below the lower limit , and was bad in creep rupture properties . no . 30 had the c content that was below the lower limit and the o content that exceeded the upper limit , and was bad in strength , toughness , and creep rupture properties . no . 31 had the c content , the mn content , and the mo content , which each exceeded the upper limit , and had the a value that was below the lower limit , and was therefore bad in toughness , temper embrittlement resistance , and creep rupture properties . no . 32 had the si content that exceeded the upper limit and the cr content and the o content , which were each below the lower limit , and was bad in toughness and sr crack resistance . no . 33 had the mn content and the v content , which were each below the lower limit , the al content that exceeded the upper limit , and had the z value that was below the lower limit , and was therefore bad in strength , toughness , temper embrittlement resistance , sr crack resistance , and creep rupture properties . no . 34 had the cr content , the w content , and the ti content , which each exceeded the upper limit , and had the a value that was below the lower limit , and was therefore bad in toughness , sr crack resistance , and creep rupture properties . no . 35 had the mo content that was below the lower limit , and was bad in strength and creep rupture properties . in some case , low strength results in degradation in creep rupture properties . the comparative example no . 35 corresponds to such a case . no . 36 had the v content and the b content , which each exceeded the upper limit , and was bad in toughness and sr crack resistance . no . 37 had the nb content that was below the lower limit , and was bad in strength and creep rupture properties . in some case , low strength results in degradation in creep rupture properties . the comparative example no . 37 corresponds to such a case . no . 38 had the nb content that exceeded the upper limit , and was bad in toughness . no . 39 had the n content that exceeded the upper limit , and was bad in toughness . no . 40 had the cu content that exceeded the upper limit , and was bad in toughness . no . 41 had the ni content that exceeded the upper limit , and was bad in toughness . nos . 42 to 44 each had the z value that was below the lower limit , and were each bad in temper embrittlement resistance and / or creep rupture properties . as shown in tables 8 and 9 , nos . 1 to 23 satisfied the scope of the invention , and showed good results in all evaluation items . on the other hand , nos . 24 to 46 did not satisfy the scope of the invention , and showed the following results . nos . 24 to 28 each had the z value that was below the lower limit , and were each bad in temper embrittlement resistance and creep rupture properties . no . 29 had the a value that was below the lower limit , and was bad in creep rupture properties . no . 30 had the c content that was below the lower limit , and had the a value that was below the lower limit , and was therefore bad in strength and creep rupture properties . no . 31 had the c content that exceeded the upper limit and the cr content that was below the lower limit , and was bad in toughness and sr crack resistance . no . 32 had the si content that exceeded the upper limit and the mn content that was below the lower limit , and was bad in strength , toughness , and sr crack resistance . no . 33 had the mn content that exceeded the upper limit , and was bad in toughness and temper embrittlement resistance . in the comparative example no . 33 , temper embrittlement resistance was degraded , and resultantly toughness did not satisfy the predetermined value after step cooling . no . 34 had the cr content , the mo content , and the cu content , which each exceeded the upper limit , and had the a value and the z value that were each below the lower limit , and was therefore bad in toughness , temper embrittlement resistance , and creep rupture properties . no . 35 had the mo content that was below the lower limit and the al content that exceeded the upper limit , and was bad in strength , toughness , and creep rupture properties . in some case , low strength results in degradation in creep rupture properties . the comparative example no . 35 corresponds to such a case . no . 36 had the v content that was below the lower limit , the b content that exceeded the upper limit , and had the z value that was below the lower limit , and was therefore bad in toughness , temper embrittlement resistance , sr crack resistance , and creep rupture properties . in the comparative example no . 36 , temper embrittlement resistance was degraded , and resultantly toughness did not satisfy the predetermined value after step cooling . no . 37 had the v content and the w content , which each exceeded the upper limit , and was bad in toughness . no . 38 had the nb content and the ti content , which each exceeded the upper limit , and was bad in toughness and sr crack resistance . no . 39 had the nb content and the o content , which were each below the lower limit , and had the a value and the z value that were each below the lower limit , and was therefore bad in strength , toughness , temper embrittlement resistance , and creep rupture properties . nos . 40 and 41 each had the z value that was below the lower limit , and were each bad in temper embrittlement resistance and creep rupture properties . no . 42 had the z value that was below the lower limit , and was bad in temper embrittlement resistance . no . 43 had the z value that was below the lower limit , and was bad in creep rupture properties . no . 44 had the n content that exceeded the upper limit , and was bad in toughness . no . 45 had the o content that exceeded the upper limit , and was bad in toughness . no . 46 had the ni content that exceeded the upper limit , and was bad in toughness . the samples nos . 42 and 43 were prepared to simulate the existing weld metals described in ptl 6 and ptl 7 , respectively . as shown in this example , such existing weld metals each do not satisfy a certain level in at least one of the evaluation items . consequently , this example has objectively demonstrated that the weld metal according to the invention is better than the existing weld metals . although the invention has been described in detail with the embodiment and the example hereinbefore , the gist of the invention is not limited to the above - described matter , and the scope of the rights of the invention must be widely interpreted based on the description of claims . it will be appreciated that the subject matter of the invention can be widely modified or altered based on the above - described description . the present application is based on japanese patent application ( jp - 2013 - 019560 ) filed on feb . 4 , 2013 , the content of which is hereby incorporated by reference . according to the invention , a weld metal used under environment of high temperature and pressure , such as environment in a boiler or a chemical reaction container , and a welded structure including the weld metal each stably have temper embrittlement resistance , creep rupture properties , strength , toughness , and sr crack resistance even at a welding condition with large heat input . | 2 |
referring to fig1 and fig2 , the exterior of the device 10 comprises a mouthpiece 11 , a tubular case 12 , and the base 14 of a butane tank 21 . the mouthpiece is removable and creates an airtight seal with the interior of the case . with the mouthpiece removed , a tobacco cartridge ( fig5 ) is introduced to vaporization chamber 15 of a heater 16 . the mouthpiece is then reinserted to close the device . the mouthpiece is made of a high - temperature and food - safe material such as ceramic , glass , or various high - temperature plastics such as pei resin ( brand name ultem ). design is simplified by use of high temperature materials , but standard plastics or wood , etc , could also be used with the addition of an insulating component that prevents any excessive heat from reaching the user &# 39 ; s lips . to activate the device , the butane tank is pulled axially outward , partially removing it from the case . this starts the flow of butane by opening a master valve 18 , and then activating a piezoelectric igniter 13 . the tank remains in the partially removed position for the duration of use . while the master valve is open , butane flows through a thermal regulator 17 , and into the carburetor 20 . ambient air enters the case through slot 19 . a venturi in the carburetor entrains air , causing it to mix with the butane . the mixture then flows into the heater 16 . the lead of the ignitor is positioned in the heater . with the spark of the ignitor ( immediately following the start of gas flow ) the gas ignites and heat starts conducting throughout the heater . heat transfers to the cartridge by conduction , convection , and radiation . the cartridge is shaped to fill the chamber , so as to maximize surface contact for thermal conduction . as the cartridge heats , vapor generates within the cartridge and in the space immediately above it . when a user draws on the device , fresh air enters through air inlet 22 , mixes with the vapor , and the mixture is delivered to the user via the inhalation passage 23 . in the preferred embodiment , the air inlet or inlets are directed downward , so as to improve the extraction of vapor from the cartridge . they could also be directed along a diagonal through the mouthpiece , or laterally through the case itself , above the cartridge . fig3 depicts a detailed view of the heater 16 . the heater comprises a thermally conductive shell 26 and catalyst 27 . the shell could be comprised of one material , or a combination of materials welded or pressed together . the catalyst could be platinum - or palladium - impregnated metal or glass , or other suitable material known to those skilled in the art . the catalyst provides for efficient flame - less combustion of the butane . the vent 28 of the heater is positioned such that it is visible through the slot 29 of the body as shown in fig1 . this allows the user to see the catalyst which , when heated , can glow red to indicate that the device has been activated . referring again to fig3 , adjacent to the heater and in intimate thermal contact is the thermal regulator 17 . as the temperature of the heater increases , so does that of the regulator . the regulator is designed to restrict the flow of butane as the temperature increases , thus creating a feedback loop . in the preferred embodiment , the regulator consists of a bimetallic strip 60 and silicone tubing 61 which is the conduit of the butane . the two are arranged such that as the bimetallic strip heats up , it curls to pinch the silicone tube and thereby restrict the flow of butane . the reduced flow of butane results in less heat generated . the heater subsequently cools down , and so does the regulator , allowing more butane to flow again . the overall result is that a stable operating temperature is established in the heater . such a system can be readily tuned to achieve an operating temperature that varies by less than +/− 5 degrees fahrenheit . the regulator further comprises a moveable backplate 62 which allows adjustability of the operating temperature by adjusting the temperature at which the bimetallic actuator closes the tube valve . this is to be performed once at manufacture , to calibrate the device . in alternate embodiments , a control means could be used to allow the target temperature of the device changed during operation . in the preferred embodiment , the regulator comprises in part a bimetallic strip and silicone tubing valve . in alternate embodiments , the regulator could be comprised of other materials and configurations , as described later . for the purposes of vaporizing most botanicals in this device , the desired operating temperature is below 400 f ; preferably below 350 f . in the preferred embodiment , the air inlet diameter is sized such that inhalation is somewhat inhibited . this allows time for ambient air entering the chamber to heat up and not affect operating temperature considerably . it also increases velocity of the entering air , which improves circulation and mixing in the vaporization chamber . it also creates a partial vacuum , lowering the vapor point temperature for material contained in the vaporization chamber . the reduction in draw rate can also serve to give the impression of drawing on a cigarette or pipe . both the fresh air inlet and inhalation passage can be adjusted to provide appropriate draw rate for the operating temperature of the device , and the perception intended for the user . once the cartridge is consumed , the device is turned off by pushing the tank back into the case , closing the master valve . the spent tobacco cartridge is removed by opening the device and turning the body over . in the preferred embodiment , the cartridge simply falls out . in alternate embodiments , a mechanism could be used to quickly and easily remove the cartridge . this mechanism could include , but does not require , the use of a pin or slide part to eject the cartridge as another part of the device is moved or removed . the removal mechanism could also involve introduction of a foreign object . in an alternate embodiment , the mouthpiece is permanently attached to the body . in that case , the vaporization chamber could be accessed by operating a sliding or hinged door , or similar means , built into the device . the heater of the device is fitted into the case with an insulator 24 . the insulator could be made of pei ( brand name ultem ), ceramic , or other insulating material . the insulator serves to minimize thermal transfer from the heater to the case , while creating an air - tight seal . the seal prevents exhaust gases produced by the heater from entering the vaporization chamber . exhaust gases are instead vented out the case slots . since the air inlet is distant from the slots , there is substantially no contamination of the inhaled vapor mixture by heater exhaust gases . in an alternate embodiment , the insulator could be a partially hollow shell , containing a sealed vacuum . in another embodiment , the heater might be sealed directly to the case by braising in a vacuum furnace , so as to create a vacuum between the two and obviate need for an insulator component . in the preferred embodiment , the tank is made of a translucent material . this allows the user to determine the level of fuel remaining by looking at the base of the tank . in the preferred embodiment , the case is made of a material that is either a good thermal conductor ( such as aluminum ), or a poor one ( such as ceramics ). in both cases , the effect is that the body remains cool enough to touch over a large portion of its surface . in the preferred embodiment , a bimetallic actuator is used in the regulator . in alternate embodiments , a shape memory alloy actuator such nickel - titanium alloys (“ nitinol ”) could be used . alternatively , a paraffin - filled component that expands and contracts to modulate butane flow could be employed . alternatively , a system could be employed to measure the current temperature , e . g ., with a thermocouple sensor and compare it to a prescribed temperature , e . g ., with a micro - controller , and by controlling an electromechanical valve , e . g ., servo or solenoid valve . in an embodiment with user - selected temperature , as described above , the selected temperature could be used as an input to this system . in the preferred embodiment , a thermal regulator is used . in an alternate embodiment , the device is constructed without an active regulating element . this could result in reduced complexity and in lowering the overall cost of the device . in this case , the flow of butane is set at a low level . in use , the temperature inside the chamber increases until an equilibrium point where additional heat introduced equals the heat lost to the environment . heat is lost by conduction through the body of the device , and with the vapor delivered to the user . this equilibrium point determines the operating temperature of the device . by changing the butane flow rate , size and material of the burner , and other factors , the system can be calibrated to provide a fairly stable desired operating temperature . the principal advantage of the preferred bimetallic regulator feedback loop methods over the equilibrium method is that the operating temperature is not dependent on environmental factors such as ambient temperature and wind . in the preferred embodiment , a piezo - electric ignitor is used . other ignitors could be used , such as , a flint starter or battery - powered resistive coil . in the preferred embodiment , the butane tank is meant to be refillable , and has a port 25 for that purpose . as an alternate embodiment , the tank might be disposable once its fuel is exhausted . a release mechanism such as a pin or cam would be employed allowing the user to quickly remove the depleted tank and replace it with a full one . the replaceable tank might include additional parts of the device including , but not limited to , the ignitor and heater . butane is the preferred fuel source , but could be replaced by other liquid fuels , such as ethanol . in alternate embodiments of the present invention , various means of feedback could be used to indicate the following states or metrics of the device : 1 ) the device is on , 2 ) the current temperature of the vaporization chamber , 3 ) the chamber is below a prescribed operating temperature , 4 ) the chamber has reached a prescribed operating temperature and vapor is ready for consumption , and 5 ) the chamber has exceeded a prescribed operating temperature . the means of the feedback includes both physical and electronic implementations . possibilities include thermochromatic paint , light - emitting diodes and liquid crystal display . the sensing and control means for electronic feedback could be implemented by use of thermocouple and micro - controller , as is known to those skilled in the art . active elements contained in botanicals vaporize at different temperatures . in the preferred embodiment , the device is calibrated to establish a single stable temperature , intended for vaporizing solely tobacco or solely chamomile , for example . in alternate embodiments , a control means would be used to select a variety of temperature settings . the user would choose which setting based on the type of cartridge used . the control means could effect a desired temperature mechanically , such as by changing flow rate of the valve , or electronically , such as by electromechanical valve and micro - controller intermediary . butane was found to be the most energy - dense and practical fuel source . in alternate embodiments of the invention , the butane heating system is replaced by a battery - powered electric heater or other compact heat source . fig4 depicts a cutaway view of an alternate embodiment which more closely resembles a traditional pipe form . in this embodiment the device retains all of the critical elements from the preferred embodiment . the user inserts a tobacco cartridge 40 , under a sliding top piece 41 , where the cartridge mates with the heater 42 . fuel held in the tank 43 is released by turning dial 44 to open master valve 45 . the fuel travels through the regulator 51 , and then through the carburetor 46 where it draws in air through the intake port 47 and catalyzes in a manner similar to that of the preferred embodiment . as the cartridge 40 reaches its operating temperature the user places the mouthpiece 48 in their mouth and draws air in through the inhalation intake port 49 and through the vapor passage 50 where it is pre - cooled . fig5 depicts a sectional view of the tobacco cartridge 30 . in the preferred embodiment , it consists of tobacco material 31 , enclosed in a wrapper 32 , with perforations 33 , and aeration wells 34 . the wrapped cartridge allows for the easy insertion and disposal of tobacco material without creating a mess , while the perforations allow the formed vapor to be released . when the cartridge is used up it can be easily disposed of in its entirety . here , tobacco or tobacco material is defined as any combination of natural and synthetic material that can be vaporized for pleasure or medicinal use . as an example , one test cartridge was prepared as embodiment of the present invention using flue - cured tobacco , glycerin , and flavorings . those skilled in the art of tobacco product manufacture are familiar with these and other ingredients used for cigarettes , cigars , and the like . the test cartridge was produced by chopping tobacco into fine pieces ( less than 3 mm diameter , preferably less than 2 mm ), adding the other ingredients , and mixing until even consistency was achieved . in the preferred embodiment , the cartridge is primarily cylindrical . in other embodiments , the form could be modified for various reasons . as an example , the walls of the cartridge might be drafted for easier insertion into the vaporization chamber . or , the bottom of the cartridge might possess receptacles , which when combined with complimentary features on the surface cavity of the vaporization chamber would allow for more surface contact and hence improved thermal conduction . any material could be used for the wrapper , provided that when heated to the operating temperature , it does not produce significant amounts of harmful gases . aluminum foil and parchment paper are two examples . with papers , the cartridge would be manufactured in a folded - cup design , similar to that shown in fig6 . with films or metal foils , the wrapper could be pressed or blow - molded to the appropriate shape . during manufacture of the preferred embodiment , the cartridge is enclosed on all sides , and perforated on the top so that vapors can emanate upwards . in the perforation step , or in an additional step , the optional aeration wells would be created . in an alternate embodiment , the cartridge might be wrapped on all sides but leaving the top exposed , as shown in fig7 . this is possible since the purpose of the wrapper is primarily to prevent tobacco material from touching the sides and bottom of the vaporization chamber . in another embodiment , the material for the top of the cartridge might be vapor - permeable , such that perforations are not necessary . in another embodiment , the cartridge as purchased by the user has no openings , but is punctured prior to insertion into the device , or upon introduction to the vaporization device . the latter could be achieved by adding a hollow puncturing means to the mouthpiece part of the device . for example , the inhalation passage of the mouthpiece could be extended by a hollow tube . when the mouthpiece is reinserted to close the device , it pierces the cartridge previously introduced , and allows a path for vapor to exit to the user . in the preferred embodiment , the tobacco material is a homogenous mixture . in another embodiment , there might be two layers , as shown in fig8 . the moist layer 35 has higher content of vapor - forming material than the dry layer 36 , which consists of dry tobacco or other material acting as a filter . the dry layer serves to prevent any liquid from bubbling up and out of the cartridge during heating . in another embodiment of the cartridge , a lower compartment might consist entirely of a vapor - forming medium , such as glycerine . an upper region would consist of the tobacco material to be vaporized , and the two would be separated by a material that only allows the medium to pass in a vapor or gaseous phase . gore - tex ( brand name ) is one such material . in use , vapor generated in the lower region would pass through the semi - permeable membrane , volatize the active components of the tobacco , and a mix of the two would be delivered to the user upon inhalation . in another embodiment , the consistency of the tobacco material is such that the wrapper is not necessary . this is possible if at least the outer surface of the cartridge is dry and cohesive enough to not leave deposits inside the device . such a cartridge can be made by forming tobacco material in a mold . if the resulting surface is excessively moist , it can be dried by heating the cartridge in an oven . it is to be understood that the present invention is not limited to the embodiments described above , but encompasses any and all embodiments within the scope of the following claims . | 0 |
referring now more particularly to fig1 of the drawing , apparatus 10 according to the present invention for practicing golf putting strokes comprises a putting surface part 12 arranged for receiving a ball b to be putted , and a putter head guide or path defining part 14 associated with part 12 for permitting a head h of a putter p to follow unfettered an arc reflecting a natural swing when moved by a golfer g . as can be seen putting surface part 12 forms a substantially planar first surface while path defining part 14 forms a substantially planar second surface arranged extending at a predetermined angle related to the first surface . putting surface part 12 includes a planar member 16 constructed from a suitable material , such as sheet metal , and the like , forming a straight edge 18 along one side thereof from which extends an upstanding ledge 20 terminating in a lip 22 generally coplanar with member 16 . ledge 20 partially cooperates with member 16 , and with guide part 14 to be discussed below , to form a trough 24 arranged for receiving a head h of a putter p as seen in fig2 . provided on an upwardly facing surface of planar member 16 is a detent arrangement 26 , 26 &# 39 ; including a plurality of side - by - side dimples 28 , 28 &# 39 ; capable of restraining a golf ball b from movement prior to being struck by head h of a putter p . the reason for duplication of the detent arrangement 26 , 26 &# 39 ; is to permit adjustment , in a manner to be described in detail below , of apparatus 10 for use by either left handed or right handed golfers . associated with dimples 28 , 28 &# 39 ; are grooves 30 , 30 &# 39 ;, respectively , extending transversely of the trough 24 portion of part 12 to act as a guide for squaring a putter , or bringing it perpendicular to the intended travel path of a ball when lining up a shot . the edge of planar member 16 parallel to but spaced from edge 18 is provided with a downwardly extending rib 32 which can form a slight point as illustrated for penetration into a carpet , ground , or other suitable surface having sufficient give in order to anchor member 16 on the associated surface , earth e as illustrated , and prevent apparatus 10 from movement during use . putter head path defining part 14 includes a planar sheet 34 , also constructed from sheet metal , and the like , defining a longitudinal edge 36 from which depends at an appropriate angle , 72 ° as illustrated , a flange 38 . as best seen in fig2 flange 38 abuts the upper surface of planar member 16 adjacent the edge thereof from which rib 32 depends , and is removably attached to member 16 by a fastener assembly 40 . the uppermost edge of sheet 34 , that being the edge spaced from edge 36 , advantageously terminates in a downwardly turned rim 42 so as to strengthen sheet 34 and prevent warpage thereof . by using the illustrated angle of 72 ° between flange 38 and sheet 34 , the latter will have an angle relative to a perpendicular extending upwardly from the upper surface of member 16 of approximately 18 °, which angle has been found to provide a natural swing plane when a putter head h is moved along the upwardly facing surface of sheet 34 . fastener assembly 40 includes two pair of holes 44 , 44 &# 39 ; formed in flange 38 , and a pair of apertures 46 formed in the portion of planar member 16 disposed near the edge in which rib 32 is provided spaced to match either of the pairs of holes , 44 , 44 &# 39 ; in order to selectively cooperate with one pair of same and accomodate either right handed or left handed golfers by moving guide part 14 longitudinally relative to surface part 12 . suitable fasteners such as the illustrated bolts 48 and cooperating wingnuts 50 can be employed to releasibly retain guide part 14 in a desired relationship with respect to surface part 12 . as illustrated in fig1 through 3 , apparatus 10 is set - up to accomodate a right handed player . by moving guide part 14 with the respect to surface part 12 such that holes 44 &# 39 ; register with apertures 46 , it will be appreciated that a left handed golfer can use apparatus 10 by placing a ball b on one of the dimples 28 &# 39 ; of detent arrangement 26 &# 39 ; in a manner not shown . as shown in fig3 the holes 44 and 44 &# 39 ; are elongated which allows adjustable positioning of the path defining part 14 relative to the ledge 20 of the putting surface part 12 . such adjustable positioning is advantageous in that it allows putter heads of different lengths , i . e ., the distance between the heel and toe of the head , to be used in the apparatus 10 . this adjustable feature accounts for the aligned plural dimples 28 , 28 &# 39 ; of the detent arrays 26 , 26 &# 39 ; provided on the upwardly facing surface of the putting surface part 12 , which allow the ball b to be properly placed at the sweet spot of the variously sized putter heads usable in conjunction with the apparatus 10 . referring now to fig4 of the drawings , wherein the arcuate path a , that the head h of the putter p will take when swung , is illustrated diagrammatically . as is apparent from the arcuate path a when swung , the putter head h will be elevated relative to the putting surface part 12 during the backswing and will return to the putting surface part 12 during the downswing . this is apparent from the putter head positions illustrated in phantom lines in fig4 with the position i being an intermediate position of a backswing or downswing and the position t being indicated of the top of the backswing . however , it will be noted that when a natural swing is made , the arcuate path a will be in a plane which is parallel to the planar sheet 34 of the path defining part 14 , as indicated by the putter head position t in fig2 and that maintaining such parallelism is important in teaching and / or mastering a proper putting stroke . therefore , when utilizing the apparatus 10 of the present invention , the golfer g may place the heel of the putter head h in engagement with the slanted outwardly facing surface of the planar sheet 34 , as shown in fig2 and maintain such engagement throughout the backswing and downswing portions of the putting stroke . in this manner , the golfer will get the feel of a natural swing . it will be appreciated however , that since the sheet 34 defines the plane of a natural putting stroke , the above discussed engagement of the putter head h with the sheet 34 is not essential in that a simple visual indication of the proper swing plane will aid the golfer in mastering proper execution of the proper putting stroke . by configuring the apparatus 10 as hereinbefore described , a putting stroke which deviates excessively from the natural swing plane may cause the putter head h to move into contact with either the upstanding ledge 20 of the putting surface part 12 or the slanted sheet 34 of the path defining part 14 , thus correcting such an improper swing . accordingly , the apparatus 10 can train one to putt with a natural swing plane in a simple and efficient manner , without necessarily fettering any part of the putter being used . as can be seen from fig5 of the drawings , a wedge - shaped element 52 having a slot 54 extending inwardly from the pointed end thereof can be selectively inserted between flange 38 and planar member 16 for changing the angle between member 16 and planar sheet 34 to , for example , approximately 90 ° as illustrated . element 52 can be retained in place by use of the aforementioned fasteners which attach flange 38 to member 16 . more specifically , a bolt 48 can pass through an aperture 46 , slot 54 of element 52 , and either a hole 44 , 44 &# 39 ;, as appropriate , to be retained in place by a wingnut 50 , and the like . either element 52 can be made sufficiently long to extend between a pair of holes 44 or 44 &# 39 ;, with a pair of slots 54 spaced appropriately , or a pair of elements 52 , each provided with a slot 54 , can be used as desired . as can be readily understood from the description above and from the drawings , putting practice apparatus according to the present invention permits one to develop a natural arc putting stroke in a simple and efficient manner without actually fettering or restraining the putter . as long as the user of the apparatus is stroking with a natural swing , no part of the apparatus will necessarily be contacted . if , however , the user &# 39 ; s swing deviates excessively from a natural swing , the apparatus will be contacted by the head of the putter , thus correcting the swing . while it has been indicated above that the apparatus can be constructed from sheet metal , and the like , it is to be understood that the device can be constructed in any suitable known manner from any suitable material , such as a suitable synthetic resin . further , the manner of attachment of the surface part and guide part to one another can be varied , such as by using different bolt fasteners , slot - and - tab class of attachment and arrangements , or any other suitable mode of attachment , none of which are shown . further , adhearance of the surface part of the apparatus to an associated supporting surface can be accomplished in any suitable manner , such as by suitable , known suction devices ( not shown ) which could adhear the apparatus to a tile floor or other suitable hard surface . while the principles of the invention have now been made clear in an illustrated embodiment , there will be immediately obvious to those skilled in the art , many modifications of structure , arrangements , proportions , the elements , materials , and components used in the practice of the invention , and otherwise , which are particularly adapted for specific environments and operation requirements without departing from those principles . the appended claims are therefore intended to cover and embrace any such modifications within the limits only of the true spirit and scope of the invention . | 0 |
with reference first to the figure , there is illustrated an advantageous environment for use of the concepts of the invention . in this discussion , the following terms will be used : ______________________________________product : the item which is being manufactured ( e . g ., lemonade ) additive : a chemical or mixture of chemicals that are the ingredients in a product ( e . g ., powdered lemonade mix and water ) chemical component : distinct chemicals that make up an additive ( e . g ., sugar and lemon flavor in the powdered lemonade mix ) ______________________________________ it is to be understood that chemical components include both those chemicals directly added to the additive and contaminants that are not purposely added but are residual of the manufacturing process , naturally occurring in the additive , etc . the above definitions should not be interpreted as a limiting factor in this disclosure . rather , they are included simply to allow one skilled in the art to more clearly understand the present invention . to further assist those skilled in the art , the figure shows the flow diagram for the present invention . as the first step of the present invention , appropriate information is gathered on the chemical additive . this information can be conventionally placed in the memory of any suitable computer . this information can be , typically , obtained from material safety data sheets ( msds ), supplier technical bulletins , direct requests to the manufacturer for information , etc . the information needed includes , but is not limited to , standard names of the chemical components and the concentration of the chemicals in the additive . if the concentration of the chemical in the additive is unknown , the quantity can be estimated or determined by appropriate analysis . information is also needed on the amount of chemical additive to be used in the product being manufactured . information on the intended use of the material , where it is added in the production process , citation of regulatory compliance , appropriate regulatory limits and other information that the user of the invention may deem useful , while not required may be included in the database . the applicable toxicity values also need to be included . this information can be obtained from numerous sources , e . g ., california environmental protection agency &# 39 ; s safe drinking water and toxic enforcement act of 1986 ( proposition 65 ), national institute for occupational safety and health &# 39 ; s registry of toxic effects of chemical substances , msds sheets , etc . unfortunately , toxicity information can be expressed by several different methods and these need to be converted to the appropriate uniform unit . for this example , the toxicity values are converted to an allowable daily dose ( add ). adds represent an estimation of the dose resulting in a one - in - a - million risk ( or other level of risk deemed appropriate by the user ) of toxicological effect . because long term toxicity is considered to be more reliable for evaluating chronic risk than short term data , long term data is typically used , when available , to calculate adds . adds are in units of milligrams of chemical per kilogram of body weight per day ( mg / kg / day ). adds express the value which can be ingested , inhaled , etc . without toxicological effects at a defined level of risk . as mentioned above , toxicity values are expressed by a number of different methods , each of which require different techniques to convert it to an add . the following are several examples of the calculation and are not intended to be an exhaustive exhibition of all techniques , but rather they are simply illustrative of the conversion process . for carcinogens , the allowable daily dose can be calculated by ( eq . 1 ) using the cancer slope factor reported by the u . s . environmental protection agency ( usepa ) and a one - in - a - million risk . ## equ1 ## where ______________________________________add = allowable daily dose ( mg / kg / day ) csf = cancer slope factor ( mg / kg / day ). sup .- 1 risk = 10 . sup .- 6 , which represents a one - in - a - million risk______________________________________ for non - carcinogens with chronic toxicity , the allowable daily dose is calculated by ( eq . 2 ) using the usepa reference dose for chronic , non - cancer toxicity : for chemicals for which the epa has established maximum contaminant levels in drinking water , the allowable daily dose is calculated by ( eq . 3 ) as follows : ## equ2 ## where ______________________________________add = allowable daily dose ( mg / kg / day ) mcl = maximum contaminate level ( mg / liter ) w = volume of water consumed by an adult in a day = 2 liter / day bw = body weight of an adult human = 70 kg______________________________________ as stated above , the allowable daily dose in these examples is an estimation of the dose resulting in a one - in - a - million risk of a toxicological effect . the next part of the present invention converts this allowable daily dose ( add ) to an exposure based upon the use of the product . for example , for products to be used for food packaging the appropriate equation ( eq . 4 ) is as follows : ## equ3 ## where ______________________________________ac = allowable concentration ( mg of chemical / kg of paperboard ) add = allowable daily dose ( mg / kg / day ) fc = food - contact per surface area of packaging = 10 grams / inch . sup .- 2 f = total intake of food per day = 3 kilogram / day cf = fraction of food in contact with packaging ( defined as the &# 34 ; consumption factor &# 34 ; by the fda ) bw = body weight of an adult human = 70 kg m = migration factor______________________________________ by choice of an appropriate consumption factor ( cf ) value , equation ( 4 ) is applicable for polymer - coated paperboard ( cf = 0 . 21 ), uncoated paperboard ( cf = 0 . 1 ), glass ( cf = 0 . 08 ) or polymers ( cf = 0 . 41 ). other modifications to this equation can include choosing a different value for body weight that reflects a targeted subgroup of the human population . one also needs to assign a value for the migration factor . for food packaging , this factor reflects the percentage of chemical migrating from the package into the food . the most conservative assumption for food packaging would be to assume that all of the component chemical migrates from the packaging , which is m = 1 . this highly conservative approach is preferred unless specific and appropriate migration information is available . as noted above , this example calculates the toxicological risk associated with the use of food packaging ; however , other exposure scenarios can be calculated . for example , one can calculate the toxicological risk to a worker of a chemical migrating from paper being handled in the office . using the above values and choosing , for this example , food packaged in both polymer coated and uncoated paperboard ( i . e ., cf = 0 . 1 + 0 . 21 = 0 . 31 ), equation ( 4 ) can be simplified to eq . 5 : in equation ( 5 ) the allowable daily dose based upon a one - in - a - million risk of toxicological effect can be converted into a concentration of a chemical in the paper packaging which has the same one - in - a - million risk . many manufacturers track their ingredient usage by calculating the weight of additive per weight of a final product . for example , this could be grams of additive per kilogram of polymer , pounds of additive per ton of pulp , etc . thus , to make the present invention of more utility , the allowable concentration of a chemical component in paperboard ( ac ) should be converted to an &# 34 ; allowable addition rate &# 34 ;, based upon the concentration of the chemical component in the additive . this can be expressed as follows in ( eq . 6 ): ## equ4 ## where ______________________________________aar = allowable addition rate of an additive in paper - board per kilogram of dry fiber ac = allowable concentration of chemical component per kilogram of dry fiber c . sub . c = concentration of chemical component in the additive c . sub . v = conversion factor = 10 . sup . 6 milligram / 1 kilogram______________________________________ it is to be understood that equation ( 6 ) is solely based upon the toxicity of the chemical component , the concentration of the component in the additive and conservative assumptions regarding the migration characteristics of the chemical component . this equation specifically does not include information about the actual addition rate of the additive used by the manufacturer . the resulting value ( aar ) in equation ( 6 ) is no longer in terms of the individual chemical component , but rather it has been converted to a term based upon the additive . as previously mentioned , this is important because measurements in a manufacturing facility are , typically , based upon , and measured , using addition rates . it is important to remember that a single additive will 35 typically have multiple chemical components . since these different chemical components will likely have different toxicity characteristics , by implication from equations presented above , an additive will have multiple allowable addition rates . the calculated allowable addition rate for each chemical component in an additive from equation ( 6 ) is compared to the actual addition rate used in the production facility . if the aar ( i . e ., the toxicologically allowable addition rate ) is greater than the actual addition rate used in production , then no further work needs to be performed . however , in the event that the actual addition rate used in production exceeds the allowable addition rate , then the additive and the specific chemical are clearly identified and marked ( or flagged ). the specific flag used for a chemical component is dependent on the difference between the actual addition rate and the calculated allowable addition rate . if the difference is small , i . e ., & lt ; 10 %, then the program responds by listing certain easily performed actions . as the difference between values increases , the complexity and the cost of the resolution increases . the following table illustrates examples of the relative differences and association actions . ( note : these examples are not intended to limit the scope of the invention .) table______________________________________difference in toxicological and actual addition rates action of options______________________________________less than 10 % review values entered into the program and any assumptions contact suppliers to ascertain if values provided reflect current product supplied to facility have results reviewed by a qualified toxicological analyst less than 100 % contact suppliers to ascertain if values provide reflect current product supplied to facility have qualified professional review the physical properties of the specific chemical to identify if the compound is eliminated during processing , i . e ., the volatilization of compounds with low boiling points . have results reviewed by a qualified toxicological analyst greater than two consider performing specific migration analysis orders of for the chemical in question magnitude (& gt ; 100 %) have results reviewed by a qualified toxicological analyst______________________________________ the flagging step is very important to the present invention because it acts as a filter for the data . this filtering eliminates all the non - essential information about the chemical components which allows the user to focus on those items that require further work . furthermore , the present invention enables a person not suitably skilled to use the present invention ; therefore , people skilled in the art ( i . e ., toxicologists , etc .) only have to investigate flagged chemical components and not all chemicals that make up an additive . this affords a significant cost savings . it is to be understood that the flow chart of the figure , equations 1 - 6 and the table can be conventionally placed in a suitable computer so that they can be more easily utilized when attempting to employ the novel aspects of the present invention . it is to be understood that the utility of the present invention is not limited to determining product safety . it can also be modified for use in identifying potential environmental and safety problems . for example , one could assume that all materials with a boiling point less than a certain temperature will be volatilized during the manufacturing process . therefore , one could calculate if the amount of these chemicals exceeds various safety and environmental limits . once given the above disclosure , many other features , modifications or improvements will become apparent to the skilled artisan . such features , modifications or improvements are , therefore , considered to be a part of this invention , the scope of which is to be determined by the following claims . | 6 |
the aspects of the present disclosure and the various features and advantageous details thereof are explained more fully with reference to the non - limiting aspects and examples that are described and / or illustrated in the accompanying drawings and detailed in the following description . it should be noted that the features illustrated in the drawings are not necessarily drawn to scale , and features of one aspect may be employed with other aspects as the skilled artisan would recognize , even if not explicitly stated herein . descriptions of well - known components and processing techniques may be omitted so as to not unnecessarily obscure the aspects of the present disclosure . the examples used herein are intended merely to facilitate an understanding of ways in which the present disclosure may be practiced and to further enable those of skill in the art to practice the aspects of the present disclosure . accordingly , the examples and aspects herein should not be construed as limiting the scope of the present disclosure , which is defined solely by the appended claims and applicable law . moreover , it is noted that like reference numerals represent similar parts throughout the several views of the drawings . surgical intervention for back pain may occur for people with chronic back pain , perhaps for which other treatments have failed . surgery may be required , for example , for people who have chronic lower back pain and sciatica ( often diagnosed with a herniated disc ), spinal stenosis , spondylolisthesis ( vertebra of the lumbar spine slips out of place ), vertebral fractures with nerve involvement , or other indications as assessed by a medical professional . also , surgery may be necessary for people with discogenic lower back pain ( e . g ., degenerative disc disease ) that may occur as part of the aging process . in these situations , among others , implants may be included in a course of treatment . generally , the goal may be to achieve supplemental fusion or complete fusion of the spine . with reference to fig1 - 9 , an embodiment of the fixation device 10 is shown . in the exemplary embodiment , the fixation device 10 includes a first endplate 20 , a second endplate 40 , first and second fixed plates 60 , 70 , a pair of sliding plates 80 , 90 , a central ramp 110 , and a driving ramp 130 . each of the endplates 20 , 40 includes a body 22 , 42 extending between opposed ends 21 , 23 ; 41 , 43 . in the illustrated embodiment , each endplate body 22 , 42 defines an outer surface 24 , 44 connecting the first end 21 , 41 and the second end 23 , 43 , and an inner surface 26 , 46 connecting the first end 21 , 41 and the second end 23 , 43 . in an embodiment , each endplate 20 , 40 defines a through opening 25 , 45 . the through openings 25 , 45 , in an exemplary embodiment , are sized to receive bone graft or similar bone growth inducing material and further allow the bone graft or similar bone growth inducing material to be packed in a central area of the device 10 . the outer surface 24 , 44 of each endplate 20 , 40 may be flat and generally planar to allow the outer surface 24 , 44 of the endplate 20 , 40 to engage with an adjacent vertebral body . alternatively , one or both of the outer surfaces 24 , 44 can be curved convexly or concavely to allow for a greater or lesser degree of engagement with the adjacent vertebral body . it is also contemplated that the outer surfaces 24 , 44 can be generally planar but include a generally straight ramped surface or a curved ramped surface , angled , or otherwise configured . the presence of one or more ramped surfaces may allow for engagement with the adjacent vertebral body in a lordotic fashion . while not illustrated , in an exemplary embodiment , one or both outer surfaces 24 , 44 may include texturing or other surface features to aid in gripping the adjacent vertebral bodies . although not limited to the following , the texturing or other surface features can include teeth , ridges , friction increasing elements , keels , gripping or purchasing projections , or the like . referring to fig3 and 9 , the inner surface 26 of the first endplate 20 defines a first pair of spaced apart extensions 30 at the first end 21 of the body 22 and a second pair of spaced apart extensions 34 at the second end 23 of the body . the extensions 30 at the first end 21 are positioned oppositely of the extensions 34 at the second end 23 , e . g ., on the first end 21 , the extension 30 on the right side is at the edge while the extension on the left side is inward of the edge and on the second end 23 , the extension 34 on the right side is inward of the edge while the extension on the left side is at the edge . similarly , the inner surface 46 of the second endplate 40 defines a first pair of spaced apart extensions 50 at the first end 41 of the body 42 and a second pair of spaced apart extensions 54 at the second end 43 of the body . with the second endplate 40 , the extensions 50 , 54 are opposite of those on the first plate 20 i . e . on the first end 41 , the extension 50 on the right side is inward from the edge while the extension on the left side is at the edge and on the second end 43 , the extension 54 on the right side is at the edge while the extension on the left side is inward of the edge . with this configuration , the extensions 30 of the first endplate 20 overlap the extensions 50 of the second endplate 40 and the extensions 54 of the second endplate 40 overlap the extensions 34 of the first endplate 20 . each of the extensions 30 , 34 , 50 , 54 defines a respective ramped surface 31 , 35 , 51 , 55 . the ramped surfaces 31 , 35 , 51 , 55 are configured to be engaged by ramped surfaces on the central ramp 110 and the driving ramp 130 , as will be described hereinafter . each of the extensions 30 , 34 , 50 , 54 also defines a respective groove 33 , 37 , 53 , 57 . the grooves 33 , 37 , 53 , 57 are configured to be engaged by projections on the central ramp 110 and the driving ramp 130 to maintain the device 10 in an assembled condition and to guide movement of the endplates 20 , 40 , as will be described hereinafter . each endplate 20 , 40 includes a fixed plate 60 , 70 attached along one side edge of the body 22 , 42 . each fixed plate 60 , 70 of the illustrated embodiment includes a body 62 , 72 extending from a fixed end 61 , 71 to a free end 63 , 73 . the fixed plate bodies 62 , 72 may have any desired shape to complement the intended engagement with respective spinous processes , and may be mirror images of one another or may be distinct from one another . the inner surface 64 , 74 of each fixed plate 60 , 70 includes a plurality of spikes 66 , 76 or the like to grip the spinous processes when engaged therewith . the outer surface of each fixed plate may include a blind bore 67 , 77 , through bore or the like . the bores 67 , 77 , in an exemplary embodiment , are sized to receive bone graft or similar bone growth inducing material . a lateral adjustment bar 28 , 48 extends outwardly from the opposite side edge of the body 22 , 42 of each end plate 20 , 40 to a free end 29 , 49 . the adjustment bars 28 , 48 support respective sliding plates 80 , 90 . each sliding plate 80 , 90 of the illustrated embodiment includes a body 82 , 92 extending from a connection end 81 , 91 to a free end 83 , 93 . the sliding plate bodies 82 , 92 may have any desired shape to complement the intended engagement with respective spinous processes , and may be mirror images of one another or may be distinct from one another . the inner surface 84 , 94 of each fixed plate 80 , 90 includes a plurality of spikes 86 , 96 or the like to grip the spinous processes when engaged therewith . the outer surface of each fixed plate may include a blind bore 87 , 97 , through bore or the like . the bores 87 , 97 , in an exemplary embodiment , are sized to receive bone graft or similar bone growth inducing material . the connection end 81 , 91 of each sliding plate 80 , 90 includes a connection assembly 88 , 98 which allows the sliding plate 80 , 90 to be mounted on a respective lateral adjustment bar 28 , 48 such that the sliding plate 80 , 90 is laterally adjustable but rotationally fixed . in the illustrated embodiment , each connection assembly 88 , 98 defines a receiving bore 85 , 95 extending laterally through the body 82 , 92 and configured to receive the respective lateral adjustment bar 28 , 48 . the receiving bores 85 , 95 and the lateral adjustment bars 28 , 48 have complementary shapes which allow lateral adjustment but prevent relative rotation . in the illustrated embodiment , the receiving bores 85 , 95 and lateral adjustment bars 28 , 48 have complementary rounded rectangle shapes , but other non - circular shapes are possible . to set the position of the sliding plate 80 , 90 along the respective lateral adjustment bar 28 , 48 , a set screw 100 extends into a through bore 89 , 99 defined in the respective connection assembly 88 , 98 and intersects with the receiving bore 85 , 95 . each set screw 100 includes a threaded portion 102 and a driving head 104 with an engagement end 103 extending toward the receiving bore 85 , 95 . the threaded portion 102 is configured to engage threads within the through bore 89 , 99 . a retaining ring 105 or the like may be positioned about each set screw 100 and engage a groove within the through bore 89 , 99 to retain the set screw 100 with the through bore 89 , 99 after assembly . once the sliding plate 80 , 90 is positioned at a desired lateral position along the respective lateral adjustment bar 28 , 48 , the set screw 100 is threadably advanced such that the engagement end 103 engages the lateral adjustment bar 28 , 48 and fixes the sliding plate 80 , 90 relative to the respective endplate 20 , 40 . the central ramp 110 includes a body 112 extending from a first end 111 to a second end 113 . a through bore 114 extends through the body 112 from the first end 111 to the second end 113 and is configured to receive a drive screw 120 therethrough . the drive screw 120 has a threaded portion 122 and drive head 124 . a flat washer 126 and a drag reducing washer 128 may be positioned within the through bore 114 between the drive head 124 and an internal shoulder defined within the through bore 114 ( not show ) to facilitate driving of the central ramp while minimizing drag . notches 119 or the like may be defined along the central ramp body 112 configured for engagement with a delivery / positioning tool ( not shown ) or the like . the second end 113 of the central ramp 110 defines a first pair of ramps 116 and a second pair of ramps 117 . the first ramps 116 are aligned with and configured to slidably engage the ramps 31 on the first endplate 20 . the second ramps 117 are aligned with and configured to engage the ramps 51 on the second end plate 40 . projections 118 adjacent the ramps 116 extend into the grooves 33 on the first endplate 20 while projection adjacent to the ramps 117 ( not shown ) extend into the grooves 53 on the second endplate 40 . engagement between the projections 118 and grooves 33 , 53 maintains the central ramp 110 assembled to the endplates 20 , 40 and guides movement of the endplates 20 , 40 as the central ramp 110 is advanced . the driving ramp 130 includes a ramp body 132 and a screw receiving portion 134 . a threaded blind bore 139 extends into the screw receiving portion 134 and is configured to receive the threaded portion 122 of the drive screw 120 . as such , rotation of the drive screw 120 in the advancement direction causes the central ramp 110 and the driving ramp 130 to move toward one another . the ramp body 132 of the driving ramp 130 defines a pair of first ramps 136 and a pair of second ramps 137 ( see fig3 ). the first ramps 136 are aligned with and configured to slidably engage the ramps 55 on the second endplate 40 . the second ramps 137 are aligned with and configured to engage the ramps 35 on the first end plate 20 . projections 138 adjacent the ramps 136 extend into the grooves 57 on the second endplate 40 while projections 138 adjacent to the ramps 137 extend into the grooves 37 on the first endplate 20 . engagement between the projections 138 and grooves 37 , 57 maintains the driving ramp 130 assembled to the endplates 20 , 40 and guides movement of the endplates 20 , 40 as the driving ramp 130 is advanced . having generally described the components of the fixation device 10 , operation thereof will generally be described . the fixation device 10 may be inserted at its fully collapsed height as illustrated in fig1 , 4 and 5 to allow for easy insertion into a collapsed interspinous space . during insertion , the spikes 66 , 76 of the fixed plates 60 , 70 may be compressed into the respective spinous processes . after insertion , the fixation device 10 may be expanded by rotating the drive screw 120 in an advancement direction . as the drive screw 120 is rotated , the central ramp 110 and driving ramp 130 are drawn toward one another , with the ramps 31 riding up the ramps 116 , the ramps 51 riding up the ramps 117 , the ramps 35 riding up the ramps 137 , the ramps 55 riding up the ramps 136 . such movement causes the endplates 20 , 40 to move away from one another , thereby increasing the height of the fixation device 10 to get the desired fit , or used to distract the interspinous space to relieve pressure on neurological elements . as the endplates 20 , 40 move away from one another , the fixed plates 60 , 70 and sliding plates 80 , 90 move in conformity therewith . after expansion of the endplates 20 , 40 , the sliding plates 80 , 90 are moved along the lateral adjustment bars 28 , 48 and compressed onto the spinous processes . once positioned , the sliding plates 80 , 90 are locked into position using the set screws 100 . referring to fig1 - 16 , another embodiment of the fixation device 10 ′ is shown . the fixation device 10 ′ of the present exemplary embodiment is similar to the fixation device 10 of the previous embodiment and includes a first endplate 20 ′, a second endplate 40 ′, first and second fixed plates 60 , 70 , a pair of sliding plates 80 , 90 , a central ramp 110 ′, and a driving ramp 130 ′. only the differences between the embodiments will be described . otherwise , the fixation devices 10 , 10 ′ operate is substantially the same manner . in the present embodiment , the endplates 20 ′ and 40 ′ and the central ramp 110 ′ are configured to cause pivoting between the endplates 20 ′, 40 ′ prior to expansion thereof . as in the previous embodiment , each endplate 20 ′, 40 ′ includes a body 22 ′, 42 ′ extending from a first end 21 ′, 41 ′ to a second end 23 ′, 43 ′. referring to fig1 , in the present embodiment , the first ends 21 ′, 31 ′ do not include extensions , but instead have a tapered end surface which defines the ramps 31 ′ 51 ′. the second ends 23 ′, 43 ′ are similar to the previous embodiment and include extensions 34 ′, 54 ′ defining the ramps 35 , 55 . the extensions 34 ′ 54 ′ also define inward ramps 36 , 56 . inward of the extensions 34 , 54 , each endplate body 22 ′, 44 ′ defines a retaining notch 29 , 49 . the retaining notches 29 , 49 are configured to be engaged by an inward end 113 ′ of the central ramp 110 ′ and prevent inward advancement of the central ramp 110 ′ until the endplates 20 ′ 40 ′ have pivoted relative to one another . the central ramp 110 ′ includes a body 112 ′ extending from a first end 111 ′ to a second end 113 ′ with the body 112 ′ having a longer length compared to the central ramp body 112 of the previous embodiment . a through bore 114 extends through the body 112 ′ from the first end 111 ′ and is configured to receive the drive screw 120 therethrough . the first end 111 ′ of the central body 110 ′ defines ramps 116 ′ and 117 ′. the ramps 116 ′ and 117 ′ are configured to engage the ramps 31 ′ and 51 ′, respectively . the second end 113 ′ of the central ramp 110 defines a pair of extensions 123 on a first surface thereof and a pair of extensions 125 on the opposite surface . the extensions 123 are aligned with and configured to be received in the notches 29 defined by the first endplate 20 ′ and the extensions 125 are aligned with and configured to be received in the notches 49 defined by the second endplate 40 ′ ( see fig1 ). the extensions 123 also define forward ramps 127 while the extensions 125 define forward ramps 129 . the driving ramp 130 ′ includes a ramp body 132 ′ and a screw receiving portion 134 ′. the screw receiving portion 134 ′ is shorter in length than in the previous embodiment . a threaded blind bore 139 extends into the screw receiving portion 134 ′ and is configured to receive the threaded portion 122 of the drive screw 120 . the ramp body 132 ′ of the driving ramp 130 ′ defines a pair of ramps 136 ′ aligned with and configured to slidably engage the ramps 55 on the second endplate 40 ′. the ramp body 132 ′ also defines a pair of ramps 137 ′ which are aligned with and configured to engage the ramps 35 on the first end plate 20 ′. projections 138 ′ adjacent the ramps 136 ′, 137 ′ extend into the grooves 37 , 57 on the endplates 20 ′, 40 ′. engagement between the projections 138 ′ and grooves 37 , 57 maintains the driving ramp 130 ′ assembled to the endplates 20 ′, 40 ′ and guides movement of the endplates 20 ′, 40 ′ as the driving ramp 130 ′ is advanced . having generally described the components of the fixation device 10 ′, operation thereof will generally be described with reference to fig1 - 16 . the fixation device 10 ′ may be inserted at its fully collapsed height as illustrated in fig1 and 13 to allow for easy insertion into a collapsed interspinous space . as illustrated , in the collapsed position , the extensions 123 and 125 are positioned in the respective notches 29 , 49 . during insertion , the spikes 66 , 76 of the fixed plates 60 , 70 may be compressed into the respective spinous processes . after insertion , the angular relation between the endplates 20 ′, 40 ′ is adjusted by rotating the drive screw 120 in an advancement direction . during initial advancement of the drive screw 120 , engagement of the extensions 123 , 125 in the notches 29 , 49 prevents the central ramp 110 ′ from advancing . only the driving ramp 130 ′ is able to advance . as the driving ramp 130 ′ advances , the ramps 35 ride up the ramps 136 ′ and the ramps 55 ride up the ramps 137 ′. as illustrated in fig1 , such causes the endplates 20 ′, 40 ′ to pivot relative to one another with the ends 23 ′ and 43 ′ moving away from one another . once the endplates 20 ′, 40 ′ have pivoted a maximum amount ( fig1 ), the extensions 123 , 125 are clear of the notches 29 , 49 . as such , with continued rotational advancement of drive screw 120 , the central ramp 110 ′ is free to move toward the driving ramp 130 ′, with the central ramp 110 ′ and the driving ramp 130 ′ drawn to one another , with the ramps 31 ′ riding up the ramps 116 ′, the ramps 51 ′ riding up the ramps 117 ′, the ramps 35 riding up the ramps 136 ′, the ramps 55 riding up the ramps 137 ′, and the forward ramps 127 , 129 riding along the inward ramps 36 , 56 , as illustrated in fig1 and 16 . such movement causes the endplates 20 ′, 40 ′ to move away from one another , thereby increasing the height of the fixation device 10 to get the desired fit , or used to distract the interspinous space to relieve pressure on neurological elements . as the endplates 20 ′, 40 ′ pivot and then move away from one another , the fixed plates 60 , 70 and sliding plates 80 , 90 move in conformity therewith . after expansion of the endplates 20 ′, 40 ′, the sliding plates 80 , 90 are moved along the lateral adjustment bars 28 , 48 and compressed onto the spinous processes . once positioned , the sliding plates 80 , 90 are locked into position using the set screws 100 . the expandable fixation devices 10 , 10 ′ may be manufactured from a number of suitable biocompatible materials including , but not limited to , titanium , stainless steel , titanium alloys , non - titanium metallic alloys , polymeric materials , plastics , plastic composites , peek , ceramic , elastic materials , or other suitable biocompatible materials . in an exemplary embodiment , bone graft or similar bone growth inducing material can be introduced around and / or within the fixation device 10 , 10 ′ to further promote and facilitate the intervertebral fusion . the fixation device 10 , 10 ′, in one embodiment , is preferably packed with bone graft or similar bone growth inducing material to promote the growth of bone through and around the fixation device . such bone graft may be packed between the endplates of the adjacent vertebral bodies prior to , subsequent to , or during implantation of the fixation device . some advantages of the devices described in this disclosure are the ability to insert a spinous process fusion implant at a reduced height and then increase the height after insertion to achieve an accurate anatomical fit . since the size of the implant is adjustable , it also greatly reduces the complexity of inserting an interspinous device since one device covers a wide range of implant sizes , negating the need for several variations of implant lengths and widths . the implant may be preassembled , greatly reducing the number of steps required to insert the device , which simplifies the overall procedure and reduces operating room time . while the present disclosure has been described in terms of exemplary aspects , those skilled in the art will recognize that the present disclosure can be practiced with modifications in the spirit and scope of the appended claims . these examples given above are merely illustrative and are not meant to be an exhaustive list of all possible designs , aspects , applications or modifications of the present disclosure . | 0 |
with reference to the schematic drawing illustrated in fig2 in a first preferred embodiment of the invention , the performance and efficiency of the transistor action associated with field effect transistor 2 is enhanced by use of bipolar parasitic transistor 4 connected at its collector and emitter to a respective drain / source of transistor 2 . a drain / source of field effect transistor 6 is connected to the base of transistor 4 while the other drain / source of field effect transistor 6 is connected to the drain / source of field effect transistor 2 . the gates of transistors 2 and 6 are connected together . fig3 illustrates a top view of the foregoing discussed circuit elements fabricated as an integrated circuit . gate 8 overpasses drain / source regions 10 . drain / source regions 10 can also serve as an emitter or a collector of bipolar transistor 4 shown in fig2 . base region 12 underlies gate 8 and is connected to a drain / source region 10 through interconnect 14 . the actual interconnection of base region 12 to a drain / source region 10 can be made , for instance , by silicide . there are many advantages associated with the use of the foregoing described structure shown in fig2 and 3 . for instance , fig4 illustrates inverter 13 , including load transistor 14 . preferably , load transistor 14 is a p - channel transistor as is illustrated . a drive transistor , shown here as a n - channel transistor 2 , is active after the voltage at its gate ( and thus the input of the inverter ) has transitioned from a logic low to a logic high level ( assuming an enhancement mode transistor ). as shown in the graph of inverter input and inverter output vs . time in fig5 after the input has transitioned from a logic low to a logic high , under heavily loaded conditions , there is a portion of time during which the output of the inverter remains at a logic high level . during this portion of time , transistor 6 conducts and turns bipolar transistor 4 on . transistor 2 conducts to discharge the load charge and continues to do so even after trnsistor 4 is off at v out ( where v out is the output voltage )= v sat where v sat is the saturation voltage between the collector and emitter of bipolar transistor 4 ). switching speed of an inverter made according to the invention is increased by virtue of using parasitic bipolar transistor 4 to drop the voltage at the output of inverter 13 . the advantages offered by the invention include the use of a smaller load device ( as compared with a comparable conventional load transistor of a cmos inverter ) for a given drive while maintaining the low power advantage of cmos . such assistance can be delivered for the other transition ( low to high output ) as well by making use of a pnp parasitic transistor associated with a p - channel load transistor . fig6 illustrates a schematic drawing of the invention with such a modification , in which parasitic bipolar transistor 15 is used with load transistor considering the input transition from high to low , as shown in the graph of inverter input and inverter output vs . time in fig5 there is a portion of time during which the output of the inverter remains at a logic low level . during this portion of time , p - channel transistor 16 conducts and turns bipolar transistor 15 on . transistor also conducts during this time and continues to conduct beyond the point when transistor 15 turns off . switching speed of an inverter made according to the invention is increased by virtue of using parasitic bipolar transistor 15 to pull - up the voltage at the output of inverter 13 . the foregoing invention can be fabricated as an integrated circuit on a semiconductor , such as silicon , according to well known methods of semiconductor transistor fabrication . further , the invention is particularly well suited for fabrication as a silicon - on - insulator ( soi ) device . since the field effect transistors are not required to provide all the current , they can be relatively small as compared with other transistors used in conjunction with the invention . for instance , transistors 6 and 16 of fig4 and 6 can be constructed of minimal width and length since the leakage between drain and source is likely inconsequential . the foregoing described invention allows high on - chip density and results in high speed capability while maintaining its low power advantages . the invention is particularly useful for drive heavy loads . although the invention has been described in detail herein with reference to its preferred embodiment , it is to be understood that this description is by way of example only , and it is not to be construed in a limiting sense . it is further understood that numerous changes in the details of the embodiments of the invention , and additional embodiments of the invention , will be apparent to , and may be made by , persons of ordinary skill in the art having reference to this description . it is contemplated that all such changes and additional embodiments are within the spirit and true scope of the invention as claimed below . | 7 |
fig1 provides a simplified representation of a typical drilling rig 99 . boreholes 110 are drilled into the earth with a drill string comprising a drill bit 106 connected to the surface by multiple joints of drill pipe 107 . a downhole acoustic transmitter and sensors 105 may be located near the bit , to provide information about the formation geology , fluid pressure , wellbore geometry , etc . additional and / or alternative bottom hole assembly ( bha ) components such as positive displacement motors , air hammers , rotary steerable devices , and other devices may be present . the drill pipe 107 is threaded into a square or hexagonal section pipe called a kelly 104 which is driven by a rotary table 101 . typically , the kelly 104 is attached to the swivel 100 via a saver sub 103 . the swivel 100 is supported by a bail 102 which is carried by a hook 111 , attached to traveling blocks 112 . the traveling blocks 112 are lifted and lowered by a cable assembly 113 . according to an embodiment of the invention , and referring to fig2 , an apparatus 1 for receiving downhole acoustic signals is removably attachable to an above - surface rotating component of the drill string , below the bearing surface of the swivel 100 , and preferably on the saver sub 103 , or the top portion of the kelly 104 . these preferred locations provide the optimum acoustic location on the drilling rig 99 ; the bearing surface and the change in acoustic impedance between the drill string and the swivel 100 act as an acoustic reflector , and thus all points above the swivel 100 only contains a small fraction of the acoustic energy generated downhole . while the description of the apparatus 1 is in the context of use on a drilling rig , it is to be understood that the apparatus 1 may also be attached to a service rig , slant rig , well head , or other surface equipment associated with boreholes in the earth . the apparatus 1 includes a plurality of housings 10 each linked together with a bolt 12 and nut 13 which act as a pivot for a hinge 14 integrated into each housing 10 . the housings 10 contain instruments 2 for receiving acoustic signals , processing the acoustic signals into electronic data , and transmitting the data as rf signals to an above - surface monitoring station 108 ( as shown in fig1 ). the acoustic signals are transmitted from the downhole acoustic transmitter 105 , and through a transmission medium , typically the drill pipe 107 , kelly 104 , and the saver sub 103 . referring to fig8 , the instruments 2 comprise two accelerometers 3 which are electrically communicative with conditioning circuitry 4 . the accelerometers 3 measure axial accelerations associated with acoustic wave signals transmitted from the downhole acoustic transmitter 105 . as acoustic waves pass through the saver sub 103 , the sub 103 and the housing 10 attached to it are moved in a oscillating manner . since the accelerometers are attached to the housing which is oscillating , they are also oscillated . the accelerometers measure the accelerations associated with the oscillations by producing a voltage signal proportional to the magnitude of the acceleration they experience . signals from the accelerometers 3 are electrically transmitted to the signal conditioning circuitry 4 for conditioning , then output of the signal conditioning circuitry 4 is sampled by an analog - to - digital converter ( adc ) 5 . the sample signals are transmitted to a processor 6 , which takes these samples , and encodes them in a suitable communication protocol , and transmits the encoded signal through an interface 7 to a transmitting radio - frequency ( rf ) modem 8 . a power supply 9 such as batteries are electrically connected to the instruments 2 to power same . alternatively , the accelerometers 3 can be calibrated to receive downhole acoustic signals from sources other than the acoustic transmitter 105 . in such case , the apparatus 1 serves as a monitor of downhole conditions , and for example , can be used to monitor the operation of a downhole air hammer ( not shown ) by monitoring the acoustic signals emitted by the air hammer as a result of its operation . referring now to fig1 , 8 , and 9 , rf signals are transmitted by the modem 8 via an antenna 42 and are received by a monitoring station antenna 109 in a safe area monitoring station 108 . the received signal is transmitted from the antenna 109 to a connected receiving rf modem 110 , where the signal is decoded and transmitted to a connected portable computer 114 or other similar display device . this wireless transmission allows the apparatus 1 to operate continuously , regardless of the rotation state of the drill string . it also provides the additional benefit of eliminating the need to run cabling around the drill rig 99 and monitoring station 108 , which would be prone to damage or interfering with the drilling operation . the modem 8 and antenna 42 can also receive signals transmitted by the monitoring station 108 , and as such serves as a wireless rf transceiver . referring again to fig2 and 3 , the housing 10 serves as a protective enclosure for the instruments 2 against the harsh outside environment of the drilling rig 99 . the housing 10 includes a cover 15 and an instrument bay 16 covered by the cover 15 . the instrument bay 16 has side walls and a base ; two sets of hinges 14 protrude from the outside surface of the base , one set at each longitudinal edge thereof . the cover 15 seals against an o - ring seal ( not shown ) located in a groove ( not shown ) in the lip of the instrument bay side walls . in the event the apparatus 1 is used in hazardous conditions , the seal prevents potentially explosive gases from entering into the housing 10 and coming in contact with a source of ignition . the seal also prevents rain , dust , oil , or other contaminants from entering the housing 10 , which could damage the instruments 2 . the instruments 2 may be shock isolated by an elastomer ( not shown ) inside the housing 2 ; such isolation is especially preferred where the apparatus 1 operates in high shock and vibration environments . four housings 10 are provided to house the instruments 2 and power supply 9 ; the housings 10 are pivotably interconnected at their respective hinges 4 by the bolts 12 and nuts 13 . at the housing 10 at one end of the line of interconnected housings 10 , one set of hinges is pivotably connected to a spacer member 17 . the spacer member 17 has a slab - like body with two sets of hinges , with each set of hinges located at each longitudinal edge of the body . the other set of hinges of the spacer member 17 is pivotably attached to a hook 21 , which has three spaced - apart teeth 30 . the hook 21 is one component of a fastening assembly 28 . the fastening assembly 28 also includes a pair of rod end eyebolts 19 pivotably attached at their proximal end to the housing 10 at the other end of the interconnected housings 10 . the eyebolts 19 are spaced apart and generally parallel to each other , and extend perpendicularly from the pivot bolt 12 . a bolt bar 20 has a pair of holes extending transversely through its body , that are configured to allow the eyebolts 19 to slide through the bolt bar 20 . the eyebolts 19 are threaded near their distal ends , and tightening nuts 18 are used to secure the bolt bar 20 to the eyebolts 19 . the fastening assembly 28 engages by hooking the hook 21 onto the bolt bar 20 such that the eyebolts 19 extend between the spaces between the hook teeth 30 . referring to fig3 , the apparatus 1 can be wrapped around a tubular portion ( e . g . the saver sub 103 ) and secured in place by tightening the nuts 18 against the eyebolts 19 . contact teeth 22 are provided to enhance the physical attachment of the apparatus 1 to the tubular portion . the teeth 22 also serve to enhance acoustic conduction between the rotating component and the housing 10 , by providing a high pressure contact interface . the teeth 22 protrude from base of the instrument bay 16 ; in this embodiment , the teeth are an integral part of the protruding hinges 14 , but the teeth 22 may also separately protrude from the instrument bay 16 base . referring to fig4 , additional spacer members 17 ( b ), 17 ( c ), 17 ( c ), 17 ( d ), and 17 ( e ) may be added to the first spacer member ( now referred to as 17 ( a )) to enable the apparatus 1 to surround larger diameters tubes such as the 12 ″ section shown in fig4 , or to other larger perimeter components . also , the number of housings 10 may be increased or decreased depending on the number of instruments 2 needed . multiple housings 10 in the apparatus 1 are desirable to enable the diametrical profile ( the height of the side walls ) of the housings 10 to be minimized . this enables the apparatus 1 to be attached to and rotate with an above - surface rotating component without coming into contact with non - rotating parts of the drilling rig 99 . referring now to fig5 and 6 , a flexible hydraulic hose 23 may be used to provide a protected conduit between adjacent housings 10 , for electrical connectors ( not shown ) to interconnect instruments 2 in the adjacent housings 10 . a drilled hole 25 is provided in each adjacent housing 10 , and each end of the hose 23 has a hollow barbed fitting 24 that secures each end of hose 23 in the hole 25 of each housing 10 . the barbed fitting 24 expands the hydraulic hose in the drilled hole 25 , thereby forming a secure sealed connection . external tapered ridges ( barbs ) 26 are provided on the fitting 24 prevent the fitting 24 from coming out of the hole 25 due to flexure or vibration . the hydraulic hose 23 protects the electrical connectors from moisture or contact with rig equipment that may otherwise damage it . during rotary drilling , the apparatus 1 will rotate with the drill string , but must still be able to communicate with a display device , typically a portable computer located in a safe area , and thus a hardwired communication means is not possible . the current invention uses a rf modem to provide this communication link . referring now to fig7 a & amp ; b , the rf antenna 42 is enclosed in the instrument bay 16 of one of the housings 10 . this housing 10 has a rf - transparent cover 41 , and retaining plate 40 for the cover 41 . an o - ring ( not shown ) located in a groove 43 machined in the instrument bay 16 to form a seal against the rf - transparent cover 41 . the rf - transparent cover 41 is preferably made from an impact - resistant plastic , such as polycarbonate , compatible with the temperature extremes found on drilling locations . although the rf transmission occurs substantially perpendicular to the plane of the rf transparent cover 41 , the reflections in the rig structure provide what is known to those skilled in the art as a multi - path environment . in effect , multiple reflections provide a substantially continuous rf path between transmitter and receiver pair , thereby enabling continuous data transmission . this effect is particularly important as the transmitter may be rotating due to the operation of the drill string . optionally , the apparatus 1 may be configured to send as well as receive acoustic signals from the downhole acoustic transmitter 105 . while the present invention has been described herein by the preferred embodiments , it will be understood by those skilled in the art that various changes may be made and added to the invention . the changes and alternatives are considered to be within the spirit and scope of the present invention . | 4 |
detailed descriptions of the preferred embodiment are provided herein . it is to be understood , however , that the present invention may be embodied in various forms . therefore , specific details disclosed herein are not to be interpreted as limiting , but rather as a basis for the claims and as a representative basis for teaching one skilled in the art to employ the present invention in virtually any appropriately detailed system , structure or manner . the present invention provides a system , method and process for automatic formation flight control for use in either a commercial or military flight application , helicopter and space vehicles . it is used to avoid mid - air collisions during formation flight and provide guidance to vehicles requiring close maneuvering in flight regimes , orbital flight and maneuvering as part of some of the exemplary embodiments . for instance , as illustrated in fig2 , the system may be used to initiate automatic formation flight control by aircraft 210 that aircraft 210 has entered the correct formation selection , iff code and password to initiate communications with aircraft 230 on which resides as illustrated in fig1 , processor 110 , communications transceiver 120 and autopilot 130 with an aircraft communications bus 140 . as conceptually illustrated in fig1 , the system generally includes a processor 110 , a communications transceiver 120 , an autopilot 130 and a communications bus 140 all of which are located on the vehicle ( e . g . on aircraft 210 and 230 in fig2 or aircraft 100 in fig1 ). thus the exemplary embodiment of which is illustrated in fig1 might include aircraft 100 plus others in the formation with the same capability . as an overview , automatic formation flight control system 110 initiates the formation communications with n + x aircraft in the formation and repeatedly interrogates the other systems as well as each other individually as to the position in the fz ( formation zone ) 260 as illustrated in fig2 with a computation of rfp ( relative formation point ) 240 as illustrated in fig2 . this is a composite of airspeed , ias ( indicated airspeed ), position as known through gps ( global positioning calculations ), look ahead calculations to include turbulence and winds aloft at the current altitude and wingtip clearance selection 250 as illustrated in fig2 . the system includes an automatic reversion function if the flight leader is loss due to either a mechanical or action related event . an automatic formation flight control system according to the present invention may be a system installed on a vehicle , or may include the vehicle itself or other vehicles . in any case , the present invention may require additional hardware , or may be constructed , all or in part , using hardware already installed on the vehicle , e . g . for other purposes . in some embodiments , such as illustrated in fig2 , the vehicle is a flight of two aircraft ( e . g . 210 and 230 ). however , the vehicle may be another type of vehicle such as a helicopter or a space vehicle or platform . in addition , in other embodiments , the vehicle may be a orbiting space platform in which there is a landing or docking zone that requires a synchronizing of flight paths to match velocity , position and axial movement , a group of unmanned remote piloted vehicles , or generally any other vehicle configured to move in a controlled formation . referring to fig2 , a formation selection of a “ flight of two ”, results in the leader 210 initiating the formation with the appropriate iff ( identification friend or foe ) code along with the password for this mission with the wingman 230 and the associated system on that aircraft . upon receiving the correct acknowledgment fig3 ( transaction process initiation of formation request ), the automatic formation flight control system ( affcs ) begins to poll the other aircraft for the data required such as the fz 260 ( formation zone ) calculations and the rfp 220 ( relative formation point ) as illustrated in fig2 in addition to the display of the formation on the display as part of the processor system 110 as illustrated in fig1 . course , speed , altitude , turbulence and look ahead flight plan corrections are then shared and sent to the respective autopilot and / or autothrottle to alter the course to prevent a mid - air collision . any navigational procedures can be utilized as part of the affcs system to control a mission profile ( e . g . a joint bombing run on a target ). although described herein as being separate systems or components , as would be understood by a person skilled in the art , conceptual components described herein of these and other systems may be combined in the same equipment or may be part of other systems or equipment unrelated to the present invention . a formation zone ( fz ) 260 as illustrated in fig2 is generally an area of spatial interest , which locates a vehicle controlled by an affcs system . it may be comprised of the computed rfp closest to next aircraft , a computed volume or protected fz around the vehicle and may also be comprised of a box or sphere . the data would include position as determined by gps ( global positioning ), tas ( true airspeed ), ias ( indicated airspeed ), altitude , radar altimeter , ivsi ( instantaneous vertical speed indicator ), wingtip clearance selection , look ahead trending ( turbulence and / or weather ) and the creation of a six sided box or sphere around the vehicle with calculated corners or volume and rfp 240 ( relative formation point ) as illustrated in fig2 . multiple rfp &# 39 ; s may be created as required by the formation selection , which might include vehicles above , and below the leader 210 . this results in the creation of a spatial relationship between the vehicles and the ability then to display the formation under affcs control on the displays in each of the vehicles . in many embodiments , the formation zones ( fz ) 260 are particular calculated spatial areas relative to the other vehicles also calculated formation zones . however , the formation zone in accordance with the present invention may be defined relative to other references or coordinate systems provided the calculation systems ( processor 110 ) are capable of providing information relative to those references or coordinate systems , or that can be converted to such . the processor system 110 is typically located on the vehicles that are participating in controlled formation flight and provides the input and output to the autopilot 130 , the communications transceiver 120 , the display 160 and via message packets data to other vehicles ( n + x ) under control of affcs . processor 110 may be a computer or computer processor , typically capable of performing operations and manipulating data . as illustrated in fig1 , processor 110 receives information from various inputs such as gps , ivsi , radar altimeter , ias , tas , pressure altimeter , wingtip clearance selection , formation selection and calculates the fz 260 and rfp 240 for the vehicle . the processor then creates a message packet to be sent to the other vehicles under affcs control so that they can monitor and update their individual displays , relative positions and clearance requirements . the processor 110 also receives message packets from the other vehicles and uses that data to determine the display parameters for display 160 and trend analysis for the entire flight formation . processor 110 is configured to initiate , or provide controlling input to , the autopilot 130 , the processor on vehicles under affcs control , and the occupants of the vehicle , such as the pilot or similar flight officer . processor 110 may have other responsibilities or be part of another system such as , for example , a navigation computer , a control system , or a flight management system ( fms ). processor 110 may be programmed in a computer language such as c ++, typically in ways familiar to a person skilled in the art of programming . for example , processor 110 may be programmed or configured to calculate the fz 260 and the rfp 240 and initiate formation flight control to multiple vehicles participating through the unique iff and mission password . the leader 210 as illustrated in fig2 has the main authority for the formation . processor 110 may be programmed to continuous calculations of spatial position and share this information via message packets with the other vehicles processors in a coordinated manner so as to avoid conflicts and mid - air collisions . in the more complex embodiments , processor 110 may be configured to take into consideration the motion , relative position ; spatial trends as affected by winds aloft and weather . processor 110 may then suggest adjustments in the formation profile and pass this information along to the other vehicles so that a uniform formation clearance is maintained . the amount of adjustment , for instance , may be proportional , or otherwise related to , the speed , position , altitude , fz 260 , buffer control zone 220 ( which takes into account the wingtip clearance selection and trend analysis ) and recommended to the leader vehicle via autopilot and autothrottle plus also statused to the other vehicles in the formation for update or action . processor 110 may utilized display color change ( e . g . from blue to yellow ) to highlight a potential conflict in the formation flight in order to alert the pilot or pilots to a future possible conflict . processor 110 will recommend actions and immediately react to the trend if it determines that it has the potential of creating a mid - air situation by directing the autopilot or autothrottle 130 to move the control surfaces in a manner that eliminates the conflict or increase or reduce speed via the autothrottles to place the vehicle in conformance with the overall formation . this action is typical throughout the entire embodiment of this invention . referring to the embodiment in fig2 , the automatic formation flight control system provides the means to reduce mid - air collisions during close formation flight regimes which at current speeds and maneuverability capabilities exceed the man / machine interface and require , especially in coordinated flight maneuvers ( e . g . bombing missions ), accurate control of the entire formation . this is especially critical in low visibility or night operations where the elements of stealth or surprise are important to the mission success . in embodiments on aircraft , such as aircraft 210 in fig2 , existing systems on the aircraft may provide most of the hardware required . for instance , the fms may perform the processing , communications ; positioning , input / output processing and the cdu may provide the visual display . in some embodiments only wiring and software changes may be required . for instance , a fz , rfp and buffer zone algorithm may be required . fig3 illustrates a method according to the present invention . the method is one of many which is used by the processor 310 to establish and maintain communications and thereby control of a flight formation under affcs . typically , the vehicle occupants or pilots begin the affcs operation by selecting the formation 340 , entering the iff and mission password on the processor 310 , it then creates a message packet to send to the other vehicle 350 via the communications transceiver 320 , it is received and confirmed by the other vehicles 360 , it is then acknowledged 370 in the processor and the autopilot engage command is sent 380 to the autopilot 330 and the formation is displayed on 390 . feedback is provided 335 to the processor 310 to assist in calculating turbulence dampening requirements for the formation . likewise all previous actions described in detail within these specifications are acted upon by the processor in similar manner . in the foregoing specification , the invention has been described with reference to specific exemplary embodiments . however , one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below . accordingly , the specification and figures are to be regarded in an illustrative rather than a restrictive sense and all such modifications are intended to be included within the scope of the present invention . in addition , benefits , other advantages , and solutions to problems , and any element ( s ) what may cause any benefit , advantage , or solution to occur or become more pronounced are not to be construed as critical , required , or essential feature or element of any or all the claims . as used herein , the terms “ comprises ”, “ comprising ”, or any other variation thereof are intended to cover non - exclusive inclusion , such that a process , method , article , or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process , method , article , or apparatus . while the invention has been described in connection with a preferred embodiment , it is not intended to limit the scope of the invention to the particular form set forth , but on the contrary , it is intended to cover such alternatives , modifications , and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims . | 1 |
the term &# 34 ; mechanical transmission &# 34 ; is used to designate a change - speed or change - gear transmission having a plurality of selectable gear ratios between the input and output shafts thereof , which may be selectively engaged and disengaged by the selective engagement and disengagement of positive jaw clutches . the term &# 34 ; downshift &# 34 ; as used herein shall mean the shifting from a higher speed gear ratio to a lower speed gear ratio . as is known , a lower speed gear ratio ( such as 8th speed ) will have a higher numerical value than a higher gear ratio ( such as 9th speed ). downshifting includes a downshift by a single ratio , such as a 9th - speed - to - 8th - speed downshift , and skip downshifting , such as a direct shift from 10th speed to 8th speed . fig1 schematically illustrates a vehicular automated mechanical transmission system 10 including an automated multiple - speed , change - gear transmission 12 driven by a fuel - controlled engine 14 , such as a well - known diesel engine , through a non - positive coupling such as a master friction clutch 16 . the output of the automated transmission 12 is output shaft 18 , which is adapted for driving connection to an appropriate vehicle component such as the differential of a drive axle , a transfer case or the like . the crankshaft 20 of engine 14 will drive the driving plates 22 of the master friction clutch 16 , which are frictionally engageable to driven plates 24 for driving the input shaft 26 of transmission 12 . the aforementioned powertrain components are acted upon , monitored by and / or controlled by several devices , each of which will be discussed briefly below . these devices include a throttle pedal position or throttle opening monitor assembly 28 , which senses the operator - set position of the operator - controlled throttle device 30 , a brake - applied monitor assembly 32 which senses operator operation of a brake pedal 34 , and a shift control monitor assembly 36 by which the operator may select a reverse ( r ), neutral ( n ) or forward drive ( d ) mode of operation of the vehicle . other types of shift control devices may be used , such as the up and down pulser illustrated in aforementioned u . s . pat . no . 4 , 648 , 290 and / or the shift control device illustrated in u . s . pat . no . 5 , 441 , 463 , the disclosure of which is incorporated herein by reference . the devices also may include a fuel control device 38 for controlling the amount of fuel to be supplied to engine 14 , an engine speed sensor 40 which senses rotational speed ( es ) of the engine , a clutch operator 42 which engages and disengages master clutch 16 , which also may provide information as to the status of the clutch , an input shaft speed sensor 44 for sensing the rotational speed ( is ) of transmission input shaft 26 , a transmission operator 46 , which is effective to shift the transmission 12 into a selected gear ratio and / or to provide a signal indicative of a gear neutral and / or of the currently engaged gear ratio of the transmission , and an output shaft speed sensor 48 for sensing the rotational speed ( os ) of output shaft 18 . an engine brake 50 may be provided for selectively retarding the rotational speed of the engine 14 under the control of a manually operated engine brake operator 52 , usually in the vehicle cab , allowing the operator to selectively apply the engine brake . preferably , the engine 14 is electronically controlled and is equipped to provide information on and to receive information from an electronic data link conforming to a known protocol , such as sae j1922 or sae j1939 or iso 11898 . the sensors may be of any known type of construction for generating analog and / or digital signals proportional to the control parameter monitored thereby . similarly , the operators may be of any known electric , hydraulic , pneumatic or combination type for executing operations in response to command output signals . the aforementioned devices supply information to and / or accept command output signals from a central processing unit or control 54 . the central processing unit 54 may include analog and / or digital electronic calculation and logic circuitry , as is well known in the prior art . an electrical power source ( not shown ) and / or a source of pressurized fluid ( not shown ) provides electrical and / or fluid power to various sensing and / or operating and / or processing units . in addition to direct inputs , the central processing unit 54 may be provided with circuits for differentiating input signals from the various sensors to provide a calculated signal indicative of the rates of change thereof . as is known and as disclosed in aforementioned u . s . pat . no . 4 , 595 , 986 , central processing unit 54 is adapted to receive various input signals 54a from the sensors and to process same according to predetermined logic rules to issue command output signals 54b to the appropriate system actuators . in fully or partially automated mechanical transmission systems of the type illustrated in fig1 synchronization of the jaw clutch members associated with engagement of a target gear ratio is normally accomplished by selectively increasing or decreasing engine speed , with the master clutch engaged , to cause the input shaft to rotate at a speed generally equal to the product of the output shaft speed and the numerical value of the target gear ratio ( i . e ., es = is = os * gr ). for downshifts , where input shaft speed must generally be increased , increased fueling of the engine will provide the desired increase in engine speed . upon manual or automatic selection of an allowable downshift , i . e ., a downshift into a target gear ratio ( gr t ), wherein the product of the numerical value of the gear ratio and the output shaft speed will not exceed a maximum allowable engine speed , implementation of the downshift is normally accomplished in a sequence involving disengagement of the currently engaged gear ratio , which may involve disengagement of the master clutch and / or manipulation of engine fueling , reengagement and / or maintaining engaged the master friction clutch , increasing engine fueling to cause the engine to rotate at a substantially synchronous speed for engaging the target gear ratio under current vehicle operating conditions and , upon sensing synchronous conditions , commanding that the jaw clutches associated with the target gear ratio be brought into positive engagement . under certain conditions , the vehicle engine may not accelerate sufficiently to cause the engine speed to reach a substantially synchronous value for engagement of the target gear ratio . such conditions may involve deliberate or inadvertent application of the vehicle engine brake , a fault in the engine controller or engine fuel supply and / or excessive acceleration of the vehicle . according to the present invention , a control method and system is provided which will sense such conditions and will automatically initiate a degraded mode of operation wherein a new downshift target gear ratio , a degraded mode downshift target gear ratio ( gr dmt ), is selected such that the new ratio is the lowest available gear ratio which may be successfully synchronized at the highest sensed engine speed sensed during attempts to synchronize for the original downshift target gear ratio . fig2 is a schematic illustration , in flow chart format , of the control logic utilized by the control method and system of the present invention . briefly , at initiation of an attempted downshift into a target gear ratio , the transmission is caused to assume a neutral condition , the master clutch is caused to engage , the engine is commanded to a synchronous speed for downshifting into the target gear ratio , and a timing sequence is initiated . if prior to expiration of a predetermined reference period of time , such as about 2 . 0 seconds , the engine speed achieves a substantially synchronous value , the transmission actuator is commanded to cause engagement of the jaw clutches associated with the target gear ratio and the timer is reset to zero and turned off . if , however , the period of time expires prior to the engine accelerating to the required engine speed for synchronous engagement of the target gear ratio , a degraded mode of operation is declared and a degraded mode downshift target gear ratio ( gr dmt ) is determined as a function of the maximum sensed engine speed and current output shaft speed . the engine is then commanded to the synchronous speed for engaging the degraded mode target gear ratio and , upon achieving the synchronous speed , the transmission actuator is caused to engage the degraded mode target gear ratio . accordingly , it may be seen that a new and improved downshift control for a fully or partially automated vehicular transmission system is provided which will sense conditions indicative of an inability to synchronize for a selected downshift target gear ratio and , in such circumstances , will enter into a degraded mode of operation wherein the best available downshift target ratio in view of achievable engine speed will be engaged . although the present invention has been described with a certain degree of particularity , it is understood that various modifications are possible without departing from the spirit and scope of the invention as hereinafter claimed . | 1 |
exemplary embodiments of the present invention will now be described in detail with reference to the annexed drawings . in the following description , a detailed description of known functions and configurations incorporated herein has been omitted for clarity and conciseness . the harq scheme proposed in embodiments of the present invention is designed to support both a sharq scheme and a aharq scheme in one system . in the proposed harq scheme , during data transmission , a transmitter first determines whether it will transmit data with the sharq scheme or the aharq scheme preferably according to a predetermined rule . thereafter , the transmitter includes an id for the determined harq scheme in control information and transmits the control information . a data receiver then detects an id for the harq scheme from the control information to determine with which harq scheme the data was transmitted , and adaptively receives the data according thereto . in determining the harq scheme , if the data transmission is a forward transmission from a base station to a mobile station , a base station scheduler can determine a harq scheme to be used for this transmission at every transmission time . however , if the data transmission is a reverse transmission from a mobile station to a base station , the mobile station transmits data with a harq scheme predetermined by the base station . the harq scheme is preferably determined depending on service type , size of transmission packet data , class of the mobile station , load of the current network , and so forth . in the following description , the term “ sharq ” denotes a scheme that has fixed initial transmission time and retransmission time , and transmits a control channel including control information only at the initial transmission as described in fig1 . however , in yet other embodiments of the present invention the included sharq scheme can be the modified sharq scheme pursued by a particular system . the modified sharq scheme includes a scheme for transmitting control information even at the retransmission time . for example , the modified sharq scheme has the fixed initial transmission time and retransmission time , but it transmits a small amount of control information even at the retransmission time unlike the common sharq scheme shown in fig1 . in the modified sharq scheme , because the initial transmission time and the retransmission time are fixed , the ms id , data control information , arq id , and sub - packet id in the control information as shown in table 1 , are not transmitted during retransmission . however , if a change in an mcs level is permitted during retransmission of the modified sharq scheme , the mcs information can be transmitted even at the retransmission . in addition , if it is allowable to differentiate the amount and positions of resources used for a data channel during modified sharq retransmission from those at the initial transmission , the used control information can be used even at the retransmission . it should be noted that such modifications can also be modified in embodiments of the present invention . although embodiments of the present invention will be described with reference to the common sharq scheme described in fig1 , it can also be applied to the modified sharq scheme . that is , embodiments of the present invention will be described with reference to the sharq scheme that transmits no control information during retransmission . however , it should be noted that embodiments of the present invention can be applied even to the modified sharq scheme that transmits a small amount of control information during retransmission . fig3 is a block diagram illustrating a structure of a transmitter according to an exemplary embodiment of the present invention . with reference to fig3 , a description will now be made of a structure and operation of a transmitter according to an exemplary embodiment of the present invention . a response channel receiver 301 receives a response signal transmitted by a receiver , and outputs the received response signal to a scheduler 303 . that is , the response channel receiver 301 receives a signal indicating ack or nack for the packet transmitted from the receiver through a data channel , and provides the received signal to the scheduler 303 . a data buffer 305 comprises a memory for storing data to be transmitted to a specific receiver . the data buffer 305 provides information on the data to be transmitted to the receiver , to the scheduler 303 . that is , the data buffer 305 provides information indicating whether there is stored data to be transmitted to the receiver and , if any , the amount of the stored data . the data buffer 305 comprises a retransmission buffer ( not separately shown in fig3 ) for storing retransmission data . that is , the data buffer 305 includes the retransmission buffer for storing the data until it receives an ack for the transmitted data or the current transmission reaches the maximum number of retransmissions , or until upper layer processing is completed . in addition , the data buffer 305 can provide information on a characteristic of the transmission data or a type of the service according to embodiments of the present invention , and can also provide information on the class type of the receiver . alternatively , the information on the characteristic of the transmission data or the type of the service , and the information on the class type of the receiver can be provided by a controller 311 . the scheduler 303 receives the ack / nack information provided from the response channel receiver 301 , and the information on the characteristic of the transmission data or the type of the service and the information on the class type of the receiver , provided from the data buffer 305 or the controller 311 . further , the scheduler 303 receives system load information from the controller 311 . based on the received information , the scheduler 303 determines the data to be transmitted next , and also determines a transmission scheme . that is , the scheduler 303 determines the information on the harq scheme , mcs level of transmission data , transmission time , data rate , and allocated resources , and provides the information to the controller 311 . the controller 311 can provide the scheduler 303 with the information on the characteristic of the transmission data or the type of the service and the information on the class type of the receiver when necessary . the controller 311 also controls the reset of the retransmission buffer in the data buffer 305 . further , the controller controls a data channel transmitter 309 and a control channel transmitter 307 . the controller 311 generates control information to be transmitted to the control channel transmitter 307 using the information received from the scheduler 303 . the information that the controller 311 generates using the information received from the scheduler 303 is shown by way of example in table 2 below . referring to table 2 , it can be noted that a 1 - bit id for a harq scheme is added in addition to the fields described above in table 1 . this bit indicates whether the sharq scheme is used or the aharq scheme is used , when retransmission is performed on the packet initially transmitted in the corresponding transmission interval . the other fields are substantially the same as those in table 1 , so further description thereof will be omitted . the controller 311 generates the new control information shown in table 2 , including the harq scheme information , and provides the generated control information to the control channel transmitter 307 . that is , compared with table 1 , table 2 further includes the field indicating whether the transmission packet is transmitted with the sharq scheme or the aharq scheme , to thereby indicate with which harq scheme the packet is to be transmitted at the next transmission . the controller 311 controls the data channel transmitter 309 depending on the control information , such that the data channel transmitter 309 performs coding and modulation according to a predetermined mcs level and transmits the packet using the allocated resource at the time determined by the scheduler 303 . a detailed description thereof will now be made with reference to the control flow given below . the control channel transmitter 307 , under the control of the controller 311 , transmits the control information shown in table 2 through a control channel . the data channel transmitter 309 , under the control of the controller 311 , generates a packet by coding and modulating transmission data according to the predetermined mcs level , and transmits the packet through the data channel using the allocated resources . herein , the transmitted packet can be a sub - packet as described above . in the following description , the packet and the sub - packet have the same meaning unless stated otherwise . fig4 is a block diagram illustrating a structure of a receiver according to an exemplary embodiment of the present invention . with reference to fig4 , a description will now be made of a structure and operation of a receiver according to an exemplary embodiment of the present invention . a control channel receiver / demodulator 401 , under the control of a controller 411 , receives a control channel transmitted from a transmitter , demodulates the received control channel , and provides the demodulated information to the controller 411 . a data channel receiver / demodulator 403 , under the control of the controller 411 , receives a control channel transmitted from the transmitter , performs demodulation and decoding on a data channel transmitted from the transmitter using the control information provided from the controller 411 , and provides a crc result thereon to the controller 411 . the controller 411 stores the control information received from the control channel receiver / demodulator 401 in a memory 407 , reads the control information stored in the memory 407 when necessary , and provides the read control information to the data channel receiver / demodulator 403 . that is , when data is transmitted according to the sharq scheme , the controller 411 reads the control information from the memory 407 , and provides the read control information to the data channel receiver / demodulator 403 , so as to demodulate and decode the data . further , the controller 411 generates a response signal to be transmitted to the transmitter according to the crc result received from the data channel receiver / demodulator 403 , and provides the response signal to a response channel transmitter 405 . the response channel transmitter 405 , under the control of the controller 411 , transmits the received response signal to the transmitter through a response channel . herein , the response signal can be ack / nack information for the demodulation / decoding result on the received packet . fig5 is a flowchart illustrating a packet transmission operation in a transmitter according to an exemplary embodiment of the present invention . with reference to fig5 , a detailed description will now be made of a packet transmission operation in a transmitter according to an exemplary embodiment of the present invention . in step 500 , a scheduler 303 of the transmitter performs scheduling on an initial transmission packet and determines an harq scheme . herein , the expression “ perform scheduling ” refers to determining to which user the base station will transmit the data in a forward data transmission process . the scheduling further includes for example , determining data rate , transmission scheme , modulation scheme , and the amount of resources to be used , for the determined user . the “ amount of resources to be used ” refers to the amount of resources to be allocated to the receiver in the system . for example , in the cdma system , the amount of resources to be used is the amount of codes to be used , and in the ofdma system , the amount of resources to be used is the amount of sub - carriers to be used . in the case of reverse transmission , the expression “ perform scheduling ” refers to indicating for which user the base station will permit data transmission . in this case as above , the scheduling includes for example , determining data rate , transmission scheme , modulation scheme , and the amount of resources to be used . that is , the expression “ perform scheduling ” is considered to indicate the operation in which the base station makes a decision on the control information shown in table 2 , except for the harq scheme information . in step 500 , the scheduler 303 additionally determines a harq scheme to be used , in addition to the determined control information . herein , the expression “ determine a harq scheme ” refers to determining which of the sharq scheme and the aharq scheme the transmitter will use . as described in fig3 , in embodiments of the present invention , the scheduler 303 can determine the harq scheme based on service type of the data transmitted this time , size of the packet transmitted this time , class of the mobile station , load of the current network , and so forth . an exemplary reason for proposing the harq scheme for each individual service type is as follows . the use of the sharq scheme is advantageous to real - time traffic service that is susceptible to time delay , where small packets are generated frequently , like voip and gaming services . however , the use of the aharq scheme is advantageous to service that is less susceptible to time delay , where larger packets are generated on a burst basis , like download and web surfing services . that is , the sharq scheme having lower overhead for control information transmission is efficient for real - time traffic service where small packets are generated frequently , because small packets should be transmitted frequently in real - time traffic service . however , the aharq scheme having higher overhead for control information transmission but having greater scheduling freedom is advantageous to service that is less susceptible to time delay , where larger packets are generated on a burst basis , because a larger packet is transmitted at one transmission using the large amount of resources in this service . an exemplary reason for proposing the harq scheme depending on a size of the packet data transmitted in this transmission interval is as follows . if the size of the packet data to be transmitted in this transmission interval is small , the packet data is preferably transmitted with the sharq scheme . however , if the size of the packet data to be transmitted in this transmission interval is large , the packet data is preferably transmitted with the aharq scheme . this is because the aharq scheme has a disadvantage of high overhead due to the control information transmission . however , if the size of the packet data to be transmitted in this transmission interval is large , the overhead of the control information is lower . therefore , the disadvantage of the sharq scheme is less , so the packet is transmitted with the aharq scheme having an advantage of greater scheduling freedom . however , if the size of the packet data to be transmitted in this transmission interval is small , the packet data is transmitted with the sharq scheme having low overhead for the data control information . an exemplary reason for proposing the harq scheme depending on the class of the mobile station is as follows . as described above , the sharq scheme has fixed initial transmission time and retransmission time , indicating that the sharq scheme performs retransmission immediately when the retransmission is necessary . therefore , for a high - class mobile station , the sharq scheme having a short packet delay time is selected , and for a low - class mobile station , the aharq scheme having a long packet delay time is selected . finally , an exemplary reason for proposing the harq scheme depending on the network load is as follows . for a low - load network , because scheduling freedom is less important , the sharq scheme is selected , thereby securing fast retransmission . however , for a high - load network where there are many users , the aharq scheme having high scheduling freedom is preferable . therefore , the harq scheme can be determined using one or more of the foregoing methods . in step 502 , after completion of the scheduling and the decision on the harq scheme , the controller 311 generates control information including harq scheme information . the control information including the harq scheme information can be generated as shown in table 2 . after generating the control information , the controller 311 proceeds to step 504 where it controls the control channel transmitter 307 and the data channel transmitter 309 so as to demodulate and transmit the generated control information , and to generate and transmit a packet using the data stored in the data buffer 305 . thereafter , in step 506 , the transmitter receives a response signal transmitted from the receiver through the response channel receiver 301 . this signal is the information indicating whether the receiver has normally received the transmitted packet . the process of transmitting the response signal will be described in greater detail with reference to fig6 . upon receipt of the response signal from the response channel receiver 301 , the scheduler 303 determines in step 508 whether the received response signal indicates an ack . if it is determined that the response signal indicates an ack , the scheduler 303 returns to step 500 and repeats the foregoing processes . however , if it is determined in step 508 that the response signal received through the response channel is a nack , the scheduler 303 determines in step 510 whether the current transmission on the packet has reached a maximum number of retransmissions . herein , the maximum number of retransmissions denotes a number of retransmissions , predefined in the system . that is , the maximum number of retransmissions indicates the number of retransmissions , defined such that even though the packet was transmitted a specified number of times taking the system load into account , if the receiver fails to normally receive the corresponding packet , the transmitter no longer performs retransmission . such a process can be omitted according to system design . if it is determined in step 510 that the current transmission has reached the maximum number of retransmissions , the controller 311 returns to the initial transmission of step 500 , because it is defined in the system that the transmitter no longer performs retransmission . however , if the current transmission has not reached the maximum number of retransmissions , the controller 311 determines in step 512 whether the initially transmitted packet was transmitted with the sharq scheme . such information can be previously stored in a separate memory or a control memory ( not shown in fig3 ), and then read when necessary . if it is determined that the initial transmission was performed with the sharq scheme , the controller 311 proceeds to step 514 where it performs retransmission at a predetermined time . that is , because the sharq scheme has a constant time interval between the initial transmission and retransmission , and a constant time interval between first retransmission and second retransmission , if a predetermined time elapses from the previous transmission , the controller 311 automatically performs retransmission . in this case , the controller 311 does not transmit the control channel . this is because the sharq scheme does not transmit a control channel during retransmission as described above . however , in the modified sharq scheme , the controller 311 can transmit a limited amount of control information . however , if it is determined in step 512 that the initially transmitted packet was transmitted with the aharq scheme , the scheduler 303 performs scheduling on the retransmission packet and generates control information in step 516 . in this scheduling process , the scheduler 303 newly determines an arbitrary retransmission time . after the retransmission time is determined , the controller 311 proceeds to step 518 where it generates control information based on the scheduling result and a packet based on the packet data , and transmits the control information and the packet by controlling the control channel transmitter 307 and the data channel transmitter 309 . in determining the harq scheme , it is also possible to take into account other factors as well , in addition to the service type , size of the packet data , class of the mobile station , load of the network , and so forth . fig6 is a flowchart illustrating a packet reception operation in a receiver according to an exemplary embodiment of the present invention . with reference to fig6 , a detailed description will now be made of a packet reception operation in a receiver according to an exemplary embodiment of the present invention . the controller 411 of the receiver determines in step 600 whether to receive the initially transmitted packet . that is , the controller 411 determines whether it will receive the initially transmitted packet or the retransmitted packet . for this operation , the controller 411 determines whether it transmitted an ack or a nack through a response channel for the previously received packet , or whether the current reception has reached the maximum number of retransmissions or is the initial reception . if it is determined that the receiver is to receive the initially transmitted packet , the controller 411 receives the initially transmitted packet using the data channel receiver / demodulator 403 , and receives a control channel using the control channel receiver / demodulator 401 in step 602 . this is because both the sharq scheme and the aharq scheme receive the control channel at the initial transmission . upon receipt of the control channel , the controller 411 demodulates the control channel by controlling the control channel receiver / demodulator 401 in step 604 . the controller 411 demodulates the data received from the control channel and acquires the control information as shown in table 2 in step 606 . after demodulating the control information , the controller 411 demodulates and decodes the packet data received by the data channel receiver / demodulator 403 using the control information in step 608 . the data channel receiver / demodulator 403 then provides the demodulation and decoding result back to the controller 411 . the demodulation and decoding result can be a crc result value . the controller 411 determines in step 610 whether there is any error in the received packet , using the crc result value . if it is determined that there is no error in the received packet , the controller proceeds to step 612 where it controls the response channel transmitter 405 so as to transmit an ack through a response channel . however , if it is determined from the crc result value that there is an error in the received packet , the controller 411 determines in step 614 whether the received packet is the initially transmitted packet and was transmitted with the sharq scheme . if the received packet is the initially transmitted packet and was transmitted with the sharq scheme , the control information for the initially transmitted packet preferably should be stored , because the control information will not be transmitted at the next transmission . therefore , if the received packet is the initially transmitted packet and was transmitted with the sharq scheme , the controller 411 stores the control information in the memory 407 in step 616 . an exemplary reason for storing the control information in the foregoing condition is because in the sharq scheme , the control information is not transmitted at the next transmission . in this case , therefore , the control information should be stored in the memory 407 . however , in the aharq scheme , because the control information is continuously transmitted at the next transmission , there is no need to store the control information in the memory 407 . further , in the modified sharq scheme , newly received information should be used as the partial information in the information stored in the memory 407 . however , if the received packet is not the initially transmitted packet or was transmitted with the aharq scheme , the controller 411 proceeds to step 618 where it controls the response channel transmitter 405 so as to transmit a nack through the response channel . if it is determined in step 600 that the received packet is not the initially transmitted packet , the controller 411 determines in step 620 whether the current transmission scheme is the sharq scheme . if it is determined that the current transmission scheme is the sharq scheme , the controller 411 receives the retransmitted packet at a predetermined time in step 622 . the sharq scheme can receive the retransmitted packet at a predetermined time because a time interval between the initial transmission time and the retransmission time , or between the previous retransmission time and the current retransmission time , is predetermined , and only the data channel is transmitted without the control channel . in step 624 , the controller 411 reads control information for the retransmitted packet from the memory 407 , and then proceeds to step 608 . the information read in the data reading process is control information and has predetermined values . for example , information such as data information size , mcs information , used resource information , and arq id is unchanged and comprises the information regardless of the initial transmission or the retransmission , or information that is estimated . however , only the sub - packet id has a value that is increased by one from the previous one . for example , if the previous sub - packet id was ‘ 1 ’, the present sub - packet id is ‘ 2 ’, since the sub - packet id is used for identifying each retransmission among several retransmissions of one packet data . however , in the modified sharq scheme , the mcs information and the used resource information can be changed , and the changed information is received together with the packet data in step 622 . however , if it is determined in step 620 that the current transmission is the aharq transmission , the controller 411 receives the retransmitted packet and the control channel in step 626 . herein , because the transmission time of the retransmission packet and the control channel is unknown , the controller 411 continuously waits for the control information including an id of the mobile station or an id of the receiver . upon receipt of the control information , the controller 411 determines that the retransmission packet and the control channel are received . upon receipt of the control channel and the retransmitted packet , the controller 411 extracts control information from the demodulated control channel in step 628 . the control information indicates the control information as shown in table 2 . thereafter , the controller 411 proceeds to step 608 and performs succeeding steps thereby transmitting a response channel . as can be understood from the foregoing description , embodiments of the present invention adaptively use the sharq scheme and the aharq scheme in combination in one system using the harq scheme , thereby securing higher system capacity with limited wireless resources . while the invention has been shown and described with reference to certain exemplary embodiments thereof , 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 as defined by the appended claims and equivalents . | 7 |
referring to fig1 of the drawings , the binary tree computing system 11 of the invention interconnects a number of processor elements ( pes ) with each other and with a host computer 13 over a binary tree - bus . the tree - bus of the system illustrated in fig1 consists of three bus control nodes 15 , 17 and 19 designated as nodes bc1 , bc2 and bc3 , respectively . the three nodes connect seven pes , designated as pe1 through pe7 , to the host 13 . all of the pes are identical and in the illustrated embodiment consist of a microprocessor , such as an ibm powerpc 603e microprocessor , and associated ram memory with a bridge circuit interconnecting the two . node bc1 15 is the root node and attaches the tree to the host 13 through a driver 14 an interface , such as pci bus 16 . node bc1 15 is connected to its own pe , designated as pe1 , and to left child node bc2 17 and to the right child node bc3 19 . the nodes bc2 and bc3 are each connected to their own pe &# 39 ; s , pe2 and pe3 respectively , and to left and right child pes , pe4 and pe5 , and pe6 and pe7 , respectively . pe4 through pe7 are referred to as the leaf pe &# 39 ; s since they have no other children . the system of fig1 illustrates the basic structure of the binary tree parallel computer system of the invention . each node bcx is connected upstream to a parent node , except for the root node bc1 , which is connected to the host . each node bcx is also connected downstream to its own pe and either to two child nodes bcx , or in the case of the nodes at the extremes of the tree , to right and left leaf pes . referring to fig2 of the drawings , the binary tree - bus of the embodiment of fig1 includes a host interface ( hif ) 21 , three tree - bus control nodes bc1 15 , bc2 17 and bc3 19 and seven processor input / outputs ( pios ) 23 , 25 , 27 , 29 , 31 , 33 and 35 , one for each pe . the hif 21 interfaces the binary tree - bus with the connection bus of the host computer 13 . in the illustrated embodiment of the invention , this bus is preferably a pci bus , although others could be used . the bcxs act as buffered repeaters that transfer function calls and data from the host computer to the selected pe ( s ), and data with its fault message from the selected pe to the host computer . the pios transfer data between their respective pes and the binary tree - bus in compliance with the function call requirements , and arbitrate access of the ram associated with the respective pe between the needs of the pe &# 39 ; s microprocessor and the binary tree - bus . referring to fig3 of the drawings , the pio 37 controls the read / writes of both the pe microprocessor 39 and the binary tree - bus with the ram 41 of the pe . data flows between the binary tree - bus and ram 41 under the control of the pio control 43 of pio 37 . the pio 37 also includes a buffer 45 that acts to accommodate delays in data transfer that may be caused by memory arbitration conflicts . the hif 21 contains a similar buffer for the same reason . in the illustrated embodiment , data on the binary tree - bus is four bytes wide plus four parity bits . when flowing toward the ram 41 , the data from the tree - bus is assembled by the pio control 43 into eight byte words with associated parity bits into a buffer 45 . data is transmitted from the buffer 45 to the ram 41 in burst mode , unless only one double word is to be written . likewise , data is read from ram 41 in burst mode and stored in pio 37 &# 39 ; s buffer 45 . the data in the buffer 45 is then disassembled into a four byte format and transmitted on the tree - bus through the tree - bus interface 47 under the control of the binary tree - bus control node bcx and the pio control 43 . the hif , bcxs and pios are each preferably implemented with field programmable gate arrays ( fpgas ). in the illustrated embodiment , a fixed word length of eight byes ( 64 - bits ) plus an odd - parity bit per byte is used for data . data are transferred on the tree - bus four bytes in parallel on each clock cycle signal . function call information is interpreted by the bcx . in the binary tree computer system of the illustrated embodiment of the invention , the host computer 13 generates instructions referred to as function calls to control the operation of the system . the following are the function calls generated by the host computer in the illustrated embodiment of the invention : sreset function call causes one or all pes to be reset . lfpga function call is used to establish logic controls used by the field programmable gate arrays ( fpga &# 39 ; s ) in the binary tree - bus control nodes ( bcxs ), pio &# 39 ; s , and hif . initialization function call causes the bcxs to establish the identification ( id ) of each pe in the system as a function of the id contained in the function call . identification of pes is then maintained by the bcxs . load function call causes the binary tree - bus control nodes to route data to the pe specified by id and its pio to load its memory without involving the microprocessor . no microprocessor interrupts are involved . examine function call causes data read from a pe &# 39 ; s memory to be transferred to the host without involving the microprocessor of the pe . release ( reset ) function call signals each microprocessor in the system to be operational . write function call causes the binary tree - bus control nodes to route data and a job specification to a specified pe and to write them into its memory . the interrupt is used to notify the microprocessor of a new job and that its data is available . the microprocessor acknowledges the acceptance of the new job . the microprocessor , however , may continue with the job being performed when the interrupt is acknowledged and then perform the new job as it occurs in a job queue . read function call uses an interrupt to the pe specified to ascertain whether data is ready to be read . when found to be ready , data is read from the pe &# 39 ; s memory and transferred to the host computer . broadcast function call causes data and a job specification to be simultaneously transferred from the host computer to all of the pes . interrupt is involved in the same manner as write above . resolve function call involves both read and write type functions with interrupt . when ready , data is read from the farthermost pes and written into the pes at the next level of the tree bus toward the host computer . in the case of the leaf pes , the data is read into the pe of the bc to which they are connected . the pe at that level selects the &# 34 ; best results &# 34 ;, according to a prescribed criteria , among its and the &# 34 ; best results &# 34 ; received . the &# 34 ; best results &# 34 ; are then transferred toward the host to the next level of the tree bus when a read function is received from that level . this process continues until the &# 34 ; best results &# 34 ; resolved by pe1 are transferred to the host computer . fig4 illustrates an example of the resolve function call . the &# 34 ; best results &# 34 ; are computed by the lpe 53 and the rpe 55 and are stored in their associated memory starting at address &# 34 ; data dma &# 34 ;. the best results are then transferred from lpe 53 &# 39 ; s memory via bc2 57 to the memory of pe 59 , starting at address data dms lpe by bc1 61 . next the best results are transferred from the memory of rpe 55 via bc3 63 to the memory of pe 59 starting at location data dma rpe by bc1 61 . finally , pe 59 selects the best results among those received from lpe 53 and rpe 55 and that which pe 59 itself computed and the results are stored in pe 59 &# 39 ; s memory starting at location data dma . time - outs included in function calls involved with data transfer are used by bcs to monitor slack times and prevent the system from getting hung up without a means to restart . time - out values are set by the host software and may be changed if experience demonstrates them to be too short or too long . time - outs are used by bcs when data transfer flow is interrupted or while waiting for a job &# 39 ; s completion . there is time - out counter in each of the bcs . the time - out field in the function call is one byte ( 8 - bit ), however , the time - out counter has a precision of two bytes ( 16 - bits ). the value in the time - out field of the function call is compared to the more significant byte of the time - out counter . the time - out counter is reset to all zeros each time before it is used . the time - out timer is advanced by the clock signal used for data transfer . if the time - out elapses while waiting for a data transfer to occur during a read function , the bc completes the transfer of n double words filled with blanks with the fault message appended . if the time - out in the function call is set to all zeros , time - outs are not performed . if more than one time out fault occurs during a function , the one nearest to the host computer is reported . a &# 34 ; fault message &# 34 ; is appended to the end of each stream of data being transferred to the host computer . it consists of four bytes that contain the id of the pe or bc in which the fault condition is detected followed by two bytes that identify the fault condition . a fault message is also appended when no fault is detected to indicate as such . the fault message is originated by a pio and can be amended by a bc . if more than one fault condition is detected , the one nearest the host is used . if more than one fault has been detected in a pio or bc , the one occurring last is reported . most sequences of function calls involve alternating &# 34 ; read &# 34 ; and &# 34 ; write &# 34 ; functions . fault conditions detected during a &# 34 ; write &# 34 ; function are reported on the subsequent &# 34 ; read &# 34 ; function provided the same pe / bc is involved in both . typical fault conditions in the system of the illustrated embodiment of the invention include function call faults , time - outs , parity errors , incomplete data transfer , memory address out of range and microprocessor faults . if a non - admissible code occurs in a function call , the condition is usually detected by bc1 15 . a non - existing id is detected by a bc at the furthermost level from the host computer 13 when none of its leaf &# 39 ; s ids match with id . parity errors can occur during function call or data transfers on the tree - bus . parity errors may also be detected during data / address transfers in the microprocessor or in pe &# 39 ; s memory . if a total of n double words are not transferred , a fault is indicated by the pio involved . a data overflow fault is declared if data is lost during data transfer . this should also be detected if other than n words are transferred . fig5 of the drawings illustrates the tree - bus signal lines . such signal lines are illustrated as being between a block 49 , which can be the hif 21 or a bcx , and another block 51 , which can be another bcx or a pio connected to a pe . tree - bus signal lines used to transfer function calls and data consist of : idb ( function / data bus ) thirty two bi - directional parallel lines used to transfer data and function information . idp ( function / data parity ) four bi - directional lines used to transfer the odd parity bits for the corresponding bytes on the idb bus . rfd ( ready for data ) the hif , bcx or pio is ready to receive the next two bytes of data . ndp ( new data present ) the hif , bcx or pio has new data present to be transferred . additional signals used that are not in the tree - bus include clock for timing cycles , hard reset , and load logic . bus control nodes ( bcx ) operate as repeaters to act collectively as a bucket brigade to transfer data between the hif and the pes , and pes to pes . referring to the timing diagram of fig6 this is accomplished with the use of the &# 34 ; ready for data &# 34 ; rfd and &# 34 ; new data present &# 34 ; ( ndp ) signals . as illustrated in fig6 data are transferred through the bcx ( data in and data out ) on consecutive clock cycles until rfd ( in ) is unasserted by the next down - stream bc in the chain indicating that it is not ready to accept another data transfer . this causes the bcx to unassert rfd ( out ) to cause the data transfer to pause - up stream . in this case , rfd ( in ) is reasserted such that data transfer may resume . bcx retains data until the transfer process continues so that there is no loss of data when the flow of transfers in momentarily interrupted . in accordance with an aspect of the present invention , the binary tree computer system can advantageously be constructed from a plurality of sub - units . for instance , the seven pe version of the invention illustrated in fig1 and 2 of the drawings is made up of a three pe unit ( a &# 34 ; peu &# 34 ;) 67 connected to a four pe expansion unit (&# 34 ; pexu &# 34 ;) 69 . the smallest set of pes in a system in accordance with the invention is three . in such a configuration , pe2 and pe3 are in the leaf positions . this configuration can be scaled to seven pes by using a 3 - peu in conjunction with a four 4 - pexu expansion unit that conveniently can be disposed on a single printed circuit board . in this configuration pe4 through pe7 are leafs by virtue of being located at &# 34 ; leaf &# 34 ; physical locations on the printed circuit board . to scale - up from a three to seven pe system the bc of the 3 - peu is connected to the first bc of the 4 - pexu which is connected to the host interface . as illustrated in fig7 of the drawings , by adding an additional 4 - pexu , the configuration can continue to be expanded to eleven pes . this results in an asymmetrical tree which is permitted in the architecture . the eleven pe configuration can be expanded further into the fifteen pe configuration depicted in fig8 by the addition of another 4 - pexu . this process can be continued indefinitely bu adding further 4 - pexu &# 39 ; s to construct a binary tree of the desired size . in general , a tree constructed in accordance with this aspect of the invention will be constructed from one 3 - peu and as many 4 - pexu &# 39 ; s as necessary . therefore the binary tree can be expanded indefinitely with only two printed circuit board types , i . e . 3 - peu and 4 - pexu . the 4 - pexu has optional connections from the first bc . for example , in fig1 and 7 , bc1 is routed to bc2 . in fig8 bc1 is routed to bc3 on the same printed circuit board . it is significant that , as seen from fig1 and 8 , the pe &# 39 ; s positioned along one edge of the printed circuit boards are always leaf pe &# 39 ; s . therefore , the bcx &# 39 ; s know which pe &# 39 ; s attached to them are leaf pe &# 39 ; s . the binary tree computer system of the present invention is particularly useful in dealing with applications such as speech or other pattern recognition , where a series of units of data have to be compared with a large number of possible values in order to find the best match for each unit . in solving such types of problems , the speech or other pattern data that is to be interpreted is broken into short segments that are then compared against a large data base of standards to find the best match for each . the best matches are then assembled to identify the words being spoken . the binary tree computer system of the present invention is particularly suited to the solution of such problems since they involve a very large number of similar calculations and comparison functions that can be accomplished efficiently in parallel with the best results brought back to the host . the host first distributes the necessary comparison software and different subsets of the standards against which speech segments are to be compared during the recognition process to the pes over the tree - bus . using the broadcast function call , the host then sequentially broadcasts the successive speech segments to all of the pes in parallel . the pes each compare the speech segments with the data base stored in its associated memory to determine the closest match and stores an identification and closeness of the match in a predetermined location in its associated memory . if no match exists within a defined comparison distance , the pe merely stores an indication of no match in such memory location . then , using the resolve function call , the host causes the left and right leaf pes of each bc at the extremes of the tree , in the manner described above , to transfer their results to the bc &# 39 ; s own pe where the closest of all three matches is selected and sent to the next level up the tree . this process is repeated at each level until the closest match determined by any of the pes is calculated by the root pe and forwarded to the host . the assembly of the recognized segments into words is performed in the host . a plurality of speech segments can be stored in the memory of each pe by the host computer without interrupting the pe . the pe performs its comparison calculations at its own speed and stores the results in the appointed memory locations without having to wait for the host or other pes of the tree . the tree bus then moves the results toward the host at a rate determined by the host and the tree bus clock . in this manner the pes can work at peak efficiency without having to wait for other parts of the system , and system throughput is maximized . the pio &# 39 ; s arbitrate any conflicting demands for memory access by the bc and the microprocessor of the pe . if a bc of the tree bus is not ready to receive or send information up or down the tree , it unasserts its rfd signal which causes all the bcs in the path of the information to pause until the signaling bc is ready . thus any temporary bottlenecks in the system are absorbed by the tree bus rather than being allowed to slow down the pes . | 6 |
the following description is merely exemplary in nature and is in no way intended to limit the disclosure , its application , or uses . for purposes of clarity , the same reference numbers will be used in the drawings to identify similar elements . as used herein , the phrase at least one of a , b , and c should be construed to mean a logical ( a or b or c ), using a non - exclusive logical or . it should be understood that steps within a method may be executed in different order without altering the principles of the present disclosure . as used herein , the term module may refer to , be part of , or include an application specific integrated circuit ( asic ), an electronic circuit , a processor ( shared , dedicated , or group ) and / or memory ( shared , dedicated , or group ) that execute one or more software or firmware programs , a combinational logic circuit , and / or other suitable components that provide the described functionality . referring now to fig1 , a computing device 10 includes a flash memory module 12 . the computing device 10 may include , but is not limited to , a computer , media player , mobile phone , personal digital assistant , or any other device that may include the flash memory module 12 . the flash memory module 12 may be a removable memory module such as a memory card or a usb flash drive . the flash memory module 12 includes a processor module 14 , flash memory 16 , non - volatile memory 18 , and main memory 20 . the processor module 14 executes instructions of software and firmware of the flash memory module 12 . for example , the processor module 14 may execute instructions of firmware stored in the non - volatile memory 18 . the processor module 14 may also read and execute instructions stored in the main memory 20 . for example , the main memory 20 may include volatile memory such as random access memory ( ram ). the flash memory module 12 communicates with a host 22 of the computing device 10 . the host 22 communicates with input devices 24 and output devices 26 , and may communicate with secondary storage such as hdd 28 . the input devices 24 include , but are not limited to , a keyboard or keypad , a mouse , a touch screen , a touch pad , a microphone , and / or other input devices . the output devices 26 include , but are not limited to , a display , a speaker , and / or other output devices . the computing device 10 stores data in the flash memory module 12 . the flash memory module 12 may emulate an hdd . for example , data is stored in the hdd 28 according to a logical block address ( lba ), which corresponds to a physical block address ( pba ) of the hdd 28 . typically , an hdd lba is 512 bytes . in other words , the host 22 references the data in the hod 28 according to the lba , while the hdd 28 references the data according to the pba . conversely , data is stored in the flash memory module 12 ( i . e . in the flash memory 16 ) according to a logical allocation address ( laa ), which corresponds to a physical allocation address ( paa ) of the flash memory 16 . for example only , the laa is 4096 bytes . a flash allocation unit ( au ) corresponds to a read or write unit of the flash memory 16 and may be equivalent to one laa . a wide erase block unit ( weru ) is an erase operation unit and corresponds to multiple ( e . g . 2048 ) paas . when the computing device 10 writes data to an laa , the flash memory module 12 ( e . g . firmware of the flash memory module 12 ) selects a corresponding paa , which is referred to as “ allocation .” for example , the processor module 14 processes commands according to firmware stored in the non - volatile memory 18 to read and write data to the flash memory 16 . the flash memory module 12 stores the data to the paa of the flash memory 16 and stores metadata in the main memory 20 that indicates the relationship between the laa and the corresponding pm . for example , the metadata may include a lookup table ( lut ) that associates laas with paas . the lut associates each allocated laa with a paa . if a particular laa is not allocated , the laa may be associated with a recognizable invalid pm value . the metadata also includes weru description data , including , but not limited to a pm validity map , werus link information , and erase information . each weru includes an identifier that associates the weru with a particular bin . for example , a weru may be associated with a free bin , a valid bin , a partial bin , or a working bin . free bins include werus whose paas are all ready to be written to . valid bins include werus whose paas are all valid data . partial bins include werus that include both paas with valid data and paas with invalid data ( i . e . paas whose laa data is subsequently written elsewhere ). working bins include werus that are currently being written to . the metadata also includes data that corresponds to internal operations of the flash memory module 12 , which includes , for example only , wear leveling , cleanup , and static management data . when the computing device 10 reads from an laa , the lookup table stored in the main memory 20 indicates which paa to read the data from and the flash memory module 12 retrieves the data accordingly . conversely , when the computing device 10 writes to a previously written laa , the flash memory module 12 allocates an unused paa to the laa . the data is stored in the new paa and the lut is updated accordingly . thus , the metadata stored in the main memory 20 enables allocation and retrieval of data from the proper paas in the flash memory 16 . the metadata stored in the main memory 20 is updated as data is written to the flash memory module 12 . before the computing device 10 ( and therefore the flash memory module 12 ) is powered down , the metadata is transferred from the main memory 20 to the flash memory 16 . when the computing device 10 is powered up , the metadata is transferred from the flash memory 16 to the main memory 20 to establish proper associations between the laas and the paas . for example , the metadata may be transferred to the main memory 20 during a power up procedure of the computing device 10 . any changes made to the metadata stored in the main memory 20 during operation of the computing device 10 after power up are not made to the flash memory module 12 until power down , or in response to internal metadata save commands that may be generated periodically by the firmware of the flash memory module 12 . when power is lost unexpectedly during operation of the computing device 10 , the changes made to the metadata stored in the main memory 20 may be lost . accordingly , the metadata stored in the flash memory 16 is not updated ( i . e . the metadata is old ) and corresponds to a previous proper power down of the computing device 10 . at a subsequent power up , the old metadata is transferred from the flash memory 16 to the main memory 20 , leading to improper allocation and retrieval of the data in the flash memory 16 . referring now to fig2 , a metadata lut 100 stored in the main memory 20 associates laas 102 with paas 104 of the flash memory module 12 . for example , when a read command requests data associated with laa 106 , the data is actually retrieved from a corresponding paa 108 . for example only , as shown in fig2 , solid blocks indicate the laas 102 that are associated with one of the paas 104 and empty blocks indicate the laas 102 that are not associated with one of the paas 104 . similarly , with respect to the paas 104 , solid blocks indicate the paas 104 that store data and are allocated to one of the laas 102 . empty blocks indicate the paas 104 that do not contain data . for example , laa 106 corresponds to paa 108 . accordingly , data requested from the laa 106 will be retrieved from the paa 108 . similarly , data requested from laa 110 will be retrieved from paa 112 . conversely , when data is to be written to an empty laa 114 , a paa ( e . g . paa 116 ) that is empty or does not contain valid data is selected during allocation . accordingly , the data written to the laa 114 will actually be written to the paa 116 or another one of the paas 104 in a working weru . for example only , each of werus a - g may include a group of three of the paas 104 . for example , the werus a and e are working werus ( i . e . werus that are currently being written to ). the werus b and d are partial werus . the weru c is a valid weru . the werus f and g are free werus . when data is written to an laa 120 that already is associated with a paa 122 , a second paa 124 is allocated to the laa 120 . when data is again written to the laa 120 , a third paa 126 is allocated to the laa 120 . in other words , the paas 122 and 124 store old or stale data previously associated with the laa 120 and the pm 126 stores new data . lut 130 represents , the lookup table stored in the flash memory 16 . the lut 130 is transferred to the main memory 20 as the lookup table 102 during power up . any changes made to the lut 102 are not reflected in the lut 130 stored in the flash memory 16 . for example , the lut 130 may not indicate subsequent changes made to laas 132 and 134 . as shown in fig2 , the metadata including the lut 100 stored in the main memory 20 is updated as data is written to the paas 104 but is not updated in the flash memory 16 . for example , the metadata stored in the flash memory 16 is indicative of a status of the lut 100 at a most recent power up of the computing device 10 . accordingly , the metadata stored in the flash memory 16 may indicate that the laa 120 is still associated with the pm 122 . if the computing device 10 loses power unexpectedly , the metadata stored in the main memory 20 is lost . at the next power up , the metadata stored in the flash memory 16 is transferred to the main memory 20 . accordingly , requests to read data from one of the laas 102 that was written to before the loss of power will retrieve old data from one of the paas 104 . for example , for a request to read data from the laa 120 , data will be retrieved from the pm 122 instead of from the pm 126 . referring now to fig3 , the metadata stored in the main memory 20 includes data that associates each weru with a particular one of bins 200 . for example , the werus a and e are associated with a working bin 202 . the werus b and d are associated with a partial bin 204 . the weru c is associated with a valid bin 206 . the werus f and g are associated with a free bin 208 . the metadata stored in the main memory 20 includes a weru activity log ( wal ). the wal indicates when a particular weru changes status . for example , the wal indicates when a weru moves from one of the bins 200 to another of the bins 200 . for example , as data is written to the free weru f , the free weru f moves to the working bin 202 , and then to the partial bin 204 . when the weru f is filled with valid data , the weru f moves to the valid bin 206 . referring now to fig4 , the metadata stored in the main memory 20 includes a reverse lookup table ( rlut ) 300 . the rlut 300 associates paas 302 of the flash memory 16 with laas 304 . a portion of the rlut 300 is periodically stored in the flash memory 16 . for example , when a particular weru moves from the working bin 202 to the valid bin 206 , a portion of the rlut 300 corresponding to the weru that moved to the working bin 202 is stored in the flash memory 16 . the most recent ( i . e . correct ) associations between the paas 302 and the laas 304 ( and the laas 102 and the paas 104 as shown in fig2 ) can be recovered after an unexpected power loss using the lut 100 , the rlut 300 , and the wal . for example only , as shown in fig4 , solid blocks indicate paas 302 that store data and are allocated to one of the laas 304 . empty blocks indicate the paas 302 that do not contain data . with respect to the laas 304 , solid blocks indicate the laas 304 that are associated with one of the paas 302 and empty blocks indicate the laas 304 that are not associated with one of the paas 302 . referring now to fig5 , the processor module 14 includes a recovery module 400 . for example only , the recovery module 400 may include or execute firmware stored in non - volatile memory 18 . at power up , the computing device 10 transfers the metadata stored in the flash memory 16 to the main memory 20 and the recovery module 400 determines whether to perform metadata recovery . for example , after a normal ( i . e . scheduled or intentional ) power down , the metadata may indicate that a user initiated a power down . if the metadata does not indicate that the user initiated a power down , the recovery module 400 may determine that an unexpected loss of power occurred and therefore perform the metadata recovery . during metadata recovery , the recovery module 400 identifies werus that were written to and / or erased prior to the power loss based on the wal . the wal indicates when a particular weru moves from one of the bins 200 to another of the bins 200 . the wal includes a time ( e . g . a timestamp ) for each weru that indicates when the weru was written to or erased . therefore , the wal indicates which of the werus were written to ( i . e . moved to the working bin 202 ) and / or erased ( i . e . moved to the free bin 208 ). the recovery module 400 updates the metadata stored in the main memory 20 based on the wal and the rlut 300 . for example , the recovery module 400 updates the weru bins and the lut 100 . the recovery module 400 moves each of the werus to the proper bin . in other words , if the metadata indicates that a weru is in the free bin 208 and the wal indicates that the weru was written to and is filled with valid data , the recovery module 400 moves the weru to the valid bin 206 . the recovery module 400 moves each weru to an appropriate one of the bins 200 based on the wal . when the werus are in the proper bins , the recovery module 400 updates the lut 100 based on the rlut 300 . beginning with the werus having the most recent activity ( i . e . the werus that were most recently written to and / or erased based on the timestamp ), the recovery module 400 performs reverse allocation for each of the werus . referring again to fig4 , only portions of the rlut 300 corresponding to werus that moved from one bin to another are stored to the flash memory 16 . for example , no data was written to the werus f and g . accordingly , the werus f and g remain associated with the free bin 208 and the portion of the rlut 300 corresponding to the werus f and g are not written to the flash memory 16 . during metadata recovery , the recovery module 400 does not need to update the portions of the lut 100 that correspond to the werus f and g . conversely , the werus a and d moved , for example , from the free bin 208 to the partial bin 204 and the rlut 300 stored in the flash memory 16 is updated accordingly . therefore , the data in the lut 100 stored in the main memory 20 may not reflect changes made to the werus a and d before the unexpected power loss . for example , each of paas 310 , 312 , and 314 may be associated with a single laa 316 . during metadata recovery , the recovery module 400 identifies the werus a and d as werus that moved from one of the bins 200 to another based on the wal . the recovery module 400 further determines that the most recent changes were made to the weru a based on the wal . consequently , the recovery module 400 determines that the pm 310 includes the newest data and is properly associated with the laa 316 based on the wal , the rlut 300 , and reverse allocation . the recovery module 400 updates the lut 100 with the proper association for each weru . in some circumstances , the recovery module 400 may be unable to determine which of the laas 304 that one of the paas 302 is associated with . each of the paas in the flash memory 16 includes data that indicates which laa that the paa is associated with . the recovery module 400 may read the data stored in the paa to determine the proper laa association . the recovery module 400 also updates weru description data including , but not limited to , a weru validity map , link information , and erase information ( e . g . a number of times each weru is erased ). the weru description data may include an allocation map that indicates each time a paa is read for werus in the working bin 202 . referring now to fig6 , a metadata recovery method 500 is shown . at 502 , the computing device 10 is powered on . at 504 , the recovery module 400 transfers the metadata from the flash memory 16 to the main memory 20 . at 506 , the recovery module 400 determines whether the computing device 10 was properly powered down . if true , the method 500 continues to 508 . if false , the method 500 continues to 510 . at 508 the computing device 10 proceeds to normal operation without performing metadata recovery . at 510 , the recovery module 400 moves each weru to the proper bin based on the wal . at 512 , the recovery module 400 updates the lut 100 based on the wal and the rlut 300 . at 514 , the recovery module 400 updates the lut 100 based on laa association data stored in any remaining paas . at 516 , the recovery module 400 updates weru description data and the computing device 10 proceeds to normal operation . the broad teachings of the disclosure can be implemented in a variety of forms . therefore , while this disclosure includes particular examples , the true scope of the disclosure should not be so limited since other modifications will become apparent upon a study of the drawings , the specification , and the following claims . | 6 |
the present invention provides a second coolant transport duct that can form a heat exchanger on the opposite side of the electronic circuit housing from the first coolant transport duct described above but is thermally coupled to the circuit device in which heat is generated differently than is the first duct . the first duct is thermally coupled to the heat generating circuit devices primarily by conduction . those devices are supported on a sequence of thermally conductive material layers each in contact with its adjacent neighbor or neighbors in the circuit housing structure thereby providing a direct thermally conductive path between the heat generating circuit devices and the first duct . however , the presence of electrical circuit interconnections of various sorts on the sides of the heat generating circuit devices opposite the sides thereof nearest the first duct prohibits use of solid material layers forced against these opposite sides for good conductive thermal contact , especially use of any electrically conductive material layers which are often also the choice in other circumstances for good thermal conductivity materials . thus , an alternative heat transfer arrangement is needed between the heat generating circuit devices and the second duct . fig1 shows a cross - sectional side view of a diagrammatic representation for such an alternative electronic circuit housing arrangement , 10 . a first duct , 11 , is formed of two separated aluminum plate - like structures with the upper one having a thermal grease , 12 , thereon to keep it well thermally coupled to the electronic circuit component enclosure structure adjacent thereto . the separation space between the two separated aluminum plate - like structures in first duct 11 provides the passageway through which a coolant liquid , 13 , represented by directed arrows , is caused to flow to transport away with it heat absorbed thereby from the plate - like structures in duct 11 . various structures are brazed together ( not shown ) in forming duct 11 with its plate - like structures and the passageway connections therein through which coolant 13 is supplied to flow through the separation space passageway between its plate - like structures when cooling is desired . finned structures ( not shown ) can be provided in this passageway thermally coupled ( typically through brazing ) to the plate - like structures forming same to aid in the transfer of heat transferred to these structures to coolant 13 . coolant 13 , although possibly a gas in some circumstances , is typically a liquid such as polyalphaolefin or a propylene glycol and water mixture which alternatives both have relatively large thermal conductivities and specific heats for transferring heat but also have relatively low viscosity to thereby keep pressure drops relatively small along the passageway during coolant flows . a first thermal transfer , or base , plate , 14 , formed of copper , is fastened to first duct 11 with thermal grease 12 between a first side of that plate and duct 11 . this fastening typically is provided by some sort of fastening screws ( not shown ), and the resulting arrangement provides for conducting heat from plate 14 to coolant 13 . a component enclosure structure , 15 , in electronic circuit housing arrangement 10 is provided based on plate 14 , and so the opposite side of base plate 14 has supported directly thereon , and bonded thereto , a plurality of mounting pedestals , 16 , each having a lower direct bond copper layer , 17 , and another upper direct bonded segmented copper layer , 17 ′, bonded to opposite sides of an electrical insulator layer , 17 ″, formed of either aluminum oxide or nitride . the segments of upper copper layer 17 ′ in each mounting pedestal 16 form electrical interconnections for a corresponding one of a plurality of substantial electrical power management semiconductor material transistor chips , 18 , also mounted on a segment of layer 17 ′ of that pedestal , and which chip so mounted is electrically connected to such pedestal segments by a corresponding set of wire bonds , 19 . heat generated in operating the electrical circuits containing chips 18 is in part conducted from each of those chips through the corresponding one of mounting pedestals 16 to plate 14 , and subsequently conducted to flowing coolant 13 in duct 11 to thereby be transported away . pedestals 16 and power transistor chips 18 are shown in fig1 submerged in a dielectric liquid , 20 , contained in the enclosed space in component enclosure structure 15 , in which bubbles containing vapors of that liquid ( shown as circles in liquid 20 in fig1 ) form due to part of the heat generated in chips 18 during operations of the circuits containing them ( boiling of liquid 20 ) as a single component working fluid in a two phase system . these bubbles buoyantly float up to the surface of liquid 20 to join the accumulating vapor of that liquid in a space , 21 , above that liquid and accumulate there about a thermally conductive finned structure , 22 , in that enclosed space . heat is taken up by liquid 20 undergoing a phase change from liquid to vapor 21 thereby accomplishing the absorption of significant amounts of heat in providing the latent heat of vaporization needed to convert small amounts of liquid to the vapor shown as the circles in liquid 20 in the figure . accumulated vapor 21 condenses on the fins of finned structure 22 so that the latent heat of vaporization released in doing so is taken up in those fins and conducted from there to second heat transfer plate 24 . liquid 20 in such a single component , two phase working fluid system can be taken from the general fluid classes of novec ™ hydrofluoroether ( hfe ), such as hfe - 7100 fluid , or fluorinert ™ ( fc ), such as fc - 72 or fc - 84 fluid , all sold by the 3m co . alternatively , dielectric liquid 20 can be provided as a single component working fluid in just a single phase by providing liquid 20 in a quantity sufficient to fill , or essentially fill , the enclosed space of the component enclosure structure ( not shown in fig1 ). this arrangement will thereby eliminate , or nearly eliminate , vapor space 21 so that liquid 20 is in direct contact with both transistor chips 18 and finned structure 22 thereby allowing heat from the former to be conducted to the latter . liquid 20 in this latter arrangement can be a silicone cooling fluid such as dow corning ® 550 sold by the dow corning corporation . however , such a single component , single phase working fluid leads to a greater thermal gradient along the heat transport path in the electronic circuit housing structure than does a single component , two phase working fluid , and more of liquid 20 for the single component , single phase working fluid is needed to fill or essentially fill the electronic circuit housing structure thereby adding to both the cost and the weight of housed circuit components . both liquid 20 and vapor 21 ( if present ) are , as indicated , contained in the enclosed space provided in component enclosure structure 15 in electronic circuit housing arrangement 10 that results from base plate 14 therein being bonded at a surface thereof , opposite that surface adjacent to first duct 11 , to one end of an enclosing housing side , 23 , and by a second thermal transfer plate , 24 , being bonded at a first side thereof to the opposite end of housing side 23 . housing side 23 is formed of formed of a high temperature plastic with a temperature coefficient of expansion not too different from that of base plate 14 . such a material can be any of 25 to 40 % fiber reinforced polyphenyl sulphide ( pps ) having a maximum operating temperature of 210 ° c . and a temperature coefficient of 29 × 10 − 6 /° c ., 25 to 40 % fiber reinforced polyether sulfone ( pes ) having a maximum operating temperature of 210 ° c . and a temperature coefficient of 23 × 10 − 6 /° c ., or 25 to 40 % fiber reinforced polyester having a maximum operating temperature of 150 ° c . and a temperature coefficient of 20 × 10 − 6 /° c . as circuit and housing operating temperatures allow . bonding can be either adhesive bonding or ultrasonic bonding . second heat transfer plate 24 is formed of aluminum with finned structure 22 being thermally coupled thereto at the first side thereof . this coupling can come about through finned structure 22 being integral to that plate by being formed from a starting aluminum plate that is thicker than the final thickness of plate 24 from which starting plate the material initially between the resulting fins has been removed such as by etching or sawing . alternatively , finned structure 22 can be formed as a separate structure subsequently fastened to plate 24 in a thermally coupled manner such as by brazing them together . thermal grease , 25 , on a second side of second heat transfer plate 24 thermally couples the component enclosure structure to a second duct , 26 , in electronic circuit housing arrangement 10 which duct is formed as is first duct 11 of two separated aluminum plate - like structures forming the walls of a passageway in the separation space therebetween . here , too , thermal grease 25 is located between a second side of plate 24 and duct 26 to transfer heat from component enclosure structure 15 to this duct , and they are fastened to each other typically again with some sort of fastening screws ( not shown ). again , various structures are brazed together ( not shown ) in forming duct 26 with its plate - like structures and the passageway connections therein through which a coolant , 27 , again represented by directed arrows and typically of the same substance as that used for coolant 13 , is supplied to flow through the separation space passageway between those plate - like structures when cooling is desired . as before , finned structures ( not shown ) can be provided in this passageway thermally coupled to the plate - like structures forming same ( typically by brazing ) to aid in the transfer of heat , that has been transferred to these structures , to coolant 27 . thus , a heat portion represented by directed arrows , 28 , that has been taken up by finned structure 22 from chips 18 and liquid 20 and its vapors , is then conducted to second heat transfer plate 24 and from there conducted through thermal grease 25 to duct 26 and then to flowing coolant 27 to thereby be transported away . another portion of the heat generated in chips 18 is conducted through pedestals 16 and liquid 20 to base plate 14 , as described above , and represented by directed arrows , 29 , and this portion is conducted to coolant 13 for removal . as a further alternative to just having dielectric liquid 20 being provided as a single component working fluid in only a single phase , as described above , there is shown in fig2 a cross - sectional side view of a diagrammatic representation of another electronic circuit housing arrangement , 10 ′. in addition to providing a fill in the unoccupied space in electronic component enclosure 15 based on the same kind of liquid as liquid 20 as was provided in this space in this electronic circuit housing arrangement ( as in the alternative described above for fig1 leaving no vapor space 21 ), a very large number of electrically insulative , thermally conductive nanoparticles are added as the dispersed phase to that liquid serving as the continuous phase in a liquid particle suspension mixture , or colloidal system like a sol , 20 ′. liquid particle suspension mixture 20 ′ has a larger effective thermal conductivity as a result of being a mixed phase heat transporting working fluid than does that of liquid 20 used alone . powders of boron nitride ( bn ), optimally distributed in some sense in being dispersed in the liquid phase , can serve as the nanoparticles , but nanoparticles of alumina ( al 2 o 3 ) are a suitable alternative . finned structure 22 is shown present in component enclosure 15 in arrangement 10 ′ as this will enhance conductive heat transfer from liquid particle suspension mixture 20 ′ to coolant 27 through plate 24 , thermal grease 25 and duct 26 , but this finned structure is not as necessary here as it is in arrangement 10 of fig1 because here there need not be surface for condensing a vapor , and so this structure could be omitted . in yet another alternative , there is shown in fig3 a cross - sectional side view of a diagrammatic representation of another electronic circuit housing arrangement , 10 ″, with another kind of colloidal system based on a soft matter , or compliant , electrically insulative encapsulant material such as a gel that can be used in place of liquid 20 at least in part for a continuous phase . again , electrically insulative , thermally conductive nanoparticles , such as the kinds indicated above , are dispersed therein to increase the thermal conductivity of the resulting mixture . a silicone gel is suitable for this purpose . the compliance of the resulting gel based mixture , 20 ″, reduces any stress that may otherwise occur on wire bonds 19 . finned structure 22 is again shown in component enclosure space 15 thermally coupled to plate 24 to enhance heat transfer but again could be omitted . although the present invention has been described with reference to preferred embodiments , workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention . | 7 |
due to drugs mentioned above , immunotherapy , biological therapy or alternatives not only have non - satisfactory results but also produce adverse effects or important secondary side effects . for this reason , we suggest to evaluate the biodrug , collagen - polyvinylpyrrolidone ( fibroquel ®, reg . no . 210m95 ssa ) in ra or oa patients . based on the fact that the addition of extracellular matrix proteins to t lymphocyte cultures is capable of modulating t cell response ( easter d w , hayt d b , ozkan a n . immunosuppression by a peptide from the gelatin binding domain of human fibronectin . j surg res 1988 ; 45 : 370 - 5 ; rybski j a , lause d b , reese a c . effect of fibronectin on antigen - induced lymphoproliferation and antibody synthesis in rats . j leuk biol 1989 ; 45 : 35 - 45 ; rueg c r , chiquet - ehrismann r , alkan s s . tenascin , an extracellular matrix protein , exerts immunomodulatory activities . proc natl acad sci usa 1989 ; 86 : 7437 - 41 ; furuzawa - carballeda j , alcocer - varela j , díaz de león l . collagen - pvp decreases collagen turnover in synovial tissue cultures from rheumatoid arthritis patients . ann n y acad sci 1999 ; 878 : 508 - 602 ); that oral administration of type ii collagen ( thompson hsg , staines na . gastric administration of type ii collagen delays the onset and severity of collagen - induced arthritis in rats . clin exp immunol 1985 ; 64 : 581 - 6 ; trentham d e , dynesius - trentham r a , orav e j , combitchi d , lorenzo c , sewell k l , hafler d a , weiner h l . effects of oral administration of type ii collagen on rheumatoid arthritis . science 1993 ; 261 : 1727 - 30 ) or type i or iii collagen ( zhang z j , lee ch s y , lider o , weiner h l . suppression of adjuvant arthritis in lewis rats by oral administration of type ii collagen . j immunol 1990 ; 145 : 2489 - 94 ) modulates peripheral immune system in ra and also that collagen - pvp has anti - inflammatory properties , as mention below . collagen - pvp is a y - irradiated mixture of pepsinized porcine type i collagen and pvp in a citric buffer , that stabilizes ph . in culture medium at 37 ° c . and neutral ph , collagen - pvp does not form a gel like other collagens and its electrophoretic , physicochemical and pharmacological properties are modified by the covalent binding between protein and pvp . it has been demonstrated in vitro and in vivo that the components alone ( collagen and pvp ) do not have the same properties than collagen - pvp ( chimal - monroy j , bravo - ruiz t , krötzsch - gómez f e , díaz de león l . implantes de fibroquel aceleran la formación de hueso nuevo en defectos óseos inducidos experimentalmente en craneos de rata : un estudio histologico . rev biomed 1997 ; 8 : 81 - 8 ). this biodrug has demonstrated to modulate collagen metabolism , pro - inflammatory cytokine expression , to improve skin wound repair , as well as other tissues . previous data have been determined by experiments performed in wistar rats and humans , where intralesional treatment of collagen - pvp of surgical wounds stimulates an increase of the granulation tissue on day 7 after surgery and tissues exhibit better skin architecture at day 28 , when compared to non treated group . improvement include cutaneous appendages presence in the wounded zone ( sebaceous glands and hair follicles ) together with a normal skin like collagen bundle arrangement ( krötzsch - gómez f e , guerrero - padilla e , díaz de león l . morphological studies on the effects of fibroquel during wound of surgical wounds in rats . j cell biochem 1993 ; suppl , 17e : 137r506 ). femoral diaphisary fractures were performed in wistar rats , after that 0 . 2 ml of collagen - pvp were administered in situ during the 3 first days after lesion . bone consolidation parameters were evaluated and 67 % of the treated animals showed total bone repair at day 30 vs . only 20 % for the control group . histological analysis demonstrated an early turnover of the mesenchymal cells in the collagen - pvp treated group by cartilage tissue first , and later by osteoblasts and trabecular bone ( days 16 and 23 ). also , it was determined higher osteopontin and osteonectin expression , meanwhile type i collagen and fibronectina were similar in experimental and control groups . results suggest that collagen - pvp modulates mesenchymal cell growth factors and extracellular matrix protein expression , stimulating migration , proliferation and differentiation of chondrogenic and osteogenic cells , improving bone repair ( almazán díaz a , de la cruz garcia j c , lira romero j m , arrellin g , chimal monroy j , díaz de león l , furuzawa - carballeda j , krötzsch gómez f : investigaci6n experimental de la regeneración ósea en fémures de rata después de la aplicación de colágena i polimerizada : estudio radiológico , histológico e inmunohistoquimico . rev mex ortop traum 1996 ; 10 : 142 - 52 ; chimal - monroy j , bravo - ruiz t , furuzawa - carballeda g j . lira r j m , de la cruz g j c , almazán d a , krötzsch - gómez f e , arrellin r g , díaz de león l . collagen - pvp accelerates new bone formation of experimentally induced bone defects in rat skull and promotes the expression of osteopontin and sparc during bone repair of rat femora fractures . ann ny acad sci 1998 ; 857 : 232 - 6 ). also , collagen - pvp effect was evaluated in diaphisary fractures of tibia in a phase i clinical trial in 20 patients ( 10 experimental and 10 placebo ). the study included early closed fractures and all of them were stabilized in the first 7 days . collagen - pvp or placebo ( 0 . 2 ml ) were administered intralesionally during surgery at days 1 , 7 and 30 , through the surgical wound . at day 30 , 80 % of the patients treated with collagen - pvp reported pain absence and the other 20 % mild pain . in contrast , 50 % of the control group patients exhibited moderate pain and the other 50 % mild pain . also , collagen - pvp treated group did not show inflammatory signs in the damaged area , but 50 % of the control group showed it . besides , serum alkaline phosphatase was increased in the collagen - pvp treated group , when compared with controls . at day 30 , radiographic bone repair according to meller scale , was grade i and ii in the 100 % of collagen - pvp treated patients at days 30 and 90 , respectively ; different to controls where they were 50 % and 100 % grade i at days 30 and 90 , respectively . bone repair of the collagen - pvp treated group was appropriate , all patients tolerated bipedal displacement , and there were not knee or ankle movement limitation . all these patients exhibited progressive walk before week 12 , and none of them required specific rehabilitation . control group also exhibited bone repair , although they did not tolerate bipedal displacement without external support at the same 12 week . four of them required specific rehabilitation due to muscle atrophy . in summary , collagen - pvp accelerate bone repair process by up regulation of osteopontine , osteonectin and alkaline phosphatase , whom favors differentiation to the mesenchymal tissue towards cartilage , hypertrophic cartilage later and finally to bone tissue . perhaps that regulation was due to down modulation of pro - inflammatory cytokine expression ( mainly il - 1 y tnf - α ), adhesion molecules ( elam - 1 , vcam - 1 e icam - 1 ) and some proteinases and in consequence early pain control because prostaglandin synthesis regulation ( de la cruz garcia j c . efecto de la colágena tipo i polimerizada al 1 % inyectable en la consolidación ósea ( reporte preliminar ). tesis . hospital de traumatologia y ortopedia de “ lomas verdes ”. unam . 1997 ). patients with tibia pseudoarthrosis aged 6 to 72 years old received 1 ml of collagen - pvp or placebo during 6 weeks . after treatment , from the collagen - pvp treated group 16 patients ( 51 . 6 %) exhibited excellent bone repair ( grade iii , according to meller scale ), in 12 patients ( 38 . 7 %) was good ( grade 11 ) and only in 3 of them ( 9 . 68 %) was not appropriate ( grade 1 ). meanwhile in the placebo treated group no bone repair was observed in any of the treated patients . histological analysis showed appropriate osteoblastic activity in the collagen - pvp treated group . besides pain was diminished in patients treated with the copolymer , may be through inflammatory factor modulation , via cox ( prostaglandin production ), and in consequence patients showed strength and appropriate muscle tone in the affected limb ( bermúdez - hickey r , nésme - ávila w , ruiz - flores l , suárez e . tratamiento de la pseudoartrosis de tibia con colágeno - polivinilpirrolidona . rev mex ortop traum 1999 ; 13 : 148 - 51 ). clinical experience in dermal fibotic diseases associated to chronic inflammation : collagen - pvp treatment of hypertrophic scarring or morphea . intralesional injection of biodrug once per week during 1 to 3 months in human hypertrophic scars or scleroderma lesions diminishes pruritus , pain , erythema , volume , and inflammatory infiltrates . it makes that tissue architecture resembles normal skin . moreover , the biodrug modulates ecm turnover , mainly types i and iii collagen , and down - regulates the expression level of il - 1 □, tnf -□, pdgf and vcam - 1 ( krötzsch - gómez f e , furuzawa - carballeda j , reyes - márquez r , quiróz - hernández e and díaz de león l . cytokine expression is downregulated by collagen - polyvinylpyrrolidone in hypertrophic scars . j invest dermatol , 1998 ; 111 : 828 - 834 . furuzawa - carballeda j , krötzsch e , espinosa - morales r , alcalám , barile - fabris l . subcutaneous administration of collagen - polyvinylpyrrolidone down - regulates il - 1β , tnf - α , tgf - β1 , elam - 1 and vcam - 1 expression in scleroderma skin lesions . clinical and experimental dermatology . 2005 ; 30 : 83 - 86 ). collagen - pvp immunomodulating effect was also observed in scleroderma skin lesions , due to treated lesions at the same posology prescribed above during 3 months , improved texture and appearance skin . histologically , collagen - pvp - treatment recovered cutaneous appendages , type iii collagen in papillary dermis and type i / iii collagen proportion , whilst thick bundles of type i collagen decreased . it was also determined by immunohistochemistry that , collagen - pvp down - regulated il - 1β and elam - 1 expression ( barile l , furuzawa - carballeda j , krötzsch - gömez fe , espinosa - morales r , alcalá m , díaz de león l . comparative study of collagen - polyvinylpyrrolidone vs . triamcinolone acetate in systemic sclerosis . clin exp rheumatol 1998 ; 16 : 370 ). based on the results that collagen - pvp down - regulates some proinflammatory cytokines , adhesion molecules and collagen turnover in skin fibrotic disorders , associated with chronic inflammation , we suspected that the biodrug could have the same effect on inflamed synovial tissue cultures from ra patients . assays showed a marked proliferation of purified lymphocytes when cultured in plates with phytohaemaglutinin ( pha ) or with pha and collagen - pvp in serum - free culture system . moreover , no proliferation above baseline was observed when cells were cultures with collagen - pvp alone . these results suggest that the biodrug was not able to stimulate lymphocyte proliferation . the scge assay or “ comet assay ” was carried out with a cell suspension of lymphocytes embedded in an agar gel sandwich on a microscope slide , lysed and electrophoresed for a short time under alkaline conditions . lysis removes cell contents except for the nuclear material and dna remains highly supercoiled in the presence of a small amount of non - histone protein ; when placed in alkali , it starts to unwind from sites of strand breakage . cells with increased dna damage display increased migration of dna from the nucleus towards the anode under an electrical current , giving the appearance of a “ comet tail ”. in this work , the analysis of dna damage has demonstrated that cultures incubated with or without collagen - pvp did not induce any change in dna migration in lymphoid cell cultures . therefore , these data suggest that the exposure to collagen - pvp did not have a genotoxic effect . safety , follow - up , clinical evaluation and laboratory tests have been performed in healthy volunteers and patients with hypertrophic scars or scleroderma . hematological tests ( white blood cells index , blood chemistry , serum calcium levels ), urinalysis , liver function test did not show differences before and after collagen - pvp administration . these findings indicate that the treatment did not induce any adverse immediate clinical reaction . total serum samples were tested by means of elisa for reactivity against porcine type i collagen or collagen - pvp . serum samples from 110 healthy volunteers no treated with the biodrug were used as a negative control to establish baseline levels of reactivity . serum samples from 37 ssc patients were used as a positive control , because previous reports have identified circulating human anti - collagen antibodies in several patients . serum samples from 44 individuals treated with collagen - pvp , were used to examine serologic reactivity to collagen - pvp , these samples were plotted according to the number of collagen - pvp doses ( less than 5 , 6 to 10 , 11 to 20 , 21 to 100 and more than 100 administrations ). also , serum sample reactivity was compared using an average group analysis according to dunnett test in at least two different dilutions . a significant difference was observed by the presence of antibodies against porcine type i collagen between healthy donors and ssc patients ( p & lt ; 0 . 05 ); no positive correlation could be determined on antibodies against collagen - pvp ( even considering factors such as the dosage , number of doses or patient age ) ( furuzawa - carballeda j , castillo i , rojas e , valverde m , díaz de león e , krótzsch e . cellular and humoral responses to collagen - polyvinylpyrrolidone administered during short and long periods in humans . can j pharmacol physiol 2003 ; 81 . 1029 - 35 ). on the other hand , the safety of the polymer , pvp , is useful in many pharmaceutical formulations , foods , cosmetics and toiletries as well as industrial applications , due to its particular physical and chemical properties ( the homopolymer of n - vinyl - 2 - pyrrolidone ) is a biologically inert and safe polymer . many studies have been shown its innocuity . pvp used in collagen - pvp is low molecular weight ( robinson et al . 1990 ). pvp used to manufacture collagen - pvp is of low molecular weight material due to it is excreted by the kidney . there are no reported adverse effects following intravenously administration as a plasma expansor , or of high doses orally , subcutaneous or intramuscular post - administration ( robinson b v , sullivan f m , bazelleca j f , schwartz s l . pvp . a critical review of the kinetics and toxicology of polyvinylpyrrolidone ( povidone ). lewis publishers , inc . 1990 ). preclinical assays in synovial tissue cultures from rheumatoid arthritis ( ra ) patients : collagen - pvp effect in synovial tissue cultures from ra patients . to evaluate whether collagen - pvp produces an effect either on cell metabolism or on cell concentration , we measured the dna content . there were no statistically significant differences in dna content when treated and control cultures were compared ( table 1 ). it is important to mention that dna content in non - ra synovium was 8 to 10 - fold lower than that determined in ra synovial tissue . there were no differences between control and collagen - pvp - treated cultures . morphological evaluation of non - ra synovium cultured with 1 % collagen - pvp showed unaltered tissue architecture on the 3 rd and 7 th culture day ( fig1 a ). the addition of collagen - pvp to non - ra synovium cultures did not modify tissue architecture , fiber collagen thickness or type i / iii collagen proportion ( fig1 b ). however , histological evaluation of synovial tissue from ra control cultures showed a variable content of inflammatory cells and fibrosis with abundant type i collagen ( red fibers in fig1 c ) at 3 rd , and 7 th culture day . in contrast , paired 1 % collagen - pvp - treated cultures showed recovery of type iii collagen ( blue fibers in fig1 d , at 7 th culture day ), similar to normal synovial tissue . relative percentage of types i and iii collagen in synovial tissue cultures from non - ra and ra patients . in order to confirm the change in the relative proportions of types i and iii collagen , duplicates of synovium homogenates at each point of culture were evaluated by interrupted gel electrophoresis and densitometric analysis . under reducing conditions , the inter - chain disulfide bonds are cleaved , releasing □ 1 ( iii ) monomers of collagen , which migrate more slowly than □ 1 ( i ) chains of type i collagen . fig2 a shows the fine band of □ 1 ( iii ) in the synovial tissue control cultures . densitometric analysis showed that the addition of collagen - pvp to non - ra synovium cultures did not produce any modification in the relative percentage of type i or type iii collagen ( fig2 b ). however , ra synovium cultures treated at 7 th day displayed a 1 . 7 fold increase in the □ 1 ( iii ) band , in a time - dependent fashion ( p & lt ; 0 . 009 , treated vs . untreated cultures ; fig2 c ). in contrast a thin type i collagen band was observed . during the progression of ra the proteolytic activity at the site of inflammation is increased . thus , synovia from 10 patients with ra and 5 non - ra patients were examined immunohistochemically in detail using specific antisera to mmp - 1 . the ra synovia showed a considerable high range in mmp - 1 distribution compared with non - ra synovia . there was no difference between treated versus control group ( fig3 d , e ). on the other hand , in ra supernatants from collagen - pvp - treated cultures , levels of total collagenolytic activity were 1 . 6 - fold lower than those in control cultures ( p & lt ; 0 . 05 ; fig3 a ). calcium - dependent collagenases ( mmps ) in supernatants from synovial tissue treated cultures were measured by the difference between the degradation of 3 h - collagen in a cacl 2 buffer and in an edta buffer ( total collagenolytic activity — calcium - independent collagenases ). this proteolytic activity exhibited slightly lower levels in supernatants from biocompound - treated cultures than untreated - ones ( fig3 b ). collagenase activity of proteinases that did not require calcium for their stability ( putatively elastase and / or g cathepsin ) was 2 . 2 - fold lower compared to untreated tissue cultures ( p & lt ; 0 . 008 ; fig3 c ). it is important to highlight that calcium - dependent as well as calcium - independent collagenolytic proteases have similar activity levels . this suggests that in ra pathogenesis , calcium - independent enzymes participate with the same magnitude to that observed for calcium - dependent enzymes . sections of ra synovium stained with anti - timp - 1 showed strong immunoreactivity in blood vessel and stromal cells in collagen - pvp - treated synovial tissue from ra patients ( fig3 g ). collagen - pvp has not any effect on synovium from non - ra patients ( fig3 f ). however , timp - 1 levels in supernatants from control cultures contained 1 . 7 - fold higher levels of the glycoprotein than treated cultures at the 7 th day ( p = 0 . 04 ; fig3 h ). adhesion molecule expression in synovial tissue cultures from non - ra and ra patients . in order to establish whether icam - 1 and vcam - 1 molecules , inflammatory markers , were modified by collagen - pvp treatment , they were detected in synovium . the icam - 1 expression in cultures from non - ra patients was similar between control and collagen - pvp - treated group ( 11 - 17 %; table 2 ). however , in treated cultures from ra patients , both icam - 1 and vcam - 1 molecules showed lower levels of intensity and immunoreactivity than control cultures ( table 2 ). the levels were statistically significant for icam - 1 at the 7 th culture day in blood vessels ( p = 0 . 03 ) and stromal cells ( p = 0 . 04 ) and the percentage of positive icam - 1 cells from treated cultures was similar to that determined for normal synovial tissue cultures ( table 2 ) [ 30 ]. in addition , vcam - 1 expression in blood vessels and stromal cells from treated cultures also showed a substantial down - regulation ( p & lt ; 0 . 05 ; table 2 ). in ra many factors are involved in synovial inflammation , where the cytokines such as il - 1 , tnf - α , il - 6 and il - 8 , have emerged as regulatory factors of particular importance . in order to establish the effect of collagen - pvp on the expression of these cytokines , we determined these proteins in the synovium by immunohistochemistry . results showed that il - 8 was expressed at significantly higher levels in non - treated synovial tissue cultures from ra patients than in non - ra and ra treated cultures ( fig4 a , b ). meanwhile il - 6 did not show any difference between ra treated cultures and control cultures ( table 2 ). since collagenolytic activity , cams and timp - 1 expression levels were down - modulated with collagen - pvp treatment , we suspected that the production of il - 1 □ and tnf - α was modified . the exogenous addition of the biodrug to non - ra tissue cultures did not produce any effect on tnf - α expression in blood vessels nor stromal cells ( fig4 c ). tnf - α expression was down - modulated by collagen - pvp in tissue from ra patients at statistical significant levels compared with non - treated cultures ( p & lt ; 0 . 05 ; fig4 d ). moreover , collagen - pvp down - regulated tnf - α protein concentration ( 4 - fold ) in supernatants ( p & lt ; 0 . 02 ; fig4 e ). the same down - regulated pattern of il - 1β expression was observed in ra tissue treated with collagen - pvp ( p & lt ; 0 . 05 ; fig4 f ) and in supernatants ( 3 - fold ; p & lt ; 0 . 03 ; fig4 g ). cox - 1 is a constitutively enzyme that synthesized prostaglandins pathway arachidonic acid metabolism . prostaglandins likely contribute to synovial inflammation by increasing local blood flow and potentiating the effects of mediators such as bradykinin and il - 1 that induce vasopermeability . in this vein , the immunohistochemistry showed that collagen - pvp induced a negative modulation on the expression of cox - 1 in ra tissue compared with untreated cultures ( table 2 ). however , biodrug did not show effect on non - ra tissue ( table 2 ). expression of fas / apo95 and detection of dna strand breaks in apoptotic synovial cells by in situ nick translation . it has been shown that fas antigen is expressed on the surface of synovial cells and mediates cell death of the fas expressing synovial cells when stimulated with agonistic anti - fas . however , defective apoptosis is intimately associated with ra thus , the function of the fas / fasl system seems to be incapable of eliminating cells in the proliferative ra synovium . due to , we examined whether fas antigen was expressed on synovium as well as the presence of apoptotic cells . we found that fas / apo95 was predominantly up - regulated on blood vessel cells from ra synovium collagen - pvp - treated ( table 2 ). when we applied the in situ cell death detection assay for ra synovial tissues to detect apoptotic cells , tunel technique showed an up - regulation mostly in blood vessel and stromal cells ( 50 %) ( table 2 ) treated with collagen - pvp ( furuzawa - carballeda j , rodriguez - calderón r , díaz de león l , alcocer - varela j . mediators of inflammation are down - regulated while apoptosis is up - regulated in rheumatoid arthritis synovial tissue by polymerized collagen . clin exp immunol 2002 ; 130 : 140 - 9 ). demographic and clinical characteristics of patients at the time on their basal visit and last dose of collagen - pvp are summarized in table 3 . subcutaneous administration of collagen - pvp during 3 months in the 8 painful joints showed that swollen and tender joint ( ritchie index or ri ) counts ( fig5 ) have improved rapidly ( ri : δ − 10 . 2 ≅− 46 . 4 %; swollen joint count : δ − 10 . 7 ≅− 71 . 8 %). this improved was sustained during long - term therapy . besides , very similar and highly significant differences in changes in other variables of disease activity such as morning stiffness and visual analogue scale pain ( morning stiffness : δ − 32 . 3 ≅− 68 . 6 %; vas : δ − 39 . 9 ≅− 63 . 8 %; fig5 ). patients also had a statistically significant improvement in disease activity score ( das ) ( das : δ − 1 . 35 ≅− 70 . 5 %, p & lt ; 0 . 02 ). the improvement was also determined using twenty , fifty and seventy percent american college of rheumatology response criteria ( acr20 , acr50 and acr70 ). the acr20 was achieved by 80 . 0 % of patients at 3 months ( 8 from 10 patients ). similarly , 60 . 0 % of patients achieved the acr50 ( 6 from 10 patients ) and 20 . 0 %, the acr 70 ( 2 from 10 patients ) at this time ( fig6 ). the physical functional status ( spanish - had - di ), also showed a significant difference in change from their baseline values and 3 months of collagen - pvp treatment ( haq - di : δ − 0 . 5 ≅− 48 . 5 %; p & lt ; 0 . 05 , 1 vs . 13 weeks ; fig6 ). all patients have not modified their oral methotrexate and dosage of concomitant nsaids during 3 months of the study ( table 3 ). there was no change in erythrocyte sedimentation rate , hematological constants ( hemoglobin , hematocrit , blood chemistry , red blood cells count , leukocytes and platelets ), neither c reactive protein nor rheumatoid factor . none of the patients were positive for antibodies to double chain of dna and ribonucleoprotein at baseline and after treatment . radiological analysis was no different at baseline and after treatment . however , is important to mention that there was no narrowing joint space , bone erosion nor cartilage degradation ( furuzawa - carballeda j , cabral a r , zapata - zúñiga m , alcocer - varela j . subcutaneous administration of polymerized - type i collagen for the treatment of patients with rheumatoid arthritis . j rheumatol 2003 ; 30 : 256 - 9 ). in vitro study evaluated the anti - inflammatory and apoptotic effect of polymerized type i collagen ( collagen - pvp ), as well as collagen turnover in synovial tissue from ra patients . based on these results , we suggest that collagen - pvp added to ra synovium cultures , modulates collagen turnover , since the biodrug decreases collagenolytic activity , as well as timp - 1 production , and increases the amount of type iii collagen and timp - 1 to similar levels observed in normal synovium . the chronic inflammatory process is altered by collagen - pvp action , as described previously by krötzsch - gómez et al ., and barile et al ., ( krötzsch - gómez f e , furuzawa - carballeda j , reyes - márquez r , quiróz - hernández e , díaz de león l . cytokine expression is downregulated by collagen - polyvinylpyrrolidone in hypertrophic scars . j invest dermatol 1998 ; 111 : 828 - 34 ; barile l , furuzawa - carballeda j , krótzsch - gómez f e , espinosa - morales r , alcalám , díaz de león l . comparative study of collagen - polyvinylpyrrolidone vs . triamcinolone acetate in systemic sclerosis . clin exp rheumatol 1998 ; 16 : 370 ), presumably due to the down - regulation of il - 1β , tnf - α , il - 8 as well as cell adhesion molecules and inducing cox - 1 activation . besides cell binding through integrin - extracellular matrix interaction generates signals that regulate mmp expression ( larjava h , lyons j , salo r , makela m , koivisto l , birkedal - hansen h , akiyama s k , yamada k m , heino j . anti - integrin antibodies induce type iv collagenase gene expression in keratinocytes . j cell physiol 1993 ; 157 : 190 - 200 ; romanic a m , madri j a . the induction of 72 kd gelatinase in t cells upon adhesion to endothelial cells is vcam - 1 dependent . j cell biol 1994 ; 125 : 1165 - 78 ; tremble p , chiquet - ehrismann r , werb z . the extracellular matrix ligands fibronectin and tenascin collaborate in regulating collagenase gene expression in fibroblasts . mol biol cell 1994 ; 5 : 4390 - 3 ; rükonen t , westermarck j , koivisto l , broberg a , kähäri v m , heino . integrin □ 2 □ 1 is a positive regulator of collagenase ( mmp - 1 ) and collagen □ 1 ( i ) gene expression . j biol chem 1995 ; 270 : 13548 - 52 ) suggesting that cell adhesion molecules can also participate in ra tissue destruction . also , down production of il - 1 □ and tnf -□ seems to stimulate synovial cell death via apoptosis in synovium cultures , the last may contributed to inhibit the outgrowth of synovial cells that eventually leads to hyperplasia or pannus formation and the destruction of ra joints ( furuzawa - carballeda j , rodriguez - calderón r , díaz de león l , alcocer - varela j . mediators of inflammation are down - regulated while apoptosis is up - regulated in rheumatoid arthritis synovial tissue by polymerized collagen . clin exp immunol 2002 ; 130 : 140 - 9 ). in conclusion , we showed that the addition of collagen - pvp to synovial tissue cultures induced a down - modulation but not an inhibition of inflammatory parameters in rheumatoid synovium . this study was seminal to consider the collagen - pvp as a coadjuvant for the ra treatment . the last affirmation was based on the knowledge that type i collagen is phylogenetically , one of the oldest extracellular matrix proteins . it possesses a very low antigenicity and it is relatively easy to metabolize . furthermore , it is able to stimulate cells to form new tissues , it means , collagen has informational character ( pohunlová h , adam m . reactivity and the fate of some composite bioimplants based on collagen in connective tissue . biomaterials 1995 ; 16 : 67 - 71 ). in 1981 , the food and drug administration ( fda ) approved the use of an injectable form of reconstituted purified bovine collagen ( zyderm ; collagen corp ., palo alto , calif .) as a medical device for augmenting the volume of soft tissues ( clark d p , hanke c w , swanson n a . dermal implants : safety of products injected for soft tissue agumentation . j am acad dermatol 1989 ; 21 : 992 - 8 ). current interest in this injectable form of collagen is focused on defining broader clinical applications and the development of new products . until now , most of the injectable collagen or collagen implants were derived from bovine dermal or tendinal atelopeptide collagen ( zyderm , zyplast and atelocollagen ) ( soo ch , rahbar g . moy r l . the immunogenicity of bovine collagen implants . j dermatol surg oncol 1993 ; 19 : 431 - 434 ; charriere g , bejot m , schnitzler l , ville g , hartmann d j . reactions to a bovine collagen implant . j am acad dermatol 1989 ; 21 : 1203 - 1208 ). however , the present study used polymerized - porcine type i collagen . it has anti - inflammatory properties ( krötzsch - gómez f e , furuzawa - carballeda j . reyes - márquez r , quiróz - hernández e , díaz de león l . cytokine expression is downregulated by collagen - polyvinylpyrrolidone in hypertrophic scars . j invest dermatol 1998 ; 111 : 828 - 34 ; barile l , furuzawa - carballeda j , krötzsch - gómez f e , espinosa - morales r . alcalá m , díaz de león l . comparative study of collagen - polyvinylpyrrolidone vs . triamcinolone acetate in systemic sclerosis . clin exp rheumatol 1998 ; 16 : 370 ). collagen - pvp which is made pepsinized porcine type i dermal collagen ( atelopeptidic ) due to it is a week immunogen . we preferred , porcine type i collagen due to pigs are among the primary animal species proposed as sources for xenografts in a variety of practical , ethical , and safety reasons including the high homology with human collagen ( weiss r a . xenografts and retroviruses . science 1999 ; 285 : 1221 - 1222 ; paradis k , langford g , long z , heneine w , sandstrom p , switzer w m , chapman l e , lockey ch , onions d , otto e . search for cross - species transmission of porcine endogenous retrovirus in patients treated with living pig tissue . science 1999 ; 1236 - 1241 ; beard h k , faulk w p , conochie l b , glynn l e . some immunological aspects of collagen . progr allergy 1977 ; 22 : 45 - 106 ). on the other hand , electrophoretic data suggest that collagen - pvp binds covalently to pvp . the covalent binding with pvp conveys both increased collagen stability and reduced collagen antigenicity . because of its unique chemical nature , low molecular weight makes pvp biologically inert and safe ( clark d p , hanke c w , swanson n a . dermal implants : safety of products injected for soft tissue agumentation . j am acad dermatol 1989 ; 21 : 992 - 8 ; soo ch , rahbar g , moy r l . the immunogenicity of bovine collagen implants . j dermatol surg oncol 1993 ; 19 : 431 - 434 ). besides , the homopolymer of n - vinyl - 2 - pyrrolidone or pvp confers on the biodrug pharmaceutical properties different than those observed in collagen or pvp alone . in contrast to bovine collagen implants , we did not find any adverse side effect with collagen - pvp , such as those previously described ( hypersensitivity reactions , mild erythema , urticaria , localized swelling , and specific anti - type i collagen antibody production ) ( mcclelland m , delustro f . evaluation of antibody class in response to bovine collagen treatment in patients with urinary incontinence . j urol 1996 ; 155 : 2068 - 73 ; delustro f , fries j , kang a . immunity to injectable collagen and autoimmune disease : a summary of current understanding . j dermatol surg oncol 1988 ; 14 ( suppl i ): 57 - 65 ; singh g , fries j f . autoimmune disease and collagen dermal implants . ann int med 1994 ; 120 : 524 ; lewy r i . autoimmune disease and collagen dermal implants . ann int med 1994 ; 120 : 525 ). at difference of the study of sieper , et al ., ( 1996 ) with collagen administration we did not find any adverse effect after administration of collagen - pvp nor elevation in laboratory test ( c reactive protein , erythrocyte sedimentation rate nor rheumatoid factor ) ( sieper j , kary s , sorensen h , alten r , eggens u , hüge w , hiepe f , kühne a , listing j , ulbrich n , braun j , zink a , mitchison n a . oral type ii collagen treatment in early rheumatoid arthritis . a double - blind , placebo - controlled , randomized trial . arthritis rheum 1996 ; 39 : 41 - 9 ). the collagen - pvp administration scheme was consistent with tarkowski &# 39 ; s scheme ( 1999 ) who demonstrated that the effect of 3 daily vs . 3 weekly treatments with equivalent doses of cholera - toxin b subunit - type ii collagen conjugate on days 7 , 14 , 21 after disease induction in mice diminished significantly then incidence of arthritis compared with mice treated daily with unconjugated type ii collagen or a control cholera toxin b ( tarkowski a , sun j - b , holmdahl r , holmgren j , czerkinsky c . treatment of experimental autoimmune arthritis by nasal administration of a type ii collagen - cholera toxoid conjugate vaccine . arthritis rheum 1999 ; 42 : 1628 - 34 ). in accordance with doses ( 1 . 7 mg of collagen ), administration pathway ( subcutaneous ), and the frequency of administration , we suggest that collagen - pvp could act also , like a tolerance - inducing - molecule more effective than the other ways of administration and with less toxic effects . based on the background of collagen - pvp , we think that it generates cytokine - secreting regulatory cells more than anergy ( furuzawa - carballeda j , cabral a r , zapata - zúñiga m , alcocer - varela j . subcutaneous administration of polymerized - type i collagen for the treatment of patients with rheumatoid arthritis . j rheumatol 2003 ; 30 : 256 - 9 ). using acr criteria , the 20 % response rate with 1 . 6 ml of collagen - pvp was 80 . 0 % at month 3 . good results were seen with more demanding criteria ( 60 . 0 % response at acr50 and a 20 . 0 % response at acr70 ). these values were similar to that obtained by etanercept in a phase ii trial ( moreland l w , baumgartner s , schiff m h , et al . treatment of rheumatoid arthritis with a recombinant human tumor necrosis factor receptor ( p75 )- fc fusion protein . n engl j med 1997 ; 337 : 141 - 7 ). in most cases , there was a continuous improvement over the 12 th week , this could be taken as evidence that a longer treatment period might be more favorable . given these encouraging results and the fact that this therapy has no known side effects further studies evaluating its effectiveness , optimal doses , mechanism of action , a placebo controlled study and other pathways of administration are warranted . collagen - pvp for the treatment of patients with rheumatoid arthritis . effect of intramuscular administration in a double blind placebo - controlled study . the study was a prospective , longitudinal , double blind placebo - controlled and included 30 patients with active ra ( acr ). patients on stable doses of methotrexate were treated in a freyberg scheme with intramuscular injections of 0 . 4 ml of collagen - pvp ( 3 . 33 mg of collagen ) or 0 . 4 ml of placebo during 6 months . the primary endpoints included disease activity score ( das ) and improvement was determined using american college of rheumatology response criteria ( acr20 , 50 and 70 ) that refers a mean change in 3 from 5 evaluations including the ritchie index ( ri ), swollen joint count , spanish - health assessment questionnaire ( haq - di ), pain intensity on a visual analogue scale ( vas ) and erythrocyte sedimentation rate ( esr ) or c - reactive protein ( crp ). statistical analysis was performed using double tail mann whitney u - test . collagen - pvp was safe and well tolerated . patients had a statistically significant improvement ( p & lt ; 0 . 05 ) in collagen - pvp - treated vs . placebo at 6 months of treatment in : swollen joint count ( 8 . 1 ± 3 . 7 vs . 17 . 9 ± 4 . 8 ), ri ( 10 . 7 ± 3 . 3 vs . 17 . 8 ± 5 . 4 ), morning stiffness ( 9 . 4 ± 4 . 6 vs . 37 . 8 ± 6 . 7 ), rheumatoid factor ( 207 . 7 ± 179 . 1 vs . 518 . 8 ± 293 . 2 ), c reactive protein ( 2 . 7 ± 3 . 9 vs . 28 . 1 ± 24 . 5 ), haq ( 46 . 7 ± 15 . 6 vs . 18 . 8 ± 13 . 7 ), das ( 3 . 5 ± 0 . 7 vs . 4 . 8 ± 0 . 9 ), acr20 ( 100 vs . 77 . 8 %), acr50 ( 67 . 6 vs . 11 . 1 %) y acr70 ( 33 . 3 vs . 0 %). serological or hematological parameters remained unchanged . there were no adverse events . collagen - polyvinylpyrrolidone exhibits an important downmodulatory effect on inflammation , on apoptosis induction , as well as collagen turnover in the synovial tissue of the patients suffering ar , perhaps through peripheral immune tolerance . this copolymer modifies , more cellular metabolism than proliferation . this is suggested since type iii collagen relative rate is increased , meanwhile type i collagen diminishes in the synovia treated with the drug , although total content of collagen is not modified . also , collagen - polyvinylpyrrolidone reduces proteolityc activity , due to calcium independent collagenases , modifying ecm protein turnover , mainly collagen and reestablishing the content of type iii collagen . the information expressed above suggests that collagen - polyvinylpyrrolidone induction of the reduction of collagenolityc activity could contribute to diminish rheumatoid synovitis secuelae , cartilage and bone invasion by inflammatory cells and their erosion and degradation . even more , collagen - polyvinylpyrrolidone induces the increase of timp - 1 in ar tissues , suggesting that ecm turnover could be diminished by a mechanism that involves mmps blockade by timp - 1 . in consequence , collagen - polyvinylpyrrolidone avoids inflammatory cell invasion and fibrosis , due to the drug downmodulates cell adhesion molecules and this effect prevents cell - cell attachment . according to this information , we suggest that collagen - polyvinylpyrrolidone immunomodulatory effects are focused to modulate adhesion molecule expression in stromal and endothelial cells through the leukocyte traffic reduction to the synovial joint . finally , in ar the copolymer downmodulates three pro - inflammatory cytokines : il - 8 , tnf - α and il - β . physiologically they can induce cox - 1 activation , an in consequence they can increase pge 2 synthesis , as well as joint cartilage and bone resorption . also , the previously mentioned cytokines , have been related to the beginning and ar sickness burst , in vitro and in vivo in a murine model . it is well known , that tnf - α and il - 1β are capable to induce synthesis and release of several other cytokines , such as gm - csf , il - 6 and il - 8 , and all of them increase mmp production and activity , diminution in elam - 1 , vcam - 1 and icam - 1 capillary expression in synovia from ar patients . in conclusion , the subcutaneous treatment of the eight more painful joints with collagen - polyvinylpyrrolidone to patients suffering ar , when they are receiving low doses of metotrexate and / or nsaids , improves sickness index ( das ) and an important change in at least 3 of the 5 following measures ( acr20 ), ritchie index ( painful joints ), inflamed joint evaluation , general assessment of the patient about the sickness activity ( haq ), the relative pain scale ( eva ), as well as acute phase proteins . collagen - polyvinylpyrrolidone treatment does not stimulate changes in blood or serum and the copolymer exhibits the advantage that is a biological copolymer that , until now , does not produce any risk for the patient , nor stimulate anti - type i collagen or anti - collagen - polyvinylpyrrolidone antibodies or anti ssa / ssb or anti - dna antibodies , even when patients have been treated during long periods ( more than 12 months ). collagen - polyvinylpyrrolidone is a safe and an efficient biomolecule for the short term ar treatment . | 0 |
referring specifically to fig1 a semiconductor chip 20 is illustrated on semiconductor chip package 10 . semiconductor chip 20 contains a monolithic integrated circuit consisting of three stages . the three stages are : matching circuit 30 , class a gain stage 40 , and class b gain stage 50 . the main component of matching circuit 30 is a common gate n - channel field effect transistor ( fet ) 34 . the source of fet 34 receives a signal from input pin 15 . also coupled to the source of fet 34 is a grounded resistor 32 . the drain of fet 34 is coupled to an inductor 36 . inductor 36 forms a path to pin 12 on package 10 . the drain of fet 34 is also coupled along an independent path to class a gain circuit 40 . the main component of class a gain circuit 40 is a n - channel fet 44 . coupled between the gate of fet 44 and the drain of fet 34 is a blocking capacitor 41 . a grounded bias resistor 42 is coupled between the gate of fet 44 and blocking capacitor 41 . the source of fet 44 is coupled to a parallel combination of resistor 47 and capacitor 48 . both resistor 47 and capacitor 48 are also connected to ground . pin 16 on package 10 is also coupled to the parallel combination of resistor 47 and capacitor 48 . an inductor 46 is coupled between the drain of fet 44 and pin 11 . the drain of fet 44 is also coupled along the independent path to class b gain circuit 50 . the main component of class b gain circuit 50 is open drain fet 54 . coupled between the gate of fet 54 and the drain of fet 44 is a blocking capacitor 51 . a bias resistor 52 having a first terminal coupled between the gate of fet 54 and blocking capacitor 51 , and a second terminal coupled to pin 13 is also utilized in class b gain circuit 50 . the source of fet 54 is coupled to both a grounded capacitor 58 and pin 19 . the open drain of fet 54 is coupled to output pin 17 . while ignored to this point , it should be noted that inductors 61 , 62 , 63 , 64 , 65 , 66 , 67 , 68 represent the parasitic inductances due to wire bonding between semiconductor chip package 10 and semiconductor chip 20 . furthermore , it should be noted that semiconductor chip 20 is most efficient when it is comprised of gallium arsenide and fets 34 , 44 , and 54 are metal semiconductor field effect transistors ( mesfets ). the drain of fet 34 and the drain of fet 44 are coupled to a bias node 77 via inductor 72 and inductor 71 , respectively . bias node 77 is coupled to a grounded capacitor 74 , and is also capable of receiving a bias voltage supply . it should be apparent to those skilled in the art that , while in fig1 a common bias node and grounded capacitor are utilized , separate bias nodes and grounded capacitors could be used for fet 34 and fet 44 . the functioning of the circuit shown in fig1 is described below : a signal is received at input pin 15 on package 10 , passes through inductor 61 , and enters matching circuit 30 . the reason that matching circuit 30 is called such is that when the gate of fet 34 is grounded , there is very little reflection of the input signal . this is true over a broad frequency range . when bias node 77 is connected to a bias voltage supply ( typically 5 - 7 volts ), bias resistor 32 is used to set up a potential difference between the gate and the source of fet 34 . this allows fet 34 to turn on . typically , bias resistor 32 will be 180 ohms and the current flow through it will be 10 ma . an rf signal will also pass from the drain of fet 34 to class a gain circuit 40 . inductors 36 , 62 , and 72 operate as a choke to prevent loss of the rf signal from the drain of fet 34 to bias node 77 . the purpose of blocking capacitor 41 is to insure that none of the dc bias current is permitted to go from the drain of fet 34 to the gate of fet 44 . the bias voltage supply connected to bias node 77 also is applied to fet 44 . this creates a dc current flow through resistor 47 . bias resistor 42 helps create a bias which allows fet 44 to turn on . capacitor 48 operates as an open circuit at dc , but is used to help set the ac load line . since fet 44 is on , it operates to magnify the rf signal . the rf signal is then passed from the drain of fet 44 to class b gain circuit 50 . inductors 46 , 63 , and 71 operate as a choke to prevent loss of the rf signal emanating from the drain of fet 44 . bypass capacitor 74 is utilized to eliminate any rf signal that does get through to bias node 77 , thus ensuring an rf ground at node 77 . blocking capacitor 51 serves the identical purpose of blocking capacitor 41 by preventing any dc bias current from going from the drain of fet 44 to the gate of fet 54 . bias resistor 52 is used to bias the gate of fet 54 by applying a source to pin 13 . capacitor 58 is once again used to set the ac load line , and the rf output is passed through the open drain of fet 54 to output pin 17 . the open drain of fet 54 allows for great flexibility since it can be connected to a number of other circuits . it is most common for the drain of fet 54 to be connected to a power fet and then an antenna . the class b gain circuit 50 allows for an efficiency reading of approximately 80 percent compared to an approximate 47 percent efficiency rating of a class a gain circuit . class b gain circuit 50 also allows idling at a low 0 - 10 ma . this means that when no rf signal is applied to input pin 15 , the amplifier of chip 20 will draw minimal current , thus saving battery lifetime . when components if fig1 are given values as indicated , the gain from input pin 15 to output pin 17 is shown in fig2 for frequencies between 0 and 1 . 5 ghz . the magnitude of the gain in decibels is higher than the desired 25 db at the commonly used frequencies of 450 mhz and 900 mhz . while a specific embodiment of this invention has been shown and described , further modifications and improvements will occur to those skilled in the art . we desire to be understood , therefore , that this invention is not limited to the particular form shown and we intend to cover all modifications which do not depart from the spirit and scope of the invention . | 7 |
fig1 is a perspective view of a conveyance section 100 according to various embodiments of the invention . the conveyance section 100 comprises a first transport belt 110 , a second transport belt 120 , a plurality of rollers 150 , and optional support protrusions 130 . the plurality of rollers 150 are configured to guide and optionally support the first transport belt 110 and the second transport belt 120 . the support protrusions are typically coupled with the first transport belt 110 and the second transport belt 120 and configured to support an article such as a foup 170 . in various embodiments , the first transport belt 110 and / or the second transport belt 120 may be vertically oriented , horizontally oriented , or slanted between horizontal and vertical . in some embodiments , at least some portion of the first transport belt 110 and / or the second transport belt 120 may be substituted with alternative support members such as rollers . in these embodiments , support protrusions may also optionally be coupled with the alternative support members and configured to support an article such as a foup 170 . the conveyance section 100 is configured to convey the foup 170 in a conveyance direction 180 along a conveyance path between the first transport belt 110 and the second transport belt 120 . the conveyance section 100 may be configured with multiple instances of conveyance sections 100 . fig2 a illustrates a conveyance section 200 comprising a first transport belt 110 , a second transport belt 120 , a plurality of optional support protrusions 130 , and a lift 210 . in various embodiments , the conveyance section 200 may comprise any embodiment of the conveyance section 100 further comprising the lift 210 . the lift 210 is configured to include a kinematic interface , according to various embodiments of the invention . the lift 210 may be disposed between the transport belts 110 and 120 such that the lift 210 can be raised and lowered along a vertical axis 190 under the foup 170 when the foup 170 is disposed in a location above the lift 210 . in some embodiments , the lift 210 may be configured to raise the foup 170 above a horizontal plane of the transport belts 110 and 120 within the conveyance section 200 . in other embodiments , the lift 210 may be configured to lower the foup 170 below the horizontal plane of the transport belts 110 and 120 within the conveyance section 200 . in still other embodiments , the lift 210 may be configured to both raise and lower the foup 170 above and below the horizontal plane of the transport belts 110 and 120 within the conveyance section 200 . fig2 b illustrates the conveyance section 200 in which the lift 210 rotates the foup 170 in a direction of rotation 230 . as the conveyance section 200 moves the foup 170 proximate to the lift 210 , the conveyance section optionally stops the foup 170 in a position approximately over the lift 210 . interface features , such as kinematic coupling pins 215 disposed on a top surface of the lift 210 , may optionally interact and couple with corresponding interface features on a bottom surface of the foup 170 , such as three kinematic holes . the kinematic coupling pins 215 and related features are configured to support proper alignment between the foup 170 and the lift 210 . after the foup 170 is aligned and coupled with the lift 210 , the lift 210 may be used to lift the foup 170 above a surface of the transport belts 110 and 120 and / or support protrusions 130 . once the foup 170 is above and no longer in substantial contact with the transport belts 110 and 120 and / or the support protrusions 130 , the lift 210 may rotate the foup 170 freely in a rotational direction 230 along a horizontal plane . in some embodiments , the lift 210 may rotate in a rotational direction opposite the rotational direction 230 . the lift 210 may rotate the foup 170 by approximately a positive or negative 90 degrees , 180 degrees , 270 degrees , or 360 degrees . fig2 c illustrates the conveyance section 200 after the lift 210 has rotated the foup 170 by approximately 90 degrees . as illustrated in fig3 , the foup 170 is characterized by a longer width 330 parallel to the foup door 310 relative to a length 320 perpendicular to the foup door 310 . for example , in various embodiments , the width 330 may be approximately 390 mm , and the length 320 may be approximately 356 mm . the spacing between transport belts 110 and 120 is typically configured to support the foup 170 when the foup 170 is oriented such that the width 330 and foup door 310 are perpendicular to the transport belts 110 and 120 along the horizontal axis 195 . therefore , when the lift 210 rotates that foup 170 in approximately a multiple of ninety degrees , the smaller foup length 320 will be perpendicular to the transport belts 110 and 120 along the horizontal axis 195 . when the foup 170 is oriented in this manner , the conveyance section 200 is configured to provide a clearance 240 ( fig2 c ) between the foup 170 and the support protrusions 130 of the transport belts 110 and 120 . the clearance 240 enables the lift 210 to lower the foup 170 down between the transport belts 110 and 120 without contacting the transport belts 110 and 120 or the support protrusions 130 . the lift 210 may be configured to lower the foup 170 below the horizontal plane of the transport belts 110 and 120 by any amount as needed to deliver the foup 170 to its next destination . once the foup 170 has been lowered below the horizontal plane of the transport belts 110 and 120 , the foup 170 may be rotated by any arbitrary amount as appropriate or necessary to align the foup 170 with another conveyance section 200 or other destination , or held in place . because the clearance 240 is not required for the lift 210 to raise the foup 170 above a horizontal plane of the transport belts 110 and 120 , the lift 210 is not required to rotate the foup 170 before raising the foup 170 along the vertical axis 190 . furthermore , the lift 210 may rotate the foup 170 by any arbitrary amount before , during , or after raising the foup 170 along the vertical axis 190 as appropriate or necessary to align the foup 170 with another conveyance section 200 or other destination . in various embodiments , specific mechanical , electrical , and software interfaces are defined to enable a variety of devices to directly access the foup 170 disposed on the transport belts 110 and 120 . embodiments of such interfaces include a mechanical interface such as the kinematic interface defined by the trade organization semi in the document number e57 - 0600 entitled “ mechanical specification for kinematic couplings used to align and support 300 mm wafer carriers ” and the electrical interface and software communications interface defined by the semi standard e84 - 0305 entitled “ specification for enhanced carrier handoff parallel i / o interface .” the kinematic interface features three kinematic coupling pins on a kinematic mount , the kinematic coupling pins being configured to mate with three corresponding depressions disposed on the bottom of the foup 170 when the foup 170 is placed in proper alignment with the kinematic mount . fig4 illustrates a method of using the lift 210 as shown in fig2 a , 2b , and 2 c to lower the foup 170 from the conveyance section 200 to another location , according to various embodiments of the invention . the method may be implemented using a combination of computer systems comprising both hardware and software coupled with the conveyance section 200 . the method is employed when a foup 170 is supported by a pair of transport belts 110 and 120 above a lift 210 . in step 401 , a command to transport foup 170 to a destination is received . the command may be first determined and transmitted by a computer system and / or operator configured to control the movement of foups 170 throughout a transport system comprising a plurality of conveyance sections 200 and other related transport devices . the destination is typically a location within the transport system , and may be proximate a lift 210 or a conveyance section 200 . in step 402 , a primary route between the current location of the foup 170 and the destination is determined . in step 403 , a determination is made regarding whether the destination is below the transport belts 110 and 120 . if the destination is determined to not be below the transport belts 110 and 120 , the method ends at a step 404 , and the lift 210 is not utilized . if the destination is determined to be below the transport belts 110 and 120 in step 403 , then step 405 is performed . in step 405 , the transport belts 110 and 120 are used to convey the foup 170 along the route to the lift 210 as illustrated in fig1 . step 405 ends when the foup 170 is located directly above the lift 210 , at which time step 406 is executed . in step 406 , the lift 210 is raised to couple with the foup 170 . after step 406 is completed , step 407 may optionally be performed . in optional step 407 , an output of a sensor disposed on lift 210 is read in order to assure that foup 170 is properly coupled with lift 210 . in optional step 408 , the output of the sensor - read in step 407 is evaluated to determine whether the foup 170 is properly coupled with the kinematic coupling pins 215 on the lift 210 . if the evaluation indicates that the foup 170 is not properly coupled with the lift 210 , then step 409 is performed . otherwise , step 411 is performed . in optional step 409 , an error is reported . following the reporting of the error , the method is stopped at step 410 . in step 411 , the lift 210 rotates the foup 170 by approximately a multiple of 90 degrees . in step 412 , the lift 210 lowers the foup 170 along a vertical axis 190 to a destination level of the intended destination . at the conclusions of step 412 , the method ends at step 413 . fig5 a , 5b , 5 c , and 5 d illustrate a side view of the conveyance sections 200 shown in fig2 a , 2b , and 2 c at various steps of the method illustrated in fig4 , according to various embodiments of the invention . in these embodiments , the lift 210 lowers the foup 170 along a vertical axis 190 from a first set of transport belts 110 a and 120 a to a second set of transport belts 110 b and 120 b . the second set of transport belts 111 b and 120 b may be configured to transport the foup 170 in any desired direction . as illustrated in fig5 a , 5b , 5 c , and 5 d , the second set of transport belts 110 b and 120 b are configured to transport the foup 170 in a direction approximately 90 degrees from the conveyance direction 180 of the first set of transport belts 110 a and 120 a . using the lift 210 , an intersection 510 between the first set of transport belts 110 a and 120 a and the second set of transport belts 110 b and 120 b can be created without physically interfering or modifying either the first set of transport belts 110 a and 120 a and the second set of transport belts 110 b and 120 b . therefore , neither the first set of transport belts 110 a and 120 a nor the second set of transport belts 110 b and 120 b need to begin or end a conveyance section 200 at any specific point . the intersection 510 may be located anywhere along a length of a conveyance section 200 , such as towards the middle or near either end . flexibility in placement of the intersection 510 along a conveyance section 200 allows conveyance sections 200 to be deployed and relocated without being configured as having specific lengths . as illustrated in fig5 a , the foup 170 is conveyed along transport belts 110 a and 120 a toward the intersection 510 . as illustrated in fig5 b , the foup 170 is disposed at the intersection 510 where the lift 210 is configured to move along a vertical axis 190 between the first set of transport belts 110 a and 120 a and the second set of transport belts 110 b and 120 b . the lift 210 is used to lift the foup 170 from the first set of transport belts 110 a and 120 a . as illustrated in fig5 c , the foup 170 is rotated approximately 90 degrees and the lift 210 lowers the foup 170 through a space between the first set of transport belts 110 a and 120 a . once below a horizontal plane of the transport belts 110 a and 120 a , the lift 210 optionally rotates the foup 170 by an angle defined as the angle between the conveyance direction 180 of the first set of transport belts 110 a and 120 a and a conveyance direction of the second sets of transport belts 110 b and 120 b . once properly oriented , the foup 170 may be lowered onto the second set of transport belts 110 b and 120 b as illustrated in fig5 d . the second set of transport belts 110 b and 120 b may transport the foup 170 in a new conveyance direction . fig6 a and 6b illustrate a transfer system 600 comprising a conveyance section 200 , a robotic hoist 630 , and machine load ports 610 , according to various embodiments of the invention . after a conveyance section 200 conveys a foup 170 via transport belts 110 and 120 to an equipment transfer location 680 near the location of a destination process or metrology equipment 620 , the transfer system 600 may transfer the foup 170 onto the equipment for processing or metrology . in some embodiments , the conveyance section 200 comprising transport belts 110 and 120 may be disposed above the process or metrology equipment 620 . the lift 210 may lift the foup 170 from the transport belts 110 and 120 , rotate the foup 170 , and then lower the foup 170 to an intermediate location 660 as shown in fig6 b . the destination processing or metrology equipment 620 may be configured to access the foup 170 while the foup 170 is located at the intermediate location 660 , open the foup front door 310 , and process or perform measurements of the contents such as semiconductor wafers disposed within the foup 170 . alternatively , when the processing or metrology equipment 620 is ready to receive the foup 170 , the transfer system 600 may transfer the foup 170 from the intermediate location 660 onto an equipment load port 610 using a device such as a robotic hoist 630 comprising a gripper 640 . the robotic hoist 630 may be configured to use the gripper 640 to grasp a top handle disposed on a top surface of the foup 170 , lift the foup 170 from the lift 210 at the intermediate location 660 , move the gripper 640 horizontally until the gripper 640 is over the destination equipment load port 610 , lower the foup 170 along a vertical axis 190 until the foup 170 rests on or couples with the equipment load port 610 , and release the foup 170 . in various embodiments , the robotic hoist 630 is integrated with the conveyance section 200 comprising the transport belts 110 and 120 . integration of the robotic hoist 630 with the conveyance section 200 reduces mis - alignment between the gripper 640 , the intermediate location 660 , and the load ports 610 . in addition , the robotic hoist 630 may be configured to share a common power and communications infrastructure as well as mechanical and seismic supports with the conveyance section 200 . in some embodiments , the lift 210 may be integrated with a load port of the processing or metrology equipment 620 . in these embodiments , the lift 210 may also be integrated with a load port foup front door opening device . such integration between the equipment load port and the lift 210 of the transfer system 600 eliminates intermediate steps and mechanisms . the lift 210 integrated with the load port 610 may be configured to transfer the foup 170 directly from the transport belts 110 and 120 to a machine load port location 670 at a load port 610 . after the foup 170 is transferred to the machine load port location 670 , the equipment may open the foup door and access material such as semiconductor wafers located within the foup 170 . in various embodiments , the transfer system 600 is configured to transfer a foup 170 from the transport belts 110 and 120 to the processing or metrology equipment 620 without stopping the motion of the foup 170 on the transport belts 110 and 120 . the lift 210 with the kinematic interface may be configured with an additional axis of motion such that the lift 210 may be moved horizontally along the conveyance direction 180 in synchronization with the movement of the foup 170 along the transport belts 110 and 120 in the conveyance direction 180 . when the position along a vertical axis 190 and speed along the conveyance direction 180 of the kinematic lift 210 and the foup 170 is about equal , the lift 210 may be raised to couple with the foup 170 , lift the foup 170 , rotate the foup 170 , and lower the foup 170 . the kinematic lift 210 may then move the foup 170 in both horizontal and vertical directions to position the foup 170 at the destination load port 610 . the kinematic lift 210 that is configured to move along the horizontal conveyance direction 180 as well as raise and lower along a vertical axis 190 enables the transport belts 110 and 120 to maintain their full speed when the foup 170 is removed from or placed on the transport belts 110 and 120 . in some embodiments , the transport belts 110 and 120 may be slowed down when a foup 170 is loaded or unloaded to assure that no collision occurs between the foup 170 being loaded or unloaded from transport belts 110 and 120 and other foups 170 being transported on the same transport belts 110 and 120 . fig7 a , 7b , 7 c , 7 d , and 7 e illustrate cross - sectional views of a transfer system 700 comprising two conveyance sections 200 , rotatable rails 710 and 720 , a lift 210 , and a foup 170 in different states of transfer , according to various embodiments of the invention . in some embodiments , additional clearance is required to lower the foup 170 between the transport belts 110 a and 120 a . in these embodiments , the transport belts 110 a and 120 a are optionally mounted on rotatable rails 710 and 720 , respectively , so that the transport belts 110 a and 120 a can be rotated about an axis at the outside of their lateral dimension , such as axes 715 and 725 , respectively . as illustrated in fig7 a , the foup 170 is supported by the transport belts 110 a and 120 a at an intersection 510 above a lift 210 . as illustrated in fig7 b , the lift 210 lifts the foup 170 from the transport belts 110 a and 120 a . as illustrated in fig7 c , the rotatable rail 710 coupled with the transport belt 110 a is rotated away from the foup 170 about the axis 715 in a direction of rotation 730 and the rotatable rail 725 coupled with the transport belt 120 a is rotated away from the foup 170 about the axis 725 in a direction of rotation 740 such that the support protrusions 130 are no longer oriented along a horizontal axis in the horizontal plane of the conveyance section 200 . the rotation of the rotatable rails increases the open space between the transport belts 110 a and 120 a . as illustrated in fig7 d , using this additional space , the lift 210 can lower the foup 170 from above the transport belts 110 a and 120 a , through the open space between them down to another conveyance section 200 comprising transport belts 110 b and 120 b . the additional open space between the transport belts 110 a and 120 a provided by the rotatable rails 710 and 720 decreases the possibility of interference between the foup 170 and the transport belts 110 a and 120 a . as illustrated in fig7 e , after the lift 210 has lowered the foup 170 from the transport belts 110 a and 120 a to the transport belts 110 b and 120 b , the rotatable rails 710 and 720 are rotated back to their original positions as previously illustrated in fig7 a and 7b . in an alternative embodiment , rather than using rotatable rails , the conveyance section 200 may be configured to shift the horizontal position of the transport belts 110 a and 120 a along the horizontal axis 195 away from another , by a sufficient amount , such as a few centimeters , to allow sufficient clearance for the lift 210 to lower the foup 170 through the space between the transport belt 110 a and the transport belt 120 a . fig8 illustrates a transport section 800 comprising a conveyance section 100 and an overhead gripper system 830 , according to various embodiments of the invention . the conveyance section 100 , further comprising transport belts 110 and 120 , is configured to convey a foup 170 along a conveyance direction 180 below the overhead gripper system 830 . the overhead gripper system 830 is configured to support and move an overhead gripper 810 in a horizontal direction along the conveyance direction 180 in parallel with the conveyance direction 180 of the conveyance section 100 . the gripper 810 may be configured to allow some flexibility and increase reliability of the foup 170 transfer . for example , the gripper 810 may be configured to include a simple device with fingers , such as gripper fingers 840 , to actively grasp the foup 170 top handle such as is commonly used by hoists to handle foups in a production environment . this grasping action can occur while foup 170 is moving along transport belts 110 and 120 . the overhead gripper system 830 is configured to lower the gripper 810 toward the foup 170 , grasp a top handle of the foup 170 using gripper fingers 840 , and lift the foup 170 off the transport belts 110 and 120 . the gripper system 830 may be configured to grasp and lift the foup 170 as it travels along the conveyance direction 180 on the transport belts 110 and 120 without requiring the transport belts 110 and 120 to slow down or stop . the gripper system 830 may cause the speed of the gripper 810 along the conveyance direction 180 to match the speed of the foup 170 on the transport belts 110 and 120 along the conveyance direction 180 . when the speed is matched , the gripper 810 is lowered into place on the top handle of the foup 170 until the gripper fingers 840 can grasp the foup 170 . once the foup 170 is securely held by the gripper fingers 840 , the gripper 810 may lift the foup 170 from the transport belts 110 and 120 and transfer the foup 170 to a variety of locations such as a buffer location , an equipment load port , or another section of transport belt in another location , altitude , or orientation . in some embodiments , the transport belts 110 and 120 may be significantly slowed or stopped prior to the gripper system 830 positioning the gripper 810 above the foup 170 , lowering the gripper 810 onto the top handle of the foup 170 , grasping the foup 170 using the gripper fingers 840 , and lifting the foup 170 off the transport belts 110 and 120 . fig9 illustrates a top profile of a transport section 900 comprising a conveyance section 100 in conjunction with overhead gripper belts 930 and 940 , according to various embodiments of the invention . in these embodiments , an overhead gripper system 910 comprises a pair of gripper belts 930 and 940 with features designed to engage a top handle 690 of the foup 170 . the gripper belts 930 and 940 may be substantially vertical belts , horizontal belts , or slanted belts oriented between horizontally and vertically . as illustrated in fig9 , the transport belts 110 and 120 are conveying the foup 170 in a conveyance direction 180 while being supported by support protrusions 130 . two gripper belts 930 and 940 may be positioned line with the top handle 690 of the foup 170 . the speed of the transport belts 110 and 120 and the gripper belts 930 and 940 may be sufficiently matched such that the gripper belts 930 and 940 may engage the top handle 690 of the foup 170 without significant relative motion between the top handle 690 of the foup 170 and the gripper belts 930 and 940 . alternatively , the gripper belts 930 and 940 may be configured to reduce relative motion between the top handle 690 of the foup 170 and the gripper belts 930 and 940 by enabling a servo - motor or gear coupled with the gripper belts 930 and 940 to be released from active driving and allow the gripper belts 930 and 940 to move freely with the motion of the foup 170 . once the gripper belts 930 and 940 fully engage the foup 170 , the gripper system 910 may lift the foup 170 and remove the foup 170 from the original transport belts 110 and 120 . once lifted from the transport belts 110 and 120 , the gripper system 910 may stop and / or move the foup 170 to an alternative location such as a buffer , transport rail , or process equipment load port . fig1 illustrates a transport system 1000 comprising an overhead ramped gripper 1010 in conjunction with a conveyance section 100 , according to various embodiments of the invention . in some embodiments , the gripper belts 930 and 940 , as illustrated in fig1 , are constructed with a ramp feature . in these embodiments , the overhead ramped gripper 1010 grasps the foup 170 and lifts the foup 170 from the surface of the transport belts 110 and 120 using the gripper belts 930 and 940 , and then moves the foup 170 upwards along a gripper belt ramp 1020 . the overhead ramped gripper system 1010 is configured such that a conveyance path of the gripper belts 930 and 940 follows a shape of the gripper ramp 1020 without separate mechanism to move the gripper belts 930 and 940 . once the ramped gripper system 1010 moves the foup 170 above the transport belts 110 and 120 , the ramped gripper system 1010 may stop movement of the foup 170 and hold the foup 170 in buffer as needed . alternatively , the ramped gripper belt system 1010 may be curved rather than piece - wise linear as illustrated in fig1 . in other embodiments , the ramped gripper belt system 1010 may be curved in a horizontal axis 195 out of vertical alignment with the conveyance section 100 . in still other embodiments , the ramped gripper belt system 1010 may be moved along a combination of a vertical axis 190 , a horizontal axis 195 , and / or a conveyance direction axis 180 using external motors to move the foup 170 and lower the foup 170 onto a different location , such as a different set of transport belts 110 and 120 . fig1 illustrates a profile view of the gripper belts 930 and 940 , according to various embodiments of the invention . in these embodiments , the gripper belts 930 and 940 are moved around pulleys 1110 and 1120 , respectively , to match a speed of transport belts 110 and 120 as they transport the foup 170 along a conveyance direction 180 . fig1 a and 12b illustrate a transport system 1200 comprising several conveyance sections 100 and a turntable 1220 , according to various embodiments of the invention . when transport belts such as transport belts 110 and 120 transport the foup 170 , the foup 170 may be removed from the transport belts 110 and 120 to be placed on an equipment load port 1250 . in some embodiments , the foup 170 is engaged to a load port 1250 specially configured to have a low complexity mechanism with a small delay in operations involving the foup 170 . as illustrated in fig1 a , the transport belts 110 and 120 convey the foup 170 along a conveyance direction 180 toward a turntable 1220 . the foup 170 is conveyed onto the turntable 1220 . the turntable belts 1260 and 1270 may be configured to be stationary when the turntable 1220 rotates . alternatively , the turntable belts 1260 and 1270 may be configured to move as the turntable 1220 rotates . the turntable belts 1260 and 1270 may be configured to match a speed of the transport belts 110 and 120 when the transport belts 110 and 120 convey the foup 170 onto the turntable belts 1260 and 1270 . the turntable 1220 is configured to rotate about a central axis of rotation 1225 ( perpendicular to the plane of the drawing ) to change the direction of travel of the foup 170 . the turntable belts 1260 and 1270 may be configured to significantly slow or stop motion of the foup 170 while the turntable 1220 rotates to change the direction of travel of the foup 170 . the turntable 1220 may rotate the foup 170 by , for example , approximately ninety degrees , to orient the turntable belts 1260 and 1270 such that the turntable belts 1260 and 1270 are in approximate alignment with destination transport belts such as the transport belts 1230 and 1240 . using the turntable belts 1260 and 1270 , the turntable 1220 can move the foup 170 onto the transport belts 1230 and 1240 . the transport belts 1230 and 1240 are configured to guide the foup 170 from the turntable 1220 directly to a specially configured load port 1250 of a process or metrology equipment or wafer sorting device , as illustrated in fig1 b . the load port 1250 may be configured to utilize a kinematic interface to clamp the foup 170 in place between the transport belts 1230 and 1240 from below . by clamping the foup 170 in place , the foup 170 may not move during processing . in various embodiments , the foup door 310 is pressed against the load port 1250 of the equipment such that the load port 1250 can open or remove the foup door 310 and the equipment can access the materials such as semiconductor wafers stored within the foup 170 . once the process , metrology or sorting equipment has completed its task using the materials stored within the foup 170 , the foup door 310 can be closed or replaced . the load port 1250 may now release the latch holding the foup 170 in place if needed . the transport belts 1230 and 1240 may thereafter move the foup 170 backwards to the turntable 1220 . the turntable 1220 may then rotate the foup 170 to orient the foup 170 to travel on a selected pair of transport belts 110 and 120 to a next destination . typically , the transport system 1200 is mounted at approximately the industry standardized load port height of 900 mm , or alternatively additional load ports 1250 may be provided on the process , metrology , or sorting equipment at a height of the installed transport belts 1230 and 1240 . in some embodiments , the transport belts 1230 and 1240 may be ramped to move the foup 170 from a height of the turntable 1220 to a height of the equipment load port 1250 . fig1 illustrates a method of using the transport system 1200 illustrated in fig1 a and 12b to transfer a foup 170 to and from a machine load port , according to various embodiments of the invention . the method may be implemented using a combination of computer systems comprising both hardware and software coupled with the transport system 1200 over a communications transmission path . in step 1301 , a command to process wafers within the foup 170 is received . the command may be first determined and transmitted by a computer system and / or operator configured to control the movement of foups 170 throughout a transport system comprising a plurality of transport systems 1200 , conveyance sections 200 , and other related transport devices . in step 1302 , the transport belts 110 and 120 move the foup 170 onto the turntable belts 1260 and 1270 disposed on the turntable 1220 . in step 1303 , the turntable 1220 rotates the foup 170 to align the turntable belts 1260 and 1270 with the transport belts 1230 and 1240 . in some embodiments , the turntable belts 1260 and 1270 may be significantly slowed or stopped while the turntable 1220 rotates . in step 1304 , the turntable belts 1260 and 1270 move the foup 170 onto the transport belts 1230 and 1240 . the transport belts 1230 and 1240 then move the foup 170 to the equipment load port 1250 . in step 1305 , a mechanism coupled with the equipment load port 1250 optionally locks the foup 170 in place relative to equipment load port 1250 . the mechanism may employ a three point kinematic interface to couple with the foup 170 . in step 1306 , the mechanism coupled with the equipment load port 1250 opens or removes the foup door 310 . in step 1307 , the equipment load port 1250 removes material such as semiconductor wafers from within the foup 170 for processing , measuring , or sorting by equipment attached to the equipment load port 1250 . in step 1308 , the equipment load port 1250 replaces material such as semiconductor wafers to the foup 170 after processing , measuring , or sorting by equipment attached to the equipment load port 1250 . in step 1309 , the mechanism coupled with the equipment load port 1250 replaces or closes the foup door 310 . in step 1310 , the mechanism coupled with the equipment load port 1250 optionally unlocks the foup 170 in place relative to equipment load port 1250 . the transport belts 1230 and 1240 then move the foup 170 from the equipment load port 1250 onto the turntable belts 1260 and 1270 . the turntable 1220 then rotates the foup 170 to approximately align the turntable belts 1260 and 1270 with the transport belts 110 and 120 . in step 1311 , the transport belts 110 and 120 transport the foup 170 along a conveyance direction to another location . fig1 illustrates a vertical conveyance section or elevator 1400 , according to various embodiments of the invention . the elevator 1400 may be configured to move the foup 170 along a vertical axis 190 from one horizontal plane to another horizontal plane to change the elevation of the foup 170 . the elevator 1400 may be useful , for example , to move the foup 170 from one location at a first horizontal plane , such as a first conveyance section 100 , to another location at a second horizontal plane , such as second conveyance section 100 . in some embodiments , as illustrated in fig1 , the elevator 1400 raises or lowers the foup 170 along a vertical axis 190 as transport belts 110 and 120 transport the foup 170 along a horizontal conveyance direction 180 . a horizontally aligned segment of the transport belts 110 and 120 may be placed on the elevator 1400 such that the foup 170 may be disposed on the transport belts 110 and 120 while the horizontally aligned segment is moved up or down along a vertical axis 190 to a desired elevation . the horizontally aligned segment of the transport belts 110 and 120 may then move the foup 170 off of the horizontally aligned segment to another location . as illustrated in fig1 , elevator belts 1410 and 1420 may be placed in alignment with and perpendicular to the transport belts 110 and 120 . a pair of elevator supports 1430 and 1440 are attached to the elevator belts 1410 and 1420 and configured to be positioned below the level of the foup 170 . the elevator belts 1410 and 1420 are configured to raise the elevator supports 1430 and 1440 along the vertical axis 190 such that the elevator supports 1430 and 1440 lift the foup 170 up from the transport belts 110 and 120 to a new level . at the new level , another transport mechanism such as a conveyance section 100 , lift 210 , gripper 810 , overhead gripper belts 910 , or the like may be configured to move the foup 170 to another location . in various embodiments , the elevator 1400 is configured to rotate the foup 170 about an axis such that the elevator moves the foup 170 to a location at a different elevation and along a different horizontal conveyance direction than the conveyance direction 180 from which the elevator 1400 receives the foup 170 . the elevator 1400 may be configured to rotate by an angle of approximately 90 degrees , 180 degrees , 270 degrees , or other arbitrary angles between zero degrees and 180 degrees . fig1 illustrates a transport system 1500 comprising several conveyance sections 100 and an elevator 1400 as illustrated in fig1 . the transport belts 110 a and 120 a at one horizontal plane are configured to transport the foup 170 to the elevator 1400 . the rollers 1530 may also be configured to guide the foup 170 onto the elevator belts 1410 and 1420 in conjunction with the transport belts 110 a and 120 a . after the foup 170 is transferred from the transport belts 110 a and 120 a to the elevator belts 1410 and 1420 , the elevator 1400 is configured to lower or raise the foup 170 along a vertical axis 190 ( perpendicular to the plane of the drawing ) to a destination height of the transport belts 110 b and 120 b . after the foup 170 reaches the destination height of the transport belts 110 b and 120 b , the roller 1530 or additional transport belts 110 and 120 may be configured to move the foup 170 off the elevator belts 1410 and 1420 onto another set of transport belts 110 b and 120 b at the new height . the rollers 1530 or transport belts 110 and 120 may be configured to move laterally along the horizontal axis 195 such that they provide greater clearance between them and the foup 170 when the elevator 1400 raises or lowers the foup 170 along the vertical axis 190 . alternatively , the rollers 1530 or transport belts 110 and 120 may be rotated out of the way to provide greater clearance for the foup 170 as illustrated in fig7 . fig1 illustrates a method of transferring a foup in a vertical direction 190 using the elevator 1400 as illustrated in fig1 and 15 . the method may be implemented using a combination of computer systems comprising both hardware and software coupled with the elevator 1400 . in step 1601 , a command to move the foup 170 to another level is received . the command may be first determined and transmitted by a computer system and / or operator configured to control the movement of foups 170 throughout a transport system comprising a plurality of elevators 1400 , conveyance sections 100 , and other related transport devices over a communications transmission path . in step 1602 , the elevator supports 1430 are positioned just below a vertical level of the foup 170 . in step 1603 , the foup 170 is moved to the center of the elevator , for example by transport belts 110 and 120 and / or rollers 1530 . in step 1604 , the foup 170 is moved to another level along the vertical axis 190 using the elevator 1400 . fig1 illustrates a transport section 100 comprising a first transport belt 110 and a second transport belt 120 , the transport section 100 being configured to provide air bearings along a conveyance path between the first transport belt 110 and the second transport belt 120 . the one or more air bearings are provided to additionally support an article while the first transport belt 110 and the second transport belt 120 guide the article in a conveyance direction 180 . as illustrated in fig1 , region 1740 represents a location where such air bearings can be provided , either below or above the article . exemplary air bearing generators for providing air bearings within region 1740 are described with respect to fig1 a - 18c . in various embodiments , the first transport belt 110 and the second transport belt 120 are vertical belts , horizontal belts , slanted belts that are oriented in a direction between vertical and horizontal , or combinations thereof . in some embodiments , at least some portion of the first transport belt 110 and / or the second transport belt 120 are substituted with rollers such as vertical rollers or horizontal rollers . in some embodiments , one or more air bearings are disposed between adjacent conveyance sections 100 . in these embodiments , the air bearings are typically configured to support an article as the article is transported between a first conveyance section 100 and an adjacent conveyance section 100 along a conveyance direction 180 . an air bearing may serve as an air - cushion non - contact supporting system , as described in u . s . patent application publication 2006 / 0054774 entitled “ high - performance non - contact support platforms ” which is incorporated herein by reference . in some embodiments , a plurality of air bearings are provided proximate to one another and approximately in a line parallel to the conveyance direction 180 along the conveyance path . in other embodiments , a plurality of air bearings are provided proximate to one another and approximately in a line perpendicular to the conveyance direction 180 along the conveyance path . in still other embodiments , a plurality of air bearings are provided proximate to one another in two dimensional groupings . in additional embodiments , one or more air bearings are provided in irregular locations and patterns between transport belt 110 and transport belt 120 . in some embodiments , the air bearings are configured to additionally support the article in a central region of the article between edges of the article that are supported by the transport belt 110 and the transport 120 . in various embodiments , the article comprises a substrate including glass , polymer , or semiconductor material . the article may also comprise substrates for the manufacture of liquid crystal , organic light emitting diode or other types of display devices , a memory substrate ( such as a hard drive platter substrate or an optical storage device substrate ), a photovoltaic device substrate , a battery substrate , or the like . by supporting the central region of the article , the air bearings may reduce stress on the article , and prevent damage or breakage due to bending caused by uneven support across the width of the article between the transport belt 110 and the transport belt 120 . in some embodiments , the air bearings may support an article such as a substrate characterized by an area less than 1 square meter , between 1 square meter and 5 square meters , between 5 square meters and 6 square meters , or between 6 square meters and 7 square meters . the air bearings may also reduce physical contact between the conveyance section 100 and the article in comparison with alternative support members such as rollers , consequently reducing friction and vibration . reduced contact and friction may also reduce contamination of the article and the ambient environment , for example by minimizing scrubbing of material contacting the article during transport . fig1 a , 18b , and 18 c illustrate air bearing generators configured to generate the air bearings illustrated in fig1 . fig1 a illustrates various embodiments of an air bearing generator 1810 . in these embodiments , the air bearing generator 1810 may be configured to generate an air bearing 1890 by generating an upward air stream 1820 . the upward air stream 1820 forms the air bearing 1890 by providing physical support to the article when the article travels above the air bearing 1890 along the conveyance path . the air bearing generator 1810 may be configured to emit one or more air streams 1820 emanating from one or more holes in a tube or support member . a velocity and quantity of air within the one or more air streams 1820 determines a level of support provided by the one or more air streams 1820 to the article , such as a substrate . the air bearing generator 1810 may optionally be configured to output a significantly reduced air stream 1820 or no air stream 1820 when the article is not in a path of the air stream 1820 . for example , the air bearing generator 1810 may be configured to only output the air stream 1820 directly upward if the article is above the air bearing 1890 , and to output a reduced air stream 1820 when there is no article above the air bearing 1890 . in some embodiments , turbulent limited orifices , such as those described in u . s . pat . no . 6 , 523 , 572 entitled “ apparatus for inducing forces by fluid injection ” which is incorporated herein by reference , may be used to limit the air stream 1820 when there is no article above the air bearing 1890 . fig1 b illustrates an alternative embodiment of an air bearing generator 1830 utilizing ultrasonic levitation . u . s . pat . no . 5 , 810 , 155 entitled “ object levitating apparatus object transporting apparatus and object levitating bearing along with an object levitating process and object transporting process ,” which is incorporated herein by reference , discloses various embodiments of an object levitating apparatus using ultrasonic excitation . ultrasonic levitation may typically be used to levitate an article , which may be characterized by thicknesses of approximately 1 mm to 2 mm , above a support surface 1840 . ultrasonic levitation uses ultrasonic waves generated between the support surface 1840 and the article to drive airflow into a space between the article and the support surface 1840 , and to inhibit air from flowing out of the space between the article and the support surface 1840 . in this way , the air bearing generator 1830 creates an air pressure differential between the article and the support surface 1840 compared to the ambient air pressure around the article . the air pressure differential creates an upward force 1850 that forms an air bearing 1890 that in turn levitates the article above the support surface 1840 . fig1 c illustrates alternative embodiments of an air bearing generator 1860 utilizing a venturi vacuum support system . a venturi vacuum support system supports an article such as a substrate from above rather than from underneath . as an air stream 1870 emanates downward through a venturi nozzle disposed in the air bearing generator 1860 , a vortex or venturi is created in the center of the venturi nozzle . the center of the venturi or vortex is characterized by a lower air pressure than the ambient air pressure , thereby creating a localized vacuum and a suction force 1880 tending to lift the article upward toward the center of the venturi nozzle . the air stream 1870 which escapes below the venturi nozzle in the air bearing generator 1870 forms an air bearing 1890 . the air bearing 1890 creates an equilibrium between the upward suction force 1880 and a downward force caused by the air stream 1870 emanating from the venturi nozzle within the air bearing generator 1860 . several embodiments are specifically illustrated and / or described herein . however , it will be appreciated that modifications and variations are covered by the above teachings and within the scope of the appended claims without departing from the spirit and intended scope thereof . for example , while the transportation of foups in semiconductor manufacturing have been used herein as an illustrative example , systems and methods of the invention may be configured for transporting alternative materials , such as for example , substrates for the manufacture of liquid crystal , organic light emitting diode or other types of display devices , a memory substrate ( such as a hard drive platter substrate or an optical storage device substrate ), a photovoltaic device substrate , a battery substrate , or the like . further , the vertical rollers and vertical belts discussed herein need not be perfectly vertical . the spacing of vertical rollers as illustrated herein is for illustrative purposes only . in various embodiments , vertical rollers may be disposed in a wide variety of spacings , from closely packed to widely dispersed including a single roller or rollers located only at each end of a belt . in various embodiments , horizontal rollers may be disposed in place of vertical rollers , and horizontal belts may be disposed in place of vertical belts . in various embodiments , various disclosed elements such as transfer devices and conveyance sections may be disposed in conjunction with , coupled with , and / or integrated with various other disclosed elements so as to configure a system comprising multiple disclosed elements to transport an article from one location to another location . for example , an elevator may be integrated with an equipment load port or a turntable . support elements such as transition wheels and air bearings may be disposed in any appropriate location throughout a conveyance section or transfer system as appropriate to support and / or guide articles being conveyed through the conveyance section or transfer system . attributes disclosed with respect to one disclosed element , such as a conveyance section or a transport belt , may be applicable to another disclosed element , such as a gripper belt or an elevator . in further embodiments of the lift 210 , the lift 210 can be additionally configured to purge the interior of the foup 170 . this would allow the foup 170 to be purged with a gas such as clean dry air , or nitrogen , while the foup 170 is engaged with the lift 210 . to accomplish the purge , the lift 210 can include one or more needle valves that are positioned to interface with the foup valves 1900 shown in the bottom view of the foup 170 in fig1 . for example , two such needle valves can be used to inject the gas and two can be used to allow the foup 170 to vent . in various embodiments , each of the various belts discussed herein may be replaced by two or more belts . likewise , each of the various belts discussed herein may be replaced by a combination of belt ( s ) and guide wheel ( s ), the guide wheels configured to support a foup directly without use of a belt between the guide wheel and the foup . in various embodiments , any one or more of the belts discussed herein are each supported by more than two guide wheels . the embodiments discussed herein are illustrative of the present invention . as these embodiments of the present invention are described with reference to illustrations , various modifications or adaptations of the methods and or specific structures described may become apparent to those skilled in the art . all such modifications , adaptations , or variations that rely upon the teachings of the present invention , and through which these teachings have advanced the art , are considered to be within the spirit and scope of the present invention . hence , these descriptions and drawings should not be considered in a limiting sense , as it is understood that the present invention is in no way limited to only the embodiments illustrated . | 1 |
with reference to fig1 is it schematically shown therein parts of an apparatus for forming a web of a particulate material such as wood or synthetic fibers , said apparatus comprising a forming head 1 with a distribution chamber 2 and a nozzle 4 oscillating about a shaft 3 and with its orifice positioned in the upper part of the distribution chamber 2 and communicating with a container ( not shown ) via a supply pipe 5 for supplying the particulate material in a carrier air stream . an air permeable belt or wire 6 runs in a loop around a plurality of rollers 7 , the roll 7a being the driving one . the wire 6 is arranged to run horizontally through the distribution chamber 2 , with its surface exposed in order to continuously receive particles flowing down through the distribution chamber 2 . the forming head 1 also includes a suction means in the form of a suction box 8 located below the wire 6 and the distribution chamber 2 , with which the suction box is aligned . the suction box 8 has an outlet 9 with fan 10 arranged to generate a suitable subatmospheric pressure in the suction box 8 and to remove the carrier air drawn into the suction box from the distribution chamber 2 through the wire 6 . as will be seen more clearly in fig2 the suction box 8 is provided with a plurality of vertical partitions 11 mounted parallel to the longitudinal direction of the wire and dividing the suction box 8 into a plurality of separate , adjacent suction sections 12 . each suction section 12 is provided in its lower area with a throttle 13 to enable adjustment of a suction gap 14 between section 12 and outlet 9 . in the embodiment shown , each of the throttles 13a and 13b belonging to the two outermost suction sections is connected to a setting device in the form of a hydraulic cylinder 16 , whose piston rod 15 actuates the throttle 13a or 13b , respectively , to adjust the suction gap 14 to the desired size , thus altering the subatmospheric pressure in the two outermost suction sections 12 in relation to that in the other sections . alternatively the throttles may be set by a common setting device . in another alternative embodiment ( not shown ) a group of two or more of the suction sections close to the two longitudinal sides of the suction box , i . e . at the two edge portions of the web , are controlled in this way , either individually , or by a common hydraulic cylinder . the setting devices may be pneumatic cylinders , step motors or motor - driven screw - and - nut devices . as will be seen in fig1 the distribution chamber 2 has a horizontal outlet 17 in connection to the wire 6 through which the wire 6 and a web 18 of particulate material formed thereon pass . the apparatus shown in fig1 is also provided with an adjustment means 19 located downstream of the forming head 1 and comprising a hood 20 fitted above the wire with a horizontal rotating scalper roll 21 , arranged at a predetermined distance from the wire 6 in order to cut excess material from the web 18 passing beneath the scalper roll 21 . the hood 20 , forming a vertically movable unit with the scalper roll 21 , communicates by way of a sliding connection with an upper outlet 22 in which a fan 23 is arranged to suck off the excess material removed by scalper roll 21 . between the forming head 1 and the adjustment means 19 are web sensor means depicted as three sensors 24 for level measurements , distributed across the width of the web 18 and secured to the hood 20 by support arms 25 . each sensor 24 is provided with a pivotable element 26 arranged to lie in contact with the web 18 to sense the level of the upper surface 27 in relation to a reference plane , and thus react to any changes in this level . these changes are recorded in a suitable manner via a connecting arm 28 . vertical movement of the hood 20 up or down results in a change in reference plane in relation to the wire plane . said recorded levels thus form the thickness profile of the web 18 prior to the scalper roll 21 . signals from all three sensors 24 are processed and the average value is compared with a set point for desired thickness of the web 18 . when differences are recorded , control signals are generated which actuate the discharge of particulate material supplied from a store ( not shown ), the amount of particles supplied to the distribution chamber increasing or decreasing depending on the value of the control signal , until the desired thickness is deposited on the web 18 . these sensors can also be used to provide information as to the thickness at the edge portions of the web 18 in relation to each other or in relation to the thickness in the central portion , recorded differences being compared with set points to generate control signals to actuate the operating means ( not shown ) which causes the nozzle 4 to oscillate , thus altering the distribution of the particulate material in the distribution chamber . web sensor means depicted as three sensors 29 for level measurements are also preferably arranged after the adjustments means 19 for adjusting the surface . the sensors 29 are distributed across the web in the same way as the sensors 24 described above . the sensors 29 are rigidly mounted by means of support arms 30 to the hood 20 . as above , each sensor 29 has a pivotable element 31 sensing the level of the top surface 32 obtained by means of the scalper roll 21 , in relation to a reference plane and which react to alterations in this level . these alterations are recorded in suitable manner via a connecting arm 33 . upon vertical movement on the hood 20 up or down , the position of the reference plane is altered in relation to the wire plane . instead of being mounted on the hood 20 , one or both groups of sensors 24 and 29 may be arranged on a stand of the apparatus which does not follow the movements of the hood 20 . in the embodiment shown , suction means in the form of a suction box 34 is also arranged below the wire 6 in connection to the adjustment means 19 . the suction box 34 is provided with an outlet 35 having a fan 36 designed to generate a suitable subatmospheric pressure in the suction box 34 to draw air through the web 18 and wire 6 . as with the suction box 8 described above , this section suction box 34 is also provided with a plurality of vertical partitions 37 , as seen more clearly in fig3 . the partitions 37 are parallel to the longitudinal direction of the wire 6 and divide the suction box 34 into a plurality of separate suction sections 38 , each provided in its lower part with a throttle 39 to set a suction gap 40 between the suction section 38 and outlet 35 . in the embodiment shown , each throttle 39a and 39b of the two outermost suction sections is connected to a setting device in the form of a motor 42 , whose shaft 41 influences the throttle 39a and 39b , respectively , to set the suction gap 40 at the desired size , thus altering the subatmospheric pressure in the two outer suction sections 38 in relation to that in the other sections . alternatively , the throttles may be set by a common setting device . in another embodiment ( not shown ) a group of two or more of the suction sections close to the two longitudinal sides of the suction box , i . e . at the two edge portions of the web , are controlled in this way by a common motor or each by its own motor . the setting devices may also comprise hydraulic cylinders , pneumatic cylinders , or motor - driven screw - and - nut devices . a separate sensor for measuring the grammage of the web 18 is also arranged at a suitable position after the scalper roll 21 . in the embodiment shown ( fig1 ) this consists of a weighing plate 43 arranged after the wire 6 and before a following endless conveyor belt 44 , in order to support the web 18 while at the same time sensing its weight . the scalper roll is vertically movable and its height is adjusted by a setting device ( not shown ) in accordance with the control signals obtained from the information about grammage gained from the weighing plate 43 after comparison with a set point of the grammage . adjustment of the throttles 13 in the suction box 8 below the distribution chamber 2 , enables the subatmospheric pressure in each suction section 12 of the box 8 to be controlled individually so that a desired suitable quantity of air passes through the web 18 within each suction section 12 . the quantity of air flowing through the wire depends on the thickness of the web 18 being continuously formed on the wire in the distribution chamber 2 and on the magnitude of the subatmospheric pressure prevailing in each suction section 12 . since the thickness of the web 18 transverse to its direction of movement is substantially constant the carrier air in the distribution chamber 2 can be guided to various suction sections depending on the subatmospheric pressure set for each section by the relevant throttle . the carrier or transport air can also be guided to suitable suction sections by swinging the nozzle 4 to and fro . since the particles are carried to the wire 6 by the carrier air , by adjusting the throttles 13 and thus the subatmospheric pressure in suction sections 12 , the particles can be guided to suitable areas across the direction of movement of the wire 6 to give a different grammage within this area to the grammage in an adjacent area . in this way the edge portions of the web 18 may be given greater grammage than the central portion . the increased subatmospheric pressure necessary to effect such increased flow of material to the edge portion or other areas , also causes the particles to be packed tighter together in the web 18 . higher density of the web 18 is thus achieved within these areas . due to the elasticity of the particles , the web 18 will expand to a certain extent upon leaving the distribution chamber and this expansion will be greater where most particles have collected , thus somewhat decreasing the higher density achieved . it is therefore advantageous to subject the web 18 to additional subatmospheric pressure before the final cross - sectional profile is determined by the scalper roller 21 in order to control and further influence the grammage profile of the web 18 transverse to its longitudinal direction . since , as mentioned earlier , the web 18 acquires higher density upon increased subatmospheric pressure , by adjusting the subatmospheric pressure in the various suction sections 38 of the suction box 34 the grammage profile produced in the distribution chamber 2 can be retained . the effect can even be reinforced by greatly increasing the subatmospheric pressure in the sections of the suction box 34 in relation to that used in suction box 8 . it is suitable to have the sensors located in the area of the suction action of the suction box 38 . the above valuable adjustment of the subatmospheric pressure in various sections is achieved through the present invention by the grammage of the web being controlled fully automatically by means of a feedback control system . in the embodiment shown the control system comprises said sensors 29 which record the levels of the web at the measuring points above the wire . the levels thus indicate the thickness profile of the web after the scalper roller 21 . the control system includes means for comparing the measurements in the form of a regulator 45 which receives measured value signals from the sensors 29 and compares these with set point signals . when there are differences , control signals are generated which are permitted to actuate suction control means in the control system , which in the embodiment shown comprise setting devices as described above in the form of hydraulic cylinders 16 and motors 42 and regulation values in the form of throttles including 13a , 13b , 39a , 39b . to maintain greater grammage at the edge portions the subatmospheric pressure in the outermost suction sections is adjusted by the signal from the middle sensor 29 being subtracted from the average value for the signals from the left and right sensors 29 . the resultant measured value signal is then compared with a set point signal . in the event of a difference , a control signal is generated which is permitted to actuate said respective suction control means , changing the subatmospheric pressure until the difference signal becomes zero . when the information from sensors 29 is used as output data to automatically control the grammage profile as described , certain assumptions must be made -- depending on the number of sensors which should not be less than three -- as to the relation between the thicknesses at these measuring points and the grammage corresponding thereto which is pre - programmed into the control system . in this case the system includes a control and calculating unit such as a micro - processor or pc equipment of known type . instead of sensors 29 for level measurements , a grammage meter of a type other than a weighing plate may be located downstream and used for automatic control of the grammage profile . this offers more detailed information as to the grammage distribution across the web . this type of sensor for grammage measurements is usually placed downstream of a pre - press described in the introduction , if such is used , whereupon some of the expected squeezing out takes place in the pre - press . this also has the advantage that the measured value will be closer to the final result for controlling the process . in this case also , a control and calculating unit similar to the one mentioned above is used . in designing the suction system for the scalper roll it is important to screen off the edges of the web to prevent air from being drawn in from the side . otherwise the edge portions of the web , which are the most important areas to be controlled , will not be compressed as intended since a reduced quantity of air will pass vertically through the entire thickness of the web . such screening can be achieved with the aid of means ( not shown ) in the form of metal sheets secured to the permanent lower stand part and to the hood so that they slide close together as the scalper roll moves up and down . alternatively an airtight cloth or the like , like a roller blind , may be arranged at each edge of the web . this may be attached to the hood at the top and to the permanent lower stand part at the bottom . the cloth will then automatically be rolled or unrolled onto the curtain rod as the scalper roll moves vertically . in the drawings and specification there has been set forth a preferred embodiment of the invention , and although specific terms are employed , they are used in a generic and descriptive sense only and not for purposes of limitation . | 3 |
the present application generally provides methods and for producing scooped shaped pita chips . in certain embodiments , the chips are created using conventional pita baking equipment . that is , the chips may be formed into scoop shapes without using an appropriately shaped blank . moreover , the chips are not necessarily cut out from larger pitas . instead , according to one embodiment , each chip is created from a single pita appropriately sized so that no cutting is required . referring to fig1 and 2 , in at least one embodiment , the method of producing scooped shaped chips begins by preparing the pita dough at 102 . the pita dough is generally a mixture that includes , inter alia , flour , salt , yeast , and water that is mixed until pliable . mixing may be accomplished by hand or preferably with a mixing machine 200 that receives ingredients from one or more tanks 202 . once the dough is prepared , the dough is formed into appropriately sized essentially circular sheets of dough at 104 . the circular sheets of dough may be formed in a variety of ways . preferably , the circular sheets are formed by first sheeting the dough at 106 with a dough sheeter 204 to form a continuous sheet of dough having a thickness of about 1 . 5 mm to about 2 . 0 mm . thereafter , a dough press 206 is used to cut the circular shaped dough out of the continuous sheet of dough . the dough press 206 cuts circular shapes having a diameter of about 1 inch to about 3 inches , preferably of about 2 inches to about 2 . 5 inches , or more preferably of about 2 . 25 inches . alternatively , the circular sheets of dough may be formed by extruding and subsequently cutting the extruded dough at 108 into roughly shaped dough balls that when flattened , result in a circular sheet having the dimensions noted above . preferably , the dough balls are between about 10 grams and about 14 grams , or preferably about 12 grams . the roughly shaped balls may then be fed into a dough balling machine 208 that shapes the chunks into essentially spherical balls with a well - developed skin . the dough balls may then be fed through a sheeting machine 204 at 110 that passes rollers over the balls in two essentially perpendicular directions to flatten the balls into the desired circular shaped dough sheets . the circular sheets of dough may then be fed into a conveyorized multi - tiered proofer 210 at 112 . preferably , the proofer 210 is maintained at a temperature of between 75 ° f . and 95 ° f . and a humidity level of between 45 % and 65 %, for about 10 minutes to about 25 minutes . once proofed , the circular sheets may then be fed into a baking oven 212 for baking at 114 at a temperature of over 500 ° f . for a sufficient time to cause the planer surfaces of the circular sheet to sear on the outside and subsequently to cause the circular sheet to separate into layers and balloon as the steam within the pita expands . as the ballooned sheet continues to cook , the initially uncooked inside of the pita solidifies to lock in the balloon shape . that is , each of the upper and lower layers of the pita is form into a cupped shape . the baking occurs from about 25 seconds to about 90 seconds , depending on the dimensions of the pita . after baking , the ballooned shaped pitas are cooled at 116 for about 20 minutes to about 40 minutes . because of the relatively small size of the pitas , the pitas retain the ballooned shape after cooling . once cooled , the ballooned pitas are then passed onto a horizontal band slicer 214 at 118 that is adjusted to slice the ballooned pitas at the seam , i . e ., at the intersection of the upper and lower layers . slicing of the ballooned pitas is described in further detail with respect to the description of fig3 through fig8 . once split at 118 , an individual pita will result in two concave pita halves . the pita halves may be 2 - 2 . 5 inches round or slightly oval in dimension . the pita halves may then be sprayed with oil and seasoned at 120 , and then passed into a toasting or drying oven at 122 . the drying oven is preferably set between 275 ° f . to about 375 ° f . and the pita halves are dried for about 7 minutes to about 20 minutes depending on the temperature and airflow in the drying oven . alternatively , the oil and seasoning may be applied to the pita halves after drying . fig3 presents a conveyorized slicing system for cutting scooped shaped pita chips according to at least one embodiment . as described above , the baked pitas 310 are transported to a horizontal band slicer after cooling . the baked pitas may take the form of “ pocket ” pitas comprising a piece of dough that blisters while baking in the oven such that a pocket is formed with a top and bottom layer . according to another embodiment , the baked pitas may be “ pocketless .” the horizontal band slicer is capable of slicing both pocket and pocketless pitas . a continuous feed of pitas are carried on a belt 302 by belt pulley 306 from a first location to a second location on the conveyorized system . at the second location , the pitas 310 reach belt pulley 308 and come into contact with a belt 304 that is above the belt 302 and pitas 310 such that pitas 310 are disposed between belt 302 and belt 304 . belt 302 and belt 304 are pulled via belt pulley 306 and belt pulley 312 , respectively . according to one embodiment , the belts may be wrapped around pressing rollers to double task the pressing rollers ( 204 ) as belt pulleys . in such a configuration , the belts remain in constant contact with the pitas all the way through the pressing and slicing at the blade so there is no loss of traction . a gap is allocated between belt 302 and 304 for the pitas 310 . the gap is adjustable and is configured to a predetermined size suitable for fitting the baked pitas . while disposed between belts 302 and 304 , the pitas 310 can be carried towards and fed to a blade and blade guide configuration 312 at a third location on the conveyorized system comprising the horizontal band slicer 400 , as illustrated in fig4 . horizontal band slicer 400 includes a blade 402 , blade guide 404 and blade pulleys 406 . the horizontal band slicer 400 is capable of operating blade 402 in a circular or rotating slicing motion . according to one embodiment , the slicing motion of blade 402 moves in a direction perpendicular to the planes of belts 302 and 304 . blade and blade guide 312 may be configured wherein a portion of blade 402 and / or blade guide 404 are configured in a gap approximately an equidistance between belts 302 and 304 . the portion of the blade configured in the gap herein referred to as the “ slicing portion .” the blade 402 may be configured in a plane parallel with or substantially parallel with the belts 302 and 304 . pitas 310 approach the slicing portion of blade 402 as seen from the front view presented in fig5 and sliced with blade 402 on the front side ( slicing side ) of horizontal band slicer 400 . fig6 and fig7 present an overhead view and a cross section view of blade 402 and blade guide 404 , respectively . the blade guide 404 may be configured at the back side of the horizontal band slicer 400 , opposite the slicing side , and partially around the top and bottom sides of the slicing portion of the blade 402 , leaving the portion of the front side ( slicing side ) of the blade exposed . fig8 presents a cross section view of the blade 402 , blade guide 404 , belt 302 , belt 304 , and a pita 310 a . a portion of belt 302 and belt 304 ( e . g ., the second or third location of the conveyorized system ) may be angled in a “ v ” shape towards blade 402 and blade guide 404 in a fashion to allow for the two pita halves to pass through between the belt pulleys 306 and 312 and the blade guide . blade guide 404 provides two channels where a pair of pita halves ( resulting from the bifurcation of a pita ) may be directed by belts 302 and 304 pass the blade 402 . the two channels may vary from approximately ¼ of an inch to half an inch in width . the blade guide 404 illustrated in fig8 includes sections that follow along the top and bottom sides of the slicing portion of the blade 402 and angles or tapers towards the front side of the blade . pita 310 a upon contacting with blade 402 is sliced into two halves . the blade guide 404 is configured to stabilize and maintain blade 402 straight , prohibiting movement to occur as pita 310 a makes contact with the front side of the blade 402 . according to one embodiment , blade guide 404 is substantially thin towards the front of blade 402 , tapering in width from approximately ⅛ ″- ¼ ″ in the front to approximately ½ ″ in the back , and includes a center gap about ⅛ ″- ¼ ″ in width for configuration of blade 402 . the thin front of the blade guide 404 allows fitment of blade 402 between and allows belts 302 and 304 to be brought extremely close together . a thicker back of the blade guide 404 helps create the a respective channel for each sliced half of pita 310 a in addition to providing a backbone / support to the blade guide 404 that prevents movement of the blade 402 when pitas make contact with blade 402 , thereby ensuring each pita is slice perfectly in half . a given pita 310 a is extremely thin ( about half an inch ) and the top and bottom skins resulting from slicing the pita 310 a into halves , each approximately have half the thickness of pita 310 a ( ¼ of an inch ). one pita half may be transported by belt 302 on the bottom side of the blade guide 404 while the other pita half may be transported by belt 304 on the top side of the blade guide 404 . thereafter , the pita halves may be seasoned and toasted . by slicing the pitas in the described manner , there is a 95 % success rate slicing every pita perfectly in half . while the foregoing has been described in some detail for purposes of clarity and understanding , it will be appreciated by one skilled in the art , from a reading of the disclosure , that various changes in form and detail can be made without departing from the true scope of the invention . | 0 |
hereinbelow , a preferred embodiment will be described in accordance with the accompanying drawings wherein like numerals refer to like parts throughout . fig1 represents an embodiment . a data processing apparatus 10 according to the embodiment has central processing units ( cpu ) 20 a , 20 b and 20 c ( having a cpu core 21 and a primary cache 22 ), and a secondary cache 30 ( having a cache control apparatus 31 ) shared by the cpus 20 a , 20 b and 20 c . the secondary cache 30 is connected to a main storage apparatus , though it is not represented in the drawing . the cpu core 21 has a command decoder 211 and can execute a no - move - in store command as a store command which does not require move - in ( transferring data from the secondary cache 30 to the primary cache 22 ) in addition to various known commands . when the cpu core 21 executes the no - move - in store command , the cpu core 21 outputs a move - in prohibition signal s 1 ( signal representing that move - in is not required ) to the primary cache 22 . the primary cache 22 has cache random access memories ( ram ) 221 a and 221 b , selectors 222 , 223 and 224 , tag rams 225 a and 225 b , an address comparator 226 , a cache state information storing circuit 227 , and a control circuit 228 . for example , in the primary cache 22 , a write - allocating system is used . in addition , in the primary cache 22 , the mosi cache coherency protocol / system is used for assuring a cache coherency . the cache rams 221 a and 221 b write output data of the selector 222 into an entry depending on an output address of the cpu core 21 according to writing instructions of the control circuit 228 . further , the cache rams 221 a and 221 b read data from the entry depending on the output address of the cpu core 21 according to reading instructions of the control circuit 228 and output the read data to the selector 223 . the selector 222 selects output data of the cpu core 21 or output data of the secondary cache 30 according to selecting instructions of the control circuit 228 and outputs the selected output data to the cache rams 221 a and 221 b . the selector 223 selects output data of the cache ram 221 a or output data of the cache ram 221 b according to selecting instructions of the control circuit 228 and outputs the selected output data to the selector 224 and the secondary cache 30 . the selector 224 selects output data of the selector 223 or output data of the secondary cache 30 according to selecting instructions of the control circuit 228 and outputs the selected output data to the cpu core 21 . the tag rams 225 a and 225 b write a part of an address into the entry depending on the output address of the cpu core 21 according to writing instructions of the control circuit 228 . the tag rams 225 a and 225 b read the address from the entry depending on the output address of the cpu core 21 according to reading instructions of the control circuit 228 and output the read address to the address comparator 226 . the address comparator 226 compares a part of the output address of the cpu core 21 with the output address of the tag rams 225 a and 225 b and outputs an address comparing result signal s 2 ( signal representing whether the addresses match or not ) to the control circuit 228 . the cache state information storing circuit 227 stores state information of each entry which is embodied by a register or the like and is used for controlling cache coherency . the state information is set to any one of a modified ( m ) state , an owned ( o ) state , a shared ( s ) state and an invalid ( i ) state by the control circuit 228 . the control circuit 228 performs various operations for controlling the entire primary cache 22 . the control circuit 228 determines a cache hit / cache miss hit based on the address comparing result signal s 2 . when the control circuit 228 recognizes occurrence of the cache miss hit , upon output of the move - in prohibition signal s 1 by the cpu core 21 , a no - move - in store request signal s 3 ( signal representing that a cache miss hit occurs when executing a no - move - in store command ) is output to the secondary cache 30 ( cache control apparatus 31 ). the cache control apparatus 31 performs an operation for controlling data transfer between the primary cache 22 ( control circuit 228 ) of the cpus 20 a , 20 b and 20 c and the secondary cache 30 , an operation for assuring the cache coherency or the like . various control signals such as a move - in request signal ( signal for requesting data transfer from the secondary cache 30 to the primary cache 22 ) are output from the primary cache 22 ( control circuit 228 ) of the cpus 20 a , 20 b and 20 c to the secondary cache 30 ( cache control apparatus 31 ) when necessary , though it is not represented in the drawing . further , various control signals such as a flush request signal ( signal for requesting to write back dirty data ) or an invalidate request signal ( signal for requesting to set the state information to the invalid state ) are output from the secondary cache 30 ( cache control apparatus 31 ) to the primary cache 22 ( control circuit 228 ) of the cpus 20 a , 20 b and 20 c when necessary . fig2 a and 2b represent an operation of a conventional data processing apparatus . the conventional data processing apparatus 10 ′ has cpus 20 a ′, 20 b ′ and 20 c ′ and a secondary cache 30 ′. the cpus 20 a ′, 20 b ′ and 20 c ′ are the same as the cpus 20 a , 20 b and 20 c represented in fig1 except that the cpus 20 a ′, 20 b ′ and 20 c ′ do not have a mechanism related to the no - move - in store command . the secondary cache 30 ′ is the same as the secondary cache 30 represented in fig1 except that the secondary cache 30 ′ does not have a mechanism related to the no - move - in store request signal . the operations represented in fig2 a and 2b are performed when a cache miss hit occurs upon executing a store command for designating an address a as a store destination address at the cpu 20 a ′ ( primary cache ) in the case where line data corresponding to the address a does not exist in the modified cache state in the cpus 20 b ′ or 20 c ′ ( primary cache ). in addition , it is previously known that the line data corresponding to the address a is never referred to at the cpu 20 a ′. when the cache miss hit occurs , upon executing the store command for designating the address a as a store destination address at the cpu 20 a ′, as represented in fig2 a , a move - in request signal is output from the cpu 20 a ′ to the secondary cache 30 ′ ( cache control apparatus 31 ′) ( o 1 ). with this operation , as represented in fig2 b , data of the corresponding line ( line corresponding to the address a designated by the cpu 20 a ′) is transferred from the secondary cache 30 ′ to the cpu 20 a ′ by the move - in operation ( o 2 ). at the cpu 20 a ′ ( primary cache ), after the data transferred from the secondary cache 30 ′ is written in the corresponding entry , the execution of the store command is completed by writing the store data into the corresponding entry . thereafter , the state information of the corresponding entry of the cache state information storing circuit 227 ′ is updated from “ i ” to “ m ” ( o 3 ). since there is the circumstance when data transferred from the secondary cache 30 ′ to the cpu 20 a ′ by the move - in operation is never referred to at the cpu 20 a ′, data transfer ( move - in ) from the secondary cache 30 ′ to the cpu 20 a ′ is uselessly performed . fig3 a and 3b represent operations of the data processing apparatus represented in fig1 . the operations represented in fig3 a and 3b are performed when a cache miss hit occurs and executing a no - move - in store command for designating an address a as a store destination address at the cpu 20 a ( primary cache ) in the case where line data corresponding to the address a does not exist in the modified cache state in the cpus 20 b or 20 c ( primary cache ). in addition , it is previously known that the line data corresponding to the address a is never referred to at the cpu 20 a . when the cache miss hit occurs , upon executing the no - move - in store command for designating the address a as a store destination address at the cpu 20 a , as represented in fig3 a , not a move - in request signal but a no - move - in store request signal is output from the cpu 20 a to the secondary cache 30 ( cache control apparatus 31 ) ( o 1 ). with this operation , as represented in fig3 b , the move - in operation is not performed ( o 2 ), but only an operation related to assuring cache coherency is performed in the cache control apparatus 31 of the secondary cache 30 . at the cpu 20 a , upon outputting the no - move - in store request signal , the cpu 20 a completes execution of the store command by writing ( i . e ., directly writing ) the store data into the corresponding primary cache 22 entry . thereafter , the state information of the corresponding entry of the cache state information storing circuit 227 is updated from “ i ” to “ m ” ( o 3 ). as described above , the data processing apparatus 10 represented in fig1 differs from the conventional data processing apparatus 10 ′ ( represented in fig2 a and 2b ), so that useless data transfer from the secondary cache 30 to the cpu 20 a associated with the move - in operation is avoided and data coherency among the cpus 20 a , 20 b and 20 c is assured . fig4 a and 4b represent another operation of the conventional data processing apparatus . the operations represented in fig4 a and 4b are performed when a cache miss hit occurs and executing a store command for designating an address a as a store destination address at the cpu 20 a ′ ( primary cache ) in the case where line data corresponding to the address a exists in the modified cache state in the cpu 20 c ′ ( primary cache ). in addition , it is previously known that the line data corresponding to the address a is never referred to at the cpu 20 a ′. when the cache miss hit occurs , upon executing the store command for designating the address a as a store destination address at the cpu 20 a ′, as represented in fig4 a , a move - in request signal is output from the cpu 20 a ′ to the secondary cache 30 ′ ( cache control apparatus 31 ′) ( o 1 ). with this operation , as represented in fig4 b , a flush request signal is output from the secondary cache 30 ′ ( cache control apparatus 31 ′) to the cpu 20 c ′ ( o 2 ). therefore , dirty data of the corresponding line is transferred from the cpu 20 c ′ to the secondary cache 30 ′ by the flush operation ( o 3 ), and at the cpu 20 c ′, the state information of the corresponding entry of the cache state information storing circuit 227 ′ is updated from “ m ” to “ i ” ( o 4 ). thereafter , data transferred from the cpu 20 c ′ to the secondary cache 30 ′ is transferred from the secondary cache 30 ′ to the cpu 20 a ′ by a move - in operation ( o 5 ). at the cpu 20 a ′ ( primary cache ), after data transferred from the secondary cache 30 ′ is written into the corresponding entry , the execution of the store command is completed by writing store data into the corresponding entry and the state information of the corresponding entry of the cache state information storing circuit 227 ′ is updated from “ i ” to “ m ” ( o 6 ). since data transferred from the secondary cache 30 ′ to the cpu 20 a ′ by the move - in operation is never referred to at the cpu 20 a ′, data transfer ( flush ) from the cpu 20 c ′ to the secondary cache 30 ′ and data transfer ( move - in ) from the secondary cache 30 ′ to the cpu 20 a ′ are uselessly performed . fig5 a and 5b represent another operation of the data processing apparatus represented in fig1 . the operations represented in fig5 a and 5b are performed when a cache miss hit occurs and executing a no - move - in store command for designating an address a as a store destination address at the cpu 20 a ( primary cache ) in the case where line data corresponding to the address a exists in the modified cache state in the cpu 20 c ( primary cache ). in addition , it is previously known that the line data corresponding to the address a is never referred to at the cpu 20 a . when the cache miss hit occurs , upon executing the no - move - in store command for designating the address a as a store destination address at the cpu 20 a , as represented in fig5 a , not a move - in request signal but a no - move - in store request signal is output from the cpu 20 a to the secondary cache 30 ( cache control apparatus 31 ) ( o 1 ). with this operation , as represented in fig5 b , not a flush request signal but an invalidate request signal is output from the secondary cache 30 ( cache control apparatus 31 ) to the cpu 20 c ( o 2 ). therefore , the flush operation is not performed ( o 3 ), and at the cpu 20 c , the state information of the corresponding entry of the cache state storing circuit 227 is updated from “ m ” to “ i ” ( o 4 ). further , a move - in operation is not performed ( o 5 ), and at the cpu 20 a , upon outputting the no - move - in store request signal , the cpu 20 a completes execution of the store command by writing ( i . e ., directly writing ) the store data into the corresponding primary cache 22 entry . thereafter , the state information of the corresponding entry of the cache state information storing circuit 227 is updated from “ i ” to “ m ” ( o 6 ). as described above , the data processing apparatus 10 represented in fig1 differs from the conventional data processing apparatus 10 ′ ( represented in fig4 a and 4b ), so that useless data transfer from the cpu 20 c to the secondary cache 30 associated with the flush operation and useless data transfer from the secondary cache 30 to the cpu 20 a associated with the move - in operation are avoided and data coherency among the cpus 20 a , 20 b and 20 c is assured . as described above , the data processing apparatus 10 according to the embodiment can reduce useless data transfer ( memory access ) between the primary cache 22 of the cpus 20 a , 20 b and 20 c and the secondary cache 30 with / while assuring cache coherency . this will substantially contribute to improvement of the processing performance and reduction of the power consumption in the data processing apparatus 10 . according to an aspect of the embodiments of the invention , any combinations of the described features , functions , operations , and / or benefits can be provided . the embodiments can be implemented as an apparatus ( machine ) that includes computing hardware ( i . e ., computing apparatus ), such as ( in a non - limiting example ) any computer that can store , retrieve , process and / or output data and / or communicate ( network ) with other computers . according to an aspect of an embodiment , the described features , functions , operations , and / or benefits can be implemented by and / or use computing hardware and / or software . the apparatus ( e . g ., the data processing apparatus 10 ) comprises a controller ( cpu ) ( e . g ., a hardware logic circuitry based computer processor that processes or executes instructions , namely software / program ), computer readable recording media ( e . g ., primary / secondary caches 30 , 22 , main storage apparatus , etc . ), transmission communication media interface ( network interface ), and / or a display device , all in communication through a data communication bus . the results produced can be displayed on a display of the computing apparatus . a program / software implementing the embodiments may be recorded on computer readable media comprising computer - readable recording media , such as in non - limiting examples , a semiconductor memory ( for example , ram , rom , etc .). while the present invention has been described in detail , it is to be understood that the foregoing embodiment is only an exemplary embodiment . the present invention is not limited to the above embodiment and various changes / modifications and equivalents can be made within the spirit and scope of the present invention . | 8 |
fig1 shows a wafer 1 which comprises a plurality of chips 2 . the chips 2 are shown diagrammatically only and without any further details in fig1 . each chip 2 has a given chip surface area , which chip surface area lies within chip boundaries 3 . in the example shown , the chip surface area of each chip 2 is square in shape , such that the chip boundaries 3 are of the same length . rectangular chip surface areas are also possible and known . the chip surface areas and the chip boundaries 3 of each chip 2 have been defined in known manner by exposure fields which are generated in the manufacture of the chips by means of irradiation masks . narrow , elongate separating zones 4 are provided between the chips 2 . the separating zones 4 are designed for breaking up the wafer 1 so as to obtain the individual chips 2 . the breaking - up of the wafer 1 takes place along sawing lanes 5 in the present case , only two sawing lanes 5 being indicated in fig1 with dash - dot lines . the wafer 1 can be broken along the sawing lanes 5 , special saw blades being used for the separation . instead of saw blades , a laser cutting device or some other cutting device may be alternatively used . the separation may also be achieved by means of an etching process . each chip on the wafer 1 has a plurality of connection lines 6 , which connection lines 6 are not shown in fig1 for reasons of clarity . such a connection line 6 is shown in fig2 , which will be described below . fig2 shows a portion of a chip 2 , whose two chip boundaries 3 visible in fig2 are indicated with dash - dot lines . the two separating zones 4 extend alongside the two chip boundaries 3 visible in fig2 . in the one separating zone 4 extending from top to bottom in fig2 , the sawing lane 5 belonging to this separating zone 4 is indicated with a dash - dot line . the chip 2 has a first circuit portion 7 and a second circuit portion 8 and a third circuit portion 9 and a fourth circuit portion 10 and a first conductor track 11 and a second conductor track 12 , which circuit portions and conductor tracks of the chip 2 are visible in fig2 . obviously , the chip 2 comprises a plurality of further circuit portions and conductor tracks . as was noted above , the chip 2 comprises a plurality of connection lines 6 . such a connection line 6 is visible in fig2 . the connection line 6 projects from the chip 2 at a chip boundary 3 and enters a separating zone 4 adjoining the chip 2 . the connection line 6 is initially electrically conductive , i . e . before a separation of the wafer 2 along the sawing lane 5 in the separating zone 4 that extends from top to bottom in fig2 and adjoins the chip 2 . the connection line 6 can be interrupted during a separation of the wafer 1 along the sawing lane 5 in the separating zone 4 extending from top to bottom in fig2 and adjoining the chip 2 , i . e . in that the connection line 6 is cut through or severed . the connection line 6 comprises two mutually adjoining conductor portions , i . e . a first conductor portion 13 and a second conductor portion 14 . the two mutually adjoining conductor portions 13 , 14 project beyond the chip boundary 3 into the separating zone 4 that extends from top to bottom in fig2 and adjoins the chip 2 . in this separating zone 4 , the two conductor portions 13 , 14 are electrically conductively interconnected by a connecting portion 15 . the connection line 6 has a u - shape in the present case . the first conductor portion 13 of the connection line 6 is connected to the third circuit portion 9 , and the second conductor portion 14 is connected to the first circuit portion 7 . the first circuit portion 7 and the third circuit portion 9 here form part of a test device of the chip 2 . the test device serves to test an error - free operation of at least a portion of the chip 2 , which operation is tested before the chip 2 is separated off . after a test has been carried out on the error - free operation , the test device should be put out of action reliably , which takes place during the separating - off of the chip 2 in that the connection line 6 is interrupted . such a connection line 6 is also denoted a sawing loop in the art . such connection lines 6 are also provided for other circuit portions and functions of the chip 2 , for example , a programming device may be provided instead of a test device . such connection lines 6 may alternatively be provided in combination with pads of an ic , which pads have to be made inoperative after the ic has been completed so as to avoid undesirable short - circuits . the chip 2 is covered by a planar protecting layer 16 , often denoted passivating layer in the art . the planar protecting layer 16 is made of nitride in the present case , which has also long been known . the chip 2 comprises two mutually adjoining protecting strips for the connection line 6 , i . e . a first protecting strip 17 and a second protecting strip 18 . the two mutually adjoining protecting strips 17 and 18 are made of nitride in the present case , as is the planar protecting layer 16 , which has also long been known . the two mutually adjoining protecting strips 17 and 18 project from the planar protecting layer 16 at the chip boundary 3 of the chip 2 and enter the separating zone 4 that extends from top to bottom in fig2 and adjoins the chip 2 . the two mutually adjoining protecting strips 17 and 18 here cover the two mutually adjoining conductor portions 13 , 14 of the connection line 6 , and the two mutually adjoining protecting strips 17 and 18 are interconnected by a protecting portion 19 in the separating zone 4 extending from top to bottom in fig2 . the protecting portion 19 covers the connecting portion 15 of the connection line 6 . fig2 shows a chip 2 according to the prior art . in the chip 2 of fig2 , the two conductor portions 13 and 14 and the two protecting strips 17 , 18 are of constant width along their total longitudinal dimensions . it was found in this known construction that a separation of the wafer 1 in the separating zone 4 extending from top to bottom in fig2 , for which the saw blade ( not shown ) is moved along the sawing lane 5 in the direction of an arrow 20 , may comparatively easily lead to the formation of a fracture zone 21 , which extends from the separating zone 4 , i . e . from the region of the severed conductor portions 13 , 14 and the severed protecting strips 17 , 18 disadvantageously into the chip 2 itself , which leads to a destruction of circuit portions or conductor tracks in the chip 2 , as is visualized by the fracture zone 21 indicated in fig2 . to avoid such fracture zones 21 entering into the chip 2 , therefore , all that can be done according to the prior art is to dimension the separating zones 4 so wide that fracture zones 21 penetrate a chip 2 only very occasionally . this has the disadvantage that comparatively wide separating zones 4 must be provided in an arrangement according to the prior art , which leads to an undesirable waste of expensive wafer material . fig3 shows a construction of a chip 2 according to the invention , which chip 2 is the result of the separation from a wafer according to the invention , and in which chip 2 the problems described above have been eliminated or strongly reduced down to an acceptable level . in the chip 2 of fig3 , each protecting strip 17 , 18 has a strip portion 26 , 27 and 28 , 29 that is wider than the remaining portion of the respective protecting strip 17 , 18 at both sides 22 , 23 and 24 , 25 of the respective protecting strip 17 , 18 in its region adjoining the planar protecting layer 16 . each widened strip portion 26 , 27 and 28 , 29 has a triangular shape here , more exactly an equilateral triangular shape the widened strip portion 26 , 27 and 28 , 29 may alternatively be rectangular or square or in the shape of a circular sector . in the construction of the chip 2 of fig3 , a weak spot traversing the protecting strip 17 , 18 is realized in each of the two protecting strips 17 , 18 , i . e . a first weak spot 30 and a second weak spot 31 . the second weak spot 31 provided in the second protecting strip 18 is clearly visible in fig4 . the second weak spot 31 is realized in that a smaller layer thickness is realized in the manufacture of the second protecting strip 18 in the region of the second weak spot 31 . the same holds for the first weak spot 30 . it should be noted that the second conductor portion 14 is also visible in fig4 . an intermediate layer 32 is provided between the second protecting strip 18 and the second conductor portion 14 . part of the substrate 33 of the wafer is shown below the second conductor portion 14 in fig4 . in the chip 2 of fig3 , furthermore , an additional weak spot 34 is provided in the planar protecting layer 16 along the chip boundaries 3 of the chip 2 , two weak spot portions 34 a and 34 b of this additional weak spot 34 being visible in fig3 . this additional weak spot 34 extending along the chip boundaries 3 provides a substantial additional contribution to the protection function for the chip 2 , i . e . in keeping away fracture zones or chip cracks from the chip region proper . it was found in many series of experiments with the chip 2 of fig3 that the fracture zones that may be caused upon a severing of the wafer for separating the chips 2 , which is done in that a saw blade is moved in the direction of the arrow 20 along the sawing lane 5 , preferentially issue from the weak spots 30 , 31 provided in the protecting strips 17 , 18 and practically exclusively extend in a separating zone 4 , and accordingly enter a chip 2 very seldom only . the reject rate of chips owing to fracture zones 21 entering a chip upon separating of the wafer could be reduced by approximately 10 % by means of the measures according to the invention . it should be noted here that the construction of the chip 2 of fig3 is also possible in a modified form , i . e . in that beveled edges as are provided at the free end of the connection line 6 in the region of the two protecting strips 17 , 18 and the protecting portion 19 , which beveled edges are indicated with dash - dot lines in fig3 . it should be noted here that in a modification of the embodiment of the chip 2 as shown in fig3 a single protecting strip is provided instead of two protecting strips 17 , 18 , which single strip has two sides whose positions correspond to the two sides 22 and 25 of the two protecting strips 17 , 18 of the chip 2 of fig3 , thus covering the two mutually adjoining conductor portions 13 , 14 of the modification of the embodiment of chip 2 . in this modified embodiment of chip 2 according to fig3 , again , good results have been achieved as regards an avoidance of undesirable fracture zones and the resulting undesirable chip cracks . fig5 shows a chip 2 in which again a connection line 6 with two conductor portions 13 , 14 and a connecting portion 15 is provided , but here the two conductor portions 13 , 14 and the connecting portion 15 substantially have a wedge shape . the two protecting strips 17 , 18 are adapted correspondingly , and the protecting portion 19 is substantially given a wedge shape . in the chip 2 of fig5 , each protecting strip 17 , 18 has a strip portion 26 , 28 that is wider than the remaining portion of the protecting strip 17 , 18 only at one side 22 , 24 of the respective protecting strip 17 , 18 in its region adjoining the planar protecting layer 16 of the chip 2 . in this case , too , the two widened strip portions 26 , 28 are triangular in shape , but here the triangles have different side lengths . as is apparent from fig5 , the widened strip portions 26 , 28 are provided at those sides 22 , 24 of the protecting strips 17 , 18 that will be reached first by a saw blade when this saw blade is moved along the sawing lane 5 in the direction of arrow 20 . this is because the greatest risk of a fracture zone being created exists where the saw blade hits against the protecting strips 17 , 18 and against the conductor portions 13 , 14 . it should finally be noted that the separation of the wafer 1 in the separating zones 4 along the sawing lanes 5 severs the connection lines 6 and accordingly interrupts them . this has the result that in an individual , completed chip 2 only remnants of the two conductor portions 13 , 14 and of the two protecting strips 17 , 18 will be present . | 7 |
for simplicity and illustrative purposes , the principles of the present invention are described by referring mainly to exemplary embodiments thereof . however , one of ordinary skill in the art would readily recognize that the same principles are equally applicable to , and can be implemented in , all types of secure distributed environments and that any such variations do not depart from the true spirit and scope of the present invention . moreover , in the following detailed description , references are made to the accompanying figures , which illustrate specific embodiments . electrical , mechanical , logical and structural changes may be made to the embodiments without departing from the spirit and scope of the present invention . the following detailed description is , therefore , not to be taken in a limiting sense and the scope of the present invention is defined by the appended claims and their equivalents . embodiments pertain generally to a method of sharing a security token among applications within a session . more particularly , a user may insert a security token , such as a smart card , into a secure computing machine and begin logging into the secure machine . an application may detect the presence of the inserted smart card and prompt the user to begin the log - on process . the user may authenticate to the security daemon , which then authenticate to the security token with the user entered authentication information . the security daemon may be configured to capture the authentication state and represent the authenticated security token to other applications in the session . in other words , the security daemon would log into the token , keep the token logged in and then use the fact that it has the token opened and logged in to perform operations on behalf of the user . as a result , the security daemon appears to the rest of the processes in the session that the security token is inserted through a public key cryptography standard ( pkcs ) # 11 interface . applications that require authentication may query the security daemon for authentication using the same pkcs # 11 calls as they do in conventional smart card systems . moreover , the security daemon may “ own ” the representation of the security token being inserted , i . e ., the authentication state , by locking access to the card . as a result , other processes and / or applications cannot co - opt the authentication state in tokens that do not hold separate authentication states for different processes such as those defined in the piv standards . other embodiments relate to accessing remote computers . more specifically , the security daemon provides a mechanism for secure shell ( ssh ) access to remote computing machines . more particularly , a local machine may securely connect to the remote machine using ssh protocols . the ssh application may advertise a pkcs # 11 port that receives pkcs # 11 calls on the remote client . during the authentication process , the remote computer may pass queries for authentication through the advertised port over the secured connection between the local and remote machines . the queries are directed to the security daemon , which presents the authentication state to the remote machine . after authentication , a user has access to the resources on the remote computer as though the user was physically logged - on in at the remote computer . fig1 illustrates an exemplary secure system 100 in accordance with an embodiment . it should be readily apparent to those of ordinary skill in the art that the system 100 depicted in fig1 represents a generalized schematic illustration and that other components may be added or existing components may be removed or modified . moreover , the system 100 may be implemented using software components , hardware components , or combinations thereof . as shown in fig1 , the secure system 100 includes a server 105 , clients 110 and a local network 115 . the server 105 may be a computing machine or platform configured to execute secure and unsecure ( or open ) applications through a multiple user operating system ( not shown ) in conjunction with the clients 110 . the server 105 may be implemented with server platforms as known to those skilled in the art from intel , advanced micro devices , hewlett - packard , etc . the server 105 may interact with the clients over the local network 115 . the local network 115 may be a local area network implementing an established network protocol such as ethernet , token ring , fddi , etc . the local network 115 provides a communication channel for the server 105 and clients 110 to exchange data and commands . the clients 110 may be computing machine or platform ( machine ) configured to execute secure and open applications through the multi - user operating system . the clients 110 may be implemented with personal computers , workstations , thin clients , thick clients , or other similar computing platform . each client 110 may be configured to interface with a security device 120 . the security device 120 may be configured to act as a gatekeeper to the client 110 . more particularly , a user may use a security token , such as a smart card , to access the respective client 110 . each client 110 may have a security daemon 125 executing to monitor the security device 120 , which is illustrated in fig2 . as shown in fig2 , a client 110 may be executing a multi - user operating system ( os ) 205 . the os may be linux , hpux , or other similar operating systems . the security daemon 125 executes within the os 205 . the os 205 may also interface with the secured applications 210 as well as unsecured applications ( not shown ). secure application 210 may any type of software that requires authentication from the smart card to initialize and execute . the os 205 may also interface with an application program interface ( labeled as api in fig2 ) 215 . the api 215 provides an interface between devices and the os 205 transmitting and receiving data and commands therebetween . fig2 shows the security device 120 and a network interface 220 interfaced with the api 215 . the network interface 220 may also be configured to interface with local network 115 . a client may use the network interface 220 to initiate secure shell ( ssh ) protocols to form a secure connection with remote computers from the client 110 . ssh applications are well - known to those skilled in the art . returning to fig1 , the security daemon 125 may be configured to detect the presence of the inserted security token and prompt the user to begin the log - on process . the user may authenticate to the security daemon 125 , which then authenticates to the security token with the user entered authentication information . the security daemon 125 may be configured to capture the authentication state and represent the authenticated security token to other applications in the session . the security daemon 125 may also be configured to interface with other processes and / or applications in the session with a pkcs # 11 interface . pkcs # 11 is a cryptographic token interface standard known to those skilled in the art . the secure system 100 may also comprise a second network 130 that may be interfaced with local network 115 . a remote client 110 ′ may be connected with the second network 130 . the remote client 110 ′ may be similar to client 110 with a security device 120 ′. the security device 120 ′ may also function as a gatekeeper to the remote client 110 ′. accordingly , a user may remote login to the remote client 110 ′ from one of the client 110 using secure shell ( ssh ) protocols . ssh protocols are well - known to those skilled in the art . during the remote log - in , the client 110 may create a secure connection using ssh protocols to connect with the remote client 110 ′. the ssh application may be configured to publish the pkcs # 11 port of the client computer 110 to the remote client 110 ′. the remote client 110 ′ may forward authentication queries through the pkcs # 11 port over the secure connection to the client 110 . the security daemon 125 on the client 110 presents its authentication state to answer the authentication queries of the remote client 110 ′. since the user of client 110 is a valid user , the remote client 110 ′ may grant access to the client 110 as though the user was logged on at the remote client 110 ′. this process may also be used to remote access client 110 from another client 110 . fig3 illustrate a flow diagram 300 executed by the security daemon 125 in accordance with another embodiment . it should be readily apparent to those of ordinary skill in the art that the flow diagram 300 depicted in fig3 represents a generalized illustration and that other steps may be added or existing steps may be removed or modified . as shown in fig3 , the security daemon 125 may be configured to be in an idle state , in step 305 . more particularly , the security daemon 125 may have been instantiation as part of the normal boot sequence . in some embodiments , the security daemon 125 may be instantiated by a system administrator or in response to an event such as the insertion of a security token in the security device 120 . in step 310 , the security daemon 125 may be configured to detect the presence of the security token ( i . e ., a smart card , piv smart card , etc .) in the security device 120 . the security daemon 125 may then be configured to prompt the user to begin log - on , in step 310 . more particularly , the security daemon 125 may prompt the user for authentication information such as personal identification number ( pin ), a password or biometric parameter ( retinal scan , fingerprint , etc ) or enter the same into some trusted patch device . the security daemon 125 may display a dialog box to requesting the user for the authentication information . in step 320 , the security daemon 125 may be configured to pass the user authentication information to the security token for verification or to request that the token read the authentication information from it &# 39 ; s trusted path . if the security token fails to verify , the authentication information , in step 325 , the security daemon 125 may be configured to inform the user of the verification failure . in some embodiments , the security daemon 125 may prompt the user to re - enter the authentication information in step 315 . alternatively , the security daemon 125 may inform the user that verification failed and return to the idle state of step 305 . alternatively , the security token may detect too many failed attempts to authenticate and the security daemon 125 may be configured to inform the user that the security token is locked . otherwise , if the authentication information is verified , in step 325 , the security daemon 125 may be configured to capture and hold the authentication state of the inserted security token , in step 335 . more specifically , this may be done by holding a pkcs # 11 session open and attaching the security token with which the security daemon 125 could perform additional requests against the security token . the security daemon 125 may then represent itself as the authenticated security token to other applications through a pkcs # 11 interface . in other words , the security daemon 125 appears to the rest of the processes in the session that the security token is inserted . in step 340 , the security daemon 125 may be configured to bind the authentication state with the current session state of the user . more particularly , in the situation where an application requests requests an initial authentication of the smart card . the application may initially authenticate to the security daemon 125 with some user session mechanism ( usually something initialized at login ) that does not involve user action ( i . e ., application authentication ). the security daemon 125 would present that authentication information on behalf of the user for that application . typical implementations of application authentication would include passing magic cookies , environment variables , file descriptors , shared memory segments , etc . to child processes of the parent session , using os access controls , etc . if an application is part of the session , the security daemon 125 may be configured to implement the steps of fig3 or could choose to only allow a single user session to be logged in . fig4 depicts a flow diagram 400 executed by secure applications 210 in accordance with yet another embodiment . it should be readily obvious to one of ordinary skill in the art that existing steps may be modified and / or deleted and other steps added in fig4 . as shown in fig4 , a user may initiate a secure application 210 , in step 405 . more specifically , once the user has logged into a session , the user may click on an icon that represents the secure application 210 . alternatively , a command line prompt or menu selection may be used to invoke the secure application 210 . in step 410 , as part of the instantiation of the secure application 210 , the secure application 210 may be configured to query the security device 120 to determine whether the user has privileges to execute the secure application 210 . typically , secure applications 210 execute a call to the pkcs # 11 interface . for these embodiments , the pkcs # 11 interface may be connected to the security daemon 125 . in step 415 , the secured application 210 call to the pkcs # 11 interface may be answered by the security daemon 125 , which holds the authentication state of the security token . the pkcs # 11 interface returns a message that the security token is inserted and begins verification between the secure application 210 and the security daemon 125 . if verification fails , in step 420 , the secure application 210 may display a dialog message informing that access to the secure application is denied , in step 425 . otherwise , if verification is successful , in step 420 , the secure application 215 continues to instantiate and the user is granted access , in step 430 . fig5 depicts a flow diagram 500 implemented by a client 10 accessing a remote client in accordance with yet another embodiment . it should be readily obvious to one of ordinary skill in the art that existing steps may be modified and / or deleted and other steps added in fig5 . as shown in fig5 , a user may initiate a secure shell ( ssh ) application on a client 110 to access a remote client , in step 505 . more specifically , once the user has logged into a session , the user may click on an icon that represents the ssh application . alternatively , a command line prompt or menu selection may be used to invoke the ssh application . in step 510 , the ssh application may be configured to form a secure connection from the client 110 to the remote client . once connected to the remote computer , the two clients may begin authentication . in step 515 , the client 110 may receive authentication queries from the remote client over the secure connection . more specifically , the remote client may execute a call to the pkcs # 11 interface which is forwarded to the pkcs # 11 interface of the security daemon 125 on the client 110 . in step 520 , the forwarded call to the pkcs # 11 interface may be answered by the security daemon 125 , which holds the authentication state of the security token . the pkcs # 11 interface returns a message that the security token is inserted to the remote client and begins verification between the remote client and the security daemon 125 . if verification fails , in step 525 , the remote client may display a dialog message informing that access is denied , in step 530 . otherwise , if verification is successful , in step 525 , the remote client may grant access to the client computer , in step 535 . fig6 illustrates an exemplary block diagram of a computing platform 600 where an embodiment may be practiced . the functions of the security daemon may be implemented in program code and executed by the computing platform 600 . the security daemon may be implemented in computer languages such as pascal , c , c ++, java , etc . as shown in fig6 , the computer system 600 includes one or more processors , such as processor 602 that provide an execution platform for embodiments of the security daemon . commands and data from the processor 602 are communicated over a communication bus 604 . the computer system 600 also includes a main memory 606 , such as a random access memory ( ram ), where the security daemon may be executed during runtime , and a secondary memory 608 . the secondary memory 608 includes , for example , a hard disk drive 610 and / or a removable storage drive 612 , representing a floppy diskette drive , a magnetic tape drive , a compact disk drive , etc ., where a copy of a computer program embodiment for the security daemon may be stored . the removable storage drive 612 reads from and / or writes to a removable storage unit 614 in a well - known manner . a user interfaces with the security daemon with a keyboard 616 , a mouse 618 , and a display 620 . the display adapter 622 interfaces with the communication bus 604 and the display 620 and receives display data from the processor 602 and converts the display data into display commands for the display 620 . certain embodiments may be performed as a computer program . the computer program may exist in a variety of forms both active and inactive . for example , the computer program can exist as software program ( s ) comprised of program instructions in source code , object code , executable code or other formats ; firmware program ( s ); or hardware description language ( hdl ) files . any of the above can be embodied on a computer readable medium , which include storage devices and signals , in compressed or uncompressed form . exemplary computer readable storage devices include conventional computer system ram ( random access memory ), rom ( read - only memory ), eprom ( erasable , programmable rom ), eeprom ( electrically erasable , programmable rom ), and magnetic or optical disks or tapes . exemplary computer readable signals , whether modulated using a carrier or not , are signals that a computer system hosting or running the present invention can be configured to access , including signals downloaded through the internet or other networks . concrete examples of the foregoing include distribution of executable software program ( s ) of the computer program on a cd - rom or via internet download . in a sense , the internet itself , as an abstract entity , is a computer readable medium . the same is true of computer networks in general . while the invention has been described with reference to the exemplary embodiments thereof , those skilled in the art will be able to make various modifications to the described embodiments without departing from the true spirit and scope . the terms and descriptions used herein are set forth by way of illustration only and are not meant as limitations . in particular , although the method has been described by examples , the steps of the method may be performed in a different order than illustrated or simultaneously . those skilled in the art will recognize that these and other variations are possible within the spirit and scope as defined in the following claims and their equivalents . | 7 |
generally , the present invention provides an improved bursting assembly and method for reliably separating inserts provided in a continuous web at a relatively high rate . the present invention relates to improvements to the inventions described in u . s . pat . no . 5 , 079 , 901 and u . s . patent application ser . no . 370 , 779 , filed dec . 23 , 1994 , which is a continuation of application ser . no . 010 , 759 , filed jan . 29 , 1993 . the subject matter of each of these applications and patent is incorporated herein by reference . a device according to the present invention receives a continuous web of inserts and , upon receipt of a first control signal , operates to move the forwardmost insert in a controlled fashion in a feeding operation . in a bursting operation , the apparatus controls the operation of the burst and feed rollers first to buckle or arc a selected portion of the web supply disposed between the burst rollers and the feed rollers , and then to snap the forwardmost insert away from the continuous web upon receipt of a second control signal . the device of this invention is intended to be integrated into a full service processing system , typically supplying successive inserts into the containers at a processing stage where the containers have been formed , may or may not yet be filled , and have not yet been closed . by way of example , the device of this invention may be adapted to supply inserts to bags of snack food containers , cereal boxes , bread sacks , or any other container using the teachings described herein . in addition , the invention may be used to supply seasoning pouches , condiments and other samples to the containers . fig1 illustrates an inserting assembly 10 according to this invention . the inserting assembly 10 comprises a housing 12 with various housing components including opposed idler frame pieces 12a , 14a ( see fig1 and 2 ). the idler frame pieces 12a , 14a are each subtended by a side frame piece 12b , 14b in abutting relation with the respective idler frame pieces . a pair of opposed side cover pieces 12d , 14d are spaced outwardly from the respective idler frame and side frame pieces , each of which are respectively separated therefrom by opposed side cover frame pieces 12c , 14c . a motor housing 16 is spaced inwardly from the side frame pieces 12b , 14b . the side cover pieces 12d , 14d are readily removable in order to gain ready access to the internal components of the inserting assembly 10 . the housing 12 may be mounted on a pedestal ( not shown ) or other suitable means adapted for pivotal and / or rotational movement to locate the inserting assembly 10 in a desired orientation , such as , toward a processing line spaced proximate to a stream of moving containers . the containers are typically provided along a conveyor system or other handling system as would be understood by those skilled in the art . a continuous web supply of inserts is typically provided to the inserting assembly 10 in a fan - folded or a traverse fan - folded format as will be understood by those skilled in the art . the web supply may also be packaged in a continuous circular reel , rotatably mounted via a support ( not shown ) proximate the assembly 10 . it is contemplated that the invention may be utilized in conjunction with any number of insert types . as an example , the web supply may be a continuous supply of paperboard or cardboard coupons physically connected to each other but connected to each other by perforations or otherwise connected to each other by weakened web portions which extend transversely of the web . in addition , the web supply may be a packaged premium or other insert comprising small prizes , condiments or the like that are contained in plastic wrappers or pouches and are successively connected together by separable portions . the assembly 10 preferably includes an infeed guide 18 which channels the web for downstream processing . the infeed guide 18 includes a pair of opposed channeling brackets 18a , 18b which are placed at opposite sides of the insert path . the brackets 18a , 18b are mounted to a supply platform 20 having an inclined section 20i , a relatively planar feeding section 20f , and a relatively planar bursting section 20b disposed between a feed roller subassembly 21 and a burst roller subassembly 42 . this arrangement maintains the proper web flow as the web is processed by the inserting assembly 10 . the assembly 10 may alternatively include opposed tensioning rolls rotatably mounted to the housing 12 . in this regard , an upper tensioning roll may be provided as an idler roll and an opposed lower tensioning roll may be connected to an adjustable resistance device of the type known to those skilled in the art thus providing tension between tensioning rolls to ensure uniformity in the web and to minimize bending or folding of the web during further processing operations . fig1 and 2 illustrate a feed roller subassembly 21 including an upper feed roller 24 and a lower feed roller 26 . as best seen in fig1 the upper feed roller 24 is mounted to a rotary shaft 28 . the shaft 28 is placed within a suitable bearing 30 disposed on a first idler pivot arm 32 and is freely rotatable relative thereto . the lower feed roller 26 is mounted to a drive shaft 34 , and substantially traverses , and in most applications extends beyond , the width of coupons to be processed . at one end , the lower feed roller drive shaft 34 is mounted within a suitable bearing disposed in the side frame piece 12b and is freely rotatable relative to the side frame 12b . a pulley 36 is attached to the opposed end of shaft 34 and is coupled via a belt 38 to a servo drive motor 40 ( see fig2 ). the feed roller subassembly 21 operates in a controlled fashion to receive the insert supply in a nip formed between the upper and lower feed rollers 24 , 26 . thus , the feed rollers 24 , 26 define a bight which receives the leading edge of the forwardmost insert in the continuous web . fig1 and 2 also show a burst roller subassembly 42 including an upper burst roller 44 and a lower burst roller 46 . as with the upper feed roller 24 , the upper burst roller 44 is mounted to a rotary shaft 48 . the shaft 48 is disposed within a suitable bearing 50 disposed on a second idler pivot arm 52 . the lower feed roller 46 is mounted to a rotary drive shaft 54 . at one end , the lower feed roller drive shaft 54 is mounted within a suitable bearing disposed in the side frame piece 12b and is freely rotatable relative to the side frame 12b . a pulley 56 is attached to the opposed end of shaft 54 and is coupled via a belt 58 to a servo drive motor 60 ( see fig2 ). the burst rollers 44 , 46 define a bight which receives the leading edge of the forwardmost insert in the continuous web . both the feed rollers 24 , 26 and burst rollers 44 , 46 may be fabricated from of a polyurethane material for increased durability . alternatively , the rollers may be fabricated from rubber to provide increased frictional properties due to moisture build - up on the rollers . the use of rubber rollers , therefore , is advantageous in applications where the inserts being handled frequently become wet or cause slight amounts of leakage . the vertical spacing between the upper and lower feed rollers 24 , 26 is adjusted via a construction including the first idler pivot arm 32 , an adjustment screw 62 threaded within the idler frame piece 12a , and a compression spring 64 disposed between the first idler pivot arm 32 and the adjustment screw 62 . likewise , the vertical spacing between the upper and lower burst rollers 44 , 46 is adjusted with the second idler pivot arm 52 , an adjustment screw 66 , also threaded within the idler frame piece 12a , and a compression spring 68 that is similarly disposed between the second idler pivot arm 52 and adjustment screw 66 . the idler pivot arms 32 , 52 are rotatably mounted to the idler frame piece 12a with pivots 70 , 72 so that the upper feed roller and upper burst roller may be moved relative to the lower feed roller and lower burst roller , respectively . thus , adjustment of screws 62 , 66 provides an adjustment of the amount of downward force applied to the pivot arms 32 , 52 . in this way , the adjustment screws 62 , 66 are utilized to set the amount of nip force in both the feed rollers and the burst rollers . it should be understood that this same arrangement is also disposed on the opposite ends of the upper feed roller and upper burst roller as well . in practice , the idler pivot arms 32 , 52 can be adjusted within a range on the order of one - quarter of an inch in order to set the proper gripping tension while permitting the rollers to process inserts having varying cross sectional thicknesses . in an alternative embodiment , the upper feed roller may be replaced by a pair of feed rollers axially spaced from each other . likewise , the upper burst roller may also be replaced with a pair of axially spaced rollers . inasmuch as the axial spacing of the upper feed rolls and the upper burst rolls is readily adjustable , an insert having a raised center portion and lateral sides which may be substantially flattened , such as prizes and the like contained in a wrapper , may be handled by engagement of the side portions of the insert in the nip formed between the spaced upper feed rollers and the lower feed roller on lateral sides of the insert and also between the spaced upper burst rollers and the lower burst roller . in this manner , small prizes or other three - dimensional premiums may be handled . fig2 and 3 also show a photoelectric sensor or photosensor 74 positioned relative to an insert dispensing location disposed within the bursting platform section 20b between the feed roller subassembly 21 and the burst roller subassembly 42 . as described in greater detail below , the leading edge of an insert intercepts the light beam emitted by the photoelectric sensor 74 ( denoted by arrow 76 ). in response , the photoelectric sensor 74 provides a sensing signal indicative of the detection of an insert registered between the feed roller subassembly 21 and the burst roller subassembly 42 . in other instances , the photosensor 74 detects whether the web supply is disposed between the feed rollers and the burst rollers and provides signals indicative of the presence or the absence of the web supply . the inserting assembly 10 uses two servo motors , a feed drive servo motor 40 and a burst drive servo motor 60 , each of which is disposed within the motor housing 16 . as noted above , servo motor 40 is coupled with the lower feed roller 26 while servo motor 60 is coupled with the lower burst roller 46 . in the preferred embodiment , the servo motors are type mpm891 frme - p of reduced size , manufactured by custom servo motors . inc . the two motors 40 , 60 are independently controlled to eliminate the need for any clutches or other mechanical coupling or decoupling means . further , the use of independently operated servo motors 40 , 60 eliminates the need for additional pulleys and belts . the coupon inserting assembly 10 is stopped , in emergency situations , via an emergency stop button 78 located on the housing . the servo motors 40 , 60 operate in response to control signals provided by an electronic controller ( see fig4 ) to rotate the feed rollers and the burst rollers in a controlled fashion so that the appropriate sequences of operation may be performed on the web supply , as shown schematically in fig3 a through fig3 f . fig3 a illustrates the lower feed roller 26 being rotated ( under control of the feed drive servo motor 40 ) in the direction of arrow 80 . inasmuch as the upper feed roller 24 is an idler roller , it is rotated in the opposite direction ( denoted by arrow 82 ) so that when the web supply is drawn into the bight between feed rollers , it is moved downstream in the direction denoted by arrow 84 . as the feed rollers 24 , 26 continue to rotate , the web is advanced toward the burst rollers 44 , 46 and the web detecting photosensor 74 as shown in fig3 b . the photoelectric sensor 74 thereafter senses the leading edge of the forwardmost insert as it passes a selected location disposed between the feed rollers 24 , 26 and the burst rollers 44 , 46 as shown in fig3 c . the sensor 74 supplies a sensing signal to the electronic controller 90 indicative of the detection of the leading edge of the forwardmost insert at the sensing location . as discussed in more detail below , the electronic controller 90 then provides appropriate control signals to activate the servo burst drive motor 60 , thereby rotating the burst rollers 44 , 46 in the directions denoted by arrows 86 , 88 respectively as seen in fig3 c . in this loading operation , the feed rollers 24 , 26 and the burst rollers 44 , 46 are preferably rotated at the same speeds . the continuous web is advanced until the forwardmost insert is received in a nip formed between the burst rollers 44 , 46 and thereafter moved to the position shown in fig3 d . this position is a typical bursting position inasmuch as the continuous web is retained in tension between the feed rollers 24 , 26 and the burst rollers 44 , 46 . both the feed rollers 24 , 26 and the burst rollers 38 , 44 are deactuated when the web supply is moved to a position where the perforation separating the forwardmost insert from the next succeeding insert is disposed between the feed rollers 24 , 26 and the burst rollers 44 , 46 , preferably at an upstream location with respect to the insert sensor 74 . as described in greater detail below , the inserting apparatus 10 awaits a signal related to the time in which the forwardmost insert will be separated from the web so that it may be dispensed into a moving container as the container passes a dispensing location . in many applications , the burst rollers 44 , 46 may be accelerated when the web is moved to the position shown in fig3 d to provide a sufficient tension force to the web such that the forwardmost insert is separated at the weakened web portion or perforation . for example , many inserts fabricated from elastomeric pouches or as three - dimensional premiums may be readily separated at a fairly low failure rate . however , for other applications , such as the case where the inserts are fabricated from paper or cardboard , it is necessary to apply an increased tension force to the web supply in order to effect a reliable bursting operation . accordingly , a higher failure rate results . the present invention overcomes this potentially problematic situation by operating in a mode that applies a greater impulse of energy to effect a bursting operation . as shown in fig3 e , the web supply is advanced from the normal bursting position ( shown in fig3 d ) by actuating the feed rollers so that they are rotated in the directions shown by arrows 80 , 82 at a greater relative speed than the burst rollers 44 , 46 . in the exemplary embodiment shown in fig3 e , the burst rollers 44 , 46 are deactuated while the feed rollers 24 , 26 are actuated . the web then begins to buckle or arc with the perforation separating the forwardmost insert from the next succeeding insert preferably disposed proximate to the apex of the arc . the perforation , however , is disposed upstream from the photosensor 74 , as shown in fig3 e , so that the leading edge of the next coupon to be processed can be detected as it is moved past the photosensor 74 . those skilled in the art will appreciate that the web may alternatively be buckled or arced by either ( 1 ) increasing the speed of the feed rollers 24 , 26 while maintaining , decreasing , or even reversing rotational speed of the burst rollers 44 , 46 ; or ( 2 ) maintaining the speed of the feed rollers 24 and 26 constant while decreasing , halting or reversing the rotation of the burst rollers 44 , 46 . after the web moved to the position shown in fig3 e , the feed rollers 24 , 26 are deactuated . at the appropriate time , the burst rollers 44 , 46 are rapidly accelerated as shown in fig3 f . such rapid acceleration generates a snapping or whipping action of the web thereby separating the forwardmost insert from the continuous web along the perforation . this action greatly reduces the amount of torque required by the burst servo motor to effect a burst . for example , the present invention provides on the order of an 80 percent reduction in torque for processing a string of paperboard coupons as compared to conventional bursting techniques . moreover the present invention permits reliable bursting of other coupon types having high relatively tensile strength in the weakened web portions of the web . alternative ways to snap the web include ( 1 ) increasing the speed of the burst rollers 44 , 46 while maintaining , decreasing , or reversing the rotational speed of the feed rollers 24 , 26 ; or ( 2 ) maintaining the speed of the burst rollers 44 , 46 constant while decreasing , halting or reversing the rotation of the feed rollers 24 , 26 . there are several variables which effect the operation of the inserting assembly 10 . one variable is the relative position of the perforation with respect to the feed rollers 24 , 26 and burst rollers 44 , 46 . the perforation in the web should remain upstream from the photosensor 24 during the bursting operation . when the web buckles , the position of the perforation may be equidistant from the burst rollers 44 , 46 and the feed rollers 24 , 26 , positioned closer to the feed rollers 24 , 26 , or positioned closer to the burst rollers 44 , 46 . second , the amount of buckling of the web determines the amount of tension force which is imparted to break the perforation . generally , a greater force will be imparted to the web as the arc of the web is increased . fig4 illustrates one specific control system that may be utilized in practicing this invention . the electrical circuitry described hereinafter is typically located in a housing module remote from the inserter assembly and protected by suitable isolation circuitry , as will be understood by those skilled in the art . as shown in fig4 an electronic controller 90 receives an insert dispense timing signal from a container processing line sensor or other suitable timing circuitry on a line 92 , an insert detect signal indicative of the detection of the leading edge of an insert or of the presence or the absence of the web supply at the sensing location by the photoelectric sensor 74 on a line 94 , and an insert verification signal on a line 96 . in addition , the electronic controller 90 receives various input command signals from a hand - held terminal or pendant 98 via a line 100 . these input command signals may include signals relating to an insert length preset , a total count request or other desired parameters . in the preferred embodiment , the electronic controller 90 is a microprocessor - based controller . the electronic controller 90 operates in a logical fashion to provide output signals to a servo feed drive control module 102 on a line 104 and to a servo burst drive control module 106 on a line 108 . the servo feed drive control module 102 and the burst drive control module 106 are preferably a type mpa - 03 / 06 sl , manufactured by custom servo motors , inc . the drive control modules 102 , 106 operate in a known manner to provide output drive pulses to the servo feed drive motor 40 and the servo burst drive motor 60 on the lines 110 , 112 respectively . the dispense timing signal supplied on line 92 is processed to determine the appropriate time to initiate a burst operation . optionally , coupon length preset input information , dispense delay information and other information may additionally be used to determine the appropriate time to initiate the burst operation . the dispense timing signal on line 92 may be supplied from any number of external sources including existing product line control , a photoelectric sensor arrangement for detecting passing containers , proximity detection , an encoder scheme or any other suitable source . likewise , this signal may be used by the controller 90 to determine the rate at which to feed inserts during a feed operation . as noted above , the insert detect signal on line 94 is generated by the photoelectric sensor 74 to register the position of the leading edge of the web , and also to verify the presence or the absence of the web supply . the insert verification signal on line 96 may optionally be employed to verify that the forwardmost insert has been successfully delivered to its target . this signal may be based on photocell detection of an exiting insert or even on a sonic sensor which detects arrival of an insert within a container . the controller may also be implemented to maintain a count corresponding to the number of inserts contained in the web . this count is decremented upon execution of a burst sequence . in addition , the controller 90 may supply an output signal to a counter 114 on a line 116 to indicate the total number of delivered inserts . fig5 is a logical flow chart for system operation of the inserting assembly 10 according to the present invention . as shown , the system begins at a start block 118 . the system then advances to a next block 120 at which initial conditions are set . specifically , the system initializes parameters for motion and timing calculation for delivery of an insert of a specific length at a desired rate and for a particular amount of buckling of the web before bursting , and monitoring of system inputs and outputs . at a next block 122 , the operator arms the machine with the first insert during the initial system start - up . the forwardmost insert is moved upstream of the feed rollers 24 , 26 so that its trailing edge is disposed between the feed rollers 24 , 26 and the burst rollers 44 , 46 , at a location between the feed rollers and photoelectric sensor 74 . the system then advances to a decision block 124 which determines whether a dispense signal is received which corresponds to the time in which the forwardmost insert is to be separated from the continuous web and inserted at a selected location , such as , into a moving container . if at decision block 124 the system receives the dispense signal , the system advances to a next decision block 126 . the system then determines whether a delay time has been input . if yes , the system advances to a block 128 and waits the requested time interval in order to initiate a bursting operation . the system then advances to a next decision block 130 . similarly , at decision block 126 , if the system determines that no delay interval has been requested , the system advances to the decision block 130 . at decision block 130 , the system determines whether the insert sensor ( denoted as reference numeral 74 in fig2 - 3a - 3f ) is blocked . this indicates that the insert stream is disposed between the feed rollers 24 , 26 and the burst rollers 44 , 46 . if no , the system advances to a block 132 and makes appropriate corrective action . for example , the system may provide warning signals or a message to the pendant 98 indicating to the operator that intervention is required . on the other hand , if at decision block 130 the system determines that the web is present at the sensing location between the feed rollers and the burst rollers , the system advances to a next block 134 . the sequence of steps performed in this block corresponds to a burst operation . in particular , the electronic controller 90 provides control signals to the servo burst drive output circuit 106 ( see fig4 ). this circuit , in turn , drive the servo burst motor 60 at a sufficient rotational speed to accelerate the burst rollers 44 , 46 and separate the forwardmost insert from the web . the insert is then advanced by the burst rollers to a selected location such as into a passing container . the system then advances to a next decision block 136 and determines whether the photosensor is clear or unblocked which indicates that the forwardmost insert was successfully separated from the web . if the leading edge photosensor 74 is not clear , the system advances to a block 138 and handles the bursting error . on the other hand , if the system determines that the photosensor 74 is clear at decision block 136 , the system advances to a next block 140 . at block 140 , the system provides appropriate control signals to advance the web supply . the system then advances to a decision block 142 and determines whether the web supply has advanced to a position where the leading edge of the next insert has blocked the photosensor . if no , the system advances to a decision block 144 and determines whether the feeding operation has completed . if , at decision block 144 , the system determines that the feeding operation has completed , the system advances to a block 146 and handles the missing web error . on the other hand , if the system determines that the feeding operation has not yet completed , the system returns to decision block 142 . this operation is also shown diagrammetrically in fig3 b . once the system determines that the leading of the next insert is positioned at the coupon sensor at decision block 142 , the system advances to a next block 148 . at this block , the system provides appropriate control signals to advance both the feed rollers 24 , 26 and the burst rollers 44 , 46 . this sequence generally corresponds to the sequence shown in fig3 c - 3d . the system then advances to a decision block 150 and determines whether the snap and burst operation sequence is enabled . typically , the snap and burst is enabled in one of two ways . first , the snap and burst can be enabled via a manual input to the electronic controller 90 . second , the snap and burst can be enabled automatically with the use of appropriate sensing circuitry employed to monitor the amount of current drawn by the servo burst motor 60 . this sensing circuit provides signals to the electronic controller 90 indicative of the servo motor load . depending on the amount of current drawn by the servo motor 60 , the electronic controller 90 can estimate the amount of torque applied to the burst rollers 44 , 46 . if the amount of torque exceeds a certain amount , the electronic controller 90 automatically enables the snap and burst routine in order to lessen the amount of torque required of the servo burst motor 60 , while increasing the impulse of force applied to separate the forwardmost insert . if , at decision block 150 , the system determines that the snap and burst sequence is enabled , the system advances to a next block 152 . the electronic controller 90 provides control signals to advance the feed rollers 24 , 26 to buckle the web when the web is disposed between the feed rollers and the burst rollers . this operation is also shown diagrammetrically in fig3 e . the system then returns to decision block 124 and continues . if , at decision block 150 , the system determines that the snap and burst routine is not enabled , the system returns to decision block 124 and continues . in this mode , the bursting operation is performed without buckling . as noted above , the upper feed roller and upper burst roller arrangements are mounted to the idler frame pieces 12a , 14a , while the lower feed rollers and burst rollers are mounted to the side frame pieces 12b , 14b . thus , the particular feed roller and burst roller configurations may be readily modified depending on the particular application simply by removing the idler frame and side frame pieces . as set forth above , an improved snap and burst system and method of using the same has been described . various modification as would be apparent to one of ordinary skill in the art and familiar with the teaching of this application are deemed to be within the scope of this invention . | 1 |
the existing several method for forming an sot wafer may destroy crystal lattices of a monocrystalline silicon wafer to thereby degrade the insulating performance of the soi wafer or suffer from complex processes , a high manufacturing cost and degrading of the quality of the resulting soi wafer . according to embodiments of the invention , trenches and cavities are formed in a monocrystalline silicon wafer , and then insulating layers and an insulating material layer are formed in the trenches and the cavities as an insulating layer of an sio wafer , where the insulating material layer in the cavities separates the monocrystalline silicon wafer into a silicon substrate and a top layer silicon . in this process , insulating silicon oxide is formed through deposition or spin coating to thereby address the problem in the method of separation by implanted oxygen that crystal lattices of the monocrystalline silicon wafer may be destroyed due to the oxygen gas implantation and annealing processes to degrade the insulating performance of the insulating layer , also obviate the problem in the method of “ bonding soi ” that gaps may occur at the bonding interface due to contamination on the bonding surface ( s ) or unevenness of the bonding surface ( s ) with poor flatness , and further achieve easiness of the procedure , a low manufacturing cost and the resulting sot wafer of high quality as compared with the method of “ smart cut ”. fig1 illustrates a flow chart of an embodiment of forming an soi wafer according to the invention . as illustrated in fig1 , the step s 11 is performed to prepare a monocrystalline silicon wafer on which a mask layer is formed ; the step s 12 is performed to etch the mask layer and the monocrystalline silicon wafer to form several trenches ; the step s 13 is performed to form a first insulating layer on the sidewalls and the bottoms of the trenches ; the step s 14 is performed to etch and thus remove the first insulating layer on the bottoms of the trenches ; the step s 15 is performed to etch along the trenches the monocrystalline silicon wafer beneath the trenches to form cavities ; the step s 16 is performed to process the inner walls of the cavities to form a second insulating layer ; and the step s 17 is performed to fill up the trenches and the cavities with an insulating material layer . the soi wafer formed based upon the above embodiment includes : the monocrystalline silicon wafer ; the trenches arranged in the monocrystalline silicon wafer ; the cavities arranged in the monocrystalline silicon wafer and interconnected with the trenches ; the first insulating layer arranged on the sidewalls of the trenches ; the second insulating layer arranged on the inner walls of the cavities ; and the insulating material layer filling up the trenches and the cavities . an embodiment of the invention will be detailed below with reference to the drawings . fig7 , fig8 , fig9 , fig1 , fig1 a , fig1 b , fig1 a , fig1 b , fig1 a and fig1 b illustrate schematic diagrams of the embodiment of a process for forming an soi wafer according to the invention . as illustrated in fig7 , a monocrystalline silicon wafer 100 with a thickness or 500 μm to 1500 μm is prepared ; a first film layer 102 a made of silicon oxide with a thickness of 1 nm to 1 μm is formed on the monocrystalline silicon wafer 100 through thermal oxidization ; and a second film layer 102 b made of silicon nitride with a thickness of 1 nm to 1 μm is formed on the first film layer 102 a through chemical vapor disposition , where the first film layer 102 a and the second film layer 102 b constitute a mask layer 102 which functions to prevent the monocrystalline silicon wafer 100 from being damaged during subsequent etching and grinding . referring to fig8 , several trenches 103 are formed in the monocrystalline silicon wafer 100 . a specific formation process is as follows : a photoresist layer ( not illustrated ) is formed on the mask layer 102 through spin coating and is exposed and developed to define several trench photoresist patterns on the photoresist layer ; the mask layer 102 is etched along the trench photoresist patterns using the photoresist layer as a mask to form trench patterns ; and the photoresist layer is removed and then the monocrystalline silicon wafer 100 is etched along the trench patterns using the mask layer 102 as a mask to form the trenches 103 . in this embodiment , the trenches 103 have a width of 10 nm to 50 μm , a depth of 50 nm to 50 μm and the number of the trenches 103 is dependent upon whether the cavities to be formed subsequently beneath the trenches 103 can be interconnected to separate the monocrystalline silicon wafer 100 into a silicon substrate and a top layer silicon . as illustrated in fig9 , a first insulating layer 104 with a thickness of 1 nm to 10 μm is formed on the mask layer 102 and the sidewalls of the trenches and the first insulating layer 104 is made of silicon oxide or silicon nitride for the purpose of isolation to prevent any material to be filled subsequently into the trenches from being diffused into the monocrystalline silicon wafer 100 , where if the first insulating layer 104 is made of silicon oxide , it can be formed through thermal oxidation , and if the first insulating layer 104 is made of silicon nitride , it can be formed through thermal nitrification or chemical vapor deposition . referring to fig1 , the first insulating layer 104 on the mask layer 102 and the bottoms of the trenches is removed through dry etching using gas of argon . as illustrated in fig1 a and fig1 b , isotropic etching is performed along the trenches on the monocrystalline silicon wafer 100 beneath the trenches through wet etching using a solution of xef 2 or a mixed solution of hno 3 and hf to form cavities . in this embodiment , the cavities 106 have a depth of 50 nm to 50 μm . if one cavity 106 were sufficient to separate the monocrystalline silicon wafer 100 , then it would be sufficient to form one trench in the monocrystalline silicon wafer 100 . however the monocrystalline silicon wafer 100 typically has a relatively large area , and more than one trench has to be formed as restricted in the process , so that isotropic etching is performed on the monocrystalline silicon wafer 100 to thereby form the cavities 106 separating the monocrystalline silicon wafer 100 . therefore there are relatively large number of trenches formed in the monocrystalline silicon wafer 100 , and after isotropic etching , fig1 a illustrates a case where the cavities 106 are spaced at an interval of approximately 10 nm to 1000 nm , and fig1 b illustrates another case where the cavities 106 are interconnected completely . referring to fig1 a and fig1 b , the inner walls of the cavities 106 are processed to form a second insulating layer 108 with a thickness of 10 nm to 1000 nm , where the second insulating layer 108 is made of silicon oxide or silicon nitride for the purpose of isolation to prevent any material to be filled subsequently into the cavities from being diffused into the monocrystalline silicon wafer 100 , where if the second insulating layer 108 is made of silicon oxide . it can be formed through thermal oxidation , and if the second insulating layer 108 is made of silicon nitride , it can be formed through thermal nitrification . referring to fig1 a again , the cavities 106 are spaced at an interval during formation thereof and are interconnected through oxidization of the inner walls thereof to thereby separate the monocrystalline silicon wafer 100 . referring to fig1 b , the cavities 106 have been interconnected completely during formation thereof in this case to thereby separate the monocrystalline silicon wafer 100 . therefore , it is sufficient for the purpose of isolation to form the second insulating layer 108 on the inner walls of the cavities 106 . as illustrated in fig1 a and fig1 b , the trenches and the cavities 106 are filled up with an insulating material layer 110 . a specified process is as follows : the insulating material layer 110 is formed on the monocrystalline silicon wafer 100 through low - pressure chemical vapor disposition ; the trenches and the cavities 106 are filled up with the insulating material layer 110 ; and the insulating material layer 110 is planarized through chemical mechanical polishing until the mask layer 102 is exposed . in this embodiment , the insulating material layer 110 is made of tetraethyl orthosilicate , polysilicon , silicon glass , etc . the first insulating layer 104 , the second insulating layer 108 and the insulating material layer 110 constitute the insulating layer of the soi wafer and separate the monocrystalline silicon wafer into the silicon substrate 100 b and the top layer silicon 100 a . the soi wafer formed based upon the above embodiment includes : the monocrystalline silicon wafer 100 ; the trenches 103 with a depth of 50 nm to 50 μm arranged in the monocrystalline silicon wafer 100 ; the cavities 106 with a depth of 50 nm to 50 μm arranged in the monocrystalline silicon wafer 100 and interconnected with the trenches 103 ; the first insulating layer 104 arranged on the sidewalls of the trenches 103 ; the second insulating layer 108 arranged on the inner walls of the cavities 106 , each of the cavities 106 being interconnected directly or through the second insulating layer 108 ; and the insulating material layer 110 filling up the trenches 103 and the cavities 106 . particularly , the first insulating layer 104 and the second insulating layer 108 function to prevent the insulating material layer 110 filled into the trenches 103 and the cavities 106 from being diffused into the monocrystalline silicon wafer 100 . particularly , the first insulating layer 104 , the second insulating layer 108 and the insulating material layer 110 separate the monocrystalline silicon wafer into the silicon substrate 100 b and the top layer silicon 100 a . although the invention has been disclosed as above in connection with the preferred embodiments thereof , the scope of the invention will not be limited thereto , and any skilled in the art can make various variations and modifications without departing from the spirit and scope of the invention . accordingly , the protection scope of the invention shall be as defined in the appended claims . | 7 |
with reference now to fig3 there can be seen a block diagram of an electronic ballast system 50 which constitutes a presently preferred embodiment of the present invention . as with the conventional ballast system described hereinabove , the ballast system 50 of the present invention includes an emi filter 52 and a rectifier 56 , e . g ., a half - bridge or full - bridge rectifier . however , rather than the non - isolated boost converter of the conventional ballast system the ballast system 50 of the present invention includes a high - frequency pfc converter 58 which incorporates an isolation transformer ( not shown in fig3 ) which isolates the ac utility line and the lamp 60 . an energy storage capacitor ce is connected across the pfc converter 58 on the primary side of the isolation transformer . the output of the isolated pfc converter 58 is a dc voltage which is well - regulated by the control circuit a . this well - regulated dc voltage is then inverted into a high - frequency ac voltage by a high - frequency dc - ac inverter 62 , e . g ., a standard half - bridge or full - bridge ac - dc inverter or a half - bridge or full - bridge pwm ac - dc inverter . the high - frequency ac voltage produced by the dc - ac inverter 62 is delivered to the lamp 60 as a sinusoidal ( ac ) current for ignition thereof the control circuit b regulates the sinusoidal lamp current . the switching frequency of the pfc converter 58 is significantly higher than the switching frequency of the dc - ac inverter 62 , which is the same as the lamp current frequency . in this connection , the switching frequency of the pfc converter 58 is preferably & gt ; 500 khz , whereas the switching frequency of the dc - ac inverter 62 and the lamp current frequency is preferably in the range of 25 - 50 khz , in order to prevent excessive emi radiation from the lamp 60 , although the specific switching frequencies employed are not limiting to the present invention . with reference now to fig4 there can be seen a partial schematic , partial block diagram of an exemplary implementation of the above - described presently preferred embodiment of the present invention . with this particular implementation , the pfc converter 58 is comprised of a dither power factor correction circuit 70 and a high - frequency dc - dc converter 72 . the dither power factor correction circuit 70 includes an inductor l1 , diodes d1 and d2 , mosfet switches q1 and q2 , and energy storage capacitor ce . the dc - dc converter 72 includes the mosfet switches q1 and q2 , capacitors c1 and c2 , transformer t , a full - bridge rectifier comprised of the diodes d3 - d6 , and capacitors c3 and c4 . the dc - ac inverter 62 is a half - bridge inverter comprised of the capacitors c3 and c4 , mosfet switches q3 and q4 , and an l - c tank circuit comprised of an inductor lr and a capacitor cr connected across the lamp 60 . with reference now to fig5 a - 5d , the operation of the dither power factor correction circuit 70 will now be described . with particular reference first to fig5 a , when the line voltage vi is positive and the switch q1 is turned on , the line voltage vi is applied to the inductor l1 through the diode d1 and the switch q1 . the current through l1 rises linearly from zero to a positive peak value , and the energy is stored by the inductor l1 . with particular reference now to fig5 b , when the line voltage v1 is positive and the switch q1 is turned off , the positive inductor current flows to the energy storage capacitor ce through the body diode of the switch q2 , to thereby transfer the energy stored in the inductor l1 when the switch q1 is turned on , to the energy storage capacitor ce . the current through the inductor l1 falls linearly from its positive peak value to zero . with particular reference now to fig5 c , when the line voltage v1 is negative and the switch q2 is turned on , the line voltage v1 is applied to the inductor l1 through the diode d2 and the switch q2 . the current through l1 rises linearly from zero to a negative peak value , and the energy is stored by the inductor l1 . with particular reference to fig5 d , when the line voltage vi is negative and the switch q2 is turned off , the negative inductor current flows to the energy storage capacitor ce through the body diode 78 of the switch q1 , to thereby transfer the energy stored in the inductor l1 when the switch q2 is turned on , to the energy storage capacitor ce . the current through the inductor l1 falls linearly from its negative peak value to zero . with reference again to fig4 the control circuit a receives a full - wave rectified feedback signal from the output of the dc - dc converter 72 , and modulates the switching frequency of the switches q1 and q2 in such a manner as to effect power factor correction . the switches q1 and q2 are turned on and off in complementary fashion , with a nominal 50 % duty ratio , at high frequency , e . g ., & gt ; 500 khz , so that the current through the inductor l1 is in discontinuous conduction mode ( dcm ). after the high - frequency components of the current through the inductor l1 are filtered by the emi filter 52 , the line current is a semi - sinusoidal wave in phase with the line voltage . the power factor is close to unity and the total harmonic distortion is low . thus , the input power is controlled by the frequency modulation of the mosfet switches q1 and q2 . with reference now to fig6 there can be seen the equivalent circuit for the dc - dc converter 72 , in which the secondary side is reflected to the primary side , and the output is replaced by a voltage source vo . as can be seen , the transformer t has leakage inductances llk1 and llk2 , and a magnetizing inductance lm . before the switch q1 is turned on , the current ilk2 is negative . after the switch q1 is turned on , a positive voltage v1 is applied to the primary side of the transformer t , but a negative voltage vo is applied to the secondary side of the transformer t through the diodes d4 and d6 . the current ilk1 flowing through llk1 and the current im flowing through lm rise up . when ilk1 exceeds im , the current ilk2 (= ilk1 - im ) through llk2 becomes positive and flows through diodes d3 and d5 . when the switch q2 is turned on , the operation is similar , but in reverse . the operating waveforms are depicted in fig7 . the dc - dc converter 72 can be designed to be operated with zero - voltage - switching in order to reduce switching losses and switching noise . in this connection , the duty ratio control signals a1 , a2 applied by the control circuit a to the gates of the mosfet switches q1 and q2 , respectively , are held inactive during a dead time , so that both switches q1 and q2 are turned off during this dead time . during the dead time , the current ilk1 through the leakage inductance llk1 is used to charge and discharge the drain - source capacitances cds1 and cds2 of the switches q1 and q2 , respectively . if the energy stored in the leakage inductance llk1 is not enough to effect complete charge and discharge of the drain - source capacitances cds1 and cds2 , the energy stored in the magnetizing inductance continues to charge and discharge these capacitances . the dc - dc converter 72 can be designed for zero - voltage - switching over a full load and input voltage range . with reference again to fig4 the high - frequency half - bridge dc - ac inverter 62 is conveniently the same as that in the conventional ballast circuit , except that the isolation transformer is eliminated , due to its inclusion in the pfc converter 58 . the control circuit b receives a lamp current feedback signal and , in response thereto , modulates the switching frequency of the switches q3 and q4 , in such a manner as to regulate the sinusoidal lamp current to a nearly constant rms value . in the preferred embodiment , the switches q3 and q4 are turned on and off in complementary fashion , with a nominal 50 % duty ratio , at a high frequency , e . g ., 25 - 50 khz . thus , the output power is regulated by the frequency modulation of the switches q3 and q4 . if the resonant frequency of the l - c circuit ( lr , cr ) is lower than the switching frequency of the dc - ac inverter 62 , the inverter 62 can also be designed to be operated with zero - voltage - switching in order to reduce switching losses and switching noise . in this connection , the duty ratio control signals b1 , b2 applied by the control circuit b to the gates of the mosfet switches q3 and q4 , respectively , are held inactive during a specified dead time , so that both switches q3 and q4 are turned off during this dead time . with reference now to fig8 there can be seen a first alternative embodiment of the ballast system of the present invention , which is the same as the exemplary implementation of the presently preferred embodiment depicted in fig4 except that a high - frequency half - bridge pfc converter 80 is substituted for the high - frequency dither pfc converter 58 . the half - bridge pfc converter 80 is comprised of a half - bridge power factor correction circuit 82 and a dc - dc converter 84 . the half - bridge power factor correction circuit 82 includes a full - bridge rectifier comprised of diodes d1 - d4 , an inductor l1 and diode d5 , mosfet switches q1 and q2 , and energy storage capacitor ce . the dc - dc converter 84 is comprised of the mosfet switches q1 and q2 , capacitors c1 and c2 , transformer t , a full - bridge rectifier comprised of diodes d6 - d9 , and capacitors c3 and c4 . with reference now to fig9 there can be seen a second alternative embodiment of the ballast system of the present invention , which is the same as the exemplary implementation of the presently preferred embodiment depicted in fig4 except that a high - frequency push - pull pfc converter 90 is substituted for the high - frequency dither pfc converter 58 . the push - pull pfc converter 90 is comprised of a push - pull power factor correction circuit 92 and a dc - dc converter 94 . the push - pull power factor correction circuit 92 includes an inductor l1 and diode d5 connected in series between a node n1 and a first terminal 96 of the primary winding of the transformer t , and an inductor l2 and diode d6 connected in series between the node n1 and a second terminal 98 of the primary winding of the transformer t , in parallel with the inductor l1 and diode d5 . the node n1 is coupled to the output junction node n2 of a full - bridge rectifier comprised of diodes d1 - d4 . a first mosfet switch q1 is connected between the first terminal 96 of the primary winding of the transformer t and bottom rail 99 , and a second mosfet switch q2 is connected between the second terminal 98 of the primary winding of the transformer t and the bottom rail 99 , in parallel with the first switch q1 . the energy storage capacitor ce is connected between the center tap 100 of the transformer t and the bottom rail 99 . the remaining elements of the ballast system of this embodiment are the same as the corresponding elements of the ballast system of the presently preferred embodiment described hereianbove , and thus , a description thereof will be omitted . with reference now to fig1 , there can be seen a third alternative embodiment of the ballast system of the present invention , which is the same as the exemplary implementation of the presently preferred embodiment of the present invention depicted in fig4 except that a high - frequency pulse - width modulated ( pwm ) dc - ac inverter 110 is substituted for the standard half - bridge dc - ac inverter 62 . the pwm dc - ac inverter 110 may be a half - bridge pwm inverter as shown in fig1 , or a full - bridge pwm inverter as shown in fig1 . the half - bridge pwm inverter works in the following manner . the pulse width of the duty ratio control signals b1 , b2 issued by the control circuit b are modulated by a relatively low - frequency signal ( e . g ., a 25 - 50 khz signal ), resulting in a pulse - width modulated voltage vab across points a and b . this pulse - width modulated voltage vab is filtered by the l - c circuit comprised of the inductor lo and the capacitor co , to thereby produce a regulated , relatively low frequency output voltage ( e . g ., 25 - 50 khz ac voltage ) for driving the lamp 60 . the corner frequency of the l - c filter can be designed for operation at a frequency at least one decade higher than the modulation frequency , e . g ., 250 khz , thereby enabling the size of the l - c filter to be significantly reduced . the switching frequency of the pwm inverter 110 ( i . e ., the nominal frequency of the duty ratio control signals b1 , b2 ) can be at least one decade higher than the corner frequency of the l - c filter , e . g ., 2 . 5 mhz . during ignition of the lamp 60 , the modulation frequency is on the same order as the corner frequency of the l - c filter so that a high - voltage output can be obtained to ignite the lamp 60 , due to resonance of the l - c circuit . during steady - state operation of the lamp 60 , the modulation frequency is kept to 25 khz in order to prevent excessive emi radiation from the lamp 60 . thus , the control circuit b regulates the lamp current by current mode control . the operating waveforms for the half - bridge pwm dc - ac inverter are depicted in fig1 , and the operating waveforms for the full - bridge pwm dc - ac inverter are depicted in fig1 . although a presently preferred and various alternative embodiments of the present invention have been described in detail hereinabove , it should be clearly understood that many variations and / or modifications of the basic inventive concepts herein taught which may appear to those skilled in the pertinent art will fall within the spirit and scope of the present invention as defined in the appended claims . in this connection , for a more detailed understanding of various elements and facets of the present invention , and permissible variations thereof , reference is made to the following references . namely , for a more detailed understanding of power factor correction converters and dc - dc converters , reference is made to : d . chambers and d . wang , &# 34 ; dynamic power factor correction in capacitor input off line converters &# 34 ;, powercon &# 39 ; 79 proceedings , pp . b3 - 1 - b3 - 6 , may , 1979 ; c . zhou and m . m . jovanovic , &# 34 ; design trade - offs in continous current - mode controlled boost power factor correction circuits &# 34 ;, high frequency power conversion conference record &# 39 ; 92 , pp . 202 - 220 , may , 1992 , c . solva , &# 34 ; power factor correction with uc3854 &# 34 ;, application note , unitrode integrated circuit , c . zhou , &# 34 ; design and analysis of an active power factor correction circuit &# 34 ;, m . s . thesis , virginia polytechnique institute and state university , blacksburg , va ., may 1990 ; c . p . henze , &# 34 ; a digitally controlled ac to ac power conditioner that draws sinusoidal input current &# 34 ;, ieee pesc &# 39 ; 86 record , june 1986 ; r . erickson , m . madigan and s . singer , &# 34 ; design of a simple high power factor rectifier based on the flyback converter &# 34 ;, ieee apec &# 39 ; 90 proceedings , pp . 792 - 801 , february 1990 ; w . tang , y . jiang , g . c . hua and f . c . lee , &# 34 ; power factor correction with flyback converter employing charge control &# 34 ;, vpec seminar &# 39 ; 92 proceeding , virginia polytechnique institute and state university , blacksburg , va ., september 1992 ; m . h . kheraluwala , r . l . steigerwald and r . gurumoorthy , &# 34 ; a fast response high power factor converter with a single power stage &# 34 ;, ieee pesc &# 39 ; 91 record , pp . 769 - 779 , june 1991 ; m . madigan , r . erickson and e . ismail , &# 34 ; integrated high quality rectifier - regulator &# 34 ;, ieee pesc &# 39 ; 92 , pp . 1043 - 1051 , june 1992 ; i . takahashi and r . y . igarashi , &# 34 ; a swtiching power supply of 99 % power factor by dither rectifier &# 34 ;, ieee intelec &# 39 ; 91 proceedings , pp . 714 - 719 , november 1991 ; y . jiang , g . c . hua , w . tang and f . c . lee , &# 34 ; a novel single - phase power factor correction scheme &# 34 ;, vpec seminar &# 39 ; 92 proceedings , virginia polytechnique institute and state university , blacksburg , va ., september 1992 ; and , b . a . miwa , d . m . otten and m . f . schlect , &# 34 ; high - efficiency power factor converter using interleaving techniques &# 34 ;, ieee apec &# 39 ; 92 proceedings , pp . 557 - 568 , february 1992 . for a more detailed understanding of zero - voltage - switching and soft - switching converters , including pwm dc - ac converters / inverters , reference is made to : c . p . henze , h . c . martin and d . w . parley , &# 34 ; zero - voltage - switching in high - frequency power converters using pulse width modulation &# 34 ;, proceedings of 1988 ieee applied power electronics conference , pp . 33 - 40 , february 1988 ; r . w . erickson , a . f . hernandez , a . f . witulski and r . xu , &# 34 ; a nonlinear resonant switch &# 34 ;, record of 1989 ieee power electronics specialists conference , pp . 43 - 50 , june 1989 ; v . vorperian , &# 34 ; quasi - square - wave converters : topologies and analysis &# 34 ;, ieee , transactions on power electronics , vol . 3 , no . 2 , pp . 183 - 191 , april 1988 ; k . watanabe , s . takeishi , i . norigoe and r . hiramatsu , &# 34 ; self running converter utilizing partial resonance &# 34 ;, proceeding of 1988 ieee international telecommunication energy conference , pp . 186 - 193 , october 1988 ; k . harada and h . sakamoto , &# 34 ; non - resonant converter for mega hertz switching &# 34 ;, record of 1989 ieee power electronics specialists conference , pp . 889 - 894 , june 1989 ; k . harada and h . sakamoto , &# 34 ; switched - snubber for high - frequency switching &# 34 ;, record of 1990 ieee power electronics specialists conference , pp . 181 - 188 , june 1990 ; k . harada and h . sakamoto , &# 34 ; on the saturable inductor commutation for zero - voltage - switching &# 34 ;, record of 1989 ieee power electronics specialists conference , pp . 189 - 196 , june 1990 ; g . c . hua , f . c . lee and m . m . jovanovic , &# 34 ; an improved zero - voltage - switched pwm converter using a saturable inductor &# 34 ;, record of 1989 ieee power electronics specialists conference , pp . 189 - 194 , june 1991 ; w . j . gu and k . harada , &# 34 ; novel self - excited pwm converters with zero - voltage - switched resonant transition using a saturable core &# 34 ;, proceedings of 1992 ieee applied power electronics conference , pp . 58 - 65 , february 1992 ; w . j . gu and k . harada , &# 34 ; a novel , self - excited , pwm forward converter with zvs resonant transition using two minor - loop - operated saturable cores &# 34 ;, record of 1992 ieee power electronics specialists conference , pp . 85 - 92 , june 1992 ; g . c . hua , c . s . leu and f . c . lee , &# 34 ; novel zero - voltage - transition pwm converters &# 34 ;, record of 1992 ieee power electronics specialists conference , pp . 55 - 61 , june 1992 ; u . s . pat . no . 3 , 517 , 300 , issued to w . mcmurray , jun . 23 , 1970 ; and , k . harada , h . sakamoto , and m . shoyama , &# 34 ; phase - controlled dc - ac converter &# 34 ;, ieee transactions on power electronics , vol . 3 , no . 4 , pp . 406 - 411 , october 1988 . for a more detailed understanding of ballast systems , in general , reference is made to : b . m . wolfframm , &# 34 ; ballasts - past , present , and future &# 34 ;, record of the 1984 ieee industry application society annual meeting , pp . 1288 - 1292 , 1984 ; r . j . haver , &# 34 ; electronic ballasts &# 34 ;, pcim magazine , pp . 52 - 56 , april 1986 ; r . verderber , o . morse and f . m . rubinstein , &# 34 ; performance of electronic ballast and controls with 34 - and 40 - watt f40 fluorescent lamps &# 34 ;, ieee transactions on industry applications , vol . 25 , no . 6 , pp . 1049 - 1059 , december 1989 ; european patent application publication number 0507399a2 , issued to blom et al ., and assigned to n . v . philips ; u . s . pat . no . 4 , 958 , 108 , issued to jorgensen , and assigned to avtech corporation ; u . s . pat . no . 4 , 870 , 327 , issued to jorgensen , and assigned to avtech corporation ; and , u . s . pat . no . 4 , 412 , 156 , issued to ota , and assigned to elmo company . | 7 |
the present inventor has ascertained that residual stresses in friction welded precipitation hardened super alloy assemblies may be extremely high , that conventional pwht may not accommodate these high levels of residual stresses , and that cracking that occurs during pwht may be the result of these high levels of residual stresses . as such , the inventor has proposed an innovative intermediate stress relief ( isr ) to be performed prior to the conventional pwht of precipitation hardened super alloys . the isr relieves the residual stresses present in the weld , and welds subject to the isr prior to the conventional pwht have been found to have fewer or no cracks . without being bound to any particular theory , it is believed that the presence of these residual stresses during pwht is part of the mechanism that causes the strain age cracking , and so relieving the residual stress prior to pwht reduces or eliminates the strain age cracking that occurs during pwht . precipitation hardened ( i . e . precipitation strengthened ) super alloys may be subjected to a pwht in order to develop maximum strength in a final assembly . maximum strength is the result of proper ( i . e . homogenous ) distribution of precipitates throughout the material , as well as a proper volume of precipitates etc . prior to welding a precipitation hardened super alloy the precipitates present in the pin and / or substrate may be reduced from a maximum - strength level by an appropriate heat treatment to increase ductility in order to facilitate welding . during the welding process of a precipitation hardened super alloy a uniformity of the distribution of the precipitates may be disturbed . in order to return to a desired uniformity and volume etc of the precipitates in the final assembly ( and weld ), the assembly is subjected to a conventional pwht . conventional pwht of a welded precipitation hardened super alloy is a two step process where the assembly is treated at a solutionizing temperature , and then treated at an aging temperature ( i . e . precipitation strengthening or precipitation hardening temperature ). during the solutionizing treatment alloying elements in the assembly are returned to solution and are free to diffuse uniformly throughout the assembly microstructure . as a result the alloying elements transition from a non - uniform distribution to a more uniform distribution . during aging , the more uniformly distributed alloying elements fall out of solution and form precipitates that increase the strength of the substrate . secondarily , during both pwht processes residual stresses may be relieved to some degree . cold working , such as that which happens during friction welding , induces high levels of residual stresses due to dislocations and tangles etc in the microstructure . when heated the microstructure may realign its microstructure to varying degrees , which in turn reduces the cold work induced residual stresses . however , the residual stresses may not be relieved entirely during the pwht , and it is also sometime during the pwht that cracks form . it is believed that a combination of low ductility ( possibly resulting from the formation of precipitates ) and high residual stresses ( possibly resulting from cold working during welding and possibly material shrinkage during precipitation formation ) may contribute to crack formation . however , it is unknown exactly what mechanism or combination of mechanisms is causing the cracks to form , and at what point ( s ) in the pwht the cracking occurs . thus , in an embodiment the inventor proposes to relieve residual stresses prior to any of the conventional pwht processes . as a result , in an embodiment the proposed isr seeks to permit realignment of the microstructure , for example by reforming of crystals , thereby reducing residual stress , but seeks to do so without solutionizing and without permitting too much ( or any ) precipitation formation . however , reduction of residual stresses may be achieved by alternate heat treatments that may overlap processes involved in conventional pwht , and such alternate heat treatments are envisioned to be within the scope of this disclosure . for example , the isr treatment may overlap or be made part of the solutionizing temperature under conditions when cracking is found to occur primarily during the aging process or later in the solutionizing process etc . the isr treatment seeks to reduce residual stress , but not to an exact level or by an exact amount . the isr treatment will reduce residual stress in friction welded super alloys more than occurs in conventional pwht of friction welded super alloys . specifically , the isr treatment will reduce residual stress more than any incidental residual stress reduction that occurs during any of : heating ( ramping up ) of an assembly to a solutionizing temperature of conventional pwht ; during the solutionizing process of conventional pwht ; and during the aging process of conventional pwht . applicant considers approximately a 20 % reduction in residual stresses to be more than incidental . it has been measured experimentally that residual stresses present in the assembly weld after welding are at least of the order of 43 % of the material yield strength . in other certain locations residual stresses likely approach 100 % of yield strength ( as is common in most welds ). given that residual stresses will vary throughout a weld , absolute stress reductions and percentages of stress reduction may vary throughout a weld . for example , stress in a significant portion of the weld may be 43 % of the yield strength and in another portion may be 100 %. both areas may experience a stress reduction due to the isr heat treatment , but the significant portion may not respond exactly like the other portion , and thus the amount of stress reductions , in absolute and in percentage terms , of the significant portion may vary from that of the other portion for example . however , both will experience more than incidental stress reduction . thus , a stress reduction as described herein refers to a reduction in stress for a given location within a weld . it has been measured experimentally that isr will reduce a residual stress in an assembly to as little as 3 % of that material &# 39 ; s yield strength . for example , for a gamma prime strengthened nickel based superalloy , the yield strength is approximately 690 mpa . following inertia friction welding , residual stresses as high as 42 ksi ( 290 mpa ) have been measured throughout a significant portion of the weld , which is approximately 43 % of the material &# 39 ; s yield strength . ( in other locations in the weld residual stresses still approach 100 % of the material &# 39 ; s yield strength .) when the same material is subjected to the instant isr treatment , residual stresses on the order of 3 ksi ( 21 mpa ) were found in the significant portion of the weld , which is approximately 3 % of a gamma prime strengthened nickel based super alloy &# 39 ; s yield strength . this shows the isr treatment yields a substantial reduction in residual stress . thus , any non - incidental reduction of residual stress in friction welded super alloys , prior to the crack formation that occurs at some point in conventional pwht , is considered to be within the scope of the invention . for example , a 20 % reduction in residual stresses of 43 % of the material yield strength produces residual stresses of less than about 35 % of the material yield strength . an embodiment describing how the reduction of residual stress is achieved and at what point with respect to the conventional pwht the residual stress is reduced is discussed below , but the embodiment discussed below is not meant to be limiting . in an embodiment an isr treatment follows the profile shown in fig3 . according to the isr profile in this embodiment , the assembly is heated to between 870 ° c . and 879 ° c . for approximately 247 minutes . a ramp time to isr treatment temperature is about 102 minutes . following the isr treatment the assembly may be cooled , or it may begin the solutionizing treatment of a conventional pwht . this . isr treatment profile was used on an assembly where both the pin and substrate were made of cm - 247 - lc ®, a gamma prime strengthened nickel based super alloy manufactured by cannon - muskegon corporation of muskegon mi . as a result of this isr profile , residual stresses were reduced from the above - mentioned 42 ksi ( 290 mpa ) to 3 ksi ( 21 mpa ). fig4 shows the final assembly after the isr treatment and then conventional pwht . notably , there is no crack present at the interface of the plug and substrate in the isr treated assembly . it is important to note that the isr treatment profile used is not meant to be limiting , but instead exemplary , as stress relief of other hard - to - weld super alloys may require different isr process temperature , duration , and / or ramp - up etc . however , the idea of more - than incidental residual stress relief regardless of the exact isr treatment profile applies across all materials . the isr treatment may be used to repair cracks in superalloy components such as those used in gas turbine engines . for example , rotor blades and vanes made of gamma prime strengthened nickel based alloys may develop cracks over time in service . prior to the isr treatment , repairing a cracked super alloy component with a friction welding process was likely to produce a repaired part with a crack in the repair . now , the quality of the repair is greatly improved . this may improve the longevity of gas turbine engine parts and reduce the repairs needed throughout their lives , saving money and reducing down time . such repairs may be conducted as depicted in fig5 - 11 . in fig5 a schematic of a portion of a precipitation hardened super alloy substrate 100 ( i . e . a blade ) with a crack 102 is visible . the crack 102 may be of any length , direction , and branched configuration . surrounding the crack 102 is a perimeter 104 of a region to be excavated during the repair . such excavation may be accomplished by milling , for example . in fig6 a first excavated portion 106 ( i . e . a tapered pocket ) can be seen . fig7 shows a cross section of the first excavated portion 106 . tapered walls 108 are visible and are used to ensure alignment with a plug and path for metal extrusion during subsequent friction welding . however , crack repair is not limited to shallow , tapered pockets . in fig8 a plug 110 with a tapered tip 112 has been spun and friction welded into the first excavated portion 106 , material has been plasticized , and the plug 110 and substrate 100 have been bonded ( i . e . welded ). excess plug material is removed from the substrate 100 in fig9 , thereby forming an assembly 114 . however , assembly 114 retains significant residual stresses from the cold working of the inertia welding , and is to undergo the above disclosed isr treatment followed by conventional pwht . upon completion , the repair will be complete . crack repair is not limited to cracks of size and configuration that enable a single weld repair . for example , in fig1 a precipitation hardened super alloy substrate 116 with a larger crack 118 is visible . the larger crack 118 is such that a single excavation and single inertia welding operation would not encompass an entirety of the larger crack 118 . to accommodate such larger cracks 118 , multiple regions may be excavated and multiple welds made . for example , two regions of material may be excavated , as indicated by a perimeter of a first region to be excavated 120 , and a perimeter of a second region to be excavated 122 . any number of excavations may be considered and are considered within the scope of this disclosure . in such a multi - excavation repair , each repair may be made as a discrete repair , and all repairs together will encompass the entirety of the crack . for example , as shown in fig1 , a first region 124 of a multi region repair 126 may be excavated , inertia welded , and excess plug material removed . a second region 128 may then be excavated , inertia welded , and its excess plug material removed . the multi region repair 126 may then be sent for isr treatment that may be followed by conventional pwht to produce a multi region repaired substrate 130 . any alternate pocket geometry that may work is considered within the scope of the disclosure . furthermore , instead of removing a pocket , as shown in fig1 a through - hole 132 may be drilled into a substrate 134 , and a plug 136 may be inertia friction welded through the substrate , and excess material trimmed from both sides . plugging may access such through hole from one or both sides of the hole either sequentially or simultaneously and may involve single or multiple tapers . the isr treatment and repair techniques disclosed above are not limited to the example material given , but apply to any precipitation hardened super alloy undergoing a plastic weld technique where the residual stresses have produced cracks in conventional pwht . in addition , as in conventional welding of super alloys , the materials to be welded , such as a pin and substrate , may be preheated . preheating may reduce precipitates and increase ductility , making the materials more weldable . preheating may also reduce temperature gradients and reduce residual stresses . alternately , welding in a chill fixture or under water or under other cooling medium could minimize maximum temperature excursion and time . this could be of advantage in particularly heat sensitive materials that would otherwise form deleterious precipitates , which may be problematic during subsequent heat treatments . it has been disclosed that the inventor has identified an intermediate stress relief treatment that can avoid the mechanism that form cracks in plastically welded super alloy assemblies undergoing conventional pwht . the isr reduces cold worked residual stresses present in the as - welded assemblies , and this reduction of residual stresses reduces crack formation in conventional pwht of these assemblies . this technique may increase production yield of crack - free parts , and may be utilized in the repair of super alloy components in service that have developed cracks . increased yield , and improved crack repair represent cost savings and are an improvement over the state of the art . while various embodiments of the present invention have been shown and described herein , it will be obvious that such embodiments are provided by way of example only . numerous variations , changes and substitutions may be made without departing from the invention herein . accordingly , it is intended that the invention be limited only by the spirit and scope of the appended claims . | 2 |
in accord with the present invention , a method of blocking the tetracycline efflux system of tetracycline resistant cells is obtained by treating tetracycline resistant cells with an efflux blocking agent , i . e ., a tetracycline analog or another type of agent which interferes with the action of the tet a and / or tet b proteins or protein domains and thus decreases efflux of tetracyclines from the cell . this method renders formerly resistant cells non - resistant , i . e ., sensitive to tetracycline . inhibition of the tetracycline efflux system may be demonstrated by a comparison of the transport of tetracycline with and without an efflux blocking agent by susceptible cells and by resistant cells . preferably , tetracycline type antibiotics are administered in conjunction with , or shortly after treatment with the efflux blocking agent . by &# 34 ; tetracycline - type antibiotic &# 34 ;, tetracyclines , or the tetracycline family , as used herein , is meant tetracycline and its analogs , which are compounds having the structural formula : ## str1 ## wherein r 1 to r 5 may be hydrogen , hydroxy , alkyl , substituted alkoxy , alkylene , halogen , etc . see korolkovas et al ., essentials of medicinal chemistry ( john wiley & amp ; son , inc ., 1976 ), at 512 - 17 , the disclosure of which is incorporated herein by reference . preferably r 1 and r 2 are hydrogen or hydroxy , r 3 is hydrogen or methyl , r 4 is hydrogen , halogen , preferably chlorine , or amino , preferably dimethylamino , and r 5 is hydrogen , n - methyl pyrole , ( as in rolitetracycline ) or ## str2 ## ( as in lymecycline ). r 2 and r 3 together may be methylene , as in methacycline . in tetracyline sensitive cells , tetracycline is accumulated so that the intracellular concentration of tetracyclines exceeds the extracellular level . part of the uptake occurs via an initial energy - independent phase of antibiotic uptake as detailed in antimicrobial agents 14 ( 2 ), supra at 201 . however , at least half of the uptake occurs via an energy dependent system sensitive to metabolic inhibitors . in resistant organisms , an additional energy - demanding and carrier - mediated active efflux system is incorporated by the presence of resistance - determinator genetic material , such as a tet resistant gene encoded by a plasmid . resistance does not occur by means of inactivation of the tetracycline molecule . rather the total efflux rate is increased , so that , at a steady state , the resistant organism has a low intracellular level of tetracycline . this resistance mechanism is an active system for pumping the drug out of the cell . we have now found that efflux of tetracycline type antibiotics can be blocked by use of a blocking agent which binds , associates with , or otherwise deactivates the carrier protein ( s ) which are active in effluxing tetracyclines from the cell . while not wishing to be bound by theory , it is believed that the proteins or protein domains known as tet a and tet b , or other similar carrier proteins , e . g . from other tetracycline resistance determinants , actively instill resistance in microorganisms by binding to or otherwise associating with the tetracycline type antibiotic and transporting the antibiotic out of the cell . it further appears that both tet a and tet b proteins or protein domains have a critical and supportive role in affecting the efflux system , and thus it is possible to block the efflux system and convert resistant microorganisms to sensitive microorganisms , by use of a blocking agent which binds or associates with either tet a and / or tet b proteins . in accord with the present invention , the preferred blocking agents are analogs or derivatives of tetracyclines , or compounds which contain a sufficient part of the tetracycline structure such that they are recognized by and bound to or otherwise associated with at least one of the carrier protein molecules or domains which are responsible for effluxing tetracycline - type antibiotics , and thus are efficient in disrupting the efflux system of the microorganism involved . suitable blocking agents include but are not limited to the known tetracycline antibiotics , including oxytetracycline , chlorotetracycline , demeclocycline , doxycycline , b - chelocardin , minocycline , rolitetracycline , lymecycline , sancycline and methacycline , and other compounds including latent forms of tetracycline , such as apicycline , clomocycline , guamecycline , meglucycline ; mepycycline , penimepicycline , pipacycline , etamocycline , penimocycline , etc . tetracycline ( s ) may also be used in salt form , e . g . as a tetracycline lactate , t . lauryl sulfate , t . phosphate complex , t . cyclohexyl sulfamate , or other pharmaceutically acceptable salts . the amount of blocking agent to be used varies with the efficiency of its blocking activity , its absorption by the organism being treated , and the degree of resistance of the microorganism . sufficient amounts of the blocking agent should be used to make the microorganism susceptible to a pharmaceutically acceptable level of tetracycline in the man , animal or plant being treated . the molar ratio of blocking agent to tetracycline or tetracycline type antibiotic which is administered may generally be from 0 . 01 to 100 , preferably from 0 . 05 to 2 . 0 and more preferably 0 . 05 to 1 . 0 . in in vivo treatment , the blocking agent may be administered in amounts which are sufficient to exhibit blocking effect , but which do not adversely affect the subject . this does not apply to use of this invention in vitro , e . g ., in processing chemical reactions , etc . generally , the daily dosage of blocking agent for treatment of disease in mammals may range from 0 . 01 to 100 mg / kg normal body weight , preferably in an amount of about 0 . 1 to 50 mg / kg body weight . the blocking agent may be administered separately from the tetracycline type antibiotic , but preferably is administered simultaneously with the tetracycline type antibiotic . typically , tetracycline - type antibiotics will be administered in a regular daily course of treatment , to attain and maintain a concentration in the blood or the bodily fluids which will inhibit the microorganism being treated . since the presence of the blocking agent deactivates the resistance of the microorganism to the tetracycline type antibiotic , the blocking agent should also be utilized in a continuing treatment to render the antibiotic treatment effective . non - tetracycline based compounds may be utilized as blocking agents , provided that their structure is such as to interact with the carriers which cause antibiotic efflux so as to prevent or decrease that efflux . the efficiency of blocking agents in reducing efflux of tetracycline type antibiotics can be determined by testing against a tetracycline resistant bacteria . the bacteria used may be naturally occurring tetracycline resistant bacteria , or may be made by incorporating plasmids which code for tetracycline resistance into other bacteria hosts . preferably the blocking agent and a tetracycline type antibiotic are combined in a pharmaceutical composition with a pharmaceutically acceptable carrier . the active ingredients may be administered by any route appropriate to the condition to be treated , suitable routes including oral , nasal ( e . g ., by spray ) and parenteral ( including subcutaneous , intramuscular and intravenous ). it will be appreciated that the preferred route will vary with the condition to be treated . while it is possible for the blocking agent to be administered as the raw chemical , it is preferable to present it as a pharmaceutical formulation preparation . the formulations , for veterinary , agricultural and human use , of the present invention comprise the active ingredient , e . g . blocking agent plus tetracycline family drug , as above defined , together with one or more acceptable carriers therefore and optionally other therapeutic ingredients . the carrier ( s ) must be &# 34 ; acceptable &# 34 ; in the sense of being compatible with the other ingredients of the formulation and not deleterious to the recipient thereof . desirably the formulation should not include oxidizing agents and other substances with which these antibiotics and their derivatives and blocking agents are known to be incompatible . the formulations include those suitable for oral or parenteral ( including subcutaneous , intramuscular and intravenous ) administration , although the most suitable route in any given case will depend upon for example , the active ingredient and the condition to be treated . the formulations may conveniently be presented in unit dosage form and may be prepared by any of the methods well known in the art of pharmacy . all methods include the step of bringing into association the active ingredient with the carrier which constitutes one or more accessory ingredients . in general the formulations are prepared by uniformly and intimately bringing into association the active ingredients with liquid carriers or finely divided solid carriers or both , and then , if necessary , shaping the product into the desired formulation . formulations of the present invention suitable for oral administration may be presented as discrete units such as capsules , cachets or tablets each containing a predetermined amount of the active ingredient ; as a powder or granules ; or as a solution or a suspension in an aqueous liquid or a non - aqueous liquid ; or as an oil - in - water liquid emulsion or a water - in - oil liquid emulsion . the active ingredient may also be presented as a bolus , nasal spray , suppository , electuary or paste . a tablet may be made by compression or moulding , optionally with one or more accessory ingredients . compressed tablets may be prepared by compressing in a suitable machine , the active ingredient in a free - flowing form such as a powder or granules , optionally mixed with a binder , lubricant , inert diluent , lubricating , surface active or dispersing agent . moulded tablets may be made by moulding in a suitable machine , a mixture of the powdered compound moistened with an inert liquid diluent . formulations suitable for parenteral administration conveniently comprise sterile aqueous solutions of the active ingredient which solutions are preferably isotonic with the blood of the recipient . such formulations may be conveniently prepared by dissolving the active ingredient in water to produce an aqueous solution , and rendering said solution sterile . these formulations may be presented in unit or multi - dose containers , for example sealed ampoules or vials . it should be understood that in addition to the aforementioned ingredients the formulations of this invention may include one or more additional ingredients such as diluents , buffers , flavouring agents , binders , surface active agents , thickeners , lubricants , preservatives ( including anti - oxidants ) and the like . where the formulation , for human or for veterinary use , is presented in unit dosage form , for example those unit dosage forms specifically mentioned above , each unit thereof conveniently contains the active ingredient ( as above defined ) in an amount in the range of about 1 mg to about 1000 mg . to review , a sensitive cell is constantly accumulating tetracycline via an active uptake system and a passive diffusion mechanism . in the resistant cell , there is an active efflux in addition to the active and passive uptake of the drug . the present invention overcomes the problems associated with the plasmid mediated tetracycline resistance by blocking the efflux system with an inhibitor administered in combination with tetracycline analogs . it has been discovered that by blocking the active efflux , the resistant cell accumulates the tetracycline analog just the same as does the sensitive cell . the present invention teaches that if the efflux system of the resistant cell is blocked , the resistant cell reverts to sensitive cell characteristics . since the tet proteins are an expression of resistance mediated by the plasmid , blocking the action of the tet a and / or b protein or protein domain ( s ) will block the action of the efflux system thereby rendering the resistant cell sensitive to tetracycline analogs once again . the effectiveness of a particular blocking agent can simply be determined by testing for minimum inhibitory concentration ( mic ) of the tetracycline type antibiotic of choice , and comparing the mic of that antibiotic alone , with its mic when used in combination with the blocking agent . the mic of the antibiotic or antibiotic blocking agent combination can be determined for example by following the procedure outlined in antimicrobial agents , 14 ( 2 ) supra at 202 . other methods of measuring mic &# 39 ; s are well known in the art . uptake and / or efflux of tetracycline - type antibiotics or other agents may also be directly measured by counting the amount of radiolabeled drug in whole cells . the advantage of the whole cell method is that transport system saturation can be directly demonstrated . there is a point where the amount of tetracycline influx is greater than simple diffusion or the amount of tetracycline lost via active efflux . another method of assaying the effectiveness of blocking agents is the vesicle method , which utilizes everted inner membrane vesicles . pro . nat . acad . sci . u . s . a ., 77 ( 7 ), supra at 3974 - 5 ; mcmurry et al ., &# 34 ; active uptake of tetracycline by membrane vesicles from susceptible escherichia coli , antimicrobial agents and chemotherapy 20 ( 3 ): 307 - 13 ( 1981 ), which are incorporated herein by reference . using the everted vesicles , the normal efflux system may be observed as an influx system . the vesicle method has the advantage of measuring competition or binding with the efflux system when increasing amounts of tetracycline - type analogs or other agents are employed . the following examples are set forth to further illustrate the present invention . the invention was demonstrated by use of minocycline , a semisynthetic analog of tetracycline , to interfere with the efflux system of a resistant cell , allowing the formerly tetracycline resistant cell to accumulate tetracycline actively . this example demonstrates that both analogs were effluxed by the same carrier in resistant cells and that by saturating the efflux system with the analog minocycline , tetracycline net efflux from the resistant cell was stopped . the significance of this observation is combined with the further observation that addition of the efflux blocking agent does not affect the active uptake system for tetracycline . thus , tetracycline continues to accumulate in the resistant cell . the presence of a blocking agent reduces the necessary extracellular concentration of tetracycline to achieve a mic . minocycline is a semisynthetic analog of tetracycline and is much more lipophilic than tetracycline . plasmids which specify resistance to tetracycline offer much less resistance to its more lipophilic analog minocycline . the level of minocycline resistance is generally 1 % to 10 % that of tetracycline . plasmid r222 contains the class b tetracycline resistance determinant on tn10 . minocycline resistance of r222 is only 6 % of the tetracycline resistance level . minocycline resistance for another r plasmid , pip7 , which bears the class a tetracycline resistance determinant , is only 1 % of the tetracycline resistance level . these plasmids were utilized to compare the transport of the two tetracyclines by susceptible and by two different resistant cells . in sensitive cells , at low levels of drugs , net actively - accumulated minocycline was about 60 times the external concentration ; for tetracycline , the value was 7 - 8 times the external concentration . steady state accumulation of labeled tetracyclines was measured ( 30 min after addition of label ) in resistant cells as a function of external drug concentration in the presence and absence of dinitrophenol . these experiments were identical to those described by mcmurry and levy , supra , antimicrobial agents and chemotherapy 14 ( 2 ) for susceptible cells . net active efflux was declared if steady - state uptake in the whole cells in the presence of the energy inhibitor dnp was greater than that in its absence . normally , addition of energy inhibitors such as dnp or cyanide to resistant cells causes an increase in steady state tetracycline levels , nature , supra , at 90 , since active efflux is inhibited in these deenergized cells , proc ., supra at 3974 . however , if this efflux were saturated , accumulation in energized cells would no longer be lower . in fact , if resistant cells retained the active uptake system of the host cell ( which is unsaturable ), this active uptake system might become detectable at external drug levels when the efflux system had been saturated . net efflux of tetracycline in cells bearing plasmid r222 was unimpaired even at external tetracycline levels of 1000 μm . the findings were different with minocycline . while an efflux of minocycline was seen at concentrations less than 6 - 7 μm , an active uptake of minocycline was clearly revealed above this level . above 20 μm the active uptake was 100 times the external concentration , nearly equal to the 200 fold factor for susceptible cells . in contrast to these results with r222 , cells harboring pip7 , which had a three - fold lower resistance to tetracycline and a twenty - fold lower resistance to minocycline , showed that active tetracycline efflux in cells disappeared at about 5 μm of tetracycline . as the external level increased , active uptake appeared . however , the amount of tetracycline within the cells remained below that of susceptible cells at the same external concentration ( indicating that the tetracycline efflux was not yet saturated ) until an abrupt step - up which occurred between 250 and 400 μm . active efflux of minocycline in these cells was only below 0 . 6 μm . above this level an active uptake of minocycline was demonstrated . these results demonstrated that the host - mediated active uptake system for the tetracyclines was retained in resistant cells bearing either type of resistance determinant . to ascertain whether each of the tetracyclines would interfere with the efflux system of the other , steady - state accumulation was measured of labeled tetracycline in the presence of unlabeled minocycline and vice versa . cells bearing r222 were used . first , various concentrations of unlabeled minocycline were added with 3 . 4 μm [ 3 h ] tetracycline . at about 10 μm unlabeled minocycline , the efflux disappeared , and at higher minocycline levels an active tetracycline uptake was seen . at 200 μm unlabeled minocycline , the highest concentration tested , the in / out ratio ( ratio of internal to external concentration ) of energized cells was 50 , and of deenergized cells 5 . this demonstrated that minocycline was interfering with the tetracycline efflux system . at about 100 μm unlabeled tetracycline , efflux of [ 14 c ] minocycline ( at 1 . 8 μm ) disappeared and an active uptake appeared , indicating that unlabeled tetracycline could also block the active efflux of minocycline . at 400 μm tetracycline , the highest concentration tested , the in / out ratio of [ 14 c ] minocycline in energized vs . deenergized cells was 30 and 15 respectively , so the minocycline efflux system had only begun to saturate . thus , the efflux of both analogs probably occurred via the same saturable carrier since each analog antagonized the efflux of the other . this finding was further verified by temperature sensitive efflux of both drugs in cells bearing a temperature sensitive tetracycline resistance determinant on r222 . this example has demonstrated that tetracycline and minocycline are accumulated in susceptible cells by both energy - independent and energy - dependent uptake systems . this host - mediated energy - dependent uptake of both analogs was still present in tetracycline - resistant cells . the plasmid - mediated active efflux system previously described for tetracycline also effluxed the more lipophilic analog , minocycline , in resistant cells . in a similar manner competition experiments have been performed which have demonstrated that another tetracycline analog , chlortetracycline , effectively blocked efflux of minocycline via a cryptic efflux system newly discovered in sensitive e . coli cells . this example demonstrates that the minimum inhibitory concentration of tetracycline could be significantly reduced by the addition of subinhibitory levels of the tetracycline analogs . in this example , minocycline hydrochloride ( received from lederle laboratories , n . y . and described above ) and thiatetracycline ( received from e . merck of darmstadt , germany ), an analog of tetracycline , were employed . the level of thiatetracycline resistance in resistant cells is generally 1 % that of tetracycline . e . coli strain d1 - 209 ( described in proc . natl . acad . sci . 77 ( 7 ), supra at 3974 ) was employed for this example . cells used in the uptake experiments were grown from a 530 = 0 . 1 to a 530 = 0 . 8 at 37 ° c . in medium a with 0 . 5 % glycerol as previously described . plasmid bearing cells were induced with 4 μm tetracycline during growth . cells were washed as previously described . the optical density was then reduced to 10 - 5 by dilution of the medium . subsequently , one ml of the dilute cellular stock solution was added to tubes containing various analogs and concentrations . the lowest concentration of antibiotic which prevented turbidity starting from an initial inoculum at a 530 = 10 - 5 was designated the minimal inhibitory concentration . the antibiotic concentrations chosen increased in increments of approximately 15 % of the magnitude of an initial approximate mic . increments began at about 20 % of the mic and terminated at about 200 %. fresh solutions of drugs at 5 mm for minocycline and thiatetracycline and at 40 mm for tetracycline were prepared weekly and stored at - 15 ° c . thiatetracycline was dissolved in ethanol . other chemicals were utilized as described in example i . one ml of the stock solution was added to each tube containing various levels of tetracycline to give the final concentrations . the mic &# 39 ; s for the stock solutions at 17 . 5 hours were 480 μm for tetracycline , 20 μm for minocycline , and 3 . 5 μm for thiatetracycline . addition of 4 μm of minocycline to the tetracycline stock solution produced an mic for tetracycline at 400 μm . addition of 8 μm of minocycline reduced the mic of tetracycline to 320 μm . addition of 0 . 2 μm thiatetracycline into the tetracycline stock solution did not produce a change from the tetracycline mic . however , addition of 0 . 8 μm of thiatetracycline reduced the tetracycline mic to 300 μm . therefore , example iii has confirmed the results of example i by using a subinhibitory concentration of another tetracycline analog in combination with tetracycline . thus , it has been demonstrated that the plasmid - mediated tetracycline - resistance efflux system transports more than one kind of tetracycline . different tetracycline analogs have been demonstrated to have been transported at different rates in example i . since tetracycline is being constantly accumulated within the sensitive or resistant cell , it is only necessary to block the efflux system . similarly , addition of blocking agents such as minocycline and thiatetracycline greatly enhances the effectiveness of tetracyclines on previously resistant microorganisms . these results are in accord with the scope of this invention , which teaches that if tetracycline - type analogs or other products are administered in combination with tetracycline to tetracycline - resistant cells , the analogs or other factors effectively inhibit the efflux of tetracycline allowing normal accumulation of tetracycline within the cell . in addition , lower concentrations of tetracycline were needed to kill resistant cells when tetracycline was administered in combination with tetracycline analogs . thus , if the efflux system of the resistant cell is blocked , the resistant cell reverts to sensitive cell characteristics . | 0 |
the delivery of treating agents such as medicaments , nutritional agents and moisturizers to parts of the body is important for comfort and medical reasons . current systems , as described above , have not entirely met the needs of users . the inventors have found a novel composition which is simple , easy to apply and that may be used to deliver other agents . because the compositions of this invention are long lasting , they allow for the controlled release of additional treating agents . the release of the active agent over a period of time , is an important requirement for many effective treatments . the composition of the invention , though primarily directed toward use with the human body , may also be used in veterinary applications , particularly for mammals . the application of the invention to animals will , of course , require modification of the amounts of ingredients to compensate for different body temperatures and will also require tailoring the amounts of any additional ingredients so that they will be effective . dogs , for example , have a normal body temperature of about 38 . 5 ° c . such modification is within the contemplated scope of the invention and within the ability of those skilled in the art . this invention is concerned with the gelling of the inventive composition in response to temperature , i . e ., thermo - gelling , rather than other factors , since it is a more general characteristic than others , ( i . e . ; it doesn &# 39 ; t vary as greatly throughout the typical mammalian body as do ph and ionic composition ). as used herein , the term “ gel ” is defined as a colloid in which a disperse phase has combined with a continuous phase to produce a viscous , jelly - like product . generally speaking , the disperse phase will be a solid and the continuous phase will be an aqueous liquid . the gels formed according to the present invention may be relatively “ stiff ” and can be characterized as a semisolid containing a certain quantity of water . a colloidal solution with water is often also called a “ hydro - sol ”. as used herein , the term “ themo - gel ” or “ thermo - gelling ” refers to a colloidal system that responds to temperature changes by changing from a liquid to a gel . for purposes of the present invention , the “ thermo - gel ” refers to colloidal systems that change from a liquid to a gel upon an increase in temperature . the colloidal systems of the present invention are different from more well known colloidal systems that change from a liquid to a gel upon a decrease in temperature . the system of this invention uses a thermo - gelling composition that includes a base of water , methylcellulose or hydroxypropyl methylcellulose ( hereinafter referred to collectively as methylcellulose ) and citric acid and salts thereof . desirably , the aqueous liquid is de - ionized water . it is contemplated that water may be combined with small amounts of other compatible liquids such as , for example , glycerin . the thermo - gelling composition is a suitable base to which may be added various “ treating agents ” which may be medicinal agents , cosmetic agents , nutritional agents , adjuvants , moisturizers and other ingredients as desired without appreciably changing the gelling properties of the base . the resulting therapeutic compositions have a wide range of uses and applications . as noted above , temperature responsive or thermo - gelling solutions respond to temperature changes , in this case temperature increases , by changing from a liquid to a gel . the temperature range of interest for the invention is between about 25 and 40 ° c ., more particularly between about 35 and 39 ° c . or still more particularly around that of the human body ( 37 ° c .). compositions that change state at about this temperature are useful because they will remain in a body cavity , for example , after they have been delivered . a liquid would have difficulty in remaining in place in many locations of the body , particular with movement of the individual . therapeutic compositions containing the thermo - gelling base of the invention may be used on any mucosal surface location of the body such as in vaginal , rectal , oral cavity , ophthalmic and nasal locations . it may also be used a topical and transdermal composition and as an injectable in - situ gelling composition for subcutaneous or intramuscular applications to deliver specific medicaments where needed . in the case of injectable applications , after injection , the thermo - gelling composition along with the active ingredients becomes a semisolid gel and forms a drug “ reservoir ” in contact with body fluid and so enables the sustained release of the active ingredients . this approach helps to lower the injection frequency and hence improves patient compliance , which is especially important for drugs currently only available through injection . this includes drugs such as protein / peptide ( e . g . insulin and growth hormones ) drugs , for example . it has also been found that the thermo - gelling composition may be used as a soft tissue replacement in , for example , foot cushions , articular cartilage , and wound dressings . in these applications , the thermo - gelling composition is applied as a liquid to minimize disturbance to the site and to accommodate the configuration of the target site . it then solidifies in situ to provide mechanical support and barrier functionality . methylcellulose ( fig1 ) and hydroxypropyl methylcellulose ( fig2 ) have a polymeric backbone made of cellulose , a natural carbohydrate that contains a basic repeating structure of anhydroglucose units . these polymers are commercially available from a number of sources including the dow chemical company of midland , mich . the inventors have found that the molecular weight of the methylcellulose is important to the success of the composition , particularly that it be relatively low , i . e ., producing a viscosity for a 2 weight percent water solution which should be less than 1000 mpa · s at 20 ° c . methylcellulose concentration should be relatively high , i . e ., between 0 . 5 and 10 weight percent . a solution of methylcellulose may be made in cold water ( about room temperature or below ) by simply mixing the desired amount of methylcellulose in water with mild agitation . alternatively , the methylcellulose may be first dispersed in hot water ( about 50 - 90 ° c . ), and cold water added to the suspension to dissolve the methylcellulose . citric acid ( 2 - hyroxy , 1 , 2 , 3 propanetricarboxylic acid ) is colorless , odorless and acidic tasting . citric acid is also commercially available from numerous manufacturers . citric acid can be in its acid form ( hydrate or anhydrate ) or salt form ( e . g . sodium potassium salts ). it is desired that the thermo - gelling composition of this invention have from a positive amount to about 6 weight percent of citric acid and salts thereof and from about 0 . 5 to 10 weight percent of methylcellulose with the balance water ( preferably de - ionized ) as a base . any optional medicaments , moisturizers and other ingredients may be added as desired . more particularly the citric acid and salts thereof can be present in an amount between a 0 . 5 and 3 weight percent and the methylcellulose in an amount between about 2 and 7 weight percent with the balance water and any medicaments and / or moisturizers . the final composition should have a ph ranging from 2 to 9 . the additional treating agents mentioned above include active agents and medicaments selected generally from the classes of medicinal agents , ( i . e ., pharmaceutically active agents ), cosmetic agents , moisturizers , adjuvants and nutritional agents , as well as other desirable ingredients . the treating agent may be used singly or as a mixture of two or more such agents . exemplary medicinal agents include agents for treating infections such as antibacterial , anti - fungal and antibiotic agents ; for treating cardiovascular conditions such as chlorothiazide ( diuretic ), propranolol ( antihypertensive ), hydralazine ( peripheral vasodilator ), isosorbide or nitroglycerin ( coronary vasodilators ), metoprolol ( beta blocker ), procainamide ( antiarrythmic ), clofibrate ( cholesterol reducer ) or coumadin ( anticoagulant ); agents for treating internal conditions such as conjugated estrogen ( hormone ), tolbutamide ( antidiabetic ), levothyroxine ( thyroid conditions ), propantheline ( antispasmodic ), cimetidine ( antacid ), phenyl propanolamine ( anti - obesity ), atropine or diphenoxalate ( anti - diarrheal agents ), docusate ( laxative ), or prochlorperazine ( antinauseant ); agents for treating mental health conditions such as haloperidol or chlorpromazine ( tranquilizers ), doxepin ( psychostimulant ), phenytoin ( anticonvulsant ), levo dopa ( anti - parkinism ), benzodiazepine ( anti - anxiety ) or phenobarbital ( sedative ); anti - inflammatory agents such as fluorometholone , acetaminophen , phenacetin , aspirin , hydrocortisone , or predisone ; anti - histamines such as diphenhydramine hydrochloride or dexchlorpheniramine maleate ; antibiotics such as sulfanilamide , sulfamethizole , tetracycline hydrochloride , penicillin and its derivatives , cephalosporin derivatives or erythromycin ; chemotherapeutic agents such as sulfathiazole , doxorubicin , cisplatin or nitrofurazone ; topical anaesthetics such as benzocaine ; cardiac tonics such as digitalis or digoxin ; antitussives and expectorants such as codeine phosphate , dextromethorphan or isoproterenol hydrochloride ; oral antiseptics such as chlor hexidine hydrochloride or hexylresorcinol ; enzymes such as lysozyme hydrochloride or dextronase ; birth control agents such as estrogen ; ophthalmic treating agents such as timolol or gentamycin , and the like . in addition , medicinal treating agents may also include whole proteins such as the vp3 capsid protein ( also known as the vpthr and vp1 capsid proteins in other nomenclature systems ) as described in u . s . pat . no . 4 , 140 , 763 , insulin or interferon ; polypeptide treating agents such as endorphins , human growth hormone , or bovine growth hormone , or still lower molecular weight polypeptides or conjugates of those polypeptides linked protein carriers . exemplary cosmetic agents include sunscreens such as p - dimethylaminobenzoic acid or glyceryl p - aminobenzoate , a skin softener such as urea , keratolytic agents such as salicylic acid ; acne treating agents such as benzoyl peroxide or sulfur ; perfumes , and the like . the composition can be used as a moisturizing formulation with or without out pharmaceutically active ingredients . suitable moisturizers are known in the art and include vitamin e , aloe , glycerin , propylene glycol , alpha - hydroxy acid . one or more adjuvants may also be included with another treating agent , and when so used , an adjuvant is included in the meaning of the phrase “ treating agent ” as that phrase is used herein . exemplary of useful adjuvants are chelating agents such as ethylenediaminetetracetic acid ( edta ) that bind calcium ions and assist in passage of medicinal agents through the mucosa and into the blood stream . nutritional agents such as vitamins and / or minerals like riboflavin and iron , respectively , and combinations thereof may also comprise useful treating agents herein . the composition can also include effective amounts of other desirable ingredients ( other than methylcellulose , citric acid , and other active ingredients ) including ph adjusting acids / bases , e . g . hydrochloric acid or sodium hydroxide , tonicity adjusters , e . g . sodium chloride and mannitol , preservatives , e . g . parabens , benzoic acid , and benzalkonium chloride , antioxidants , e . g . ascorbic acid , and polymeric thickeners / viscosity adjusters , e . g ., alginate and chitosan and combinations thereof . if present , these are generally effective in amounts from a positive amount to about 5 weight percent . the treating agent or medicament is present in the compositions of this invention in an amount that is sufficient to prevent , cure and / or treat a condition for a desired period of time for which the composition of this invention is to be administered , and such an amount is referred to herein as “ an effective amount ”. as is well known , particularly in the medicinal arts , effective amounts of medicinal agents vary with the particular agent employed , the condition being treated and the rate at which the composition containing the medicinal agent is eliminated from the body , as well as varying with the species in which it is used , and the body weight of that individual . consequently , effective amounts of treating agents may not be defined for each agent . thus , an effective amount is that amount which in a composition of this invention provides a sufficient amount of the treating agent to provide the requisite activity of treating agent in or on the body of the treated individual for the desired period of time , and is typically less than that amount usually used . since amounts of particular treating agents in the blood stream that are suitable for treating particular conditions are generally known , as are suitable amounts of treating agents used in cosmetics , it is a relatively easy laboratory task to formulate a series of controlled release compositions of this invention containing a range of such treating agents to determine the effective amount of such a treating agent for a particular composition . while the effective amount for all treating agents cannot be stated , typical compositions of this invention may contain about one microgram to about one gram of treating agent per dose administered . the following embodiments illustrate the invention in varying scope . all the following example formulations were tested for their thermogelation property by the inverting - flow test method . in this test method , glass vials ( about 12 . 7 mm diameter ) containing the formulations are maintained at a given temperature for a specific time period , and are then inverted to see the flow behavior . a gel was defined as systems without notable flow by this method . aqueous solutions of 10 weight percent methocel a15lv methylcellulose ( dow chemical ) in de - ionized water were prepared using the hot / cold technique described above . methocel a15lv methylcellulose has a viscosity of 15 mpa · s measured at 2 weight percent concentration in water at 20 c . a 15 weight percent citric acid solution was prepared by mixing 15 . 8 grams citric acid and 4 . 3 grams sodium hydroxide into 85 ml de - ionized water at room temperature . these stock solutions were used in the following examples at varying amounts . the specific solutions were made by mixing the desired amount of the two solutions and then diluting with de - ionized water . the solutions were then kept overnight ( about 18 hours ) at 4 ° c ., then placed in another area at room temperature for 1 hour and finally placed in an oven at 37 ° c . the samples ( about 1 ml ) were in glass vials in the oven for 30 minutes ( table 1 ) and 2 hours ( table 2 ) and then inverted in the oven for two minutes as described above . the results are given in tables 1 and 2 where the methylcellulose concentration ( mc %) is given horizontally across the bottom of each table ( x - axis ), the citric acid concentration is given in the first vertical column ( y - axis ) and the result is in the box at the intersection of the desired solution . as used in the following tables , the term “ gel ” means the solution remained inverted for at least two minutes without running and the term “ not ” means the solution did not gel sufficiently to pass the inverting - flow test . a series of sample solutions were prepared similar to those in example 1 , with different methylcellulose and citric acid concentrations . benzoic acid was added to these samples as a preservative with weight concentration of 0 . 2 %, and all the solutions were adjusted to ph 4 . 0 ± 0 . 1 by naoh . the test was similar to that in example 1 except that a 37 ° c . water bath was used instead of an oven , and the samples were removed from the water bath and held at room temperature for the inversion tests which were done for 5 - 10 seconds instead of 2 minutes because of the reduced testing temperature . the result is shown in table 3 . a series of sample solutions were prepared similar to those in example 1 , with different methylcellulose and citric acid concentrations . methocel a4c methylcellulose ( dow chemical ) was used for these experiments in de - ionized water containing benzoic acid as a preservative at a weight concentration 0 . 2 %. solutions were prepared with differing amounts of citric acid by first dispersing the methylcellulose in hot water between about 50 - 90 ° c . and then adding cold water to dissolve the methylcellulose . methocel a4c methylcellulose has a viscosity of 400 mpa · s measured at 2 weight percent concentration in water at 20 ° c . all the solutions were adjusted to ph 4 . 00 ± 0 . 25 by naoh . a 37 ° c . water bath was used as in example 2 . samples were inverted for 5 - 10 seconds to observe flow behavior . the results are shown in table 4 . the preceding examples show the invention to be effective in gelling at the desired temperature range . such a composition is useful in delivering other desirable compounds to the body and for soft tissue replacement . as will be appreciated by those skilled in the art , changes and variations to the invention are considered to be within the ability of those skilled in the art . examples of such changes are contained in the patents identified above , each of which is incorporated herein by reference in its entirety to the extent it is consistent with this specification . such changes and variations are intended by the inventors to be within the scope of the invention . | 0 |
the “ x ” and “ y ” directions utilized in the “ xy pattern ” of the embossments and apertures of the instant articles are defined as follows . the absorbent article has a longitudinal centerline l which runs along the “ x ” axis , as shown in fig8 , and 10 . the term “ longitudinal ” as used herein refers to a line , axis or direction in the plane of the absorbent article that is generally aligned with ( e . g ., approximately parallel to ) a vertical plane which bisects a standing wearer into left and right body halves when the absorbent article is worn . the “ length ” of the absorbent article is the linear measurement of the absorbent article in the x - direction . the transverse , lateral or “ y direction ”, as used herein , refers to a line , axis or direction that is generally perpendicular to the longitudinal direction . the lateral direction is shown in fig4 , 9 , and 10 as the “ y ” direction . the “ width ” of the absorbent article is the linear measurement of the absorbent article taken in the y - direction . as used herein the “ z ” direction , shown in fig4 is a direction parallel to the vertical plane described above and shown in fig4 . as used herein “ upper ” refers to an orientation in the z - direction toward the wearer &# 39 ; s head . as used herein “ lower ” or downwardly refers to an orientation in the z - direction toward the wearer &# 39 ; s feet . as used herein the “ height ” of the absorbent article is the linear measurement of the absorbent article taken in the z - direction . disclosed herein is a system of feminine protection products designed for and selected by the consumer on the basis of panty styles . there are numerous ways to characterize or categorize panty styles . fig1 is a drawing that provides such a characterization as a function of leg cut and waist height . the first row of panties , which is labeled “ a ”, all have high waists , while their leg cuts become progressively lower as the chart moves to the right . rows “ b ”, “ c ”, and “ d ” each show panties with a progressively lower waist cut , while the height of the leg cut becomes lower to the right . future panty designs may have dimensions between those shown . other considerations include panty crotch dimensions and curvatures , materials used , etcetera . preferred embodiments of the absorbent articles , chosen from the instant systems , are possible because selection of specific newly available absorbent materials , combinations of these absorbent materials and configuration of these materials , allows body fluids delivered to the center of a topsheet to be moved quickly and easily , not only into the interior of the absorbent core but also outward to the periphery of the napkin , where they can be securely stored . such performance allows the design of sanitary napkins to be based on physical measurements of specific panty styles for improved fit , comfort and aesthetics , while maintaining excellent absorbency . regardless of the panty styles on the market at any given time , a system of selecting feminine hygiene products , based on a predetermined range of panty styles , enables a consumer to quickly and accurately determine which feminine hygiene product will provide optimum fit . below is a chart illustrating five styles of panties , categorized by 1 ) crotch dimensions taken at three places in the crotch area of the panty ( minimum crotch width , front crotch width and back crotch width , 2 ) rise , 3 ) side seam width and 4 ) leg cut . the front and back crotch width was measured 90 mm from minimum crotch width . while the five styles illustrated below are among the most widely distributed , other variations are currently marketed . style a style b style c style d style e minimum crotch width , mm average / st dev 55 67 / 8 66 / 8 70 / 8 69 / 9 range 47 - 68 55 - 83 52 - 78 56 - 90 48 - 85 front * crotch width , mm average 115 133 / 24 149 / 32 130 / 15 175 / 36 range 102 - 150 89 - 198 109 - 210 96 - 160 127 - 250 back * crotch width , mm average 28 170 / 28 191 / 44 170 / 32 188 / 47 range 24 - 37 125 - 222 120 - 290 103 - 295 124 - 320 rise , mm average not 239 / 17 256 / 17 299 / 23 336 / 33 range available 270 - 210 225 - 295 250 - 350 220 - 413 side seam width , mm average not 53 / 18 91 / 28 74 / 17 205 / 34 range available 25 - 81 35 - 130 40 - 105 133 - 278 leg cut , mm average 272 186 / 24 165 / 32 225 / 21 134 / 38 range 213 - 329 238 - 140 120 - 230 172 - 280 70 - 255 variation in feminine hygiene product design in the past was based on body size and / or the level of absorbency , which was required to prevent body exudates from leaking onto the wearer &# 39 ; s garments . the sanitary napkin design embodiments disclosed by this specification are , primarily , based on the design of the wearer &# 39 ; s panty . for example , both absorbent core and wing shape and dimensions are contoured to the panty crotch dimensions . style a , from the table above , referred to as “ thong ” style in the u . s ., tends to have a high waist and sharply cut leg openings in the front with minimal coverage in the back . sanitary napkins and panty liners , designed for style a panties and disclosed in this specification , are designed to be wider in the front and very narrow in the back to accommodate the extremely narrow back configuration of this type of panty . when “ wings ” are utilized on style a napkins they are designed to accommodate the very narrow crotch and large leg openings which are typical of this panty style . referring to fig3 panty “ a ” illustrates a thong . style b , referred to as “ bikini ” style in the u . s ., tends to have a low rise at the waist and narrow side seams . examples of style b panties are illustrated in fig2 as panties 7 and 8 . typically , sanitary napkins designed for style b panties are shorter and narrower due to the fact that this style is used more frequently by smaller women . as with the napkins designed for style a panties , wing design is based on crotch contour . style c , referred to as “ hipster ” in the u . s . has a moderate rise and moderate side seams . examples of style c panties are shown in fig2 as panties 5 and 9 . style d , known as “ french cut ” or “ high cut ” in the u . s ., is characterized by a high rise at the waist and high cut leg openings . examples of style d are shown in fig2 as panties 1 and 4 . back views of examples of style d are illustrated in fig3 as panties d and e . a significant percentage of women of all sizes and ages wear panties of style d . style e panties , which are referred to as “ briefs ” in the u . s ., have the highest rise at the waist and the lowest leg cut openings combined with a wide / symmetrical crotch . examples of typical style e panties are shown in fig2 as panties 2 , 3 , and 6 . a back view of a style e panty is shown in fig3 as panty f . larger , older women are most likely to wear brief style panties . feminine hygiene products designed for briefs optimally have front and back core widths , which are essentially symmetrical to follow the panty crotch shape . such products preferably include a 3 - dimensional height element to allow the product to be held in closer proximity to the body , since the lower leg cut and high rise tend to locate the panty crotch further away from the body . as mentioned above , due to the materials and processes now available these sanitary napkin styles have shapes dictated , not by the necessity to place maximum amounts of absorbency in the center of the napkin , but rather by the style of panty preferred by the user . fig8 through 10 illustrate napkins designed for thong , french cut ( also referred to as high cut ), and bikini panties . the perimeter of the napkins closely follows the panty perimeter in the crotch areas , those areas of the napkin away from the panty crotch are designed to maximize storage . these new designs , while they vary according to panty style , are typically narrow at the front of the napkin and wider toward the rear . because of the superior fluid handling abilities of the materials utilized in preferred embodiments of the instant napkins , absorbed fluids are transported away from the site at which they are first deposited onto the napkin to be stored at the ends . therefore , storage capacity need not be concentrated in the crotch area as in the past . absorbent articles comprise an absorbent core , which provides the means for absorbing body fluids , with the optional addition of a topsheet , backsheet , side wrapping elements etc . the absorbent core can comprise any material used in the art for such purpose . non - limiting examples include natural materials , including comminuted wood pulp , which is generally referred to as airfelt , creped cellulose wadding , hydrogel - forming polymer gelling agents , modified cross - linked cellulose fibers , absorbent foams , absorbent sponges , synthetic staple fibers , polymeric fibers , peat moss or any equivalent material or combinations of materials . in a preferred embodiment , the absorbent core comprises an absorbent open cell foam . in a more preferred embodiment , the absorbent core comprises an open cell foam of the “ high internal phase emulsion ” ( hipe ) type . in a particularly preferred embodiment , the absorbent core is comprised of a “ thin after drying ” ( tad ) hipe foam absorbent material . such foam absorbent materials have cells and holes small enough to provide a high capillary absorptive pressure but large enough to prevent or minimize blockage by the insoluble components of blood and blood - based liquids such as menses . this structure provides foam materials capable of absorbing such liquids and then moving these absorbed liquids efficiently to other regions of the foam . the fluid pervious topsheet , when present , is in close proximity to the skin of the user . the topsheet is preferably as compliant , soft feeling and non - irritating to the user &# 39 ; s skin as possible . the topsheet should further exhibit good strikethrough and a reduced tendency to rewet , permitting bodily discharges to rapidly penetrate it and flow toward the core , but not allowing such discharges to flow back through the topsheet to the skin of the wearer . the topsheet is preferably well integrated with the absorbent core , for example , through ultrasonic bonding or commingling of the materials used in the topsheet and the absorbent core . the backsheet prevents the exudates absorbed and contained in the absorbent core from wetting articles , which contact the sanitary napkin . the backsheet may comprise a woven or nonwoven material , polymeric films such as thermoplastic films of polyethylene or polypropylene , or composite materials such as a film coated nonwoven material . the backsheet is preferably impervious to liquids , but may permit vapors to escape from the absorbent core ( i . e . breathable ). a preferred feature of the articles of the instant invention is a side wrapping element which varies according to the curve of the perimeter of the crotch area for each panty style . use and placement of elastics is dependent upon the panty style . fig8 - 10 illustrate side wrapping elements which vary by panty type , and are particularly designed for the panty crotch style . an example of a sanitary napkin designed for use with a thong panty is shown in fig8 . the front portion of the sanitary napkin 81 is designed to correspond to the front crotch area of the thong . the rear portion of the sanitary napkin 82 is narrower to correspond to the thong &# 39 ; s distinctive back . 83 indicates the side wrapping element . an example of a sanitary napkin designed for use with a bikini panty is shown in fig9 . the front portion of the sanitary napkin 91 is designed to correspond to the front crotch area of the panty . the rear portion of the sanitary napkin is indicated as 92 . 93 indicates the side wrapping element . an example of a sanitary napkin designed for use with a high cut panty is shown in fig1 . the front portion of the sanitary napkin 101 corresponds to the front crotch area of the panty . the rear portion of the sanitary napkin is indicated as 102 . 103 indicates the side wrapping element . | 0 |
fig1 shows a tie rod 1 of a wheel suspension . the wheel suspension itself is not shown . the operation and attachment of the tie rod 1 is known , for which reason no details thereof will be given here . the tie rod 1 is formed by two rod parts 2 and 3 . the rod part on the left in the plane of the drawing , i . e . the first rod part 2 , has a compensating space 4 , which is of cylindrical design when viewed in longitudinal section and is open at one end , e . g . toward the right - hand plane of the drawing . the compensating space 4 is filled with a compensating medium , preferably a fluid , more preferably a hydraulic oil . to seal off the compensating space 4 , a cap - type cover 6 is provided , said cover being described in greater detail below . the engagement end 7 of the other , i . e . second , rod part 3 , which is on the right in the plane of the drawing , passes through the cap - type cover 6 and reaches into the compensating space 4 . by way of example , the engagement end 7 has a piston rod 8 that has a flange 9 at the end , said flange having an effective piston surface 11 and an annular surface 12 on the opposite side therefrom . the piston rod 8 has a smaller diameter than the rest of rod part 3 . by way of example , a ball joint 13 is arranged on rod part 3 , at the opposite end from the engagement end 7 , but the way in which the first rod part 2 is attached is not shown . as illustrated , the compensating space 4 is bounded by a wall 14 . a connecting element 16 , preferably embodied as a duct 16 , is formed in the wall 14 . the duct 16 can be drilled . the duct 16 is arranged at the opposite end from the open side of the compensating space 4 , which is closed by means of the cap - type cover 6 . connected to the duct 16 is a switching element 17 which , for its part , is connected to a medium reservoir 18 , for which purpose a connecting duct 19 is provided . the switching element 17 can be embodied as a solenoid valve 17 . a pressurization element 21 is arranged in the medium reservoir 18 . by way of example , the pressurization element 21 has a spring - loaded pressure plate 22 , which is fixed on a wall of the medium reservoir 18 in such a way that it can be moved axially by means of an energy accumulator 23 or spring 23 in the direction of or counter to the spring force , i . e . in the direction of the connecting duct 19 or away from the latter . the cap - type cover 6 has a central opening 27 and two contact lips 24 and 26 spaced apart in the vertical direction when viewed in longitudinal section . in the illustrative embodiment depicted , an inner contact lip 24 is longer when viewed in the axial direction than the outer contact lip 26 . it is , of course , also possible for both contact lips 24 , 26 to be of the same length or for the outer lip to be longer than the inner lip . the spacing between the two contact lips 24 and 26 can preferably be made such that the cover 6 is fixed in a manner which is sufficiently leaktight and secure in terms of position , taking into account also the prevailing internal pressure , through contact between the contact lips 24 and 26 and the respective sides of the wall of the compensating space 4 . the cap - type cover 6 can simply be pushed or screwed onto the first rod part 2 . the inner contact lip 24 serves inter alia as a guide for the piston rod 8 , with a longer length improving guidance — the length of the outer contact lip 26 , on the other hand , can be designed for adequately firm seating of the cap - type cover 6 . the central opening 27 has a passage with two passage sections 28 and 29 . a first passage section 28 extends from the outside inward and merges stepwise into a second passage section 29 , which opens into the interior of the compensating space 4 . the first passage section 28 has a smaller clear diameter than the second passage section 29 relative to a center line x of the tie rod 1 . in a preferred embodiment , the diameter of the first passage section 28 is matched to an outer circumference of the engagement end 7 or piston rod 8 thereof in such a way that sealing is possible even when the piston rod 8 is moving axially . it is , of course , also possible to provide additional sealing measures , e . g . sealing lips . by way of example , an annular gap 31 is arranged between the outer circumference of the piston rod 8 and the inside diameter of the second passage section 29 . of course , the cap - type cover 6 can be embodied with a central opening which has just one passage section of constant diameter , which case the diameter should then be matched to the outer circumference of the piston rod 8 to ensure sealing , and secondary sealing measures can be provided if this is required . the cap - type cover 6 can be formed from a suitable material , e . g . from a plastic . it is possible to embody the cap - type cover 6 in several parts and to combine them into a single component including the piston rod 8 . it is also conceivable first of all to introduce the piston rod 8 into the compensating space 4 , to push on the cap - type cover 6 onto the piston rod 8 from the free end of the latter , and then to connect the piston rod 8 to the rest of the second rod part 3 , e . g . by welding , adhesive bonding or some other suitable connecting method . fig1 shows an assembled condition of the two rod parts 2 and 3 , in which the tie rod 1 can advantageously adapt its compliance virtually automatically , in particular as a function of a vehicle speed . on the one hand , the pressurized medium reservoir 18 serves to accommodate the compensating medium displaced from the compensating space 4 . the switching element 17 is then arranged between the compensating space 4 and the medium reservoir 18 . the medium reservoir 18 is advantageously pressurized by means of the pressurization element 22 . under the action of a spring force , the pressure plate 23 tends to push the compensating medium back into the compensating space 4 . by means of the interaction between the medium reservoir 18 , the compensating space 4 , the pressurization element 23 and the switching valve 17 , the adjustable springiness or compliance of the tie rod 1 can be set to match the application , preferably according to the differing speeds of the vehicle . the engagement end 7 , which enters the compensating space 4 , or the effective piston surface 11 thereof displaces the compensating medium transferred to the medium reservoir 18 by the switching element 17 or solenoid valve 17 . the pressurization of the medium reservoir 18 , on the other hand , means that the compensating fluid has a tendency to push back through the switching element 17 into the compensating space 4 . if the pressurization of the medium reservoir 18 is greater than the tendency of the engagement end 7 of the tie rod 1 to enter the compensating space 4 , the engagement end 7 is pushed back out of the compensating space 4 , and the tie rod returns to the initial position / design position , which is preferably defined by the inner contact lip 24 . the advantage of the inner contact lip 24 is evident here , it being possible for the axial extent thereof to be dimensioned such that the initial position / design position of the tie rod 1 can be set in a defined manner by limiting the possible axial movement . provision is preferably made for the switching element 17 or solenoid valve to be switched only in an on / off manner . here too , the movement limitation provided by the inner contact lip 24 is extremely advantageous . it would thus be possible to provide for switching of the switching element at a predetermined speed . it would be possible to bring this about by connection to a control unit or to the already existing central control unit of the vehicle , in which a large number of data can be collected , and which could generate an appropriate switching signal for the switching element . fundamentally , the design position or initial position , i . e . the length of the tie rod 1 , has to be maintained for reasons connected with steering kinematics . holding the piston rod 8 fast at a position other than the defined design position would produce an unwanted constant change in the steering angle , even without the action of a transverse force . purely on the basis of external transverse forces during steering at high speed , an activatable compliance can be permitted according to the &# 39 ; invention . retraction of the piston rod 8 against the spring pressure produces a desired countersteering effect . to this extent , activation / deactivation of the switching element is preferred . however , it is also possible to produce advantageous variable damping behavior through stepwise / stepless variation of the aperture cross section in the switching element 17 . however , the switching element 17 should always be slightly open for return flow , i . e . not completely closed , to enable the link , i . e . the tie rod to be pushed back as quickly as possible , that is to say virtually immediately , into the design position , in a manner defined by the inner contact lip 24 , in the case of an equilibrium of forces between a declining transverse force ( e . g . transition from cornering to straight ahead travel ) and the spring force in the medium reservoir 18 . the spring force of the tuning parameters is advantageous here for transverse force understeer of the desired intensity . the lockable oil column is used as a medium for transmitting force to the piston or piston rod 8 . of course , the gaps that can be seen in fig1 between the pressure plate 22 and the medium reservoir 18 are sealed off or capable of being sealed off . | 1 |
one possible overall arrangement of an elevator installation utilizing the device according to the present invention is illustrated in fig1 . the illustrated elevator installation requires a temporary protective space at both ends ( upper end 4 a and lower end 4 b ) of a car travel path . a car 1 is provided with a car safety brake device 5 acting at both sides . the car safety brake device 5 is actuated by a speed limiter 9 by way of an associated actuating unit 6 for the safety brake device 5 and a speed limiter cable 10 in the case of excess speed of the car 1 . the actuated car safety brake device 5 brings the car 1 to a standstill . according to the present invention , an abutment 13 is fastened in the speed limiter cable 10 . a first stop device 14 is fastened at the top , and a second stop device 17 at the bottom , in a shaft 4 . as shown in fig2 and 3 , forks 15 at the top and bottom stop devices 14 , 17 are brought by an actuating element 16 into a stopping position s or into an open position o . in the open position o , the abutment 13 can pass the stop devices 14 , 17 unhindered . thus , the car 1 can reach the end positions provided in accordance with the elevator installation . in the stopping position s , the abutment 13 is limited in its travel path by the stop devices 14 , 17 . the abutment 13 fastened to the speed limiter cable 10 , on reaching one of the stop devices 14 , 17 , stops the speed limiter cable 10 , which thus actuates the car safety brake device 5 and necessarily leads the car 1 to a standstill . the car 1 can no longer reach the end positions of the shaft 4 . the requisite temporary protective spaces 4 a , 4 b at the lower and upper ends respectively of the car travel path are thus provided . the illustrated solution gives an economic possibility for securing the requisite temporary protective space . it is simple to install and the function can be visually checked at any time by the maintenance personnel , since the setting of the stop devices 14 , 17 is readily apparent visually . in a preferred version , each of the stop devices 14 , 17 is additionally designed in such a manner , as shown in fig2 and 3 , that it can apply the required actuating force in only one travel direction and does not obstruct movement in the opposite travel direction . this allows that a special monitoring unit does not have to observe the location of the car 1 on movement out of the stop devices 14 , 17 . if , for example , the car 1 is disposed at the lowermost stop when the stop device 17 is moved out , i . e . within the space 4 b to be protected , the stop device 17 nevertheless can be moved out to the stopping position s . a risk does not thereby arise , since access to the shaft pit is blocked via the car 1 standing at the lowermost stop . however , the car 1 can now be moved at low speed to outside the protective space 4 b without this being prevented by the stop device 17 . however , after travelling past the stop device 17 in the opposite direction return travel into the protective space 4 b is prevented . the advantage of this solution is to be seen in that on the one hand the elevator installation can be moved in a simple manner for maintenance purposes , but , also in evacuation operation , the evacuation is not prevented by the illustrated solution . in a preferred version , the abutment 13 is , as illustrated in fig1 , arranged in a counter run 10 a of the speed limiter cable 10 . this has the advantage that a large measure of freedom exists in placement of the stop devices 14 , 17 , since there is no collision with the actuating unit 6 of the safety brake device 5 . alternatively , the abutment 13 is connected together with a coupling point 7 at the actuating unit 6 of the safety brake device 5 to form a subassembly . in the individual case this enables a better possibility of placement of the stop devices 14 , 17 . the abutment 13 is constructed , as shown in fig5 by way of example , in the form of a cylinder with rounded end regions . it is clamped onto the speed limiter cable 10 in the counter run 10 a of the speed limiter cable 10 or forms , together with the coupling point 7 , a subassembly . the embodiment shown in fig5 , without a specific resilient characteristic , is primarily suitable for car safety brake devices 5 with a blocking function . this embodiment is particularly economic to realize and simple to install . in the case of an alternate embodiment abutment 13 ′ shown in fig6 , opposed abutment ends 22 are connected with an abutment block 20 by means of biased springs 21 . the abutment block 20 is clamped onto the speed limiter cable 10 in the counter run 10 a of the speed limiter cable or forms , together with the coupling point 7 , a subassembly . the abutment ends 22 and springs 21 are guided in a guide 23 . this embodiment makes possible for the speed limiter cable 10 , after actuation of the car safety brake device 5 , a further movement in correspondence with the stopping travel of the car 1 , wherein the abutment ends , after resetting of the car 1 into the shortened shaft region , automatically return to the starting setting . this embodiment is preferably suitable for car safety brake devices 5 with a braking characteristic ( braking safety brake devices ). the stop devices 14 , 17 are preferably constructed , as shown in fig4 , in the form of a fork 15 . the fork 15 in the stopping position s of the stop device 14 , 17 encloses the speed limiter cable 10 on three sides . the speed limiter cable 10 is thereby substantially guided . this embodiment is economic and simple to execute . if the fork 15 of the stop device 14 , 17 is supported , for example as shown in fig3 , by means of a resilient element on the shaft wall support , there is similarly made possible for the speed limiter cable 10 a further movement in correspondence with the stopping travel of the car 1 . the proposed construction allows the fork 15 to push back into the desired setting as soon as the car 1 is reset into the shortened shaft region . the position of the stop device 14 , 17 is , as illustrated in fig2 and 3 , preferably controlled in each instance by the actuating element 16 in the form of a stroke magnet . this enables a reliable and cost - optimal actuation of the stop devices 14 , 17 in correspondence with the desired control . if a car safety brake system acting at both sides is used , a respective stop device is employed for limiting the travel path in both end zones . in the case of fastening of the abutment 13 in the counter run 10 a , the stop device 14 installed in the upper shaft region is , as shown in fig1 , 2 and 3 , used for furnishing a temporary protective space at the bottom and in the case of a corresponding requirement the stop device 17 is selectively employed in the lower shaft region for furnishing a temporary protective space at the top . the association is correspondingly changed with the arrangement of the abutment 13 at the coupling point 7 . the optional use of the stop devices 14 , 17 allows a solution , which is appropriate to requirements and thus cost - efficient , for furnishing a temporary protective zone . the parts required for furnishing a temporary protective zone , such as the abutment 13 , one or more stop devices 14 , 17 and switching elements , can be mounted in a simple manner in the elevator installation . the function is readily apparent . the device according to the present invention is suitable for existing installations and also for new installations . the stopping position s of the abutments 14 , 17 is electrically monitored ( not illustrated in the figures ). a normal travel is thus prevented in the stopping position s . on actuation of the car safety brake device 5 , a safety contact of the car safety brake device 5 is necessarily opened , which leads to an electrical switching - off of the drive . a provided evacuation device ( not shown ) enables a return movement of the car from the overrun zone into the shortened shaft region . a rapid evacuation of trapped persons is thereby possible . several possibilities exist for controlling or switching the stop device for the stop devices 14 , 17 . the stop devices 14 , 17 are advantageously moved out on manual opening of a shaft closure , for example for carrying out maintenance operations within the shaft 4 . a resetting of the stop devices 14 , 17 can be undertaken only from outside the shaft 4 by an authorized person . checking of the authorization is carried out by known elements such as a key , input of a code or a similar method . alternatively , the resetting can be blocked by additional systems such as , for example , detectors of a presence in the shaft space . in the case of multiple shafts , the stop devices 14 , 17 can additionally be checked by monitoring of the intermediate barriers . the intermediate barriers are , for example , gratings which are installed between two adjacent car travel paths and which are usually provided with passage openings . with knowledge of the present invention the elevator expert can change the set forms and arrangements as desired . for example , the illustrated pivot format of the stop devices can also be replaced by a thrust format or there can be used , for switching the stop device , apart from stroke magnets , also other mechanical elements such as , for example , bowden pulls , or electromagnetic elements such as , for example , setting motors , other electromagnets or further elements . in accordance with the provisions of the patent statutes , the present invention has been described in what is considered to represent its preferred embodiment . however , it should be noted that the invention can be practiced otherwise than as specifically illustrated and described without departing from its spirit or scope . | 1 |
the following examples illustrate the invention . in the following examples and , if applicable , in the description above , the abbreviations of chemical names have the following meanings : edci : 1 -( 3 - dimethylaminopropyl )- 3 - ethylcarbodiimide , hobt : 1 - hydroxybenzotriazole , dbu : 1 , 8 - diaza - bicyclo -[ 5 , 4 , 0 ]- undec - 7 - ene , tnoc : 8 , 9 - difluoro - 3 - methyl - 6 - oxo - 2 , 3 , 3a , 6 - tetrahydronaphtho -[ 1 , 8 - de ][ 1 . 3 ] oxazine - 5 - carboxylic acid , acn : acetonitrile , thf : tetrahydrofurane , dmf : dimethylformamide , lihmds : lithium - hexamethyldisilylazide , dmap : dimethylaminopyridine , tfa : trifluroacetic acid , boc : tert - butoxycarbonyl , cbz : benzyloxycarbonyl ms : mass spectrum , esi + : positive ion electrospray ionization . nmr : the spectra were determined on spectrometers of the 300 or 400 mhz type , the proton and carbon spectra being respectively recorded at 300 and 75 mhz or 400 and 100 mhz , in solution in cdcl 3 , or dmso - d 6 , meoh - d 4 . the values recorded are expressed in δ ( ppm ) and represent the s , d , t , quad , dd and m values . the constant jab is expressed in hz . unless otherwise indicated , the reactions are carried out under dry inert gas and at ambient temperature . “ general method a ” ( coupling ) consists of reacting the product “ tnoc ” ( 1 . 0 equivalent ) and the aminated derivative in suspension in pyridine ( 0 . 2m ) in a sealed chamber overnight at 120 ° c . under stirring . the solvent is evaporated off and toluene and / or methanol are added . after concentration to dryness , the crude product is triturated in methanol and separated then dried . “ general method b ” ( boc deprotection ) consists of adding a large excess of tfa to a solution in dichloromethane at 0 ° c . of protected amino derivative ( n - boc ). the reaction is carried out at ambient temperature and followed by chromatography over silica . the solution is concentrated to dryness and toluene and / or methanol are added . the crude product is obtained in the form of a trifluoroacetate . “ general method c ” ( peptide coupling ) consists of adding 1 . 2 to 2 . 0 equivalents of edci and 1 . 2 to 2 . 0 equivalents of hobt or dmap and 1 . 2 to 2 . 0 equivalents of heteroaryl carboxylic acid , at 0 ° c ., to a 0 . 2 to 0 . 6m solution within dmf of protected amino ( piperidine ) derivative n - boc or n - cbz . the mixture is maintained under stirring at ambient temperature for 16 to 18 hours , then diluted with ethyl acetate and washed with water . the solution is then dried and concentrated to dryness under reduced pressure , then the residue is purified by chromatography over silica eluting with the cyclohexane - ethyl acetate mixture . in a sealed tube , 40 ml of dry toluene was degazed with argon during 15 minutes , palladium acetate ( 165 mg , 0 . 24 mmol , 0 . 04 eq .) and racemic - 2 , 2 ′- bis ( diphenylphosphino )-, 1 ′- binaphthyl ( 152 mg , 0 . 24 mmol , 0 . 04 eq .) were added and the mixture was degazed with argon for 10 minutes . then 2 - chloropyrazine ( 700 mg , 6 . 11 mmol , 1 . 0 eq . ), 3 - aminomethyl - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 1 . 5 g , 7 . 33 mmol , 1 . 2 eq .) and sodium tert - butoxide ( 822 mg , 8 . 55 mmol , 1 . 4 eq .) were added and the mixture was stirred at 70 ° c . overnight . the reaction was concentrated in vacuum . the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 1 : 1 to 0 : 1 ) to afford a mixture of 3a and 3b ( 900 mg , 2 : 1 , over yield 38 %). the mixture of 3a and 3b ( 900 mg ) was dissolved in dichloromethane ( 25 ml ) and trifluoroacetic acid ( 3 ml ) was added . the mixture was stirred at room temperature for 6 hours . the reaction was concentrated in vacuum and co - evaporated with toluene and methanol . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 7n nh 3 methanol ( gradient from 5 % to 100 % of 7n nh 3 methanol ) 4a and 4b were separated during the flash chromatography purification to afford quantitatively 4a and 4b as colorless oils . 4a : ms ( esi + ) (+ 0 . 1 % hcooh ): 179 . 21 [ c 9 h 14 n 4 + h ] + ( m / z ) 4b : ms ( esi + ) (+ 0 . 1 % hcooh ): 257 . 14 [ c 13 h 16 n 6 + h ] + ( m / z ) step c : preparation of 8 - fluoro - 3 - methyl - 6 - oxo - 9 -[ 3 -( pyrazin - 2 - ylaminomethyl )- pyrrolidin - 1 - yl ]- 2 , 3 - dihydro - 6h - 1 - oxa - 3 , 3a - diazaphenalene - 5 - carboxylic acid ( 5a ) in a sealed tube , 8 , 9 - difluoro - 3 - methyl - 6 - oxo - 2 , 3 , 3a , 6 - tetrahydronaphto [ 1 , 8 - de ][ 1 , 3 ] oxazine - 5 - carboxylic acid — tnoc -( 200 mg , 0 . 71 mmol , 1 . 0 eq .) and 4a ( 447 mg , 2 . 51 mmol , 3 . 53 eq .) were suspended in 3 ml of dry pyridine and 1 ml of n - methylmorpholine . the reaction mixture was stirred at 120 ° c . for 16 hours . the reaction was cooled to room temperature and the precipitate was filtered . the precipitate was triturated with dichloromethane and methanol and then evaporated . the residue was sonicated in ethanol , refluxed and then filtrated to afford the title compound as a yellow solid ( 275 mg , 74 %) hplc ( gradient 20 % to 80 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 441 . 2 [ c 21 h 21 fn 6 o 4 + h ] + ( m / z ) the compound 5b was obtained from tnoc ( 180 mg , 1 . 0 eq .) 4b ( 330 mg , 1 . 29 mmol , 2 . 02 eq .) following the procedure described for the preparation of 5a . the mixture was evaporated and co - evaporated with toluene , sonicated with ethanol , refluxed and filtrated to afford the title compound as a yellow solid ( 145 mg , 43 %). hplc ( gradient 20 % to 80 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 519 . 0 [ c 25 h 23 fn 8 o 4 + h ] + ( m / z ) utilizing the procedure described for the preparation of 3b except substituting 2 - chloropyrazine for 2 - chloropyridine ( 4 . 4 mmol ). the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 1 : 1 to 2 : 8 ) the title compound was obtained as a colorless oil ( 0 . 5 g , 32 %). 3c ( 1 . 4 g , 3 . 9 mmol ) was dissolved in dichloromethane ( 40 ml ) and 4n hcl in dioxane ( 10 ml ) was added . the mixture was stirred at room temperature for 4 hours . the reaction was concentrated in vacuum . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 7n nh 3 in methanol ( gradient from 5 % to 20 % of 7n nh 3 in methanol ). the title compound was obtained as colorless oil ( 0 . 7 g , 70 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 255 . 15 [ c 15 h 18 n 4 + h ] + ( m / z ) the compound 5c was obtained from tnoc ( 259 mg , 0 . 92 mmol , 1 . 0 eq .) and 4c ( 700 mg , 2 . 76 mmol , 3 . 0 eq .) in 5 ml of pyridine and n - methyhnorpholine ( 0 . 2 ml , 1 . 84 mmol , 2 . 0 eq .) following the same procedure described for 5b . the mixture was evaporated , the residue was triturated in water and the precipitate was filtrated . the solid was triturated with methanol and filtrated . the crude residue was purified by preparative tlc purification eluting with dichloromethane and 5 % of methanol to afford the title compound as a yellow solid ( 249 mg , 52 %) hplc ( gradient 5 % to 80 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 517 . 14 [ c 27 h 25 fn 6 o 4 + h ] + ( m / z ) to a 0 ° c . solution of the commercially available 3 - hydroxymethyl - pyrrolidine - 1 - carboxylic acid tert - butyl ester 6 ( 1 . 5 g , 7 . 19 mmol , 1 . 2 eq . prepared according wo2007 / 21982 ) in dry thf ( 25 ml ), triphenylphosphine ( 2 . 4 g , 8 . 98 mmol , 1 . 5 eq .) was added . after complete dissolution , diethylazodicarboxylate − 40 % w / v in toluene -( 4 ml , 8 . 98 mmmol , 1 . 5 eq .) was added dropwise followed by thiazol - 2 - yl - carbamic acid tert - butyl ester 7a ( 1 . 2 g , 5 . 99 mmol , 1 . 0 eq .). the mixture was stirred at room temperature for 18 hours . the reaction was evaporated under reduced pressure . the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 9 : 1 to 8 : 2 ) to afford 8a as a colorless gum ( 1 . 95 g , 85 %) 8a ( 1 . 95 g , 5 . 08 mmol , 1 . 0 eq .) was dissolved in ethyl acetate ( 10 ml ) and 4n hcl in dioxane ( 10 ml ) was added . the mixture was stirred at room temperature for 6 hours . the reaction was concentrated in vacuum . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — methanol ( gradient from 5 % to 10 % methanol ) then dichloromethane — 7n nh 3 in methanol ( gradient from 4 % to 70 % of 7n nh 3 in methanol ). the title compound was obtained as a colorless oil ( 915 mg , 95 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 184 . 23 [ c 8 h 13 n 3 s + h ] + ( m / z ) following the procedure described for the preparation of 5a , 10a was obtained from tnoc ( 450 mg , 1 . 59 , 1 . 0 eq .) and 9a ( 915 mg , 5 . 0 mmol , 3 . 1 eq .) to afford the title compound as a yellow solid ( 421 mg , 60 %). an analytical sample was obtained by preparative tlc purification eluting with dichloromethane — methanol ( gradient from 2 . 5 % to 5 % of methanol ). hplc ( gradient 5 % to 80 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 446 . 1 [ c 20 h 20 fn 5 o 4 s + h ] + ( m / z ) 5 - methyl -[ 1 , 3 , 4 ] oxadiazol - 2 - ylamine ( 500 mg , 5 . 04 mmol , 1 . 0 eq .) was dissolved in 5 ml of dry pyridine and di - tert - butyl dicarbonate ( 1 . 1 g , 5 . 04 mmol , 1 . 0 eq .) was added , the mixture was stirred at 70 ° c . for 16 hours . the reaction was evaporated and co - evaporated with toluene . the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 9 : 1 to 0 : 1 ) to afford 7b ( 513 mg , 51 %) as a white solid . compound 8b was obtained following the procedure described in the preparation of 8a except substituting 7a for 7b . the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 9 : 1 to 1 : 1 ) to afford 8b as sticky oil ( 1 . 7 g , contaminated with mitsunobu reagents ). utilizing the procedure described in the preparation of 4a - 4b except substituting 3a - 3b for 8b , the title compound was obtained as a colorless oil ( 180 mg , 21 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 183 . 27 [ c 8 h 14 n 4 + h ] + ( m / z ) utilizing the procedure for the preparation of 5b , 10b was obtained with tnoc ( 140 mg , 0 . 49 mmol , 1 . 0 eq .) and 9b ( 180 mg , 0 . 98 mmol , 2 . 0 eq .). an analytical sample was obtained by preparative tlc purification eluting with dichloromethane — methanol ( gradient from 2 . 5 % to 5 % of methanol ) to afford the title compound as a yellow solid ( 76 mg , 34 %). hplc ( gradient 5 % to 80 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 446 . 9 [ c 20 h 21 fn 6 o 5 + h ] + ( m / z ) to a 0 ° c . solution of furan - 2 - carboxylic acid ( 1 . 1 g , 9 . 81 mmol , 1 . 3 eq .) in dry dmf ( 20 ml ) were added edc ( 1 . 88 g , 9 . 81 mmol , 1 . 3 eq .) and hobt ( 1 . 32 g , 9 . 81 mmol , 1 . 3 eq .). the mixture was stirred at room temperature for 20 minutes and 1 ( 1 . 1 g , 9 . 81 mmol , 1 . 0 eq .) was added . the reaction was stirred at room temperature for 16 hours . the mixture was diluted with ethyl acetate and washed first with water and then with a saturated aqueous nahco 3 solution , the organic extracts were dried over anhydrous magnesium sulphate and were evaporated under reduced pressure . the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 8 : 2 to 1 : 1 ) to afford 11 ( 1 . 8 g , 81 %) as a colorless gum . utilizing the procedure described in preparation of 4a - 4b except substituting 3a - 3b for 11 , the title compound was obtained as a colorless oil ( 1 . 0 g , 85 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 195 . 19 [ c 10 h 14 n 2 o 2 + h ] + ( m / z ) utilizing the procedure for the preparation of 5a , 13 was obtained from tnoc ( 520 mg , 1 . 84 mmol , 1 . 0 eq .) and 12 ( 1 . 0 g , 5 . 55 mmol , 3 . 0 eq .). the mixture was evaporated and co - evaporated with toluene , sonicated with methanol , refluxed and filtrated to afford the title compound as a yellow solid ( 645 mg , 78 %). hplc ( gradient 5 % to 80 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 457 . 1 [ c 22 h 21 fn 4 o 6 + h ] + ( m / z ) utilizing the procedure described in preparation of 3a - 3b except substituting 3 - aminomethyl - pyrrolidine - 1 - carboxylic acid tert - butyl ester for 3 - amino - pyrrolidine - 1 - carboxylic acid tert - butyl ester 14 { alegria , 2004 # 20 }, the title compound was obtained as a colorless oil ( 800 mg , 69 %). utilizing the procedure described in preparation of 4c except substituting 3c for 15 ; the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 7n nh 3 in methanol ( gradient from 5 % to 20 % of 7n nh 3 in methanol ) to afford the title compound was obtained as a colorless oil ( 500 mg , quantitative ). ms ( esi + ) (+ 0 . 1 % hcooh ): 165 . 18 [ c 8 h 12 n 4 + h ] + ( m / z ) utilizing the procedure described in preparation of 5c except substituting 4c for 16 ( 500 mg , 3 . 05 mmol , 3 . 0 eq . ), the title compound was obtained as a yellow solid ( 175 mg , 41 %). hplc ( gradient 5 % to 80 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 427 . 15 [ c 20 h 19 fn 6 o 4 + h ] + ( m / z ) to a − 78 ° c . solution of 2 - fluoropyridine ( 1 . 0 ml , 11 . 29 mmol , 1 . 0 eq .) and 1 - benzyl - pyrrolidin - 3 - ylamine ( 2 . 0 g , 11 . 29 mmol , 1 . 0 eq .) in dry thf ( 5 ml ) was added lihmds im in thf ( 23 ml , 22 . 57 mmol , 2 . 0 eq .). the reaction was stirred at room temperature for 1 hour and then at 90 ° c . overnight . the reaction was diluted with water and extracted with ethyl acetate ; the organic extracts were dried over anhydrous magnesium sulphate and were evaporated under reduced pressure . the resulting crude product was purified by flash chromatography on silica gel , eluting with 100 % ethyl acetate to afford 20 ( 2 . 08 g , 72 %) as a colorless gum . ms ( esi + ) (+ 0 . 1 % hcooh ): 254 . 06 [ c 16 h 19 n 3 + h ] + ( m / z ) to a solution of 20 ( 2 . 08 g , 8 . 22 mmol ) in methanol ( 25 ml ) were added 2 drops of trifluoroacetic acid and pd / c ( 500 mg ). the mixture was submitted to hydrogenation at atmospheric pressure and at 40 ° c . for 36 hours . the reaction was filtered over celite ® and evaporated under reduced pressure . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — methanol ( gradient from 5 % to 10 % methanol ) then dichloromethane — 7n nh 3 in methanol ( gradient from 10 % to 20 % of 7n nh 3 in methanol ). the title compound was obtained as an orange oil ( 1 . 3 g , 97 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 164 . 16 [ c 9 h 13 n 3 + h ] + ( m / z ) utilizing the procedure described in the preparation of 5a except substituting 4a for 21 ( 1 . 3 g , 7 . 96 mmol , 3 . 2 eq . ), the title compound was obtained as a yellow solid ( 900 mg , 85 %). hplc ( gradient 20 % to 80 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 426 . 1 [ c 21 h 20 fn 5 o 4 + h ] + ( m / z ) utilizing the procedure described in preparation of 8b except substituting 6 for 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 1 . 1 g , 5 . 87 mmol ) 23 { hansen , 2003 # 1 }. the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 9 : 1 to 1 : 1 ) to afford 24b as sticky oil ( 2 . 5 g , contaminated with mitsunobu reagents ). utilizing the procedure described in preparation of 4a - 4b except substituting 3a - 3b for 24b , the title compound was obtained as a colorless oil ( 200 mg , 20 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 169 . 24 [ c 7 h 12 n 4 o + h ] + ( m / z ) utilizing the procedure for the preparation of 10b except substituting 9b for 24c ( 200 mg , 1 . 19 mmol , 2 . 0 eq .). the precipitate was filtered and washed with water then diethyl ether to afford the title compound as a yellow solid ( 62 mg , 25 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 431 . 2 [ c 19 h 19 fn 6 o 5 + h ] + ( m / z ) utilizing the procedure described in preparation of 8a except substituting 6 for 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 1 . 88 g , 10 . 0 mmol , 1 . 0 eq .) 23 { hansen , 2003 # 1 } and 7a for 25a { gravestock , 2003 # 2 }( 1 . 62 g , 8 . 06 mmol , 0 . 8 eq .). the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 9 : 1 to 8 : 2 ) to afford 25b as sticky oil ( 1 . 63 g , 54 %). utilizing the procedure described in preparation of 4a - 4b except substituting 3a - 3b for 25b ( 2 . 7 g , 7 . 29 mmol ). the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — methanol ( gradient from 5 % to 10 % methanol ) then dichloromethane — 7n nh 3 in methanol ( gradient from 10 % to 40 % of 7n nh 3 in methanol ). the title compound was obtained as a colorless oil ( 951 mg , 76 %). utilizing the procedure for the preparation of 5a except substituting 4a for 25c ( 950 mg , 5 . 59 mmol , 3 . 0 eq .). the precipitate was filtered and washed with water ; the residue was triturated in hot methanol and gave after filtration the title compound as a yellow solid ( 688 mg , 73 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 90 % ms ( esi + ) (+ 0 . 1 % hcooh ): 433 . 1 [ c 18 h 17 fn 6 o 4 s + h ] + ( m / z ) utilizing the procedure described in preparation of 8a except substituting 6 for 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 1 . 2 g , 6 . 41 mmol , 1 . 0 eq .) 23 { hansen , 2003 # 1 } and 7a for 26a { gravestock , 2003 # 2 }( 1 . 03 g , 5 . 13 mmol , 0 . 8 eq .). the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 9 : 1 to 8 : 2 ) to afford 26b as sticky oil ( 2 . 03 g , 85 %). utilizing the procedure described in preparation of 4a - 4b except substituting 3a - 3b for 26b ( 2 . 0 g , 5 . 40 mmol ). the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — methanol ( gradient from 5 % to 20 % methanol ) then dichloromethane — 7n nh 3 in methanol ( gradient from 5 % to 40 % of 7n nh 3 in methanol ). the title compound was obtained as a colorless oil ( 1 . 0 g , quantitative ). utilizing the procedure for the preparation of 25d except substituting 25c for 26c ( 1 . 0 g , 5 . 88 mmol , 2 . 5 eq .). the residue was triturated with hot methanol and filtrated . the title compound was obtained as a yellow solid ( 614 mg , 61 %). hplc ( gradient 5 % to 95 %% acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 433 . 2 [ c 18 h 17 fn 6 o 4 s + h ] + ( m / z ) utilizing the procedure for the preparation of 7a except substituting 2 - aminothiazole for 2 - amino - 4 , 5 - dimethylthiazole hydrochloride ( 2 . 5 g , 15 . 2 mmol , 1 . 0 eq .). the title compound was obtained as a white solid ( 1 . 07g , 31 %). utilizing the procedure described in preparation of 8a except substituting 6 for 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 1 . 1 g , 5 . 83 mmol , 1 . 0 eq .) 23 { hansen , 2003 # 1 } and 7a for 27a ( 1 . 07 g , 4 . 67 mmol , 0 . 8 eq .). the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 1 : 0 to 8 : 2 ) to afford 27b as a colorless oil ( 1 . 45 g , 78 %). utilizing the procedure described in preparation of 4c except substituting 3c for 27b ( 1 . 45 g , 3 . 65 mmol ) with 15 ml of 4n hcl in dioxane . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 7n nh 3 in methanol ( gradient from 5 % to 20 % of 7n nh 3 in methanol ). the title compound was obtained as a colorless oil ( 940 mg , quantitative ). ms ( esi + ) (+ 0 . 1 % hcooh ): 198 . 21 [ c 9 h 15 n 3 s + h ] + ( m / z ) utilizing the procedure described in preparation of 5c except substituting 4c for 27c ( 940 mg , 4 . 76 mmol , 4 . 0 eq .). the reaction was evaporated under reduced pressure ; the residue was triturated with water and filtrated . the resulting solid was triturated and filtrated first with methanol , then with dichloromethane , and finally with methanol ; the title compound was obtained as a yellow solid ( 143 mg , 26 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 460 . 4 [ c 21 h 22 fn 5 o 4 s + h ] + ( m / z ) utilizing the procedure described in the preparation of 8a except substituting 6 for 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 1 . 1 g , 5 . 83 mmol , 1 . 0 eq .) 23 { hansen , 2003 # 1 } and 7a for 28a { hadida ruah , 2007 # 3 }( 1 . 0 g , 4 . 67 mmol , 0 . 8 eq .). the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 1 : 0 to 8 : 2 ) to afford 28b as a colorless oil ( 1 . 45 g , 87 %). utilizing the procedure described in the preparation of 4c except substituting 3c for 28b ( 1 . 55 g , 4 . 04 mmol ) with 7 ml of 4n hcl in dioxane . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 7n nh 3 in methanol ( gradient from 5 % to 10 % of 7n nh 3 in methanol ). the title compound was obtained as a white solid ( 1 . 0 g , quantitative ). ms ( esi + ) (+ 0 . 1 % hcooh ): 184 . 15 [ c 8 h 13 n 3 s + h ] + ( m / z ) utilizing the procedure described in the preparation of 5c except substituting 4c for 28c ( 1 . 0 g , 5 . 46 mmol , 4 . 0 eq .). the reaction was evaporated under reduced pressure ; the residue was triturated with water and filtrated . an analytical sample was obtained by preparative tlc purification eluting with dichloromethane — methanol ( gradient from 2 . 5 % to 5 % of methanol ) to afford the title compound as a yellow solid ( 100 mg , 33 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 446 . 2 [ c 20 h 20 fn 5 o 4 s + h ] + ( m / z ) utilizing the procedure for the preparation of 7a except substituting 2 - aminothiazole for 2 - amino - 5 - methylthiazole ( 2 . 0 g , 17 . 5 mmol , 1 . 0 eq . ), the title compound was obtained as a white solid ( 1 . 07 g , 45 %). utilizing the procedure described in the preparation of 8a except substituting 6 for 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 1 . 86 g , 9 . 92 mmol , 1 . 0 eq .) 23 { hansen , 2003 # 1 } and 7a for 29a ( 1 . 7 g , 7 . 93 mmol , 0 . 8 eq .). the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 1 : 0 to 1 : 1 ) to afford 29b as a yellow oil ( 2 . 1 g , 69 %). utilizing the procedure described in the preparation of 4c except substituting 3c for 29b ( 2 . 1 g , 5 . 48 mmol , 1 . 0 eq .) with 15 ml of 4n hcl in dioxane . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 7n nh 3 in methanol ( gradient from 5 % to 20 % of 7n nh 3 in methanol ). the title compound was obtained as a white solid ( 930 mg , 93 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 184 . 15 [ c 8 h 13 n 3 s + h ] + ( m / z ) utilizing the procedure described in the preparation of 5c except substituting 4c for 29c ( 930 mg , 5 . 13 mmol , 4 . 0 eq .). the reaction was evaporated under reduced pressure ; the residue was triturated with water and filtrated . an analytical sample was obtained by preparative tlc purification eluting with dichloromethane — methanol ( gradient from 2 . 5 % to 5 % of methanol ) to afford the title compound as a yellow solid ( 72 mg , 25 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 446 . 1 [ c 20 h 20 fn 5 o 4 s + h ] + ( m / z ) utilizing the procedure described in the preparation of 8a except substituting 6 for 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 1 . 7 g , 9 . 08 mmol , 1 . 0 eq .) 23 { hansen , 2003 # 1 } and 7a for 30a { butira , 2004 # 4 } ( 1 . 94 g , 9 . 08 mmol , 1 . 0 eq .). the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 9 : 1 to 7 : 3 ) to afford 30b as a yellow oil ( 2 . 9 g , 84 %). utilizing the procedure described in the preparation of 4a - 4b except substituting 3a - 3b for 30b ( 2 . 9 g , 7 . 57 mmol , 1 . 0 eq .). the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — methanol ( gradient from 5 % to 10 % methanol ) then dichloromethane — 7n nh 3 in methanol ( gradient from 10 % to 30 % of 7n nh 3 in methanol ). the title compound was obtained as a colorless oil ( 1 . 0 g , 72 %). utilizing the procedure for the preparation of 10b except substituting 9b for 30c ( 1 . 0 g , 5 . 46 mmol , 3 . 0 eq .). the reaction was evaporated under reduced pressure ; the residue was triturated with ethanol and filtrated ( 251 mg ). an analytical sample was obtained by preparative tlc purification eluting with dichloromethane — methanol ( gradient from 2 . 5 % to 7 . 5 % of methanol ) to afford the title compound as a yellow solid ( 42 mg , 10 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ) : 446 . 26 [ c 20 h 20 fn 5 o 6 s + h ] + ( m / z ) utilizing the procedure described in the preparation of 8a except substituting 6 for 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 0 . 47 g , 2 . 52 mmol , 1 . 0 eq .) 23 { hansen , 2003 # 1 } and 7a for 31a { gravestock , 2003 # 2 } ( 0 . 4 g , 2 . 02 mmol , 0 . 8 eq .). the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 95 : 5 to 6 : 4 ) to afford 31b as a white solid ( 0 . 5 g , 67 %). utilizing the procedure described in the preparation of 4c except substituting 3c for 31b ( 0 . 6 g , 1 . 63 mmol , 1 . 0 eq .) with 10 ml of 4n hcl in dioxane . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 7n nh 3 in methanol ( gradient from 5 % to 20 % of 7n nh 3 in methanol ). the title compound was obtained as a white solid ( 230 mg , 84 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 168 . 43 [ c 8 h 13 n 3 o + h ] + ( m / z ) utilizing the procedure described in the preparation of 5c except substituting 4c for 31 c ( 230 mg , 1 . 38 mmol , 2 . 0 eq .). the reaction was evaporated under reduced pressure ; the residue was triturated with water and filtrated . an analytical sample was obtained by preparative tlc purification eluting with dichloromethane — methanol ( gradient from 2 . 5 % to 5 % of methanol ) to afford the title compound as a yellow solid ( 50 mg , 17 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 430 . 2 [ c 20 h 20 fn 5 o 5 + h ] + ( m / z ) utilizing the procedure described in the preparation of 8a except substituting 6 for 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 4 . 25 g , 22 . 7 mmol , 1 . 0 eq .) 23 { hansen , 2003 # 1 } and 7a for 32a { almansa rosales , 2006 # 5 } ( 3 . 6 g , 18 . 2 mmol , 0 . 8 eq .). the resulting cru product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 1 : 0 to 8 : 2 ) to afford 32b as a colorless oil ( 1 . 8 g , 27 %). utilizing the procedure described in the preparation of 4c except substituting 3c for 32b ( 1 . 8 g , 4 . 9 mmol , 1 . 0 eq .) with 10 ml of 4n hcl in dioxane . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 7n nh 3 in methanol ( gradient from 5 % to 20 % of 7n nh 3 in methanol ). the title compound was obtained as a white solid ( 1 . 0 g , quantitative ). ms ( esi + ) (+ 0 . 1 % hcooh ): 168 . 22 [ c 8 h 13 n 3 o + h ] + ( m / z ) utilizing the procedure described in the preparation of 5c except substituting 4c for 32c ( 1 . 0 g , 5 . 98 mmol , 4 . 0 eq .). the reaction was evaporated under reduced pressure ; the residue was triturated first with ethanol and filtrated and secondly with methanol to afford the title compound as a yellow solid ( 532 mg , 83 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 430 . 25 [ c 20 h 20 fn 5 o 5 + h ] + ( m / z ) mp = 263 ° c ., dec . utilizing the procedure described in the preparation of 8a except substituting 6 for ( r )- 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester 33a ( 1 . 0 g , 5 . 34 mmol , 1 . 1 eq .) and 7a ( 1 . 17 g , 5 . 87 mmol , 1 . 0 eq .). the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 95 : 5 to 85 : 15 ) to afford 34a as a colorless oil ( 1 . 8 g , 97 %). utilizing the procedure described in preparation of 4c except substituting 3c for 34a ( 1 . 8 g , 4 . 87 mmol , 1 . 0 eq .) and dichloromethane for ethyl acetate with 20 ml of 4n hcl in dioxane . the reaction was stirred one hour at 60 ° c . and evaporated under reduced pressure . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — methanol ( gradient from 5 % to 10 % methanol ) then dichloromethane — 7n nh 3 in methanol ( gradient from 20 % to 50 % of 7n nh 3 in methanol ). the title compound was obtained as a white solid ( 780 mg , 94 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 170 . 15 [ c 7 h 11 n 3 s + h ] + ( m / z ) utilizing the procedure for the preparation of 10b except substituting 9b for 35a ( 780 mg , 4 . 61 mmol , 3 . 0 eq .). the reaction was evaporated under reduced pressure ; the residue was triturated with methanol and filtrated ( 462 mg ). an analytical sample was obtained by preparative tlc purification eluting with dichloromethane — methanol ( gradient from 2 . 5 % to 5 % of methanol ) to afford the title compound as a yellow solid ( 30 mg , 17 %). hplc ( gradient 5 % to 80 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 432 . 18 [ c 19 h 18 fn 5 o 4 s + h ] + ( m / z ) utilizing the procedure described in the preparation of 8a except substituting 6 for ( s )- 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester 33b ( 1 . 0 g , 5 . 34 mmol , 1 . 0 eq .) and 7a ( 1 . 07 g , 5 . 34 mmol , 1 . 0 eq .). the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 1 : 0 to 8 : 2 ) to afford 34b as an colorless oil ( 1 . 8 g , quantitative ). 1 h nmr ( cdcl 3 ): δ 7 . 60 ( d , 1h , j = 3 . 7 ), 7 . 02 ( d , 1h , j = 3 . 6 ), 5 . 73 - 5 . 62 ( m , 1h ), 3 . 40 - 3 . 31 ( m , 1h ), 3 . 74 - 3 . 67 ( m , 3h ), 2 . 52 - 2 . 39 ( m , 1h ), 2 . 22 - 2 . 13 ( m , 1h ), 1 . 57 ( s , 9h ), 1 . 46 ( s , 9h ). utilizing the procedure described in the preparation of 4c except substituting 3c for 34b ( 1 . 8 g , 4 . 87 mmol ) with 15 ml of 4n hcl in dioxane . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 7n nh 3 in methanol ( gradient from 5 % to 20 % of 7n nh 3 in methanol ). the title compound was obtained as a white solid ( 900 mg , quantitative ). ms ( esi + ) (+ 0 . 1 % hcooh ): 170 . 17 [ c 7 h 11 n 3 s + h ] + ( m / z ) utilizing the procedure described in the preparation of 5c except substituting 4c for 35b ( 900 mg , 5 . 32 mmol , 4 . 0 eq .). the reaction was evaporated under reduced pressure ; the residue was triturated with water and filtrated . the resulting residue was triturated with methanol and filtrated to afford the title compound as a yellow solid ( 440 mg , 77 %) hplc ( gradient 5 % to 80 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 432 . 12 [ c 19 h 18 fn 5 o 4 s + h ] + ( m / z ) to a − 78 ° c . solution of 14 ( 1 . 5 g , 8 . 05 mmol , 1 . 0 eq .) in dry dichloromethane ( 40 ml ), thiocarbonylimidazole ( 1 . 81 g , 9 . 66 mmol , 1 . 2 eq .) was added . the mixture was then allowed to reach slowly room temperature overnight . the reaction mixture_was washed with water , the organic extracts were dried over anhydrous sodium sulfate and evaporated under reduced pressure . the residue was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 9 : 1 to 7 : 3 ) to afford 37 as a colorless oil ( 1 . 29 g , 70 %). to a solution of 37 ( 1 . 87 g , 8 . 19 mmol , 1 . 0 q .) in dry thf ( 30 ml ) were added triethylamine ( 2 . 3 ml , 16 . 38 mmol , 2 . 0 eq .) and 2 - chloroethylamine hydrochloride ( 1 . 14 g , 9 . 33 mmol , 1 . 14 eq .). after 18 hours at room temperature the reaction mixture was refluxed for one day . after cooling the salts were filtrated and the filtrate was evaporated under reduced pressure . the residue was purified by flash chromatography on silica gel , eluting with 100 % ethyl acetate then with dichloromethane — methanol ( gradient from 5 % to 15 % of methanol ) to afford 38 as an colorless oil ( 1 . 9 g , 85 %). utilizing the procedure described in preparation of 4a - 4b except substituting 3a - 3b for 38 ( 1 . 9 g , 7 . 00 mmol ). the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — methanol ( gradient from 5 % to 10 % methanol ) then dichloromethane — 7n nh 3 in methanol ( gradient from 10 % to 30 % of 7n nh 3 in methanol ). the title compound was obtained as a colorless oil ( 0 . 5 g , 42 %). utilizing the procedure for the preparation of 10b except substituting 9b for 39 ( 500 mg , 2 . 92 mmol , 2 . 7 eq .). the reaction was filtrated ( 125 mg ). an analytical sample was obtained by preparative tlc purification eluting with dichloromethane — methanol ( gradient from 2 . 5 % to 5 % of methanol ) to afford the title compound as a light yellow solid ( 30 mg , 6 . 5 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 434 . 0 [ c 19 h 20 fn 5 o 4 s + h ] + ( m / z ) prepared according to the procedure reported in us2003 / 0225107 except substituting 5 ( r )- 3 -[ 4 -( 1 - cyanocyclopropan - 1 - yl ]- 5 - hydroxy methyloxazolidin - 2 - one for 23 ( 1 . 6 g , 8 . 54 mmol , 1 . 0 eq . ), tetramethylazodicarboxamide for diethylazodicarboxylate , butylphosphine for triphenylphosphine and benzene for tetrahydrofurane . the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 7 : 3 to 0 : 1 ) to afford 42a - 42b as a colorless oil ( 845 mg , 42 %). utilizing the procedure described in preparation of 4a - 4b except substituting 3a - 3b for 42a - 42b ( 950 mg , 3 . 98 mmol ). the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — methanol ( gradient from 5 % to 10 % methanol ) then dichloromethane — 7n nh 3 in methanol ( gradient from 10 % to 30 % of 7n nh 3 in methanol ). 43a - 43b was obtained as a light yellow oil ( 555 mg , quantitative ). ms ( esi + ) (+ 0 . 1 % hcooh ): 139 . 22 [ c 6 h 10 n 4 + h ] + ( m / z ) the title compound was prepared utilizing the procedure for the preparation of 5a except substituting 4a for 43a - 43b ( 555 mg , 4 . 02 mmol , 2 . 8 eq .). the precipitate was filtered and washed with water ; the residue was triturated in hot methanol and gave after filtration the title compound as a yellow solid ( 371 mg , 65 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( est +) (+ 0 . 1 % hcooh ): 401 . 2 [ c 18 h 17 fn 6 o 4 + h ] + ( m / z ) the title compound was prepared according to the procedure reported in us2003 / 0225107 except substituting 5 ( r )- 3 -[ 4 -( 1 - cyanocyclopropan - 1 - yl ]- 5 - methanesulfonyloxymethyloxazolidin - 2 - one for 45 { genevois - borella , 2005 # 21 }( 1 . 6 g , 8 . 53 mmol , 1 . 0 eq .). the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 1 : 0 to 1 : 1 ) to afford 47a - 47b as a white solid ( 1 . 4 g , 69 %). utilizing the procedure described in the preparation of 4c except substituting 3c for 47a - 47b ( 1 . 9 g , 7 . 97 mmol , 1 . 0 eq .) with 10 ml of 4n hcl in dioxane . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 7n nh 3 in methanol ( gradient from 0 % to 1 0 % of 7n nh 3 in methanol ). the title compound was obtained as a white solid ( 807 mg , 73 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 139 . 05 [ c 6 h 10 n 4 + h ] + ( m / z ) utilizing the procedure described in the preparation of 5c except substituting 4c for 48a - 48b ( 800 mg , 5 . 79 mmol , 3 . 0 eq .). the reaction was poured in ethanol ; the precipitate was filtrated and washed with methanol to afford the title compound as a yellow solid ( 641 mg , 83 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 400 . 99 [ c 18 h 17 fn 6 o 4 + h ] + ( m / z ) the title compound was prepared according to the procedure reported in us2003 / 0225107 except substituting 5 ( r )- azidomethyl - 3 -[ 4 -( 1 - cyanocyclopropan - 1 - yl ) phenyl ] oxazolidin - 2 - one for 50 ( ep1500643 , 1 . 5 g , 7 . 07 mmol , 1 . 0 eq .). the reaction mixture was evaporated under reduced pressure to afford 47a as a yellow oil ( 1 . 7 g , quantitative ). utilizing the procedure described in preparation of 4c except substituting 3c for 47a ( 1 . 7 g , 7 . 07 mmol ) with 10 ml of 4n hcl in dioxane . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 7n nh 3 in methanol ( gradient from 0 % to 5 % of 7n nh 3 in methanol ). the title compound was obtained as a white solid ( 900 mg , 92 %). utilizing the procedure described in preparation of 5c except substituting 4c for 48a ( 1 . 03 g , 7 . 45 mmol , 4 . 0 eq .). the reaction was poured in ethanol , the precipitate was filtrated and washed with methanol to afford the title compound as a yellow solid ( 580 mg , 78 %) hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 401 . 19 [ c 18 h 17 fn 6 o 4 + h ] + ( m / z ) to a solution of 45 ( 4 . 66 g , 18 . 7 mmol , 1 . 0 eq .) in acetonitrile ( 10 ml ) was added tetrabutylammonium cyanide ( 10 . 0 g , 37 . 4 mmol , 2 . 0 eq . ), the reaction mixture was stirred at 65 ° c . overnight . after cooling the mixture was diluted with ethyl acetate and washed with a saturated aqueous nahco 3 solution . the organic extracts were dried over anhydrous sodium sulphate and evaporated under reduced pressure . the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 1 : 0 to 1 : 1 ) to afford 51 as a yellow oil ( 2 . 9 g , 79 %). to a solution of 51 ( 1 . 0 g , 5 . 1 mmol , 1 . 0 eq .) in toluene ( 10 ml ) were added sodium azide ( 0 . 497 g , 7 . 64 mmol , 1 . 5 eq .) and triethylamine hydrochloride , the reaction mixture was stirred at 100 ° c . for 24 hours . after cooling the mixture was diluted with ethyl acetate and washed with water . the organic extracts were dried over anhydrous sodium sulphate and evaporated under reduced pressure . the resulting crude product was purified by flash chromatography on silica gel , eluting with dichloromethane and 5 % of methanol to afford the title compound as a yellow oil ( 1 . 0 g , 82 %). utilizing the procedure described in the preparation of 4c except substituting 3c for 52 ( 1 . 09 g , 4 . 56 mmol , 1 . 0 eq .) with 10 ml of 4n hcl in dioxane . the residue was triturated with dichloromethane and filtrated . the resulting solid was triturated in 7n nh 3 methanol and evaporated under reduced pressure . the title compound was obtained as a beige solid ( 780 mg , quantitative ). utilizing the procedure described in the preparation of 5c except substituting 4c for 53 ( 780 mg , 5 . 61 mmol , 4 . 0 eq .). the reaction was poured in ethanol , the precipitate was filtrated . the residue was triturated and filtrated firstly with water , secondly with methanol and at last with dichloromethane to afford the title compound as a yellow solid ( 60 mg , 11 %) hplc ( gradient 5 % to 95 % can in h 2 o ): & gt ; 90 % ms ( esi + ) (+ 0 . 1 % hcooh ) : 402 . 28 [ c 17 h 16 pn 7 o 4 + h ] + ( m / z ) utilizing the procedure described in the preparation of 11 except substituting 1 for 14 ( 1 . 0 g , 4 . 97 mmol , 1 . 0 eq . ), the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 8 : 2 to 0 : 1 ) to afford 55a ( 1 . 29 g , 92 %) as a white solid . utilizing the procedure described in the preparation of 4c except substituting 3c for 55a ( 1 . 29 g , 4 . 60 mmol , 1 . 0 eq .) with 10 ml of 4n hcl in isopropanol and dichloromethane for ethyl acetate . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 10 % methanol then dichloromethane — 7n nh 3 in methanol ( gradient from 0 % to 10 % of 7n nh 3 in methanol ). the title compound was obtained as a white gum ( 725 mg , 87 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 181 . 33 [ c 9 h 12 n 2 o 2 + h ] + ( m / z ) utilising the procedure for the preparation of 5a , except substituting 4a for 56a ( 725 mg , 4 . 02 mmol , 3 . 0 eq . ), after cooling the reaction was filtered . the crude solid was triturated with boiling ethanol and filtrated to afford the title compound as a beige solid ( 497 mg , 84 %). hplc ( gradient 5 % to 80 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 443 . 1 [ c 21 h 19 fn 4 o 6 + h ] + ( m / z ) utilizing the procedure for the preparation of 55b , except substituting cyclopentanecarbonylchloride for 3 , 3 , 3 - trifluoro - propionyl chloride ( 2 . 3 g , 15 . 30 mmol , 1 . 5 eq . ), the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 8 : 2 to 1 : 1 ) to afford 55c ( 1 . 4 g , 46 %) as a pale yellow oil . utilizing the procedure described in the preparation of 4a - 4b except substituting 3a - 3b for 50c ( 1 . 4 g , 4 . 72 mmol , 1 . 0 eq .). the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — methanol ( gradient from 5 % to 15 % methanol ) 56c ( tfa salt ) was obtained as a light yellow oil ( 1 . 4 g , quantitative ). ms ( esi + ) (+ 0 . 1 % hcooh ): 197 . 13 [ c 7 h 11 f 3 n 2 o + h ] + ( m / z ) utilizing the procedure for the preparation of 5a , except substituting 4a for 56c ( 1 . 4 g , 4 . 51 mmol , 4 . 0 eq . ), was evaporated under reduced pressure the crude solid was triturated with methanol and filtrated then the precipitate was triturated with boiling methanol and filtrated to afford the title compound as a yellow solid ( 277 mg , 57 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 90 % ms ( esi + ) (+ 0 . 1 % hcooh ): 459 . 0 [ c 19 h 18 f 4 n 4 o 5 + h ] + ( m / z ) to a 0 ° c . solution of 14 ( 1 . 67 g , 8 . 96 mmol , 1 . 0 eq .) in dichloromethane ( 25 ml ), et 3 n ( 2 . 5 ml , 17 . 93 mmol , 2 . 0 eq .) was added . after 30 minutes , trifluoroacetic anhydride ( 1 . 9 ml , 13 . 45 mmol , 1 . 5 eq .) was added slowly with 20 mg of dmap and the reaction was stirred at room temperature overnight . the mixture was diluted with dichloromethane and washed with water ; the organic extracts were dried over anhydrous sodium sulfate . the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 9 : 1 to 7 : 3 ) to afford 55d ( 2 . 03 g , 80 %) as a clear oil . utilizing the procedure described in the preparation of 4a - 4b except substituting 3a - 3b for 55d ( 2 . 03 g , 7 . 21 mmol , 1 . 0 eq .). the residue was used without further purification ; 56d ( tfa salt ) was obtained as a light yellow oil ( 2 . 44 g , quantitative ). ms ( esi + ) (+ 0 . 1 % hcooh ): 182 . 91 [ c 6 h 9 f 3 n 2 o + h ] + ( m / z ) utilizing the procedure for the preparation of 5a , except substituting 4a for 56d ( 1 . 2 g , 4 . 05 mmol , 3 . 0 eq . ); the reaction mixture was filtered and the precipitate was triturated with boiling methanol and filtrated to afford the title compound as a yellow solid ( 263 mg , 42 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 444 . 9 [ c 18 h 16 f 4 n 4 o 5 + h ] + ( m / z ) utilizing the procedure for the preparation of 5a , except substituting 4a for 56e { herling , 2003 # 23 }( 1 . 0 g , 3 . 38 mmol , 3 . 0 eq .). the reaction mixture was filtered and the precipitate was triturated with boiling methanol and filtrated to afford the title compound as a yellow solid ( 64 mg , 13 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 445 . 3 [ c 18 h 16 f 4 n 4 o 5 + h ] + ( m / z ) utilizing the procedure for the preparation of 5a , except substituting 4a for 56f { hudson , 2006 # 8 } 1 . 5 g , 5 . 06 mmol , 3 . 0 eq .). the reaction mixture was filtered and the precipitate was triturated with boiling methanol and filtrated to afford the title compound as a yellow solid ( 375 mg , 50 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 445 . 2 [ c 18 h 16 f 4 n 4 o 5 + h ] + ( m / z ) to a 0 ° c . solution of 14 ( 1 . 5 g , 8 . 05 mmol , 1 . 0 eq .) in dichloromethane ( 30 ml ), et 3 n ( 3 . 4 ml , 24 . 16 mmol , 3 . 0 eq .) was added . after 15 minutes , trifluoromethanesulfonic anhydride ( 1 . 7 ml , 9 . 66 mmol , 1 . 2 eq .) was added slowly and the reaction was stirred at room temperature for 6 hours . the mixture was diluted with dichloromethane and washed with a saturated aqueous nahco 3 solution ; the organic extracts were dried over anhydrous sodium sulfate and evaporated under reduced pressure . the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 9 : 1 to 6 : 4 ) to afford 58a ( 1 . 1 g , 42 %) as a pale yellow oil . utilizing the procedure described in the preparation of 4a - 4b except substituting 3a - 3b for 58a ( 1 . 1 g , 3 . 45 mmol , 1 . 0 eq .). the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — methanol ( gradient from 5 % to 15 % methanol ) 59a ( tfa salt ) was obtained as a yellow oil ( 1 . 0 g , 87 %). utilizing the procedure for the preparation of 5a , except substituting 4a for 59a ( 1 . 0 g , 3 . 01 mmol , 3 . 5 eq . ), was evaporated under reduced pressure . the crude solid was triturated with methanol and filtrated then the precipitate was triturated with boiling methanol and filtrated to afford the title compound as a yellow solid ( 30 mg , 6 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 459 . 0 [ c 17 h 16 f 4 n 4 o 6 s + h ] + ( m / z ) utilizing the procedure described in the preparation of 5c except substituting 4c for 59b { ueda , 1999 # 24 }( 1 . 22 g , 7 . 44 mmol , 4 . 0 eq .). the reaction was evaporated under reduced pressure ; the residue was triturated with ethanol and filtrated . the solid was then triturated with a mixture of dichloromethane / methanol and filtrated to afford the title compound as a yellow solid ( 390 mg , 49 %) hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 426 . 87 [ c 17 h 19 fn 4 o 6 s + h ] + ( m / z ) 73a was prepared according to the procedure described by di cesare , et al , j . med . chem 1992 , 35 ,( 22 ) 4205 - 13 , but starting with the (±) pantolactone . to a solution of 73a ( 1 . 0 g , 4 . 87 mmol , 1 . 0 eq .) in methanol ( 20 ml ), pd / c ( 100 mg ) and sn hcl in isopropanol ( 1 . 95 ml , 9 . 74 mmol , 2 . 0 eq .) were added . the reaction mixture was submitted to hydrogenation at atmospheric pressure and room temperature for 48 hours . the mixture was filtrated over celite ® and evaporated under reduced pressure . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 7n nh 3 in methanol ( gradient from 5 % to 40 % of 7n nh 3 in methanol to afford the title compound as a white solid ( 170 mg , 30 %). utilizing the procedure described in the preparation of 5c except substituting 4c for 74a ( 170 mg , 1 . 48 mmol , 2 . 0 eq .). the reaction was evaporated under reduced pressure ; the residue was triturated with water and filtrated . the solid was then triturated with ethanol , filtrated and washed with methanol . an analytical sample was obtained by preparative tlc purification eluting with dichloromethane — 2 % methanol to afford the title compound as a yellow solid ( 40 mg , 14 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 90 % ms ( esi + ) (+ 0 . 1 % hcooh ): 377 . 69 [ c 18 h 20 fn 3 o 5 + h ] + ( m / z ) 74b was prepared according to the procedure described by di cesare , et al , j . med . chem 1992 , 35 ,( 22 ) 4205 - 13 , but starting with the (±) pantolactone . utilizing the procedure described for the preparation of 5a , 75b was obtained with tnoc ( 304 mg , 1 . 07 mmol , 1 . 0 eq . ), 74b { di cesare , 1992 # 11 } ( 370 mg , 3 . 24 mmol , 3 . 0 eq .) in pyridine and n - methylmorpholine ( 0 . 24ml , 2 . 16 mmol , 2 . 0 eq .). the mixture was evaporated ; the residue was purified on scx cartridge eluting with methanol — triethylamine ( gradient from 0 % to 1 % of triethylamine ) to afford the title compound as a yellow solid ( 40 mg , 21 %) hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 376 . 93 [ c 18 h 21 fn 4 o 4 + h ] + ( m / z ) utilizing the procedure described for the preparation of 5a , 75c was obtained with tnoc ( 630 mg , 2 . 23 mmol , 1 . 0 eq . ), 74c { di cesare , 1992 # 11 } ( 1 . 1 g , 7 . 30 mmol , 3 . 3 eq .) in pyridine and n - methylmorpholine ( 1 . 0 ml , 9 . 10 mmol , 4 . 0 eq .). the mixture was evaporated ; the residue was triturated several times with boiling methanol and ethanol and filtrated to afford the title compound as a yellow solid ( 144 mg , 10 %) hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 377 . 4 [ c 18 h 21 fn 4 o 4 + h ] + ( m / z ) utilizing the procedure described for the preparation of 5a , 75d was obtained with tnoc ( 140 mg , 0 . 50 mmol , 1 . 0 eq . ), 74d ( 200 mg , 1 . 33 mmol , 2 . 7 eq .) in 5 ml of pyridine and n - methylmorpholine ( 0 . 20 ml , 0 . 91 mmol , 3 . 6 eq .). the mixture was evaporated ; the residue was triturated several times with boiling methanol and filtrated to afford the title compound as a yellow solid ( 60 mg , 31 %) hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 90 % ms ( esi + ) (+ 0 . 1 % hcooh ): 377 . 4 [ c 18 h 21 fn 4 o 4 + h ] + ( m / z ) to a − 70 ° c . solution of bromothiazole ( 0 . 8 ml , 8 . 77 mmol , 1 . 1 eq .) in diethyl ether , 2 . 5 n butyl lithium in hexanes ( 3 . 2 ml , 7 . 98 mmol , 1 . 0 eq .) was added . after 15 minutes , a solution of 3 - oxo - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 1 . 47 g , 7 . 98 mmol , 1 . 0 eq .) in tetrahydrofurane ( 20 ml ) was added . the mixture was allowed to reach room temperature after 45 minutes . a saturated aqueous ammonium chloride was added with 20 ml of ethyl acetate , the mixture was decanted and the organic phase was washed with water . the organic extracts were dried over sodium sulphate and evaporated under reduced pressure . the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 9 : 1 to 7 : 3 ) to afford 80 ( 1 . 41 g , 66 %) as a light yellow oil . utilizing the procedure described in the preparation of 4a - 4b except substituting 3a - 3b for 80 ( 1 . 41 g , 5 . 21 mmol ). the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — methanol ( gradient from 5 % to 20 % methanol ). the title compound ( trifluoroacetic acid salt ) was obtained as a light brown oil ( 1 . 4mg , 74 %). utilizing the procedure described for the preparation of 5a , 82 was obtained with tnoc ( 475 mg , 1 . 68 mmol , 1 . 0 eq . ), 81 as a trifluoroacetic acid salt -( 1 . 4 g , 5 . 05 mmol , 3 . 0 eq .) in 6 ml of pyridine and n - methyhnorpholine ( 1 . 5 ml ). the reaction was evaporated under reduced pressure and the residue was triturated with boiling methanol and filtrated to afford the title compound as a yellow solid ( 476 mg , 67 %) hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 432 . 9 [ c 19 h 17 fn 4 o 5 s + h ] + ( m / z ) compound 84 was prepared according to the preparation reported in w02005 / 026154 except substituting 1 -( 1r - phenyl - ethyl )- pyrrolidin - 2 - one for the commercially available 1 - benzyl - 2 - pyrrolidinone ( 7 . 0 g , 39 . 95 mmol , 1 . 0 eq .). 84 was obtained as a brown oil ( 9 . 15 g , 84 %). compound 85 was prepared according to the preparation reported in wo2005 / 026154 except substituting 3 -( 2 , 2 , 2 - trifluoro - acetyl )- 1 -( 1r - phenyl - ethyl )- pyrrolidin - 2 - one for 84 ( 3 . 25 g , 11 . 9 mmol , 1 . 0 eq .) and zinc borohydride for potassium borohydride . 85 was obtained as a pale yellow oil ( 2 . 95 g , 89 %). compound 86 was prepared according to the preparation reported in wo2005 / 026154 except substituting 3 -( 2 , 2 , 2 - trifluoro - 1 - hydroxy - ethyl )- 1 -( lr - phenyl - ethyl )- pyrrolidin - 2 - one for 84 ( 2 . 95 g , 10 . 79 mmol , 1 . 0 eq . ), 86 was obtained as a pale yellow oil ( 2 . 68 g , 94 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 260 . 17 [ c 13 h 16 f 3 no + h ] + ( m / z ) to a solution of 86 ( 1 . 7 g , 6 . 55 mmol , 1 . 0 eq .) in methanol ( 25 ml ), pd / c ( 200 mg ) and sn hcl in isopropanol ( 3 . 0 ml , 15 . 0 mmol , 2 . 3 eq .) were added . the reaction mixture was submitted to hydrogenation at 8 bars and at 40 ° c . for 24 hours . the mixture was filtrated over celite ® and evaporated under reduced pressure . the residue was purified by flash chromatography dichloromethane — methanol ( gradient from 5 % to 20 % of methanol ) to afford the title compound ( 208 mg , 15 %) as a pale green oil . ms ( esi + ) (+ 0 . 1 % hcooh ): 170 . 1 [ c 6 h 10 f 3 n 0 + h ] + ( m / z ) utilizing the procedure described for the preparation of 5a , 88 was obtained from tnoc ( 300 mg , 1 . 06 mmol , 1 . 0 eq .) and 87 as a hydrochloride salt -( 707 mg , 3 . 44 mmol , 3 . 2 eq .) in 10 ml of pyridine and triethylamine ( 0 . 80 ml , 5 . 73 mmol , 5 . 4 eq .). the reaction was evaporated under reduced pressure and the residue was purified by preparative tlc purification eluting with dichloromethane and 5 % of methanol to afford the title compound as a yellow solid ( i9 mg , 7 %) hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 432 . 3 [ c 18 h 17 f 4 n 3 o 5 + h ] + ( m / z ) compound 89 was prepared according to the procedure reported in w02005 / 026154 except substituting benzyloxycarbonyl - pyrrolidin - 3 - yl - methanol for the commercially available 3 - hydroxymethyl - pyrrolidine - 1 - carboxylic acid tert - butyl ester 6 ( 3 . 4 g , 17 . 06 mmol , 1 . 0 eq .). 89 was obtained as a yellow oil ( 2 . 15 g , 82 %). compound 90 was prepared according to the procedure reported in w02005 / 026154 except substituting benzyloxycarbonyl - pyrrolidin - 3 - yl - thiazol - 2 - yl - methanol for 89 ( 2 . 15 g , 10 . 79 mmol , 1 . 0 eq .). 89 was obtained as a yellow oil ( 2 . 39 g , 78 %). utilizing the procedure described in the preparation of 4a - 4b except substituting 3a - 3b for 89 ( 1 . 65 g , 5 . 80 mmol ). the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — 20 % methanol then dichloromethane — 20 % 7n nh 3 in methanol , the title compound was obtained as a colorless oil ( 1 . 3 g , quantitative ). ms ( esi + ) (+ 0 . 1 % hcooh ): 185 . 02 [ c 8 h 12 n 2 os + h ] + ( m / z ) utilizing the procedure for the preparation of 10b except substituting 9b for 91 ( 1 . 3 g , 7 . 05 mmol , 3 . 6 eq .). the reaction was evaporated under reduced pressure ; the residue was triturated with boiling methanol and filtrated to afford the title compound as a yellow solid ( 610 mg , 70 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 446 . 9 [ c 20 h 19 fn 4 o 5 s + h ] + ( m / z ) to a 0 ° c . solution of 90 ( 2 . 35 g , 8 . 26 mmol , 1 . 0 eq .) in dichloromethane ( 60 ml ), triethylamine ( 2 . 3 ml , 16 . 50 mmol , 2 . 0 eq .) and methanesulfonyl chloride ( 1 . 3 ml , 16 . 80 mmol , 2 . 0 eq .) were added . the reaction mixture was stirred at room temperature for 6 hours and washed first with aqueous 1 n hcl and then with a saturated aqueous nahco 3 solution . the organic extracts were dried over sodium sulphate and evaporated under reduced pressure . the crude residue was dissolved in dimethylformamide and sodium azide ( 2 . 7 g , 41 . 53 mmol , 5 . 0 eq .) were added , the reaction was heated at 85 ° c . for 16 hours . a saturated aqueous ammonium chloride solution was added and the mixture was extracted with ethyl acetate , the solution was then washed with water twice , the organic extracts were dried over sodium sulphate and evaporated under reduced pressure . the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 7 : 3 ) to afford 93 ( 2 . 1 g , 82 %) as a yellow oil . compound 94 was prepared according to the procedure described in ep1182202 except substituting 4 -( r )-[ 1 - azido - 1 -( thiazol - 2 - yl ) methyl ]- 1 -[ 1 -( r )- phenylethyl ]- 2 - pyrrolidinone for 93 ( 1 . 5 g , 4 . 84 mmol , 1 . 0 eq .). 94 was obtained as a colorless oil ( 1 . 3 g , 70 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 384 . 3 [ c 18 h 29 n 3 o 4 s + h ] + ( m / z ) compound 95 was prepared according to the procedure described in e1182202 except substituting 3 -( r )-[ 1 - tert - butoxy carbonylamino - 1 -( thiazol - 2 - yl ) methyl ]- 1 benzyloxycarbonyl pyrrolidine for 94 ( 1 . 3 g , 3 . 39 mmol , 1 . 0 eq .). 95 ( di - trifluoroacetic acid salt ) was obtained as a colorless oil ( 1 . 35 g , quantitative ). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 184 . 1 [ c 8 h 13 n 3 s + h ] + ( m / z ) utilizing the procedure described for the preparation of 5a , 96 was obtained from tnoc ( 80 mg , 0 . 28 mmol , 1 . 0 eq .) and 90 ( 200 mg , 0 . 49 mmol , 1 . 7 eq .) in 5 ml of pyridine and triethylamine ( 1 . 3 ml ). the reaction was evaporated under reduced pressure and the residue was purified by preparative tlc purification eluting with dichloromethane and 5 % of methanol to afford the title compound as a yellow solid ( 34 mg , 27 %) hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 446 . 1 [ c 20 h 20 fn 4 o 5 s + h ] + ( m / z ) to a − 78 ° c . solution of oxalyl chloride ( 0 . 5 ml , 5 . 73 , mmol , 2 . 2 eq .) in dichloromethane ( 30 ml ) were added dimethylsulfoxide ( 0 . 75 ml , 10 . 58 mmol , 4 . 0 eq .) and a solution of 9 -{ 3 - hydroxy - pyrrolidin - 1 - yl }- 8 - fluoro - 3 - methyl - 6 - oxo - 2 , 3 - dihydro - 6 - h - 1 - oxa - 3 , 3a - diaza - phenalene - carboxylic acid benzyl ester 102 ( 1 . 16 g , 2 . 64 mmol , 1 . 0 eq .) in dichloromethane ( 30 ml ). after 1 hour at - 78 ° c ., triethylamine ( 2 . 2 ml , 15 . 78 mmol , 6 . 0 eq .) was added . the reaction mixture was stirred 1 hour at − 78 ° c ., and then 1 hour at room temperature . the mixture was diluted with dichloromethane and washed with water ; the organic extracts were dried over sodium sulphate and evaporated under reduced pressure . 103 was obtained as a beige solid ( 1 . 15g , quantitative ). ms ( esi + ) (+ 0 . 1 % hcooh ): 438 . 3 [ c 23 h 20 fn 3 o 5 + h ] + ( m / z ) to a suspension 103 ( 1 . 15 g , 2 . 63 mmol , 1 . 0 eq .) in ethanol ( 25 ml ) and thf ( 15 ml ) were added methoxylamine hydrochloride ( 820 mg , 9 . 82 mmo , 3 . 7 eq ) and a solution of sodium bicarbonate ( 750 mg , 8 , 93 mmol , 3 . 4 eq ) in water ( 8 ml ). the mixture was strirred at 40 ° c . for 16 hours . the reaction was concentrated under reduced pressure . the residue was dissolved in ethyl acetate and washed first with water and then with brine . the organic extracts were dried over anhydrous sodium - sulphate and were evaporated under reduced pressure to afford the title compound as a beige solid ( 1 . 19 g , 97 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 90 % ms ( esi + ) (+ 0 . 1 % hcooh ): 467 . 4 [ c 24 h 23 fn 4 o 5 + h ] + ( m / z ) a suspension of 104 ( 1 . 19 g , 2 . 55 mmol , 1 . 0 eq ) in dichloromethane ( 25 ml ) and methanol ( 10 ml ) was added palladium on activated carbon 10 % ( 300 mg , 0 . 25 mmol , 0 . 1 eq ). the mixture was submitted to hydrogenation at room temperature under 1 atmosphere for 3 hours . the reaction mixture was filtered through celite and evaporated . the residue was triturated with methanol and the solid was filtered to afford the title compound as a yellow solid ( 800 mg , 83 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 377 . 2 [ c 16 h 17 fn 4 o 5 + h ] + ( m / z ) in a sealed tube , 30 ml of dry toluene was degazed with argon during 15 minutes , palladium acetate ( 114 mg , 0 . 17 mmol , 0 . 04 eq .) and racemic - 2 , 2 ′- bis ( diphenylphosphino )- 1 , 1 ′- binaphthyl ( 106 mg , 0 . 17 mmol , 0 . 04 eq .) were added and the mixture was degazed with argon for 10 minutes . then 2 - chloropyrazine ( 500 mg , 4 . 37 mmol , 1 . 0 eq . ), 4 - amino - 1 - boc - piperidine ( 1 . 05 g , 5 . 24 mmol , 1 . 2 eq .) and sodium tert - butoxide ( 587 mg , 6 . 11 mmol , 1 . 4 eq .) were added and the mixture was stirred at 70 ° c . overnight . the reaction was concentrated in vacuum . the resulting crude product was purified by flash chromatography on silica gel , eluting with 100 % ethyl acetate to afford 106a ( 1 . 0 g , 82 %). according to general procedure b except substituting tfa for 4n hcl in dioxane , 28a ( 1 . 4 g , 5 . 03 mmol , 1 . 0 eq .) was deprotected ; the residue was purified by flash chromatography on silica gel , eluting with eluting dichloromethane 7n nh 3 in methanol ( gradient from 5 % to 20 % of 7n nh 3 in methanol ) to afford 107a ( 900 mg , quantitative ). ms ( esi + ) (+ 0 . 1 % hcooh ): 179 . 24 [ c 9 h 14 n 4 + h ] + ( m / z ) according to general procedure a , tnoc ( 355 mg , 1 . 26 mmol , 1 . 0 eq .) was coupled with 29a ( 900 mg , 5 . 05 mmol , 4 . 0 eq .) and n - methylmorpholine ( 0 . 28 ml , 2 . 53 mmol , 2 . 0 eq .). the residue was triturated several times with hot methanol to afford the title compound as a beige solid ( 67 mg , 12 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 441 . 14 [ c 21 h 21 fn 6 o 4 + h ] + ( m / z ) utilizing the procedure described for the preparation of 107a except substituting 2 - chloropyrazine for 2 - chloropyridine ( 4 . 4 mmol ). the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 1 : 1 ) to afford 106b ( 1 . 2 g , 98 %). according to general procedure b , 106b ( 1 . 2 g , 4 . 31 mmol , 1 . 0 eq .) was deprotected ; the residue was purified by flash chromatography on silica gel , eluting with eluting dichloromethane 7n nh 3 in methanol ( gradient from 0 % to 20 % of 7n nh 3 in methanol ) to afford 107b ( 1 . 0 g , quantitative ). ms ( esi + ) (+ 0 . 1 % hcooh ): 178 . 18 [ c 10 h 15 n 3 + h ] + ( m / z ) according to general procedure a , tnoc ( 530 mg , 1 . 88 mmol , 1 . 0 eq .) was coupled with 107b ( 1 . 0 g , 5 . 54 mmol , 3 . 0 eq .) and n - methylmorpholine ( 0 . 41 ml , 3 . 76 mmol , 2 . 0 eq .). the residue was triturated several times with hot methanol , an analytical sample was obtained by preparative tlc purification eluting with dichloromethane — methanol ( gradient from 2 . 5 % to 5 % of methanol ) to afford the title compound as a yellow solid ( 80 mg , 10 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 440 . 1 [ c 22 h 22 fn 5 o 4 + h ] + ( m / z ) to a 0 ° c . solution of the commercially available tert - butyl 4 - hydroxy - 1 - piperidine - carboxylate ( 1 . 5 g , 7 . 45 mmol , 1 . 2 eq .) in dry thf ( 20 ml ), triphenylphosphine ( 2 . 4 g , 9 . 31 mmol , 1 . 5 eq .) was added . after complete dissolution , diethylazodicarboxylate — 40 % w / v in toluene - ( 4 ml , 9 . 31 mmol , 1 . 5 eq .) was added dropwise followed by thiazol - 2 - yl - carbamic acid tert - butyl ester g , 5 . 99 mmol , 1 . 0 eq .). the mixture was stirred at rt for 18 hours . the reaction was evaporated under reduced pressure . the resulting crude product was purified by flash chromatography on silica gel , eluting with cyclohexane - ethyl acetate ( 95 : 5 to 85 : 15 ) to afford 109 as a colorless gum ( 1 . 95 g , 85 %) 109 ( 1 . 95 g , 5 . 08 mmol ) was dissolved in ethyl acetate ( 10 ml ) and 4n hcl in dioxane ( 10 ml ) was added . the mixture was stirred at room temperature for 6 hours and one hour at 60 ° c . with few drops of tfa . the reaction was concentrated in vacuum . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — methanol ( gradient from 5 % to 10 % methanol ) then dichloromethane — 7n nh 3 in methanol ( gradient from 20 % to 50 % of 7n nh 3 in methanol ). the title compound was obtained as a white solid ( 875 mg , 93 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 184 . 18 [ c 8 h 13 n 3 s + h ] + ( m / z ) according to general procedure a , tnoc ( 336 mg , 1 . 19 mmol , 1 . 0 eq .) was coupled with 34 ( 875 mg , 4 . 77 mmol , 4 . 0 eq .) and 1 ml of n - methylmorpholine . the residue was triturated with water and filtered ( 227 mg crude ), an analytical sample was obtained by preparative tlc purification eluting with dichloromethane — methanol ( gradient from 2 . 5 % to 5 % of methanol ) to afford the title compound as a beige solid ( 36 mg , 7 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 445 . 9 [ c 20 h 20 fn 5 o 4 s + h ] + ( m / z ) according to general procedure c , 112 was obtained with 4 - amino - 1 - boc - piperidine ( 3 . 7 g , 18 . 60 mmol , 1 . 0 eq . ), edci ( 5 . 1 g , 27 . 88 mmol , 1 . 5 eq . ), hobt ( 3 . 61 g , 27 . 88 mmol , 1 . 5 eq .) and furan - 2 - carboxylic acid ( 2 . 5 g , 22 . 30 mmol , 1 . 2 eq .). the mixture was washed with a saturated solution of sodium bicarbonate ; the residue was purified by flash chromatography on silica gel , eluting with eluting with cyclohexane - ethyl acetate ( 8 : 2 to 0 : 1 ) to afford 112 as a colorless oil ( 5 . 1 g , 97 %). according to general procedure b , 112 ( 5 . 1 g , 17 . 32 mmol , 1 . 0 eq .) was deprotected ; the residue was purified by flash chromatography on silica gel , eluting with eluting with dichloromethane — 10 % methanol then dichloromethane — 7n nh 3 in methanol ( gradient from 10 % to 30 % of 7n nh 3 in methanol ) to afford 113 as a white foam ( 3 . 0 g , 89 %). according to general procedure a , tnoc ( 340 mg , 1 . 20 mmol , 1 . 0 eq .) was coupled with 37 ( 700 mg , 3 . 60 mmol , 3 . 0 eq .) and 1 ml of n - methylmorpholine . the residue was triturated with methanol and filtered to afford the title compound as a beige solid ( 175 mg , 32 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 457 . 0 [ c 22 h 21 fn 5 o 6 + h ] + ( m / z ) according to general procedure a , tnoc ( 391 mg , 1 . 39 mmol , 1 . 0 eq .) was coupled with n -( 4 - piperidino ) piperidine ( commercially available ) ( 700 mg , 4 . 16 mmol , 3 . 0 eq .) in 5 ml of pyridine and n - methylmorpholine ( 0 . 305 ml , 2 . 77 mmol , 2 . 0 eq .) the reaction was evaporated under reduced pressure , the residue was purified by preparative tlc purification eluting with dichloromethane — methanol ( gradient from 2 . 5 % to 10 % of methanol ) to afford the title compound as a yellow solid ( 65 mg , 11 %) hplc ( gradient 5 % to 80 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 431 . 27 [ c 22 h 27 fn 4 o 4 + h ] + ( m / z ) according to general procedure a , tnoc ( 300 mg , 1 . 06 mmol , 1 . 0 eq .) was coupled with 4 -( 1 - pyrrolidinyl ) piperidine ( commercially available ) ( 500 mg , 3 . 24 mmol , 3 . 0 eq .) in 5 ml of pyridine and 1 ml of n - methyhnorpholine . the reaction was evaporated under reduced pressure ; the residue was triturated with boiling methanol to afford the title compound as a yellow solid ( 240 mg , 54 %) hplc ( gradient 5 % to 80 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 417 . 0 [ c 21 h 25 fn 4 o 4 + h ] + ( m / z ) utilizing the procedure described for the preparation of 5a , 117 was obtained from the corresponding 8 - des - fluoro - 9 - fluoro compound ( prepared according to the procedure described in u . s . pat . no . 4 , 801 , 584 ) ( 100 mg , 0 . 38 mmol , 1 . 0 eq .) and 56e ( 340 mg , 1 . 15 mmol , 3 . 0 eq .) in 2 . 5 ml of dry pyridine and n - methylmorpholine ( 0 . 2 ml , 1 . 82 mmol , 4 . 8 eq .). the reaction was evaporated under reduced pressure . the residue was triturated with boiling methanol to afford the title compound as a yellow solid ( 25 mg , 15 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 427 . 05 [ c 18 h 17 f 3 n 4 o 5 + h ] + ( m / z ) utilizing the procedure described for the preparation of 5a , 118 was obtained from the 8 - des - fluoro - 9 - fluoro compound ( prepared according to the procedure described in us4801584 ) ( 100 mg , 0 . 38 mmol , 1 . 0 eq .) and 35b ( 480 mg , 1 . 21 mmol , 3 . 2 eq .) in 2 . 5 ml of dry pyridine and n - methylmorpholine ( 0 . 2 ml , 1 . 82 mmol , 4 . 8 eq .). the reaction was evaporated under reduced pressure . the residue was triturated with boiling methanol and purified by preparative t . l . c . to afford the title compound as a yellow solid ( 20 mg , 13 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 414 . 0 [ c 19 h 19 n 5 o 4 s + h ] + ( m / z ) by using the preparation method of 5a , product x is obtained starting with the corresponding 8 - des - fluoro - 9 - fluoro product ( prepared according to the method described in us - 4 , 801 - 584 ) ( 80 mg , 0 . 30 mmol , 1 . 0 eq .) and from product 56e ( 200 mg , 1 . 33 mmol , 4 . 4 eq .) in 3 ml of anhydrous pyridine and 0 . 30 ml of n - methylmorpholine ( 2 . 73 mmol , 9 . 0 eq .). the reaction mixture is evaporated under reduced pressure and the residue is triturated in methanol , and then purified by preparative tlc . the expected product is obtained as a yellow solid ( 11 mg , 12 %). a suspension of tnoc ( 10 . 0 g , 35 . 43 mmol , 1 . 0 eq ) in an aqueous solution of 5n naoh ( 200 ml ) was stirred at 95 ° c . for 6 hours . the mixture was cooled to room temperature and an aqueous solution of 6n hcl was added until precipitation . the precipitate was filtered , washed with water and diethylether and dried to afford the title compound as a white solid ( 9 . 1 g , 95 %). ms ( esi + ) (+ 0 . 1 % hcooh ): 271 . 0 [ c 11 h 8 f 2 n 2 o 4 + h ] + ( m / z ) in a sealed tube , 119 ( 1 . 5 g , 5 . 55 mmol , 1 . 0 eq .) and acetaldehyde ( 40 ml , 713 mmol ) were suspended in 100 ml of dry dioxane . the reaction mixture was stirred at 110 ° c . for 18 hours . the reaction was cooled to room temperature , the precipitate formed was filtered , washed with methanol and diethylether , and dried to afford the title compound as a white solid ( 1 . 1 g , 69 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 297 . 0 [ c 13 h 10 f 2 n 2 o 4 + h ] + ( m / z ) utilizing the procedure described for the preparation of 5a , 121 was obtained from 120 ( 100 mg , 0 . 34 mmol , 1 . 0 eq .) and 56e ( 300 mg , 1 . 01 mmol , 3 . 0 eq .) in 2 ml of dry pyridine and n - methylmorpholine ( 0 . 2 ml , 1 . 82 mmol , 5 . 0 eq .). the reaction was evaporated under reduced pressure . the residue was recristallized in methanol to afford the title compound as a yellow solid ( 54 mg , 35 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 459 . 3 [ c 19 h 18 f 4 n 4 o 5 + h ] + ( m / z ) utilizing the procedure described for the preparation of 120 , 122 was obtained from 119 ( 500 mg , 1 . 85 mmol , 1 . 0 eq .) and dry acetone ( 6 . 2 ml , 89 mmol ) in 20 ml of dry dioxane . the reaction was evaporated under reduced pressure . the residue was triturated with boiling methanol to afford the title compound as a white solid ( 610 mg , 100 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 311 . 1 [ c 14 h 12 f 2 n 2 o 4 + h ] + ( m / z ) utilizing the procedure described for the preparation of 5a , 123 was obtained from 122 ( 100 mg , 0 . 32 mmol , 1 . 0 eq .) and 56e ( 280 mg , 0 . 96 mmol , 3 . 0 eq .) in 2 ml of dry pyridine and n - methylmorpholi ( 0 . 2 ml , 1 . 82 mmol , 5 . 0 eq .). the reaction was evaporated under reduced pressure . the residue was purified by preparative t . l . c . and triturated in diethylether to afford the title compound as a yellow solid ( 35 mg , 23 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 473 . 2 [ c 20 h 20 f 4 n 4 o 5 + h ] + ( m / z ) compound 124 was prepared according to the procedure described in u . s . pat . no . 4 , 801 , 584 . utilizing the procedure described for the preparation of 120 , 125 was obtained from 124 ( 400 mg , 1 . 43 mmol , 1 . 0 eq .) and acetaldehyde ( 12 . 0 ml , 214 mmol ) in 30 ml of dry dioxane . the reaction was evaporated under reduced pressure . the residue was triturated with boiling methanol to afford the title compound as a brown solid ( 305 mg , 77 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 90 % ms ( esi + ) (+ 0 . 1 % hcooh ): 279 . 0 [ c 13 h 11 fn 2 o 4 + h ] + ( m / z ) utilizing the procedure described for the preparation of 5a , 126 was obtained from 125 ( 100 mg , 0 . 36 mmol , 1 . 0 eq .) and 56e ( 210 mg , 1 . 05 mmol , 2 . 9 eq .) in 2 ml of dry pyridine and n - methylmorpholine ( 0 . 2 ml , 1 . 82 mmol , 5 . 0 eq .). the reaction was evaporated under reduced pressure . the residue was triturated in diethylether and purified by t . l . c . preparative to afford the title compound as a yellow solid ( 21 mg , 13 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 441 . 2 [ c 19 h 19 f 3 n 4 o 5 + h ] + ( m / z ) utilizing the procedure described for the preparation of 120 , 127 was obtained from 124 ( 400 mg , 1 . 43 mmol , 1 . 0 eq .) and dry acetone ( 4 . 0 ml , 57 . 3 mmol ) in 13 ml of dry dioxane . the reaction was evaporated under reduced pressure . the residue was triturated with boiling methanol to afford the title compound as a brown solid ( 338 mg , 70 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 293 . 1 [ c 14 h 13 fn 2 o 4 + h ] + ( m / z ) utilizing the procedure described for the preparation of 5a , 128 was obtained from 127 ( 110 mg , 0 . 38 mmol , 1 . 0 eq .) and 56e ( 340 mg , 1 . 15 mmol , 3 . 0 eq .) in 2 ml of dry pyridine and n - methylmorpholine ( 0 . 2 ml , 1 . 82 mmol , 5 . 0 eq .). the reaction was evaporated under reduced pressure . the residue was triturated in methanol and purified by preparative t . l . c . to afford the title compound as a yellow solid ( 20 mg , 12 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 95 % ms ( esi + ) (+ 0 . 1 % hcooh ): 455 . 1 [ c 20 h 21 f 3 n 4 o 5 + h ] + ( m / z ) utilizing the procedure described for the preparation of 5a , 129 was obtained from 120 ( 300 mg , mmol , 1 . 0 eq .) and 35b ( 620 mg , 3 . 03 mmol , 3 . 0 eq .) in 6 ml of dry pyridine and n - methylmorpholine ( 0 . 6 ml , 5 . 05 mmol , 5 . 0 eq .). the reaction was evaporated under reduced pressure . the residue was purified by flash chromatography on silica gel , eluting with dichloromethane — methanol ( gradient from 0 % to 5 % methanol ) to afford the title compound as a yellow solid ( 50 mg , 15 %). hplc ( gradient 5 % to 95 % acn in h 2 o ): & gt ; 99 % ms ( esi + ) (+ 0 . 1 % hcooh ): 446 . 0 [ c 20 h 20 fn 5 o 4 + h ] + ( m / z ) by using the method for preparing 5a , the product 130 is obtained starting with 200 mg of product 112 ( 0 . 64 mmol , 1 . 0 eq .) and product 35b ( 770 mg , 1 . 93 mmol , 3 . 0 eq .) in 4 ml of anhydrous pyridine and 0 . 35 ml of n - methylmorpholine ( 3 . 20 mmol , 5 . 0 eq .). the reaction medium is evaporated under reduced pressure and the residue is purified by chromatography on silica and then by preparative tlc . the expected product is obtained as a yellow solid ( 8 mg , 3 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 460 . 10 [ c 21 h 22 fn 5 o 4 s + h ] + ( m / z ) by using the method for preparing 5a , the product 131 is obtained starting with 190 mg of product 125 ( 0 . 36 mmol , 1 . 0 eq .) and with product 35b ( 860 mg , 2 . 16 mmole , 3 . 2 eq .) in 5 ml of anhydrous pyridine and 0 . 5 ml of n - methylmorpholine ( 4 . 55 mmol , 6 . 7 eq .). the reaction mixture is evaporated under reduced pressure and the residue is triturated in ethyl ether and then purified by chromatography on silica by eluting with a dichloromethane - methanol mixture ( 100 : 0 to 96 : 4 ) and the expected product is obtained as a yellow solid ( 20 mg , 7 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 428 . 0 [ c 20 h 21 n 5 o 4 s + h ] + ( m / z ) by using the method for preparing 5a , the product 132 is obtained starting with 200 mg of product 127 ( 0 . 68 mmol , 1 . 0 eq .) and of product 35b ( 870 mg , 2 . 19 mmol , 3 . 2 eq .) in 5 ml of anhydrous pyridine and 0 . 5 ml of n - methylmorpholine ( 4 . 55 mmol , 6 . 7 eq .). the reaction medium is evaporated under reduced pressure and the residue is triturated in methanol and then purified by preparative tlc . the expected product is obtained as a yellow solid ( 21 mg , 7 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 442 . 0 [ c 21 h 23 n 5 o 4 s + h ] + ( m / z ) by using the method for preparing 120 , the product 133 is obtained starting with 2 . 0 g of product 119 ( 7 . 40 mmol , 1 . 0 eq . ), with 6 . 6 ml of ethyl diethoxy acetate ( 89 mmol ) and 0 . 5 ml of trifluoroacetic acid ( 6 . 70 mmol , 0 . 9 eq .) in 80 ml of anhydrous dioxane . the expected product is obtained as a white solid ( 2 . 0 g , 76 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 355 . 1 [ c 15 h 12 f 2 n 2 o 6 + h ] + ( m / z ) by using the method for preparing 5a , the product 134 is obtained starting with 300 mg of product 133 ( 0 . 84 mmol , 1 . 0 eq .) and with product 35b ( 720 mg , 2 . 42 mmol , 3 . 0 eq .) in 6 ml of anhydrous pyridine and 0 . 45 ml of n - methylmorpholine ( 4 . 20 mmol , 5 . 0 eq .). the reaction medium is evaporated under reduced pressure and the residue is triturated in methanol and then purified by preparative tlc . the expected product is obtained as a white solid ( 13 mg , 3 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 504 . 05 [ c 22 h 22 fn 5 o 6 s + h ] + ( m / z ) by using the method for preparing 5a , the product 135 is obtained starting with the product 120 ( 230 mg , 0 . 78 mmol , 1 . 0 eq .) and of product 74b ( 200 mg , 1 . 33 mmol , 1 . 7 eq .) in 1 ml of anhydrous pyridine and 2 ml of anhydrous acetonitrile in the presence of dabco ( 250 mg , 2 . 23 mmol , 2 . 9 eq .). the reaction medium is filtered and the precipitate is washed with acetonitrile . the obtained solid is triturated in methanol and washed with methanol and then with ethyl ether . the expected product is obtained as a yellow solid ( 105 mg , 34 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 391 . 0 [ c 19 h 23 fn 4 o 4 + h ] + ( m / z ) by using the method for preparing 5a , the product 136 is obtained starting with the 220 mg of product 112 ( 0 . 71 mmol , 1 . 0 eq .) and of product 74b ( 200 mg , 1 . 33 mmol , 1 . 9 eq .) in 4 ml of anhydrous pyridine and 2 ml of anhydrous acetonitrile in the presence of dabco ( 250 mg , 2 . 23 mmol , 3 . 1 eq .). the reaction medium is filtered and the precipitate is washed with acetonitrile . the obtained solid is triturated in methanol and washed with methanol and then with ethyl ether . the expected product is obtained as a yellow solid ( 110 mg , 38 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 405 . 0 [ c 20 h 25 fn 4 o 4 + h ] + ( m / z ) 137 was prepared according to the method described by di cesare et al ., j . med . chem . 1992 , 35 , ( 22 ), 4205 - 13 , by using ( s )- pentolactone as starting material . the compound 138 is obtained by following the method described in the preparation of product 8a by substituting the product 137 for the product 6 . the obtained raw product is purified by chromatography on silica by eluting with a dichloromethane - methanol mixture ( 10 : 0 to 9 : 1 ) and the product 138 is obtained as a brown foam ( 385 mg , 25 %). the product 138 ( 380 mg , 0 . 98 mmol , 1 . 0 eq .) is dissolved in 5 ml of anhydrous chloroform and 0 . 28 ml of benzylchloroformate ( 1 . 99 mmol , 2 . 0 eq .) are added . the mixture is stirred at 60 ° c . for 8 hours . the reaction medium is diluted with dichloromethane and washed with a saturated sodium hydrogencarbonate solution . the isolated organic extracts are dried and the solvent is evaporated under reduced pressure . the raw expected product is obtained , which is purified by chromatography on silica by diluting with a cyclohexane - ethyl acetate mixture ( 10 : 0 to 9 : 1 ) and the expected product 139 is obtained as pale yellow oil ( 307 mg , 70 %). the product 139 ( 300 mg , 0 . 70 mmol , 1 . 0 eq .) and sodium iodide ( 420 mg , 2 . 80 mmol , 4 . 0 eq .) are dissolved in 5 ml of anhydrous acetonitrile . 0 . 35 ml of chlorotrimethyl silane ( 2 . 77 mmol , 4 . 0 eq .) are then added dropwise . the mixture is stirred at room temperature for 4 hours . the reaction medium is diluted with 5 ml of methanol and then the solvent is evaporated under reduced pressure . the raw expected product is obtained , which is purified by chromatography on silica by eluting with a dichloromethane - methanol mixture ( 10 : 0 to 9 : 1 ) subsequently with a scx column and the expected product 140 is obtained as a brown oil ( 85 mg , 61 %). stage e : 9 -[( s )- 3 , 3 - dimethyl - 4 -( thiazol - 2 - ylamino )- pyrrolidin - 1 - yl ]- 8 - fluoro - 3 - methyl - 6 - oxo - 2 , 3 - dihydro - 6h - 1 - oxa - 3 , 3a - diaza - phenalene - 5 - carboxylic acid by using the method for preparing 5a , the product 141 is obtained starting with 65 mg of “ ube - 4 ” ( 0 . 23 mmol , 1 . 0 eq .) and with the product 140 ( 80 mg , 0 . 41 mmol , 2 . 0 eq .) in 0 . 5 ml of anhydrous pyridine and 1 ml of acetonitrile in the presence of dabco ( 50 mg , 0 . 45 mmol , 2 . 0 eq .). the reaction medium is filtered and the precipitate washed with acetonitrile . the obtained solid is triturated in methanol and washed with methanol and then with ethyl ether . the expected product is obtained as a yellow solid ( 23 mg , 22 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 460 . 5 [ c 21 h 22 fn 5 o 4 s + h ] + ( m / z ) 142 was prepared according to the method described by di cesare et al ., j . med . chem . 1992 , 35 , ( 22 ), 4205 - 13 , by using ( r )- pantolactone as starting material . compound 143 is obtained by following the method described in the preparation of 8a by substituting product 142 for product 6 . the obtained raw product is purified by chromatography on silica by eluting with a dichloromethane - methanol mixture ( 10 : 0 to 93 : 7 ) and product 143 is obtained as a yellow oil ( 865 mg , 22 %). by using the method for preparing 139 , product 144 is obtained with the starting product 143 ( 860 mg , 1 . 13 mmol , 1 . 0 eq .). the expected raw product is obtained , which is purified by chromatography on silica by eluting with a cyclohexane - ethyl acetate mixture ( 10 : 0 to 9 : 1 ) and the expected product is obtained as a colorless oil ( 445 mg , 91 %). by using the method for preparing 140 , product 145 is obtained with the starting product 144 ( 420 mg , 0 . 97 mmol , 1 . 0 eq .). the raw expected product is obtained , which is purified by chromatography on silica by eluting with a dichloromethane - methanol mixture ( 10 : 0 to 9 : 1 ), subsequently with a scx column and the product 140 is obtained as colorless oil ( 165 mg , 86 %). by using the method for preparing 5a , product 146 is obtained starting with 115 mg of “ ube - 4 ” ( 0 . 41 mmol , 1 . 0 eq .) and with product 145 ( 160 mg , 0 . 81 mmol , 2 . 0 eq .) in 1 ml of anhydrous pyridine and 2 ml of acetonitrile in the presence of dabco ( 90 mg , 0 . 80 mmol , 2 . 0 eq .). the reaction medium is filtered and the precipitate washed with acetonitrile . the obtained solid is triturated in methanol and washed with methanol and then with ethyl ether . the expected product is obtained as a yellow solid ( 67 mg , 36 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 460 . 53 [ c 21 h 22 fn 5 o 4 s + h ] + ( m / z ) the product is prepared according to the method described in us 2003 / 0225107 by substituting the 3 -( s )- azido - pyrrolidin - 1 - yl carbamic acid tert - butyl ester for the 5 ( r )- azidomethyl - 3 -[ 4 -( 1 - cyanocyclopropan - 1 - yl ) phenyl ] oxazolidin - 2 - one ( 1 . 1 g , 5 . 20 mmol , 1 . 0 eq .). the raw product is purified by chromatography on silica by eluting with a dichloromethane - methanol mixture ( 100 : 0 to 97 : 3 ) and 142 is obtained as an orange oil ( 681 mg , 55 %). the method described for preparing 4c is used by substituting product 147 ( 680 mg , 2 . 85 mmol , 1 . 0 eq .) for product 3c with 17 ml of hcl 4n in dioxane . the obtained raw product is subsequently used without any subsequent purification . the method described in preparation 5c is used by substituting product 148 ( 400 mg , 2 . 30 mmol , 4 . 0 eq .) for product 4c . the reaction medium is evaporated under reduced pressure . the result is triturated in methanol and then purified by preparative tlc . the expected product is obtained as a yellow solid ( 20 mg , 22 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 401 . 4 [ c 18 h 17 fn 6 o 4 + h ] + ( m / z ) the product is prepared according the method described in us 2003 / 0225107 by substituting 3 ( r )- azido - pyrrolidin - 1 - yl carbamic acid tert butyl ester for 5 ( r )- azidomethyl - 3 -[ 4 -( 1 - cyanocyclopropan - 1 - yl )- phenyl ] oxazolidin - 2 - one ( 1 . 1 g , 5 . 2 mmol , 1 . 0 eq .). the raw product is subsequently used without any subsequent purification ( 550 mg , 44 %). the method described for preparing 4c is used by substituting product 150 ( 550 mg , 2 . 30 mmol , 1 . 0 eq .) for product 3c with 14 ml of hcl 4n in dioxane . the raw product subsequently used without any subsequent purification . the method described in preparation 5c is used by substituting product 151 ( 400 mg , 2 . 30 mmol , 4 . 0 eq .) for product 4c . the reaction medium is evaporated under reduced pressure . the result is triturated in methanol and then purified by preparative tlc . the expected product is obtained as a yellow solid ( 30 mg , 33 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 401 . 4 [ c 18 h 17 fn 6 o 4 + h ] + ( m / z ) the method described for preparing product 8a is used by substituting 3 -( s )- hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 1 . 0 g , 5 . 34 mmol , 1 . 2 eq .) for 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester , and 5 - methyl - isoxazol - 3 - yl carbamic acid tert - butyl ester ( 880mg , 4 . 4mmol , 1 . 0 eq .) for product 7a . the raw product is purified by chromatography on silica by eluting with a cyclohexane - ethyl acetate mixture ( 1 : 0 to 8 : 2 ) and product 148 is obtained as a pale pink oil ( 760 mg , 43 %). the method described for preparing product 4a is used by substituting product 153 ( 720 mg , 1 . 96 mmol , 1 . 0 eq .) for product 3a with 2 ml of trifluoroacetic acid in 20 ml of dichloromethane . the residue is purified by chromatography on silica by eluting with a dichloromethane - nh 3 7n mixture in methanol ( 0 %- 10 % 7n nh 3 gradient in methanol . the expected product is obtained as a brown oil ( 53 mg , 16 %). by using the method for preparing 5a , product 155 is obtained starting with 50 mg of & lt ;& lt ; ube - 4 & gt ;& gt ; ( 0 . 18 mmol , 1 . 0 eq .) and with product 154 ( 50 mg , 0 . 30 mmol , 1 . 7 eq .) in 0 . 5 ml of anhydrous pyridine and 1 ml of anhydrous acetonitrile in the presence of dabco ( 50 mg , 0 . 45 mmol , 2 . 5 eq .). the reaction medium is evaporated and the obtained solid is triturated in methanol and washed with methanol and then with ethyl ether . the expected product is obtained as a yellow solid ( 53 mg , 68 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 430 . 5 [ c 20 h 20 fn 5 o 5 + h ] + ( m / z ) the method described for preparing 8a is used , by substituting 3 -( r )- hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 1 . 04 g , 5 . 34 mmol , 1 . 2 eq .) for 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester , and 5 - methyl - isoxazol - 3 - yl carbarnic acid tert - butyl ester for product 7a ( 880 mg , 4 . 4 mmol , 1 . 0 eq .). the raw product is purified by chromatography on silica by eluting with a cyclohexane - ethyl acetate mixture ( 1 : 0 to 8 : 2 ) and product 151 is obtained as a colorless oil ( 840 mg , 46 %). the method described for preparing product 4a is used , by substituting product 156 ( 800 mg , 2 . 18 mmol , 1 . 0 eq .) for product 3a with 2 ml of trifluoroacetic acid in 20 ml of dichloromethane . the residue is purified by chromatography on silica by eluting with a 7n dichloromethane - nh 3 mixture in methanol ( 0 %- 10 % 7n nh 3 gradient in methanol ). the expected product is obtained as a brown oil ( 178 mg , 49 %). by using the method for preparing 5a , product 158 is obtained starting with 150 mg of “ ube - 4 ” ( 0 . 53 mmol , 1 . 0 eq .) and with product 157 ( 170 mg , 1 . 02 mmol , 1 . 9 eq .) in 1 ml of anhydrous pyridine and 2 ml of anhydrous acetonitrile in the presence of dabco ( 150 mg , 1 . 34 mmol , 2 . 5 eq .). the reaction medium is evaporated and the obtained solid is triturated in methanol and washed with methanol and then with ethyl ether . the expected product is obtained as a yellow solid ( 182 mg , 78 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 430 . 4 [ c 20 h 20 fn 5 o 5 + h ] + ( m / z ) to a solution of 2 - amino - imidazole sulfate ( 10 . 0 g , 37 . 84 mmol , 1 . 0 eq .) in 100 ml of an aqueous ( 1n ) sodium hydroxide solution , is added a solution of di - tert - butyl dicarbonate ( 16 . 5 g , 75 . 60 mmol , 2 . 0 eq .) in 100 ml of dichloromethane . the mixture is stirred at room temperature for 16 hours . the organic phase is then isolated by decantation and then washed with water , dried and then concentrated under reduced pressure . the product obtained as a pink solid ( 11 . 2 g , quantitative ) is used without any subsequent purification . by using the method for preparing 7a , product 160 is obtained starting with 159 ( 11 . 2 g , 37 . 84 mmol , 1 . 0 eq .). the raw expected product is obtained , which is purified by chromatography on silica by eluting with a cyclohexane - ethyl acetate mixture ( 10 : 0 to 4 : 6 ) and the expected product 160 is obtained as a yellow solid ( 3 . 7 g , 35 %). the method described for preparing 8a is used , by substituting 3 -( r )- hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 545 mg , 2 . 91 mmol , 1 . 5 eq .) for 3 - hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester , and product 160 ( 550 mg , 1 . 94 mmol , 1 . 0 eq .) for product 7a . the raw product is purified by chromatography on silica by eluting with a cyclohexane - ethyl acetate mixture ( 1 : 0 to 7 : 3 ) and product 161 is obtained as a colorless oil ( 455 mg , 52 %). the method described for preparing the product 4a is used , by substituting product 161 ( 450 mg , 0 . 99 mmol , 1 . 0 eq .) for product 3a with 0 . 8 ml of trifluoroacetic acid in 10 ml of dichloromethane . the medium is co - evaporated with methanol and then triturated in ethyl ether . the expected product is obtained as a white powder ( 325 mg , 66 %). by using the method for preparing 5a , product 163 is obtained , starting with 100 mg of “ ube - 4 ” ( 0 . 35 mmol , 1 . 0 eq .) and product 162 ( 305 mg , 0 . 62 mmol , 1 . 8 eq .) in 1 ml of anhydrous pyridine and 2 ml of anhydrous acetonitrile in the presence of dabco ( 80 mg , 0 . 71 mmol , 2 . 0 eq .). the reaction medium is co - evaporated with ethanol . the obtained solid is purified on an scx column , and the obtained solid is then hot - triturated in methanol and filtered . the expected product is obtained as a yellow solid ( 24 mg , 16 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 415 . 48 [ c 19 h 19 fn 6 o 4 + h ] + ( m / z ) the method described for preparing 8a is used , by substituting 3 -( s )- hydroxy - pyrrolidine - 1 - carboxylic acid tert - butyl ester ( 990 mg , 5 . 29 mmol , 1 . 5 eq .) for 3 - hydroxy - pyrrolidine - 1 - carboxylic tert - butyl ester and product 160 ( 1 . 0 g , 3 . 53 mmol , 1 . 0 eq .) for product 7a . the raw product is purified by chromatography on silica by eluting with a cyclohexane - ethyl acetate mixture ( 1 : 0 to 6 : 4 ) and the product 164 is obtained as a white foam ( 1 . 2 g , 75 %). the method described for preparing 4a is used , by substituting product 164 ( 675 mg , 1 . 49 mmol , 1 . 0 eq .) for product 3a with 1 . 2 ml of trifluoroacetic acid in 15 ml of dichloromethane . the medium is co - evaporated with methanol and then triturated in ethyl ether . the expected product is obtained as a white powder ( 484 mg , 66 %). by using the method for preparing 5a , product 166 is obtained starting with 140 mg of “ ube - 4 ” ( 0 . 50 mmol , 1 . 0 eq .) and product 165 ( 460 mg , 0 . 93 mmol , 1 . 9 eq .) in 1 . 5 ml of anhydrous pyridine and 3 ml of anhydrous acetonitrile in the presence of dabco ( 110 mg , 0 . 98 mmol , 2 . 0 eq .). the reaction medium is co - evaporated with methanol . the obtained residue is purified on an scx column and then on a sephadex ® lh - 20 column . the obtained solid is triturated in water , methanol and then in ethyl ether . the expected product is obtained as a yellow solid ( 44 mg , 21 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 415 . 49 [ c 19 h 19 fn 6 o 4 + h ] + ( m / z ) by using the method for preparing 7a , product 167 is obtained starting with 35b ( 500 mg , 1 . 26 mmol , 1 . 0 eq .). the raw product is subsequently used without any subsequent purification ( 350 mg , quantitative ). to a solution of 167 ( 340 mg , 1 . 26 mmol , 1 . 0 eq .) in 8 ml of anhydrous dmf , is added sodium hydride ( 50 mg , 1 . 25 mmol , 1 . 0 eq .). the mixture is stirred at room temperature for 30 minutes , and then methyl iodide ( 0 . 118 ml , 1 . 89 mmol , 1 . 5 eq .) is added . the mixture is stirred at room temperature for 1 hour and then evaporated . the residue is dissolved in ethyl acetate and then washed with water . the organic extracts are dried and then concentrated under reduced pressure . the raw product is purified by chromatography on silica by eluting with a cyclohexane - ethyl acetate mixture ( 1 : 0 to 6 : 4 ) and the product 164 is obtained as a yellow oil ( 270 mg , 75 %). the method described for preparing the product 4a is used , by substituting product 168 for product 3a ( 265 mg , 0 . 93 mmol , 1 . 0 eq .) with 0 . 3 ml of trifluoroacetic acid in 5 ml of dichloromethane . the medium is diluted with dichloromethane and water . the aqueous phase is alkalinized with an aqueous sodium hydroxide ( 1n ) solution and extracted with dichloromethane . the organic extracts are dried and concentrated under reduced pressure . the expected product is obtained as a pale yellow oil ( 138 mg , 73 %). by using the method for preparing 5a , product 170 is obtained , starting with 100 mg of “ ube - 4 ” ( 0 . 35 mmol , 1 . 0 eq .) and product 169 ( 130 mg , 0 . 71 mmol , 2 . 0 eq .) in 0 . 5 ml of anhydrous pyridine and 1 ml of anhydrous acetonitrile in the presence of dabco ( 120 mg , 1 . 07 mmol , 3 . 0 eq .). the reaction medium is co - evaporated with methanol . the obtained solid is triturated in methanol and in ethyl ether . the expected product is obtained as a yellow solid ( 137 mg , 88 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 446 . 5 [ c 20 h 20 fn 5 o 4 + h ] + ( m / z ) a solution of product 36b ( 200 mg , 0 . 46 mmol , 1 . 0 eq .) in trifluoroacetic anhydride ( 5 ml ) is heated to 90 ° c . for 6 hours . the reaction medium is cooled down to room temperature , the mixture is filtered and the filtrate is concentrated under reduced pressure . the obtained residue is re - crystallized from methanol and then purified by preparative hplc ( acetonitrile / h 2 o gradient ). the expected product is obtained as a beige solid ( 25 mg , 88 %). a solution of triethyl phosphonoacetate ( 2 . 6 g , 11 . 60 mmol , 1 . 3 eq .) in thf ( 5 ml ) is added dropwise to a suspension of nah ( 424 mg , 10 . 60 mmol , 1 . 2 eq .) in thf ( 8 ml ) at 0 ° c . the reaction medium is stirred at 0 ° c . for 30 minutes and a solution of 2 - formylthiazole ( 1 . 0 g , 8 . 84 mmol , 1 . 0 eq .) in thf ( 8 ml ) is added . the mixture is stirred at room temperature for 16 hours . the reaction medium is concentrated and then diluted with dichloromethane and washed with water and a saturated sodium chloride solution . the isolated organics extracts are dried and then the solvent is evaporated under reduced pressure . the raw expected product is obtained , which is purified by chromatography on silica by eluting with a cyclohexane - ethyl acetate mixture ( 10 : 0 to 85 : 15 ) and the expected product 171 is obtained as a colorless oil ( 1 . 7 g , 100 %). n - methoxymethyl )- n -( trimethylsilylmethyl )- benzyl - amine ( 466 mg , 1 . 96 mmol , 1 . 2 eq .) and a trifluoroacetic acid solution in dichloromethane ( 1n , 170 μl , 0 . 17 mmol , 0 . 1 eq .) are added to a solution of 171 ( 300 mg , 1 . 64 mmol , 1 . 0 eq .) in dichloromethane ( 5 ml ) at 0 ° c . the reaction medium is stirred at 0 ° c . for 20 minutes and at room temperature for 4 hours . the medium is then diluted with dichloromethane , washed with water and then with an aqueous saturated sodium chloride solution . the isolated organic extracts are dried and the solvent is evaporated under reduced pressure . the pure expected product is obtained as a yellow oil ( 516 mg , 98 %). a solution of 172 ( 500 mg , 1 . 73 mmol , 1 . 0 eq .) in an aqueous 6n hcl solution is stirred at room temperature for 16 hours . the reaction medium is then evaporated under reduced pressure , co - evaporated with toluene , and then dried on p 2 o 5 in vacuo . the expected product is obtained pure as a white solid ( 497 mg , 99 %). to a suspension of 173 ( 2 . 3 g , 8 . 03 mmol , 1 . 0 eq .) in tert - butyl alcohol ( 30 ml ), are added triethylamine ( 2 . 30 ml , 10 . 41 mmol , 1 . 3 eq .) and diphenylphosphoryl azide ( 2 . 30 ml , 16 . 55 mmol , 2 . 0 eq .). the reaction medium is stirred at 90 ° c . for 16 hours . triethylamine ( 2 . 30 ml , 16 . 55 mmol , 2 . 0 eq .) and di - tert - butyl dicarbonate ( 2 . 6 g , 11 . 91 mmol , 1 . 5 eq .) are added to the mixture and the latter is stirred at 55 ° c . for 3 hours . the reaction medium is concentrated under reduced pressure . the raw product is purified by chromatography on silica by eluting with a cyclohexane - ethyl acetate mixture ( 1 : 0 to 4 : 6 ) and the product 174 is obtained as a beige solid ( 296 mg , 10 %). to a solution of 174 ( 296 mg , 0 . 82 mmol , 1 . 0 eq .) in chloroform ( 4 ml ), is added chlorobenzyl formate ( 281 mg , 1 . 64 mmol , 2 . 0 eq .). the reaction medium is stirred at 60 ° c . for 7 hours . the reaction medium is concentrated under reduced pressure . the raw product is purified by chromatography on silica by eluting with a cyclohexane - ethyl acetate mixture ( 1 : 0 to 4 : 6 ) and the product 175 is obtained as a beige foam ( 220 mg , 67 %). to a solution of 175 ( 250 mg , 0 . 62 mmol , 1 . 0 eq .) in acetonitrile ( 4 . 5 ml ), are added sodium iodide ( 371 mg , 2 . 47 mmol , 4 . 0 eq .) and trimethylsilyl chloride ( 269 mg , 2 . 47 mmol , 2 . 0 eq .). the reaction medium is stirred at room temperature for 1 hour and methanol is then added ( 5 ml ). the reaction medium is concentrated under reduced pressure . the raw product is purified on a sephadex ® lh - 20 column and then on an scx column . the product 176 is obtained as a colorless oil ( 62 mg , 59 %). by using the method for preparing 5a , product 177 is obtained starting with 52 mg of “ ube - 4 ” ( 0 . 18 mmol , 1 . 0 eq .) and with product 176 ( 62 mg , 0 . 36 mmol , 2 . 0 eq .) in 0 . 5 ml of anhydrous pyridine and 1 ml of anhydrous acetonitrile in the presence of dabco ( 101 mg , 0 . 91 mmol , 2 . 5 eq .). the reaction medium is co - evaporated with methanol . the obtained solid is triturated in methanol and purified by preparative tlc . the expected product is obtained as a yellow solid ( 19 mg , 22 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 432 . 4 [ c 19 h 18 fn 5 o 4 s + h ] + ( m / z ) the product is prepared according to the method described in us 2003 / 0225107 by substituting 3 - hydroxy - pyrrolidinol with 3 -( s )- hydroxy - pyrrolidinol ( 1 . 0 g , 5 . 34 mmol , 1 . 0 eq .). 178 is obtained as an orange oil ( 1 . 2 g , 100 %). to a solution of product 178 ( 907 mg , 4 . 27 mmol , 1 . 0 eq .) in 25 ml of methanol , palladium on charcoal ( 454 mg , 0 . 43 mmol , 0 . 1 eq .) is added . the reaction medium is submitted to hydrogenation at atmospheric pressure and at room temperature for 6 hours . the reaction medium is then filtered on celite and concentrated under dry conditions under reduced pressure . the expected compound is obtained as a yellow oil ( 740 mg , 93 %). the method described in the preparation of 3a - 3b is used by substituting 3 -( r )- amino - pyrrolidine - 1 - carboxylic acid tert - butyl ester 179 for 3 - aminomethyl - pyrrolidine - 1 - carboxylic acid tert - butyl ester . the expected compound is obtained as a yellow solid ( 482 mg , 55 %). the method described in the preparation of 4c is used , by substituting product 180 for product 3c . the expected compound is obtained as a yellow solid ( 368 mg , 100 %). the method described in the preparation of 5c is used , by substituting product 181 ( 367 mg , 1 . 8 mmol , 1 . 8 eq .) for product 4c , the expected compound is obtained as a yellow solid ( 23 mg , 6 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 427 . 2 [ c 20 h 19 fn 6 o 4 + h ] + ( m / z ) the product is prepared according to the method described in us 2003 / 0225107 by substituting 3 - hydroxy - pyrrolidinol with 3 -( r )- hydroxy - pyrrolidinol ( 2 . 0 g , 10 . 68 mmol , 1 . 0 eq .). 183 is obtained as a yellow liquid ( 2 ; 0 g , 89 %). to a solution of product 178 ( 2 . 0 g , 9 . 42 mmol , 1 . 0 eq .) in 40 ml of methanol , palladium on charcoal ( 1 . 0 g , 0 . 94 mmol , 0 . 1 eq .) is added . the reaction medium is submitted to hydrogenation at atmospheric pressure and at room temperature for 6 hours . the reaction medium is then filtered on celite and concentrated under dry conditions under reduced pressure . the expected compound is obtained as a yellow oil ( 1 . 7 g , 97 %). the method described in the preparation of 3a - 3b is used by substituting 3 -( s )- amino - pyrrolidin - 1 - carboxylic acid tert - butyl ester 184 for 3 - aminomethyl - pyrrolidin - 1 - carboxylic acid tert - butyl ester . the expected compound is obtained as a yellow solid ( 510 mg , 26 %). the method described in the preparation of 4c is used by substituting product 185 for product 3c . the expected compound is obtained as a yellow solid ( 470 mg , 100 %). by using the method for preparing 5a , product 187 is obtained starting with 100 ml of “ ube - 4 ” ( 0 . 35 mmol , 1 . 0 eq .) and with product 186 ( 150 mg , 0 . 91mmol , 2 . 6 eq .) in 0 . 5 ml of anhydrous pyridine and 1 . 5 ml of anhydrous acetonitrile in the presence of dabco ( 100 mg , 0 . 89 mmol , 2 . 5 eq .). the obtained precipitate is filtered and then washed with acetonitrile and ethyl ether . the expected product is obtained as a yellow solid ( 120 mg , 80 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 432 . 4 [ c 20 h 19 fn 6 o 4 + h ] + ( m / z ) mp = 257 - 259 ° c . a solution of n - butyllithium ( 2 . 5m / hexane , 8 . 3 ml , 20 . 68 mmol , 4 . 4 eq .) is added to a solution of monoethyl malonate ( 1 . 36 g , 10 . 35 mmol , 2 . 2 eq .) in thf ( 15 ml ) at 0 ° c . the reaction medium is cooled to − 50 ° c . and a solution of 2 , 3 , 4 , 5 - tetrafluorobenzoyl chloride in thf ( 5 ml ) is added dropwise . the mixture is then stirred at room temperature for 16 hours . the reaction is hydrolyzed by an aqueous 1n hcl solution , and then the organic phase is extracted with ethyl acetate . the isolated organic extracts are dried and the solvent is then evaporated under reduced pressure . the raw expected product is obtained , which is purified by chromatography on silica by eluting with a cyclohexane - ethyl acetate mixture ( 1 : 0 to 9 : 1 ) and the expected product 188 is obtained as a pale orange oil ( 600 mg , 50 %). a mixture of product 188 ( 1 . 8 g , 6 . 70 mmol , 1 . 0 eq . ), triethyl orthoformate ( 1 . 7 ml , 10 . 05 mmol , 1 . 5 eq .) and acetic anhydride ( 2 . 7 ml , 26 . 80 mmol , 4 . 0 eq .) is stirred at 125 ° c . in a sealed tube for 16 hours . the medium is concentrated under reduced pressure and the product 189 ( 1 . 8 g , 88 %) is used without any subsequent purification . a solution of boc - hydrazine ( 870 mg , 6 . 55 mmol , 1 . 1 eq .) and of product 189 ( 1 . 8 g , 5 . 95 mmol , 1 . 0 eq .) in toluene ( 9 ml ) is stirred at 80 ° c . for 4 hours . the reaction is hydrolyzed by adding water , and the organic phase is then extracted with ethyl acetate . the isolated organic extracts are dried and the solvent is then evaporated under reduced pressure . the raw expected product is obtained , which is purified by chromatography on silica by eluting with a cyclohexane - ethyl acetate mixture ( 1 : 0 to 5 : 5 ) and the expected product 190 is obtained as a pale yellow solid ( 800 mg , 35 %). to a solution of product 190 ( 600 mg , 1 . 55 mmol , 1 . 0 eq .) and of triphenyl phosphine ( 615 mg , 2 . 30 mmol , 1 . 5 eq .) in thf ( 6 ml ) at 0 ° c ., are added diethyl azodicarboxylate ( 1 . 08 ml , 2 . 30 mmol , 1 . 5 eq .) and 2 - fluoroethanol . the reaction medium is stirred at room temperature for 16 hours . the reaction is hydrolyzed by adding water , and the organic phase is then extracted with ethyl acetate and washed with an aqueous 1n hcl solution . the isolated organic extracts are dried and the solvent is then evaporated under reduced pressure . the raw expected product is obtained , which is purified by chromatography on silica by eluting with a cyclohexane - ethyl acetate mixture ( 1 : 0 to 5 : 5 ) and the expected product 191 is obtained as a yellow solid ( 495 mg , 73 %). the method described for preparing the product 4a is used , by substituting for product 3a , product 191 ( 514 mg , 1 . 19 mmol , 1 . 0 eq .) with 2 . 5 ml of trifluoroacetic acid in 5 ml of dichloromethane . the medium is diluted with dichloromethane and water . the aqueous phase is alkalinized with an aqueous ( 1n ) sodium hydroxide solution and extracted with dichloromethane . the organic extracts are dried and concentrated under reduced pressure . the expected product is obtained as a pale yellow oil ( 315 mg , 79 %). a suspension of product 192 ( 310 mg , 1 . 19 mmol , 1 . 0 eq .) and of paraformaldehyde ( 1 . 2 g , 39 . 90 mmol , 40 . 0 eq .) in water is stirred at 110 ° c . in a sealed tube for 48 hours . the medium is cooled at room temperature and the obtained precipitate is filtered , washed with methanol , and ethyl ether . the expected product is obtained as a white solid ( 254 mg , 77 %). a suspension of product 194 ( 600 mg , 1 . 66 mmol , 1 . 0 eq .) in thf ( 35 ml ) is heated to reflux in less than 5 minutes and tbaf ( 3 . 7 ml , 3 . 67 mmol , 2 . 2 eq .) is added very rapidly . the reaction medium is stirred at reflux for 20 minutes . the mixture is then poured onto a saturated sodium carbonate solution , and the organic phase is then separated and then extracted with ethyl acetate . the isolated organic extracts are dried and the solvent is then evaporated under reduced pressure . the residue is taken up in ethyl acetate and a precipitate is formed by adding ethyl ether . the precipitate is filtered and dried in vacuo . the expected product is obtained as a beige solid ( 240 mg , 42 %). lithium hydroxide ( 227 mg , 5 . 40 mmol , 5 . 0 eq .) is added to a solution of product 195 ( 370 mg , 1 . 08 mmol , 1 . 0 eq .) in a water / thf mixture ( 4 ml / 4ml ). the reaction medium is stirred at room temperature for 7 hours . the formed precipitate is filtered , washed with ethyl ether and then dried in vacuo . the expected product is obtained as a white solid ( 286 mg , 84 %). by using the method for preparing 5a , product 196 is obtained starting with 100 mg of product 195 ( 0 . 32 mmol , 1 . 0 eq .) and with product 35b ( 108 mg , 0 . 64 mmol , 2 . 0 eq .) in 0 . 8 ml of anhydrous pyridine and 1 . 5 ml of anhydrous acetonitrile in the presence of dabco ( 72 mg , 0 . 64 mmol , 2 . 0 eq .). the reaction medium is evaporated under reduced pressure . the result is triturated in methanol and then purified by preparative tlc . the expected product is obtained as a yellow solid ( 18 mg , 12 %). ms ( esi + ) (+ 0 . 1 %, hcooh ): 432 . 4 [ c 20 h 19 f 2 n 5 o 4 s + h ] + ( m / z ) in order to assess the anti - infectious activity , a test to determine the minimal inhibitory concentrations ( mic ), of the synthesized molecules is implemented . this comparative test , using a reference fluoroquinolone , measures the minimum inhibitory concentrations for the principal reference and in - situ bacteria , isolated from human and animal pathologies ( canine , feline , bovine or porcine ). these bacteria represent different resistance populations vis - a - vis the fluoroquinolones for each bacterial species selected and come from vetoquinol s . a .&# 39 ; s private collection or atcc references , m . haemolytica ( 2 ); b . bronchiseptica ; p . aeruginosa ( 2 ); e . coli ( 3 ); s . aureus ( 3 ); s . uberis ; m . bovis and bovirhinis ; c . perfringens . mic determination is carried out by microdilution in a liquid medium . the method used for the aerobic and anaerobic bacteria is based on the clsi ( nccls ) m31 - a ( may 2002 ) guideline “ performance standards for antimicrobial disk and dilution susceptibility tests for bacteria isolated from animals ”. the method used for the mycoplasma is based on the clsi ( nccls ) m3 1 - a ( may 2002 ) guideline and the article by f . poumarat and j . l . martel . for each molecule , the concentrations to be tested vis - a - vis the strains are : acceptable results of these controls validate the results obtained for each molecule . the results obtained for each of the molecules are summarized in table form in order to : | 2 |
often filament substrates are provided as a product of coal tar pitch produced in accordance with u . s . pat . no . 3 , 595 , 946 , granted july 27 , 1971 to joo et al and the improvements thereof described in my co - pending application , entitled &# 34 ; a carbon filament coated with boron and method of making same &# 34 ;, ser . no . 230 , 867 , filed mar . 1 , 1972 , the disclosure and references cited in said patent and application , the disclosures of all of which are incorporated herein by reference as though set out at length herein . the substrate is passed through a tubular reactor and heated either by passage of electrical current therethrough , or indirectly , to a temperature of 1 , 100 °- 1 , 400 ° c ., and preferably 1 , 300 ° c ., and an atmosphere of boron trichloride vapor and hydrogen is maintained therein , flowing either co - current or counter current to the direction of movement of the substrate filament which rapidly passes through the reactor with the result that the hot substrate is exposed to the gaseous environment of the reactor for a short period of time to produce a layer of boron essentially uniformly on the substrate in a thickness of about 0 . 1 - 2 . 5 microns . this process is called chemical vapor deposition , and , at times , pyrolitic deposition . with or without an intermediate step of cooling to room temperature , the flash - coated carbon filament is brought up to a temperature of about 2 , 500 ° c . and passed through a reactor containing an inert environment provided by argon or other inert gas flushing , for a period of about a second . the latter step results in a conductivity rise of at least two times for the flash - coated carbon filament . a skin layer of oriented graphite is produced . subsequently , the so - treated carbon filament is passed through a further reactor for chemical vapor deposition of boron in some conventional way , for example , as described in my said application ser . no . 230 , 867 , first cited above , or u . s . pat . no . 3 , 679 , 475 . the resultant product contains three separate and distinct zones -- the amorphous carbon core , the intermediate graphite skin layer , produced by catalytic conversion , and the outer boron coating . it was found in actual practice of the above described embodiment , and variations of such practice , that the boron catalyst was essential for forming the oriented graphite layer under the time and temperature conditions described above and that the layer would not form without the boron . with the boron catalyst , repeated deposition runs were enabled in which final boron coat layers more than one mil thick could be coated without catastrophic breakage of the carbon substrate . this breakage normally would occur without the boron flash coating and heat treatment as a result of growth strains imposed on the substrate by the final boron coat growth phenomenon . it was also observed that there was lesser tendency with the boron catalyst than without for carbonaceous debris to occur at the entrance of the boron coating reactor . such debris when it would occur would tend to cause serious flaws in short run lengths in the product . the following characteristics of treated and non - treated carbon monofilament have been observed . when a carbon monofilament , produced from coal tar pitch , is heated in the range of 1 , 100 °- 2 , 500 ° c ., its resistance will drop . however , following the boron flash and graphite skin treatments , the treated monofilament has a resistance per unit of length less than one half as great as the lowest resistance per unit length of the above - mentioned untreated carbon monofilament . more significantly , when a boron coating is deposited on an untreated carbon monofilament , which has been heated above 1 , 100 ° c ., such as , to 2 , 500 ° c ., the problem , which the addition of a boron flash cures , persists . a carbon monofilament that has undergone boron flash and graphite skin treatments contains a visually observable skin layer . the skin layer is definitely not b 4 c . as b 4 c is a semiconductor , it would cause a rise in resistance at room temperature . there have been indications that small quantities of boron in combination with carbon acts as a catalyst to convert amorphous carbon catalytically to graphite when the amorphous carbon containing a boron is raised to elevated temperatures . the demonstrable drop in resistance noted above is consistent with the development of a highly oriented graphitic skin coating . the most widely used boron filament has a nominal diameter of 4 . 0 mils . a nominal 1 . 3 mil carbon core is used . in practice , the core may vary from 1 . 0 - 1 . 4 mils in diameter . the graphite skin layer appears to contain some elemental boron and boron in combination with carbon . these inclusions appear in very small amounts and do not materially affect the performance of the graphite skin layer . untreated , the 1 . 3 mil carbon monofilament core has a resistance of about 700 ohms / inch when made . this can be reduced by heating the carbon monofilament above 2 , 100 ° c to about 550 ohms / inch . typically , a 0 . 1 - 2 . 5 microns flash coating of boron is applied , with 0 . 1 - 1 micron being preferred . when the carbon monofilament with boron flash is heated as prescribed , a 0 . 02 - 0 . 05 mil skin layer of oriented graphite is produced . preferably , the skin layer of graphite should not exceed 0 . 2 mil . the aforementioned 0 . 1 - 2 . 5 micron boron flash coating appears to be a narrow window . the procedure deteriorates with heavier boron flash coatings . the preferred procedure is successive flash coatings of 0 . 1 - 2 . 5 microns followed by heat treating to produce thick graphite skin layers , in the order of 0 . 1 - 0 . 2 mil . the resistance of the 1 . 3 mil carbon monofilament with a graphitic skin layer is typically in the order of , but generally less than 200 ohms / inch . it is evident that those skilled in the art , once given the benefit of the foregoing disclosure , may now make numerous other uses and modifications of , and departures from the specific embodiments described herein without departure from the inventive concepts . consequently , the invention is to be construed as embracing each and every novel feature and novel combination of features present in , or possessed by , the apparatus and techniques herein disclosed and limited solely by the scope and spirit of the appended claims . | 8 |
in an exemplary embodiment of the method of the present invention , the magnetically coated media is extracted from its native operating environment and mounted on a device which can perform magnetically recorded data reading operations under user control . generally , the magnetic media is installed on a device which is capable of positioning a magnetoresistive transducer over a user - selectable location and drive mechanism for producing a change in magnetic flux about the magnetoresistive transducer at the user - selected location , where the change in magnetic flux corresponds to previously - written , magnetically polarized regions on the magnetically coated media . for the case of hard disk drives , the carrier of magnetically coated media is a thin , rigid disk , which , in accordance with an exemplary embodiment of the present invention , is mounted on a sophisticated device called a spin - stand . such a spin - stand , and associated equipment , is illustrated in fig1 . as is shown in the figures , the hard disk 30 is a standard magnetically coated hard disk having a plurality of annular , magnetic tracks formed thereon , as is well - known in the art . the disk 30 is mounted on a spindle motor 20 of the spin - stand system 12 . magnetoresistive transducer 40 is mechanically coupled to magnetoresistive transducer positioning means 45 of spin - stand imaging system 12 . the positioning means 45 is used to position the magnetoresistive transducer 40 to a user - selected location ( radius ) over hard disk 30 . positioning means 45 may be , but is not limited to , a voice coil actuator , stepper motor , or piezoelectric positioning apparatus . magnetoresistive transducer positioning means 45 needs only provide fine positioning of magnetic head 40 to within a predefined tolerance ( usually on a sub - micron scale ). magnetic head 40 is mounted to spin - stand system 12 via positioning means 45 to provide the scanning capability of the individual tracks of the disk 30 . spindle 20 is the rotational drive for rotating disk 30 beneath magnetic head 40 so as to provide relative motion between hard disk 30 and magnetic head 40 . the relative motion produces a change in magnetic flux from regions of varying magnetic polarity on hard disk 30 about magnetic head 40 . as is well - known , the change in magnetic flux is coupled to magnetic head 40 to produce a voltage signal responsive thereto . thus , whereas the rotational drive system of spin - stand imaging system 12 is an exemplary embodiment , any means to produce a change in magnetic flux about magnetoresistive transducer 40 is within the scope of the present invention . magnetic head 40 is in electrical communication with a read channel circuitboard 50 which may include an amplifier and associated circuits to boost the voltage signal produced at the output of magnetic head 40 . in the exemplary embodiment illustrated in fig1 , the output of read channel circuitboard 50 is electrically coupled to an oscilloscope 60 or other signal display / processing device . oscilloscope 60 displays readback voltage 70 and is electrically coupled to central processing unit 90 via cable 80 . central processing unit 90 includes a processing chip and storage means , as is well - known in the art . the central processing unit 90 translates the electrical signals generated by the read channel circuitboard 50 into isi - free data by means of the method of the present invention . spin - stands are routinely used in the magnetic recording industry to characterize heads , media and recording channels . it is therefore an issue of great commercial interest when one can recover the magnetization patterns recorded on hard disks mounted on a spin - stand . recent advances in technology have allowed the compensation of the eccentricity of the disk and the instability of the trigger signal so that large - scale images of hard disk data may be obtained . a portion of such an image is illustrated in fig2 . in the figure , the dark regions represent changes in magnetization in opposite directions and the unshaded portions represent regions where there is zero magnetization or no change in magnetization at all . the image of fig2 , being only a very small portion of a much larger image , shows the servo burst region 210 , the gain ( preamble ) region 220 and a portion of the user - data region 230 . the recent advances in technology of high - speed , massive , spin - stand imaging alone is not adequate , however , for the purpose of data recovery . this is because a spin - stand image of a hard disk represents only a raw image of the isi - ridden head readback signal . additional effort must be exerted to remove these isi - distortions before converting the analog signals into decoded binary data that the operating system can understand . it is this effort of isi - removal that is an object of the method of the present invention . the effectiveness of the subject method is illustrated in fig3 a and fig3 b . the raw readback signal of fig3 a was captured from a hard disk taken from a commercial hard drive with track density of 60 , 000 tracks per inch and mounted on a spin - stand . the method of the present invention was utilized to remove the isi from the signals . fig3 b portrays the reconstructed , isi - free signal where , clearly , all the peaks in the raw readback signals have been restored to their correct amplitude and locations after using the subject method . the present invention is a recovery technique that can remove the distortions in the readback signal of a gmr head caused by isi . this can be viewed as a process of image reconstruction . the purpose of the reconstruction is to remove the distortion from the raw isi - ridden readback signal and to retrieve the underlying actual magnetization distributions . image reconstruction can thus be viewed as the transformation of the physical quantity of interest from that of the temporal signal of the magnetic read head to that of the magnetization patterns on the media . this image reconstruction technique is based on the response function characterization of the gmr element and is described below . as illustrated in fig4 , the position of the scanning gmr element can be identified by the x coordinate of its center . the recorded magnetization distribution can be characterized by the equivalent distribution of virtual magnetic charges σ m ( x ′). the density of these charges is related to the magnetization by the expression σ m ( x ′ ) = - μ 0 h ∇ · m = - μ 0 h ( ∂ m x ∂ x + ∂ m y ∂ y ) , ( 1 ) where h is the thickness of the recording media . it is assumed that the recorded magnetization is uniform over the media thickness and , for this reason , the divergence of m has the meaning of “ surface ” divergence . for the purpose of regular data recovery , only the readback signal at the track center is of interest . therefore , one can further assume that the magnetization is uniform over the width of the track . under this assumption , equation ( 1 ) can be simplified as follows : σ m ( x ′ ) = - μ 0 h ∇ · m = - μ 0 h ∂ m x ∂ x ( 2 ) the above one - dimensional treatment of the magnetization is possible only under the condition that the readback signal at the track center is all that is relevant . this is opposed to the case of recovery of overwritten data where the readback signal at the track edges is of importance . this other case by its very nature is a two - dimensional isi - removal problem , and it requires a 2 - d treatment of the magnetization , which will be discussed in paragraphs that follow . the previously - used term “ equivalent distribution of virtual magnetic charges ” comes from the fact that this distribution creates the same magnetic field as the actual magnetization distribution . this magnetic field gives rise to the signal collected by the gmr element . this signal can be viewed as the superposition of the signals due to the elementary magnetic charges distributed over the disk surface . this superposition can be written as a convolution integral whose kernel has the physical meaning of the response function of the gmr element . mathematically , the last assertion can be expressed as follows : s ( x )=∫ r ( x − x ′) σ m ( x ′) dx ′ ( 3 ) here , s ( x ) is the isi - ridden signal of the gmr element , while r ( x − x ′) can be interpreted as the response function of the gmr element . this function has the physical meaning of the signal induced in the gmr element at position x by the line unit magnetic charge located at position x ′ ( see fig4 ). it is worth stressing that equation ( 3 ) follows from the translational invariance of the readback process . in other words , equation ( 3 ) is the weighted superposition of spatially - shifted head response function . there are two ways to obtain the response function r ( x − x ′). the first approach is a direct one . in this approach , an isolated and very sharp transition is first written as illustrated in fig4 . as a result , a “ thin ” isolated stripe of magnetic charges is written that can be viewed as an approximation to an ideal line charge . the gmr reading element can then be used to measure the signal as a function of relative position with respect to the recorded “ line ” magnetic charge . this signal can be interpreted as an approximate version of r ( x − x ′); the sharper the transition , the more accurate it will be to the actual response function . another way to determine the response function is to write a well - defined pattern of magnetization ( magnetic charge ). for this pattern , the gmr element signal s ( x ) is measured as a function of x . then equation ( 3 ) can be interpreted as an integral equation in which s ( x ) and σ m ( x ′) are known , while r ( x − x ′) is unknown . by solving this integral equation , the response function can be determined . having determined the response function , equation ( 3 ) can be viewed as a convolution integral equation that relates the raw , isi - ridden signal s ( x ) to the distribution of virtual , isi - free magnetic charges σ m ( x ′). this integral equation can be solved by using a one - dimensional fourier transform : f ~ ( k x ) = ∫ - ∞ ∞ f ( x ) ⅇ - ⅈ k x x ⅆ x ( 4 ) σ ~ m ( k x ) = s ~ ( k x ) r ~ ( k x ) ( 5 ) having found { tilde over ( σ )} m , which is unique to the distribution m x , the fourier transform of m x can be determined . by fourier transforming equation ( 2 ), one can derive the following relation for { tilde over ( m )} x : ik x m ~ x = - σ ~ m μ 0 h ( 6 ) m ~ x = i σ ~ m μ 0 hk x ( 7 ) by performing inverse fourier transform on equation ( 7 ), and by using equation ( 5 ), the following explicit formula for the actual distributions of m x is derived : m x ( x ) = ft - 1 [ i s ~ ( k x ) μ 0 hk x r ~ ( k x ) ] ( 8 ) this reconstructed m x ( x ) is decoupled from any distortion caused by isi . as mentioned , the above one - dimensional treatment of the magnetization reconstruction is only valid for the recovery of data where the information is concentrated near the center of the track . for the recovery of overwritten data , however , a two - dimensional treatment of the recovery problem is required because the overwritten information , if any , resides at the edges of the track . track edges usually contain remnant data of previous recordings because exact overwriting will almost never occur due to track misregistration . as the disk platters of hard drives will have even higher coercivity in the future , the fringe field of the write head may not be sufficient to overwrite the data at the track edges , leaving the regions there with old information . with respect to recovering these overwritten data at the track edges , the invented data recovery technique has a natural extension to remove even readback distortions caused by 2 - d isi . the theoretical formulation of this 2 - d data recovery , isi - removal technique is as follows . the position of the center of the gmr element is identified by the coordinate ( x , y ). the recorded magnetization distribution can be characterized by the equivalent distribution of virtual magnetic charges σ m ( x ′, y ′). the density of these charges is related to the magnetization by the expression σ m ( x ′ , y ′ ) = - μ 0 h ∇ · m = - μ 0 h ( ∂ m x ∂ x + ∂ m y ∂ y ) ( 9 ) where , once again , h is the thickness of the recording media and it is assumed that the recorded magnetization is uniform over the media thickness . in the 2 - d case , the isi - ridden readback signal , s ( x , y ) can be expressed as follows : s ( x , y )=∫∫ r ( x − x ′, y − y ′) σ m ( x ′, y ′) dx ′ dy ′ ( 10 ) here , r ( x − x ′, y − y ′) is the response function of the gmr element . it has the physical meaning of the signal induced in the gmr element at position ( x , y ) by the point unit magnetic charge located at position ( x ′, y ′) ( see fig5 a ). there are again two ways to obtain this response function r ( x − x ′, y − y ′). in the first approach , an isolated sharp transition is first written . this transition is then trimmed by using dc erasure on both sides of the same track ( see fig5 b ). as a result , a “ tiny ” isolated spot of magnetic charges is written that can be viewed as an approximation to a point charge . the gmr reading element can now be used to measure the signal as a function of relative position with respect to the recorded “ point ” magnetic charge . this signal can be interpreted as an approximate version of r ( x − x ′, y − y ′). another way to determine the response function is to write a well - defined pattern of magnetization ( magnetic charge ). for this pattern , the gmr element signal s ( x , y ) is measured as a function of x and y . then equation ( 10 ) can be interpreted as an integral equation in which s ( x , y ) and σ m ( x ′, y ′) are known , while r ( x − x ′, y − y ′) is unknown . by solving this integral equation , the response function can be determined . having determined the response function , equation ( 10 ) can be viewed as a convolution integral equation that relates the raw , isi - ridden image s ( x , y ) to the distribution of virtual , isi - free magnetic charges σ m ( x ′, y ′). this integral equation can be solved by using a two - dimensional fourier transform , f ~ ( k x , k y ) = ∫ ∫ - ∞ ∞ f ( x , y ) ⅇ - ⅈ ( k x x + k y y ) ⅆ x ⅆ y ( 11 ) σ ~ m ( k x , k y ) = s ~ ( k x , k y ) r ~ ( k x , k y ) ( 12 ) having found { tilde over ( σ )} m , the fourier transforms of m x and m y can be determined . here , we shall use the known fact that only the curl - free component of magnetization can be retrieved from gmr measurements . this is because the curl - free component of magnetization distribution is the field producing part of the total magnetization distribution . for this reason , only this component is sensed by the gmr element . thus , m x and m y in equation ( 9 ) are meant to satisfy the additional equation curl z m = ∂ m y ∂ x - ∂ m x ∂ y = 0 ( 13 ) by fourier transforming equations ( 9 ) and ( 13 ), one can derive the following simultaneous equations for { tilde over ( m )} x and { tilde over ( m )} y : i ( k x m ~ x + k y m ~ y ) = - σ ~ m μ 0 h ( 14 ) by solving equations ( 14 ) and ( 15 ), the following equations are readily derived : m ~ x ( x , y ) = i σ ~ m ( k x , k y ) k x μ 0 h ( k x 2 + k y 2 ) ( 16 ) m ~ y ( x , y ) = i σ ~ m ( k x , k y ) k y μ 0 h ( k x 2 + k y 2 ) ( 17 ) by performing the inverse fourier transforms on equations ( 16 ) and ( 17 ), and by using equation ( 12 ), we arrive at the following explicit formulas for the actual isi - free distributions of m x and m y : m x = ft - 1 [ i s ~ ( k x , k y ) k x μ 0 h r ~ ( k x , k y ) ( k x 2 + k y 2 ) ] ( 18 ) m y = ft - 1 [ i s ~ ( k x , k y ) k y μ 0 h r ~ ( k x , k y ) ( k x 2 + k y 2 ) ] ( 19 ) while the recovery of ordinary data on the track center is a 1 - d isi - removal problem , that of overwritten data is intrinsically a 2 - d isi - removal issue . it is expected that no recovery of such overwritten data is possible on the readback signal alone , which is severely distorted by 2 - d isi . in view of formulas ( 18 ) and ( 19 ) described above , it is indeed possible to recover such overwritten data through the current recovery technique . in addition , the industry practice of write - wide - read - narrow also makes possible the recovery of overwritten data . this is the practice where the write head writes a track wider than the read head senses . user data is especially susceptible to recovery if newer generation heads that have narrower read widths are used to read hard disk data recorded with older technologies . the issues of numerical noise from the computation of the reconstructed images are addressed here . by examining formula ( 8 ) for the 1 - d case and formulas ( 18 ) and ( 19 ) for the 2 - d case , it is clear in the event that the denominators are zero , the numerators have to be forced to zero as well to prevent singularities . for the 1 - d case , for example , if k x is zero , then { tilde over ( s )}( o ) has to be zero . specifically , from equation ( 4 ), the following condition must be satisfied when k x is zero : s ~ ( 0 ) = ∫ - ∞ ∞ s ( x ) ⅆ x = 0 ( 20 ) in other words , the raw isi - distorted signal must have a zero mean over the length of consideration . similarly , for the 2 - d case , if both k x and k y are zero , then { tilde over ( s )}( 0 , 0 ) has to be zero as well . from equation ( 11 ), the following condition is required : s ~ ( 0 , 0 ) = ∫ ∫ - ∞ ∞ s ( x , y ) ⅆ x ⅆ y = 0 ( 21 ) that is , the raw isi - distorted image must have a zero mean over the region of consideration . apart from the issue of singularity , there are two other potential sources of numerical errors . first , small values of { tilde over ( r )}( k x ) in equation ( 8 ) and { tilde over ( r )}( k x , k y ) in equations ( 18 ) and ( 19 ) might amplify the noise level . second , since differentiation of the reconstructed magnetization is needed in order to obtain the readback signal , changes in magnetization might create undesirable noise after differentiation . due to the above reasons , some special scheme is required to suppress and remove the noise . to this end , it has been demonstrated that the numerical noise can be eliminated by suitably exploiting the properties of the arctangent function . the most salient properties of the arctangent function are that ( 1 ) it accentuates its argument when there is a change in polarity ( switching ) in the argument ; and ( 2 ) it de - emphasizes the changes in the amplitude of its argument when these changes occur outside the switching region . therefore , the arctangent function is a natural and extremely effective tool to suppress any numerical noise in the computation of the reconstructed images . it is a natural choice because magnetization patterns themselves are often modeled by arctangent transition . specifically , noise can be significantly removed if , instead of differentiating the magnetization directly , the arctangent of the magnetization is differentiated . in this way , the level of noise removal can also be controlled by multiplying the amplitudes of the magnetization by a scalable number . the equation below describes the arctangent operation : s recovered ( x ) = ⅆ ⅆ x [ arctan ( α m ( x ) ) ] ( 22 ) where α is a scalable factor that controls the level of noise reduction . as an illustration , fig6 a – 6d show the effect of the arctangent operation in reducing the noise level of the recovered readback signal of tribit patterns . here , the dashed lines in each figure represent the same raw isi - distorted patterns while the solid lines are the recovered patterns . in the figures , the values of α go from one in fig6 a to some optimum value in fig6 d . as is evident , the arctangent operation has effectively suppressed the noise in the reconstructed readback signals . it is known in the art that the scaling of the head response function can greatly improve the accuracy of the reconstructed magnetization . here , in the case of isi - removal , similar improvement in the recovered readback signal has also been demonstrated . fig7 a – 7d presents the improvement in the accuracy of the recovered tribit signals as one scales down the 1 - d head response function ( the dashed and solid lines assume their usual meanings ). when no scaling is performed ( fig7 a ), the two peaks at locations 1 . 2 μm and 1 . 27 μm cannot be resolved . however , as one gradually scales down the head response function ( from fig7 b to 7d ), all the peaks of the tribit patterns are eventually recovered . referring now to fig8 a – 8c , there is graphically shown data from tribit patterns with known isi in the readback signals which were written onto a hard disk . a tribit pattern is one that has three consecutive transitions . in the presence of isi , the middle transition ( generally indicated at 500 ) in the readback signal will be increasingly corrupted as the data density increases . fig8 a – 8c show the reconstructed readback signals ( solid lines ) superimposed on the isi - distorted readback signals ( dashed lines ) of tribit patterns with increasing densities ( from fig8 a to 8c ). the reconstructed readback signals were obtained through the use of the method of the present invention . it is clear that the middle transitions of the tribit patterns , which are not legible due to varying degrees of isi , have been successfully reconstructed utilizing the subject technique . fig9 a – 9c show similar results , where the data originally written correspond to hexadecimal f6 patterns ( i . e ., binary pattern of “ 11110110 ”) were written with increasing data density . the figures show two periods of the reconstructed readback signals ( solid lines ) superimposed on the isi - distorted readback signals ( dashed lines ) of the f6 patterns . as is clearly shown , the special signatures associated with the f6 patterns have been recovered after the isi has been removed from the original raw readback f6 signals . fig1 is a flow chart of the process steps of an exemplary embodiment of the method of the present invention . first , as is indicated at block 1000 , the raw isi - distorted readback signal s ( x ) is acquired from the spin - stand imaging system of fig1 . from the readback signal s ( x ), the length of the signal , n x , is determined , where n x is the number of samples taken of signal s ( x ). next , as shown at block 1020 , a spatial mesh x is defined as : where dx = l x /( n x − 1 ) and l x is the along - track distance over which the readback signal s ( x ) has been acquired . as is shown in block 1030 , a similar mesh is defined for the frequency domain , where the frequency mesh is designated k x . k x is defined as : for the exemplary embodiment of the subject method of fig1 , it is assumed that the magnetoresistive transducer response function r ( x ) has been determined in accordance with the procedures outlined hereinabove . then , as is shown at block 1040 , the response function r ( x ) is scaled according to the scaled response function r ′( x ) is then normalized in amplitude according to as is shown at block 1050 . at block 1060 , the normalized response function r ″( x ) is centered at the origin by either delaying or advancing in space the response function r ″( x ). when the raw data has been acquired , and the response function scaled , normalized and centered , flow is transferred to block 1070 where the fourier transform of r ″( x ) and s ( x ) is performed to produce r_ft ( k x ) and s_ft ( k x ), respectively . then , as is indicated at block 1080 , the fourier transform of the recovered magnetization is obtained from the scaled and rotated ratio of fourier transform s_ft ( k x ) and r_ft ( k x ) according to the equation : m_ ft ( k x ) = i s_ft ( k x ) k x r_ft ( k x ) the recovered magnetization in the spatial domain is then obtained by taking the inverse fourier transform of m_ft ( k x ) as shown at block 1090 . when recovered magnetization m ( x ) has been obtained , a noise reduction technique such as the application of the arctangent function as discussed hereinabove , is applied to produce where α is a user - scalable factor . the noise reduced signal m ′( x ) is differentiated to produce the recovered isi - free readback signal according to : s ′ ( x ) = ⅆ ⅆ x m ′ ( x ) as shown at block 1110 . the isi - free readback signal as recovered by the method of the present invention is then output as s ′( x ) as shown at block 1120 . fig1 is a flow chart of the process steps of the two - dimensional version of the method of the present invention . the process steps are self - explanatory in view of the previous discussion of fig1 with the obvious extension to the two - dimensional case . the process steps 2000 – 2120 are basically identical to process steps 1000 – 1120 , respectively , with the exception that the former set of process steps take into account the across - track variations as previously discussed . although the invention has been described herein in conjunction with specific embodiments thereof , many alternatives , modifications and variations will be apparent to those skilled in the art . the present invention is intended to embrace all such alternatives , modifications , and variations that fall within the spirit and broad scope of the appended claims . | 6 |
referring now to fig1 - 5 , there is shown the deck suspension mechanism 10 according to the present invention . the deck suspension mechanism 10 is adapted for use with a lawn tractor vehicle 12 , as best seen in fig1 having a mower deck 14 carried beneath the lawn tractor 12 between the tractor &# 39 ; s front and rear pairs of wheels 16 . at least one mower blade rotates within the mower deck 14 for cutting grass beneath the deck 14 . a drive mechanism 20 such as a belt drive system transmits rotational power from the vehicle power source or engine 22 to the mower deck spindles 24 to which the cutting blades are coupled . a first deck suspension linkage 26 couples the front or first portion 28 of the deck 14 to the tractor 12 . a pair of plate members 30 are fixed as by welds to the front portion 28 of the deck 14 . the plate members 30 define hooks 32 that open generally rearwardly and upwardly . a suspension member or rod member 34 is provided which includes a laterally extending portion 36 which is engaged with the hooks 32 of the plate members 30 . the rod member 34 is shaped to define a forward portion 38 which extends generally longitudinally with respect to the lawn tractor 12 . the forward portion 38 of the rod member 34 includes a threaded end portion 40 which receives a ball member 42 and a nut 44 . the nut 44 holds the ball member 42 in place for engagement with socket portion 45 of a structural member 46 that is fixed as by welds to the pivotal front axle 48 of the lawn tractor 12 . the front axle 48 pivots about an axis 50 as the front wheels 16 of the lawn tractor 12 encounter ground undulations during operation . the forward end portion 38 of the rod member 34 is positioned within a slot 52 formed in a generally planar surface portion 54 of the structural member 46 . the slot 52 extends generally vertically according to the preferred embodiment of the present invention . during operation the end portion 38 of the rod member 34 is pulled downwardly and rearwardly by the weight of the deck 14 to the lowermost end portion 56 of the slot 52 . the top portion 58 of the slot 52 includes an enlarged portion 60 which is sized large enough to allow the ball member 42 and nut 44 to pass there - through when the operator wishes to remove the deck 14 from the lawn tractor 12 . a cross pin 62 is positioned within a pair of openings 64 in the structural member 46 , and is held in position by a spring pin 66 or other suitable device . the cross pin 62 is positioned generally across the slot 52 beneath the enlarged portion 60 of the slot 52 , and thereby prevents or blocks the rod member 34 from rising up out of the lowermost end portion 56 of the slot 52 during mowing operations . the cross pin 62 thereby blocks the end portion 38 of the rod member 34 from shifting or bouncing upwardly within the slot 52 to a position whereat the ball 42 and nut 44 could pass through the enlarged portion 60 of the slot 52 . a second deck suspension linkage 68 is provided which couples the rear or second portion 70 of the mower deck 14 with the vehicle 12 . as seen in fig1 and 2 , a pair of link members 72 extend upwardly from the rear 70 of the deck 14 . a pair of lift arms 74 operatively engage the link members 72 , and are mounted to a laterally extending pivot shaft 76 . the pivot shaft 76 is selectively pivotable by the operator by way of a manual lift mechanism 78 . as the operator engages hand lever 79 , the lift mechanism 78 pivots the pivot shaft 76 , and the lift arms 74 will pivot therewith , causing the link members 72 to shift up or down with the rearward end of the lift arms 74 . this serves to lift or lower the deck 14 to the desired cutting height . a pair of brackets 80 are also coupled with the rear portion 70 of the deck 14 . a pair of straps 82 are coupled between respective brackets 80 and portions of the vehicle frame . the straps 82 and front rod member 34 act as a four bar linkage that raises and lowers the deck 14 in the proper orientation . the straps 82 bear little or no weight of the deck 14 during operation . next , the operation of the present invention will be discussed in greater detail . during operation , the threaded front end portion 40 of the rod member 34 is positioned within the lowermost end portion 56 of the slot 52 , and the laterally extending rear portion 36 of the rod member 34 is engaged by the plate hooks 32 . the rod member 34 is in tension between the structural member 46 and the plates 30 . the nut 44 threaded onto the end portion 38 of the rod member 34 abuts the ball member 42 , which in turn abuts against the structural member 46 . the nut 44 prevents the threaded end portion 40 of the rod member 34 from shifting longitudinally along its axis and out of the slot 52 . the ball member 42 abuts the rounded socket portion 45 of the structural member 46 for allowing the rod member 34 to pivot easily in response to the deck 14 swinging or shifting up and down as ground undulations are encountered or during cutting height adjustments . the socket portion 45 generally mates with the shape of the ball member 42 and helps retain the ball member 42 in the lowermost end portion 56 of the slot 52 . the cross pin member 62 extends generally across the slot 52 at a location directly above the threaded front end portion 40 of the rod member 34 . the cross pin 62 prevents the rod member 34 from shifting up within the slot 52 during operation , and thereby generally blocks the rod member 34 from shifting out of the enlarged portion 60 of the slot 52 during operation . the operator can remove the deck 14 for maintenance such as blade sharpening or blade replacement . the first deck suspension linkage 26 according to the present invention makes removal of the front portion 28 of the deck 14 a relatively simple operation . the operator simply removes the spring pin 66 from the cross pin 62 , and then removes the cross pin 62 from the openings 64 in the structural member 46 . with the cross pin 62 removed from the structural member 46 , clearance is provided for the threaded end portion 40 of the rod member 34 to shift upwardly within the slot 52 to the enlarged portion 60 . with the cross pin 62 removed , the operator can grasp the rod member 34 and slide the rod member 34 upwardly within the slot 52 . the ball member 42 will slide in contact with the surface 54 of the structural member 46 . the surface 54 is inclined slightly and is oriented approximately perpendicular with the longitudinal axis 84 of the threaded end portion 40 of the rod member 34 . this allows the operator to shift the rod member 34 upwardly relatively easily without requiring the operator to pull forwardly on the rod member 34 with a large force . as the rod member 34 enters the enlarged portion 60 of the slot 52 , the rod member 34 will be pulled rearwardly through the enlarged portion 60 of the slot 52 by the weight of the front portion 28 of the deck 14 . the front portion 28 of the deck 14 can then be lowered to the ground , and the rear 70 of the deck 14 can then be detached for complete removal of the deck 14 from the lawn tractor 12 . the present invention therefore allows an operator to uncouple the front portion 28 of the deck 14 from the lawn tractor vehicle 12 without the use of tools such as power wrenches , and without requiring the operator to exert large forces to lift the deck 14 in an awkward manner . after blade sharpening or other maintenance operations have been completed , the operator can re - attach the deck 14 to the lawn tractor 12 . to do so the operator slides the deck 14 laterally to a position beneath the lawn tractor 12 and reattaches the rear portion 70 of the deck 14 to the vehicle 12 . the operator can then re - couple the front 28 of the deck 14 to the lawn tractor 12 . with the laterally extending portion 36 of the rod member 34 positioned within the plate hooks 32 , the operator can position the threaded portion 40 within the enlarged portion 60 of the slot 52 . the operator can then pull upwardly and forwardly on the rod member 34 until the nut 44 and ball member 42 pass forwardly through the enlarged portion 60 of the slot 52 . the rod member 34 , nut 44 and ball member 42 can then be lowered until the rod member 34 is positioned in the lowermost end portion 56 of the slot 52 . lowering the rod member 34 , nut 44 and ball member 42 to this position is facilitated by the orientation of the surface 54 of the structural member 46 which extends generally perpendicular to the threaded end portion 40 of the rod member 34 . the ball member 42 is allowed to easily slide down along the surface 54 without requiring the operator to apply a large lifting force to the rod 34 . with the end portion 38 of the rod 34 lowered into position , the nut 44 will maintain the ball member 42 in abutment against the structural member 46 such that the rod member 34 is supported and the front portion 28 of the deck 14 is suspended in proper operating position above the ground . the operator can then position the cross pin 62 within the openings 64 in the structural member 46 , and the spring pin 66 can be inserted into the cross pin 62 . the nut 44 can be adjusted on rod member 34 for adjusting the position of the front portion of the deck so that the deck remains properly oriented after long periods of operation . the present invention allows the operator to re - couple the front portion 28 of the deck 14 to the lawn tractor 12 without requiring the use of tools . the operator can lift the rod 34 upwardly through the enlarged portion 60 of the slot 52 , and is not required to lift the deck 14 with one hand at one location and couple the deck 14 to the vehicle 12 at another location in an awkward fashion . since the operator does not adjust or remove the nut 44 during the deck removal or re - attaching procedures , the deck 14 will automatically be returned to its proper position and orientation when re - attached . | 8 |
referring now to fig1 the spray head 10 of the invention comprises a generally cylindrical metallic housing sleeve 12 which has a through passageway that has internal threads 14 on its upstream end 16 and a lesser diameter concentric passageway 18 at its discharge end 20 . the housing sleeve 12 also has an intersecting orthogonal through bore 22 which is of sufficient diameter to receive the turret member as described hereinafter . the opposite sidewalls 24 of the discharge end 20 of the sleeve have arcuate notches 26 to provide clearance for the spray pattern emitted by the orifice tip . the housing sleeve 12 is received in a longitudinal through bore 28 of the spray guard 30 , which has a molded plastic body 32 having a generally rectangular cross section . the spray guard 30 has a pair of diverging wings 34 on its discharge face 36 which provide sufficient obstructions to prevent the user from placing a finger in the path of the high pressure spray liquid emitted from the spray head . the wings can have various apertures 38 to reduce their mass . the body 32 of the spray guard 30 also has arcuate notches 40 in its opposite sidewalls to provide clearance for the spray pattern emitted from the spray tip . the spray guard body 30 has an orthogonal through bore 42 which aligns with the orthogonal through bore 22 of the housing sleeve 12 in the assembly to permit reception of the rotatable turret subassembly 44 . the housing sleeve 12 receives an adaptor 46 to permit assembly of the spray head 10 on the threaded end of a conventional spray gun . this adaptor 46 comprises a cylindrical plug 48 having an externally threaded downstream end 50 which is received in the internally threads 14 on the upstream end 16 of the housing sleeve 12 . a seal washer 52 having a cylindrically concave face 54 is received in the longitudinal passageway 18 of the housing sleeve 12 and is sealed therein . an annular groove 51 is provided about the body of the seal washer 52 , and an o - ring 53 is seated in groove 51 to provide an additional seal . at its upstream end 56 , the adaptor 46 has a cylindrical boss 58 having internal threads 60 to receive the threaded end of the plug 62 , which has a hexagonally broached recess 64 to receive a conventional allen key for assembly . the plug 62 is received inside of the retainer nut 66 which has an annular flange ( not shown ) that captures the head 68 of the plug 62 , thereby assembling the retainer nut on the adapter 46 . the retainer nut 66 has an internally threaded upstream end 70 which fits the externally threaded discharge ends of conventional spray guns . the plug 62 also has , on its upstream face , an o - ring seal 72 , which seals against the end of the barrel of the spray gun , when the retainer nut is tightened on the spray gun barrel . the rotatable turret subassembly 44 is a subassembly of two sectored cylinders . the major sectored cylinder 74 is sectored along a face 76 to provide approximately 70 % of the assembled cylinder and is assembled to a minor piece sectored cylinder 98 by a key and slot interlock on each end face , such as the key and slot interlock 78 . the turret subassembly 44 and the spray guard 30 also have indexing means such as the prong 80 on the turret subassembly 44 , which is received in the discontinuous annular groove 82 of the spray guard body 32 . a slot 31 in the top wall of the spray guard body 32 opens to the discontinuous annular groove 82 . the discontinuous annular groove 82 extends through an arc of approximately 200 ° to 230 ° so that its opposite ends serve as stops for the prong 80 which permit rotation of the turret subassembly 44 through an arc of 180 °, thereby orienting the turret subassembly 44 in spray and cleaning positions . the turret subassembly 44 has a through bore 84 and internally houses a flat orifice tip member as described hereinafter with reference to fig2 . the turret subassembly 44 is retained in the assembled spray head by a spring lock washer 86 which seats in an annular groove 88 about the lower end of the turret subassembly 44 . the turret subassembly 44 also has a handle 90 which includes handle shaft 92 projecting from the upper end of the cylindrical subassembly 44 with a cross arm 94 to provide a hand grip and which has a pointed end 96 which indicates the directional orientation of the orifice tip within the turret subassembly 44 . referring now to fig2 the cylindrical turret subassembly 44 will be described . as illustrated , the turret subassembly 44 comprises a major sectored cylinder 74 and a minor sectored cylinder 98 , which mate along their sectored faces 100 and 102 , thereby forming a cylindrical turret subassembly 44 . the key and slot interlock at the upper end of the subassembly 44 comprises a dovetail key 104 on the major sectored cylinder 74 , and a mating dovetail slot 106 in the end face of the minor sectored cylinder 98 . the key and slot can be of any desired configuration ; the preferred dove - tail shape is illustrated . the minor sectored cylinder 98 has a circular base 108 which is received against the bottom end wall 110 of the major sectored cylinder , and a second key and slot interlock is provided by a rectangular slot 112 in the circular base 108 of the minor sectored cylinder , which receives a mating rectangular key 114 on the bottom end wall 110 of the major sectored cylinder . the circular base 108 has an annular groove , previously mentioned , to receive the spring lock washer 86 , to retain the turret subassembly 44 in the spray head 10 . the rotatable turret subassembly 44 houses a conventional flat orifice tip 116 . the flat orifice tip has a generally cylindrical housing with a circular base and a small diameter through passageway in which is permanently seated a small orifice tip member . the major sectored cylinder has a recess 118 of sufficient diameter to receive the metal housing 120 of the flat orifice tip 116 and an entrance 126 of greater diameter to receive the circular base 122 of the flat orifice tip 116 . the internal annular shoulder 124 formed between the entrance 126 and recess 118 provides a stop to position the flat tip orifice 116 at a precise axial location in the through bore 84 of the turret subassembly 44 . the conventional flat orifice tip case 120 has opposite flats 128 which index to flats 130 in the recess 118 to orient the angular position of the flat orifice tip 116 . the flat tip orifice 116 is sealed in the assembly by washer 132 which has an annular groove 134 in which is seated a conventional o - ring seal 136 . the minor sectored cylinder 98 has a small diameter through bore 84 which aligns coaxially with the entrance 126 , recess 118 and thorough bore of the major sectored cylinder 74 . when the turret subassembly is in the spray guard , and the spray tip is tightly secured to the discharge barrel of a spray gun by retainer nut 66 , the seals of the spray tip are compressed to seal against the applied pressure of the spray liquid . this also tightly secures the major sectored cylinder 74 in the assembly and prevents its removal , until the tension on the retainer nut is loosened . the assembly of the minor and major sectored cylinders in the spray guard 30 and housing 20 also presses the seal washer 132 against the flat face of the base 122 of the flat fit orifice . this effects a frictional fit of the sectored cylinders which prevents their accidental dislodgement from the assembled spray tip even when the retainer nut has been loosened . the turret subassembly 44 provides a very efficient and secure mounting for a conventional flat orifice tip . the subassembly uses simple but highly effective seals , specifically the seal washer and o - ring seal to secure the flat orifice tip in the assembly . the turret subassembly 44 is assembled by interlocking the sectored cylinders together along relatively expansive flat faces of the two pieces , which avoids weakening of the turret structure . each sectored cylinder also presents a smooth uninterrupted cylindrical face for engagement by the floating seal 52 within the housing sleeve 12 , and thus avoids any compromise in available sealing surface area . the assembly also provides for very facile disassembly . the flat orifice tip 116 can be removed or interchanged quite easily simply by loosening the tension on the retainer nut 66 , and withdrawing the major sectored cylinder 74 from the assembly , and extracting the seal washer 132 and the flat tip 116 . no special tools are required and the spray head can be restored to service by inserting a new flat orifice tip in the major sectored cylinder , reinserting it into the spray head 10 , and completing the assembly by tightening of the retainer nut 66 on the spray gun barrel to compress the internal seals sufficiently to prevent leakage of the liquid being sprayed . the invention has been described with reference to the illustrated and presently preferred embodiment . it is not intended that the invention be unduly limited by this disclosure of the presently preferred embodiment . instead , it is intended that the invention be defined , by the means , and their obvious equivalents , set forth in the following claims : | 1 |
fig1 a - 1 c show a first embodiment of the components of the fastening modules 1 , used with a system for fastening solar modules 2 , in particular photovoltaic modules on a trapezoid metal roof 14 with an arrangement of parallel - extending high beads 15 , meaning a trapezoid metal roof structure . fig3 and 4 in this case show variants of a solar module 2 that is fastened with the aid of a fastening system formed with fastening modules 1 . the fastening system in this case consists solely of a plurality of such fastening modules 1 , meaning no other elements are required for fastening the solar module 2 on the trapezoid metal roof 14 . a module carrier 3 , shown in fig1 a , represents the first component of a fastening module 1 , wherein fig1 a depicts a cross - sectional view of the module carrier 3 . the module carrier 3 is embodied in the shape of a rail , wherein the cross section is constant over the complete length of the module carrier 3 . the module carrier 3 is adapted to the structure of the trapezoid metal roof 14 which has an alternating sequence of high beads 15 and low beads , in a manner known per se , for which the longitudinal axes typically extend in the direction of inclination of the trapezoid metal roof 14 . the length of the module carrier 3 is dimensioned such that when this carrier is mounted on the trapezoid metal roof 14 , it rests transverse to its low beads precisely on two high beads 15 , for example as shown in fig3 a . the module carrier 3 comprises a bottom part 3 a with therein provided three bores 3 e . fastening screws or the like can be inserted into these bores 3 e in order to fasten the module carrier 3 on the trapezoid metal roof 14 . to permit the fastening on two high beads 15 of a trapezoid metal roof 14 , an additional row of three bores 3 e is worked into the module carrier 3 . respectively one row of bores 3 e thus serves for the fastening of the module carrier 3 on respectively one high bead . two identically embodied side parts 3 b project vertically upward from the bottom part 3 a of the module carrier 3 . the side parts 3 b are embodied integrally with the bottom part 3 a and extend at a distance parallel to each other . in the present case , the upper edges of the side parts are embodied as u - shaped profile sections 3 c . a downward pointing projection 4 is provided on the inside , lower edge of each profile section 3 c . the space between the two side parts 3 b of the module carrier 3 forms a receptacle to accommodate a slide block 5 , as shown in fig1 b , which represents another component of the fastening module 1 . the slide block 5 is positioned so as to be displaceable inside the receptacle and meets the function of a clamping device and spacer . the slide block 5 consists of a solid base body 5 a , from which extensions 5 b extend downward at an angle , symmetrical to its symmetry axes . each top side of an extension 5 b is provided with a groove 6 which , following the insertion of the slide block 5 into the module carrier 3 , engages in a shoulder 4 of a profile sections 3 c of the module carrier 3 , thereby defining the position of the slide block 5 in the module carrier 3 . the external side surfaces of the extensions 5 b form sliding surfaces which allow the slide block 5 to fit against the inside surfaces of the side parts 3 b of the module carrier 3 , so as to be displaceable . the base body 5 a , belonging to the slide block 5 , projects over the top side of the module carrier 3 . an additional component of the fastening module 1 is the module clamp 7 , illustrated in fig1 c . the module clamp 7 comprises two wing arms 7 a , embodied symmetrical to the axis of symmetry for the module clamp 7 , which make it possible to clamp in two adjacent solar modules 2 . the module clamp 7 is connected to the slide block 5 via a fastening means that is not shown in fig1 c , meaning the slide block 5 meets the additional function of connecting the module clamps 7 to the module carrier 3 . fig2 a - 2 c illustrate a design variant of the components for the fastening module 1 , shown in fig1 a - 1 c . a comparison of these figures shows that the embodiment of the module carrier 3 according to fig2 a essentially corresponds to the embodiment shown in fig1 a . the only difference is that in place of the profile sections 3 c , plate - shaped projections 3 d are provided at the upper ends of the side parts 3 b , wherein the projections 4 are provided on the inside - positioned , lower edges . with the exception of slight geometric deviations , the slide block 5 according to fig2 b corresponds to the slide block 5 according to fig1 b . in the same way , the module clamp 7 according to fig2 c corresponds to the module clamp 7 shown with fig1 c . fig3 a , 3 b show a first exemplary embodiment for the fastening system according to the invention , namely for the flat or transverse mounting of solar modules 2 on a trapezoid metal roof 14 . fig3 a shows the mounting of a solar module 2 on the trapezoid metal roof 14 . with this exemplary embodiment , the fastening system comprises the fastening modules 1 as shown in fig2 a to 2 c . fig3 b shows two identically embodied solar modules 2 which are fastened with the fastening modules 1 of the fastening system on the trapezoid metal roof 14 . in general , a larger number of solar modules 2 are fastened with the aid of the fastening modules 1 on the trapezoid metal roof 14 . the solar modules 2 in the present case are embodied as framed solar modules 2 . as a result of the framing , the fastening modules 1 do not come in direct contact with the limit surfaces of the solar modules 2 which are composed of glass laminate . the pitch or angle of inclination for the trapezoid metal roof 14 is indicated therein with an arrow given the reference n . with the arrangement shown in fig3 b , the left fastening module 1 is arranged at the lower longitudinal side of the left solar module 2 while the right fastening module 1 is arranged at the upper longitudinal side of the left solar module 2 and , simultaneously , is connected to the lower longitudinal side of the adjacent right solar module 2 . as can be seen in fig3 a , all module carriers 3 for the fastening modules 1 rest on high beads 15 of the trapezoid metal roof 14 and are fastened with rivets 9 on these beads . the lengths of the module carriers 3 are dimensioned in such a way that these always rest precisely on two high beads 15 . in place of rivet connections , screw connections can also be used for fastening the module carriers 3 on the trapezoid metal roof 14 . a slide block 5 , which fits along the edge against the insides of the side parts 3 b of the module carrier 3 , is guided in the module carrier 3 of each fastening module 1 . the shoulders 4 on the profile sections 3 c of the side parts 3 b for the module carrier 3 engage in the grooves 6 on the extensions 5 b on the slide block 5 , thereby fixing its orientation in the module carrier 3 . the slide block 5 comprises a base body 5 a which projects over the top side of the module carrier 3 . as can be seen in particular in fig3 b , a screw 10 is provided as means for connecting the module clamp 7 to the slide block 5 of a fastening module 1 . the screw 10 extends through respectively one axial bore in the module clamp 7 and the slide block 5 . besides the bore , the slide block 5 is provided with a screw thread which accommodates the screw 10 , thereby causing a clamping effect . the head of the screw 10 is exposed on the top of the module clamp 7 , thus providing easy access for an operator . a further component of a fastening module 1 is a plate - shaped spacer element 8 which functions as spacer between the module carrier 3 and the module clamp 7 . this spacer element 8 comprises a flat bottom which rests on the flat top of the projection 3 d on the module carrier 3 . provided at the upper edge of the spacer element 8 is a t - shaped guide element 8 a which is inserted into a recess 7 b on the wing arm 7 a of the module carrier 3 and is guided therein . the contour of the recess 7 b is adapted to the contour of the guide element 8 a . by varying the height of the spacer elements 8 , the fastening module 1 can be adapted to solar modules 2 with different structural heights , meaning thicknesses . the fastening module 1 embodied in this way fixates the solar module 2 along its edge . for this , the module clamp 7 is fitted from the top onto the solar module 2 , wherein the contact surface is formed by spacer elements 8 . the lower edge of the solar module 2 rests on the projection 3 d of the side part 3 b of the module carrier 3 . the side surface of the solar module 2 furthermore fits against the base body of the slide block 5 which projects over the module carrier 3 . as a result , the slide block 5 of a fastening module 1 that is arranged at the lower edge of the solar module 2 functions as anti - slip device for the solar module 2 . fig4 a , 4 b show a second exemplary embodiment for the fastening system according to the invention , namely a vertical installation of a solar module 2 . the solar module 2 shown in fig4 a corresponds precisely to the solar module 2 according to fig3 a . the components of the fastening module 1 of the fastening system are also identical to the arrangements shown in fig3 a and 4 a . in particular for the arrangements shown in fig3 a and 4 b , the module carriers 3 of the fastening modules 1 are mounted in the same way on the trapezoid metal roof 14 , namely such that their longitudinal axes extend perpendicular to the high beads 15 of the trapezoid metal roof 14 , wherein each module carrier 3 rests on two high beads 15 . in order to change from a transverse mounting of the solar module 2 , as shown in fig3 a , to mounting aligned with the pitch direction , as shown in fig4 a , it is only necessary to displace the slide blocks 5 inside the module carriers 3 to adjust the spacing to match the narrow side of the solar module . in addition , the module clamps 7 and the spacer elements 8 are rotated relative to the screw 10 by 90 °, as compared to the orientation for the transverse mounting , so that the module clamps 7 with the spacer elements 8 now fit against the side of the solar module 2 , as shown in fig4 a . as a result of the 90 ° rotation , the longitudinal axes of the module clamps 7 and the spacer elements 8 no longer extend parallel to the longitudinal axes of the respective module carriers 3 , but are arranged perpendicular thereto , as shown in fig4 a and 4 b . as can be seen in particular in fig4 b , the underside of the spacer element 8 now rests on the top sides of both projections 3 d of the module carrier 3 . the solar module 2 is secured in that it rests with its underside on the projections 3 d of the module carrier 3 . one wing arm 7 a of the module clamp 7 rests on the top of the solar module 2 . by tightening the screw 10 , the solar module 2 is clamped in and secured in place between the projections 3 d of the module carrier 3 and the module clamp 7 . since the fastening modules 1 for the mounting aligned with the pitch direction as shown in fig4 a , 4 b rest against the side of the solar module 2 , these fastening modules 1 do not function as anti - slip protection for the solar module 2 . fig5 shows an embodiment of a fastening module 1 of the fastening system according to the invention which is used to mount a non - framed solar module 2 on a trapezoid metal roof 14 , meaning components of the fastening module 1 in that case come in direct contact with the limit surfaces of the solar module 2 , which are composed of glass laminate . coinciding with the arrangement shown in fig3 and 4 , the fastening module 1 according to fig4 is also provided with a module carrier 3 , a slide block 5 , a module clamp 7 , fastening rivets 9 for mounting the module carrier 3 on the trapezoid metal roof 14 , and a screw 10 for connecting the slide block 5 to the module clamp 7 . the module carrier 3 and the slide block 5 correspond precisely to the embodiment shown in fig2 a and 2 b . in contrast thereto , the module clamp 7 for the example shown in fig5 consists of two parts , namely an upper part 11 and a lower part 12 . the upper and lower parts 11 , 12 are respectively provided with two wing sections , analogous to the module clamp 7 shown in fig1 c , so that a fastening module 1 can be mounted on two solar modules 2 . the upper part 11 and the lower part 12 initially rest loosely one on top of the other . both elements are provided with a bore through which the screw 10 extends which engages in the bore with thread in the slide block 5 . the clamping together of the upper part 11 and the lower part 12 is achieved by screwing the screw 10 into the screw thread of the slide block 5 . elastic elements in the form of ethylene propylene diene monomer ( epdm ) seals 13 are respectively arranged on the limit surfaces for the upper and lower part 11 , 12 , which face the solar module 2 . when tightening the screw 10 , the epdm seals 13 are pressed against the top and bottom side of the solar module 2 , composed of glass laminate , thereby securing the solar module 2 in its position . the elastic characteristics of the epdm seals 13 prevent damage to the solar modules 2 when these are secured with the aid of the fastening modules 1 . for a transverse mounting as shown in fig5 , perpendicular webs 11 a , 12 a on the upper and lower parts 11 , 12 of the module clamp 7 function as anti - slip protection for the solar module 2 since , in that case , the fastening module 1 fits against the underside of the solar module 2 . these perpendicular webs 11 a , 12 a are coated with epdm , so that the glass laminate of the solar module 2 is not damaged . by displacing the slide block 5 inside the module carrier 3 and subsequently rotating the module clamps 7 by 90 °, it is possible to realize a mounting of a solar module 2 aligned with the pitch direction , analogous to the embodiment shown in fig4 a , 4 b , wherein the fastening modules 1 which are used for this mounting again fit against the side of the solar module 2 . | 5 |
an embodiment 2 of the inventive adaptor is depicted in fig1 - 5 . embodiment 2 is particularly well suited for adapting a butane - burning device to the use of propane fuel . inventive adaptor 2 comprises : a housing 4 including an inlet fitting / coupling 6 removably attached to an outlet fitting / coupling 8 ; a probe 10 projecting from inlet fitting 6 ; a valve assembly 12 projecting from outlet fitting 8 ; a flow passage 14 extending through probe 10 and housing 4 to valve assembly 12 ; and an orifice element 16 positioned in flow passageway 14 between probe 10 and valve assembly 12 . inlet fitting 6 and probe 10 are of a type structured for attachment to and activation of most of the small , camping - type propane canisters available on the market . however , as will be apparent , generally any type of attachment structure and activation element can be used depending upon the structure of the fuel supply container to which inventive adaptor 2 is to be attached . the inlet fitting 6 depicted in fig1 - 5 comprises : a larger diameter , cylindrical rearward section 8 having a rearward end 20 ; a large diameter rearward bore 22 having internal threads 24 formed therein for releasable attachment to an externally - threaded propane discharge fitting ; a threaded second bore 26 extending from the forward end of large bore 22 ; a threaded third bore 30 extending from the forward end of second bore 26 ; an externally threaded forward section 34 extending from rearward section 18 and having an external diameter smaller than that of section 18 ; a bore 36 extending into the forward end 38 of externally threaded section 34 ; a small , frusto 15 conical counter bore extending from forward bore 36 to third bore 30 ; and a groove 40 formed in the forward end 38 of inlet fitting 6 for receiving an o - ring 42 or other sealing element . inlet fitting 6 further includes a raised lip or hub 44 provided around the rearward end of second bore 26 . thus , a flat radial groove 46 is formed at the forward end of large bore 22 for receiving a rubber gasket 48 or other sealing element . when the discharge fitting of the propane canister is threadedly received in large bore 22 , gasket 48 seals against the end of the propane discharge fitting . probe 10 comprises : an elongate segment 50 which projects from the rearward end 20 of inlet fitting 6 ; a threaded forward segment 52 which is threadedly received in second bore 26 ; an enlarged segment 54 between rearward segment 50 and forward segment 52 and having flats 56 provided thereon for tightening threaded segment 52 into second bore 26 ; a longitudinal flow channel 58 extending through probe 10 ; and a cap 60 provided on he distal end of rearward segment 50 . a lateral slot 62 is provided across cap 60 in fluid communication with the rearward end of longitudinal flow channel 58 . when the forward end 52 of probe 10 is received in interior threaded bore 26 of inlet fitting 6 , a washer 64 is preferably positioned between the enlarged segment 54 of probe 10 and the end of the lip / hub 44 formed in large bore 22 . washer 64 preferably extends radially a sufficient distance to hold gasket 48 in groove 46 . the discharge fittings of propane canisters of the type used for camping will typically include a valve stem which is surrounded by an externally threaded coupling . propane is released from the canister when the valve stem is depressed inwardly . thus , probe 10 is constructed to interact with valve elements of this type such that , as the large threaded bore 22 of inlet fitting 6 is screwed on to the discharge fitting of the propane canister , the cap 60 of probe 10 contacts the forward end of the propane valve stem and eventually depresses the propane valve stem a sufficient distance to cause propane to be released from the canister . the released propane flows through the lateral slot 62 of probe cap 60 and into longitudinal flow channel 58 . orifice element 16 comprises : an externally threaded rearward section 66 which is received in the small , threaded , bore 30 of inlet fitting 6 ; a larger diameter forward section 68 having flats 70 provided on the exterior thereof for tightening orifice element 16 into threaded bore 30 ; a longitudinal flow channel 72 provided through orifice element 16 ; and an end wall , cap , plug or other element 74 provided at the forward end of , or elsewhere in , orifice element 16 and having a small flow restriction orifice 78 formed therethrough . orifice 78 is in fluid communication with the flow channel 72 of orifice element 16 . orifice 78 is sized to restrict the flow of propane from the propane canister and reduce the pressure of the flowing propane sufficiently to enable the propane fuel to be used in the butane - burning device to which the other end of inventive adaptor is attached . the outlet fitting / coupling 8 and the valve assembly 12 of embodiment 2 of the inventive adaptor 2 are structured to attach to a gas inlet fitting of a type commonly employed on butane - burning camp devices . outlet fitting 8 includes a radial flange 80 on the forward end 82 thereof . a slot 84 is provided in radial flange 80 for receiving a post which will typically be included in the appliance fitting . outlet fitting 8 can thus be secured to the appliance by positioning the post of the appliance in slot 84 and rotating the inventive adaptor a quarter turn . as will be understood by those skilled in the art , the appliance fitting will typically include a plurality of fingers or latches which contract onto and grasp flange 80 as the adaptor is turned . outlet fitting 8 further comprises : a rearward segment 86 having an internally threaded bore 88 for threadedly receiving the forward end 34 of inlet fitting 6 ; an interior radial wall 90 provided at the forward end of threaded bore 88 ; a forward bore 92 extending into the forward end 82 of outlet fitting 8 ; an annular groove 94 formed in forward bore 92 for receiving an o - ring or other sealing element associated with the appliance fitting ; a hub 96 extending from interior radial wall 90 into forward bore 92 ; a passageway 98 extending through interior wall 90 and hub 96 ; and a radial lip 100 provided at the forward end of hub 96 and projecting into passage 98 . internal threads 102 are provided in at least the rearward portion of passage 98 . valve assembly 12 comprises : a valve stem 104 which projects from the forward end of hub 86 ; a valve cage 106 which slidably receives and retains an enlarged rearward portion 121 of valve stem 104 and which includes an externally threaded forward portion 110 which is received in threaded hub 96 ; an o - ring or other sealing element 112 positioned in hub 96 between hub lip 100 and the forward end of valve cage 106 ; a cap 114 threadedly secured over the rearward end of valve cage 106 ; and a spring 116 contained within cage 106 between cap 114 and the enlarged rearward portion 121 of valve stern 104 . spring 116 continuously urges valve stem 104 outwardly . cap 114 has a port 118 provided therethrough which allows gas to flow from orifice element 16 into valve cage 106 . valve stem 104 includes a flow passage 124 having an outlet port 120 provided at the forward end of valve stem 104 and an inlet port 122 provided through the side wall of the valve stem . inlet port 122 is positioned such that , when inventive adaptor 2 is not attached to the gas burning device and valve stem 104 is thus held fully outward by spring 116 , valve inlet port 122 will be positioned forwardly of o - ring 112 . thus , inlet port 122 will not be in fluid communication with the remainder of adaptor flow passage 114 so that valve assembly 12 will be closed . valve assembly 12 is depicted in closed position in fig4 . as adaptor 2 is attached to the inlet fitting of the appliance , valve stem 104 is automatically pushed rearwardly to an open position wherein inlet port 122 is positioned within cage 106 behind o - ring 112 . the open position of valve assembly 12 is depicted in fig5 . thus , when inventive adaptor 2 is fully assembled with inlet fitting 6 secured to the discharge coupling of a propane canister and outlet fitting 8 attached to the inlet fitting of a butane appliance , the entire flow passage 14 of inventive adaptor 2 is open such that the propane fuel flows into and through the flow channel 58 of probe 10 , the flow channel 72 and flow restriction orifice 78 of orifice element 16 , the aperture 118 of cap 114 , the interior of valve cage 106 , and the inlet port 122 of valve stem 104 . as will be apparent , the inlet 6 and outlet 8 fittings of inventive adaptor 2 could be configured to mate with any common type of gas discharge and appliance fittings . additionally , other types of restriction elements suitable for restricting the flow and reducing the pressure of the gas flowing through the inventive adaptor will be apparent to those skilled in the art . examples of such elements include needle valves or other types of valve elements , adjustable or fixed regulators , tubing of a length and inside diameter sufficient to obtain a desired restriction in flow , multiple orifice elements , etc . thus , the present invention is well adapted to carry out the objects and attain the ends and advantages mentioned above as well as those inherent therein . while presently preferred embodiments have been described for purposes of this disclosure , numerous changes and modifications will be apparent to those skilled in the art . such changes and modifications are encompassed within the spirit of this invention as defined by the appended claims . | 5 |
the invention encompasses developable bottom antireflective coating ( dbarc ) compositions comprising a polymer containing pendant aromatic moieties and pendant aliphatic alcohol - containing moieties . these dbarc compositions are characterized by the ability to apply them to substrates using conventional spin - coating and conventional solvents commonly used for casting resist materials . the compositions are further characterized by their ability , upon adequate baking ( e . g ., above about 150 ° c . ), to undergo little or no significant intermixing with the subsequently applied resist layer . additionally , the dbarc compositions of the invention provide good reflectivity control ( e . g ., k value & gt ; 0 . 15 ), good adhesion to substrate , upon adequate baking , and good dissolution properties in developer for the resist . the invention also encompasses methods of using such lithographic structures to pattern underlying material layers on a substrate . the polymer of the dbarc preferably has an ethylenic backbone . more preferably , the polymer contains vinyl , acrylate and / or methacrylate repeating units . the polymer preferably contains a first repeating unit having the structure : where r 1 is selected from h , f , br , cf 3 , cn and ch 3 and r 2 includes an aromatic moiety . the aromatic moieties are preferably independently selected from the group consisting of substituted or unsubstituted aromatic moieties or combinations thereof . more preferably , aromatic moieties are selected from the group consisting of benzene , naphthalene , anthracene , phenanthrene , pyrene , coronene and combinations thereof . the polymer preferably contains about 10 to 80 mole % of repeating units having aromatic moieties , more preferably about 15 - 70 mole %, most preferably about 20 - 65 mole %. examples of specific first repeating units are derived from one of the following structures : the polymer preferably contains a second repeating unit having the structure : where r 3 is selected from h , f , br , cf 3 , cn and ch 3 , r 4 includes an aliphatic alcohol moiety . the aliphatic alcohol moieties are preferably independently selected from the group consisting of linear , branched , and cycloaliphatic alcohols and combinations thereof . more preferably , the aliphatic alcohol moieties are selected from hydroxyadamantyl moieties , hydroxycyclohexyl , hydroxynorbornyl and hydroxyethyl moieties . the polymer preferably contains about 10 to 80 mole % of repeating units having aliphatic alcohol moieties , more preferably about 20 - 70 mole %, most preferably about 25 - 65 mole %. examples of specific second repeating units are derived from one of the following structures : the invention also encompasses photoimageable dbarc compositions where the polymer preferably further includes third repeating units derived from a monomer which includes acid - labile pendant moieties , such as tertiary alkyl carbonates , tertiary alkyl esters , tertiary alkyl ethers , acetals , and ketals . some examples of such a monomer including a tertiary alkyl ester are shown below : the dbarc compositions of the invention are not limited to any specific form of the third repeating unit . the dbarc polymer preferably includes about 10 - 65 mole % of the third repeating unit , more preferably about 15 - 50 mole %. some example dbarc polymers of the invention are described in the table below where the numbers indicate mole percent of repeating unit : the dbarc compositions of the invention preferably have an extinction coefficient k of about & gt ; 0 . 15 with respect to a radiation wavelength of 193 nm . the dbarc polymers of the invention preferably have a weight average molecular weight of at least about 1000 , more preferably a weight average molecular weight of about 1500 - 50000 , most preferably about 8000 to 15000 . the polymers of the invention may be made by conventional polymerization techniques using commercially available and / or easily synthesized monomers . if desired , blends of different polymers of the invention may be used . the invention also encompasses photoimageable dbarc compositions where the composition preferably contains a radiation sensitive acid generator . the radiation sensitive acid generators , also known as photoacid generators , used in the photoresist composition of the invention are compounds that generate an acid upon exposure to radiation . any suitable photoacid generating agent may be used , so long as the resulting dbarc composition dissolves sufficiently in the casting solvent and the resulting solution thereof forms a suitably uniform film by a film - forming process , such as spin coating or the like . some examples of classes of photoacid generators that may be employed in the dbarc compositions of the invention are : onium salts , succinimide derivatives , diazo compounds , nitrobenzyl compounds , and the like . the photoacid generators may be used singly or in a mixture of two or more . some preferred photoacid generators are onium salts , such as an iodonium salt or a sulfonium salt , and / or a succinimide derivative . more preferred photoacid generators include 4 -( 1 - butoxynaphthyl ) tetrahydrothiophenium perfluorobutanesulfonate , triphenyl sulfonium perfluorobutanesulfonate , t - butylphenyl diphenyl sulfonium perfluorobutanesulfonate , 4 -( 1 - butoxynaphthyl ) tetrahydrothiophenium perfluorooctanesulfonate , triphenyl sulfonium perfluorooctanesulfonate , t - butylphenyl diphenyl sulfonium perfluorooctanesulfonate , di ( t - butylphenyl ) iodonium perfluorobutane sulfonate , di ( t butylphenyl ) iodonium perfluorohexane sulfonate , di ( t - butylphenyl ) iodonium perfluoroethylcyclohexane sulfonate , di ( t - butylphenyl ) iodonium camphorsulfonate , and perfluorobutylsulfonyloxybicylo [ 2 . 2 . 1 ]- hept - 5 - ene - 2 , 3 - dicarboximide . the compositions of the invention may further comprise at least one solvent . suitable solvents include , but are not limited to : pgmea , ethyl lactate , ethyl 3 - ethoxypropionate , cyclohexanone , 1 - butanol , methanol , ethanol , 1 - propanol , ethylene glycol , 1 , 2 - butanediol , 1 , 3 - butanediol , 1 , 4 - butanediol , 1 , 2 - propanediol , 1 - pentanol , 2 - pentanol , 3 - pentanol , 1 - hexanol , 2 - hexanol , 3 - hexanol , 1 - heptanol , 2 - heptanol , 3 - heptanol , 4 - heptanol , 2 - methyl - 1 - pentanol , 2 - methyl - 2 - pentanol , 2 - methyl - 3 - pentanol , 3 - methyl - 1 - pentanol , 3 - methyl - 2 - pentanol , 3 - methyl - 3 - pentanol , 4 - methyl - 1 - pentanol , 4 - methyl - 2 - pentanol , 2 , 4 - dimethyl - 3 - pentanol , 3 - ethyl - 2 - pentanol , 1 - methylcyclopentanol , 2 - methyl - 1 - hexanol , 2 - methyl - 2 - hexanol , 2 - methyl - 3 - hexanol , 3 - methyl - 3 - hexanol , 4 - methyl - 3 - hexanol , 5 - methyl - 1 - hexanol , 5 - methyl - 2 - hexanol , 5 - methyl - 3 - hexanol , 4 - methylcyclohexanol , 1 , 3 - propanediol , octanol , and decane . the composition may further comprise small portion of second or third solvent to form a mixed solvent . suitable second or third solvents include , but not limited to : γ - butyrolactone , anisole , propylene carbonate , sulfolane , dimethyl succinate , and dimethyl adipate . preferably , the solvent is one used for casting of resist formulations . the amount of solvent in the composition for application to a substrate is preferably sufficient to achieve a solids content of about 0 . 5 - 5 wt . %. the compositions may include surfactants , acid quenchers or other expedients known in the art . the invention encompasses methods of forming a patterned material feature on a substrate , the method comprising : ( a ) providing a material surface on a substrate , ( b ) forming a bottom antireflective coating over the material surface , the bottom antireflective coating comprising a polymer containing a backbone component , a pendant aromatic moiety and a pendant aliphatic alcohol moiety , wherein the polymer becomes substantially insoluble in a resist casting solvent if subsequently baked at a temperature greater than about 150 ° c ., and ( a ) a solvent for the unbaked polymer , ( b ) baking the antireflective coating layer to render it substantially insoluble in casting solvent for a subsequent resist layer , ( c ) forming a resist layer over the bottom antireflective coating , ( d ) patternwise exposing the resist layer to radiation thereby creating a pattern of radiation - exposed regions in the resist layer , ( e ) selectively removing portions of the resist layer and antireflective coating to expose portions of the material surface by selective dissolution in an aqueous alkaline developer , and ( f ) etching or ion implanting the exposed portions of the material , thereby forming the patterned material feature . the material surface of the semiconductor substrate may be a metal conductor layer , a ceramic insulator layer , a semiconductor layer or other material depending on the stage of the manufacture process and the desired material set for the end product . the compositions of the invention are especially useful for lithographic processes used in the manufacture of integrated circuits on semiconductor substrates . the compositions of the invention in lithographic processes to create patterned material layer structures such as metal wiring lines , holes for contacts or vias , insulation sections ( e . g ., damascene trenches or shallow trench isolation ), trenches for capacitor structures , ion implanted si structures for transistors , etc . as might be used in integrated circuit devices . the dbarc compositions of the invention preferably will substantially reduce the substrate reflectivity with respect to 193 nm radiation . the dbarc composition of the invention is preferably applied directly over the material surface by spin - coating . the dbarc is then baked for a time and temperature sufficient to remove any solvent in the dbarc composition and to render the dbarc composition substantially insoluble in the solvent used to apply the subsequent resist layer . the baking temperature is preferably about 110 ° c . or higher , more preferably about 150 ° c . to 250 ° c . the bake time is preferably about 30 seconds to 5 minutes , more preferably about 1 to 2 minutes . for dbarcs containing acid labile groups , overbaking would result in a substantial deprotection of the polymers and would then become largely or completely dissolved away in the develop process to form the undesired undercut profiles or collapsed images . overbaking may in some instances create insoluble component such as to form residues after develop process . preferably , overbaking such as would hinder solubility of the dbarc in aqueous base developer is avoided . the resist is preferably imagable with 193 nm ultraviolet radiation . examples of suitable resist materials are described in us published patent application nos . 20050153232a1 and 20040063024a1 and u . s . pat . nos . 6 , 902 , 874 , 6 , 730 , 452 , 6 , 627 , 391 , 6 , 635 , 401 and 6 , 756 , 180 the disclosures of which are incorporated herein by reference . typically , the solvent - containing resist composition is applied using spin coating or other technique . the substrate with the resist coating is then preferably heated ( pre - exposure baked ) to remove the solvent and improve the coherence of the resist layer . the pre - exposure bake step is preferably conducted for about 10 seconds to 15 minutes , more preferably about 15 seconds to one minute . the pre - exposure bake temperature may vary depending on the glass transition temperature of the resist . if desired , a top antireflective coating may be applied to the substrate after formation of the resist layer according to conventional techniques . the resist layer is then patternwise - exposed to the desired radiation ( e . g . 193 nm ultraviolet radiation ). the patternwise exposure is conducted through a mask which is placed over the resist layer . for 193 nm uv radiation , the total exposure energy is preferably about 100 millijoules / cm 2 or less , more preferably about 50 millijoules / cm 2 or less ( e . g . 15 - 30 millijoules / cm 2 ). after the desired patternwise exposure , the resist layer is typically baked to further complete the acid - catalyzed reaction and to enhance the contrast of the exposed pattern . the post - exposure bake is preferably conducted at about 60 - 175 ° c ., more preferably about 90 - 160 ° c . the post - exposure bake is preferably conducted for about 30 seconds to 5 minutes . after post - exposure bake , if any , the resist structure with the desired pattern is obtained ( developed ) by contacting the resist layer with an aqueous alkaline developer solution which selectively dissolves the areas of the resist which were exposed to radiation in the case of a positive resist ( or the unexposed areas in the case of a negative resist ). the dbarc in the area of the dissolved resist is also removed by dissolution in the aqueous base developer solution . preferred aqueous base developer solutions are aqueous solutions of tetramethyl ammonium hydroxide . the resulting lithographic structure on the substrate is then typically dried to remove any remaining developer . the pattern from the resist structure may then be transferred to the exposed portions of underlying material of the substrate by etching with a suitable etchant using techniques known in the art ( e . g ., reactive ion etching or wet etching ) or by ion implantation in the exposed portions . the invention is especially useful where the pattern transfer is performed by ion implantation ( e . g ., dopant implantation to form source / drain features in semiconductor materials ). once the desired pattern transfer has taken place , any remaining resist may be removed using conventional stripping techniques . examples of general lithographic processes where the composition of the invention may be useful are disclosed in u . s . pat . nos . 4 , 855 , 017 ; 5 , 362 , 663 ; 5 , 429 , 710 ; 5 , 562 , 801 ; 5 , 618 , 751 ; 5 , 744 , 376 ; 5 , 801 , 094 ; 5 , 821 , 469 and 5 , 948 , 570 , the disclosures of which patents are incorporated herein by reference . other examples of pattern transfer processes are described in chapters 12 and 13 of “ semiconductor lithography , principles , practices , and materials ” by wayne moreau , plenum press , ( 1988 ), the disclosure of which is incorporated herein by reference . it should be understood that the invention is not limited to any specific lithography technique or device structure . the invention is further described by the examples below . the invention is not limited to the specific details of the examples . synthesis of terpolymers of 4 - hydroxystyrene , 1 - ethylcyclopentyl methacrylate , and 3 - hydroxy - 1 - adamantyl methacrylate ( hs / ecpma / hadma ( 30 / 20 / 50 )) ( ws - 10 ) to a round bottom flask equipped with condenser , thermometer , an argon ( ar ) inlet , and a magnetic stirrer bar , the following were added : 4 - acetoxystyrene monomer ( 2 . 43 grams ( g ), 0 . 015 mole ), 1 - ethylcyclopentyl methacrylate monomer ( 1 . 82 g , 0 . 01 mole ), 3 - hydroxy - 1 - adamantyl methacrylate monomer ( 5 . 91 g , 0 . 025 mole ), 2 , 2 ′- azobis ( 2 - methylpropionitrile ) ( aibn )( 0 . 41 g , 5 % of total moles of monomers ), and approximately 40 g of tetrahydrofuran ( thf ). the reaction mixture was stirred at room temperature and bubbled with ar flow for 45 minutes before it was heated . the reaction was carried out overnight at 72 ° c . under an inert ar atmosphere . the reaction solution was then cooled to room temperature and approximately 20 g of thf was blown away by a high flow of nitrogen bubbling into the flask . to the remaining reaction solution , 18 g of methanol and approximately 4 g ( excess ) of concentrated nh 4 oh were added and the reaction was carried out at 65 ° c . overnight . the solution was then cooled to room temperature , and small portion of the reaction mixture was removed for c 13 nmr test . the mixture was added in with equivalent of deuterated acetone for this test . after the confirmation of complete deprotection of acetoxy group ( the disappearance of 121 ppm peak ), the reaction solution was then added dropwise into a mixture of water ( 1000 ml )) and glacial acetic acid ( 30 ml ). the precipitated polymer was separated , rinsed with water ( 2 × 300 ml ) and dried in a vacuum oven at 65 ° c . for a short time . the polymer was re - dissolved in acetone and re - precipitated in a mixture of water ( 1000 ml ) and glacial acetic acid ( 30 ml ). the solid was filtered with a frit funnel , washed with water ( 2 × 300 ml ) and dried in a vacuum oven at 65 ° c . for 24 hours . synthesis of terpolymers of 4 - hydroxystyrene , t - butyl acrylate , and 3 - hydroxy - 1 - adamantyl methacrylate ( hs / tba / hadma ( 30 / 25 / 45 )) ( ws - 17 ) to a round bottom flask equipped with condenser , thermometer , an argon ( ar ) inlet , and a magnetic stirrer bar , the following were added : 4 - acetoxystyrene monomer ( 2 . 43 grams ( g ), 0 . 015 mole ), t - butyl acrylate monomer ( 1 . 6 g , 0 . 0125 mole ), 3 - hydroxy - 1 - adamantyl methacrylate monomer ( 5 . 319 g , 0 . 0225 mole ), 2 , 2 ′- azobis ( 2 - methylpropionitrile ) ( aibn )( 0 . 328 g , 4 % of total moles of monomers ), and approximately 40 g of tetrahydrofuran ( thf ). the reaction mixture was stirred at room temperature and bubbled with ar flow for 45 minutes before it was heated . the reaction was carried out overnight at 72 ° c . under an inert ar atmosphere . the rest of the synthetic procedures are the same as example 1 , except approximately 5 g of concentrated nh 4 oh was used in deprotecting the acetoxy groups from acetoxystyrene repeat units to form hydroxyl styrene repeat units of the terpolymer . formulation was prepared by dissolving 100 mg of polymer prepared in example 1 and 5 mg of tps pfbus in 4 - methyl - 2 - pentanol . it was then filtered through 0 . 2 μm ptfe filter and spincoated onto a clean silicon wafer at about 1500 rpm . the wafer was then baked at 180 ° c . for 60 sec . subsequently the wafer was coated with a arf photoresist and imaged using binary mask in a arf stepper . the wafer was baked at 100 ° c . and developed in a standard 0 . 26n developer . the x - sem of printed pattern for 135 nm lines / spaces showed improved sidewall profile compared to images created without use of the dbarc of the invention . formulation was prepared by dissolving 100 mg of polymer prepared in example 2 and 5 mg of tps pfbus in 4 - methyl - 2 - pentanol . it was then filtered through 0 . 2 μm ptfe filter and spin - coated onto a clean silicon wafer at about 1500 rpm . the wafer was then baked at 180 ° c . for 60 sec . subsequently the wafer was coated with a arf photoresist and imaged using binary mask in a arf stepper . the wafer was baked at 110 ° c . and developed in a standard 0 . 26n developer . the x - sem of printed pattern for 135 nm lines / spaces showed improved sidewall profile compared to images created without use of the dbarc of the invention . a hs - hadma ( 85 / 15 ) copolymer was prepared in the manner described in example 1 . the copolymer was spin coated onto a substrate using a casting solvent of 2 % gbl and 98 % pgmea . the sample was then baked at 185 ° c . for 1 minute . the resulting film was then contacted with an aqueous alkaline developer for 60 seconds which resulted in complete dissolution of the baked dbarc . | 6 |
reference will now be made in detail to embodiments of the invention , examples of which are illustrated in the accompanying drawings . the steps of each method for cleaning and drying a substrate will be described in conjunction with the detailed description of the system . the methods and systems presented herein may be used for cleaning a variety of substrates . the present invention is particularly suited for cleaning substrates such as textiles , as well as other flexible , precision , delicate , or porous structures that are sensitive to soluble and insoluble contaminants . the term “ textile ” is inclusive of , but not limited to , woven or non - woven materials , as well as articles made therefrom . textiles include , but are not limited to , fabrics , articles of clothing , protective covers , carpets , upholstery , furniture and window treatments . for purposes of explanation and illustration , and not limitation , exemplary embodiments of a system for cleaning textiles in accordance with the invention are shown in fig1 and 2 . as noted above , the pressurized fluid solvent used in the present invention is either a pressurized liquid solvent or a densified fluid solvent . although a variety of solvents may be used , it is preferred that an inorganic substance such as carbon dioxide , xenon , nitrous oxide , or sulfur hexafluoride , be used as the pressurized fluid solvent . for cost and environmental reasons , liquid , supercritical , or subcritical carbon dioxide is the preferred pressurized fluid solvent . furthermore , to maintain the pressurized fluid solvent in the appropriate fluid state , the internal temperature and pressure of the system must be appropriately controlled relative to the critical temperature and pressure of the pressurized fluid solvent . for example , the critical temperature and pressure of carbon dioxide is approximately 31 degrees celsius and approximately 73 atmospheres , respectively . the temperature may be established and regulated in a conventional manner , such as by using a heat exchanger in combination with a thermocouple or similar regulator to control temperature . likewise , pressurization of the system may be performed using a pressure regulator and a pump and / or compressor in combination with a pressure gauge . these components are conventional and are not shown in fig1 and 2 as placement and operation of these components are known in the art . the system temperature and pressure may be monitored and controlled either manually , or by a conventional automated controller ( which may include , for example , an appropriately programmed computer or appropriately constructed microchip ) that receives signals from the thermocouple and pressure gauge , and then sends corresponding signals to the heat exchanger and pump and / or compressor , respectively . unless otherwise noted , the temperature and pressure is appropriately maintained throughout the system during operation . as such , elements contained within the system are constructed of sufficient size and material to withstand the temperature , pressure , and flow parameters required for operation , and may be selected from , or designed using , any of a variety of presently available high pressure hardware . in the present invention , the preferred organic solvent should have a flash point of greater than 100 f to allow for increased safety and less governmental regulation , have a low evaporation rate to minimize fugitive emissions , be able to remove soils consisting of insoluble particulate soils and solvent soluble oils and greases , and prevent or reduce redeposition of soil onto the textiles being cleaned . preferably , the organic solvents suitable for use in the present invention include any of the following alone or in combination . a description of the chemical formulae of the organic solvents that can be used in the cleaning processes of the invention follows . as used herein , elemental designations are the same as used by one of skill in the relevant art . for example , as used herein , h designates hydrogen , o designates oxygen , c designates carbon , s designates sulfur , ch 3 designates methyl , ch 2 ch 3 designates ethyl , and so forth . r is a variable that designates a chemical structure as described further herein . in one embodiment of the invention , the organic solvent of the invention is composed , at least in part , of a chemical having the following general chemical structure : wherein : a = 5n and 1 ≦ n ≦ 3 ; each x is independently f , cl , br or i ; 0 ≦ z ≦ 4 ; 0 ≦ j , k ≦ 10 ; and 0 ≦( j + k )≦ 10n . in another embodiment of the invention , the organic solvent of the invention is composed , at least in part , of a chemical having the following general chemical structure : wherein : 1 ≦ n ≦ 20 ; each x is independently f , cl , br or i ; 0 ≦ j ; k ≦ 2n + 2 ; and 2n − 4 ≦(+ k )≦ 2n + 2 . in another embodiment of the invention , the organic solvent of the invention is composed , at least in part , of a chemical having the one of the following general chemical structures : r ii = c k h y x z or benzyl , phenyl , partially or fully fluorinated benzyl or phenyl ; r 1 - 4 and r 9 - 12 are independently c m h n x p , r 5 - 8 and r 13 - 16 are independently c a h b x d , r ii = c k h y x z or benzyl , phenyl , partially or fully fluorinated benzyl or phenyl ; r 1 - 3 and r 7 - 9 are independently c m h n x p , r 4 - 6 and r 10 - 12 are independently c a h b x d , in another embodiment of the invention , the organic solvent of the invention is composed , at least in part , of a chemical having the following general chemical structure : wherein : each x is independently f , cl , br or i ; 1 ≦ n ≦ 20 ; 0 ≦ r ≦ 4 ; 0 ≦ j , k ≦ 2n + 2 − r ; and 2n − 4 − r ≦( j + k )≦ 2n + 2 − r . in another embodiment of the invention , the organic solvent of the invention is composed , at least in part , of a chemical having the following general chemical structure : wherein : each x is independently f , cl , br or i ; 2 ≦ n ≦ 20 ; 0 ≦ j , k ≦ 2n + 2 ; 2n − 4 ≦( j + k )≦ 2n + 2 ; and 1 ≦ b ≦ 6 . in another embodiment of the invention , the organic solvent of the invention is composed , at least in part , of a chemical having the one of the following general chemical structures : r 1 - 4 and r 9 - 12 are independently c m h n x p , r 5 - 8 and r 13 - 16 are independently c a h b x d , r 14 and r 9 - 12 are independently c m h n x p , r 5 - 8 and r 13 - 16 are independently c a h b x d , in another embodiment of the invention , the organic solvent of the invention is composed , at least in part , of a chemical having the following general chemical structure : wherein : each x is independently f , cl , br or i ; 2 ≦ n ≦ 21 ; 1 ≦ m ≦ 3 ; 0 ≦ a ; b ≦ 2n + 2 ; and 2n − 2 ≦( a + b )≦ 2n + z . in another embodiment of the invention , the organic solvent of the invention is composed , at least in part , of a chemical having the one of the following general chemical structures : wherein : each x is independently f , cl , br or i ; 2 ≦ n ≦ 18 ; m = 1 ; 0 ≦ a ; b ≦ 2n + 2 ; and 2n − 4 ≦( a + b )≦ 2n + z . 1 ≦ j ≦ 6 0 ≦ a ; b ≦ 2j + 1 ; and 2j − 7 ≦( a + b )≦ 2j + 1 ; r 2 = c k h d x e 1 ≦ k ≦ 6 ; 0 ≦ d ; e ≦ 2k + 1 ; and d + e = 2k + 1 ; in another embodiment of the invention , the organic solvent of the invention is composed , at least in part , of a chemical having the one of the following general chemical structures : each r equals c a x y h z independently ; each r equals c a h y x z independently ; referring now to fig1 , a block diagram of a cleaning system having separate vessels for cleaning and drying textiles is shown . the cleaning system 100 generally comprises a cleaning machine 102 having a cleaning vessel 110 operatively connected to , via one or more motor activated shafts ( not shown ), a perforated rotatable cleaning drum or wheel 112 within the cleaning vessel 110 with an inlet 114 to the cleaning vessel 110 and an outlet 116 from the cleaning vessel 110 through which cleaning fluids can pass . a drying machine 104 has a drying vessel 120 capable of being pressurized . the pressurizable drying vessel 120 is operatively connected to , via one or more motor activated shafts ( not shown ), a perforated rotatable drying drum or wheel 122 within the drying vessel 120 with an inlet 124 to the drying vessel 120 and an outlet 126 from the drying vessel 120 through which pressurized fluid solvent can pass . the cleaning vessel 110 and the drying vessel 120 can either be parts of the same machine , or they can comprise separate machines . furthermore , both the cleaning and drying steps of this invention can be performed in the same vessel , as is described with respect to fig2 below . an organic solvent tank 130 holds any suitable organic solvent , as previously described , to be introduced to the cleaning vessel 110 through the inlet 114 . a pressurized fluid solvent tank 132 holds pressurized fluid solvent to be added to the pressurizable drying vessel 120 through the inlet 124 . filtration assembly 140 contains one or more filters that continuously remove contaminants from the organic solvent from the cleaning vessel 110 as cleaning occurs . the components of the cleaning system 100 are connected with line 150 – 156 , which transfer organic solvents and vaporized and pressurized fluid solvents between components of the system . the term “ line ” as used herein is understood to refer to a piping network or similar conduit capable of conveying fluid and , for certain purposes , is capable of being pressurized . the transfer of the organic solvents and vaporized and pressurized fluid solvents through the line 150 – 156 is directed by valves 170 – 176 and pumps 190 – 193 . while pumps 190 – 193 are shown in the described embodiment , any method of transferring liquid and / or vapor between components can be used , such as adding pressure to the component using a compressor to force the liquid and / or vapor from the component . the textiles are cleaned with an organic solvent such as those previously described or mixtures thereof . the textiles may also be cleaned with a combination of organic solvent and pressurized fluid solvent , and this combination may be in varying proportions from about 50 % by weight to 100 % by weight of organic solvent and 0 % by weight to 50 % by weight of pressurized fluid solvent . in the cleaning process , the textiles are first sorted as necessary to place the textiles into groups suitable to be cleaned together . the textiles may then be spot treated as necessary to remove any stains that may not be removed during the cleaning process . the textiles are then placed into the cleaning drum 112 of the cleaning system 100 . it is preferred that the cleaning drum 112 be perforated to allow for free interchange of solvent between the cleaning drum 112 and the cleaning vessel 110 as well as to transport soil from the textiles to the filtration assembly 140 . after the textiles are placed in the cleaning drum 112 , an organic solvent contained in the organic solvent tank 130 is added to the cleaning vessel 110 via line 152 by opening valve 171 , closing valves 170 , 172 , 173 and 174 , and activating pump 190 to pump organic solvent through the inlet 114 of the cleaning vessel 110 . the organic solvent may contain one or more co - solvents , water , detergents , or other additives to enhance the cleaning capability of the cleaning system 100 . alternatively , one or more additives may be added directly to the cleaning vessel 110 . pressurized fluid solvent may also be added to the cleaning vessel 110 along with the organic solvent to enhance cleaning . pressurized fluid solvent can be added to the cleaning vessel 110 via line 154 by opening valve 174 , closing valves 170 , 171 , 172 , 173 , and 175 , and activating pump 192 to pump pressurized fluid solvent through the inlet 114 of the cleaning vessel 110 . of course , if pressurized fluid solvent is included in the cleaning cycle , the cleaning vessel 110 will need to be pressurized in the same manner as the drying vessel 120 , as discussed below . when a sufficient amount of the organic solvent , or combination of organic solvent and pressurized fluid solvent , is added to the cleaning vessel 110 , the motor ( not shown ) is activated and the perforated cleaning drum 112 is agitated and / or rotated within cleaning vessel 110 . during this phase , the organic solvent is continuously cycled through the filtration assembly 140 by opening valves 170 and 172 , closing valves 171 , 173 and 174 , and activating pump 191 . filtration assembly 140 may include one or more fine mesh filters to remove particulate contaminants from the organic solvent passing therethrough and may alternatively or in addition include one or more absorptive or adsorptive filters to remove water , dyes and other dissolved contaminants from the organic solvent . exemplary configurations for filter assemblies that can be used to remove contaminants from either the organic solvent or the pressurized fluid solvent are described more fully in u . s . application ser . no . 08 / 994 , 583 incorporated herein by reference . as a result , the organic solvent is pumped through outlet 116 , valve 172 , line 151 , filter assembly 140 , line 150 , valve 170 and re - enters the cleaning vessel 110 via inlet 114 . this cycling advantageously removes contaminants , including particulate contaminants and / or soluble contaminants , from the organic solvent and reintroduces filtered organic solvent to the cleaning vessel 110 and agitating or rotating cleaning drum 112 . through this process , contaminants are removed from the textiles . of course , in the event the cleaning vessel 110 is pressurized , this recirculation system will be maintained at the same pressure / temperature levels as those in cleaning vessel 110 . after sufficient time has passed so that the desired level of contaminants is removed from the textiles and organic solvent , the organic solvent is removed from the cleaning drum 112 and cleaning vessel 110 by opening valve 173 , closing valves 170 , 171 , 172 and 174 , and activating pump 191 to pump the organic solvent through outlet 116 via line 153 . the cleaning drum 112 is then rotated at a high speed , such as 400 – 800 rpm , to further remove organic solvent from the textiles . the cleaning drum 112 is preferably perforated so that , when the textiles are rotated in the cleaning drum 112 at a high speed , the organic solvent can drain from the cleaning drum 112 . any organic solvent removed from the textiles by rotating the cleaning drum 112 at high speed is also removed from the cleaning drum 112 in the manner described above . after the organic solvent is removed from the cleaning drum 112 , it can either be discarded or recovered and decontaminated for reuse using solvent recovery systems known in the art . furthermore , multiple cleaning cycles can be used if desired , with each cleaning cycle using the same organic solvent or different organic solvents . if multiple cleaning cycles are used , each cleaning cycle can occur in the same cleaning vessel , or a separate cleaning vessel can be used for each cleaning cycle . after a desired amount of the organic solvent is removed from the textiles by rotating the cleaning drum 112 at high speed , the textiles are moved from the cleaning drum 112 to the drying drum 122 within the drying vessel 120 in the same manner textiles are moved between machines in conventional cleaning systems . in an alternate embodiment , a single drum can be used in both the cleaning cycle and the drying cycle , so that , rather than transferring the textiles between the cleaning drum 112 and the drying drum 122 , a single drum containing the textiles is transferred between the cleaning vessel 110 and the drying vessel 120 . if the cleaning vessel 110 is pressurized during the cleaning cycle , it must be depressurized before the textiles are removed . once the textiles have been placed in the drying drum 122 , pressurized fluid solvent , such as that contained in the carbon dioxide tank 132 , is added to the drying vessel 120 via lines 154 and 155 by opening valve 175 , closing valves 174 and 176 , and activating pump 192 to pump pressurized fluid solvent through the inlet 124 of the drying vessel 120 via lines 154 and 155 . when pressurized fluid solvent is added to the drying vessel 120 , the organic solvent remaining on the textiles dissolves in the pressurized fluid solvent . after a sufficient amount of pressurized fluid solvent is added so that the desired level of organic solvent has been dissolved , the pressurized fluid solvent and organic solvent combination is removed from the drying vessel 120 , and therefore also from the drying drum 122 , by opening valve 176 , closing valve 175 and activating pump 193 to pump the pressurized fluid solvent and organic solvent combination through outlet 126 via line 156 . if desired , this process may be repeated to remove additional organic solvent . the drying drum 122 is then rotated at a high speed , such as 150 – 800 rpm , to further remove the pressurized fluid solvent and organic solvent combination from the textiles . the drying drum 122 is preferably perforated so that , when the textiles are rotated in the drying drum 122 at a high speed , the pressurized fluid solvent and organic solvent combination can drain from the drying drum 122 . any pressurized fluid solvent and organic solvent combination removed from the textiles by spinning the drying drum 122 at high speed is also pumped from the drying vessel 120 in the manner described above . after the pressurized fluid solvent and organic solvent combination is removed from the drying vessel 120 , it can either be discarded or separated and recovered for reuse with solvent recovery systems known in the art . note that , while preferred , it is not necessary to include a high speed spin cycle to remove pressurized fluid solvent from the textiles . after a desired amount of the pressurized fluid solvent is removed from the textiles by rotating the drying drum 122 , the drying vessel 120 is depressurized over a period of about 5 – 15 minutes . the depressurization of the drying vessel 120 vaporizes any remaining pressurized fluid solvent , leaving dry , solvent - free textiles in the drying drum 122 . the pressurized fluid solvent that has been vaporized is then removed from the drying vessel 120 by opening valve 176 , closing valve 175 , and activating pump 193 . as a result , the vaporized pressurized fluid solvent is pumped through the outlet 126 , line 156 and valve 176 , where it can then either be vented to the atmosphere or recovered and recompressed for reuse . while the cleaning system 100 has been described as a complete system , an existing conventional dry cleaning system may be converted for use in accordance with the present invention . to convert a conventional dry cleaning system , the organic solvent described above is used to clean textiles in the conventional system . a separate pressurized vessel is added to the conventional system for drying the textiles with pressurized fluid solvent . thus , the conventional system is converted for use with a pressurized fluid solvent . for example , the system in fig1 could represent such a converted system , wherein the components of the cleaning machine 102 are conventional , and the pressurized fluid solvent tank 132 is not in communication with the cleaning vessel 100 . in such a situation , the drying machine 104 is the add - on part of the conventional cleaning machine . furthermore , while the system shown in fig1 comprises a single cleaning vessel , multiple cleaning vessels could be used , so that the textiles are subjected to multiple cleaning steps , with each cleaning step carried out in a different cleaning vessel using the same or different organic solvents in each step . the description of the single cleaning vessel is merely for purposes of description and should not be construed as limiting the scope of the invention . referring now to fig2 , a block diagram of an alternate embodiment of the present invention , a cleaning system having a single chamber for cleaning and drying the textiles , is shown . the cleaning system 200 generally comprises a cleaning machine having a pressurizable vessel 210 . the vessel 210 is operatively connected to , via one or more motor activated shafts ( not shown ), a perforated rotatable drum or wheel 212 within the vessel 210 with an inlet 214 to the vessel 210 and an outlet 216 from the vessel 210 through which dry cleaning fluids can pass . an organic solvent tank 220 holds any suitable organic solvent , such as those described above , to be introduced to the vessel 210 through the inlet 214 . a pressurized fluid solvent tank 222 holds pressurized fluid solvent to be added to the vessel 210 through the inlet 214 . filtration assembly 224 contains one or more filters that continuously remove contaminants from the organic solvent from the vessel 210 and drum 212 as cleaning occurs . the components of the cleaning system 200 are connected with line 230 – 234 that transfer organic solvents and vaporized and pressurized fluid solvent between components of the system . the term “ line ” as used herein is understood to refer to a piping network or similar conduit capable of conveying fluid and , for certain purposes , is capable of being pressurized . the transfer of the organic solvents and vaporized and pressurized fluid solvent through the line 230 – 234 is directed by valves 250 – 254 and pumps 240 – 242 . while pumps 240 – 242 are shown in the described embodiment , any method of transferring liquid and / or vapor between components can be used , such as adding pressure to the component using a compressor to force the liquid and / or vapor from the component . the textiles are cleaned with an organic solvent such as those previously described . the textiles may also be cleaned with a combination of organic solvent and pressurized fluid solvent , and this combination may be in varying proportions of 50 – 100 % by weight organic solvent and 0 – 50 % by weight pressurized fluid solvent . in the cleaning process , the textiles are first sorted as necessary to place the textiles into groups suitable to be cleaned together . the textiles may then be spot treated as necessary to remove any stains that may not be removed during the cleaning process . the textiles are then placed into the drum 212 within the vessel 210 of the cleaning system 200 . it is preferred that the drum 212 be perforated to allow for free interchange of solvent between the drum 212 and the vessel 210 as well as to transport soil from the textiles to the filtration assembly 224 . after the textiles are placed in the drum 212 , an organic solvent contained in the organic solvent tank 220 is added to the vessel 210 via line 231 by opening valve 251 , closing valves 250 , 252 , 253 and 254 , and activating pump 242 to pump organic solvent through the inlet 214 of the vessel 210 . the organic solvent may contain one or more co - solvents , detergents , water , or other additives to enhance the cleaning capability of the cleaning system 200 or other additives to impart other desirable attributes to the articles being treated . alternatively , one or more additives may be added directly to the vessel . pressurized fluid solvent may also be added to the vessel 210 along with the organic solvent to enhance cleaning . the pressurized fluid solvent is added to the vessel 210 via line 230 by opening valve 250 , closing valves 251 , 252 , 253 and 254 , and activating pump 240 to pump the pressurized fluid solvent through the inlet 214 of the vessel 210 . when the desired amount of the organic solvent , or combination of organic solvent and pressurized fluid solvent as described above , is added to the vessel 210 , the motor ( not shown ) is activated and the drum 212 is agitated and / or rotated . during this phase , the organic solvent , as well as pressurized fluid solvent if used in combination , is continuously cycled through the filtration assembly 224 by opening valves 252 and 253 , closing valves 250 , 251 and 254 , and activating pump 241 . filtration assembly 224 may include one or more fine mesh filters to remove particulate contaminants from the organic solvent and pressurized fluid solvent passing therethrough and may alternatively or in addition include one or more absorptive or adsorptive filters to remove water , dyes , and other dissolved contaminants from the organic solvent . exemplary configurations for filter assemblies that can be used to remove contaminants from either the organic solvent or the pressurized fluid solvent are described more fully in u . s . application ser . no . 08 / 994 , 583 incorporated herein by reference . as a result , the organic solvent is pumped through outlet 216 , valve 253 , line 233 , filter assembly 224 , line 232 , valve 252 and reenters the vessel 210 via inlet 214 . this cycling advantageously removes contaminants , including particulate contaminants and / or soluble contaminants , from the organic solvent and pressurized fluid solvent and reintroduces filtered solvent to the vessel 210 . through this process , contaminants are removed from the textiles . after sufficient time has passed so that the desired level of contaminants is removed from the textiles and solvents , the organic solvent is removed from the vessel 210 and drum 212 by opening valve 254 , closing valves 250 , 251 , 252 and 253 , and activating pump 241 to pump the organic solvent through outlet 216 and line 234 . if pressurized fluid solvent is used in combination with organic solvent , it may be necessary to first separate the pressurized fluid solvent from the organic solvent . the organic solvent can then either be discarded or , preferably , contaminants may be removed from the organic solvent and the organic solvent recovered for further use . contaminants may be removed from the organic solvent with solvent recovery systems known in the art . the drum 212 is then rotated at a high speed , such as 150 – 800 rpm , to further remove organic solvent from the textiles . the drum 212 is preferably perforated so that , when the textiles are rotated in the drum 212 at a high speed , the organic solvent can drain from the cleaning drum 212 . any organic solvent removed from the textiles by rotating the drum 212 at high speed can also either be discarded or recovered for further use . after a desired amount of organic solvent is removed from the textiles by rotating the drum 212 , pressurized fluid solvent contained in the pressurized fluid tank 222 is added to the vessel 210 by opening valve 250 , closing valves 251 , 252 , 253 and 254 , and activating pump 240 to pump pressurized fluid solvent through the inlet 214 of the pressurizable vessel 210 via line 230 . when pressurized fluid solvent is added to the vessel 210 , organic solvent remaining on the textiles dissolves in the pressurized fluid solvent . after a sufficient amount of pressurized fluid solvent is added so that the desired level of organic solvent has been dissolved , the pressurized fluid solvent and organic solvent combination is removed from the vessel 210 by opening valve 254 , closing valves 250 , 251 , 252 and 253 , and activating pump 241 to pump the pressurized fluid solvent and organic solvent combination through outlet 216 and line 234 . note that pump 241 may actually require two pumps , one for pumping the low pressure organic solvent in the cleaning cycle and one for pumping the pressurized fluid solvent in the drying cycle . the pressurized fluid solvent and organic solvent combination can then either be discarded or the combination may be separated and the organic solvent and pressurized fluid solvent separately recovered for further use . the drum 212 is then rotated at a high speed , such as 150 – 350 rpm , to further remove pressurized fluid solvent and organic solvent combination from the textiles . any pressurized fluid solvent and organic solvent combination removed from the textiles by spinning the drum 212 at high speed can also either be discarded or retained for further use . note that , while preferred , it is not necessary to include a high speed spin cycle to remove pressurized fluid solvent from the textiles . after a desired amount of the pressurized fluid solvent is removed from the textiles by rotating the drum 212 , the vessel 210 is depressurized over a period of about 5 – 15 minutes . the depressurization of the vessel 210 vaporizes the pressurized fluid solvent , leaving dry , solvent - free textiles in the drum 212 . the pressurized fluid solvent that has been vaporized is then removed from the vessel 210 by opening valve 254 , closing valves 250 , 251 , 252 and 253 , and activating pump 241 to pump the vaporized pressurized fluid solvent through outlet 216 and line 234 . note that while a single pump is shown as pump 241 , separate pumps may be necessary to pump organic solvent , pressurized fluid solvent and pressurized fluid solvent vapors , at pump 241 . the remaining vaporized pressurized fluid solvent can then either be vented into the atmosphere or compressed back into pressurized fluid solvent for further use . as discussed above , terpenes , halohydrocarbons , certain glycol ethers , polyols , ethers , esters of glycol ethers , esters of fatty acids and other long chain carboxylic acids , fatty alcohols and other long - chain alcohols , short - chain alcohols , polar aprotic solvents , siloxanes , hydrofluoroethers , dibasic esters , and aliphatic hydrocarbons solvents or similar solvents or mixtures of such solvents are organic solvents that can be used in the present invention , as shown in the test results below . table 1 shows results of detergency testing for each of a number of solvents that may be suitable for use in the present invention . table 2 shows results of testing of drying and extraction of those solvents using densified carbon dioxide . detergency tests were performed using a number of different solvents without detergents , co - solvents , or other additives . the solvents selected for testing include organic solvents and liquid carbon dioxide . two aspects of detergency were investigated — soil removal and soil redeposition . the former refers to the ability of a solvent to remove soil from a substrate while the latter refers to the ability of a solvent to prevent soil from being redeposited on a substrate during the cleaning process . wascherei forschungs institute , krefeld germany (“ wfk ”) standard soiled swatches that have been stained with a range of insoluble materials and wfk white cotton swatches , both obtained from testfabrics , inc ., were used to evaluate soil removal and soil redeposition , respectively . soil removal and redeposition for each solvent was quantified using the delta whiteness index . this method entails measuring the whiteness index of each swatch before and after processing . the delta whiteness index is calculated by subtracting the whiteness index of the swatch before processing from the whiteness index of the swatch after processing . the whiteness index is a function of the light reflectance of the swatch and in this application is an indication of the amount of soil on the swatch . more soil results in a lower light reflectance and whiteness index for the swatch . the whiteness indices were measured using a reflectometer manufactured by hunter laboratories . organic solvent testing was carried out in a launder - ometer while the densified carbon dioxide testing was carried out in a parr bomb . after measuring their whiteness indices , two wfk standard soil swatches and two wfk white cotton swatches were placed in a launder - ometer cup with 25 stainless steel ball bearings and 150 ml of the solvent of interest . the cup was then sealed , placed in the launder - ometer and agitated for a specified length of time . afterwards , the swatches were removed and placed in a parr bomb equipped with a mesh basket . approximately 1 . 5 liters of liquid carbon dioxide between 5 ° c . and 25 ° c . and 570 psig and 830 psig was transferred to the parr bomb . after several minutes the parr bomb was vented and the dry swatches removed and allowed to reach room temperature . testing of densified carbon dioxide was carried out in the same manner but test swatches were treated for 20 minutes . during this time the liquid carbon dioxide was stirred using an agitator mounted on the inside cover of the parr bomb . the whiteness index of the processed swatches was determined using the reflectometer . the two delta whiteness indices obtained for each pair of swatches were averaged . the results are presented in table 1 . because the delta whiteness index is calculated by subtracting the whiteness index of a swatch before processing from the whiteness index value after processing , a positive delta whiteness index indicates that there was an increase in whiteness index as a result of processing . in practical terms , this means that soil was removed during processing . in fact , the higher the delta whiteness value , the more soil was removed from the swatch during processing . each of the organic solvents tested exhibited soil removal capabilities . the wfk white cotton swatches exhibited a decrease in delta whiteness indices indicating that the soil was deposited on the swatches during the cleaning process . therefore , a “ less negative ” delta whiteness index suggests that less soil was redeposited . to evaluate the ability of densified carbon dioxide to extract organic solvent from a substrate , wfk white cotton swatches were used . one swatch was weighed dry and then immersed in an organic solvent sample . excess solvent was removed from the swatch using a ringer manufactured by atlas electric devices company . the damp swatch was re - weighed to determine the amount of solvent retained in the fabric . after placing the damp swatch in a parr bomb densified carbon dioxide was transferred to the parr bomb . the temperature and pressure of the densified carbon dioxide for all of the trials ranged from 5 ° c . to 20 ° c . and from 570 psig - 830 psig . after five minutes the parr bomb was vented and the swatch removed . the swatch was next subjected to soxhlet extraction using methylene chloride for a minimum of two hours . this apparatus enables the swatch to be continuously extracted to remove the organic solvent from the swatch . after determining the concentration of the organic solvent in the extract using gas chromatography , the amount of organic solvent remaining on the swatch after exposure to densified carbon dioxide was calculated by multiplying the concentration of the organic solvent in the extract by the volume of the extract . a different swatch was used for each of the tests . the results of these tests are included in table 2 . as the results indicate , the extraction process using densified carbon dioxide is extremely effective . it is to be understood that a wide range of changes and modifications to the embodiments described above will be apparent to those skilled in the art and are contemplated . it is , therefore , intended that the foregoing detailed description be regarded as illustrative rather than limiting , and that it be understood that it is the following claims , including all equivalents , that are intended to define the spirit and scope of the invention . | 1 |
the present invention relates to the application of a magnetic film material that is characterized as relatively - thick ( up to about 500 microns ), having relatively - high remanent magnetization ( greater than about 96 percent of saturation values ), having oriented magnetic materials , and exhibiting relatively - low microwave loss , e . g ., ferromagnetic resonance ( fmr ) linewidths of less than about 350 oe . referring to fig1 , 6 , and 7 , a method of manufacturing a self - biasing magnetic film on a substrate for use in microwave and millimeter wave applications using screen printing technology is shown . the material for the self - biasing magnetic film can include , for example and without limitation , barium ferrite , c - axis - oriented barium ferrite , m - type barium ferrite , barium - hexaferrite , barium ferrite doped with at least one of scandium , indium , aluminum or gallium , and the like . for the remainder of this disclosure , it will be assumed that the magnetic material is barium - hexaferrite . sample preparation ( step 1 ) includes preparing a wet paste comprising a magnetic material , such as barium - hexaferrite , for application to a surface of a suitable microwave or millimeter wave substrate . the barium - hexaferrite particles , or powder , can be prepared according to conventional ceramic processing techniques . ball milling the powder can reduce the diameter of the powder particles to about one micrometer ( μm ). alternative starting materials include magnetic materials processed through chemical processes . the wet paste includes a binder , e . g ., b - 75000 manufactured by the ferro corporation of cleveland , ohio , in which particles of the magnetic material and glass frit , i . e ., sio 2 , are suspended . an exemplary wet paste suitable for screen - printing consists of about 25 . 5 percent ( by weight ) binder , about 2 . 5 percent ( by weight ) glass frit , and about 72 percent ( by weight ) barium - hexaferrite . the binder provides a matrix for the magnetic materials . the glass frit enables the relatively - thick wet paste to adhere to the substrate better during the sintering process described below . a stencil , template , screen , mask , and the like 12 having a desired , predetermined thickness and a desired , predetermined pattern of discrete openings 16 can be positioned on the surface 13 of the microwave substrate 18 , e . g ., a thin , alumina substrate . the paste 10 is then applied to , e . g ., spread onto , the surface 13 of the suitable microwave substrate 18 ( step 2 ), through the various openings 16 in the stencil , template , screen , mask , and the like 12 . as with conventional screen - printing , a bladed instrument 14 can be used to spread the paste 10 across the stencil , template , mask , and the like 12 and into the openings 16 . after the paste 10 is applied to the surface 13 of the substrate 18 , the stencil , template , mask , and the like 12 can be removed . the resulting wet , magnetic film 15 and substrate 18 are then heated in a first heat treatment ( step 3 ) at a relatively - low temperature in a process called “ burn - out ”. the first heat treatment ( step 3 ) is characterized as lasting between about one ( 1 ) and about 20 minutes at a temperature between about 150 and about 250 degrees centigrade (° c . ), or about 300 and about 480 degrees fahrenheit (° f .). the relatively - low - temperature heat treatment ( step 3 ) is designed to vaporize fluid and most organic compounds in the binder material , leaving a porous magnetic film 15 of barium - hexaferrite and frit on the surface 13 of the substrate 18 . the range of temperatures for the first heat treatment ( step 3 ) is high enough to vaporize fluid and most organic compounds in the binder but cannot “ burn - out ” the binder . the resulting magnetic film 15 contains a porous residual binder . during the first heat treatment ( step 3 ), the wet paste 10 is simultaneously subjected to a relatively - large strength magnetic field ( step 4 ). using , for example , an electromagnet , a magnetic field can be applied to the “ wet ” paste 10 ( step 4 ) during the first heat treatment ( step 3 ). the purpose of the applied magnetic field is to align the barium - hexaferrite particles with respect to the direction of the magnetic field , which is perpendicular to or substantially perpendicular to the film plane , and to self - bias the barium - hexaferrite particles . the strength of the applied magnetic field is between about 500 and about 10 , 000 oe , which is sufficient to cause the alignment of , i . e ., to orient , the barium - hexaferrite particles with respect to the direction of the magnetic field and , more particularly , to cause the c - axes of the hexaferrite particles , to align along the direction of the applied magnetic field , i . e ., perpendicular to or substantially perpendicular to the film plane . the magnetic film 15 then undergoes a second ( step 5 ) and , optionally a third heat treatment ( step 6 ). the second heat treatment ( step 5 ) includes heating the magnetic film 15 and the substrate 18 in an ambient atmosphere to a temperature between about 900 ° c . and about 1300 ° c . ( about 1650 ° f . and about 2370 ° f .) for about one ( 1 ) to about 15 hours , to sinter the film 15 . during the sintering process , those organic compounds that were not burned out during the first heat treatment are vaporized . the sintering temperature is chosen based on the magnetic and microwave or millimeter wave properties desired in the resulting film 15 and on any desired loading during the sintering process , such as “ hot pressing ”. after sintering , the film 15 has a dense , polycrystalline structure with grains oriented with the c - axis , perpendicular to or substantially perpendicular to the film plane . the degree and extent of recrystallization also depends on the sintering temperature and time . the third heat treatment ( step 6 ) is sometimes required to complete the sintering , to reduce strain , and / or to cause the annealing of the magnetic film 15 . the optional third heat treatment ( step 6 ) includes heating the magnetic film 15 and the substrate 18 to a temperature between about 600 ° c . and about 1300 ° c . ( about 1110 ° f . and about 2370 ° f .) for about one ( 1 ) to about 15 hours . “ hot - pressing ” the film 15 ( step 7 ) during the sintering and / or annealing heat treatments ( steps 5 and 6 ), is desirable to improve film density and to reduce microwave losses . “ hot pressing ” includes loading an oxide substrate 14 , e . g . an alumina substrate , having a weight of about 50 to about 500 grams on top of the film 15 , causing a progressive densification of the film 15 during sintering and / or annealing . after completion of the sintering and / or the annealing step ( steps 5 and 6 ) performed in conjunction with “ hot pressing ” ( step 7 ), film density is improved by about 85 to about 97 percent . an exemplary magnetic film can be fabricated using the following process : using a hitachi s - 4800 ultrahigh resolution scanning electron microscope ( sem ), an sem image of screen - printed film after alignment and low - temperature heat treatment ( step 3 ) is shown in fig2 a , and an sem image of screen - printed film after sintering the film at about 1200 ° c . for about three hours ( step 5 ) is shown in fig2 b . in fig2 a , the grains shown are loosely aligned , which may included some alignment , and the film appear to be relatively porous . in contrast , in fig2 b , the grains have grown in size , especially along the film plane , and the film appears to have a higher density , demonstrative of the appreciable and advantageous densification and grain growth that occurs as a result of the high - temperature sintering steps . a sem cross - section image of the film depicted in fig2 b is shown in fig2 c . in this image , the top of the image is closest the top of the film 15 and the bottom of the image is closest the substrate 18 , large , columnar grains that are aligned perpendicular to the film plane are observable . in addition , isolated pores can be seen . fig3 is an x - ray diffraction pattern of the film 15 after alignment and optimized heat treatment . in the figure , the diffraction peaks indexed to ( 0 , 0 , 2n ) have been identified to have enhanced intensities consistent with preferential alignment of c - axis grains perpendicular to the sample plane . the characterization of the film morphology and structure indicates a strong crystal texture of c - axis grains normal to the sample plane , which is essential to device operation . resulting samples also exhibit a preferred direction of magnetization that is oriented perpendicular to or substantially perpendicular to the film plane and relatively - high remanent magnetization . more specifically , the sample remains magnetized perpendicular to the sample plane even after an externally applied magnetic saturation field is removed . fig4 is a plot of magnetic hysteresis loops made with the applied magnetic field aligned along the in - plane sample direction (∘) and perpendicular to the sample plane (▪). in fig4 , the square (▪) loop with high remanent magnetization corresponds to the out - of - plane orientation . thus , it is shown that the magnetization prefers the direction normal to the sample plane , and also that , upon removal of the applied magnetic saturation field , the sample retains about 96 percent of the saturation magnetization . the other loop ( o ) corresponds to the magnetic hard axes parallel the sample plane . although the present invention has been described for application with circulators , the invention is not to be construed as being limited thereto . indeed , further commercial applications can include isolators , filters , phase shifters , index lenses and index media , magnetic sensors , radiation - absorbing media , and the like . the present invention has also been described assuming that the magnetic material is barium - hexaferrite . however , this was for convenience only and the invention is not to be construed as being limited thereto . for growing relatively - thicker films over relatively - larger surface areas , multiple - pass , e . g ., two or three layers , screen - printing is possible . multiple - pass screen printing has been effective in reducing or eliminating cracking . the foregoing description is not intended to be exhaustive or to limit the invention to the precise form disclosed . the embodiment was chosen and described to provide the illustration of principles of the invention and its application . modification and variations are within the scope of invention . | 2 |
the preferred embodiments are directed to a method , system and program for consumers to purchase customized interactive learning devices , such as toys , and provide greater interactivity for the toys over any communication network , such as the internet . in the following description , reference is made to the accompanying drawings which form a part hereof and which illustrate the preferred embodiment of the present invention . it is understood that other embodiments may be utilized and structural and operational changes may be made without departing from the scope of the present invention . for example , although the preferred embodiments are described in the context of an interactive toy , the present application can apply to any device that is customized to a user &# 39 ; s preferences and tastes before delivery , and the “ development ” of the device is compared after further customization by the user . [ 0037 ] fig1 is a schematic overview diagram of the network computing environment in which the preferred embodiments are implemented . in preferred embodiments , user computers 10 can access a web server 20 using a network 15 , such as the internet . the network 15 may be comprised of any network system known in the art including tcp / ip based networks ( e . g ., an intranet , the internet ), lan , ethernet , wan , token ring , etc . alternatively , there may be separate and different networks between the components . further , because the preferred embodiment of the network 15 is the internet , there can be numerous users using the network 15 simultaneously , however only three user computers 10 are shown for illustration purposes . interactive toys 30 can be directly connected to the user computers 10 by means of a communication port , such as a serial port , parallel port or usb connection or other suitable ports known to one of ordinary skill in the art . however , in alternative embodiments , interactive toys 30 may connect to network 15 by means of a wireless internet connection avoiding the use of the user computers 10 . in addition , the network 15 also connects the web server 20 to a manufacturer computer 5 where the web server 20 can deliver customized orders for the toys 30 . [ 0038 ] fig2 illustrates software components in the preferred embodiment of the web server 20 , including a hypertext transfer protocol ( http ) server 50 , database 60 , database interface 55 , customization tool 40 , and templates 65 and 67 . the http server 50 responds to requests from the user computers 10 using http client programs , such as 1 web browser programs known in the art . upon accessing the http server 50 through the network 15 using a unique network address ( i . e . an ip address ), the database interface 55 will give specific access to certain parts of database 60 depending on the secured identification provided by the user computer 10 ( e . g . unique username , unique toy name , identification number , password , etc .). the database 60 keeps current information about the users ( or purchasers ) of the interactive toy , the interactive toys themselves , and variety of other information needed to provide information throughout the website . the database 60 comprises a database program known in the art , such as a relational database program . in the preferred embodiment , the database 60 includes six database tables 70 , 75 , 80 , 85 , 90 , and 95 . a user database table 70 , which includes user records 71 a , b , . . . n , is used in the preferred embodiment to track user information . each record 71 a , b , . . . , n belongs to a unique user keeping track of a purchaser information gathered from the user . fields within a record 71 a , b , . . . or n keeps information such as user name , password , credit card information , address , user &# 39 ; s tastes and preferences , purchase record , etc . in addition , a manual database table 75 includes records 76 a , b , . . . n which is used in the preferred embodiment to keep generic information about the website , instructions to the web server 20 , and introductory information about the interactive toys . moreover , database tables 80 , 85 , 90 , 95 , each with records 81 a , b , . . . n , 86 a , b , . . . n , 91 a , b , . . . n , and 96 a , b , . . . n , keep track of a variety of other information about the interactive toys themselves , the interaction of the toys and users within the website , and information about upgrades to both software and hardware of the interactive toys . additional detail of the database tables 75 , 80 , 85 , 90 , and 95 will be discussed with respect to fig1 . the database interface 55 may comprise a common gateway interface ( cgi ) program , a java servlet , or other web page implementation known in the art to present the information in database 60 in a presentable format ( e . g . html page , etc .). in preferred embodiments , the database interface 55 uses a secured login / password verification for identifying the individual user contacting the http server 50 . the assigning of a secured login / password can occur when the user purchases an interactive toy , visits the website , or other means known in the art . the unique identification will allow the database interface 55 to identify which user record 71 a , b , . . . n belong to the requesting party and will appropriately give read / write capabilities to the user record 71 a , b , . . . n . the server 20 further stores a display template 65 and an input template 67 , which are preferably implemented in a document in which dynamic content may be generated ( i . e . html , extended markup language ( xml ) document , etc .). differing variations of the display template 65 and input template 67 exists for both user information and the interactive toys , depending on the information to be displayed or inputted , but a single display template 65 and a single input template 67 are used for illustration purposes in fig2 . the display template 65 is used to provide the user computers 10 with specific user and toy information from the database tables 70 , 75 , 80 , 85 , 90 , and 95 . the database interface 70 generates data into the display template 65 from one or more of the records 71 a , b , . . . n , 76 a , b , . . . n , 81 a , b , . . . n , 86 a , b , . . . n , 91 a , b , . . . n , and / or 96 a , b , . . . n in the database 60 . the input template 67 is used by the web server 20 to collect data from the users or toys and stores the collected information in one or more records 71 a , b , . . . n , 76 a , b , . . . n , 81 a , b , . . . n , 86 a , b , . . . n , 91 a , b , . . . n , and / or 96 a , b , . . . n in the database 60 . the database 60 , display template 65 , and input template 67 are preferably stored in a non - volatile storage system , such as one or more hard disk drives , used by the server 10 for storage . the server 20 may load data from the storage system into volatile memory ( not shown ) when processing . as shown in fig2 the web server 20 also includes a customization tool 40 . the http server 50 will access the customization tool 40 when a purchaser desires to pre - customize the toy 30 before purchase . the http server 50 can provide a profile form to the purchaser based on the input template 67 and receive the corresponding answers inputted by the purchaser . the responses are sent to a user analyzing unit 43 of the customization tool 40 , which gives values to the responses and analyzes the response values to determine the purchaser &# 39 ; s preferences and tastes based on a predetermined valuation formula . the analysis results are passed to toy character determining unit 47 , which selects a character for the toy 30 from a group of predefined toy character patterns that best match the purchaser &# 39 ; s tastes and preferences . additional details on the workings of the customization tool 40 will be given with regards to fig6 . the server 20 , manufacturer computer 5 and user computers 30 may comprise any type of computer device known in the art , including server , personal computer , mainframe , workstation , hand held device , etc . moreover , the server 20 may comprise one or more separate computer systems to run the different program components 40 , 50 , 55 , and 60 . [ 0045 ] fig3 is a block diagram illustrating an overview construction of the system for purchasing and / or managing an interactive toy over the internet in accordance with a preferred embodiment of the present invention . as shown in fig3 the system for purchasing and managing a learning / growing type toy over the internet includes a web server 20 , a personal computer 10 , and an interactive device exemplary designated as a toy 30 . the web server 20 stores profile data for surveying and analyzing the psychology and tastes of a toy purchaser , generates data for fabricating a toy suiting a toy purchaser &# 39 ; s tastes according to the information derived from the profile data , processes an order to purchase an interactive toy , determines a degree of maturity of a toy according to the learned content of a toy inputted by the purchaser , stores the fully grown models at each step of development and provides upgraded control software and / or hardware to a user for the toy . the user or personal computer 10 is used to download profiles of interactive toys at various levels of development through the internet , to input profile responses from the purchaser , and to upload a toy &# 39 ; s learned content to the web server 20 from the toy 30 through a communication unit after a predetermined learning period elapses . the toy 30 is able to receive toy fabrication data generated in the web server 20 and to receive upgraded control software and / or hardware ordered by the purchaser over the computer 10 . alternatively , if the toy 30 has a function to be directly connected to the internet , the learned / grown content of the toy 30 can be directly inputted to the web server 20 omitting the personal computer 10 . the following gives a general description of the interaction between the various components in the system of the preferred embodiments as seen in fig3 . additional detail to each step of the process will be discussed with respect to fig5 to 15 . a purchaser makes an order for a toy to the web server 20 to purchase the toy 30 . at this time , the web server 20 poses a question to the purchaser whether he or she wants a profile form for surveying and analyzing his or her psychology and taste . the purchaser expresses his or her intention by responding ‘ yes ’ or ‘ no ’ to the question of the web server 20 , according to which the purchaser purchases a toy online or offline . if the purchaser wants to survey and analyze his or her own psychology and taste to purchase a toy to his / her preferences , the purchaser may request the profile form from the web server 20 , download a profile form through the internet from the web server 20 , fill in the form , and send back the form to the web server 20 . then , the web server 20 receives the response result of the purchaser , analyzes the results and orders a toy 30 with a suitable control software and / or hardware amongst various control software and / or hardware representing diverse character patterns of toys previously stored in the web server 20 . the toy company or manufacturer then sells it to the purchaser . after the purchaser has had the toy 30 for a certain amount of time incorporating initial training into the interactive toy , the purchaser can input by means of a internet connection , the learned content to the web server 20 and receive a fully grown model of the toy 30 at its step of development . thereafter , the web server 20 determines a degree of maturity of the toy on the basis of the learned content and the fully grown model of the toy at its step as selected by the purchaser , and the toy company provides the user with an upgraded control software and / or hardware according to the degree of maturity . the control software is provided to the purchaser through the internet according to the degree of maturity and the hardware is provided to the purchaser in a store of a pertinent area or through the internet purchasing system . accordingly , as shown in fig3 in the purchasing / managing system of a learning / growing type toy in accordance with the preferred embodiments , after the toy 30 is sold to the purchaser , it passes a predetermined learning period by the user , and a web server 20 provides the user with a growth software and / or hardware according to a learned content to further grow the toy . in the system , purchasing and management can concurrently occur . [ 0055 ] fig4 is a detailed view of a toy 30 in accordance with the preferred embodiment of the present invention . as shown in fig4 the toy 30 includes a controller 30 a for receiving and running a control software or module according to the degree of maturity corresponding to the psychology and the taste of the purchaser . the controller 30 a may include a processor for processing the control module received from the web server 20 , a display panel for displaying images and motors and associated motor control processor to control the movement of the toy 30 . in addition , the toy 30 includes a memory 30 b storing the control module and a hardware installation unit 30 c where supplementary hardware required for the grown toy 30 to perform an improved function is installed , where the hardware being installed corresponds to the psychology and taste of the purchaser . moreover , the toy 30 has a communication port 30 d , which can be used to connect to a computer 10 or a wired or wireless internet connection . the operation of the purchase system of the learning / growing toy using a web server as described above will now be explained . [ 0057 ] fig5 illustrates a purchase system of a learning / growing type toy using a web server 20 in accordance with the preferred embodiments . as shown in fig5 the purchase system includes a user computer 10 for communicating between the toy purchaser and the web server 20 ; a web server 20 for receiving a profile form for surveying and analyzing the taste of a toy purchaser , determining a character pattern of a toy to be purchased from the profile form response , and providing a precustomized control software and / or a hardware corresponding to the character pattern ; and a toy 30 having a character pattern suitable to the purchaser &# 39 ; s psychology and taste according to the control software provided from the web server 20 and / or the hardware provided from the toy company at the time of purchasing of the toy . [ 0058 ] fig6 is a flow chart of a method for purchasing a learning / growing type toy using a web server in accordance with the preferred embodiment of the present invention . as shown in fig6 control begins at block 400 , where the toy purchaser accesses the web server 20 through the internet using a browser program . the http server 50 directs the toy purchaser through standard internet purchase procedures and allows the user to order a toy 30 . the server 20 receives the purchase order ( at block 410 ) and allows an option to pre - customize the toy 30 to the user &# 39 ; s tastes ( at block 420 ). if the purchaser decides on the customization option or just to determine what type of toy would be best suited for the user , the user can request a profile questionnaire . preferably , the web server 20 builds a profile form based on an input template 67 with various questions regarding the interests and likes / dislikes of the user and sends the profile form to the user computer 10 . at this time , the profile form is displayed on the personal computer 10 and the toy purchaser responds thereto and resubmits the completed profile form to the web server 20 . the response result is received by the http server 50 ( at step 430 ), and the results are stored by the database interface 55 in the user &# 39 ; s record 71 a , b , . . . or n in the database 60 . the customization tool 40 then determines a character pattern of the toy according to the inputted response result of the purchaser , that is , according to the results of the psychology and taste test of the purchaser as stored in the database 60 ( at step 440 ). based on the results of the survey , an analysis on the psychology and taste of the purchaser is performed by the user analyzing unit 43 . the character determining unit 47 takes the analysis results from the user analyzing unit 43 and endows a character pattern previously stored in the database 60 to the toy 30 to pre - customize the toy 30 to the user &# 39 ; s tastes and preferences . in this respect , various character patterns of toys are previously stored in the database 60 . an order is sent to the toy manufacturer to incorporate the settings selected by the character determining unit 47 and to manufacture it accordingly . thereafter , the control software and / or hardware corresponding to the determined character pattern of the toy 30 is adopted to the toy 30 ( i . e . the control software corresponding to the character pattern of the toy is downloaded to the memory 30 b of the toy 30 , and supplementary hardware corresponding to the character pattern of the toy is mounted at the hardware installation unit 30 c of the toy ). the pre - customized toy 30 is then sold to users ( at step 450 ). the purchaser can purchase the toy 30 suitable to his or her taste at the point of sale . on the other hand , if the purchaser wants to directly purchase the toy , omitting the profile input form , he or she may directly purchase a toy from the toy company without the pre - customization off - line . however , even without the precustomization , standard software and hardware is included with the toy 30 which allows the toy 30 to grow and be customized based on the user &# 39 ; s interaction . [ 0063 ] fig7 illustrates a managing system for a learning / growing type toy using a web server 20 in accordance with the preferred embodiments . as shown in fig7 the managing system of a learning / growing type toy includes a toy 30 which behaves or responds to voice commands at a level corresponding to a certain learned level after being purchased ; a personal computer 10 for receiving the learned / grown content by the toy purchaser through a communication unit , that is , a serial port or a parallel port , from the toy and outputting it ; and a web server 20 for receiving the learned content , the fully grown model of the toy 30 , and the identification number from the personal computer 10 , determining a degree of maturity with a corresponding weight function , and providing the user a comparison table and a development step table according to the degree of maturity , so as to provide an improved control software and / or hardware to the toy accordingly . the operation of the managing system of the learning / growing type toy using a web server constructed as described above will now be explained . [ 0065 ] fig8 is a flow chart of a method for managing of a learning / growing type toy using a web server in accordance with the preferred embodiment of the present invention . with reference to fig8 first , whether the toy purchaser purchases a learning / growing type toy in online or offline , the user ( the toy purchaser ) has the toy 30 to learn and grow for a predetermined time period . after the predetermined learning period elapses , the web server 20 inquires the purchaser whether he or she wants to upgrade the toy 30 according to the learned degree . in response , if the purchaser wants to upgrade the toy 30 to have a further developed function ( at step 510 ), the web server 20 asks the purchaser for the learned content , an identification number ( id ) and the fully grown model of the toy 30 at its step . preferably , the toy 30 shares the content of its internal memory containing the learned data with the web server 20 . accordingly , the purchaser uploads the learned content stored in the memory 30 b of the toy 30 to the personal computer 10 through the communication unit port ( i . e . the serial port , the parallel port or a usb ). alternatively , if the toy 30 is constructed to be able to directly communicate with the web server 20 through wired or wireless communication , ( i . e . wireless internet ), the toy 30 may directly input the learned content to the web server 20 without the need of a personal computer 10 . the information is then sent together with the toy id and user &# 39 ; s selection of what stage of development the toy has reached ( i . e . the fully grown model at its step of development ) to the web server 20 ( at step 520 ). at step 530 , the web server 20 determines the degree of maturity of the toy 30 through a weight function according to fully grown models by steps as stored in database 60 . the weight function considers both the learned content uploaded from the toy 30 and the fully grown model selected by the purchaser to determine the degree of maturity of the toy 30 . thereafter , the web server 20 also provides the purchaser with a user comparison table and a development step table by growth types ( to be described ) made on the basis of the maturity . in addition , the web server 20 provides the purchaser with training guidance , a fully grown model type by steps , a game character , or the like , given to toys 30 to participate in various contest in a virtual space or in actual space . according to the degree of maturity , the toy company provides the upgraded control software and / or hardware for the toy to the user ( at block 540 ). the upgraded control software can allow the toy 30 to perform additional functions according to the growth degree of the toy 30 , and additional hardware components ( i . e ., arms , parts of a toy , etc ) may be required to perform the additional functions . the toy company can download the upgraded control software to a controller 30 a of the toy 30 through the internet , and the upgraded control hardware can be provided to the purchaser in a toy store or by using an additional purchasing system over the internet . once the improved software and / or hardware is installed , the purchaser can further train the toy 30 until the toy 30 is ready for another upgrade . the growing step as described above is repeatedly performed until the upgrading step is terminated . however , if the purchaser does not want to upgrade the toy 30 at step 510 , the managing method of the learning / growing type toy is terminated . [ 0070 ] fig9 is a diagram showing sample profile items of a toy purchaser to be provided to the web server in accordance with the preferred embodiment of the present invention , which includes items of ‘ sex of the purchaser ’, ‘ date of birth ’, ‘ blood type ’, ‘ favorite animal ’, ‘ favorite food ’, ‘ questions for testing psychology ’, etc . this information is preferably saved in the user record 71 a , b , . . . or n in the database 60 , and used by the customization tool 40 to determine the character pattern of the toy 30 during purchase process . [ 0071 ] fig1 is an exemplary illustration of questions for checking the psychology of the purchaser and determining the profile information of fig9 in accordance with the preferred embodiment of the present invention . example questions include questions such as ‘ which actors and actresses of younger generations do you know of ?’, ‘ would you take a novel medicine , if any ?’, ‘ if you meet an animal while mountain climbing , what would it be ?’, ‘ if you took out a bead from a wrapper , what color would it be ?’, ‘ if you got one billion won ( approximately one million u . s . dollars ), what would you spend the money on ?’, or ‘ if you were to die today , what three things would you like to do most ?’. the items described in fig9 and 10 are used to analyze the psychology and the taste of the purchaser . without being restricted thereto , various other items may be used to analyze the psychology and taste of the purchaser , and used to determine the character patterns given to a particular toy 30 . the character patterns of the toy 30 are stored in the character database table 80 in the database 60 and accessed by the toy character determining unit 47 in determining which character pattern best fits the preferences and tastes of the purchaser . [ 0073 ] fig1 is an exemplary illustration of control software corresponding to each character pattern of toys in accordance with the preferred embodiment of the present invention . as shown in fig1 , the character patterns include a talented type , an artistic type , a sociable type and an athletic type . corresponding characteristic of each character pattern ( i . e . interested field of the toy ) and the respective software characteristics of the controller are also listed in fig1 . thereby choosing a particular type of control software , the interactive toy 30 can be varied to the user &# 39 ; s preferences and tastes . [ 0074 ] fig1 is a diagram showing a method for determining a degree of maturity of a toy in accordance with the preferred embodiment of the present invention . the degree of maturity is determined by comparing the development of the learning / growing type toy 30 in various categories with the fully grown model at the next development step ( i . e . a weighted calculation ). categories compared include : use time of the toy 30 , the number of chargings , the number of reactions of a tactile sensor and a level of voice recognition from the purchase date to the time when the learned content of the toy is inputted to the web server 20 . the results of the weighted calculation as well as the selection of desired level by the user will allow the web server 20 to determine a maturity level of the toy 30 . [ 0075 ] fig1 is an exemplary illustration of types of fully grown models of learned / grown toys and pertinent development steps in accordance with the preferred embodiment of the present invention . for example , in case of the talented type of toy , at the first step ( i . e . level of development ), the toy 30 recognizes the voice of a greeting or a basic operation command ( i . e ., ‘ forward !’, ‘ sit ’, ‘ up ’, ‘ back ’, etc .) and does behaviors accordingly . at the second step , the toy 30 performs a function of verbally informing the user of specific events at a set time . ( i . e ., ‘ please wake up ’, ‘ it &# 39 ; s time for an appointment ’). at the third step , the toy 30 shows a dynamic reaction to a comment of the purchaser ( for example , it smiles or reacts on a comment of “ you are pretty ”). without being limited to the above described example , the dynamic reaction at the third step may come in many forms , such as reacting or changing behavior based on the chat conversation in chat room as the toy 30 is connected to the internet . another example of a fully grown model at various stages of development is the educational variety . at the first step , the toy 30 can mimic a specific , well - known character ( e . g . a teletobie ®). at the second step , the toy 30 can operate according to commands of several steps previously stored from an educational cd - rom . at the third step , the toy operates or reacts in a foreign language ( i . e ., english ). another example of a growth type is the user type . in the user type variety , the toy 30 can take on characteristics developed by other users . such characteristic types may be developed by true fanatics of the interactive toys and can take on many different forms . for example , users may develop “ flirty ” type software or “ rebel ” type software . these user created growth type software can be downloaded from the internet and stored in the memory 30 b of the toy , and operate or react accordingly thereto . according to the growth types or the development steps , the toys may participate in various contests , such as a dance contest for artistic toys , a sweet gesture contest for sociable toys , a race contest for athletic toys , a battle contest for battle - type toys to be performed in a virtual space . for the various events for the toys , the web server 20 provides image characters to each toy by growth types and the development steps , assigns an identification number to the toys , and displays the contest scene on the personal computer 10 of the purchaser through the internet . accordingly , the purchaser can watch their toys compete with other toys of other purchasers as the toys participate in the contests , and makes a relative evaluation with respect to other toys on the basis of the records of the contests . this kind of events may be held in a real space , without being restricted to the virtual space . [ 0079 ] fig1 is a graph showing comparison of the number of users of toys for a development by steps of toys in accordance with the preferred embodiment of the present invention . as shown in fig1 , the web server 20 surveys the number of purchasers owning toys by steps of development illustrated in fig1 and provides the survey result to the users through the internet . this is to inform the users of the ranking of the toys owned by the users . in order to provide various services as illustrated in fig1 and 14 , the database 60 includes database tables 75 , 80 , 85 , 90 , 95 as shown in fig2 and described in greater detail in fig1 in accordance with the preferred embodiments of the present invention . as shown in fig1 , the manual database 75 stores in one or more records 76 a , b , . . . n instructions for the web server 20 , a user manual containing instructions for learning / growing the toy and procedures to upgrade the toy according to the methods disclosed above . a character database 80 is provided to store in one or more records 81 a , b . . . n the fully grown models of learning of each step , including a fully grown model for a s talent type , a sociable type , a battle type , a security type , and a educational type . a composite database 85 contain records 86 a , b , . . . n to keep track all the interactive toys registered with the web server 20 . each record tracks an identification number ( e . g ., a serial number ), a purchase date , the toy name given by the purchaser , the fully grown model of the toy desired by the user , the current state of development of the toy 30 , and provides a maturity degree checking table and a user comparison table for each registered toy 30 . the maturity degree checking table , as shown in fig1 , stores the values of the weight function when compared to the fully grown model at each step based on use time , the number of charging , the number of reaction and the level of voice recognition . as shown in fig1 , the user comparison table provides a reference ranking by comparing the degree of maturity of toys with other toys registered with the web server 20 . finally , the user group database 95 stores information in records 96 a , b , . . . n to manage gatherings of users and provides a user message board , frequently asked questions ( faq ) and sub - group gatherings based on the development of the user &# 39 ; s toys 30 . another method in which the web server 20 directly controls the toy 30 through the internet and the personal computer 10 will now be described . the web server 20 advances the degree of maturity of the toy owned by the purchaser step by step whenever a predetermined time elapses . in addition , the web server 20 inputs a control command ( a voice or a signal ) to the toy 30 through the internet and the user computer 10 at an arbitrary time zone . according to the control command , the toy 30 shows a programmed reaction and further shows a behavior specified in the development step table of fig1 . accordingly , the purchaser has his or her own toys to learn , or compares and determines the grown state on the basis of the toy 30 learned by the information obtained from the web server 20 . in addition , by using the above method , the purchaser may also request the web server 20 to have his or her own toy 30 to learn . as so far described , the method for purchasing and managing of a learning / growing type toy using a web server has many advantages . for example , before selling a learned / grown toy to a purchaser , the psychology and the taste of the purchaser is first analyzed and then a control software and / or hardware is installed in the purchased toy , allowing the purchased toy to have a character suitable to the purchaser &# 39 ; s psychology and the taste according to the analysis . accordingly , the purchaser can be much interested in the toy at the initial stage and have the toy to learn and grow . in addition , the web server guides the learning / growing procedure , provides a user comparison table so as for the purchaser to compare his or her own toys with other ones of other purchasers for the learned / grown state of toys . and various contests are held in the cyber space to allow the purchasers to objectively compare their own toys with each other , arousing learning / growing desire of the users for their toys with much interest . moreover , since the control software and / or hardware are provided suitable to the level of each growing step , purchasers would be hardly tired of toys and have a great interest continuously . the foregoing embodiments and advantages are merely exemplary and are not to be construed as limiting the present invention . the present teaching can be readily applied to other types of interactive electronic apparatuses . the description of the present invention is intended to be illustrative , and not to limit the scope of the claims . many alternatives , modifications , and variations will be apparent to those skilled in the art . in the claims , means - plus - function clauses are intended to cover the structure described herein as performing the recited function and not only structural equivalents but also equivalent structures . | 6 |
turning now to fig1 a crystal growing apparatus 10 includes a bottom chamber 12 . the bottom chamber 12 houses a quartz crucible 110 , which is supported by a susceptor 100 . the susceptor 100 is in turn supported by a vertically moveable and rotatable shaft assembly 16 . a cylindrical heater 18 made of , for example , graphite is disposed around the susceptor 100 , which in turn is surrounded by and insulating cylinder 20 . the bottom chamber 12 also has a conduit 40 for evacuating air during start up , and process gas during crystal pulling operations utilizing a vacuum pump ( not shown ). a top chamber 24 is disposed above the bottom chamber 12 while an isolation valve 22 is disposed there between . the top chamber 24 provides a space for accommodating a grown crystal . the isolation valve 22 functions to allow a vacuum tight separation between the top chamber 24 and the bottom chamber 12 thus enabling a grown crystal to be removed from the top chamber 24 without losing vacuum or temperature in the bottom chamber 12 . the top chamber 24 has a conduit 70 that goes to a vacuum pump ( not shown ) that allows the top chamber to be evacuated of air and purge gases , so it may be rejoined with the bottom chamber 12 . when the isolation valve 22 is opened , a purge gas such as argon is introduced through conduit 70 , flowed through the entire growing apparatus 10 , and exited through conduit 40 . a winding mechanism 26 is disposed above the top chamber 24 , and includes a winding drum 28 within the winding mechanism 26 . the winding mechanism 26 is rotatable around a vertical axis with respect to the top chamber 24 . a wire 30 is wound onto the winding drum 28 , and extends downward . a seed chuck 32 for holding a crystal seed 34 is attached to the lower end of the wire 30 . when a single crystal is to be grown in the crystal growing apparatus 10 , the isolation valve 22 is in an open position so as to allow the seed 34 to be lowered into the bottom chamber 12 . both the bottom chamber 12 and the top chamber 24 are evacuated and purged of air , and an inert gas is then flowed through the apparatus for the remainder of the growing process . a charge material , such as silicon , is placed in the crucible 110 , and heated by the heater 18 , thereby making a molten material 36 . the seed crystal 34 is lowered by winding drum 28 until the end of the seed crystal 34 is lowered into the molten material 36 . after allowing the seed crystal 34 to reach temperature equilibrium with the molten material 36 , the winding drum 28 slowly begins to wind up the wire 30 , thus enabling a crystal 38 to be pulled or grown . during the growing operation , the winding mechanism 26 and thus the seed are rotating in the opposite direction of the shaft assembly 16 . as previously mentioned , at the elevated temperatures during crystal growth the crucible and susceptor interact to form co and co 2 gases and sic . the purge gas , typically argon , is used to assist in cooling the crystal and to flush out the co , co 2 , and sic from the growing chamber . typical argon flow ranges from 120 to 190 cubic liters per minute during growth , and will be significantly higher during purging processes . as shown in fig2 susceptor 100 contains two mirror - image portions 102 and 104 . an expansion gap 106 separates the two portion 102 and 104 , and allows the portions 102 and 104 to expand and contract during heating and cooling without significantly changing the dimensions of the susceptor 100 . the susceptor 100 is held together at the bottom by sitting it a cup located at the top of the rotatable shaft assembly 16 . the quartz crucible 110 is housed within the susceptor 100 , and is packed with charge material 120 that is to be melted and grown into a monocrystalline ingot . before heat is supplied to melt the charge material 120 , there is a gap between the wall of the crucible 110 and the susceptor 100 . purge gas 130 can flow downward between the walls of the crucible 110 and susceptor 100 . the only exit for the purge gas 130 to escape is through the expansion gap 106 such that the gas flow between the walls of the crucible 110 and the susceptor 100 becomes turbulent , and changes from a laminar downward directed flow to a turbulent flow swirling between the walls until it encounters and escapes through the expansion gap 106 . [ 0023 ] fig3 demonstrates the interaction of the susceptor 100 and the crucible 110 after sufficient heat has been supplied to change the charge material into a molten material 36 . at an area located approximate to the surface of the molten material 36 , the crucible wall plastically deforms and expands at 112 . as a crystal is extracted from the molten material 36 , the volume of the molten material 36 will decrease and the surface of the molten material 36 will move downward relative to the crucible wall 110 and the area of plastic deformation 112 . after the crucible 110 plastically deforms at 112 , however , it does not move downward to follow the relative position of the surface of the molten material 36 , but rather remains at a constant position . purge gas 130 flows downward between the walls of the crucible 110 and the susceptor 100 to the point of plastic deformation 112 , and is turbulently forced out at the expansion gap 106 . due to the extreme heat and chemical reactions between the susceptor 100 and crucible 110 as previously explained , the area of plastic deformation 112 is subject to a much more aggressive erosion than other parts of the susceptor 100 . as shown in fig4 to provide more escape passages for the purge gas 130 , vent holes 108 are cut through the sidewall of the susceptor portions 102 and 104 . vent holes 108 can be cut at a downward angle from the inside out to help facilitate better gas flow properties and more laminar flow . the vent holes 108 can also be cut at numerous distances from the top of the susceptor to facilitate various melt surface levels such that at least some of the vent holes 108 will be near the area of plastic deformation 112 , but will not be occluded by the wall of the crucible 100 . in this situation , there may be some vent holes 108 that are occluded by the wall of the crucible 100 , and others that are above the area of plastic deformation 112 . the physical shape of the vent holes 108 should be manufactured to reasonably facilitate desired gas flow properties . the size and quantity of vent holes 108 should not be so large as to risk structural failure of the susceptor 110 . it should be noted that the present invention may be used on graphite susceptors alone , or in conjunction with other erosion inhibiting methods . for example , a susceptor containing vent holes made out of a carbon based material such as graphite may be completely covered with a silicon carbide coating . another embodiment may utilize providing a protective coating such as silicon carbide in the area proximal to the vent holes and along the expansion gap . yet another embodiment includes enhancing erosion resistance by chemical vapor implantation of a protective layer such as silicon carbide . although the invention has been described with reference to specific embodiments , other embodiments of the present invention will be apparent to those skilled in the art from a consideration of this specification or practice of the invention disclosed herein . it is intended that the written description be considered in all aspects only as illustrative and not restrictive . the scope of the invention is , therefore , indicated by the appended claims rather than by the foregoing description . all changes that come within the meaning and range of the equivalence of the claims are to be embraced within their scope . | 2 |
in all contexts , c 1 - c 14 - alkyl is , for example , preferably methyl , ethyl , n - propyl , isopropyl , n - butyl , tert - butyl , n - pentyl , cyclohexyl , n - hexyl , n - heptyl , n - octyl , isooctyl , n - decyl and n - dodecyl . in all contexts , c 1 - c 4 - alkylene is , for example , preferably methylene , 1 , 1 - ethylene , 1 , 2 - ethylene , 1 , 1 - propylene , 1 , 2 - propylene , 1 , 3 - propylene , 1 , 1 - butylene , 1 , 2 - butylene , 2 , 3 - butylene and 1 , 4 - butylene . for the purposes of the invention , arylalkyl is , for example and with preference , an alkyl radical which is substituted as defined above by carbocyclic aromatic radicals having 6 to 10 carbon atoms , in particular phenyl or naphthyl , and the carbocyclic aromatic radicals may themselves be substituted by up to five substituents per cycle which are selected from the group of methyl , ethyl , fluorine , chlorine , bromine and c 1 - c 4 - fluoroalkyl where fluoroalkyl is an alkyl radical as defined above which is singly , multiply or fully substituted by fluorine . preferred c 1 - c 4 - fluoroalkyl radicals are trifluoromethyl , pentafluoroethyl , 2 , 2 , 2 - trifluoroethyl and nonafluorobutyl . the same applies to the aryl moiety of a diarylalkyl radical . particular preference is given to using 3 - amino - 1 , 5 - naphthalenedisulphonic acid and its mono - or dialkali metal salts , and also 1 , 3 , 5 - naphthalenetrisulphonic acid and its mono -, di - or trialkali metal salts for step a ). it is also possible to use mixtures of these compounds . very particular preference is given to using the trialkali metal salts of 1 , 3 , 5 - naphthalenesulphonic acid , for example trisodium 1 , 3 , 5 - naphthalenetrisulphonate and tripotassium 1 , 3 , 5 - naphthalenetrisulphonate , and even greater preference is given to trisodium 1 , 3 , 5 - naphthalenetrisulphonate . some of the compounds of the formula ( ii ) can occur in the form of hydrates which are not mentioned specifically , but are encompassed by the invention . the compounds of the formula ( ii ) are either commercially available , or can be prepared by literature procedures . in a preferred embodiment of the process according to the invention , the naphthalene 1 , 3 , 5 - trisulphonic acid or its mono -, di - or trialkali metal salts are prepared in such a way that i ) naphthalene is reacted with fuming sulphuric acid to give naphthalene - 1 , 3 , 5 - trisulphonic acid and ii ) the naphthalene - 1 , 3 , 5 - trisulphonic acid obtained in step i ) is optionally converted to a mono -, di - or trialkali metal salt . at this point , it is pointed out that any desired combination of the features and of the areas of preference specified are likewise encompassed by the invention . step i ) can advantageously be effected by reacting naphthalene with fuming sulphuric acid . an example of a possible procedure is to initially charge fuming sulphuric acid and add naphthalene or initially charge concentrated sulphuric acid and naphthalene and add fuming sulphuric acid , or initially charge concentrated sulphuric acid and add naphthalene and fuming sulphuric acid . the preferred procedure in step i ) is to initially charge concentrated sulphuric acid and add naphthalene and fuming sulphuric acid . for the purposes of the invention , concentrated sulphuric acid is , for example , sulphuric acid comprising 90 to 100 % by weight of h 2 so 4 . for the purposes of the invention , fuming sulphuric acid is sulphuric acid which has a content of over 100 % by weight , based on pure h 2 so 4 . another common term for fuming sulphuric acid for the purposes of the invention is oleum . typically , the content of free so 3 in commercially available oleum is specified and is , for example , 30 or 65 % by weight . preference is given to using such an amount of oleum in step a ) that the molar ratio of free so 3 to naphthalene is between 1 . 5 : 1 and 10 : 1 , preferably between 2 : 1 and 5 : 1 and more preferably between 2 . 5 : 1 and 4 : 1 . the temperature in the course of addition can be , for example , − 20 to 70 ° c ., preferably 20 to 55 ° c . the time for the addition can be , for example , between 10 min and 48 h , preferably 2 to 24 hours . subsequently , the resulting reaction mixture can optionally be heated . the temperature can be , for example , between 55 and 150 ° c ., preferably between 80 and 100 ° c . the naphthalene 1 , 3 , 5 - trisulphonic acid can be recovered from the resulting reaction mixture , for example , by adding water . alkali metal or alkaline earth metal salts of naphthalene - 1 , 3 , 5 - trisulphonic acid can be prepared according to step ii ) either from the isolated naphthalene - 1 , 3 , 5 - trisulphonic acid or directly from the reaction mixture resulting from step i ). preference is given to the preparation of alkali metal or alkaline earth metal salts of naphthalene - 1 , 3 , 5 - trisulphonic acid from the reaction mixture resulting from step i ). step ii ) can be effected , for example , in such a way that the reaction mixture resulting from step i ) is diluted , for example , by pouring into water or onto ice , and subsequently reacted with alkali metal hydroxides , hydrogencarbonates or carbonates or aqueous solutions thereof . preference is given to using alkali metal hydroxides , in particular sodium hydroxide and potassium hydroxide , or aqueous solutions thereof . particular preference is given to the reaction with aqueous solutions of sodium hydroxide . the alkali metal hydroxide content of the solutions can be , for example , between 2 and 75 % by weight , preferably from 25 to 60 % by weight . the temperature of the reaction for step ii ) can be , for example , 0 to 100 ° c ., preferably 80 to 100 ° c . the amount of alkali metal hydroxide used can be , for example , 2 to 10 times , based on the molar ratio of the naphthalene used in step i ), preferably 2 . 8 to 3 . 5 times . after workup in a manner known per se , which can be effected , for example , by filtration and optionally washing and drying the precipitated solid , alkali metal salts of naphthalene - 1 , 3 , 5 - trisulphonic acid are obtained which are either stored or preferably reacted further . optionally , the alkali metal salts of naphthalene - 1 , 3 , 5 - trisulphonic acid obtained in step ii ) may be still further purified , for example , by recrystallization , although this is unnecessary for use in step a ) of the process according to the invention . in step a ) of the process according to the invention , the compounds of the formula ( ii ) are reacted with alkali metal hydroxide and optionally alkaline earth metal hydroxide in the presence of water . the alkali metal hydroxide used may be , for example and with preference , sodium hydroxide or potassium hydroxide or a mixture thereof , for example as a solid or in the form of an aqueous solution . the amount of alkali metal hydroxide for step a ) may be selected , for example , in such a way that , for each r 1 radical in the compounds of the formula ( iii ) that is amino or so 3 m , 2 to 30 mol , preferably 3 to 10 mol , but a total of at least 2 mol , of alkali metal hydroxide are used per mole of the compound of the formula ( ii ). when m is hydrogen , the amount of alkali metal hydroxide advantageously has to be increased in accordance with the molarity . alkaline earth metal hydroxides can preferably also be added . examples of suitable alkaline earth metal hydroxides are magnesium hydroxide and calcium hydroxide , although preference is given to calcium hydroxide . the amount of alkaline earth metal hydroxide for step a ) may , for example , be selected in such a way that , for each r 1 radical in the compounds of the formula ( iii ) that is amino or so 3 m , 0 . 5 to 20 mol , preferably 1 to 20 mol and more preferably 1 . 5 to 7 mol , but a total of at least 1 mol , of alkaline earth metal hydroxide are used per mole of the compound of the formula ( ii ). the molar ratio of water to the compound of the formula ( iii ) can be 0 . 5 to 200 mol , preferably 3 to 50 mol . in a particularly preferred embodiment , the ratio of water to the sum of alkali metal hydroxide and any alkaline earth metal hydroxide added is 1 : 1 . 4 to 1 : 6 . 0 . the pressure in the reaction can be , for example , 1 to 200 bar , preferably 1 to 100 bar and most preferably that pressure which results from heating the reaction mixture to the reaction temperature in a closed vessel starting from ambient temperature . an example of a useful closed vessel is an autoclave which can be made , for example , of nickel , nickel - based alloys , silver or other , alkali - resistant material . the temperature of the reaction can be , for example , 240 to 350 ° c ., preferably 270 to 320 ° c . the reaction time can be , for example , 2 to 25 hours , preferably 3 to 8 hours . in step b ) of the process according to the invention , the reaction mixtures obtained in step a ) are at least partially neutralized with acid , optionally after adding water and optionally after the removal of insoluble constituents and optionally the removal of undesired , soluble constituents . in a preferred embodiment , water is optionally added after cooling the reaction mixture , which can be effected , for example , by pouring the reaction mixture into water or onto ice . preference is also given to removing insoluble constituents . this may be effected , for example and with preference , by filtration , centrifugation , sedimentation and decanting , optionally in the presence of assistants . examples of possible assistants include kieselguhr , for example celite ( 1 , activated carbon , for example norite ®, bleaching earth , montmorillonite or animal charcoal . preference is given to filtration , particular preference to filtration in the presence of assistants , preferably activated carbon . preference is likewise given to the removal of undesired , soluble constituents . undesired , soluble constituents are , for example , coloured organic by - products . the removal of undesired , soluble constituents may be carried out , for example , before or after the partial neutralization . an example of a possible procedure is to extract with organic solvent . examples of suitable organic solvents are esters such as ethyl acetate and butyl acetate , aliphatic or aromatic , optionally halogenated hydrocarbons , for example petroleum , benzene , toluene , xylenes , chlorobenzene , dichlorobenzenes , isopropylbenzene , petroleum ether , hexane , heptane , octane , isooctane , cyclohexane , methylcyclohexane , dichloromethane , chloroform or carbon tetrachloride ; ethers such as diethyl ether , methyl tert - butyl ether or diisopropyl ether , ketones such as 2 - butanone or methyl isobutyl ketone or mixtures of such solvents . the reaction mixture may also , for example , be freed of discolorations using a suitable adsorbent . examples of suitable adsorbents include silica gels , aluminium oxides , cellulose or activated carbon . the partial neutralization is preferably effected by setting to a ph of 8 to 13 , preferably 9 . 5 to 11 . 5 . the ph values relate to values at 25 ° c . for partial neutralization , preference is given to using acids or acidic salts having a pka in water of 5 or less . for partial neutralization , preference is given to using sulphuric acid , hydrochloric acid , phosphoric acid , nitric acid and hydrobromic acid , particular preference is given to using sulphuric acid and hydrochloric acid , and very particular preference to using sulphuric acid . in a very particularly preferred embodiment , step b ) is carried out in such a way that the reaction mixture obtained from step a ) is initially diluted with water , insolubles are removed , the ph is set to 8 to 13 and undesired , soluble constituents are removed . in step c ), the reaction mixture from step b ) is reacted with compounds of the formulae ( iva ), ( ivb ) or ( ivc ). in the compounds of the formulae ( iva ), ( ivb ) and ( ivc ), r 1 is preferably methyl , ethyl , isopropyl or benzyl , particularly preferably methyl . preferred compounds of the formula ( iva ) are methyl chloride and methyl iodide , preferred compounds of the formula ( ivb ) are methyl mesylate and methyl p - tosylate , and the preferred compound of formula ( ivc ) which is most preferred for the process according to the invention is dimethyl sulphate . the amount of compound of the formula ( iva ), ( ivb ) or ( ivc ) is , for example and with preference , selected in such a way that the molar ratio to the compound of the formula ( iii ) originally used is 1 : 1 to 10 : 1 , preferably 2 : 1 to 7 : 1 . the reaction temperature in step c ) is , for example , 0 to 120 ° c ., preferably 20 to 100 ° c . when using compounds of the formulae ( iva ), ( ivb ) and ( ivc ) which are gaseous at room temperature , such as methyl chloride in particular , the reaction may advantageously be carried out under pressure . the reaction time for step c ) can be , for example , 1 to 25 hours , preferably 2 to 10 hours . preference is further given to maintaining the ph in the course of the reaction between 8 and 13 , preferably 9 . 5 and 11 . 5 , which can be effected , for example , by adding base . useful bases are in particular alkali metal hydroxides , carbonates or hydrogencarbonates , although preference is given to sodium hydroxide and potassium hydroxide . the base can be used , for example , in solid form or in the form of aqueous solutions . subsequently , in step d ), the reaction mixture obtained in step c ) is acidified . preference is given to acidifying to a ph of 3 . 5 or less , more preferably to 0 to 3 . 5 , and most preferably to 1 to 2 . 5 . examples of useful acidifiers include acids or acidic salts having a pka of 3 . 5 or less , preferably 0 or less . particular preference is given to sulphuric acid or hydrochloric acid . in a preferred embodiment of step d ), initial acidification is effected only to a ph of above 3 . 5 and below 8 , and undesired , soluble constituents are extractively removed as described above . subsequently , the reaction mixture may then , for example , be freed of discolorations using a suitable adsorbent . examples of useful adsorbents include silica gels , aluminium oxides , cellulose or activated carbon . the temperature on acidifying is not critical , although it may be advantageous to heat the reaction mixture to boiling , in order to drive out dissolved gases or decompose any sulphites present . the acidification protonates the salts of the compounds of the formula ( i ) and at least partly converts them to the free acids of the formula ( i ). preference is given to using acids having a pka value in water of 3 or less in step d ), particular preference to hydrochloric acid or sulphuric acid , and even greater preference to sulphuric acid . the compounds of the formula ( i ) may be obtained in a manner known per se from the reaction mixtures obtained in step d ), for example by extraction with organic solvent , filtration , centrifugation or sedimentation and decanting . examples of preferred solvents for the extraction are esters such as ethyl acetate and butyl acetate , aliphatic or aromatic , optionally halogenated hydrocarbons , for example petroleum , benzene , toluene , xylenes , chlorobenzene , dichlorobenzenes , isopropylbenzene , petroleum ether , hexane , heptane , octane , isooctane , cyclo - hexane , methylcyclohexane , dichloromethane , chloroform or carbon tetrachloride ; ethers such as diethyl ether , methyl tert - butyl ether or diisopropyl ether , ketones such as 2 - butanone or methyl isobutyl ketone or mixtures of such solvents . the compounds of the formula ( i ) may be obtained after extraction in a manner known per se , for example by evaporating the solvent . when the compounds of the formula ( i ) are removed by filtration , centrifugation or sedimentation and decanting , this may be effected , for example and with preference , at 0 to 70 ° c ., more preferably 20 to 55 ° c . for further purification , the compounds of the formula ( i ) may optionally be recrystallized or reprecipitated , although this is unnecessary . the compounds of the formula ( i ) prepared by the process according to the invention , in particular 3 - methoxy - 2 - methylbenzoic acid , are particularly suitable for use in a process for preparing pharmaceuticals and agrochemicals , for example crop protection agents and insecticides , or intermediates thereof , in particular acid chlorides , acid bromides , acid hydrazides , esters , for example 3 - methoxy - 2 - methylbenzoyl chloride or bromide , 3 - methoxy - 2 - methylbenzoic hydrazide , methyl 3 - methoxy - 2 - methylbenzoate . the advantage of the processes according to the invention is the efficient preparation of compounds of the formula ( i ), which enables them to be carried out in high yields without costly and inconvenient intermediate isolation . in a nickel autoclave , 300 . 0 g of trisodium 1 , 3 , 5 - naphthalenetrisulphonate ( 70 . 9 %, determined as the free acid ) are stirred into a mixture of 232 . 0 g of aqueous sodium hydroxide solution ( 45 %) and 194 . 0 g of sodium hydroxide in such a way that a readily stirrable , pasty suspension is obtained . the autoclave is closed and heated without stirring to 190 ° c . and the mixture is heated at this temperature for 30 minutes . afterwards , the stirrer is switched on and the mixture is heated to 280 ° c . the internal pressure rises to 18 . 4 bar . the mixture is stirred at 280 ° c . for 6 hours and afterwards cooled to 90 ° c . at this temperature , 200 . 0 g of water are pumped in and the mixture is subsequently cooled to room temperature . the reaction mixture obtained in this way is filtered with suction to remove insolubles and washed with 187 . 3 g of water . 251 . 8 g of a brownish - white , finely divided solid and 795 . 7 g of a dark brown solution are obtained . a flask is initially charged with 390 . 0 g of the solution from example 1 and adjusted to a ph of 10 . 3 using 88 . 4 g of sulphuric acid ( 100 %), and the reaction mixture is heated to 40 to 45 ° c . dimethyl sulphate and sodium hydroxide solution are then simultaneously metered in at the same temperature in such a way that the ph remains in the range from 10 . 4 to 10 . 6 . a total of 147 . 5 g of dimethyl sulphate and 85 . 8 g of sodium hydroxide solution ( 30 %) are metered in within 2 hours . afterwards , stirring is continued at the same temperature for 1 hour . on completion of the continuous stirring time , the ph is increased to 11 by metering in sodium hydroxide solution and the mixture is heated to 90 ° c . stirring is continued at this temperature for 2 hours , and it is necessary to meter in further sodium hydroxide solution ( 30 %). the reaction solution is cooled to 70 ° c . 20 . 0 g of acticarbon f ® activated carbon are added and a ph of 6 . 5 is set by metering in 32 . 9 g of sulphuric acid ( 100 %). the mixture is heated to reflux , and the reaction solution is clarified and washed with 550 . 0 g of water . the clarified reaction solution is returned to the reactor , heated to 90 ° c . and set to a ph of 3 by metering in 18 . 9 g of sulphuric acid ( 100 %). the mixture is heated at 90 ° c . for 1 hour . a ph of 3 is then set using 41 . 6 g of sulphuric acid ( 100 %). the mixture is heated at 90 ° c . for 1 hour . a ph of 1 is then set using 41 . 6 g of sulphuric acid ( 100 %) and the reaction mixture is cooled to 45 ° c . within 4 hours . the product precipitates out as a white precipitate . the product is filtered off with suction and washed with 300 . 0 g of water . the precipitate is dried in a vacuum drying cabinet . 1 532 . 9 g of washing / mother liquor ( 0 . 03 % of methoxymethylbenzoic acid ) and 29 . 3 g of 3 - methoxy - 2 - methylbenzoic acid ( purity 95 . 9 %) are obtained . this corresponds to an isolated yield based on trisodium 1 , 3 , 5 - naphthalenetrisulphonate of 60 % of theory . in a nickel autoclave , 300 . 0 g of trisodium 1 , 3 , 5 - naphthalenetrisulphonate ( 70 . 9 %, determined as the free acid ) are stirred into a mixture of 356 . 0 g of aqueous sodium hydroxide solution ( 45 %) and 126 . 0 g of sodium hydroxide pastilles and 127 . 0 g of calcium hydroxide in such a way that a readily stirrable , pasty suspension is obtained . the autoclave is closed and heated without stirring to 190 ° c . and the mixture is heated at this temperature for 30 minutes . afterwards , the stirrer is switched on and the mixture is heated to 280 ° c . the internal pressure ( autogenous pressure ) rises to 29 . 6 bar . the mixture is stirred at the reaction temperature for 15 hours and afterwards cooled to 90 ° c . at this temperature , 200 . 0 g of water are pumped in and the mixture is subsequently cooled to room temperature . the suspension obtained is filtered off with suction and washed with 695 . 5 g of water . 299 . 6 g of a brownish - white , finely divided solid and 1 287 . 5 g of a dark brown solution are obtained . a flask is initially charged with 300 . 0 g of the solution from example 3 which are diluted with 50 . 0 g of water . a ph of 10 . 3 is set using 42 . 8 g of sulphuric acid ( 100 %) and the reaction mixture is heated to 40 to 45 ° c . dimethyl sulphate and sodium hydroxide solution are then simultaneously metered in at 40 to 45 ° c . in such a way that the ph remains in the range from 10 . 4 to 10 . 6 . 65 . 1 g of dimethyl sulphate and 45 . 0 g of sodium hydroxide solution ( 30 %) are metered in within 2 hours . afterwards , stirring is continued at the same temperature for 1 hour . on completion of the continuous stirring time , the ph is increased to 11 by metering in sodium hydroxide solution and the mixture is heated to 90 ° c . stirring is continued at this temperature for 2 hours , and it is necessary to meter in further sodium hydroxide solution ( 30 %). the reaction solution is cooled to 70 ° c . 3 . 0 g of activated carbon are added and a ph of 7 . 8 is set by metering in 13 . 1 g of sulphuric acid ( 100 %). the mixture is heated to reflux , and the reaction solution is clarified using activated carbon and washed with 250 g of water . the clarified reaction solution is returned to the reactor , heated to 90 ° c . and set to a ph of 4 by metering in 11 . 4 g of sulphuric acid ( 100 %). the mixture is heated at 90 ° c . for 1 hour . a ph of 1 is then set using 38 . 4 g of sulphuric acid ( 100 %) and the reaction mixture is cooled to 45 ° c . within 4 hours . the product precipitates out as a white precipitate . the product is filtered off with suction on a glass suction filter and washed with 250 g of water . the precipitate is dried in a vacuum drying cabinet . 784 . 7 g of mother liquor ( 0 . 02 % of methoxymethylbenzoic acid ), 238 . 0 g of washing liquor ( methoxymethylbenzoic acid not detectable ) and 16 . 9 g of 3 - methoxy - 2 - methylbenzoic acid ( purity 95 . 5 %) are obtained . this corresponds to an isolated yield based on trisodium 1 , 3 , 5 - naphthalenetrisulphonate of 72 . 1 % of theory . in a flat - flanged vessel , 200 . 0 g of 3 - hydroxy - 2 - methylbenzoic acid ( purity 96 . 9 %) are dissolved in a mixture of 200 . 0 g of water and 173 . 3 g of sodium hydroxide solution ( w = 30 %): this results in a ph of approx . 5 . 5 . the clear solution is heated to 40 ° c . and set to ph = 10 . 5 by metering in sodium hydroxide solution ( w = 30 %). dimethyl sulphate and sodium hydroxide solution are now metered in simultaneously at 40 - 45 ° c . in such a way that the ph remains within the range of 10 . 4 - 10 . 6 . 401 . 5 g of dimethyl sulphate and 147 . 9 g of sodium hydroxide solution ( w = 30 %) are metered in within 2 h . afterwards , the mixture is stirred at 40 - 45 ° c . for a further 2 h . afterwards , the aqueous phase is removed and discarded . the organic phase is washed with 200 . 0 g of water . the washing water is removed and discarded . 223 . 56 g of crude methyl 3 - methoxy - 2 - methylbenzoate remain . for further purification , the crude product is subjected to a vacuum distillation through a vigreux column . at a vacuum of 20 mbar , 5 . 7 g of first runnings and 205 . 5 g of main fraction ( top temperature 145 ° c ., methyl 3 - methoxy - 2 - methylbenzoate , purity 98 . 7 %) distil over . 205 . 0 g of methyl 3 - methoxy - 2 - methylbenzoate , purity 98 . 7 % of mmbe and 0 . 00 % of 3 - hydroxy - 2 - methylbenzoic acid , methyl 3 - hydroxy - 2 - methylbenzoate , 3 - methoxy - 2 - methylbenzoic acid , corresponds to 88 . 5 % of theory ( based on 3 - hydroxy - 2 - methylbenzoic acid ). in a flat - flanged vessel , 213 . 1 g of 3 - hydroxy - 2 - methylbenzoic acid ( purity 92 . 75 %) are dissolved in a mixture of 200 . 0 g of water and 173 . 3 g of sodium hydroxide solution ( w = 30 %): this results in a ph of approx . 5 . 5 . the clear , brown solution is heated to 40 ° c . and set to ph = 10 . 5 by metering in sodium hydroxide solution ( w = 30 %). dimethyl sulphate and sodium hydroxide solution are now metered in simultaneously at 40 - 45 ° c . in such a way that the ph remains within the range of 10 . 4 - 10 . 6 . 401 . 5 g of dimethyl sulphate and 127 . 2 g of sodium hydroxide solution ( w = 30 %) are metered in within 2 h . afterwards , the mixture is stirred at 40 - 45 ° c . for a further 2 h . afterwards , the aqueous phase is removed and discarded . 250 . 0 g of water are added to the organic phase and the mixture is heated to 90 ° c . the mixture is stirred at this temperature for a further 2 h and the ph is maintained at 10 . 5 - 11 by metering in sodium hydroxide solution ( w = 30 %). the organic phase disappears and a solution forms . the reaction solution is cooled to 80 ° c . a second flat - flanged vessel is charged with 250 . 0 g of water and heated to 80 ° c . the reaction mixture of the first vessel and sulphuric acid ( w = 100 %) are simultaneously metered in at 80 ° c . in such a way that a ph of 3 . 8 - 4 . 2 is maintained . the product precipitates out as a white precipitate . after metering in approx . 10 % of the reaction solution the mixture is heated for approx . 1 h . on completion of metering in , the ph is adjusted to 1 using sulphuric acid ( w = 100 %) and the mixture is cooled to 40 ° c . within 4 h . the product is filtered off with suction and washed with 2 × 500 . 0 g of water . the precipitate is dried in a vacuum drying cabinet at 60 ° c . for 16 h . 202 . 0 g of 3 - methoxy - 2 - methylbenzoic acid , purity 96 . 6 % of mmba ( 0 . 00 % of 3 - hydroxy - 2 - methylbenzoic acid , methyl 3 - hydroxy - 2 - methylbenzoate , methyl 3 - methoxy - 2 - methylbenzoate ) are obtained , corresponding to 90 . 4 % of theory ( based on 3 - hydroxy - 2 - methylbenzoic acid ). a three - necked flask is initially charged with 136 . 0 g of thionyl chloride under nitrogen and heated to 60 ° c . a melt at 180 ° c . of 136 . 0 g of 3 - methoxy - 2 - methylbenzoic acid is added dropwise within one hour . the reaction commences immediately with evolution of gas ( so 2 , hcl ). after the addition is complete , the mixture is heated to reflux ( 80 ° c .) over one hour and stirred at this temperature until the gas evolution subsides ( approx . 2 h ). the solution is cooled to approx . 50 ° c . under nitrogen and the reflux condenser is replaced by a vigreux column . 14 . 0 g of thionyl chloride are distilled off at atmospheric pressure ( liquid phase up to 170 ° c .) and the remaining liquid phase is fractionated under reduced pressure ( 10 mbar ). the distillate obtained is 139 . 4 g of 3 - methoxy - 2 - methylbenzoyl chloride ( 98 . 8 %). this corresponds to 94 . 2 % of theory . in a flask , 91 . 9 g of 3 - methoxy - 2 - methylbenzoic acid are suspended under nitrogen in 200 . 0 g of dry xylene . 119 . 0 g of thionyl chloride are metered in at room temperature . the grey suspension is heated to 80 ° c . within one hour , and the reaction commences at approx . 30 ° c . with gas evolution ( so 2 , hcl ), resulting in a homogeneous solution at about 50 ° c . afterwards , the reaction temperature is raised to 135 ° c . within a further hour . at this temperature , stirring is continued to completion of gas evolution ( 1 h ). afterwards , the reflux condenser is replaced by a small vigreux column with a distillation bridge , and first the excess approx . 45 . 0 g of thionyl chloride and afterwards , at a maximum bottom temperature of 154 ° c ., the majority of the xylene ( approx . 165 g ) is distilled off . assuming quantitative conversion , 54 . 4 % of the remaining 180 . 0 g of bottoms consists of 3 - methoxy - 2 - methylbenzoyl chloride . this corresponds to 0 . 53 mol or 97 . 8 g of 100 % 3 - methoxy - 2 - methylbenzoyl chloride . the bottoms are liquid at temperatures of approx . 30 ° c . and are used directly for the further reaction . in a flat - flanged vessel , 81 . 3 g of tert - butylhydrazine hydrochloride are dissolved in 230 . 0 g of water . a ph of 9 . 2 is set by metering in 55 . 8 g of sodium hydroxide solution ( w = 30 %). 150 . 0 g of { fraction ( 80 / 110 )} special - boiling - point gasoline ( boiling range 80 - 110 ° c .) are added and the mixture is cooled to 15 ° c . the xylenic 3 - methoxy - 2 - methylbenzoyl chloride solution prepared under example 1 and sodium hydroxide solution are now simultaneously metered in at 15 - 20 ° c . in such a way that the ph remains within the range of 9 . 0 - 9 . 5 . 180 . 0 g of xylenic mmbc solution ( w = 30 %) and 97 . 3 g of sodium hydroxide solution ( w = 30 %) are metered in within 1 . 5 h . the pump and the feeds are flushed with 43 . 0 g of xylene , and this xylene is added to the reaction mixture . on completion of metering , stirring is continued at 10 - 15 ° c . for another hour . afterwards , the reaction mixture is heated to 40 ° c . within 45 min and stirred at this temperature for 2 h to complete the reaction . the suspension is heated to 70 ° c ., and the solid dissolves completely in the organic phase . the aqueous phase is removed and discarded . the organic phase is washed with 200 . 0 g of demineralized water , and the washing water is likewise discarded . 2 . 0 g of activated carbon are added to the organic phase , and the mixture is heated to 80 ° c . and filtered through a filter paper . the filter cake is washed with 43 . 0 g of xylene , and the filtrates are combined and processed further . 300 . 0 g of { fraction ( 80 / 110 )} special - boiling - point gasoline are added to the clarified organic phase at 60 - 80 ° c . and the mixture is cooled to 5 ° c . within 6 h . at approx . 38 - 40 ° c ., the product begins to precipitate out . the precipitated product is filtered off with suction and washed with { fraction ( 80 / 110 )} special - boiling - point gasoline . the precipitate is dried at 60 ° c . and 200 mbar for 20 h in a vacuum drying cabinet . 109 . 2 g of 3 - methoxy - 2 - methylbenzoic tert - butylhydrazide ( purity 95 . 4 %, one further component visible in hplc ) are obtained . this corresponds to a yield based on 3 - methoxy - 2 - methylbenzoic acid of 83 . 2 % of theory . although the invention has been described in detail in the foregoing for the purpose of illustration , it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims . | 2 |
while the present invention may be embodied in many different forms , a number of illustrative embodiments are described herein with the understanding that the present disclosure is to be considered as providing examples of the principles of the invention and that such examples are not intended to limit the invention to preferred embodiments described herein and / or illustrated herein . with reference to fig2 , in some embodiments of the invention , a battery box 500 is provided that can be mounted between two generally parallel frame members 310 a and 310 b in a truck , tractor or the like ( such as , by way of example , similar to that depicted in fig1 ). as shown in fig2 , in the preferred embodiments , the battery box 500 is mounted to the frame members 310 a and 310 b using bracket members 600 . as best shown in fig8 ( a ) and 8 ( b ) , the battery box 500 preferably includes a cover 520 which is omitted in fig2 so as to allow for viewing inside the battery box . as shown in fig2 , the battery box 500 is preferably configured so as to support a plurality of batteries . in the illustrated and non - limiting example , four such batteries b 1 , b 2 , b 3 and b 4 are depicted . in some preferred embodiments , the battery box 500 can be mounted between such frame members 310 a and 310 b and , in turn , a deck plate 330 ( e . g ., see 330 a and / or 330 b in fig1 ) can be located there - over . fig2 to 4 ( b ) and 6 to 8 ( a ) show a first preferred embodiment of the invention in which an illustrative battery box 500 is mounted between the two frame members 310 a and 310 b . referring to fig2 , the battery box 500 in this first preferred embodiment includes a substantially rectangular container base 510 having a generally cylindrical hump 511 extending lengthwise along the floor of the base 510 to accommodate a drive shaft of the vehicle . in this embodiment , the hump 511 includes three extensions 512 , 513 and 514 extending upwardly there - from . the extensions 512 , 513 and 514 preferably include substantially flat upper surfaces for providing interior support beneath a cover 520 ( shown in fig3 and 6 to 8 ( a )). in addition , extensions 512 and 514 may also provide a place to attach a bracket 510 lp to secure the batteries as described below . while three extensions 512 , 513 and 514 are shown in the illustrated embodiment , in some other examples , the extensions can be combined to form less than three extensions ( such as , e . g ., one or two extension ( s )), while in other embodiments more than three extensions can be used . with reference to fig4 ( a ) and 4 ( b ) , the container base 510 preferably includes a bottom wall 510 bw and four walls including a front wall 510 fw , left and right side walls 510 sw , and a rear wall 510 rw . each of the four perimeter walls preferably is inclined relative to the bottom wall 510 bw so as to form an obtuse angle with the bottom wall , that is , angle slightly outwards , as best seen in , e . g ., in fig3 and 7 . the four perimeter walls and the cylindrical hump define receptacle spaces to receive batteries . as best shown in fig4 ( a ) and 4 ( b ) , the upper ends of the container base 510 preferably include cutout portions 510 co . in the preferred embodiments , the cutout portions 510 co are located proximate the comers of the base 510 as shown . in other embodiments , however , the cutout portions can be at different locations around the perimeter of the base 510 . in some preferred embodiments , the container base 510 further includes side depressions 510 sd as best seen in fig6 . among other things , the side depressions 510 sd can be employed to add to the rigidity of the structure and / or so as to help delineate sections in which the batteries reside . in addition , in some preferred embodiments , the bottom wall 510 bw includes depressions 510 bd as best seen in fig6 . among other things , the bottom depressions 510 bd can be employed to add to the rigidity of the structure , to provide fluid drainage from the battery storage areas , and / or for other purposes . as for fluid drainage functionality , the depressions 510 bd can be formed , e . g ., so as to angle downwards to openings 510 bdo as best seen in fig6 . as also shown in fig6 , a plurality of bracket members 600 is provided to mount the base 510 to the frame members 310 a and 310 b . in the preferred embodiments , the bracket members 600 are configured so as to a ) be fixedly attached to one of the frame members 310 a or 310 b , b ) to extend underneath and support the bottom wall 510 bw of the base 510 of the container , and c ) to extend up to at least one of the extension portions 512 / 513 / 514 so as to provide support there - under without interfering with the clearance space provided by the extension portions . in the preferred embodiments , as shown , rather than utilizing bracket members that span completely between the frame members 310 a and 310 b , the bracket members 600 are preferably configured so as to extend only partially across the width of the bottom wall 510 bw between the frame members 310 a and 310 b . as shown in fig6 , four brackets are provided with the ends of laterally adjacent brackets 600 preferably spaced from one another a distance d . among other things , using two brackets 600 rather than one bracket to span between frame rails enables the battery box 500 to accommodate relative movement of the frame members 310 a and 310 b during normal driving conditions ( e . g ., twisting , parallelogramming , etc .). to further account for relative movement and / vibration between parts during normal use of the device , one or more resilient members , such as , e . g ., a resilient member ( e . g ., a rubber cushion ) or grommet can be provided in between the base 510 and the brackets 600 . for example , as depicted in fig3 , a resilient member or grommet 510 g can be located between a lower end of the bottom wall 510 bw and the bottom segment 604 ( discussed below ) of the bracket 600 , and another resilient member or grommet 510 g can be located between the container base 510 and the distal portion 601 ( discussed below ) of the bracket 600 . as best shown in fig3 ( in broken lines ) and 6 , the bottom wall of the base 510 preferably includes a plurality of protrusions 510 bwp that are arranged to be received within holes 600 h cutout of the brackets 600 . in the illustrated embodiment , two protrusions are arranged to extend into two respective holes 600 h in each respective bracket 600 . with reference to fig3 , the diameter of the protrusions 510 bwp is preferably smaller than the diameter of the holes 600 h , such as , e . g ., by an amount d 2 depicted , so as to accommodate some relative motion between the bracket 600 and the base 510 . as shown in fig3 , in the preferred embodiments , the bracket 600 is formed so as to have a first region ( such as , e . g ., portion 601 ) that is attached to an underside of the base 510 ( such as , e . g ., using a threaded stud r that is fixedly attached to the portion 601 and a lock nut n and / or any other appropriate connectors ) so as to enhance the support at the upward extensions ( e . g ., 512 or 514 ), a second region ( such as , e . g ., including the portions 602 , 603 , 605 and 606 ) that extends beneath the bottom of the container 510 , and a third region ( such as , e . g ., the portion 607 ) that is attached to a frame member 310 a or 310 b ( such as , e . g ., using bolts b and / or any other appropriate connectors ). in the preferred embodiments , the brackets 600 are substantially u - shaped , as shown , and include mounting regions proximate the upper ends of the respective arms as shown . while the figures depict some illustrative arrangements of the brackets 600 , such as , e . g ., including portions 601 to 607 shown as segments in some illustrative and non - limiting embodiments , it should be understood that these are just some illustrative examples and that the brackets 600 can be modified so as to be formed of a single piece of metal bent to an appropriate shape and to have a variety of shapes and configurations depending on circumstances in other embodiments of the invention . as shown in fig4 ( a ) and 4 ( b ) , in some preferred embodiments , locking brackets 510 lp can be removably mounted on the container base 510 so as to retain the batteries b 1 to b 4 in the battery box during operation of the vehicle . in the illustrated embodiments , the locking brackets 510 lp are fastened to the upper ends of the extensions 512 and 514 and inserted in slots in the sidewalls 510 sw . by way of example , the brackets 510 lp can be attached using any appropriate connectors , such as , e . g ., bolts , screws , clasps and / or the like . in prior battery boxes , brackets for retaining batteries extended over corner portions of the batteries , resulting in corner - loading on the cases of the batteries . in the preferred embodiments , however , the brackets 510 lp advantageously extend over substantially the mid - sections of the batteries as shown . in this manner , the brackets 510 lp do not impart unnecessary loads on the battery cases inside the battery box 500 . with reference to fig3 , 6 , 7 , 8 ( a ) and 8 ( b ), in the preferred embodiments , the battery box 500 includes a cover or lid 520 . in the preferred embodiments , the cover 520 includes a generally planar top wall 520 tw , a depending front wall 520 fw , left and right depending side walls 520 sw and a depending rear wall 520 rw . among other things , the depending front wall 520 fw , depending side walls 52 sw and depending rear wall 520 rw are preferably constructed so as to angle outwards slightly relative to the top wall 520 tw as best seen in fig3 and 7 . as a result , the container base 510 flares outward in an upward direction while the cover 520 flares outward in a downward direction as shown providing a gap between the depending walls of the cover and the walls of the base . in the preferred embodiments , the depending walls 520 fw , 520 sw and 520 rw are preferably sized so as to facilitate locating of the cover over the top of the base 510 ( such as , e . g ., with the depending walls locating the cover in position over the base 510 ). in addition , preferably the depending walls 520 fw , 520 sw and 520 rw are configured so as to extend over the entire or substantially the entire height of the cutout portions 510 co , as shown in the figures . in some preferred embodiments , the cover is configured so as to distribute a load applied on the top of the cover 520 towards the sides adjacent the frame members and over the brackets . among other things , by way of example , such a construction can provide assistance in the event that , e . g ., an individual steps on the cover 520 or otherwise applies a load over the cover 520 . by way of example , as shown in fig8 ( a ) and 8 ( b ) , the cover 520 can include a stepped configuration 520 st proximate the side edges . moreover , in some embodiments , the cover 520 can even be made so as to rest only the sides 510 sw ( without deflection of the cover 520 ) such that less force is applied along a center of the battery box in many circumstances . among other things , by extending the depending walls 520 fw , 520 sw and 520 rw over the cutout portions 510 co , air vent passages vp can be advantageously formed between the cover 520 and the base 510 while the cover 520 can still be configured so as to substantially obstruct and cover the base 510 . in that regard , the air vents vp are preferably formed by the oppositely inclined depending walls of the cover 520 and the walls of the base 510 , such that even though the depending walls extend downward over the walls of the base 510 , a vent path vp is still formed there - between as best seen in fig7 . among other things , this provides for a more aesthetic appearance because the interior of the battery box is obstructed from view and also provides for , among other things , enhanced shielding of the interior of the battery box from external objects , weather or the like . by way of example , fluid flow over the cover 520 due to , e . g ., spillage , leakage , rain and / or other conditions will have a reduced likelihood of entering the battery box due to the overhanging vent structure according to the preferred embodiments . referring now to fig7 and 8 ( a ) to 8 ( b ), in some embodiments at least one latch mechanism ( s ) 520 l is provided to help retain the cover 520 upon the base 510 . in this regard , in the preferred embodiments , the latch mechanism 520 l is fixedly attached to one of the cover 520 or the base 510 and includes a distal end that is releasably engaged / disengaged with the other of the cover 520 or the base 510 . in some preferred embodiments , the latch mechanism includes a flexible or resilient material , such as , e . g ., a rubber or the like that is pivotally attached to one of the cover 520 or the base 510 and that includes an engagement member on a distal end thereof , while the other of the cover 520 or the base 510 includes a catch 510 c that can releasably engage with the engagement member . by way of example , the engagement member can include , e . g ., a widened region that can be engaged within a hook or the like on the catch 510 c . for example , in use , the resilient member can be stretched ( e . g ., manually by an individual ) and the widened region can be located within the hook so as to retain the cover 520 or the widened region can be removed from the hook so as to release the cover 520 . in the illustrated embodiment , the latch mechanism 520 l is mounted on the base 510 and the catch member 520 c is mounted on the cover , but in other embodiments , as described above , this arrangement can be reversed . among other things , the use of a flexible latch mechanism has some advantages related to , e . g ., a ) the ability to use non - conducting materials for the battery box , including the latch mechanism , b ) the enablement of lightweight and long - lasting materials to be employed , etc . referring now to fig5 , this figure shows another embodiment of the invention in which an illustrative battery box 500 is mounted between the two frame members 310 a and 310 b . in this illustrative example , the battery box 500 is similarly depicted as including a substantially rectangular container base 510 and a generally cylindrical hump 511 extending lengthwise along the floor of the base 510 . in order to allow for wiring and / or venting , a plurality of cut - outs 510 wh can be provided proximate respective battery locations as shown in fig5 . fig5 also depicts an illustrative manner of wiring the batteries contained within the battery box enclosure 500 according to some illustrative and non - limiting embodiments . various other wiring methods can be employed as would be appreciated by those in the art . in addition , while fig5 shows an embodiment that is slightly modified from that shown in fig2 to 4 ( b ) and 6 to 8 ( b ), the wiring methods used in fig5 can be employed within any of the embodiments shown herein where appropriate . moreover , while fig5 does not depict a cover 520 , it should be understood that the device of fig5 can include an appropriate cover 520 similar to that described above . fig8 ( b ) depicts yet another embodiment of the invention which is generally similar to the embodiment shown in fig5 and which includes an integrated jump stud js ( e . g ., a jump plug or battery connector ) and a disconnect switch ds . although such a jump stud js and disconnect switch ds can be integrated in some embodiments , in some preferred embodiments , such as , e . g ., shown in the other figures , jump stud and disconnect switch integration is not employed . in some other preferred embodiments , such as , e . g ., shown in fig5 , another bracket member 700 can be employed for mounting jump stud and / or disconnect switches or the like . referring again to fig2 , in some preferred embodiments of the invention , the battery box can be easily and efficiently mounted upon the vehicle frame members 310 a and 310 b . in the preferred embodiments , the ease of mounting is enhanced by constructing the battery box components in a manner to allow an individual to install the battery box without any need to access the battery box components from beneath the frame members 310 a and 310 b . in contrast , prior battery boxes have required an individual to access the battery box from beneath the battery box in order to mount it onto the vehicle . in this regard , as described above , in the preferred embodiments , the brackets 600 can be initially attached to the frame members 310 a and 310 b as shown in fig2 . then , the battery box 500 can be lowered onto the brackets such that the protrusions 510 bwp fit into the holes 600 h and such that the stud r fixed to the portion 601 extends upward through a corresponding receiving hole 510 r formed in the base 510 . thereafter , the nut n can be threaded onto the top end of the stud r from above the battery box assembly so as to retain the battery box 500 fixedly upon the frame members 310 a and 310 b . as a result of this unique mounting structure , the battery box can be easily and efficiently mounted upon the frame members 310 a and 310 b . in addition , in some of the preferred embodiments described above , the battery box 500 can be mounted in a manner that enhances the durability of the device , such as , e . g ., by isolating the battery box from vibration and / or by accommodating loads applied to the frame structure that result in , e . g ., twisting , rolling , bending , or parallelogramming of the frame members . in some embodiments , the stiffness of the battery box structure can be about ⅙ or less of the stiffness of a typical frame cross - member , resulting in , among other things , longer durability . in addition , in some of the preferred embodiments described above , the battery box can be easily and efficiently mounted as a pre - assembled , self - contained module . by way of example , in some preferred embodiments , the battery box 500 can include , e . g ., batteries mounted therein along with wiring between the batteries ( such as , e . g ., similar to that shown in fig5 ). in addition , as described above , in some embodiments , the battery box can include pre - assembled jump studs and / or disconnect switches integrated therein . in such cases , the wiring associated with such pre - assembled components can be readily contained and located inside the battery box . as a result , the battery box 500 can operate as an easy and efficient module that can be readily installed upon a vehicle . moreover , as described above , the wiring , connections and other components located inside the battery box can be well maintained and isolated from external contaminants due to , among other things , the unique venting structure as described above ( such as , e . g ., in which the vent paths vp are substantially obstructed from the environment ). in the preferred embodiments , the battery box 500 , including the base 510 and the cover 520 can be formed using plastics , polymers , fiber glass and / or the like materials . among other things , materials having some resiliency and non - conductive properties are preferable for such components . nevertheless , various other embodiments can include a variety of other materials depending on circumstances . in addition , in the preferred embodiments , the brackets 600 are formed of metal material ( s ), such as , e . g ., aluminum , stainless steel and / or any other appropriate material ( s ) as would be suitable for purposes described herein as would be understood by those in the art based upon the present disclosure . while illustrative embodiments of the invention have been described herein , the present invention is not limited to the various preferred embodiments described herein , but includes any and all embodiments having equivalent elements , modifications , omissions , combinations ( e . g ., of aspects across various embodiments ), adaptations and / or alterations as would be appreciated by those in the art based on the present disclosure . the limitations in the claims are to be interpreted broadly based on the language employed in the claims and not limited to examples described in the present specification or during the prosecution of the application , which examples are to be construed as non - exclusive . for example , in the present disclosure , the term “ preferably ” is non - exclusive and means “ preferably , but not limited to .” in this disclosure and during the prosecution of this application , means - plus - function or step - plus - function limitations will only be employed where for a specific claim limitation all of the following conditions are present in that limitation : a ) “ means for ” or “ step for ” is expressly recited ; b ) a corresponding function is expressly recited ; and c ) structure , material or acts that support that structure are not recited . in this disclosure and during the prosecution of this application , the terminology “ present invention ” or “ invention ” may be used as a reference to one or more aspect within the present disclosure . the language present invention or invention should not be improperly interpreted as an identification of criticality , should not be improperly interpreted as applying across all aspects or embodiments ( i . e ., it should be understood that the present invention has a number of aspects and embodiments ), and should not be improperly interpreted as limiting the scope of the application or claims . in this disclosure and during the prosecution of this application , the terminology “ embodiment ” can be used to describe any aspect , feature , process or step , any combination thereof , and / or any portion thereof , etc . in some examples , various embodiments may include overlapping features . in this disclosure , the following abbreviated terminology may be employed : “ e . g .” which means “ or example .” | 1 |
preferred embodiments of the invention will be described below in detail with reference to accompanying drawings . as shown in fig1 and 2 , an ink jet printer 100 which is one of recording apparatuses comprises an upper housing 101 and a lower housing 102 . the upper housing 101 and the lower housing 102 are engaged with each other by snap fitting . on the rear side of the upper housing 101 , a sheet feeding port 103 is formed . in this sheet feeding port 103 , a sheet feeding tray 110 on which sheets to be supplied are stacked is attached . the sheet feeding tray 110 is attached so as to protrude to the diagonally upper backside , and holds the sheets in a slanting state . on the front side of the upper housing 101 , a sheet ejection port 104 is formed . on the front sides of the upper housing 101 and lower housing 102 , a stacker 120 on which the ejected sheets are stacked is provided . the stacker 120 is attached to the front sides of the upper housing 101 and lower housing 102 pivotably about a rotary shaft located at its lower portion . when the stacker 120 is not used , it is pivoted upward to close the sheet ejection port 104 . when it is used , it is pivoted downward to open the sheet ejection port 104 , and stops at a position where it protrudes from the lower housing 102 to the diagonally upper front side to receive the sheet in the slanting state . this stacker 120 has two - stage structure comprising a first stacker member 121 and a second stacker member 122 which is slidably attached to the first stacker member 121 at a distal end portion thereof . the second stacker member 122 is housed in the first stacker member 121 when it is not used , and pulled out from the first stacker member 121 when it is used . a window 105 is formed from the upper portion of the upper housing 101 to the front surface thereof . this window 105 is covered with a transparent or semitransparent openable cover 106 . by opening this cover 106 , an exchanging work of ink cartridge and a maintenance work of the internal mechanism can be readily performed . further , a push button type of power switch 131 and operational switches 132 , 133 are provided on the left backside of the upper housing 101 . as shown in fig3 in the lower housing 102 , a control board 130 constituting a printer controller is placed vertically , and a recording section 140 constituting a print engine , a sheet feeder 150 and a transporter 160 shown in fig4 are installed . a control element and a memory element such as cpu , rom , ram , asic ( they are not shown ), and other various circuit elements are mounted on the control board 130 . at the upper end of the control board 130 , light emitting diodes 133 and 134 are located protrusively , which emit lights respectively when the power switch 131 or the operational switches 132 , 133 are pushed on , whereby a user can confirm switch - on . the recording section 140 comprises a carriage 141 , a recording head 142 , a carriage motor 143 , a timing belt 144 , and a suction pump 145 . on a sheet transported by the transporter 160 , data is recorded by the recording head 142 mounted on the carriage 141 scanned by the carriage motor 143 and the timing belt 144 . from ink cartridges 146 of four colors , for example , yellow , magenta , cyan , and black , housed in the carriage 141 , each color ink is supplied to the recording head 142 so that full color printing can be performed . the feeder 150 comprises the sheet feeding tray 110 , a sheet feeding guide 111 , a sheet feeding roller 151 , a hopper 152 , and a separation pad 153 . sheets p stacked on the sheet feeding tray 110 and aligned by the sheet feeding guide 111 are pushed against the sheet feeding roller 151 with the separation pad 153 by rising of the hopper 152 with rotation of the sheet feeding roller 151 , separated one by one from the uppermost sheet p , and transported to the transporter 160 . the transporter 160 comprises a feeding roller 161 , a driven roller 162 , a discharging roller 163 , a serrated roller 164 , a sheet feeding motor 165 , and the stacker 120 . the sheet p supplied from the feeder 150 is transported to the recording section 140 while being held between the feeding roller 161 driven by the sheet feeding motor 165 and the driven roller 162 , and further transported to the ejected sheet stacker 120 while being held between the discharging roller 163 driven by the sheet feeding motor 165 and the serrated roller 164 . as shown in fig5 a and 5b , the discharging roller 163 is formed so that a shaft portion 163 a made of plastics elongates longer than at least recordable maximum sheet width and has a hollowed portion 163 c extending axially . further , plural roller portions 163 b made of elastomer such as rubber are joined to the shaft portion 163 a at a constant interval . the shaft portion 163 a of the discharging roller 163 is molded by an injection method or a gas injection method which generates a void that can prevent a sink and a warp by suppressing internal stress produced when molding is performed using a die . the roller portion 163 b of the discharging roller 163 is molded on the shaft portion 163 a by an injection method . since the shaft portion 163 a of the discharging roller 163 is thus formed in the hollowed shape having larger sectional area than sectional area of the related - art discharging roller 1 , flexural rigidity of this discharging roller 163 can be enhanced more than that of the related - art discharging roller 1 . specifically , the diameter dr1 ( see fig5 b ) is 11 . 26 mm and the diameter ds1 is 8 . 25 mm . therefore , the proportion of the outer diameter of the shaft portion to the outer diameter of the roller portion is 73 . 3 %. consequently , when the sheet is tensed between the discharging roller 163 and the feeding roller 161 , deformation of the discharging roller 163 such as a flexure can be suppressed . therefore , a flip phenomenon caused by the discharging roller 163 can be avoided , and particularly recording accuracy in recording on a whole surface can be improved . as a material of the shaft portion 163 a of the discharging roller 163 , thermoplastic resin is used , for example , abs ( copolymer of acrylonitrile , butadiene and styrene ), ps ( polystrene ), pom ( polyacetal ), modified ppe ( polyphenylene ether ), pc ( polycarbonate ), pbt ( polybutylene terephthalate ), and alloy system . further , in order to heighten more the flexural rigidity , an additive such as gf ( glass fiber ), gr ( glass beads ), carbon , nylon , or potassium titanate is added . the amount of this additive is preferably 5 to 50 % and particularly 10 to 30 % in order to further enhance the flexural rigidity . as shown in fig6 in a die 200 used in molding of the shaft portion 163 a of the discharging roller 163 , according to a first embodiment of the invention , cavity portions 201 and 202 are formed in order to mold one shaft portion 163 a of the discharging roller 163 , and the die 200 comprises an upper die 210 and a lower die 220 that are divided in the radial direction of the discharging roller 163 . here , since the conventional shaft portion of the discharging roller , formed of metal is high in rigidity , distortion can be prevented by double point support structure in which both ends are supported . however , since the shaft portion 163 a of the discharging roller 163 according to the invention is formed of plastics that is lower in rigidity than the metal , five point support structure in which not only the both ends but also intermediate portions are supported is adopted to prevent the distortion . since molding accuracy of each bore part in the shaft portion 163 a of the discharging roller 163 affects greatly accuracy of rotation of the discharging roller 163 , in order to improve the molding accuracy , the upper die 210 and the lower die 220 are respectively divided into three parts at portions where a part other than the bore portions is molded . in other words , each bore section including at least one bore portion is molded by a single die ( a first upper die 211 , a second upper die 212 , a third upper die 213 , a first lower die 221 , a second lower die 222 , and a third lower die 223 ) as shown in fig6 a and 7 b . thus , through - work such as wire cut electrical discharge machining or cutting can be performed at the time of manufacturing the die , working accuracy of the die can be enhanced , and a die manufacturing cost can be reduced . accordingly , the molding accuracy of the shaft portion 163 a of the discharging roller 163 can be improved , and the eccentric rotation of the discharging roller 163 can be suppressed . further , since the sectional shape of the shaft portion 163 a of the discharging roller 163 is simplified , a cost of the discharging roller 163 can be reduced . due to limitation of a shape in the vicinity of each bore portion , there may be portions where the cavity portions 201 and 202 cannot be collectively formed . however , insert dies 214 and 224 are inserted into these portions to obtain desired shape of the cavity portions . fig8 a and 8b are perspective views showing the second lower die 222 in detail . in this second lower die 222 , five insert dies 224 are inserted . each insert die 224 , is inserted into a through hole 222 a from a bottom face 222 c side to constitute a part of the cavity portion 202 . though not shown , the first upper die 211 , the second upper die 212 , the third upper die 213 , the first lower die 221 , the third lower die 223 have also the similar structure . as shown in fig9 a fitting part 215 of the upper die 210 and a fitting part 225 of the lower die 220 are formed in the shapes of concave and convex that can be fitted to each other , and lower corners 215 a of the upper fitting part 215 and the upper corners 225 a of the lower fitting part 225 are tapered so as to facilitate the fitting operation . since the cavity portion 201 in the upper die 210 and the cavity portion 202 in the lower die 220 can be faced with each other with high accuracy , occurrence of flash extending in the axial direction of the periphery of the shaft portion 163 a can be suppressed and the molding accuracy can be improved , so that the eccentric rotation of the discharging roller 163 can be suppressed . as shown in fig1 a and 10b , the cavity portions 201 and 202 are heat - regulated . inside of this second lower die 222 , a fluid passage 204 through which cooling liquid ( e . g ., water ) for heat regulation of the cavity portion 202 flows is formed . as shown in fig1 b , the fluid passage 204 extends perpendicularly from a bottom face 222 c at one end face 222 b side , it turns at a nearly right angle , extends from one end face 222 b side to the other end face 222 d side , and thereafter turns at a nearly right angle to run through the bottom face 222 c at the other end face 222 side . such the fluid passages 204 , as shown in fig1 a , are formed respectively on both widthwise sides of the cavity portion 202 . though not shown , the similar fluid passages are formed in the first lower die 221 and the third lower die 223 . [ 0066 ] fig1 is a section view showing a state where the die 200 is attached to a die attaching portion 300 of an injection molding machine . in the die attaching portion 300 of the injection molding machine , a fluid passage 301 through which cooling liquid ( e . g ., water ) for heat - regulating the die attaching portion 300 itself flows is formed . moreover , a fluid passage 302 through which cooling liquid for heat - regulating the cavity portions 201 , 202 is formed so as to communicate to the fluid passage 204 of the die 200 . hereby , since the inner surfaces of the cavity portions 201 , 202 can be cooled , when the melted plastic is injected , the outer surface of plastic is solidified in a state where it is adhered onto the inner surfaces of the cavity portions 201 , 202 , and void is easy to be produced on the inside thereof . therefore , occurrence of internal stress of molded products for the shaft portion 163 a can be suppressed , so that a sink and a warp can be prevented . further , dimensional accuracy of outer diameter of the shaft portion 163 a can be improved , so that the eccentric rotation of the discharging roller 163 can be suppressed . further , since the die 200 is cooled relatively quickly , an operation cycle for molding can be reduced . further , as the injection method , a gas injection method can be adopted . fig1 shows this configuration as a second embodiment of the invention . to a die attaching portion of an injection molding machine of this embodiment , a die 400 and a die 450 are attached . the die 400 has the similar structure as the die 200 , in which cavity portions 401 , 402 for molding one shaft portion 163 a of a discharging roller 163 are formed . an auxiliary cavity 451 is attached to an exhaust port 404 . under a condition that the cavity portions 401 , 402 of the die 400 are heat regulated at a predetermined temperature , the predetermined amount of the melted plastic is injected from an injection port 403 of the die 400 . subsequently , the predetermined amount of gas is injected from the injection port of the die 400 . hereby , a plastic outer surface coming into contact with the inner surfaces of the cavity portions 401 , 402 is quickly cooled and pressed by gas pressure from the plastic inside . therefore , the plastic is solidified in a state where it is adhered onto the inner surfaces of the cavity portions 401 , 402 . melting plastic inside the plastic between the injection port 403 of the die 400 and the exhaust port 404 is pushed out from the exhaust port 404 by gas and fed out into the auxiliary cavity 451 . hereby , occurrence of internal stress of molded products for the shaft portion 163 a of the discharging roller 163 can be suppressed , so that the sink and the warp can be prevented . further , the dimensional accuracy of outer diameter of the shaft portion 163 a can be improved , and a uniform hollowed portion 163 c can be formed stably in the shaft portion 163 a throughout the entire region in the axial direction . therefore , the eccentric rotation of the discharging roller 163 can be suppressed . though the invention has been described in the above various embodiments , it is not limited the above embodiments but may be applied also to other embodiments within the scope of the appended claims . for example , though the ink jet printer has been described as an example of a recording apparatus , the invention is not limited to this but can be applied to another recording apparatus having a discharging roller , for example , a thermal transfer type printer , and an ink jet type or thermal transfer type facsimile or copying machine . | 8 |
in the following description , for the purposes of explanation , numerous specific details are set forth in order to provide a thorough understanding of exemplary embodiments . it should be apparent , however , that exemplary embodiments may be practiced without these specific details or with an equivalent arrangement . in other instances , well - known structures and devices are shown in block diagram form in order to avoid unnecessarily obscuring exemplary embodiments . in addition , unless otherwise indicated , all numbers expressing quantities , ratios , and numerical properties of ingredients , reaction conditions , and so forth used in the specification and claims are to be understood as being modified in all instances by the term “ about .” the present disclosure addresses and solves the current problems of process complexity , area penalty , high power requirements , unreliability , and incompatibility with cmos technologies attendant upon forming otp non - volatile memories with efuses or antifuses . in accordance with embodiments of the present disclosure , bitlines are formed as part of nwells in a substrate , and plural metal gates are formed across each bitline with no contacts between the metal gates . when a selected bit is programmed by applying a high voltage to the selected gate , an element with non - linear i - v characteristics is formed over the nwell at the selected bit , which acts as a selector , thereby eliminating the need for a separate selector for each bit . methodology in accordance with embodiments of the present disclosure includes forming nwells and pwells in a substrate , forming an n - type bitline in each nwell , and forming plural metal gates across each bitline , wherein no source / drain regions are formed between the metal gates . still other aspects , features , and technical effects will be readily apparent to those skilled in this art from the following detailed description , wherein preferred embodiments are shown and described , simply by way of illustration of the best mode contemplated . the disclosure is capable of other and different embodiments , and its several details are capable of modifications in various obvious respects . accordingly , the drawings and description are to be regarded as illustrative in nature , and not as restrictive . adverting to fig6 a through 6c , a 2 - d cross - point antifuse memory array is illustrated in accordance with an exemplary embodiment . fig6 a shows a top view , and fig6 b and 6c show cross - sectional views along lines 6 b - 6 b ′ and 6 c - 6 c ′, respectively . as illustrated , n - type active regions 601 are formed in nwells 603 . the n - type active regions 601 define shallow trench isolation ( sti ) regions 605 . the nwells , in turn , are formed within a pwell 607 in a p - type substrate 609 . the nwells 603 act as bitlines . multiple bits share the same nwell bitline . metal gates 611 are formed across active regions 601 , each with a high - k dielectric layer 613 ( an oxide having a dielectric constant greater than that of silicon dioxide , such as hafnium oxide ) thereunder . an n + well tap region 615 is formed in the active region 601 , and bitline wire out lines 617 are connected to the well tap regions . in the resulting structure a parasitic element with non - linear i - v characteristics is formed , after the metal gate - to - well breakdown , which serves as the selector . consequently , there is no sneak current in the cross - point array , and , therefore , no misreads . further , no source / drain regions for each bit , no source / drain contacts between the gates ( or wordlines ), and multiple bits sharing the same nwell bitline enable an aggressive design rule and small cell size . in addition , wordlines can be strapped by multiple metal layers in back - end - of - line processes . fig7 a through 12a and 7 b through 12 b shown cross - sectional views ( along lines 6 b - 6 b ′ and 6 c - 6 c ′, respectively ) of the method steps for forming the 2 - d cross - point antifuse memory array illustrated in fig6 a through 6c . adverting to fig7 a and 7b , sti trenches are etched in a p - type substrate 701 to a depth of 100 to 200 nm and a width of 100 to 1000 nm . the trenches are filled with an oxide and planarized , for example by chemical mechanical polishing ( cmp ), to form sti regions 703 . next , nwell 801 and pwell 803 implants are performed , as illustrated in fig8 a and 8b , by conventional methods . the wells may be formed to a depth of 100 to 500 nm . bitlines are formed in the entire nwell . the sti regions 703 are defined by an active region in upper portion of the nwell / bitline adverting to fig9 a and 9b , an oxide layer 901 is deposited over the substrate to a thickness of 1 to 3 nm , followed by a polysilicon layer 903 to a thickness of 30 to 200 nm . the two layers are then patterned and etched to form gate oxide 1001 and dummy gates 1003 , as illustrated in fig1 a and 10b . gate oxide 1001 and dummy gates 1003 are etched to a width of 14 to 500 nm . gate spacers , not shown for illustrative convenience , are formed on opposite sides of each dummy gate . as illustrated in fig1 a and 11b , n + well tap regions 1101 are formed in active region 901 by conventional source / drain implantation . although shown at opposite ends of the active region , an n + well tap region 1101 will be formed every 16 or 32 wordlines . then , an oxide interlayer dielectric ( ild ) 1201 , such as silicon dioxide , is formed over the entire substrate , filling all spaces , as illustrated in fig1 a and 12b . the oxide is planarized , for example by cmp , down to the upper surface of the polysilicon dummy gates 1003 . next a replacement gate process is performed . specifically , the polysilicon dummy gates 1003 and underlying gate oxide 1001 are removed forming cavities between the gate spacers . a thin high - k dielectric 1301 ( an oxide having a dielectric constant greater than that of silicon dioxide , such as hafnium oxide ) is deposited in the cavities to a thickness of 1 to 3 nm , thereby lining the cavitites . then , a metal gate 1303 is formed on the high - k dielectric 1301 in each cavity . the metal gate may , for example , be formed of titanium nitride ( tin ) or aluminum . further processing may include etching a contact for each active region 1101 or gate region and conventional middle - of - line ( mol ) and back - end - of - line ( beol ) processes . adverting to fig1 , the memory of fig6 a through 6c is programmed by selecting a bit ( at the intersection of a metal gate 1401 and a bitline 1403 in nwell 1405 ), supplying a positive voltage ( vpp ), for example 2 to 5 v , to the metal gate 1401 , which drives the n - type bitline 1403 ( grounded ) to accumulation . this creates a high field across the thin oxide 1407 , which causes dielectric breakdown ( at breakdown location 1409 ). at the same time , vpp / 2 is supplied to un - selected wordlines and bitlines to prevent disturbances . the gate dielectric breakdown forms an element with non - linear i - v characteristics at the breakdown location , and the high resistance at a reverse - biased condition blocks sneak current during reading . the programmed bit is read by applying a low positive voltage , e . g ., 0 . 2 to 1 v , to the metal gate to check the resistance between the wordline and the bitline . it should be noted that although the substrate has been described as a p - type substrate , and the bitlines formed in nwells , all references to n - type and p - type are merely exemplary and could be reversed . specifically , the substrate could be an n - type substrate , with the bitlines formed in pwells , which are separated by sti regions and nwells , and p + well tap regions could be formed in the pwells . if the disclosed otp memory is implemented in finfet technology , the enhanced field at the fin tip could further reduce the programming voltage . more specifically , at the top corner of the fin , the bottom oxide e field would be enhanced , thereby helping oxide breakdown during programming . the embodiments of the present disclosure can achieve several technical effects , such as a small otp cell ( about 4f 2 in the cross - point array ) with no sneak current in the cross - bar array , multiple bits sharing the same nwell bitline , low power operation , and compatibility with 20 nm and 14 nm replacement metal gate cmos process flow . this otp array is also compatible with finfet technology , to further reduce programming voltage due to field enhancement at the fin tip . the present disclosure enjoys industrial applicability in any of various types of highly integrated semiconductor devices used in microprocessors , smart phones , mobile phones , cellular handsets , set - top boxes , dvd recorders and players , automotive navigation , printers and peripherals , networking and telecom equipment , gaming systems , and digital cameras , particularly in any of various types of semiconductor devices , particularly in the 20 nm technology node and beyond . in the preceding description , the present disclosure is described with reference to specifically exemplary 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 present disclosure , as set forth in the claims . the specification and drawings are , accordingly , to be regarded as illustrative and not as restrictive . it is understood that the present disclosure is capable of using various other combinations and embodiments and is capable of any changes or modifications within the scope of the inventive concept as expressed herein . | 6 |
in the exemplary embodiments described below , components that are alike in function and structure are designated as far as possible by alike reference numerals . therefore , to understand the features of the individual components of a specific embodiment , the descriptions of other embodiments and of the summary of the invention should be referred to . the embodiments illustrated below generally relate to manufacture of semiconductor devices and to thinning of wafers and in particular to thinning of such wafers including through wafer vias which are to be exposed at a back side of the wafer by applying a thinning process to the back side of the wafer . background information relating to thinning of wafers and to wafers including through wafer vias can be obtained from u . s . pat . no . 7 , 214 , 615 b2 , u . s . pat . no . 6 , 916 , 725 b2 , us 2010 / 0038800 a1 , us 2010 / 0032764 a1 , us 2005 / 0158889 a1 and us 2010 / 0041226 a1 , wherein the full disclosure of these documents is incorporated herein by reference . further information to manufacture of semiconductor devices involving thinning of a wafer can be obtained from the article “ stress analysis on ultra thin ground wafers ” by ricardo c . teixeira et al ., journal integrated circuits and systems 2008 , v . 3 / n . 2 : 81 - 87 and from the article “ new hybrid bonding approach for 3d stacking of ics ” by anne jourdain et al ., chip scale review , august / september 2009 , pages 24 to 28 . the illustrated embodiments relate to thinning of wafers and involve optical methods used for determining a residual thickness between tip ends of through wafer vias and a back surface of a wafer and for obtaining information which can be used for controlling a thinning process . these optical methods are , however , not limited to those applications . the optical methods can be also applied to other substrates in which features are embedded in the substrate such that they are located below a surface of the substrate . fig1 is a schematic illustration of a cross section of a semiconductor wafer in a manufacturing process for semiconductor devices . the wafer 1 has a front surface 6 at a front side 3 and a back surface 5 at a back side 4 . a plurality of semiconductor devices 7 , such as field effect transistors , are formed at the front side 3 of the wafer 1 by applying a plurality of lithographic steps and other manufacturing steps to the front side 3 of the wafer 1 . through wafer vias 9 extend from the front side 3 into the substrate material of the wafer 1 . the through wafer vias 9 can be formed by conventional methods , such as etching trenches into the substrate , depositing insulating material on trench walls and filling the trenches with a conductive material , such as copper . the through wafer vias have a high aspect ratio and extend into the substrate of the wafer such that tip ends 11 of the through wafer vias 9 are located at a residual distance d 1 from back surface 5 of the wafer 1 . exemplary values of the residual distance d 1 after manufacture of the through wafer vias 9 include 630 μm and 730 μm , depending on a thickness of the wafer 1 . one or more wafer thinning processes will be applied to the wafer 1 schematically illustrated in fig1 to expose the vias 9 at the back surface of the wafer . the thinning process includes removal of substrate material from the back surface 5 of the wafer 1 . a broken line 5 ′ in fig1 illustrates a position of the back surface of the wafer after thinning such that the vias 9 are exposed and project a distance d 2 from the surface . exemplary values of the distance d 2 are 1 μm and 2 μm , for example . it is apparent that the thinning process has to be performed with a high accuracy to maintain the achieved distances d 2 within an acceptable range for all the vias 9 distributed across the substrate 1 . therefore , it is desirable to control the one or more thinning processes based on measurements . a conventional optical measurement to control wafer thinning is known from us 2005 / 0158889 a1 and measures a distance between the back surface 5 and the front surface 4 of the wafer . this conventional optical measurement method uses infrared light having a penetration depth in the wafer material which is greater than the distance between the front and back surfaces . problems in the conventional method may occur if it is not possible to precisely detect the front surface of the wafer due to a presence of a carrier substrate onto which the wafer is attached with its front side 3 , and if a depth by which the vias extend into the substrate is not exactly known or not uniform across the wafer . therefore , it is desirable to determine the residual distance d 1 between tip ends 11 and the back surface 6 of the wafer 1 directly , or to at least determine reliable information indicative of the residual distance d 1 . for example , if a predefined threshold residual distance of , for example , 5 μm or 10 μm is reached by applying a grinding method , the thinning process can be continued by applying etching until the tip ends are fully exposed . fig2 is a schematic illustration of an optical configuration which can be used to perform an optical method for determining the residual thickness d 1 of the wafer 1 schematically illustrated in fig1 . the optical configuration includes a light source 21 to generate measuring light 23 from which a beam 25 of measuring light is shaped by optics 27 . the optics 27 may include one or more lenses and one or more mirrors . the beam 25 is directed onto a portion 29 of the back surface 5 of the wafer 1 under an angle a relative to a surface normal which is greater than , for example , 10 °, 20 ° or 30 °. the portion 29 of the back surface 5 of the wafer is imaged onto a position sensitive detector 31 using imaging optics 33 . the imaging optics 33 may include one or more lenses and one or more mirrors . the position sensitive detector 31 comprises an array of pixels 35 . the position sensitive detector 31 may have a high number of pixels , such as 10 , 000 or more pixels , wherein a number of only six pixels 35 is shown in fig5 for illustrative purposes . due to the imaging with imaging optics 33 , there is a one - to - one correspondence between regions on the wafer 1 and individual pixels onto which each region is imaged . reference numeral 37 indicates an exemplary region on the substrate 1 which is imaged onto the left pixel 35 of detector 31 shown in fig2 . a lateral extension d 3 of the region 37 imaged onto the one pixel 35 is , for example , 100 μm . this lateral extension is greater than the lateral extension of the vias 9 embedded in the substrate . an exemplary value of the lateral extension of a via 9 is 2 μm to 20 μm . the optical configuration illustrated in fig2 is a dark field configuration as illustrated by an angle β shown in fig2 . the angle β is a minimum angle between rays 39 of measuring light 25 specularly reflected at the back surface 5 of the wafer and rays 41 of the portion of the measuring light scattered at the wafer 1 and received by the detector 31 . this minimum angle β is greater than 10 °, 20 ° or 30 °, for example . wavelengths of the light of the measuring beam 25 are selected to fulfil certain requirements illustrated below in more detail . for this purpose , transmissive filters allowing only certain wavelengths to traverse or reflective filters reflecting only certain wavelengths can be disposed in the beam path of the measuring light beam 25 . a same result can be achieved if the measuring light beam 25 includes a generally broad spectrum of wavelengths and wherein a wavelength selection is performed in the imaging beam path between the substrate 1 and the detector 31 by providing suitable transmissive or reflective filters . moreover , the light source 21 can be configured such that it generates substantially only light from a desired wavelength range . the portion 29 which is imaged onto the detector 31 may have a lateral extension such that plural through wafer vias 9 are located within the region 29 . the number of vias located within the region 29 may exceed 100 vias or many thousand vias . still further , the lateral extension of the region 29 can be greater than a lateral extension of dice formed from the wafer 1 later by dicing . for example , the lateral extension of the region 29 can be selected such that it includes more than one , more than two , more than five or even more dice . moreover , the region 29 imaged onto the detector 31 may include the full wafer 1 such that the lateral extension of the region 29 can be greater than 200 mm or greater than 300 mm depending on the diameter of the wafer 1 . an example of an optical configuration which can be used in optical methods illustrated in the present disclosure is illustrated in wo 2009 / 121628 a2 , the full disclosure of which is incorporated herein by reference . an alternative optical configuration which can be used in the optical methods illustrated in this disclosure is schematically shown in fig3 . this setup includes a light source 21 a generating measuring light 23 a which is shaped to a focussed beam 25 a of measuring light by optics 27 a which may comprise one or more lenses and one or more mirrors . the focused beam 25 a of measuring light is directed onto a back surface 5 a of a wafer 1 a such that a lateral extension d 3 of the beam 25 at the back surface 5 a is greater than a lateral extension of through wafer vias 9 a embedded in the wafer substrate . for example , the lateral extension d 3 can be 2 times greater , 5 times greater , 10 times greater or even 100 times greater than the lateral extension of the through wafer vias 9 a . the beam of measuring light 25 a is directed onto the substrate la under an angle a relative to a surface normal of the wafer 1 a . a detector 31 a is positioned such that a minimum angle β of rays 39 a of measuring light 25 a specularly reflected at the back surface 6 a of the wafer and rays 41 a of the measuring light received by the detector 31 a is greater than 10 °, 20 ° or 30 °, for example . the detector 31 a may include one single light sensitive element or a number of light sensitive elements . while it is possible that the detector 31 a is a position sensitive detector , this is not necessary in the illustrated configuration . an image of the wafer 1 a can be obtained by scanning the beam 25 a across the back surface 5 a of the wafer and recording light intensities detected with the detector 31 a in dependence of a position to which the beam 25 a is directed . for example , the wafer 1 a can be rotated and / or otherwise displaced relative to the beam 25 a of incident measuring light . the optical configurations illustrated above with reference to fig2 and 3 are dark field configurations in which a main direction of measuring light originating from the wafer and received by the detector is oriented substantially parallel to a surface normal of the wafer . it is , however , possible to achieve dark field configurations also with optics in which the light originating from the wafer and received by the detector has a main direction oriented under an angle relative to the surface normal . it is , in particular , also possible to direct the incident measuring light substantially orthogonal onto the wafer surface . the dark field configuration is achieved by the minimum angle between rays of specularly reflected light and rays of detected light . the minimum angle β is in particular greater than 0 ° and preferable greater than 10 °, 20 ° or 30 ° for example . other configurations of optics which can be used in the optical methods disclosed herein include bright field optical configurations in which there is an angular overlap between rays of measuring light specularly reflected off the surface of the wafer and rays received by a detector . the inventors have found that optical configurations which are conventionally used for inspection of defects located on a surface of a substrate can also be used for detection of features embedded in the substrate and located at a residual distance from the surface of the substrate . fig4 a , 4 b and 4 c show images obtained from a back side of a semiconductor wafer having embedded features . the substrate material of the semiconductor wafer is silicon , and the embedded features are through wafer vias made of copper . the three images shown in fig4 are obtained at different residual distances of tip ends of the vias from the back surface of the wafer . in fig4 a , the residual distance d 1 is 6 μm , and the features visible in the image mostly relate to grinding marks of a grinding tool used in the wafer thinning process . a number of image features which might be indicative of the presence of the through wafer vias is low . fig4 b shows an image of a wafer back side where the residual distance d 1 varies between 1 μm and 2 μm . the features visible in the image include grinding marks similar to those of fig4 a , and patterns having a structure corresponding to an arrangement pattern of through wafer vias manufactured in the substrate . the features of the grinding pattern and the features of the via pattern are provided in the image with a similar contrast . fig4 c shows an image of the back side of the wafer in which the residual distance d 1 of the vias is less than or equal to 0 . 5 μm . it is apparent that the features corresponding to the arrangement of vias is even more prominent than in fig4 b and that the features corresponding to the arrangement of vias have a higher contrast in the image than the features related to the grinding pattern . from fig4 a , 4 b and 4 c it is apparent that an image contrast and / or image intensity of patterns contained in an image of a back side of a wafer is indicative of a residual distance between features embedded in the wafer and the back surface of the wafer . the image contrast produced by features embedded in the substrate and located below the substrate surface can be enhanced by imposing restrictions to the measuring light used for the imaging . for example , it is desirable that light reflected at the front surface of the substrate or light scattered at structures provided on the front side of the substrate do not contribute to the detected image . such light travels through the substrate material along a path having a length which is at least two times greater than the thickness of the substrate . therefore , it is advantageous to select wavelengths of the measuring light contributing to the detected image such that a substantial extinction of measuring light occurs after a path length within the material greater than two times the thickness of the substrate . this can be achieved by selecting the wavelengths such that a penetration depth of the measuring light in the substrate material is smaller than 2 . 0 times , 1 . 0 times or 0 . 5 times a thickness of the substrate . in this context , the penetration depth is defined as the depth at which the intensity of the measuring light inside the substrate material falls to 1 / e ( about 37 %) of the original value at the surface . for example , if the substrate material is silicon and a thickness of the substrate can be as small as 10 μm , it is advantageous to use measuring light of wavelengths less than 900 nm , 850 nm , 800 nm or 750 nm , for example . on the other hand , the measuring light used for generating an image of an arrangement pattern of features located below a back surface of a substrate should still have a significant intensity when it reaches the buried features . therefore , it is advantageous to select the wavelengths of the measuring light such that a penetration depth of the measuring light in the substrate is greater than 0 . 2 times , greater than 0 . 5 times or greater than 1 . 5 times a residual distance between the buried features and the substrate surface . in the example where the substrate material is silicon and where the buried features are through wafer vias made of metal , it is advantageous to use measuring light having wavelengths greater than 500 nm , greater than 550 nm , greater than 600 nm or even greater than 650 nm . fig6 shows experimental data of the penetration depth in μm of light in a silicon substrate material in dependence of the wavelength of the light in nm . it is apparent that a lower limit of the wavelength which can be used to detect features more than 1 μm below the surface should be greater than 500 nm , whereas wavelengths below 900 nm should be used to detect such features in a substrate having a thickness below 35 μm . fig5 is a graph of experimental data showing the dependency of the residual distance of the through wafer vias , as shown in fig4 , in dependence of a dark field image intensity of arrangement patterns of the vias in the image . from this graph it is apparent that the dark field image intensity and contrast are well - suited to be indicative of the residual thickness . apart from the wavelengths , the measuring light used for detection can also be selected with respect to its polarization such that a high amount of the incident light enters into the substrate and / or such that the suitably polarized light generates a high image intensity or contrast . the optical methods of inspection of a semiconductor wafer can be used for obtaining information used to control a wafer thinning process in mass production of semiconductor devices . such manufacturing method is illustrated with reference to the flowchart shown in fig7 below . the method includes bonding a first substrate to a second substrate wherein through wafer vias exposed at a back surface of the first substrate are contacted by the second substrate bonded to the first substrate . in a production of wafers , a next wafer is used for processing in a step 101 . semiconductor structures and vias are formed on a front side of the wafer by lithographic processes and other processes in a step 103 . thereafter , a carrier is attached to a frond side of the wafer , and a thinning process is applied to a back side of the wafer in a step 105 . the thinning process may include , for example , grinding and / or polishing . the thinning process is controlled by grinding parameters 107 , such as , among others , a number of revolutions per unit time of a grinding or polishing apparatus , a force applied between a grinding or polishing tool and the back side of the wafer or a duration of the grinding or polishing process . the grinding parameters are selected such that a residual thickness between tip ends of the through wafer vias and the back surface of the wafer is 2 μm . thereafter the residual thickness or information indicative of the residual thickness is determined in a step 109 using optical methods as illustrated above . based on the determined residual thickness or information indicative of the residual thickness , the control parameters 107 of the thinning process 105 and control parameters 111 of a subsequent thinning process 113 are updated in a step 115 . thereafter , the further thinning process is applied to the back side of the wafer to expose the through wafer vias at the back surface of the wafer in the step 113 . such final thinning process may include an etching which selectively removes substrate material and does substantially not remove the material of the through wafer vias . also the thinning process of step 113 is controlled by process parameters 111 which may include , among others , a duration of the thinning process , a concentration , composition or temperature of an etching substance , or a plasma intensity applied in the thinning process . a second substrate is bonded to the wafer in a step 115 after exposing the vias on the back surface . the second substrate may comprise a full wafer or individual dyes of semiconductor devices which have been selected according to suitable quality requirements . thereafter , a next wafer is processed at step 101 . it is to be noted that the images obtained from the back surface of the wafer include also other features not related to the through wafer vias . these other features are , for example , generated by defects located on the surface of the substrate . examples are the grinding marks visible in fig4 a , 4 b and 4 c . an analysis of such other features can provide information which can be used to control the processing of the wafer . for example the grinding marks can be indicative of a defect of the grinding apparatus used , such that the obtained information may trigger a repair of the grinding apparatus . moreover , additional images can be obtained in an inspection step by recording one or more images using different wavelengths and polarisations of the measuring light used for imaging . the information indicative of the residual thickness of the substrate obtained in step 109 can be used to update control parameters of a thinning process applied to the same wafer subsequently . such process can be referred to as feed - forward control since it is based on information obtained from an individual wafer and is used for controlling further processing of the same wafer . the updating of control parameters of the thinning process applied to the individual wafer in step 105 is a feed - back control since it is effective only for a next wafer processed in a production line . | 7 |
the aforementioned u . s . pat . no . 5 , 451 , 321 to matkovich shows a biological fluid processing assembly for filter biological processes such as blood . an example of the matkovich apparatus is illustrated in fig1 . the apparatus has a blood collection bag 30 connected by a first conduit 31 to a leukocyte depletion device 32 . the leukocyte depletion device 32 is connected by a second conduit 33 to a blood receiving bag 34 . a gas inlet 35 having a cover or cap 36 , is provided in fluid communication with the first conduit 31 downstream of said collection bag 30 , and a gas outlet 37 is provided in second conduit 33 downstream of the leukocyte depletion device 32 . in one embodiment of the prior art , a first clamp 38 is placed on first conduit 31 downstream of the blood collection bag 30 and upstream of the gas inlet 35 , and a second clamp 39 is placed on the second conduit 33 downstream of the gas outlet 37 . in a typical operation the blood collection bag 30 is sterile and is connected to the conduit 31 as illustrated . the gas inlet 35 is comprised of a housing 41 and a porous medium barrier 42 in addition to cover or cap 36 . additional details of the barrier 42 may be obtained by reference to u . s . pat . no . 5 , 451 , 321 . prior to the start of blood processing , the inlet clamp 38 , the outlet clamp 39 , and the gas inlet 35 are all closed . the blood processing is initiated by opening the inlet clamp 38 , and allowing the blood to drain from the blood collection bag 30 . a column of blood flows through the first conduit 31 into the leukocyte depletion device 32 displacing any gas within the blood processing system . no blood enters the gas inlet device 35 since the gas inlet is closed . the displaced gas is expelled from the system through the gas outlet 37 since the second clamp 39 is closed . as substantially all the gas is expelled from the first conduit 31 and the portion of the second conduit 33 leading to the gas outlet 37 , the porous medium is wetted by the blood , and the blood flow seizes or stops at the liquiphobic bearer in the gas outlet 37 . once the gas outlet 37 is wetted , the second or outlet clamp 39 is opened , and filtered blood flows into the blood receiving bag 34 . the gas outlet 37 need not be closed prior to opening of the outlet clamp since the gas outlet is sealed by the wetted porous medium . blood flows from the collapsible blood container or bag 30 through the leukocyte depletion device 32 and into the blood receiving bag 34 until equilibrium is reached within the system and blood ceases to flow . at this point , all of the blood has not been processed through the leukocyte depletion device 32 . the first conduit 31 , the filter device 32 , and the second conduit 33 are filled with blood . removing the cover or cap 36 from the gas inlet 35 allows gas to enter the processing system and drive the blood through the leukocyte depletion device 32 . however , since the filter medium 32 a within the leukocyte depletion device 32 is wetted , the flow of blood seizes when gas fills the upstream chamber of the filter . when the blood flow seizes , the second or outlet clamp 39 is closed . it can be seen that , at this point , the downstream side of the leukocyte depletion device 32 , and the entire second conduit 33 are filled with blood . with ever increasing need for blood and blood products , those skilled in the prior art have strived to increase the recovery of blood , and such a relatively large quantity of blood being left in the device of the prior art is no longer satisfactory . in order to solve the recovery problems present in the prior art devices , the open - loop construction shown in fig2 has been developed . there is shown a biological fluid filtration system 44 having a leukocyte depletion device 45 with a filter medium 46 , an inlet 47 , and an outlet 48 . the leukocyte depletion device may be such as the biological fluid filter shown in provisional application ser . no . 60 / 083 , 484 , which has been incorporated herein by reference , or any other suitable fluid filtration or leukocyte depletion device . a blood container 49 is provided upstream from , and elevated above said leukocyte depletion device 45 . blood container 49 is connected to , or in fluid communication with , said leukocyte depletion device 45 through first conduit 50 . there is also provided a blood receiving container 52 downstream of said leukocyte depletion device 45 . leukocyte depletion device 45 is connected to blood receiving container 52 through second conduit 54 . an upstream gas inlet 56 is provided in fluid communication with said first conduit 50 , and a downstream gas inlet 58 is provided in fluid communication with said leukocyte depletion device 45 , downstream of said filter medium 46 . an inlet clamp 60 and an outlet clamp 61 may be provided . it should be understood that one or more of inlet clamp 60 and / or outlet clamp 61 may be provided , and be well within the scope of the present invention . upstream gas inlet 56 may take the form of a vent line 62 being connected to an upstream gas inlet housing 64 . vent line 62 may have a u - shaped portion 62 a to prevent drawing of gas into biological fluid filtration system 44 until substantially all of the biological fluid has drained from the biological fluid container 49 . the other end of vent line 62 should be at a sufficient height such that it is always positioned above the level of the fluid in the biological fluid container 49 . upstream gas inlet housing or vent 64 has an inlet 65 and an outlet 66 . interposed between the inlet 65 and the outlet 66 in a sealing relationship is at least one layer of a porous medium 67 . the porous medium may be such as a bacterial retention medium , a viral retention medium , or other suitable medium . in a similar manner , the downstream gas inlet 58 may comprise a second vent line 70 connected to a downstream gas inlet housing or vent 71 having an inlet 72 and an outlet 73 . a cap or other closure 74 may be used in connection with the opening and the closing of inlet 72 . interposed in the housing 71 , between the inlet 72 and the outlet 73 is a second porous medium 76 . the second porous medium 76 may also be such as a bacterial retention medium , a viral retention medium , or other suitable medium . as illustrated , upstream gas inlet housing 64 and downstream gas inlet housing 71 may be provided in a single novel inlet device 80 having a barrier or wall 81 which prevents fluid communication between the upstream gas inlet porous medium 67 and the downstream gas inlet porous medium 76 . the upstream medium 67 and the downstream medium 76 may then be formed of a single sheet . the upstream gas inlet 56 and the downstream gas inlet 58 may be placed in any practicable location as long as they are located such that the blood product being filtered never contacts the porous medium 67 . in the preferred embodiment illustrated the porous medium 67 contained within the housing 64 is elevated above the blood container 49 , but other locations are well within the scope of the present invention . in the method of blood processing embodying the present invention , the inlet clamp 60 and the outlet clamp 61 are initially closed . the cap or closure 74 covering the inlet 72 of downstream gas inlet device , housing , or housing portion 71 is also in place . the blood processing is initiated by opening the inlet clamp 60 and allowing the biological fluid to flow through the first conduit 50 . as the fluid flows past the junction 50 a , some of the fluid will flow into the upstream gas inlet 56 through vent line 62 . a column of liquid of a predetermined , desired , length ( shown as dimension a in fig2 ), between the junction 50 a and the bottom of the loop portion of 62 a , prevents gas entry into the system until substantially all of the biological fluid has been drained from the biological fluid container 49 . the upstream gas vent may be thought of as a manometer measuring the pressure at the junction 50 a . as the level of fluid within the biological fluid container 49 decreases , the pressure at the junction 50 a decreases and , therefore , the height of the fluid in the vent line 62 decreases . when substantially all of the biological fluid has drained from the biological fluid container 49 , the atmospheric pressure acting on the column of fluid within the vent line 62 will cause all of the fluid within the upstream gas inlet 56 to drain into the conduit 50 . the remaining fluid contained with the upstream gas inlet line 62 is drained into the conduit 50 because the upstream gas inlet is open to atmosphere . thus , dimension a in fig2 must be of sufficient distance such that the above described sequence of events occur . at this point , the leukocyte depletion device 45 downstream of the filter medium 46 and the second conduit 54 between the leukocyte depletion device 45 and the blood receiving container 52 , are all filled with filtered biological fluid . the filtered biological fluid or blood downstream of the filter medium 46 in the leukocyte depletion device 45 may now be recovered by opening the cap or closure 74 covering the inlet 72 of downstream gas inlet device , housing , or housing portion 71 . in place of cap 74 , a clamp ( not shown ) could be used on second vent 70 . after this step substantially all of the blood previously unrecovered by the prior art devices is in the blood receiving container 52 . any gas in the receiving container 52 and / or second conduit 54 downstream of the disconnecting point of the blood receiving container 52 may be pushed back up into the second conduit 54 by gently squeezing the blood receiving container 52 , and then the outlet clamp 61 can be closed . as is now evident , the construction shown in fig2 provides an easy method of drainage of substantially all of the biological fluid from the receiving bag 52 through the leukocyte depletion device 45 . in addition , the biological fluid filtration system 44 in its preferred embodiment utilizes only a single housing in the inlet device 80 , and a single layer of porous medium and substantially all of the filtered biological fluid is recovered . the system has a lower number of parts , is easier to manufacture , and recovers more biological fluid at a lower per unit biological fluid processing cost . alternate embodiments of the construction shown in fig2 are illustrated in fig3 - 5 , with like numerals designating corresponding parts in the several views . their operation can easily be understood by those skilled in the art in view of the foregoing description . a modification of the present invention utilizing only the upstream gas inlet 56 and a satellite bag 83 is shown in fig1 . satellite bag 83 is connected in fluid communication with blood receiving container 52 by satellite conduit 84 . satellite clamp 85 opens and closes satellite conduit 84 . in this embodiment of the present invention , the satellite bag is used to vent the gas displaced from the receiving container 52 . the volume of the satellite bag 83 should be sufficient to accept all of the gas displaced . after all the blood has flowed into the receiving container 52 , the container is gently squeezed until all of the gas is vented past the satellite clamp 85 , at which time the satellite clamp 85 is closed . referring now to fig6 there is shown a closed loop biological fluid filtration system 90 . as in previous embodiments of the present invention , there is a leukocyte depletion device 45 having a filter medium 46 , an inlet 47 , and an outlet 48 . the filter medium 46 is interposed in a sealing relationship between the inlet 47 and the outlet 48 . the system 90 also includes a blood container 49 connected by first conduit 50 to the inlet 47 of leukocyte depletion device 45 . inlet clamp 60 is provided as before . provided downstream of the leukocyte depletion device 45 is a blood receiving container 52 . a second conduit 54 is connected between the outlet 48 of the leukocyte depletion device 45 and the inlet of the blood receiving container 52 . used in place of the upstream gas inlet 56 and a downstream gas inlet 58 is a by - pass line 91 , which may be opened and closed by by - pass clamp 92 . a first end of the by - pass line 91 is connected in fluid communication with the blood container 49 proximate the outlet thereof , and the other end of the by - pass line 91 is connected in fluid communication with the blood receiving container 52 proximate the inlet thereof . the loop portion 93 of the by - pass line 91 is positioned such that when the blood container 49 is full of blood , the blood will not reach the loop portion 93 and thus , there can be no flow of blood through the by - pass line . one such position is illustrated in fig6 with the loop portion 93 elevated above the blood container 49 . in place of loop portion 93 , a one way check valve or other device may be used such that a column of gas will always separate the unfiltered biological fluid upstream of the filtration device from the filtered biological fluid downstream of the leukocyte depletion device 45 . the positioning of the loop portion 93 , and the bypass line 91 may also be varied to accomplish this . the method of operating the the closed loop embodiment of the invention differs in several respects from the method used with the open loop embodiment . as illustrated in fig6 the additional by - pass clamp 92 is needed because no gas inlet or gas outlet devices are provided , as were necessary in the prior art . prior to the start of blood processing , the inlet clamp 60 is closed and the by - pass clamp 92 is open . the blood processing is initiated by opening the inlet clamp 60 and allowing blood to drain from the blood container 49 through first conduit 50 into the leukocyte depletion device 45 and therethrough to the blood receiving container 52 . the blood does not by - pass the leukocyte depletion device 45 because of the loop portion 93 of the by - pass line 91 being elevated to a sufficient height . the gas within the closed loop biological fluid filtration system 90 is displaced by the blood flow into the blood receiving container 52 . as the blood container 49 approaches its nearly empty condition , the gas stored within the receiving container 52 automatically flows through the by - pass line 91 into the blood container 49 and allows substantially all of the blood to be processed through the leukocyte filtration device 45 . it is important to note that the chamber of the leukocyte depletion device 45 downstream of the filter media 46 at this point will be filled with blood , as will the second conduit 54 between the leukocyte depletion device and the blood receiving container 52 . if there is any gas left in the receiving container 52 it may be displaced into the by - pass line 91 by closing the outlet clamp 61 , gently squeezing the blood receiving container 52 and closing the by - pass clamp 92 . in this embodiment of the invention comprising the closed loop biological fluid filtration system , the chamber downstream of the filter medium 46 in the leukocyte depletion device 45 is not drained of blood , nor is second conduct 54 . however , the inlet device and the outlet devices of the prior art are eliminated , and a simplified system is provided . additional modifications of the closed loop biological fluid filtration system 90 are shown in fig7 - 11 . their operation can be understood by those skilled in the art from the foregoing description . a more detailed description of the biological fluid filter can be had by referring to fig1 - 25 . the biological fluid filter 100 consists of an inlet section 101 and an outlet section 102 . referring to fig1 and 15 , the inlet section 101 of biological fluid filter 100 has an inlet 103 , including port 103 a , communicating with first passage 104 , which is in fluid communication with first or inlet chamber 105 through first port or outlet 104 a . further , biological fluid filter 100 has a second passage 106 in fluid communication with both , first or inlet chamber 105 , and first vent chamber 107 . the outlet section 102 has a second vent chamber 110 in fluid communication with a third passage 111 . third passage 111 is in fluid communication with outlet 112 through port 112 a . a fourth passage 113 is in communication with the third passage 111 and the second or outlet chamber 115 . a vent filter element 117 separates the first vent camber 107 from the second vent chamber 110 , and is held in place by means to be described in more detail hereinbelow . similarly , a biological filter element 119 separates the first or inlet chamber 105 from the second or outlet chamber 115 . both the vent filter element 117 and the biological filter element 119 may consist of one or more layers , and be made of a wide variety of filter materials . in the embodiment illustrated , they are liquiphilic . in the preferred embodiment , the vent filter element 117 , and the biological fluid filter element 119 , are made of the same filter medium , which may be such as glass or nylon fibers . in use , a fluid container ( not shown ), such as a blood container is placed in fluid communication with inlet port 103 a . similarly , a biological fluid receiving bag ( not shown ) is placed in fluid communication , by means well known in the art , with outlet port 112 a . fluid flow is initiated and blood flows in the inlet port 103 a , through the first passage 104 and through first outlet 104 a into inlet chamber 105 . in operation , as the blood enters the inlet chamber 105 , the blood may wick into the filter element 119 . the blood may wick into the filter element 119 faster , or slower , than the blood level rises in the first or inlet chamber 105 . the rate at which the blood wicks into the filter element 119 will depend on the properties of the filter medium being chosen , and the biological fluid being filtered . these properties include the pore size of the medium , the density of the biological fluid , the surface tension of the biological fluid , and the contact angle of the solid - liquid - gas interface . while the blood level is rising in the inlet chamber 105 , any air entrapped in chamber 105 is either passing through a portion of the filter element 119 which is not yet wetted , or is proceeding through second passage 106 and being vented out the vent filter element 117 . as the blood level continues to rise in inlet chamber 105 , at some point , the biological filter element 119 will be sufficiently “ wetted ”, and the biological fluid being filtered will “ breakthrough ” the filter element 119 , and will start flowing into outlet chamber 115 . the fluid breakthrough depends on the pore size of the material , the surface tension and the contact angle , as well as the pressure differential across the filter element 119 . due to the pressure differential across the biological filter element 119 , the biological fluid continues to flow up into second passage 106 . if the pressure differential is sufficient , the biological fluid will contact the vent filter element 117 , which is the preferred embodiment . if the vent filter element 117 is also made of a liquiphilic media , it will become “ wetted out ”. however , by this time all the gas entrapped in inlet chamber 105 has either passed previously through biological filter element 119 or through vent filter element 117 and accomplished one of the objects of the invention . referring now to fig1 - 19 , the construction of the inlet section 101 of the biological fluid filter 100 may be clearly understood . the biological fluid filter 100 includes an inlet section 101 which is bonded to an outlet section 102 by a seal 130 . the seal 130 is preferably an ultrasonic seal . it can be understood by those skilled in the art that other seals such as heat seals , adhesive seals , or any other air tight seal may be used . inlet section 101 includes a recessed top wall 131 , and down standing side walls 132 extending around the periphery of the recessed top wall 131 . a down standing peripheral ridge 133 extends around the periphery of the down standing side wall 132 and forms a part of the mechanism which holds the vent filter element 117 and the biological filter element 119 in place , as will be more fully explained hereinafter . a first protuberance 135 extends from the recessed top wall 131 , and carries the inlet 103 and first passage 104 as previously described . first or outlet port 104 a which is in fluid communication with the first passage 104 can be seen in fig1 . a recess 136 , provided by the combination of the top surface of the recessed top wall 131 and the peripheral side walls 137 almost completely surrounds the protuberance 135 . a peripheral flange 138 depends from the peripheral sidewall 137 and forms a groove 139 extending around the periphery of the inlet section 101 of the biological fluid filter 100 . the groove 139 forms a portion of the means by which the seal 130 between the inlet section 101 and the outlet section 102 of the biological fluid filter 100 is formed . a plurality of down standing ribs 142 are provided on the lower surface of the recessed top wall 131 for purposes to be described . the inlet portion 101 of the biological fluid filtration device also has an extended portion 145 which contains second passage 106 ( fig1 ) in fluid communication with first vent chamber 107 . the same flange 138 and groove 139 are provided in the extended portion 145 of the inlet section 101 as are provided in the remainder of the inlet section 101 , so that the inlet section 101 will properly mate with the outlet section 102 to be described . a circular ridge 147 is provided about the first vent chamber 107 to aid in holding the vent filter , as will be further described . referring now to fig1 - 17 and 20 - 21 , the construction of the outlet portion 102 of the biological fluid filter 100 will be clearly understood . the shape of the outlet section 102 of the biological fluid filter 100 is complimentary in shape to the inlet section 101 so that the inlet section 101 may act as a closure to the outlet section 102 , or vice versa . it can easily be understood by those skilled in the art that the biological fluid filter 100 may be of any desired shape , such as the generally oval shape thus far described , the diamond shape of the modification shown in fig2 or 24 , or any other desired shape . similar to the inlet section 101 , the outlet section 102 of the biological fluid filter 100 has a bottom wall 150 and upstanding sidewall 151 . the top of the upstanding sidewall 151 fits into the groove 139 in the inlet portion 101 , and is preferably sonically welded to form the seal 130 . a second protuberance 154 is provided on the exterior portion of the bottom wall 150 and carries the third passage 111 , fourth passage 113 , and a portion of the vent chamber 110 . a second circular ridge 155 , complimentary in shape to the circular ridge 147 , is provided . the protuberance 154 covers a portion of the extended portion 156 of the outlet portion 102 of the biological fluid filter 100 . as seen in fig1 , a further plurality of ribs 142 is provided on the interior surface of the bottom wall 150 to help support the biological filter element 119 and provide flow in the second or outlet chamber 115 of the biological fluid filter 100 . an upstanding ridge 157 is provided in a spaced apart relationship to the upstanding sidewall 151 . as with the circular ridges 147 and 155 when the outlet portion 22 and the inlet portion 21 are in mating relationship , the down standing ridge 133 and the upstanding ridge 157 will be in a 180 ° opposed relationship . as can be seen in fig1 these ridges will provide the pinch seals 160 for the vent filter element 117 and the biological filter element 119 . an ultrasonic weld ridge 158 is provided to separate vent filter 117 and biological filter element 119 , and to provide additional support for the fluid filter 190 . referring to fig2 and 23 , there is shown a modification of the biological fluid filter 100 previously described . in this modification of the invention , the biological fluid filter 100 has a housing 163 , which may be constructed in a manner similar to that just described , or may be constructed by other means well known in the art . the housing has an inlet 164 to which a biological fluid container of the type well known in the art would be in fluid communication during operation . the housing 163 also has an outlet 165 through which the filtered fluid passes . the outlet 165 would be in fluid communication with a biological receiving container ( not shown ). a filter element 166 would be sealingly mounted within the housing between inlet 164 and outlet 165 . in this modification of the biological fluid filter 100 , instead of there being a separate and distinct vent filter element 117 , the vent filter element 117 is embedded in the biological fluid filter element 166 . the biological filter element 166 may be made of a liquiphilic filter medium , and the embedded vent filter element 167 may also be made of a liquiphilic filter medium , surrounded by a solid or liquiphobic barrier 168 . in operation , this modification of the biological fluid filter would operate in a similar manner to that just described because of the liquiphilic nature of the biological filter element 166 , until the element was completely saturated . as the blood was rising in the inlet chamber 161 , any entrapped gas would pass through the embedded vent filter element 167 until the level of the blood surpassed the solid or liquiphobic barrier 168 . at this time , virtually all of the entrapped gas would be downstream of the biological filter element 166 , the element would be completely saturated , and blood would now freely flow into the outlet chamber 162 . another modification of the biological fluid filter 100 is shown in fig2 and 25 . as before , there is a filter housing 163 having an inlet 164 communicating with an inlet chamber 161 , and an outlet 165 communicating with an outlet chamber 162 . in this modification of the invention , the biological filter element 166 has a first embedded liquiphilic gas vent 167 surrounded by a solid barrier 168 , and a second embedded liquiphobic gas vent 173 . in operation , a biological fluid container known in the art ( not shown ) will be in fluid communication with inlet 164 . as blood is released from the biological fluid container it will flow into the inlet chamber 161 and come into contact with the bottom of the biological fluid filter element 166 . since filter element 166 may be a liquiphilic porous medium , the blood level may wick up in the liquiphilic porous medium 166 faster than the level in the chamber 161 . the blood will not pass through the liquiphobic second embedded gas vent 173 . the second embedded gas vent 173 will have no effect on the operation of the biological fluid filter 100 while the liquid level continues to rise in inlet chamber 161 . however , the difference between the embodiment of the invention shown in fig2 and 23 , and 24 and 25 , becomes apparent when all of the blood has been released from the biological filter container and the level starts dropping in the inlet chamber 161 . the vent filter element 167 will stay wetted out as the level in the inlet chamber 161 drops because of the blood present in the outlet chamber 162 . however , as the level in the inlet chamber 161 continues to drop it will drop below the level of the liquiphobic second embedded gas vent 173 . since gas vent 173 did not wet out , when the blood level drops , air will pass from the inlet chamber 161 through the second embedded gas vent 173 , and aid in draining the filter element 166 , as well as the outlet chamber 162 , through the outlet 165 . therefore , by carefully studying the problems present in prior art biological filtration fluid systems , i have developed a novel method and apparatus for biological fluid filtration . in accordance with the provisions of the patent statutes , the present invention has been described in what is considered to represent its preferred embodiment . however , it should be noted that the invention can be practiced otherwise than as specifically illustrated and described without departing from its spirit or scope . | 0 |
the protective layer included in the laminated structure of the present disclosure is a polyester film which has a maximum surface roughness between about 1 , 500 nm and about 2 , 500 nm , preferably between about 1 , 700 nm and about 2 , 300 nm , and more preferably between about 2 , 000 nm and about 2 , 300 nm , measured by a 31 ) interferometer , and a sheet resistance between about 1 × 10 8 ω /□ and about 1 × 10 12 ω /□, preferably between about 1 × 10 9 ω /□ and about 1 × 10 11 ω /□, measured by a surface resistance meter ( agilent 43398 ). according to one specific embodiment of the present disclosure , the polyester film is a polyethylene terephthalate film . the protective layer of the present disclosure has good antistatic properties . in addition , the protective layer has a thickness between about 1 μm and about 100 μm , preferably between about 10 μm and about 40 μm . according to one specific embodiment of the present disclosure , the protective layer is preferably a surface - pretreated polyester film . for example , a coating composed of a polymer such as organopolysiloxane , fluorinated polyolefin , polyvinyl fluoride , and polyvinyl alcohol may be firstly formed on a surface of the protective layer to be laminated to the photosensitive resin layer so as to enhance the adhesion therebetween . the supporting layer included in the laminated structure of the present disclosure is a polyester film including polyethylene terephthalate and has a thickness between about 10 μm and about 100 μm . the photosensitive resin layer included in the laminated structure of the present disclosure may include a polymeric binder , a photopolymerizable compound containing a double bond , and a photoinitiator . addition of a photoinitiator and a photopolymerizable compound containing a double bond give rise to the free radical polymerization of a photosensitive resin composition under ultraviolet irradiation . a photosensitive resin composition of the present disclosure may optionally include other additives , for example , a dye ( such as malachite green , crystal violet or victoria blue ), a stabilizing agent ( such as triphenylphosphine ), an adjuvant ( such as benzotrizolecarboxylic acid ), a color coupler , a filler , or a combination thereof . the photopolymerizable compound containing a double bond that can be used in the present disclosure includes but is not limited to a group consisting of 1 , 4 - butanediol di ( meth ) acrylate , 1 , 6 - hexanediol di ( meth ) acrylate , neopentylglycol di ( meth ) acrylate , polyethyleneglycol di ( meth ) acrylate , neopentylglycol dipate di ( meth ) acrylate , neopentylglycol di ( meth ) acrylate hydroxypivalate , dicyclopentdienyl di ( meth ) acrylate , caprolactone modified dicyclopentdienyl di ( meth ) acrylate , allylated cyclohexyl di ( meth ) acrylate , isocyanurate di ( meth ) acrylate , trimethylol propane tri ( meth ) acrylate , dipentacrythriol tri ( meth ) acrylate , pentaerythritol tri ( meth ) acrylate , trimethyltri ( meth ) methacrylate , tris ( acryloxyethyl ) isocyanurate , dipentaerythriol penta ( meth ) acrylate , dipentaerythriol hexa ( meth ) acrylate , ethyoxyl - modified trimethylolpropane triacrylate , aliphatic urethane oligomer , and a mixture thereof . the photoinitiator that can be used in the present disclosure includes but is not limited to benzoin , benzoin alkyl ether , benzyl , ketals , acetophenones , benzophenone , 4 , 4 - dimethyl - amino - benzophenone , thioxanthones , morpholono - propanone , n - phenylglycine , imidazole dimer , and the like . the purpose of adding a polymeric binder is to enhance the film forming ability of the dry film composition . the binder that can be used in the present disclosure includes polymers such as acrylic polymers , styrenic polymers , polyurethane , polycarbonate , polyester , and epoxy vinyl resin . according to the present disclosure , the photosensitive resin layer has a thickness between about 5 μm and about 300 μm . as shown in fig1 , a laminated structure ( 10 ) of the present disclosure successively includes a supporting layer ( 1 ), a photosensitive resin layer ( 3 ) and a protective layer ( 2 ). in the embodiment that the laminated structure of the present disclosure is used as a dry film photoresist , the processing steps includes but are not limited to : peeling off the protective layer first to expose the photosensitive layer , laminating the exposed photosensitive layer to a substrate by hot - pressing roller , and then removing the supporting layer on the photosensitive resin layer . after that , a desired pattern can be transferred to the photosensitive resin layer through exposure and development , followed by etching or electroplating , and after the removal of the remaining photosensitive resin layer , a substrate having a circuit pattern can be obtained . the present disclosure will be described in terms of the following embodiments . in addition to the following embodiments , the present disclosure can be carried out in other ways without departing from the spirit of the present disclosure ; the scope of the present disclosure should not be interpreted and limited solely according to the disclosure of the specification . in addition , unless otherwise stated herein , the terms “ a / an ,” “ the ” and the like used in the specification ( especially in the appended claims ) should be understood as including both singular and plural font &# 39 ; s . additionally , for illustration , each component and region in the drawings may be drawn in an enlarged scale , but not an actual scale . the term “ about ” is used to describe the measured value including an acceptable error , depending partially on how the measurement is carried out by a person of ordinary skill in the art . a photosensitive resin composition 1 was prepared by mixing ( a ) a polymeric binder , such as 60 parts by weight of acrylic resin ( 100 % solid ) having a formulation of the following : 224 g methacrylic acid , 288 g methyl methacrylate , 104 g butyl acrylate , 120 g styrene , 64 g butyl methacrylate , and 8 g 2 , 2 ′- azobisobutyronitrile ; ( b ) a photopolymerizable compound containing a double bond , such as 20 parts by weight of ethoxyl - modified trimethylolpropane triacrylate ( photomer cognis ) and 15 . 6 parts by weight of aliphatic urethane oligomer ; ( c ) a photoinitiator , such as 0 . 1 parts by weight of n - phenylglycine ( npg , hampford ) and 3 . 6 parts by weight of imidazole dimer ( bcim , black gold ); and ( d ) a solvent such as 20 parts by weight of butanone , as shown in table 1 below . the photosensitive resin composition may additionally include malachite green as a dye ( e ). table 2 shows the properties of a protective layer using a commercial polyester film that is treated by surface pretreatment and has a low sheet resistance and the properties of a protective layer directly using a commercial polyester film or polyethylene film . a supporting layer was trimmed to a width of 40 cm and a length of 25 cm . a solution of the photosensitive resin composition 1 having a composition described in table 1 was evenly applied on the supporting layer having a thickness of 16 μm . the supporting layer was dried by a hot air convection dryer at 80 ° c . to 100 ° c . for 2 to 10 mins . a 40 μm thick photosensitive resin layer was formed on the supporting layer , and a protective layer listed in table 2 was adhered to the photosensitive resin by using a cold - pressing roller . the aforementioned sample was trimmed to a width of 30 cm and a length of 20 cm . the sample was left in an environment of 50 ° c . and 92 % relative humidity ( rh ) for 24 hours . whether the protective layer slip from the laminated structure when winding the laminated structure was observed with naked eyes . the protective layer was manually peeled off from the laminated structure , and the surface properties of the photosensitive resin layer after the protective layer was peeled off were observed . the quality of the samples was evaluated , for example , in terms of the quantity of the residual photosensitive resin composition on the protective layer , and the surface contamination on and the number of air holes in the photosensitive resin layer . slip / wrinkles : to observe with naked eyes whether the protective layer slips from the laminated structure when winding the laminated structure and whether wrinkles appeared on the surface of the photosensitive resin layer when peeling of the protective layer . slip / wrinkles was graded as follows . ◯: no slip and no wrinkles appeared on the surface of the photosensitive resin layer . δ : no slip and a few of wrinkles appeared on the surface of the photosensitive resin layer . x : slip and wrinkles appeared on the surface of the photosensitive resin layer . peeling property : to observe whether there was residual photosensitive resin composition on the protective layer after the protective layer was peeled off . the peeling property was graded as follows . ◯: no residual photosensitive resin composition on the protective layer . δ : through the observation with naked eyes , residual photosensitive resin composition on the protective layer occupied 5 % or less of the surface area of the protective layer . x : through the observation with naked eyes , residual photosensitive resin composition on the protective layer occupied more than 5 % of the surface area of the protective layer . contamination : surface contamination on the photosensitive resin layer was observed by using an optical microscope with 100 × magnification . contamination was graded as follows . number of air holes : the surface of the photosensitive resin layer was observed with an optical microscope with 100 × magnification , and the number of air holes was counted . the number of air holes was graded as follows . ◯: the number of air holes less than 20 / m 2 . δ : the number of air holes between 20 / m 2 and 300 / m 2 . x : the number of air holes greater than 300 / m 2 . in view of the properties of the protective layers of the example and comparative examples shown in table 2 and the evaluation results of surface properties shown in table 3 , the protective layer of example 1 has a sheet resistance between fix 6 × 10 9 ω /□ and 7 × 10 10 ω /□, and a maximum roughness between 1 , 800 nm and 2 , 200 nm . that is , the protective layer of example 1 meets the following characteristics of the protective layer of the present disclosure : 1 , 500 nm ≦ maximum surface roughness ≦ 2 , 500 nm , and 1 × 10 8 ω /□≦ sheet resistance ≦ 1 × 10 12 ω /□. the protective layer did not slip from the laminated structure when winding the laminated structure . when the protective layer of example 1 was peeled off from the surface of the photosensitive resin layer , no wrinkles appeared on the surface of photosensitive resin layer . there was no observation of contamination or substantial air holes on the photosensitive resin layer or residual photosensitive resin composition on the protective layer . in comparison , although the protective layer of comparative example 1 has a maximum roughness within the same range as the protective layer of example 1 , namely , a maximum roughness of between 1 , 800 nm and 2 , 200 nm , the sheet resistance thereof is between 2 × 10 14 ω /□ and 1 × 10 15 ω /□, which fails to meet the requirements for the sheet resistance of the protective layer of the present disclosure , i . e ., 1 × 10 8 ω /□≦ sheet resistance ≦ 1 × 10 12 ω /□. according to the evaluation results of the surface properties of the protective layer of comparative example 1 , although the protective layer did not slip from the laminated structure when winding the laminated structure and no wrinkles appeared on the surface of photosensitive resin layer after peeling off the protective layer , residual photosensitive resin composition ( occupying 5 % surface area of the protective layer ) was observed on the protective layer , contamination were observed on the photosensitive resin layer . on the other hand , the protective layer of comparative example 2 has a maximum roughness of between 50 nm and 100 nm , which is far lower than the maximum roughness of the protective layer of the present disclosure . the protective layer slipped from the laminated structure when winding the laminated structure and wrinkles appeared on the surface of the photosensitive resin layer after peeling off the protective layer . in addition , due to the protective layer having a sheet resistance between 2 × 10 14 ω /□ and 1 × 10 15 ω /□, residual photosensitive resin composition ( occupying more than 5 % surface area of the protective layer ) was observed with naked eyes on the protective layer and significant contamination on the photosensitive resin layer was also observed . the protective layer of comparative example 3 has a maximum roughness between 2 , 500 nm and 2 , 600 nm , and therefore , when the photosensitive resin layer was laminated to the circuit board after the protective layer was peeled off , air easily entered the interface where the circuit board was laminated to the photosensitive resin layer and formed air holes . given the above , a protective layer that meets the conditions of 1 , 500 nm ≦ maximum surface roughness ≦ 2 , 500 nm and 1 × 10 8 ω /□≦ sheet resistance ≦ 1 × 10 12 ω /□ has a low charging voltage during being peeled off , and therefore , it can be easily peeled off and electrostatic interaction upon being peeled off may be reduced . in addition , it can prevent from the slip of the protective layer relative to the laminated structure when winding the laminated structure ; or reduce the contamination on the photosensitive resin layer , the residual photosensitive resin composition on the protective layer , or the generation of wrinkles or air holes on the surface of the photosensitive resin layer after peeling of the protective layer . such excellent properties can reduce undesired effects , which come from the dry film process , appears when applying the laminated structure to a circuit board . | 2 |
with reference to fig1 through 12 , there is shown a preferred embodiment of a system and method of installation of a flow restrictor device or assembly 100 of the present invention . generally , the flow restrictor assembly contains a fitting 160 comprising a top section 110 , a bottom section 130 and an intersection 120 at which the top section 110 meets the bottom section 130 . in a preferred embodiment , the fitting 160 of the flow restrictor device 100 is formed of a metal or alloy , such as brass or copper . however , it should be understood that other metals , alloys or materials may be used as well . as shown in fig1 and 3 , the top section 110 of the flow restrictor device 100 is a cylindrically shaped portion , surrounded by an exterior screw thread 111 , which is open at the top to produce an upper edge portion 114 . the top section 110 is hollow along the inside forming a cylindrically shaped interior or cavity 112 adapted to receive a flow restrictor disk 140 and interior ring assembly 150 . the interior ring assembly 150 and flow restrictor disk 140 combine to form a flow regulator . the base of the top section 110 includes an interior ledge 113 which directly supports the interior ring assembly 150 and the flow restrictor disk 140 therein . the interior ledge 113 contains a rounded aperture 122 which continues through the intersection 120 of the flow restrictor device 100 . the bottom section 130 of the flow restrictor device 100 is substantially cylindrical in shape and meets the top section 110 at the intersection portion 120 . the base of the bottom section 130 makes up an open second end 133 of the flow restrictor device 100 whereby the open second end 133 is curved on the inside forming a rounded inside edge 135 . the exterior of the bottom section 130 is substantially curved to create an outside rounded surface 131 with the exception of at least two gripping planes 132 , 132 that are rounded on the inside edge 135 and flat on the exterior . the gripping planes 132 , 132 are preferably located opposite each other along the circumference of the open second end 133 . fig2 illustrates an exploded view of the flow restrictor assembly 100 with the flow restrictor disk 140 separated from ring 151 and ring casing 152 . the flow restrictor disk 140 comprises a perimeter with interior spaces through which water may flow at a reduced flow rate . the sizes of the spaces generally dictate the desired flow . the ring 151 and ring casing 152 come together to form the interior ring assembly 150 , wherein the ring 151 fits within the casing 152 , having a diameter that approximates that of the ring casing 152 . the relative dimensions of the casing 152 and ring 151 allow the ring 151 to be manually removed by a user if needed , but otherwise enables it to stay in place . the flow restrictor disk 140 is securely held above the ring 151 and within the ring casing 152 . in a preferred embodiment the restrictor disk 140 and ring casing 152 are formed of a resilient plastic material , while the ring , which functions like a gasket , is formed of a more flexible material . notably , it is possible to form a somewhat larger flow restrictor disk to fit snugly within the top section of the fitting 160 , without an interior ring assembly 150 . a larger disk can be utilized without the interior ring assembly 150 to restrict water flow entering from a water supply line . however , differences in water pressure may result in different flow rates . accordingly , it is desirable to utilize a regulator having a restrictor disk and an interior ring assembly which should limit water flow to a particular flow rate , regardless of differences in water pressure . fig4 and 5 show cross - sectional views of the flow restrictor fitting 160 . fig4 illustrates the fitting 160 without the flow restrictor disk 140 and interior ring assembly 150 . fig5 includes a cross - sectional view of the flow restrictor disk 140 and interior ring assembly 150 . the fitting 160 is shaped such that the flow restrictor disk 140 and interior ring assembly 150 are received by the fitting 160 and fit snugly within the cylindrically shaped interior 112 and upon the interior ledge 113 of the top section 110 . the intersection 120 contains a rounded hole 112 which is positioned below the interior ring assembly 150 and ends at the bottom section 130 creating an intersection wall 121 . when the flow restrictor assembly is in use , water passes through the spaces in the flow restrictor disk 140 , through the bottom of the interior ring assembly 150 , through rounded hole 112 and then onward eventually to the fixture . the interior ledge 113 of the top section 110 and the surrounding interior space 112 illustrated in fig4 provides continuous support for the flow restrictor disk 140 and ring assembly 150 as illustrated in fig5 . the presence of the ledge blocks movement of the assembly 150 and disk 140 in the direction of water flow . this snug fitting and corresponding dimension of the parts allow the flow restrictor 140 and ring assembly 150 to remain in place throughout use without tumbling , turning to one side or becoming dislodged , particularly when the flow of water alternates repeatedly such as when a user turns on the water , turns off the water or otherwise varies its flow . fig6 illustrates a prior art example of a showerhead arm 7 coupled with a showerhead 6 connected to a water supply line 10 . the showerhead arm 7 extends beyond a cover plate 2 that conceals an opening 5 into a cavity 4 of a shower wall 1 . inside the cavity 4 of the shower wall 1 , the showerhead arm 7 is preferably connected to an elbow 11 that attaches a water supply line 10 to the showerhead arm 7 . the elbow 11 functions as an access point to redirect the flow of water from an upward vertical direction to a horizontal direction , making the water supply available through an opening 5 in the shower wall 1 . fig7 through 11 illustrate the installation and / or removal of the flow restrictor device 100 . while the installation and removal depicted is of a showerhead , the same installation and removal process may be used for all bath fixtures , including , for example , a bathtub faucet . fig7 first shows the removal of the showerhead arm 7 coupled with a showerhead 6 from the elbow 11 that is connected to the water supply line 10 . the elbow 11 contains an internally threaded opening ( not shown ) in the horizontal direction . the showerhead arm 7 disconnects from the elbow 11 by unscrewing the external thread 8 of the second end 9 of the showerhead arm 7 from the internal thread of the elbow 11 . although it is possible to remove the cover plate 2 during installation , it does not necessarily have to be removed in order to connect or disconnect the showerhead arm 7 as the cover plate 2 has an opening that allows the showerhead arm 7 to extend beyond and pass through the shower wall 1 . this allows the second end 9 of the showerhead arm 7 to remain concealed behind the cover plate 2 when installed . fig8 shows the flow restrictor device 100 placed between the showerhead arm 7 and the elbow 11 . the external thread 111 on the top section 110 of the flow restrictor device 100 may be screwed into the internal threading of the elbow 11 . the external thread 8 of the showerhead arm 7 screws into the interior screw thread 134 of the bottom section 130 of the flow restrictor device 100 . in this manner , the flow restrictor device 100 may be installed between the showerhead arm 7 and the elbow 11 . further , once installed , the flow restrictor assembly may be concealed behind the cover plate 2 of the shower wall 1 as illustrated in fig9 . fig9 demonstrates an assembled flow restriction system including the flow restrictor device 100 and a portion of the showerhead arm 7 concealed behind the cover plate 2 of the shower wall 1 . the flow restrictor device 100 and the showerhead arm 7 are capable of being attached to the elbow without removal of the cover plate 2 as the flow restrictor assembly 100 and showerhead arm 7 are extendable through an opening 5 of the shower wall 1 . fig1 illustrates the removal of the showerhead arm 7 from the flow restrictor device 100 , leaving the flow restrictor device 100 screwed into the elbow 11 of the water supply line 10 . the flow restrictor device 100 remains behind the shower wall 1 and can only be accessed with a specialized tool 12 that can extend beyond the shower wall 1 through an opening 5 as demonstrated in fig1 . to remove the flow restrictor device 100 , a specialized tool 12 , shown in fig1 , is provided to engage gripping planes 132 on the outside surface 131 , which are hidden behind the shower wall 1 . once the gripping planes 132 are engaged with the tool 12 , the flow restrictor device 100 may be unscrewed from the elbow 11 . significantly , since the intersection wall 121 of the fitting 160 partially conceals and hinders physical access to the flow restrictor disk 140 and interior ring assembly 150 , it is difficult for a user to even notice the flow restrictor disk 140 without first removing the entire flow restrictor assembly 100 . without noticing the presence of the restrictor disk 140 , a user will likely not even attempt to engage in its removal . by the same token even after noticing the presence of a restrictor disk 140 , a user may not attempt to engage in its removal after recognizing that it will be a difficult process . it should be understood that the rough opening 5 in the shower wall 1 has minimal clearance due to a plurality of tiles 4 with grout filling that often surround the opening 5 . thus , the opening 5 would be somewhat irregular as determined by the trimming skill of the tiler and would require a specific tool 12 to engage the gripping planes 132 . the arrangement of the system shown in fig9 , and the process of removal of the flow restrictor device 100 demonstrated in fig1 and 11 illustrates one way in which a user is prevented from removing the flow restrictor device 100 . a user may desire to remove the flow restrictor device 100 , and perhaps a user may even attempt to employ the use of pliers or the like in an effort to remove the flow restrictor device 100 . however , because the flow restrictor device 100 is hidden behind the shower wall 1 , and the opening 5 has minimal clearance , there is typically not enough space to allow a pair or pliers or the like to pass in order to grip the gripping planes 132 . instead , as fig1 illustrates , a specialized tool 12 in the form of a cylindrically - shaped tube with flattened end portions to engage the gripping planes 132 , is needed in order to pass through the minimal clearance provided by the opening 5 and grip the gripping planes 132 . it should be understood that other similar tools may be formed or utilized with the same goal and to accomplish the same function as provided by specialized tool 12 . fig1 illustrates an example of a full bath fixture system including a showerhead 6 coupled with a showerhead arm 7 as well as a bathtub faucet 13 coupled with a faucet arm 14 . both the showerhead arm 7 and faucet arm 14 are each attached to a flow restrictor device 100 , resulting in reduced water flow from the water supply line 10 that is connected to the both the bathtub faucet 13 and the showerhead 6 . it should be understood that different flow restrictor disks may be used to allow for different flow rates as desired . for example , a flow restrictor disk allowing a flow rate of 2 . 5 gpm may be used in connection with water leaving out of the bathtub fixture while , at the same time , using a flow restrictor disk allowing a flow rate of 1 . 8 gpm for water leaving out of the showerhead fixture . the accompanying drawings only illustrate a flow restrictor assembly , its constituent parts , and method of use . however , other types and styles are possible , and the drawings are not intended to be limiting in that regard . thus , although the description above and accompanying drawings contains much specificity , the details provided should not be construed as limiting the scope of the embodiment ( s ) but merely as providing illustrations of some of the presently preferred embodiment ( s ). the drawings and the description are not to be taken as restrictive on the scope of the embodiment ( s ) and are understood as broad and general teachings in accordance with the present invention . while the present embodiment ( s ) of the invention have been described using specific terms , such description is for present illustrative purposes only , and it is to be understood that modifications and variations to such embodiments , including but not limited to the substitutions of equivalent features , materials , or parts , and the reversal of various features thereof , may be practiced by those of ordinary skill in the art without departing from the spirit and scope of the invention . it should also be noted that the terms “ first ,” “ second ” and similar terms may be used herein to modify various elements . these modifiers do not imply a spatial , sequential , or hierarchical order to the modified elements unless specifically stated . | 8 |
in the figures , as well as in the description , the same reference numerals are used , in order to designate the same or similar component parts or elements . by reference to fig1 an existing plastic component part of an internal combustion engine with an integrated seal according to a specific embodiment of the invention is explained by example . the displayed component part frame of fig1 could concretely be a lid , a cylinder head gasket , an oil pan or the like . the integrated seal equipped component part is designated in general as 100 in the figures , while the injection molded seal , which in this embodiment is set out by example as a double - lipped seal , is designated as 200 in the figures . the sealing profiled element of the double - lip seal is named as 210 in the figures . of course , sealing profile elements with a seal lip or several seal lips are possible . the component part 100 , that is exemplicative of the lid , the cylinder head gasket , the oil pan , etc . is prepared as described above from plastic , preferably made out of polyamide . elastomers are used as sealing substances , especially preferred are selected organic elastomers but no conventional inorganic elastomers such as , for example , silicone are used . from the domain of the organic elastomers , above all , rubbers such as , for example , fluorinated rubber ( fpm ), acrylate - rubber , polyacrylate - acrylic resin , polyacrylate ( acm ) ethylene acrylate ( aem ) are used . for the injection process , among other things , the viscosity of the useful organic elastomers and particularly the mooney - viscosity , that is , a measure of the sheer viscosity , is to be considered . according to material choice and shore a hardness the mooney - viscosity ml ( 1 + 4 ) of the organic elastomers , measured at 100 ° c ., cost - effectively should lie in a range from about 20 to 100 . in order for a chemical bonding between the existing plastic component parts and the injected seal made from aem or acm to be ensured , the mooney - viscosity ( ml ( 1 + 4 ) at 100 ° c .) with this choice of materials should be in the range of about 25 to 50 . the bonding of the plastic component parts and seal made from elastomer can result through direct adhesion joining together of the materials or with the aid of an additionally supplied adhesive . alternatively , the plastic of the component part and / or the elastomer can be modified , in order to enable the adhesion , in the form for example , of a chemical bond . moreover , for a chemical bond between component part and injection - molded seal , preferably a suitable crosslinking system of the elastomers is to be chosen , which enters into chemically compatible and suitable chemical bonding . for an existing polyamide component part the crosslinking system would be designed on the basis of hexamethylene diamine carbamate and n , n ′- di - ortho - tolylguanidine , in order to insure the chemical bonding of the polyamide with the elastomer . a good chemical bond between the plastic component part and the injection - molded seal is additionally guaranteed preferably by preheating of the component part . conveniently , the component part i heated to a temperature in the range of about 100 ° c . to 150 ° c . before the injection of the seal , that is , before the injection process . in conclusion , it is to be noted that the combination of plastic of the component part and elastomer of the seal , is provided for integration with the component part , the requirements of the use environment having to be satisfied . that is , the requirements among others , are determined for the selection of the material and / or elastomers . in particular , temperature demands , creep effects of the material ( component part materials , seal - materials ) and stiffness are to be taken into consideration . also to be considered is the combined effect of the component part with the other component part , against which the sealing should take place or against whose surface the sealing should occur . particularly of interest in this connection are variable physical properties of the materials used for the component parts in this connection . therefore , the existing - plastic , integrated seal - equipped component part seals against a component part manufactured from metal , whereby the physical properties particularly in respect to the temperature - contingent varying expansion - properties and varying rigidity properties , are to be taken into consideration . in combination with the above - described chemical bonding of the injection - molded seal based upon an organic elastomer to the component part made from plastic , an advantageous novel geometry of the component part with integrated seal is proposed within the scope of the present invention . the novel geometry concerns the flange area of the component part , in which the integrated seal is arranged . by reference to fig1 in the perspective sectional view , a cross - sectional surface 120 of the component part is shown . the flange area of the component part is formed with a generally l - shaped projection towards periphery , i . e . the flange surface is generally l - shaped . the projection is characterized in general as 130 in the figures . the flange area has a lower flange surface , also designated in the following as a sealing profile element , which in the assembled state of the component part is directed in line to a seal opposite surface of an opposite or counter component part ( not shown ) and an upper flange surface which is arranged parallel to the lower surface and is directed in the assembled state path of seal opposite surface of the opposite or counter component part . the seal is wrapped around the flange surface . this means that the seal , whose seal element profile is arranged out of the seal element profile surface , laterally encompasses towards periphery the l - shaped protrusion of the flange surface , so that a lateral flange surface of the l - shaped protrusion of the surface area of the seal is covered , and is arranged at least partially overlapping the upper flange surface of the l - shaped protrusion of the surface area . on the upper flange surface a sealing - off edge 300 is provided , up to which the elastomer - material of the seal is led and with which the seal preferably terminates flatly upwards there . furthermore , the seal also displays a sealing edge 310 , on which the arranged sealing element profile runs . that the seal laterally encompasses the flange area also has the advantage , that the seal or , respectively , the seal element profile can be arranged more in line to the lateral edge of the component part , so that the flange area can be better utilized . this is not the case , if the seal had been completely arranged on the sealing element profile surface or , respectively , on the lower flange surface and had been imprinted there accordingly on both sides . in the proposed geometry of the invention , the seal is only one - sided , and the lateral opposite edge is imprinted . the tool or the pointed tool for the deployment of the injected seal with the above - described seal geometry is provided with imprinted areas in correspondence with the sealing - off edge 300 on the upper flange surface and a sealing edge 310 on the lower flange surface or , respectively , the sealing element profile surface . in the imprint areas the tool seals off during the injection processes against the component part , so the seal geometry explained above , which provides an encirclement of the surface area , is obtained . for the mechanical reinforcement of plastic component parts , as they are discussed here , often additional reinforcement ribs 110 or other reinforcement structures of equal function are inserted , in order to strengthen the flange area of the component part , and to ensure and / or to improve the sealing effect of the seal . exemplarily , a reinforcement rib 110 is illustrated in fig1 . the encompassing or encircling seal encompasses the flange or encircles the reinforcement rib 110 , which also is encircled by a sealing - off edge 305 , which stands in connection with sealing - off edge 300 . the above - explained tool or pointed tool is adjusted in correspondence with the course of the sealing - off edges 300 and 305 , in order to enable the above explained encirclement of the reinforcement ribs 110 , or respectively , the reinforcement structures by means of the seal geometry . fig2 shows a second schematic perspective sectional view of the component part corresponding to the specific embodiment illustrated in fig1 . the sectional view displayed in fig2 shows in essence a top view on the upper flange surface and a specified screw point 150 in the component part to this assembly . for exemplary illustration the component part with three reinforcement ribs 110 is provided , which shows in each case a sealing - off edge ( 305 ) adjusted to the geometry of the reinforcement ribs 110 and is encompassed by the seal as described above . the screwing point 150 shows exemplarily a possibility , to provide an eye area or an implementation , by means of which the component part can be fastened to the counter component part . advantageously , the screwing point 150 serves for the leading through of a screw which is screwed into the counter component part , in order for the component part with the sealing element profile of the seal to be fixed against the counter component part . for the fixation , a predetermined jacking force is usually set . for mechanical stabilization and / or reinforcement , such a screwing point 150 can be provided with a reinforcement 140 such as , for example , a hollow shaft , which preferably can be manufactured from a plastic or metal material . such grommets or screwing points 150 are advantageously arranged substantially in the flange area , so that the predetermined jacking force , which is created by the fixation of the component part by means of the screwing points 150 , directly acts as much as possible on the seal or the sealing element profile . in addition , with implementations of this kind ( or , respectively , screwing points 150 ) decoupling elements for acoustic decoupling of the component part of the counter component part and / or separator can be provided . the decoupling elements or , respectively , the separator thereby can be injected together with the seal or be formed from one other material with contingent differing shore a hardness . the decoupling element or , respectively , the separator can subsequently also be provided integrated . in conclusion , fig3 shows a third schematic perspective sectional view of the component part corresponding to the specific embodiment illustrated in fig1 or 2 . the sectional view displayed in fig3 shows in essence a top view on the sealing element profile , i . e . the lower flange surface , and the screwing point 150 with hollow shaft 140 . in the perspective sectional view of fig3 the double - lipped profile of the seal is clearly recognizable . the seal is led around in the area of the screwing point 150 around the screwing point 150 with hollow shaft 140 . with sufficient space the seal is conducted around as seal lips . however , alternatively it is also possible , at points of constriction , particularly in the area of screwing points , such as the screwing point 150 to bring together the sealing element profile in the form of double lips , so that at least area - wise the sealing element profile is implemented as single lip . equivalents are also certainly valid for multi - lipped embodiments of the sealing element profile , which can be brought together to double - lips at constriction points in reduced number . advantageously , the flange surface is provided with additional pathway 220 . such pathways can be filled , for example , during the injection process for the combination of the seal with the elastomer , so that an immediate coupling of the applied seal on the upper flange surface and the applied seal on the lower flange surface is obtained , which effects a stabilization of the seal geometry supplementary to the bonding of seal and component part . alternatively , a mechanical fixation of the seal in the above - described action can also be obtained by means of an additional fixation element , which intervenes in the pathway 220 or takes vigorous action through the pathway 220 . | 5 |
the first configuration of polarization - controlled encoder in quantum key distribution system is shown in fig1 . it includes two 2 × 2 - 3 db polarization - maintained beam splitters 3 and 6 , one polarization - maintained phase modulator 5 and one polarization - maintained delay line 4 . these form a mach - zehnder interferometer . any one of the two ports 1 and 2 which are in the same side of 3 db beam splitter 3 can be the input port of polarization - controlled encoder . any one of the two ports 7 and 8 which are in the same side of 3 db beam splitter 6 can be the output port . the modulator 5 and delay line 4 ( no sequencing ) can be inserted into one arm of the mach - zehnder interferometer or two arms separately . when the system works , an optical pulse is injected into port 1 or 2 of beam splitter 3 and divided into two pulses . one pulse passes through the modulator 5 . another one pass through the delay line 4 . then they are recombined by beam splitter 6 and output from port 7 or 8 . because all the paths are polarization - maintained , the output pulses have same polarization state . when the modulator 5 and delay line 4 are in the same arm of mach - zehnder interferometer , the result is the same . the second configuration of polarization - controlled encoder in quantum key distribution system is shown in fig2 . it includes one 2 × 2 - 3 db polarization - maintained beam splitter 11 , two mirrors 13 and 15 , one polarization - maintained phase modulator 12 and one polarization - maintained delay line 14 . these two ports 9 and 10 which are in the same side of 3 db beam splitter 11 are input and output ports of polarization - controlled encoder respectively . one of the two ports which are in the other side of 3 db beam splitter 11 connects with polarization - maintained phase modulator 12 and mirror 13 in turn . the other port connects with polarization - maintained delay line 14 and mirror 15 in turn . a variation of above configuration is to connect one port of beam splitter with modulator 12 , delay line 14 and mirror in turn , and connect the other port of beam splitter with only a mirror . when the system works , an optical pulse is injected into port 9 of polarization - maintained beam splitter 11 and divided into two pulses . one pulse pass through the delay line 14 and reflected back by mirror 15 . the other pulse pass through the modulator 12 and reflected back by mirror 13 . then they are recombined by beam splitter 11 and output from port 10 . because all the paths are polarization - maintained , the output pulses have same polarization state . the variation of above configuration has same result . either port 9 is input and port 10 is output or reverse have same result . the third configuration of polarization - controlled encoder in quantum key distribution system is shown in fig3 . it includes one 2 × 2 - 3 db beam splitter 18 , two 90 degree faraday mirrors 20 and 22 , one phase modulator 19 and one delay line 21 . the two ports 16 and 17 which are in the same side of 3 db beam splitter 18 are input and output ports of polarization - controlled encoder respectively . one of the two ports which are in the other side of 3 db beam splitter 18 connects with phase modulator 19 and 90 degree faraday mirror 20 in turn . the other port connects with delay line 21 and 90 degree faraday mirror 22 in turn . when the system works , an optical pulse is injected into port 16 of beam splitter 18 and divided into two pulses . one pulse pass through the delay line 21 and reflected back by 90 degree faraday mirror 22 . the other pulse pass through the modulator 19 and reflected back by 90 degree faraday mirror 20 . then they are recombined by beam splitter 18 and output from port 17 . because the two pulses are reflected by 90 degree faraday mirrors and pass through their own path even times , the output pulses have same polarization state . either port 17 is input and port 16 is output or reverse has same result . the configuration of a variation of the third embodiment is shown in fig4 . the difference from the third embodiment is one port of beam splitter connects with modulator 19 , delay line 21 ( position of them can be exchanged ) and 90 degree faraday mirror 22 in turn , and the other port of beam splitter connects with a 90 degree faraday mirror 20 . when the system works , an optical pulse is injected into port 16 of beam splitter 18 and divided into two pulses . one pulse pass through the phase modulator 19 and delay line 21 ( no sequencing ) and reflected back by 90 degree faraday mirror 22 . the other pulse reflected back by 90 degree faraday mirror 20 . then they are recombined by beam splitter 18 and output from port 17 . because the two pulses are reflected by 90 degree faraday mirrors and pass through their own path even times , the output pulses have same polarization state . either port 17 is input and port 16 is output or reverse has same result . the fourth configuration of polarization - controlled encoder in quantum key distribution system is shown in fig6 . it includes one 2 × 2 polarization - maintained variable beam splitter 25 , two mirrors 23 and 27 , one polarization - maintained phase modulator 24 and one polarization - maintained delay line 26 . one of the two ports which are in the same side of variable beam splitter 25 is output port 28 of polarization - controlled encoder , and the other port connects with delay line 26 and mirror 27 in turn . one of the two ports which are in the other side of variable beam splitter 25 is input port 29 of polarization - controlled encoder , and the other port connects with polarization - maintained phase modulator 24 and mirror 23 in turn . a variation of above configuration is to connect one port of beam splitter with delay line 26 and modulator 24 ( no sequencing ) in turn , and connect the other port of beam splitter with only a mirror . when the system works , an optical pulse is injected into port 29 of polarization - maintained variable beam splitter 25 and divided into two pulses . one pulse exits directly from port 28 of polarization - maintained variable beam splitter 25 . the other pulse pass through the delay line 26 and reflected back by mirror 27 , and then pass through beam splitter 25 again and continue passing through modulator 24 and reflected by mirror 23 , and then pass through the beam splitter 25 at third time and output from port 28 . when splitting the optical pulse , the splitting ratio of variable beam splitter is regulated to make the two pulses exit from port 28 have equal amplitude . because all the paths are polarization - maintained , the output pulses have same polarization state . the variation of above configuration has same result . either port 28 is input and port 29 is output or reverse has same result . the fifth configuration of polarization - controlled encoder in quantum key distribution system is shown in fig7 . it includes one 2 × 2 variable beam splitter 32 , two 90 degree faraday mirrors 30 and 34 , one phase modulator 31 and one delay line 33 . one of the two ports which are in the same side of variable beam splitter 32 is output port 35 of polarization - controlled encoder , and the other port connects with delay line 33 and 90 degree faraday mirror 34 in turn . one of the two ports which are in the other side of variable beam splitter 32 is input port 36 of polarization - controlled encoder , and the other port connects with phase modulator 31 and 90 degree faraday mirror 30 in turn . a variation of above configuration is to connect one port of beam splitter with delay line 33 and modulator 31 ( no sequencing ) in turn , and connect the other port of beam splitter with only a 90 degree faraday mirror . when the system works , an optical pulse is injected into port 36 of variable beam splitter 32 and divided into two pulses . one pulse outputs directly from port 35 of variable beam splitter 32 . the other pulse pass through the delay line 33 and reflected back by 90 degree faraday mirror 34 , and then passes through beam splitter 32 again and continue passing through modulator 31 and reflected by 90 degree faraday mirror 30 , and then passes through the beam splitter 32 at third time and exits from port 35 . when splitting the optical pulse , the splitting ratio of variable beam splitter is regulated to make the two pulses output from port 35 have equal amplitude . because the two pulses are reflected by 90 degree faraday mirrors and pass through their own path even times , the output pulses have same polarization state . the variation of above configuration has same result . either port 35 is input and port 36 is output or reverse have same result . in above five configurations of polarization - controlled encoder , the phase modulator can be moved to output path to get the same result . for example , a polarization - controlled encoder with phase modulator in output path is shown in fig5 . it includes one 2 × 2 - 3 db beam splitter 18 , two 90 degree faraday mirrors 20 and 22 , one phase modulator 19 and one delay line 21 . port 16 of the two ports which are in the same side of 3 db beam splitter 18 is input port of polarization - controlled encoder , and the other port connects with modulator 19 as output port 17 of encoder . one of the two ports which are in the other side of 3 db beam splitter 18 connects with 90 degree faraday mirror 20 , and the other port connects with delay line 21 and 90 degree faraday mirror 22 in turn . when the encoder is used in receiver , the modulator which is located in output path must be moved to input path . for example , modulator 19 in encoder 49 - 5 must connect with port 16 instead of port 17 . when the system works , an optical pulse is injected into port 16 of beam splitter 18 and divided into two pulses . one pulse pass through the delay line 21 and reflected back by 90 degree faraday mirror 22 . the other pulse is reflected back by 90 degree faraday mirror 20 . then they are recombined by beam splitter 18 , pass through modulator 19 and exit from port 17 . because these two pulses are reflected by 90 degree faraday mirrors and pass through their own path even times , the output pulses have same polarization state . when this encoder is used in receiver , the modulator 19 which is located in output path must be moved to input path . either in output path of transmitter or input path of receiver , the modulator need not be polarization - maintained . the return photon separating and detecting unit in the quantum key distribution system is made up of optical circulator 38 and single photon detector 37 . the input port 39 of optical circulator is the input port of return photon separating and detecting unit . the output port 40 of optical circulator is the output port of return photon separating and detecting unit . the return photon injected into port 40 will be separated by circulator 38 and detected by single photon detector 37 . the configuration of the unit is shown in fig8 . when the system works , photons injected into port 39 of circulator pass through the circulator directly and exit from port 40 . if there are photons injected into port 40 , they will be prevented from exiting from port 39 but guided to single photon detector 37 by circulator 38 in order to detect whether there are spy photons or not . when this unit is used in receiver , single photon detector 37 could detect signal photon to get useful key information . since optical circulator and single photon detector have limited response spectrum , there may be photons whose wavelength is out of response spectrum enter the polarization - controlled encoder . a variation of the return photon separating and detecting unit is shown in fig9 . the difference from the above one is that an optical band pass filter 41 is added after input port 39 . when the system works , photons in response spectrum pass through the optical band pass filter freely , but other photons are blocked . this will improve the system &# 39 ; s ability of resisting eavesdropping . a quantum key distribution system including the polarization - controlled encoders , return photon separating and detecting unit , single photon detectors and optical pulse source is shown in fig1 . the transmitter is made up of single photon source 42 ( it can be replaced by simulative single photon source which is made up of laser and attenuator ), polarization - controlled encoder 43 and return photon separating and detecting unit 44 . the input port of encoder 43 ( it can be encoder 49 - 1 , 49 - 2 , 49 - 3 , 49 - 6 , 49 - 7 or any variation of them ) connects with the output port of single photon source 42 . the output port of encoder 43 connects with the input port of return photon separating and detecting unit 44 ( it can be return photon separating and detecting unit 50 - 1 or 50 - 2 ). the output port of unit 44 connects with quantum channel 45 . the receiver is made up of polarization - controlled encoder 47 ( it can be encoder 49 - 1 , 49 - 2 , 49 - 3 , 49 - 6 , 49 - 7 or any variation of them , wherein 49 - 3 or 49 - 7 is better ), return photon separating and detecting unit 46 ( it can be return photon separating and detecting unit 50 - 1 or 50 - 2 ) and single photon detector 48 . quantum channel 45 connects with the input port of unit 46 . the output port of unit 46 connects with the input port of encoder 47 . the output port of encoder 47 connects with single photon detector 48 . the process of quantum key distribution will be described hereinafter . one single photon pulse ( it can be obtained by attenuating high power laser to at most one photon per pulse in fact ) which is emitted from single photon source 42 enters polarization - controlled encoder 43 , and then divided into two pulses and delayed . one of these two pulses is modulated according to quantum key distribution protocol . the output two pulses pass through return photon separating and detecting unit 44 , and then enter quantum channel 45 to be transmitted to the receiver . when arrived at receiver , these two pulses pass through return photon separating and detecting unit 46 and enter polarization - controlled encoder 47 . after that , each pulse is divided into two pulses again and delayed . then these pulses are modulated according to quantum key distribution protocol and interfere . one of output interfering pulses is sent to single photon detector 48 to be measured ( in order to reduce the dark count and disturbance from un - interfering pulses , the detector should work at gate mode , and the control signal of gate could be obtained from classical signal which is sent by transmitter ), and the other passes through the return photon separating and detecting unit and be measured . according to the result of measurement and record of modulation , transmitter and receiver will get one bit of key . repeat above steps , they will get any bit of keys with unconditional security . because there are polarization - maintained paths and 90 degree faraday mirrors in polarization - controlled encoder , two output pulses have same polarization state . that makes the system has good ability of anti - jamming . when the input and output ports are the same in transmitter and receiver , circulator and y beam splitter should be added to separate input and output signal . when the encoders in transmitter and receiver are 49 - 6 or 49 - 7 , splitting ratio of beam splitter should be regulated to make two output pulses have equal amplitude . this will reduce the error rate of final keys . | 7 |
refer to fig2 a illustrating devices 232 that send data to a node array 222 of a data vortex ™ switch 234 through synchronization units 230 . devices 232 may be input output / devices 104 as illustrated in fig1 a or computing or data storage devices 170 as illustrated in fig1 b . the devices d 0 , d 1 , . . . , dn - 1 need not be synchronized with each other , and therefore , data packets arriving at synchronizing units su 0 , su 1 , . . . , sun - 1 arrive at various times . the data vortex ™ switch receives data packets of fixed length pl with the leading bit of each packet always set to one . there are fixed packet - receiving times , and thus , the data vortex ™ node array 222 of the data vortex ™ switch 234 must receive the first bit of data packets only at one of the packet receiving times . it is the function of the synchronization units to deliver the first bit of the data packets to the data receiving nodes of the data vortex ™ switch at data packet receiving times . in a preferred embodiment , the synchronization units and the data vortex ™ switch are on the same chip , and therefore , utilize the same chip clock . in the preferred embodiment , the number of synchronization units is equal to the number of nodes in the receiving node array , and each synchronization unit is associated with one node of the receiving node array . refer to fig2 b that illustrates a synchronization unit su 230 , which receives data through an input line 226 and transmits data to a node 220 of a receiving node array na 222 of a data vortex ™ switch . fig2 c illustrates details of a node array with input and output lines from the nodes . the synchronization unit 230 is an important aspect of the current invention . data packets sequentially enter the synchronization unit through line 226 , are processed by an optional error correction unit ec 260 , and then enter node 202 . in a first embodiment , the error correction unit detects and corrects errors in the entire packet ; in a second embodiment the error correction unit detects and corrects errors only in the data vortex ™ output port address ; in a third embodiment , there is no error correction unit . a re - sequencing unit in su 230 is composed of one - bit delay units that together make up a shift register . switches at select delay units ( not shown ) determine how many of the delay units a given message packet passes through . in this way , the number of delay units that a message packet bit passes through is variable , and hence , the amount of time spent in the shift register is variable . the first bit of a data packet ( always set to one ) enters delay unit 202 . responsive to the presence of this bit , a signal is sent to logic unit l 214 indicating that a new packet has entered the system . there is a minimum amount of time ( clock ticks ) that is required for a bit to pass through the variable - length shift register from the entry node 222 to the data vortex ™ receiving node 220 . this minimum time ( minimum number of ticks ), tmin , is achieved when each of the switching elements of the shift register pass data through a bypass line 250 rather than pass through a straight - through line 240 . the logic element l 214 is sent a clocking signal from the chip clock 224 via line 252 and uses this signal to calculate the number of ticks nt such that if a packet arriving at delay unit 202 passes through nt + tmin shift register elements ( one - bit delay units ), then the first bit of the packet will arrive at node 220 at a proper data packet arrival time for the switch . the logic unit is able to send the data through the correct number of shift register elements by sending the proper signals to set the switching elements 204 . fig7 illustrates a variable length fifo that is similar in design to the synchronization unit su 230 illustrated in fig2 b . the fifo illustrated in fig7 can also be employed advantageously as the fifo delay units in a circular data vortex ™ switch 234 , as illustrated in fig2 a . by doing so , a chip containing one or more data vortex ™ switches can be configured to support one of a plurality of packets sizes , which can be set as a design parameter for a particular device application . refer to figure fig2 d , which illustrates a variation of the synchronization unit 230 depicted in fig2 a . the synchronization unit 230 in this new embodiment contains one additional binary switch 238 not in the embodiment of fig2 a . the purpose of switch 238 is to allow data packets entering the synchronization unit to be synchronized for entry into a circular data vortex ™ switch at one of two data - receiving nodes , node 220 in node array 222 or node 246 in node array 244 . for example , suppose that node 220 is the node at which a data packet is injected at the beginning of a data - sending cycle and that node 246 is the node at which a data packet entering node 220 would progress to midway through the data - sending cycle , provided that the packet stayed on the entry - level ring of the data vortex ™ switch . then the logic element l 214 would examine two situations when a packet m arrives on line 226 : 1 ) the packet m could be synchronized to enter node 220 at the beginning of the next data - sending cycle or 2 ) m could be synchronized to enter node 246 at the midpoint of either the current or the next data - sending cycle . note that either method of injecting m into the data vortex ™ switch would synchronize m within the switch . the logic l chooses the method that results in injecting m into the switch at the earliest clock time and sets the binary switch 238 accordingly . refer to fig2 a , fig2 b , and fig2 e . the system illustrated by fig2 a and fig2 b assumes that if a control signal is sent on line 236 to a device dk to inform dk not to inject a packet into the switch 228 during the next data - sending cycle , then dk will receive the control signal in time to prevent sending the next packet . however , if the device dk does not receive the control signal in time to honor it in the next sending cycle ( e . g ., due to a high system clock speed or the distance of dk from the switch ), dk may send one or more packets into switch 228 before receiving the control signal request . fig2 e illustrates the addition of fifo buffers 244 to each of the synchronization units 230 of fig2 b that are used to hold packets sent by a device 232 when a control signal on line 236 indicates that a packet cannot immediately enter the switch . when the data vortex ™ switch 234 sends a control signal on line 236 to a device dk , a copy of this signal is also sent to logic unit l 214 of the corresponding synchronization unit suk . thus , if dk sends one or more packets to suk before receiving a control signal , dk and l can use counters vk and vl respectively to keep track of how many such packets have been sent . when l detects the arrival of a packet on line 212 that can not be immediately inserted into the node array 222 , it increments vl by one and instructs node 242 via line 216 to store that packet in one of the fifo buffers 244 . device dk also increments vk by one each time it determines that it has sent a packet during a sending cycle in which the control signal on line 236 was active . for each packet sent by dk while the control signal is active , dk refrains from sending a packet at a future packet injection time and then decrements vk by one . knowing the scheme used by dk , the logic unit l uses a released injection time to instruct node 242 to inject the oldest packet in the fifo buffers into the switch and then decrements vl by one . in this way , the buffers 244 are never overloaded . by using this scheme , a packet sent by a device while the control signal is active is processed by the switch during the same cycle that it would have been if device dk had received the control signal in time to delay sending the packet , i . e ., the packet is buffered in the synchronization unit instead of in the device dk . in other embodiments , the data can be injected either at the leftmost insertion point or at another insertion point distinct from the midway point . there are two types of shift register nodes in the synchronization unit : the first type is an active node that has two output ports , e . g ., nodes 242 , 204 , 206 , and 208 ; and the second type is a passive node that contains only one output port . the logic unit l sends signals through lines 216 to set the active nodes to switch to straight - through lines 240 or to switch to bypass lines 250 . the active nodes maintain the same setting until the entire packet has passed through . the logic unit sets the active nodes in such a way that the first bit of an entering data packet arrives at node 220 at a data packet insert time . the logic unit l requires a number of ticks (“ think time ”) to calculate the value of nt . there are a sufficient number of shift register elements between node 202 and node 242 for the logic l to make the necessary calculation and to set the active elements of the shift register . there are x active node elements labeled ex - 1 , ex - 2 , . . . , e 2 , e 1 , e 0 . in fig2 b , node 242 is ex - 1 , node 204 is e 2 , node 206 is node e 1 , and node 208 is node e 0 . there are 2j - 1 passive elements between active elements ej and ej - 1 . the integer j is chosen so that ( 2j - 1 )& gt ; pl . the calculation to set the active elements is based on the binary representation of nt . given that the binary representation of nt is of the form bx - 1 , bx - 2 , . . . , b 2 , b 1 , b 0 , then an active node ej is set to send the data packet through a bypass line 250 if bj = 0 and via a straight - through line 240 if bj = 1 . for example , node e 0 208 is set to send the packet through a bypass line 250 if b 0 = 0 and via a straight - through line 240 if b 0 = 1 ; node e 1 206 is set to send the packet through a bypass line 250 if b 1 = 0 and via a straight - through line 240 if b 1 = 1 ; node e 2 208 is set to send the data through a bypass line 250 if b 2 = 0 and via a straight through line 240 if b 2 = 1 ; and finally node ex - 1 242 is set to send the data through a bypass line 250 if bx - 1 = 0 and via a straight through line 240 if bx - 1 = 1 . in this manner , the data is sent through {( 2x - 1 )·( bx - 1 )+( 2x - 2 )·( bx - 2 )+ . . . +( 22 )· b 2 +( 21 )· b 1 +( 20 )· b 0 }= nt passive nodes lying between the node 242 and the node 210 . the synchronizing previously described in this disclosure is performed on the chip that contains the data vortex ™ and is an on - chip synchronization that guarantees that the first bit of a packet or packet segment enters the data vortex ™ at the correct packet entry time . in the systems treated in this section , there is also synchronization between multiple chips that is enforced by a global clock . this clock assures that data - switch chips in a stack of data - switch chips ( fig1 a 130 and fig1 b 185 ) are nearly in synch , and thus , packets segments entering such a stack are nearly in synch . this synchronization enables the scheduling of packets at given packet insertion times . an important aspect of the present invention is that the global system synchronization need not be as accurate as the on chip synchronization . refer to fig . 1 a that illustrates input / output devices 102 that send data through a plurality of data switches 126 and fig1 b that illustrates computational and data storage devices dk 170 that send data through a stack of data switches 185 . data in the form of messages are placed into a plurality of packets p 0 , p 1 , . . . , pu , and each packet pj is decomposed into a number of packet segments psj , 0 , psj , 1 , . . . , psj , v - 1 . the packet segments may also contain error correction bits . the packet segments are sent in parallel through v controlled data switches cs 0 , cs 1 , . . . , csv - 1 ( illustrated in fig3 a ). the packet segments psj , 0 , psj , 1 , . . . , psj , v - 1 belong to sending group j , with psj , m passing through csm . refer to fig3 a indicating a device dk connected to the v buffer units buk , 0 , buk , 1 , . . . , buk , v - 1 . dk sends the packet segments psj , 0 , psj , 1 , . . . , psj , v - 1 at the same time , with psj , m being sent to buffer buk , m . buk , m subsequently forwards the packet segment psj , m to controlled switch csm . csm also receives packet segments from devices d 0 , d 1 , . . . , dk - 1 and from devices dk + 1 , dk + 2 , . . . , dv - 1 . because the device dk may be far removed from the buffers buk , 0 , buk , 1 , . . . , buk , v - 1 , data packet segments that are sent simultaneously to buffers may not arrive at the buffers at exactly the same time . moreover , packets sent simultaneously to a given controlled switch may not arrive at the controlled switch exactly at the same time . however , in systems that use scheduled injection times , it is important for the proper operation of the controlled switch that packets from different devices that are scheduled to go through the controlled switch simultaneously do in fact enter the switch node array at the same time . one aspect of the present invention is to guarantee that all of the packets scheduled to go through the controlled switches in the same group are guaranteed to go through the controlled switches together , even though their arrival at the switching system may be slightly skewed in time . refer to fig3 b illustrating the data paths from dk to the controlled switch csm . the devices d 0 , d 1 , . . . , dn - 1 schedule data to go through the v controlled switches . in each approximate message arrival time j , a plurality of devices target message packet segments to arrive at the stack of controlled switches . the message packet segments that are scheduled to arrive at the controlled switches at approximate arrival time j are referred to as message packet segments in group j . referring again to fig3 b , the device dk sends a group j of packet segments destined for csm through interconnects 226 in a tree structure to buk , m sub - buffer gj . the sub - buffer gj is further divided into smaller buffers . in fig3 b , gj is subdivided into four buffers 308 , 310 , 312 , and 314 . in other embodiments gj may be divided into more than four or less than four buffers . sub - buffer 308 is first filled , then sub - buffer 310 , followed by sub - buffer 312 , and finally by sub - buffer 314 . refer to fig3 c in which the gj is subdivided into s sub - buffers labeled sb 0 , sb 1 , . . . , sbs - 1 . the sub - buffers are filled in order by filling sb 0 308 , then sb 1 310 , the sb 2 312 , and so forth , so that sbs - 1 316 is filled last . when the group j packet segments are sent from gj to csm , the data is sent in the order received , with data in sb 0 sent first , followed by the data in sb 1 , and so forth , until the data in sbs - 1 is sent . the data vortex ™ switch on chip csm must receive all of the group j packet segments at the same time . there is a time interval [ a , b ] such that packet segments arriving at the synchronization units in the time interval [ a , b ] will be aligned to enter the data vortex ™ switch at group j insertion time . there are positive numbers ε and δ such that if csm requests the data from gj at time t , then the data from gj arrives at the synchronization unit suk in the time interval [ t + δ − ε , t + δ + ε ]. the design parameters are such that the interval [ a , b ] is longer than the interval [ t + δ − ε , t + δ + ε ]. corresponding to message packet insertion event j , each of the switches in the stack of control stack requests data at the proper time to arrive at approximately time t =( a + b )/ 2 so that the interval [ t + δ − ε , t + δ + ε ] is a subset of the interval [ a , b ], and therefore all of the group j sub - packets arrive at the input ports of the switch at the same tick of the clock that controls the switch . in systems such as the systems described in incorporated patents no . 8 , no . 10 , no . 11 , no . 12 , no . 14 , no . 16 , and no . 17 each of the controlled switches cs 0 , cs 1 , . . . , csv - 1 sends data to a group of targets . if t is a target device of the stack of switches , then each of the switches in the stack of switches cs 0 , cs 1 , . . . , csv - 1 sends data to t . at a data sub - packet sending time , a target t may receive data from each of the switches in the stack . since the switches in the stack need not be perfectly synchronized , the data arriving at t from one of the switches in the stack may arrive at a slightly different time than another switch in the stack . for this reason , in a first embodiment , there is a time gap between the end of one sub - packet sending time and the beginning of a second sub - packet sending time so that when packets arrive in overlapping time intervals , they are sub - packets of the same packet . in a second embodiment , each of the packets in a group j contains the integer j in their header so that the sub - packets can be correctly reassembled into a packet . refer to fig4 which illustrates an alternate embodiment of a synchronization unit that employs fifo buffers instead of delay units . as illustrated in fig4 , each synchronization unit su 230 contains n buffers b 0 , b 1 , . . . , bn - 1 , where n is a system design parameter . each fifo buffer bk holds one message packet and consists of a plurality of sub - buffers . for illustration purposes , four sub - buffers are shown . a message packet m enters the synchronization unit su 230 via line 226 and is ( in some embodiments ) processed by an error correction unit ec 260 before entering logic unit l 414 . l decides in which buffer to insert m and when to inject the packet in each buffer into the data vortex ™ switch via line 418 and node 220 of node array 222 . each synchronization unit su 230 in the system 228 inserts message packets into the data vortex ™ switch in a round - robin fashion from its set of fifo buffers in the order b 0 , b 1 , . . . , bn - 1 , with the timing of the insertions controlled by the system clock 224 . message packets are inserted into the fifo buffers in the order b 0 , b 1 , . . . , bn - 1 in the following manner . if logic l receives a message packet m in the data - sending interval used for inserting a packet into the switch from the buffer b 0 , then m is inserted into bn - 1 . in general , a message packet received during the interval in which the packets in the buffers bk are inserted into the switch is placed into fifo buffer bk - 1 . note that if no packet is received by l during the interval reserved for sending packets from the set of buffers bk into the switch , then bk - 1 will be empty , i . e ., the first bit of the first sub - buffer is 0 . this scheme is used to ensure that all of the packets inserted into the system 228 by the set of devices d 232 during a given insertion interval are inserted as a group into the data vortex ™ switch . note that since each fifo buffer is divided into a plurality of sub - buffers . a single packet is divided into a plurality of sub - packets . a single packet fits in a fifo buffer with each sub - packet fitting into a sub - buffer . thus , the part of the packet contained in the first sub - buffer can advantageously be injected into the switch in advance of the other sub - buffers being filled with incoming data . the technology in the present patent can be conveniently incorporated into a number of systems , including systems containing data vortex ™ switches . fig1 c illustrates a method of incorporating the technology of the present patent with the technology of incorporated patent no . 13 . the devices illustrated in fig1 c , can be used in a number of systems including the systems described in incorporated patents no . 8 , no . 10 , no . 11 , no . 12 , no . 14 , no . 16 , and no . 17 . systems of this class use synchronization at the chip level , but there is no synchronization between chips . these systems have no global clock . an important difference between these systems and the systems with global clocks is that there are no scheduled packet - sending times . the sequential order of packet sending and packet arrival is , however , controlled . in these systems , there is no synchronization between the chips in stack 130 of fig1 a , nor is there synchronization between the chips in stack 185 of fig1 b . refer to fig1 b illustrating a computing system . consider the case in which a device dr wishes to receive a long message m consisting of a plurality of packets from a device ds . there is an integer nm such that the device dr can only receive nm messages from the controlled switch stack s 185 through lines 178 at a given time . device dr is not allowed to have more than nm outstanding requests for data to pass through s . as soon as dr has an available data path dp 178 to receive message m , device dr sends a request packet rp to ds through the uncontrolled switch u . rp requests that message m be sent through device dr input data path dp . the message m is sent by sending device ds to receiving device dr in np packets , p 0 , p 1 , . . . pnp - 1 , with each packet pk consisting of v segments sgk , 0 , sgk , 1 , . . . sgk , v - 1 . in an embodiment wherein each device contains nm input data paths , the switch stack s contains ( nm · v ) switches . sw 0 , 0 , sw 0 , 1 , sw 0 , v - 1 carry the data in data path zero ; sw 1 , 0 , sw 1 , 1 , . . . , sw 1 , v - 1 carry the data in data path one ; and so forth , so that swnm - 1 , 0 , swnm - 1 , 1 , . . . , swnm - 1 , v - 1 carry the data in data path nm - 1 . the packet pk is sent through the switch stack s with segment sgk , l being sent through switch swdp , l of s . each of the segments has a header with leading bit set to one to indicate the presence of data which is followed by the binary representation of r ( the address of dr ) and an identifier for the input data path dp 178 used by dr to receive the message . the header may also contain other information possibly including , a second copy of the target address r , error correction bits , the number of packets in the message , a message identifier , and other information deemed useful . in response to receiving the request packet rp , device ds sends m as soon as ds has a free message sending line 176 . device ds sends the packets through the switch stack 185 . each packet segment header contains the binary address of r and also an identifier indicating the input data path dp . an important aspect of the system with no global clock is that the controlled switches are not in synch . it is possible for a segment of packet k to pass through a switch of stack s at the same time as a segment of packet k + 1 passes through a different switch of stack s . therefore , the segments need to be aligned in order to reassemble the packet pk of the message m . this realignment is not difficult and is accomplished by assembling the packets on input data path dp into v bins . while the segments of a given data packet pk will arrive in sequential order , there may be time gaps between two consecutive segments arriving at a given bin . when the lth segment sg 0 , l of the packet p 0 arrives at bin bindp , l , it is placed in bindp , l location 0 . when the lth segment sg 1 , l of packet p 1 arrives at bin bindp , l , it is placed in bindp , l location 1 . this process continues until the lth segment sgnp - 1 , l of packet pnp - 1 arrives at bin bindp , l , and is placed in bindp , l location np - 1 . given that the minimum time for a request packet to travel from one device to another is t 1 and the minimum time for the first bit of a scheduled packet to travel from one device to another is t 2 , then t 3 = t 1 + t 2 is the minimum time that the first bit of a packet can arrive at dr after dr initiates a request for it . thus , dr can safely request that another packet be sent to input path ip while it is currently receiving data on dp , provided that the time required to receive the remaining current packet on dp is less than t 3 . dr advantageously uses this timing process to maximize the use of its input paths when it has additional data requests in its backlog . consider the case where device ds wishes to send a message m consisting of np packets through the controlled switch stack to device dr . in order to accomplish this task , device ds sends a request to dr for device dr to request the message np packets . when device dr has an available input data path dp 178 , dr will request m to be sent through a message path dp . the procedure is then carried out as described in the preceding paragraph . refer to fig1 d illustrating a communication system where there is no synchronization between the chips in the data - switch stack 130 and there is no scheduled time for messages to be sent through the data - switch stack . when a message m in the form of a sequence of packets arrives at the system at an input - output device iods and the target for m is the input - output device iodr , then iods sends a request - to - send packet to iodr . the request - to - send packet contains message packet information which may include the length of the packet , the priority of the packet , the location r of the receiving input - output device , a packet identifier , and possibly other useful information . iodr has a logic ( not shown ) that stores all of the request to send packets that it has received from various input - output devices . when iodr has a free input line from data - switch stack 130 to receive a packet then ( based on an algorithm that considers a number of factors including when the message was received and the priority of the message ) iodr requests that iods send the packet through a free input data path dp . refer to fig5 which illustrates a collection of devices , illustrated as computing devices , each consisting of a processor pk 520 and its associated memory mk 530 . the processors are interconnected by network interface cards ( nics ) 510 and communicate asynchronously with each other via a data vortex ™ network consisting of an unscheduled data vortex switch u 540 and a scheduled data vortex switch 550 . it is the responsibility of the nics to coordinate this communication in a manner that is transparent to the computing devices . a processor pj makes a request for data from another processor pk by sending the request packet via line 514 to its associated nicj 510 . pj may also specify where to store the data in its memory mj 530 . nicj then converts the request into the proper format and sends it to nick via line 506 , the unscheduled data vortex ™ switch 540 , and the line 508 . in a first embodiment , a data vortex ™ system of the type in which scheduling of data packets is used , each nic keeps track of the status of its associated processor and , thus , knows the availability of its i / o lines , memory , and time - slots . in this manner , nick can negotiate independently with nicj to select the time - slot and path for satisfying the request . prior to the selected time , nick may receive and store the requested data from pk . at the selected time , nick sends the requested data to nicj via line 502 , the scheduled data vortex ™ switch 550 , and line 504 . upon receiving the data , nicj sends it to mj via lines 512 and 516 at a time independently prearranged with pj ; this may or may not require first buffering the data in nicj . alternately , nicj may send data directly to processor memory mj via line 522 as illustrated in fig5 . in a second embodiment , a data vortex ™ system of the type in which scheduling of data packets is not used , time - slot scheduling is not employed , and negotiation between nicj and nick does not occur . instead , nicj sends a request packet to nick via line 506 , the unscheduled data vortex ™ switch 540 , and line 508 requesting that the data be sent as soon as possible . the request packet also specifies an input line 504 to nicj that will be reserved for the requested data until it is received or a time - out value is exceeded . nick receives the request , prioritizes it with other requests , and sends the data to nicj as soon as possible via line 502 , the scheduled data vortex ™ switch 550 , and specified line 504 , unless the agreed upon time - out value has been exceeded . as before , nicj sends the data to mj , at a time independently prearranged with pj , either directly via line 522 or indirectly via lines 512 and 516 . an alternative embodiment that allows a data vortex ™ to run at a different speed than the chip port speeds the embodiment described in this section applies to chips containing a circular data vortex ™ network as well as to chips containing stair - step data vortex ™ network . this embodiment applies to chips where the injection rate into the chip is equal to the injection rate into a data vortex ™ input port as well as to chips where the injection rate into an import of the chip is not equal to the injection rate into a data vortex ™ input port . the embodiment is useful in systems where there is a time delay which allows additional packets to be sent to a network chip after the chip sends a control message to a source requesting that the source temporarily suspend transmission to the network chip . refer to fig6 a illustrating a communication chip 620 containing a data vortex ™ switching core 630 . there are multiple i / o devices 610 that are positioned to send data to the communication chip 620 . one such i / o device 610 is illustrated in fig6 a . also illustrated in fig6 a is a data shaping module 602 used in some embodiments that receives data from an input port and passes that data onto other chip components . the module 602 may be a serialization - deserialization ( serdes ) module . data is transported from the data shaping module via line 612 to a data timing and storage module 640 that contains a plurality of data alignment units 650 . data passes from the data shaping unit 602 to the data alignment units 650 through a tree with edges 612 and switch vertices 680 . in one simple embodiment , the vertices switch in such a fashion that data packets are sent to the alignment units in a round robin fashion . a data packet passes from one of the alignment units 650 to one of the input ports of a data vortex ™ switch module through another tree with edges 618 and switching nodes 680 . in a simple example , data is transferred from the alignment units to the data vortex ™ in a round robin fashion . in some embodiments , the data rate through line 612 is not equal to the data rate through line 618 . multiple alignment units 650 are employed in order to buffer any additional packets sent to the communication chip 620 after the chip has used a control signal to inform an input source that additional packets should not be sent until the control signal is turned off . refer to fig6 b that is suitable for use in systems where the data rate though line 618 is synchronized to the data rate through the data vortex ™ module and the data rate in line 612 is synchronized to the data rate out of the data shaping unit . in one important application , the data rate through a line 618 exceeds the data rate through a line 612 . fig6 b illustrates an alignment unit 650 . an alignment unit 650 consists of a number of shift registers connected in a tree structure . in the example system illustrated in fig6 b , the number of shift registers in an alignment unit is four . the switch nodes 684 in the data - input tree operate so that data is input into the shift registers in a round robin fashion with the first portion of a packet entering shift register 652 ; the next portion of the packet entering shift register 654 ; the next portion of the packet entering shift register 656 ; and the final portion of the packet entering shift register 658 . data does not simultaneously enter and exit a given shift register . when the shift register 652 is full , the first bit of the packet will be in cell 662 and , at the next step , packet bits begin shifting into the shift register 654 . there is a control signal data path ( not shown ) from the top level of dv 630 to the module 650 . if at a given dv input time t there is no blocking control signal , and there is a one in cell 662 , then data will begin shifting from shift register 652 to dv 630 . shift register 654 is shorter than shift register 652 . shift register 654 can fill in the amount of time that it takes to drain shift register 652 . shift register 656 can fill in the amount of time that it takes to drain shift register 654 . shift register 658 can fill in the amount of time that it takes to drain shift register 656 . therefore , if there is a one in the cell 662 , and the data is shifted out to dv , the entire packet will be successfully transferred from the chip input port to the data vortex ™ switch module dv 630 . in the embodiment pictured in fig6 b , the shift registers run at the speed of line 612 when data is shifting in and at the speed of line 618 when data is shifting out . in an alternate embodiment pictured in fig6 c data traveling on line 612 is shifted into register 672 at the line 612 data rate . data is shifted out of register 652 on line 618 at the line 618 data rate , where the data rate through line 612 is not necessarily equal to the data rate through line 618 . when register 672 is full , it is transferred into shift register 652 in a single clock tick via lines 692 . refer to fig7 illustrating a variable length fifo that is suitable for use in the shift registers in the alignment units . this fifo is of similar construction to the fifo illustrated in fig2 b . the fifo is composed of two types of cells . a first type of cell with one data input port and one data output port is a one - bit shift register . a second type of cell ( e . g ., cells 701 , 702 , 704 ) is a switch cell with one data input port and two data output ports and acts as a one - bit shift register combined with a simple switch that can send its output to either one of two cells . the switch of a switch cell is set by a single bit sent to the switch by the length control unit lc 772 . the lc unit receives a word w of payload length l , where l is the number of switch cells in variable length fifo unit . lc sends the lowest order payload - bit of w to cell 701 , the next bit to cell 702 , the next bit to cell 704 , and so forth . multiple systems , each using a different packet length , can employ the same data vortex ™ chip by setting the length of the data vortex ™ fifo and the lengths of the shift registers in fig6 b . these shift register lengths are controlled by input word w to the lc unit . if w has a lowest order payload - bit set to 0 , then cell 701 sends data through line 740 . if w has a lowest order payload - bit set to 0 , then cell 701 sends data through line 705 . sending data through line 750 causes fifo 730 to be shortened by one bit . similarly , the sending of a one to cell 702 results in the shortening of the fifo by two bits , and the sending of a one to cell 704 results in the shortening of the fifo by four bits . in this way , the word w is the binary representation of an integer 1 , where i is the number of bits that are deleted from the shift register 730 . thus , the utilization modules 730 advantageously enables the chip containing the data vortex ™ to be used in systems that support various packet lengths . | 7 |
some embodiments of the invention will now be described in greater detail . nevertheless , it should be noted that the present invention can be practiced in a wide range of other embodiments besides those explicitly described , and the scope of the present invention is expressly not limited except as specified in the accompanying claims . in one embodiment of the present invention , a first feed containing lignocellulose , a second feed containing soft material , a third feed containing powdery adhesive , and a fourth feed containing clay are provided in a powdering process to form a powder . wherein , the powdering process further includes a grinding process to grind the first feed , the second feed , the third feed , and the fourth feed , individually . however , the amount of the fourth feed can depend on practical needs , and in some cases can even be zero . the first feed containing lignocellulose mentioned above is the material having plenty of plant fiber , and is selected from the following group : unhusked rice , straw , bagasse , wood flour , paper pulp , herbage , and the mixture thereof . . . , etc . herein , the first feed is about 40 %- 65 % weight of the resulted powder , and the preferred content is 50 %. the second feed containing soft material mentioned above has plenty of amylum , and is selected from the following group : cassava , flour , glutinous rice , and the mixture thereof . . . , etc . herein , the second feed is about 30 %- 40 % weight of the resulted powder , and the preferred content is 35 %. the third feed containing powdery adhesive mentioned above is selected from the following group : glycuronic acid , polysaccharides , hyaluronic acid , and the mixture thereof . . . , etc . herein , the third feed is more than 7 % weight of the resulted powder , and the preferred content is 14 %. the fourth feed containing clay mentioned above is selected from the following group : china clay , pot clay , brick flour , rock flour , and the mixture thereof . . . , etc . besides , the powder is about 55 %- 65 % gross weight of the provided clay , and the preferred content is 60 %. in this embodiment , a first blending process is carried out to blend the above - mentioned powder with a hardness - adjusting agent and a hue - adjusting agent to form an admixture . the hardness - adjusting agent can make the provided clay spontaneously get hard , through which to adjust the hardness of the final - shaped provided clay , and has inorganic substances containing calcium , such as calcium hydroxide or calcium oxide . herein , the hardness - adjusting agent is less than 3 % gross weight of the provided clay and the preferred content is 1 %. the hue - adjusting agent can make the hue of the provided clay lighter or darker , through which to adjust the color of the final - shaped provided clay , and has an agent for adjusting acid - alkali , such as carbonate , calcium carbonate , hydroxide , calcium hydroxide , and acid . herein , the hue - adjusting agent is less than 5 % gross weight of the provided clay , and the preferred content is 2 %. however , the first blending process and the blended elements can depend upon practical needs , and in some cases the first blending process can even be omitted . in this embodiment , after the first blending process , a second blending process is carried out to blend the admixture mentioned above with an adhering agent and a moisture - adjusting agent to form a clay containing lignocellulose . the adhering agent is employed to strengthen the adhesion function of the third feed containing powdery adhesive , and further includes a resin material , such as natural rubber , a material containing amylum and a surfactant with both lipophile and hydrophile , such as glycerin . herein , the adhering agent is formed through the follow steps : mixing the material containing amylum with a heated liquid to form a mixture , herein the temperature of the heated liquid is prefer to be 70 - 90 degrees centigrade ; adding the resin material and the surfactant with both lipophile and hydrophile into the mixture and making them well mixed to form the adhering agent . the moisture - adjusting agent is used to accelerate the moisture evaporation to control the shaping time of the provided clay . the moisture - adjusting agent could be acetic acid , sodium carbonate , calcium hydroxide , and ethanol . herein , the adhering agent is about 35 %- 45 % gross weight of the provided clay , and the preferred content is 40 %; the moisture - adjusting agent is less than 2 % gross weight of the provided clay , and the preferred content is 1 %. in this embodiment , the elements of the provided clay containing lignocellulose are individually described as followings : ( 1 ) a first feed that contains lignocellulose is about 24 %- 39 % gross weight of the provided clay , and the preferred content is 30 %. herein , the first feed is the material having plenty of plant fiber , and is selected from the following group : unhusked rice , straw , bagasse , wood flour , paper pulp , herbage , and the mixture thereof . . . , etc . ( 2 ) a second feed that contains soft material is about 18 %- 24 % gross weight of the provided clay , and the preferred content is 21 %. herein , the second feed has plenty of amylum , and is selected from the following group : cassava , flour , glutinous rice , and the mixture thereof . . . , etc . ( 3 ) a third feed that contains powdery adhesive is more than 4 % gross weight of the provided clay , and the preferred content is 8 %. herein , the third feed is selected from the following group : glycuronic acid , polysaccharides , hyaluronic acid , and the mixture thereof . . . , etc . ( 4 ) a fourth feed that contains clay is about 0 %- 30 % gross weight of the provided clay . herein , the fourth feed is selected from the following group : china clay , pot clay , brick flour , rock flour , and the mixture thereof . . . , etc . however , the amount of the fourth feed can depend upon practical needs , and in some case can even be zero . ( 5 ) a hardness - adjusting agent makes the provided clay spontaneously get hard , through which to adjust the hardness of the final - shaped provided clay , being about 0 %- 3 % gross weight of the provided clay and the preferred content is 1 %, and has inorganic substances containing calcium , such as calcium hydroxide or calcium oxide . herein , the amount of the hardness - adjusting agent can depend upon practical needs , and in some cases can even be zero . ( 6 ) a hue - adjusting agent is about 0 %- 5 % gross weight of the provided clay , and the preferred content is 2 %, and has an agent for adjusting acid - alkali , such as calcium carbonate or carbonate , calcium hydroxide , hydroxide , acid . herein , the amount of the hue - adjusting agent can depend upon practical needs , and in some cases can even be zero . ( 7 ) an adhering agent is employed to strengthen the adhesion function of the third feed , being about 35 %- 45 % gross weight of the provided clay and the preferred content is 40 %, and further has a resin material , such as natural rubber , a material containing amylum and a surfactant with both lipophile and hydrophile , such as glycerin . ( 8 ) an moisture - adjustin agent is about 0 %- 2 % gross weight of the provided clay , and the preferred content is 1 %, and is used to accelerate the moisture evaporation . for example , acetic acid , sodium carbonate , calcium hydroxide , and ethanol are all suitable moisture - adjusting agent of the present invention . as mentioned above , the present invention uses the hardness - adjusting agent , the hue - adjusting agent , and the adhering agent to auxiliarly form the provided clay . further , the ratios of the above - mentioned agents depend upon practical needs in order to have the carving , plastic , and coloring features of the provided clay . moreover , the present invention employs the moisture - adjusting agent to control the shaping time of the provided clay . besides , the provided clay can dry naturally , and does not need any oven - baking process . this saves the shaping time and the energy cost . moreover , since the provided clay has plenty of lignocellulose to make its density like wood , it shows the features of wood , such as being lighter and harder in comparison with normal clay . in another aspect , the elements of the provided clay are from the naturals , which are easily decomposed spontaneously , so the provided clay will not poison the environment . to sum up , the provided clay can meet economical benefits and industrial uses . apart from being used as clay materials for art works , the provided clay can also be used as patching materials for any constructions , such as wood buildings or furniture . additionally , the provided clay with lignocellulose added has not been on the market by far . although specific embodiments have been illustrated and described , it will be obvious to those skilled in the art that various modifications may be made without departing from what is intended to be limited solely by the appended claims . | 2 |
a word game disclosed herein comprises a plurality of gaming pieces , wherein each of the gaming pieces has one or more letters of the alphabet visible thereon . in a preferred embodiment , the number of gaming pieces which reflect a particular letter is dependent upon that letter &# 39 ; s frequency of occurrence in the written language . in general , the gaming pieces are manipulated in such a way as to spell out words in a crossword grid configuration , i . e ., the gaming pieces are positioned vertically and horizontally relative to one another , to spell out words which build off of one another . a variety of rules may be implemented regarding which type of words may or may not be spelled out in the game , such as , for example , and without limitation , precluded words may include proper nouns , obscenities , abbreviations , acronyms , and the like . additionally or alternatively , rules may be implemented in the direction in which the words may be laid out relative to one another , i . e ., words may be spelled from left to right and / or from up to down , but not from right to left and / or from down to up . additionally , players may restrict the words to a certain category and / or topic , e . g ., all of the words may be required to be a noun , a verb , an adjective , and the like ; must spell out a type of animal , color , and the like ; etc . the gaming pieces are preferably formed and dimensioned for play which encourages movement on a greater scale than which would ordinarily be involved in typical table - top or typical indoor floor play . that is , it is contemplated that the game disclosed herein be played , for example , on a larger scale , such as , for example , on one or more of a lawn , a beach , a park , a gymnasium , a classroom , an auditorium , a swimming pool , a campground , throughout a house , and the like to promote a greater range of movement when played while increasing the number of play opportunities and venues . accordingly , the material ( s ) which are used to form the gaming pieces , and the size and configuration of the gaming pieces , is / are selected according to the place and the manner in which game play is contemplated . for example , where the game is intended for play in water , such as , e . g ., a swimming pool , the gaming pieces preferably comprise a floatable , water - resistant material , such as , e . g ., foam , plastic , and the like , and is dimensioned so that the players can readily see , manipulate and maneuver around the gaming pieces while the players are in the swimming pool . furthermore , to the end of allowing the game to be played on a large scale , in an exemplary embodiment each of the playing pieces comprises a cube configuration having a height of at least 19 inches , a width of at least 4 inches , and a length of at least 4 inches , wherein in an exemplary embodiment , each of the playing pieces comprises a cube configuration comprising a height of about 3 inches , a width of about 3 inches , and length of about 3 inches . in general , the game is played by distributing an even number of gaming pieces to all of the players . as used herein and throughout , a “ player ” shall include the concept of a team , wherein a team includes two or more players working to assemble a shared crossword grid . the player manipulates his / her gaming pieces to correctly spell out one or more words which are not proscribed by the predetermined rules for that particular round of play . where more than one word is spelled out , the words preferably build off of one another and are physically positioned in a crossword grid fashion . in an exemplary embodiment , the first player to use all of his / her allotted gaming pieces to form a crossword grid wins a round . total game play may include one or more rounds of play . accordingly , a winner of a particular game is the one to win the most number of rounds of play for the particular game . in an exemplary embodiment , a game comprises a plurality of gaming pieces , wherein each of the gaming pieces is in the form of , e . g ., a tile which bears a letter of the alphabet on a face thereof . in an exemplary embodiment , the frequency of the letters is dependent upon the frequency in which the letters are used in forming words . for example , letters that are more frequently used in the spelling of english words , such as “ a ”, “ e ”, “ r ”, “ t ”, and “ 0 ”, would be represented more frequently than would letters such as “ z ”, “ x ”, and “ q ” which are less commonly used in the spelling of english words . in an especially preferred embodiment , the game comprises 144 tiles or gaming pieces , wherein each gaming piece bears a single letter from the english alphabet in a frequency according to table 1 provided directly below herein . an exemplary method of playing the exemplary game disclosed above is depicted in fig1 a - 1 c . as shown , and exemplary method comprises placing gaming pieces 12 face down to form a grouping referred to herein as a “ bunch ” 14 . in an initial selection of gaming pieces 12 , each player selects an equal and pre - determined number of gaming pieces 12 from bunch 14 , and places them face down in front of the respective player in what is referred to herein as the player &# 39 ; s “ home pile ” 16 . for games of 2 - 4 players , each player may take at least 21 gaming pieces 12 from bunch 14 ; for 5 - 6 players , each player may take at least 15 gaming pieces 12 from bunch 14 ; for 7 - 8 people , each player may take at least 11 gaming pieces 12 from bunch 14 ; etc . when one or more of the players signals , such as , for example , by calling out the word “ split ”, all of the players turn up their gaming pieces 12 from their respective home piles 16 and attempt to spell out words in a crossword grid 18 by manipulating the gaming pieces 12 and placing them in a horizontal and vertical fashion and building off of one or more of the other words . at any point during game play , any of the players may rearrange his / her words and crossword grid 18 as often as desired . in a preferred embodiment , players do not take turns , but play independently of each other and at the same time . in an exemplary embodiment , when a player has used all of his / her tiles from his / her respective home pile 16 , all of the players take a preselected number of additional gaming pieces 12 from bunch 14 , and continue forming words as described above . in an exemplary embodiment , such each player would take one additional gaming piece from bunch 14 . to indicate when the other player ( s ) must select another gaming piece from bunch 14 , the player having used all of his / her gaming pieces 12 may call out a word , such as , for example , “ peel ”. at any time , and as often as desired during play , any of the players may signal out , such as , for example , by calling out the word “ dump ”, and return a gaming piece back from his / her home pile 16 to bunch 14 , face down . the same player may then take additional gaming pieces 12 from bunch 14 , preferably three additional gaming pieces 12 , and take these gaming pieces 12 back to his / her home pile 16 . this exchange need not affect the other players . when bunch 14 has fewer than the “ additional gaming pieces 12 ” referred to in this paragraph , then the player takes all of the remaining gaming pieces 12 included in bunch 14 . play continues until there are fewer gaming pieces 12 in bunch 14 than there are players in the game . the first player with no remaining gaming pieces 12 in his home pile 16 indicates that he / she has completed his / her crossword grid 18 , such as by , for example , calling out the word “ bananas ”. the other players may then check the completed crossword grid 18 for misspelled or prohibited words . if all of the words are acceptable , that player is the winner of the round . if any word of crossword grid 18 is found to be unacceptable , i . e ., the word is misspelled or does not conform to other established rules , e . g ., the word is an acronym , a proper noun , an obscenity , and the like , the player who completed crossword grid 18 and first indicated that he / she was finished is out of the round . once out of the round , such player returns all of his / her tiles face down to bunch 14 , and the play of the round resumes for the remaining players . if there were only two players , then the other player automatically wins the round . rounds may continue in this fashion , until the players have played a desired number of rounds . the winner of the game is the player who has won the most rounds . another exemplary method of play comprises essentially all of the steps set forth above in reference to fig1 a - 1 c except that there is no “ peeling ” and “ dumping ”, i . e ., players do not exchange their gaming pieces 12 in their respective home piles 16 with those in bunch 14 , and once a player has finished constructing crossword grid 18 using all of his / her gaming pieces 12 as first collected from bunch 14 , such player is the winner so long as none of the words used by the player in crossword grid 18 violate any of the rules of the game . should the game end in a stalemate , the player with the fewest number of gaming pieces 12 remaining in the respective player &# 39 ; s home pile 16 is the winner . in another exemplary method of play , the method comprises essentially all of the steps set forth above in reference to fig1 a - 1 c , except that there is no peeling . that is , players are allowed to exchange their gaming pieces 12 according to the embodiment depicted in fig1 a - 1 c ; however , once a player has finished constructing crossword grid 18 using all of his / her gaming pieces 12 from player &# 39 ; s home pile 16 such player is the winner so long as none of the words used by the player in crossword grid 18 violate any of the rules of the game . in this embodiment , preferably each player selects at least 21 gaming pieces 12 from bunch 14 and places them in his / her home pile 16 . another exemplary method of play is especially well - suited for solitaire play . in this embodiment , the method is substantially similar to the method described with reference to fig1 a - 1 c , except that a single player takes a certain number of gaming pieces 12 , preferably at least 21 gaming pieces 12 , from bunch 14 and plays them from his / her home pile 16 . once the player can no longer figure out how to use all of his / her gaming pieces 12 in the construction of the crossword gird , the player may select one or more additional gaming pieces 12 from bunch 14 , wherein in an exemplary embodiment , the player selects one additional gaming piece from bunch 14 . in this embodiment , the player can try to beat his own best time in using all of the gaming pieces 12 from bunch 14 , try making as few words as possible to use up all of the gaming pieces 12 from bunch 14 , and the like . 144 gaming pieces are placed face down to form a bunch . for games of 2 - 4 players , each player takes 21 gaming pieces from the bunch , for 5 - 6 players , each player takes 15 gaming pieces from the bunch , and for 7 - 8 players , each player takes 11 gaming pieces from the bunch . all of the selected gaming pieces are placed face down . any one player calls out “ split ”. all players reach down to turn their own gaming pieces face up and proceed to form their individual grid of connecting and intersecting words . words may be horizontal or vertical , reading left to right or top to bottom . at any point , each player may rearrange their own words as often as desired . players do not take turns , but play independently of each other and at the same time . when a player has used all of their original gaming pieces , they call “ peel ” and take a new gaming piece from the bunch . at this point , all of the other players must also take a gaming piece from the bunch and add it to their collection of gaming pieces . this may entail some running on the part of the players depending on where the bunch is in relation to the player &# 39 ; s grids . at any time , and as often as desired during play , any player may return a gaining piece back to the bunch , face down , but must take 3 gaming pieces in return . the player declares this action to the other players by saying “ dump ”. play continues until there are fewer tiles in the bunch than there are player in the game . the first player with no remaining tiles calls out “ bananas ” and is the winner . the other players may check the winning grid for misspelled or incorrect words . if all words are acceptable , that player is the winner of that round . if any word in the grid is found to be unacceptable , that player is out of that round . such player must return all of their gaming pieces face down to the center bunch and the game resumes for the remaining players . in another exemplary embodiment , all of the gaming pieces are placed face down , and the gaming pieces are divided equally among the players , face - down . players may then play as discussed in example 1 except that there is no peeling or dumping . the first player to use all of his / her tiles calls out “ bananas ” and is the winner of that round . if the game ends in a stalemate , the player with the fewest tiles is the winner . each player takes 21 gaming pieces from the bunch . players then proceed to play the game as described in example 1 with dumping but no peeling . the first player to use all of his gaming pieces calls out “ bananas ” and is the winner . all of the gaming pieces are placed face down in an open area . 21 gaming pieces are chosen and play proceeds as described above in example 1 except that only one player is participating in game play . unlike the play described in example 1 , the player only peels when needed . the player tries to beat his own best time in using all 144 gaming pieces , or tries making as few words as possible to use all 144 gaming pieces . fig2 depicts another exemplary game . here , a game 100 comprises a scoring member 102 and a plurality of gaming pieces 104 . in an exemplary embodiment , plurality of gaming pieces 104 comprises about 24 cubes . as shown in fig3 , an exemplary gaming piece includes a cube 105 made from , e . g ., plastic , wood , tile , ceramic , marble , and the like . cube 105 comprises faces 107 each of which has at least one letter from the alphabet visible thereon . referring again to fig2 , scoring member 102 comprises a housing 106 which stores plurality of gaming pieces 104 . disposed on housing 106 is a zipper 108 and a zipper 110 , each of which respectively comprises two rows of teeth 112 and 114 , wherein rows of teeth 112 are engaged by a slider 116 and rows of teeth 114 are engaged by a slider 118 . further disposed on housing 106 is a series of numbers 120 and 122 each of which range from 0 - 10 . series of numbers 120 is aligned with zipper 108 while series of numbers 122 is aligned with zipper 110 . to begin play of game 100 , plurality of gaming pieces 104 is evenly distributed between two players . slider 116 of zipper 108 is aligned with the number 0 from series of numbers 120 , while slider 118 of zipper 110 is aligned with the number 0 from series of numbers 122 , at approximately the same time , each of the players begins to construct a crossword grid comprising words with the player &# 39 ; s allotted gaming pieces . the first player to properly use all of his allotted gaming pieces in the formation of a crossword grid gets to move his respective zipper up one point , e . g . from 0 to 1 from respective series of numbers 120 and 122 . should a player having a finished crossword grid have made a mistake in the spelling of a word and / or have used a word that is proscribed under the rules of play , then the other player receives the point and gets to move his respective slider 116 and 118 up one number from respective series of numbers 120 and 122 . once a round of play has been completed and the point earned and recorded via movement of the respective slider 116 and 118 , the gaming pieces from plurality of 104 are redistributed evenly to the players . the first player to reach a score of 10 wins the game . in another exemplary embodiment , game 100 may be played essentially as described above with reference to fig2 , except that the players may win a bonus point for each pair of rhyming words in a completed grid . in another exemplary embodiment , game 100 may be played essentially as described above with reference to fig4 , but may be awarded additional points based upon the length of a word used in the formation of the crossword grid . for example , a 7 letter word may be awarded 1 bonus point , an 8 letter word may be awarded 2 bonus points , a 9 letter word may be awarded 3 bonus points , and so on . in another exemplary embodiment , game 100 may be played essentially as described above with reference to fig4 , however , palindromes and / or semi - palindromes may receive bonus points . additionally or alternatively to any of the embodiments disclosed hereunder , players may agree that words must have at least a certain number of letters . further , players may agree that the words must belong to a particular type or category , such as , e . g ., a particular language , sports , animals , etc . specific manners of play of the game described above with reference to fig2 are described in the following examples . each player selects a zipper and keeps a running score by moving their zipper on the pouch . each player then takes 12 cubes . one of the players calls “ go ” and each player then proceeds to make a crossword grid using any side of his own cubes . words can be any length , reading top to bottom , left to right only . the first player to complete a grid with no remaining cubes calls out “ zip ” and moves his zipper 1 point . if a player &# 39 ; s grid includes a misspelling or a non - existent word or non - allowed word , that player receives no points for the round and the opponent gains 1 point . at the end of each round , all of the cubes are mixed and redistributed to each player . the first player to reach 10 on the scoring pouch calls out zip - it and is the winner of the game . the rules are played as described above in example 1 , except that players win 1 bonus point for each pair of rhyming words in a completed grid . the rules are played as described above in example 1 , except that any 7 letter word wins 1 bonus point . an 8 letter word receives 2 bonus points , and a 9 letter word receives 3 bonus points , and so forth . the rules are played as described above in example 1 , except that in a completed grid , each palindrome or semi - palindrome receives 2 bonus points . a palindrome is a word that reads the same forwards and backwards , and a semi - palindrome is a word in which letters form one word reading left to right , and a different word reading right to left . in any of these embodiments of play , players can agree to amend the rules to suit the players &# 39 ; skill level and abilities . for example , adults playing against adults may agree that words must have at least 3 letters , while children are allowed to use 2 letter words . additionally , players may modify the rules such that all of the spelled - out words must fall into a particular category , such as , e . g ., all of the words must be nouns , sports , animals , etc . while the disclosure has been shown and described with reference to certain preferred embodiments thereof , 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 disclosure . | 0 |
the present invention relates to high performance multilayer resist structures including bilayer and top surface imaging ( tsi ) and methods of fabrication thereof . the bilayer structure is depicted in fig2 a . it is produced by depositing a thin resist on the order of 1000 - 4000 å on a thick underlayer ( on the order of 1000 å - 10 μm , more preferably 3000 å - 3 . 0 μm and most preferably 4000 å - 2 . 0 μm . the underlayer functions as a planarizing layer , an antireflective coat , and provides etch resistance for transferring the pattern into the substrate pattern . the bilayer resist contains an etch resistant functionality to act as a hard mask during the transfer of the resist process , such functionality being si , boron , tin , or other metal containing resist . this structure is referred to herein as a bilayer resist ( fig2 a ). another resist structure referred to as top surface imaging uses a conventional resist which after exposure is treated to an agent that can introduce etch resistant functionality such as silylation by vapor or liquid silylating agents . this resist structure is depicted in fig2 b and is referred to as top surface imaging ( tsi ). one specific example of tsi is carl described in hien et al in proc . spie , vol . 3333 , pt . 1 - 2 , 1998 , p . 154 - 64 ; this reference is incorporated herein by reference . both bilayer and tsi require a carefully designed underlayer — an underlayer which does not interact with the resist and exhibits no interfacial mixing with the resist . in addition , products from the underlayer can not diffuse into the resist that can contaminate the resist and components from the resist can not diffuse into the underlayer . in addition , the underlayer must provide appropriate optical properties ( n and k at a given wavelength ) to function as an antireflective coating ( arc ) and have appropriate etch resistance to allow the resist pattern to be transferred into the substrate silicon dioxide , silicon , and so on . it is well known that the effective exposure dose in optical lithography varies periodically with resist thickness due to thin film interference . the swing ratio s is defined as the fractional exposure change between an interference maximum thickness and an interference minimum thickness . s is a fundamental measure of the quality of a particular resist process . by reducing the swing ratio to near zero , the resist process is able to tolerate changes in optical phase due to resist and deposited film thickness non - uniformity . the swing ratio can be calculated by the following equation : s = 4 ( r 1 r 2 ) 0 . 5 e − αd ( 1 ) where r 1 is the reflectance at the resist air interface , r 2 is the reflectance at the top resist / arc interface , α is the resist absorption coefficient and d is the resist thickness . in this invention , we are mainly concerned in the reduction of the swing ratio by reducing r 2 through the use of a bilayer resist process with optimized underlayer layer arc . a diagram explaining the significance of the above parameters is shown in fig2 . in general , bilayer resist systems can be modeled so a to find bottom layer optical parameters ( n and k values ) as well as optimum thickness . to achieve this , a knowledge of the optical constants of the entire film structure is necessary in order to compute the swing ratio reduction . in general , underlayer thickness d varies between 1000 to 10000 a depending on film absorption . the extinction coefficient k can vary between 0 . 11 to 0 . 5 . more commonly , the k values were between 0 . 11 and 0 . 3 at duv for a 10 × reduction in swing ratio . the index of refraction n vary between 1 . 65 to 1 . 95 . the most typical underlayer used in bilayer and tsi has been cross - linked novolac / diazonapthoquinone ( dnq ) systems ( w . moreau , semiconductor lithography , 1988 , plenum , chapter 12 , pg . 591 . . . , r . d . miller and g . m . wallraff , advanced materials for optics and electronics , vol . 4 , 95 - 127 ( 1994 )) the novolacs have many disadvantage as is described below . in particular , high temperature (& gt ; 200 c ) is needed to cross - link , the system must be carefully designed and controlled to prevent resist / underlayer interaction , its optical properties are significantly dependent on baking conditions . thus , to be abe to use novolac systems in a bilayer , tsi process — the chemical composition and processing conditions must be controlled as described below otherwise significant interfacial interaction with the resist is observed limiting the ultimate resolution attained with the resist . the thermal decomposition of the dnq results in the formation of a highly reactive ketene intermediate that can form crosslinking ester functionalities with the phenolic sites of the matrix novolak . the crosslinking of this resin is essential to induce insolubilization and prevent dissolution during the solvent casting of the imaging layer . however , it was shown that underlayers formed from novolak / dnq produced an interface interaction with the imaging layer that results in gross residual material or “ scumming ” after development . this artifact of the underlayer prohibits its use within this system . in an effort to remedy this situation , we have determined that in the absence of a dnq additive , novolak can be caused to insolubilize simply by thermal curing of a solvent - removed , spin cast film . prolonged curing ( 2 - 5 min .) at elevated temperature ( 225 - 275 ° c .) is preferred . films prepared in this manner were insoluble in common casting solvent and allowed for casting of the top imaging layer without severe mixing . the severity of the residue after development was greatly diminished as compared to the dnq / novolak underlayer ; however , some residue was persistent . although the mechanism of this insolubilization has not been determined , it is proposed to occur due to densification of the glassy film after prolonged heating above its glass transition temperature ( tg ) coupled with a complex combination of thermally induced oxidation and / or electrophilic aromatic substitution , resulting in a crosslinked network . evidence for these proposals lies in the dependence of the molecular weight ( mw ) and polydispersity index ( pdi ) of the novolak polymers and the dependence of the optical properties ( n & amp ; k ) on the curing conditions shown in example 5 . for example , it was found that those polymers with higher mw values resulted in underlayers that produced less scumming . this was also the case with materials of higher pdi . it is proposed that residue is largely caused by an interaction of the imaging layer with the underlayer . it is evident that the degree and / or efficiency of crosslinking of the underlayer greatly contribute to this deleterious phenomenon . the amount of residue clearly correlates inversely with both the mw and the pdi of the novolak used in the formulation . therefore , it is desirable to have a novolac of high mw and a broad pdi for minimization of residue . the degree of crosslinking is directly dependent on the presence of polymeric chains of greater length , i . e . higher mw . it also appears that the presence of lower molecular weight species is important to the degree of crosslinking , as the increased ratio of functionalized hydroxymethyl “ end - groups ” to repeat units in these oligomers is high and leads to more crosslink sites per chain . the mw of the novolac is in the range of 2k - 50k , more preferably from 2k - 25k and most preferably from 2k - 15k . another problem with the novolac is that oxidation clearly occurs in these films as is apparent by the observed change in the optical density in the near uv and visible range . the optical absorption dramatically increases with increased curing temperature and time , consistent with the formation of highly absorbing quinoidal - type species . thus , since the optical properties change with a minor change in processing conditions ( example 4 ), it is very important to tightly control the processing conditions to avoid significant variations in optical properties . the best cross - link temperatures range between 200 and 300 ° c ., more preferably from 225 - 275 ° c ., and most preferably from 225 - 260 ° c . a fundamental disadvantage of all the previously described underlayer systems is that the mechanism of insolubilization , i . e . crosslinking , is not well understood . a more optimum underlayer has been designed by including specific functional groups in the polymer and formulation that can contribute a particular attribute . a formulation consisting of a polymer matrix system , a thermal acid generator , and a polyfunctionalized crosslinker was developed . each component serves its particular purpose ( optical properties , insolubilization , and etch properties ) on the basis of its chemical composition . in concert these material provide all the desired characteristics outlined above . variation of the mass percentage of these component results , as well as processing conditions , result in different performance of these materials . therefore , compositions of this type are fully tunable both on the molecular level and the formulation composition level . additionally , process latitude has been considered in the design of the components such that a robust process can be developed without concern for performance variation with slight deviation from nominal conditions . the polymeric system in these formulations consists of a copolymer or a terpoymer , or a blend of two or more homo - or copolymers . these polymers must be phase compatible , soluble in conventional casting solvents , and able to form high integrity , planarizing films . the copolymer or terpolymer or one or more of the blend components contains a covalently bonded “ chromophore ” that can be used as a means of modulating the optical properties of the material and a variety of wavelengths . for example , a poly ( hydroxystyrene ) ( phs ) based polymer that contains some portion of the aromatics rings with a substituent anthracenylmethyl or napthalene group allows for n & amp ; k modulation at 248 nm . this function group can be incorporated into the polymer structure either by direct copolymerization or by starting with a desired polymer platform ( i . e . phs ) and attaching the moiety by acid catalyzed electrophilic aromatic substitution / condensation with anthracenemethanol . it has been shown that the optical properties ( n and k ) at 248 nm can be tuned by controlling the degree of substitution of this functional group . the optical properties of the underlayer can be further modified via the polymeric system by the inclusion of other compatible polymer of differing optical properties into the aforementioned blend . for example , unsubstituted phs can be blended with anthacenemethylated phs to derive a blend with the desired optical properties . these polymer , being aromatic in nature , have a high carbon to hydrogen ratio and are thus consistent with materials that targeted for use in etch resistance applications . the addition of grafted fused - polycyclic aromatic groups , such as anthracene , add to the etch resistance properties of these copolymers . these are demonstrated in examples 8 and 9 . these polymers are rendered insoluble by an acid catalyzed reaction of an added crosslinking molecule with the polymer matrix . the thermally generated acid is provided by a thermal acid generator ( tag ) species . the crosslinking species is one of a number of previously reported ( q . lin , spie proceedings vol . 3049 974 - 987 ( 1997 ) polyfunctional species that can react with the phenolic sites of a polymer such as phs or anthracenemethylated phs . compounds which are suitable for this application include species based on mono , di , or multi hydroxy substituted methylphenols and derivatives as described in u . s . pat . no . 5 , 296 , 332 and amino plasts as described in u . s . pat . no . 5 , 212 , 046 and ibm docket y0997185 , based on urea or glycoluril resins commercially available from american cyanamid , melamines , tags are chosen from the class of compounds that undergo catastrophic decomposition at a given threshold temperature that results in the formation of one or more molecules of a strong acid . examples of these may be chosen from the class of compounds designed for the similar application of photoacid generators ( pags ) or structural similar species such as p - nitrobenzyl tosylate . particularly useful materials will decompose at a temperature that is suitable for resist underlayer processing . other materials that can be used as optimum underlayers include polyarylsulfones such as the barl material ( example 7 ), polyhydroxystyrene based derivatives , an example being a copolymer of polyhydroxystyrene and polyhydroxystyrene reacted with anthracenemethanol that contains a cross - linker , and acid catalyst ( thermal acid generator ), polyimides , polyethers in particular polyarylene ethers , polyarylenesulfides , polycarbonates such as polyarylenecarbonates , epoxies , epoxyacrylates , polyarylenes such as polyphenylenes , polyarylenevinylenes such as polyphenylenevinylenes , polyvinylcarbazole , cyclicolefins , polyesters . for the bilayer resist , the top layer resist incorporates etch resistant functionality such as silicon , boron , tin , other metal atom . resists which are useful in practicing the current invention include si containing acrylates / methacrylates , si containing styrene derivatives , si containing norbornene type materials , silsesquioxanes , silanes , siloxanes . structures can be found in us patents am997002 and u . s . pat . nos . 5 , 296 , 332 ; 5 , 338 , 818 ; 5 , 422 , 223 ; 5 , 286 , 599 ; 5 , 238 , 773 ; 5 , 041 , 358 which are incorporated herein by reference . top surface imaging resists are based on acrylates / methacrylates , styrene based polymers , cyclic olefins and others whose structures are found in u . s . pat . nos . 5 , 322 , 765 ; 5 , 250 , 395 ; 5 , 229 , 251 ; 5 , 023 , 164 ; 4 , 908 , 298 ; 4 , 810 , 601 ; 4 , 657 , 845 ; 4 , 552 , 833 ; 4 , 613 , 398 which are incorporated herein by reference . other resist structures , cross linkers , acid catalysts useful in practicing the present invention can be found in us patents a list of resists include : uvx series ( ibm / shipley products consisting of hydroxystyrene / t - butylmethacrylate copolymers and terpolymers thereof with other polymerizable units such as styrene , methylmethacrylate , and so forth , methacrylate / acrylate polymers such as polymethylmethacrylate and derivatives thereof , snr , cgr , krs , zep , silicon containing resists , pbs ( polybutanesulfone ), organometallic resists , novolak containing resists , novolak / diazoquinone resists , and so forth . the resist can be + tone or − tone ; it can be a single layer resist or multilayer resist ; chemically amplified and non chemically amplified . the following u . s . patents describe resists useful to practice the present invention are incorporated herein by reference : u . s . pat . nos . 5 , 580 , 694 , 5 , 554 , 485 , 5 , 545 , 509 , 5 , 492 , 793 , 5 , 401 , 614 , 5 , 296 , 332 , 5 , 240 , 812 , 5 , 071 , 730 , 4 , 491 , 628 , 5 , 585 , 220 , 5 , 561 , 194 , 5 , 547 , 812 , 5 , 498 , 765 , 5 , 486 , 267 , 5 , 482 , 817 , 5 , 464 , 726 , 5 , 380 , 621 , 5 , 374 , 500 , 5 , 372 , 912 , 5 , 342 , 727 , 5 , 304 , 457 , 5 , 300 , 402 , 5 , 278 , 010 , 5 , 272 , 042 , 5 , 266 , 444 , 5 , 198 , 153 , 5 , 164 , 278 , 5 , 102 , 772 , 5 , 098 , 816 , 5 , 059 , 512 , 5 , 055 , 439 , 5 , 047 , 568 , 5 , 045 , 431 , 5 , 026 , 624 , 5 , 019 , 481 , 4 , 940 , 651 , 4 , 939 , 070 , 4 , 931 , 379 , 4 , 822 , 245 , 4 , 800 , 152 , 4 , 760 , 013 , 4 , 551 , 418 , 5 , 338 , 818 , 5 , 322 , 765 , 5 , 250 , 395 , 4 , 613 , 398 , 4 , 552 , 833 , 5 , 457 , 005 , 5 , 422 , 223 , 5 , 338 , 818 , 5 , 322 , 765 , 5 , 312 , 717 , 5 , 229 , 256 , 5 , 286 , 599 , 5 , 270 , 151 , 5 , 250 , 395 , 5 , 238 , 773 , 5 , 229 , 256 , 5 , 229 , 251 , 5 , 215 , 861 , 5 , 204 , 226 , 5 , 115 , 095 , 5 , 110 , 711 , 5 , 059 , 512 , 5 , 041 , 358 , 5 , 023 , 164 , 4 , 999 , 280 , 4 , 981 , 909 , 4 , 908 , 298 , 4 , 867 , 838 , 4 , 816 , 112 , 4 , 810 , 601 , 4 , 808 , 511 , 4 , 782 , 008 , 4 , 770 , 974 , 4 , 693 , 960 , 4 , 692 , 205 , 4 , 665 , 006 , 4 , 657 , 845 , 4 , 613 , 398 , 4 , 603 , 195 , 4 , 601 , 913 , 4 , 599 , 243 , 4 , 552 , 833 , 4 , 507 , 331 , 4 , 493 , 855 , 4 , 464 , 460 , 4 , 430 , 153 , 4 , 307 , 179 , 4 , 307 , 178 , 5 , 362 , 599 , 4 , 397 , 937 , 5 , 567 , 569 , 5 , 342 , 727 , 5 , 294 , 680 , 5 , 273 , 856 , 4 , 980 , 264 , 4 , 942 , 108 , 4 , 880 , 722 , 4 , 853 , 315 , 4 , 601 , 969 , 4 , 568 , 631 , 4 , 564 , 575 , 4 , 552 , 831 , 4 , 522 , 911 , 4 , 464 , 458 , 4 , 409 , 319 , 4 , 377 , 633 , 4 , 339 , 522 , 4 , 259 , 430 , 5 , 209 , 815 , 4 , 211 , 834 , 5 , 260 , 172 , 5 , 258 , 264 , 5 , 227 , 280 , 5 , 024 , 896 , 4 , 904 , 564 , 4 , 828 , 964 , 4 , 745 , 045 , 4 , 692 , 205 , 4 , 606 , 998 , 4 , 600 , 683 , 4 , 499 , 243 , 4 , 567 , 132 , 4 , 564 , 584 , 4 , 562 , 091 , 4 , 539 , 222 , 4 , 493 , 855 , 4 , 456 , 675 , 4 , 359 , 522 , 4 , 289 , 573 , 4 , 284 , 706 , 4 , 238 , 559 , 4 , 224 , 361 , 4 , 212 , 935 , 4 , 204 , 009 , 5 , 091 , 103 , 5 , 124 , 927 , 5 , 378 , 511 , 5 , 366 , 757 , 4 , 590 , 094 , 4 , 886 , 727 , 5 , 268 , 260 , 5 , 391 , 464 , 5 , 115 , 090 , 5 , 114 , 826 , 4 , 886 , 734 , 4 , 568 , 601 , 4 , 678 , 850 , 4 , 543 , 319 , 4 , 524 , 126 , 4 , 497 , 891 , 4 , 414 , 314 , 4 , 414 , 059 , 4 , 398 , 001 , 4 , 389 , 482 , 4 , 379 , 826 , 4 , 379 , 833 , 4 , 187 , 331 , which are described herein by reference . the multilayer resist structures described herein can be used for 248 , 193 , 157 , euv , e - beam , x - ray , and ion beam lithography . the following examples are given to illustrate the scope of the present invention . because these examples are given for illustrative purposes only , the invention embodied therein should not be limited thereto . the following example illustrates calculations for obtaining optimum bottom layer parameters of a bilayer system . parameters are optimized so as to reduce reflections at the resist / underlayer interface . computations are based on algorithms which use the fresnel coefficients as found in standard textbooks such as optics , by e . hecht and a . zajac , published in 1979 by wiley , pages 312 and 313 . these simulations can be extended to many different structures and they are not limited by the examples given below . the structure simulated in this example includes a si substrate , underlayer and photoresist . the parameters under investigation are the bottom layer optical constants n and k and film thickness d . the imaging si - containing resist index of refraction extinction coefficient k and film thickness are fixed and given by n = 1 . 78 , k = 0 . 018 and d = 2000 a at 248 nm . fig3 shows reflectivity at the underlayer / resist interface at 248 nm as a function of underlayer thickness for different values of refractive index ( n ) using a fixed value of k = 0 . 25 . the structure simulated includes a si substrate , underlayer and photoresist . these simulations show that there is no significant variation in reflectance as a function of refractive index . for instance , if 5000 a of an underlayer with 1 . 65 & lt ; n & lt ; 2 . 0 at 248 nm is chosen , a significant reflectivity reduction ( less than 0 . 01 ) can be achieved at the resist / underlayer interface . fig4 shows reflectivity at the underlayer / resist interface at 248 nm as a function of underlayer thickness , where k of the underlayer varies but n is fixed at 1 . 75 . the simulated layered structure is similar to the one described above . in this case , by increasing the extinction coefficient higher values of reflectance are obtained for a 5000 a thick underlayer . for bilayer resist structure , the extinction coefficient has a stronger impact on reflectance than does the index of refraction . an underlayer material with k value of ˜ 0 . 2 or slightly below is desirable . the optimum optical properties of the underlayer are an index of refraction in a range from 1 . 65 to 2 . 0 and an extinction coefficient from about 0 . 18 to about 0 . 22 at 248 nm . thus , by using an underlayer 5000 a or thicker , the reflectance becomes insensitive to the underlying topography . the following example illustrates how to measure the optical constants n and k of the underlayer materials . this measurement technique can be applied to a variety of different processes and it is not limited by the two example above . the optical constants were measured using an n & amp ; k analyzer manufactured by n & amp ; k technology , s . clara , calif . a description of this instrument and its operation can be found in u . s . pat . no . 4 , 905 , 170 , 1990 . they use a method based on broadband spectrophotometry and equations for optical constants derived by forouhi and bloomer ( phys . rev . b , 38 , pp . 1865 - 1874 , 1988 ). their analysis is based on a physical model for the refractive index , n , and extinction coefficient , k , applicable to a wide range of semiconductor and dielectric films , and valid over the deep ultraviolet — near infrared wavelength range . the n ( i ) and k ( i ) ( i is the wavelength ) spectra of any material cannot be measured directly but they are determined from a de - convolution of a reflectance measurements r ( i ). this measurable quantity depends on film thickness , optical constants of the films and substrate . the “ n & amp ; k method ” provides an accurate , rapid , and non - destructive way to uncouple a reflectance measurement . algorithms can be generated that compare the theoretical reflectance with the measured one . from this comparison film thickness , n ( i ) and k ( i ) spectra can be determined . fig5 ( top ) show the reflectance spectra ( from 900 to 190 nm ) measured by the n & amp ; k analyzer of novolak underlayer by the method of example 6 . the corresponding n and k values are plotted in fig5 ( bottom ). fig6 ( top ) show the reflectance spectra ( from 900 to 190 nm ) measured by the n & amp ; k analyzer of barl underlayer by the method of example 7 . fig7 ( top ) show the reflectance spectra ( from 900 to 190 nm ) measured by the n & amp ; k analyzer of phs based underlayer ( 4cu5 ) by the method of examples 8 and 9 . the films analyzed are about from 7000 and to about 8000 a thick . for these particular examples n varies from ˜ 1 . 84 to ˜ 1 . 85 and k from ˜ 0 . 15 to ˜ 0 . 22 at 248 nm which is compatible with the reflectance analysis of example 1 . the following example is given to demonstrate the tuning of optical properties of novolac / diazonapthoquinone underlayers . the optical properties of the coated novolac / diazonapthoquinone materials that described in this example are : 1 ) the index of refraction ( n ) at 248 nm , 2 ) the extinction coefficient ( k ) at 248 nm and 3 ) the absorption coefficient ( a ) 248 nm was calculated from equation ( 1 ) above . shipley grade 2 novolak had been spun coated onto 8 ″ wafers then soft baked at 120 c for 30 seconds and hard baked at four different temperatures : 225 , 250 , 252 , 275 and 300 degrees c . for 90 seconds using contact hotplates . optical properties of novolac films measured by method described in example 2 and summarized in table 1 . we have found a strong correlation between the optical properties of novolak underlayers and processing conditions . novolac underlayers found hard to control due to high dependance of n and k values on process temperature . the following example is given to demonstrate the effect of n and k values of novolak underlayer on standing waves in imaging resist . shipley grade 2 novolak had been spun coated onto 8 ″ wafers then soft baked at 120 c for 30 seconds and hard baked at four different temperatures : 225 , 252 , and 300 degrees c . for 90 seconds using contact hotplates . a thin silicon containing resist ( fig1 ) is spun on a top of novolac underlayer and baked at 120 c for 60 sec . imaging silicon containing resist used in this example previously described in ibm patent docket # am997002 and 997023 and incorporated here as a reference . then , resist is exposed to a 248 nm rediation at a dose of about 38 mj / cm2 using asml micostepper and post - exposed baked at 120 c for 60 second . then resist is developed in ldd26w shipley developer . sem cross - section pictures of 150 nm l / s developed resist shown in fig8 . fig8 ( a ) shows resist profiles obtained using of novolak underlayer described in present invention and shown no “ standing waves ” which will result in good cd control of 150 nm devices . in comparison , fig8 ( b ) and ( c ) shows pictures of resist profiles fabricated using conventional novolak materials as un underlayer . clearly , standing waves can be seen on resist profiles when conventional novolak underlayers are used . the best cross - link temperatures range between 200 and 300 c , more preferably from 225 - 275 c , and most preferably from 225 - 260 c . the following example is given to demonstrate the effects of novolak resin polydispersity on the degree of residue at the underlayer interface . molecular weights ( mw ), molecular weight distributions ( mn ) and polydispersities ( pdi ) of novolak resins that described in this example summarized in table 3 . novolak resin of various molecular weights ( mw ), molecular weight distributions ( mn ) and polydispersities ( pdi ) i , ii , and iii were dissolved in pgmea ( 15 wt . %), and spin cast onto 8 ″ si wafers . the wafers were post — application baked at 120 ° c . for 60 s and subsequently cured at 252 ° c . for 90 seconds using a contact hotplate . the silicon containing imaging resist described in example 4 was applied and processed as in the example above . sem analysis demonstrated significantly lower degree of residue when the high polydispersity novolak ( i ) was employed ( fig9 ( a )) versus either of the other novolak samples ( ii and iii ) of lower polydispersity , as shown in fig9 ( b ) and ( c ). the following example is given to demonstrate how to tune the processing conditions of novolak underlayer materials to achieve device fatures of 150 nm and below conventional novolak materials which properties have not been tunes properly , incorporated herein by reference , can not be used as an underlayer materials for multilayer resists to form device features of 150 nm and below . specially tuned as described in examples 1 - 4 shipley grade 2 novolak resin had been spun coated onto 8 ″ wafers then soft baked at 120 c for 30 seconds and hard baked at 252 c for 90 seconds using contact hotplates . a thin silicon containing resist described in example 4 is spun on a top of novolac underlayer and baked at 120 c for 60 sec . then resist is exposed to a 248 nm radiation at a dose of about 38 mj / cm2 using asml micostepper and post - exposed baked at 120 c for 60 second . then resist is developed in ldd26w shipley developer . sem pictures of 150 nm l / s patterns of developed silicon containing resist shown in fig1 . boundary between imaging silicon resist and novolak underlayer is clearly visible . note that there is a limited amount of residue “ grass ” present at silicon resist underlayer interface due to interfacial mixing during the processing . but residue is not significant and does not effect the imaging resist resolution ( fig1 ( a )). fig1 ( b ) shows resist profiles on non tuned conventional shipley novolac / diazonapthoquinone resist spr 501 used as an underlayer although novolac / diazonapthoquinone resist spr 501 was hard baked to suitably cross - linked the material to prevent interfacial mixing with the resist , significant residue was observed . resolution of 150 nm and below can not be attained with conventional novolac / diazonapthoquinone resists . the following example is given to demonstrate the use of barl as an underlayer material for multilayer resist system . barl had been spun coated onto 8 ″ wafers then baked at 225 c for 4 minutes using contact hotplates . a thin silicon containing resist described in example 4 is spun on a top of novolac underlayer and baked at 120 c for 60 sec . then resist is exposed to a 248 nm rediation at a dose of about 38 mj / cm2 using asml micostepper and post - exposed baked at 120 c for 60 second . then resist is developed in ldd26w shipley developer . fig1 shows sem picture of 125 / 150 nm l / s patterns of silicon containing resist on barl underlayer . the following example is given to demonstrate how a poly ( hydroxystyrene ) based underlayer is formulated . a four component poly ( hydroxystyrene ) based system is a blend of two polymers ( poly ( 4 - hydroxystyrene ) and 9 - anthracenylmethylated phs ), a crosslinking agent ( powderlink ), and a thermal acid generator ( p - nitrobenzyl tosylate ). fig1 shows chemical structures of poly ( 4 - hydroxystyrene ) ( fig1 ( a )), 9 - anthracenylmethylated phs ( fig1 ( b )), and tetrahydro - 1 , 3 , 4 , 6 - tetrakis ( methoxymethyl )- imidazo [ 4 , 5 - d ] imidazole - 2 , 5 -( 1h , 3h )- dione “ powderlink ” ( fig1 ( c )) and p - nitrobenzyl tosylate ( fig1 ( d )). the ratio of two polymers poly ( 4 - hydroxystyrene ) and 9 - anthracenylmethylated phs was 31 : 69 . this ratio may be adjusted between the ranges of 0 : 100 to 100 : 0 to deliver the desired optical properties . to this mixture , 10 wt -% ( based on the total polymer weight ) of the crosslinking agent - powderlink and 5 wt -% ( based on the total polymer weight ) of the thermal acid generator , p - nitrobenzyl tosylate were added . the charges of these components may be adjusted to alter the performance of the underlayer . the following example is given to demonstrate the performance of silicon containing resist on polyhydroxy styrene based underlayer which was formulater as described in the example 8 . polyhydroxy styrene based underlayer had been spun coated onto 8 ″ wafers then soft baked at 120 c for 30 seconds and then hard baked at 170 c for 90 seconds using contact hotplates . a thin silicon containing resist described in example 4 was spun on a top of the underlayer and baked at 120 c for 60 sec . then resist is exposed to a 248 nm rediation at a dose of about 38 mj / cm2 using asml micostepper and post - exposed baked at 120 c for 60 second . then resist is developed in ldd26w shipley developer . fig1 shows sem picture of 150 nm l / s patterns of silicon containing resist on polyhydroxy styrene based underlayer and shows no residue at the imaging resist / underlayer interface . while the invention has been particularly shown and described with respect to preferred embodiment thereof , it will be understood by those skilled in the art that the foregoing and other changes in form an details may be made therein without departing from the spirit and scope of the invention . | 6 |
fig1 through 14 , discussed below , and the various embodiments used to describe the principles of the present invention in this patent document are by way of illustration only and should not be construed in any way to limit the scope of the invention . those skilled in the art will understand that the principles of the present invention may be implemented in any suitable manner and in any type of suitably arranged device or system . fig1 is a partial schematic of a flyback converter 10 with an opto - coupled shunt - regulator circuit 12 and no cable compensation circuit . without cable compensation , the load voltage v load falls directly as the load current i load increases through the cable resistance r wire . while this circuit may be suitable for low current designs , it is insufficient for higher - current applications as v load drops to unacceptable voltages . flyback converter 10 is seen to include an input transformer 14 , which receives a pulsing source voltage vs and couples a transformed , rectified , and filtered voltage v out to a cable 16 . the wire resistance of the cable 16 is denoted as r wire on each cable wire 18 , and the associated voltage drop for each wire is denoted as v wire . the delivered load voltage at the termination of the cable 16 is v load , which is v out − 2v wire . wires 18 provide a continuous electrical path , where one is denoted the positive (+) wire and the other is denoted the negative wire (−). the shunt - regulator circuit 12 provides an opto - coupled feedback error signal fb based on v out at the proximal end of the cable 16 . the optical coupler t 1 provides galvanic isolation for the feedback signal fb . the shunt - regulator circuit 12 does not account for the resistance r wire of each of the cable wires 18 , even though those resistances r wire create the voltage drop v wire proportional to the load current i load . the shunt - regulator circuit 12 taps a feedback signal from v out controlled by resistive divide network resistors r fb1 and r fb2 with gain k , where the feedback signal is compared to an internal reference voltage v ref established by shunt - regulator z 1 . shunt - regulator z 1 generates a current proportional to the voltage difference between kv out and v ref to create the feedback error signal fb , which modulates the power stage ( not shown ) duty - cycle to regulate the output voltage v out . since there is no cable compensation , the load voltage v load falls directly as the load current i load increases . the regulator 12 also includes trimming components r tl , r opt , and c fb . fig2 is a partial schematic of a flyback converter 20 with an opto - coupled shunt - regulator circuit 22 which includes a remote - sense cable compensation network . like reference numerals refer to like elements including those described with reference to fig1 . the shunt - regulator 22 is responsive to both v out at the proximal end of the cable 16 and also to a remote sense voltage v rs derived from the load voltage v load of the cable 16 via wire 24 . the voltage v rs is established by a pair of remote sense resistors r rs1 and r rs2 which form a resistive divide network with gain k between the negative terminal of v load and proximal ground . advantageously , the transistor t 1 responds to a voltage relationship between v out and v rs to create the opto - coupled feedback signal fb , where the voltage reference v rs is a function of the cable resistance . remote sense wire 24 carries insignificant current and so its voltage drop is negligible . this allows the converter 20 to compensate for resistance of the cable wires 18 and their resulting voltage drops . advantageously , the compensation automatically adjusts with cable length since it accounts for the varying voltage drop from the varying resistance of the cable wires 18 . fig3 is a partial schematic of a flyback converter 30 with an opto - coupled shunt - regulator 32 which includes a local sense cable compensation network . in particular , the converter 30 implements linear cable compensation with an additional local sense resistance r sense . in some embodiments , the local sense resistance r sense is designed as a narrow section of printed circuit board ( pcb ) copper with a resistance proportional to the cable wire resistance r wire . this converter 30 is simpler than the remote sensing converter 20 , although it may be less accurate , does not adjust with cable length , and incurs additional loss . fig4 is a partial schematic of a flyback converter 40 with an opto - coupled shunt - regulator 42 which includes an amplified - sense cable compensation network . in particular , the converter 40 implements linear cable compensation with an additional local sense resistance r sense and an amplifier 44 . this approach uses a lower - valued local sense resistor r sense to reduce loss , and the amplifier 44 is used to amplify a v sense signal . in this approach , the compensation incurs higher complexity , does not adjust with cable length , and no - load losses can increase . fig5 is a partial schematic of a flyback converter 50 with an opto - coupled shunt - regulator 52 which includes v - s integration cable compensation . in particular , the converter 50 uses non - linear cable compensation with volt - second ( v - s ) integration supported by a transistor m 1 ( such as a mosfet transistor ). the transistor m 1 has a parasitic gate capacitance c iss and resistors r int1 and r int2 , which form an integrator that filters the volt - second product of the flyback output waveshape to derive an average voltage v int roughly proportional to the output current i load . as the v - s product of v sec increases , the gate voltage v int increases through the threshold region of the transistor m 1 and gradually turns the transistor m 1 on , such that the transistor m 1 responsively applies an adjusting resistance including r fb3 to the feedback sensing network of the regulator 52 . this responsively increases the voltage v out by a desired amount . the regulator 52 taps a voltage v sec from the secondary side of the transformer 14 prior to rectification and feeds it to a resistive divide network formed by resistors r int1 and r int2 . the node between this resistive divide network is coupled to the gate of the transistor m 1 . the values of r int1 and r int2 can be chosen empirically to form an integrator with c iss of the transistor m 1 , which integrates the average value of v sec and turns on the transistor m 1 gradually . fig6 a and fig6 b are charts of parameters of a 5 w source converter without load before implementing active cable compensation . referring to fig6 a , there is depicted a chart showing test data using a 5 w ( 5v out @ 1 a capability ) source converter board with no load using the converter 10 having the regulator 12 without cable compensation as shown in fig1 . fig6 b shows test data with no load using the converter 50 having the regulator 52 including cable compensation as shown in fig5 . as can be seen here , the cable compensation network of regulator 52 of fig5 could essentially make no difference in no - load operating performance . fig7 a and fig7 b are charts of parameters of a 5 w source board with load before and after v - s integration cable compensation is implemented . referring to fig7 a and fig7 b , there are depicted charts showing source voltage test data using the same test board having a load , comparing circuit parameters using the regulator 12 without cable compensation as shown in fig1 and using the regulator 52 including cable compensation as shown in fig5 . these charts illustrate the advantageous compensation for the cable wire resistance as the load current v load increases . fig8 is a chart of parameters of a 5 w test board with a load before and after active v - s cable compensation . the 5 w test board is coupled to the 5 w source converter board by a cable with total resistance of approximately 0 . 3 ohms . in particular , the chart illustrates the load voltage v load at currents corresponding to those of fig7 a and 7b with and without v - s cable compensation for a couple of operating parameters . fig8 illustrates the effective cable wire compensation achieved using the compensation regulator 52 . fig9 and 10 are diagrams depicting voltages at v out and v load from fig7 a , 7 b and 8 plotted with respect to load current for two different input parameters . in particular , fig9 and 10 illustrate graphs depicting v out and v load of the converter 10 without cable compensation and v out and v load of the converter 50 with the v - s cable compensation regulator 52 . for the converter 10 including the regulator 12 without cable compensation , the voltages v out and v load are shown to linearly decrease as the load current i load increases , where lines a reflect v out and lines b reflect v load without cable compensation . although v out declines slightly due to some source impedance , v load is seen to decline significantly due to the cable resistance . for the converter 50 with the v - s cable compensation regulator 52 , lines c show v out including the voltage compensation increase as the transistor m 1 turns on for currents over 0 . 5 a . similarly , lines d show v load including the voltage compensation increase based on v out . lines d show that v load more closely follows the original source voltage v out lines a even when the load current increases . fig1 - 14 are waveform diagrams depicting v out in response to a load - step with no compensation , in response to an unload - step with no compensation , in response to a load - step with compensation , and in response to an unload - step with compensation , respectivley . in particular , there is shown the load - step on the 5 w board without and with active cable compensation using the v - s integration technique detailed with respect to the converter 50 having the regulator 52 as shown in fig5 . in all cases , the top waveform depicts v out ac - coupled at 100 mv per division to show the transient response details , and the bottom waveform depicts v load at 5 v per division at the input to an electronic load through a cable with 0 . 3 - ohm total resistance . fig1 shows ac - coupled v out at 100 mv / div as signal e without compensation due to a positive 1 - a load step . fig1 shows v out as signal f with compensation due to the same positive 1 - a load step . fig1 shows v out as signal g without compensation due to a negative 1 - a load step , and fig1 shows v out as signal h with compensation due to the same negative 1 - a load step . the delay shown is an electronic load response time after connection to the source is made , and it is noted that active cable compensation does affect transient response . dc levels of v out are not shown due to the ac - coupling of the signal . although the above description has described specific embodiments of active cable compensation using v - s integration , various changes may be made to the active cable compensation mechanism . for example , the active cable compensation mechanism is not limited to use with the circuit of fig5 . also , the operational characteristics shown in fig6 a through 14 are examples only and do not limit the active cable compensation mechanism to any particular set of operational characteristics . it may be advantageous to set forth definitions of certain words and phrases used throughout this patent document . the term “ couple ” and its derivatives refer to any direct or indirect communication between two or more elements , whether or not those elements are in physical contact with one another . the terms “ transmit ,” “ receive ,” and “ communicate ,” as well as derivatives thereof , encompass both direct and indirect communication of information . the terms “ include ” and “ comprise ,” as well as derivatives thereof , mean inclusion without limitation . the term “ or ” is inclusive , meaning and / or . the phrase “ associated with ,” as well as derivatives thereof , may mean to include , be included within , interconnect with , contain , be contained within , connect to or with , couple to or with , be communicable with , cooperate with , interleave , juxtapose , be proximate to , be bound to or with , have , have a property of , have a relationship to or with , or the like . while this disclosure has described certain embodiments and generally associated methods , alterations and permutations of these embodiments and methods will be apparent to those skilled in the art . accordingly , the above description of example embodiments does not define or constrain this disclosure . other changes , substitutions , and alterations are also possible without departing from the spirit and scope of this disclosure , as defined by the following claims . | 7 |
fig1 a through 1f show a sample training session using the methods of the present invention . fig1 a shows a typical word processing window that accepts handwritten data . the window 100 contains a partial sentence 101 that has been entered . the insertion pointer 102 indicates where the next text data will be entered . fig1 b shows the word processing window after the handwritten data 103 has been written onto the window 100 . fig1 c shows the window 100 after the handwritten data 103 has been converted to recognized symbols . the result of the recognition was inserted into the word processing document as &# 34 ; lcitten &# 34 ; 104 . in this example , the handwritten data 103 was misrecognized . the &# 34 ; k &# 34 ; in kitten was recognized as an &# 34 ; lc .&# 34 ; at this point the user can select to train the recognizer to the correct interpretation of the user &# 39 ; s handwritten &# 34 ; k .&# 34 ; fig1 d shows the window 100 with an overlapping train window 105 after the user selects training . the train window 105 contains an ink box 106 , character boxes 107 , scroll arrows 108 , train box 110 , train button 114 , and close button 115 . the ink box 106 contains the handwritten data 103 that the user wrote on the window 100 as shown in fig1 b . the character boxes 107 contain the recognized symbols for the handwritten data displayed in the ink box 106 . if there are more recognized symbols than can be displayed at once in the character boxes 107 , the scroll arrows 108 allow the user to scroll the recognized symbols left or right into view . the ink box 106 scrolls in tandem with the character boxes 107 to insure that the handwritten data which is displayed corresponds to the recognized symbols that are visible in the character boxes 107 . fig1 e shows the selection of the misrecognized symbols 109 by the user . the user selects the misrecognized symbols 109 by tapping ( pen down and pen up ) the pen on the corresponding character boxes . the misrecognized symbols 109 are highlighted . the user can select multiple character boxes by dragging the pen across the boxes . the character boxes automatically scroll during the dragging process when the pen is dragged across the right - most or left - most visible symbol . when the misrecognized symbols are selected , the trainer displays in the ink train box 110 the handwritten data that corresponds to the selected symbols 109 . correctly recognized symbols can also be selected . in a preferred embodiment , the trainer also highlights the handwritten data in the ink box that corresponds to the selected symbols . this highlighting can be done by making the corresponding strokes thicker or using reverse video . in an alternate preferred embodiment , the user can select symbols by tapping near strokes in the ink box . the trainer selects the recognized symbol that encompasses that stroke and highlights the symbol in the character boxes . in this example , if the user tapped near the cross on the &# 34 ; t &# 34 ; the entire &# 34 ; t &# 34 ; would be highlighted . the user can also select multiple symbols by circling the corresponding data in the ink box . the display in the train box of the handwritten data corresponding to the misrecognized symbols allows the user to view the misrecognized symbols out of context with the rest of the handwritten data . this out - of - context viewing facilitates the determination of whether the misrecognition was the fault of sloppy handwriting or the fault of the recognizer . the as box 111 allows the user to input data to train the recognizer . the as box 111 contains correction box 112 and radio buttons 113 . the user enters the symbols into the correction box 112 corresponding to the handwritten data in the train box 110 . the user could enter the symbols through a keyboard , a virtual keyboard displayed on the screen , or through handwriting . the radio buttons 113 indicate whether the train box 110 contains text symbols or a gesture . after the user fills in the as box 111 , the user selects the train button 114 to train the recognizer . fig1 f shows the train window 105 after training . in a preferred embodiment , the trainer sends a message to the window 100 telling it to replace the misrecognized symbols with the correct symbols . also , if there were multiple recognition problems the user would have a chance to correct the other problems . when the user completes training , the user selects the close button 115 and control returns to the window 100 . fig2 a and 2b show a trainer window when the letter &# 34 ; g &# 34 ; in the handwritten word &# 34 ; great &# 34 ; is misrecognized and corrected . fig2 a shows the handwritten data for the word &# 34 ; great &# 34 ; in the ink box 201 . the character boxes 202 contain the recognized symbols corresponding to the data in the ink box 201 . the recognized symbols are &# 34 ; a ? reat .&# 34 ; the question mark indicates that the recognizer did not recognize corresponding handwritten data . the character &# 34 ; a &# 34 ; 203 is highlighted to indicate user selection . the train box 204 contains the handwritten data corresponding to the selected character &# 34 ; a .&# 34 ; the recognizer recognized part of the &# 34 ; g &# 34 ; as a capital &# 34 ; a .&# 34 ; fig2 b shows the handwritten data corresponding to the &# 34 ; a &# 34 ; and the unrecognized symbol . the train box 206 shows the handwritten data for the &# 34 ; g .&# 34 ; the correction box 207 shows that the user entered a &# 34 ; g &# 34 ; as the correct recognition for the handwritten &# 34 ; g .&# 34 ; the methods of the present invention allow the user considerable flexibility in training the recognizer . in the above examples , a single handwritten character was recognized as two characters . the methods also support training when multiple handwritten characters are recognized as a single character . for example , if the &# 34 ; lc &# 34 ; in &# 34 ; calces &# 34 ; is recognized as the &# 34 ; k &# 34 ; in &# 34 ; cakes ,&# 34 ; the user can then select the &# 34 ; k &# 34 ; in the character boxes and enter the &# 34 ; lc &# 34 ; in the correction box for training . similarly , the methods support training when multiple characters are incorrectly recognized as another group of multiple characters . for example , if the handwritten word &# 34 ; and &# 34 ; is misrecognized as the word &# 34 ; cued ,&# 34 ; the user can select all four characters in the character boxes -&# 34 ; cued &# 34 ;- and enter &# 34 ; and &# 34 ; into the correction box for training . the methods also support context training . for example , if the handwritten characters &# 34 ; and &# 34 ; are misrecognized as &# 34 ; aud ,&# 34 ; the user may decide that the handwritten &# 34 ; n &# 34 ; when taken out of context could be a &# 34 ; u &# 34 ; or an &# 34 ; n .&# 34 ; however , the user knows that when the handwritten &# 34 ; n &# 34 ; is within the context of the word &# 34 ; and &# 34 ; it should always be recognized as an &# 34 ; n .&# 34 ; the methods allow the user to select the &# 34 ; aud &# 34 ; in the character boxes . the methods then display the handwritten &# 34 ; and &# 34 ; in the train box . the user enters &# 34 ; and &# 34 ; in the correction box . thus , the recognizer is trained to recognize the handwritten &# 34 ; and &# 34 ; as the word &# 34 ; and &# 34 ; without recognition of the individual characters . the methods also support training with gestures . fig3 shows a character that is misrecognized as a gesture . the train box 300 shows the training when the handwritten character &# 34 ; v &# 34 ; is misrecognized as the &# 34 ; correct &# 34 ; gesture . the ink box 301 contains the handwritten data for the letter &# 34 ; v .&# 34 ; the character boxes 302 contain an indication that the handwritten data is recognized as the &# 34 ; correct &# 34 ; gesture . the as box 305 shows that the user entered a &# 34 ; v &# 34 ; as the correct recognition of the handwritten data . the methods of the present invention also support training when a gesture is misrecognized as a character . fig4 shows the as box for the train window when the handwritten data is corrected to the backspace gesture . when the gesture radio button 401 is selected , the correction box 402 displays a combo box with a list of gestures . the methods of the present invention allow for any handwritten data , whether recognized as a gesture or text , to be trained as a gesture or text . fig5 shows a window displayed by a recognizer when the recognizer verifies a training request . in a preferred embodiment , the recognizer detects that the handwritten data that is about to be trained on is very similar to an existing prototype . the recognizer displays the window 500 to verify whether training should proceed . in display field 501 , the recognizer displays the handwritten data to train on . in display field 502 , the recognizer displays the ink for the similar prototype . the recognizer prompts the user for verification to proceed with the training . this verification provides a check to ensure that the user does not train on handwritten data as one character when is should normally be recognized as a different character . in an alternate embodiment , this window can be controlled by the trainer when the recognizer returns the verification request to the trainer . fig6 shows the data structure layout the data returned by the recognizer . the recognizer returns a symbol graph . a symbol graph is a representation of possible interpretations identified by the recognizer . for example , a recognizer may interpret the handwritten word &# 34 ; dear &# 34 ; as either &# 34 ; dear &# 34 ; or &# 34 ; clear .&# 34 ; the symbol graph can be represented by the following syntax : the &# 34 ;|&# 34 ; symbol indicates that the handwritten &# 34 ; d &# 34 ; may be a &# 34 ; d &# 34 ; or a &# 34 ; cl .&# 34 ; in a preferred embodiment , a symbol graph is represented by the data structure symbol graph 601 . the symbol graph 601 contains pointer lpsyc 601a , which points to the symbol graph element to stroke table 603 , count csyc 601b , which holds the count of entries in the element to stroke table 603 , pointer lpse 601c , which points to the symbol graph element table 602 , and count csye 601d , which holds the count of the entries in the element table 602 . the element table 602 contains an entry for each element in the symbol graph . the element table corresponding to the symbol graph &# 34 ;{ d | cl } ear &# 34 ; has nine entries , one for each element . the element table 602 contains identifier syv 602a , which identifies the element type ( e . g . &# 34 ;{&# 34 ; or &# 34 ; e &# 34 ;), identifier cl 602b , which indicates the confidence the recognizer has in the recognition of the element , and index isyc 602c , which is an index into the element to stroke table 603 to the first stroke that corresponds to the element . the recognizer may give a confidence level of 0 . 9 for the &# 34 ; d &# 34 ; and 0 . 7 for the &# 34 ; cl &# 34 ; to indicate that the handwritten data is more likely &# 34 ; dear .&# 34 ; the element to stroke table 603 contains a mapping of the elements to the strokes that comprise the symbols for the symbol graph . each entry in the element to stroke table 603 contains index wstrokefirst 603a , which points to the entry in the stroke table 604 that is the first stroke in the element , index wpntfirst 603b , which points to the entry in the point table 605 that is the first point in the first stroke , index wstrokelast 603c , which points to the entry in the stroke table 604 that is the last stroke in the element , and index wpntlast 603d , which points to the entry in the point table 605 that is the first point in the last stroke . the stroke table 604 contains an entry for each stroke in the symbol graph . each entry contains index wpntfirst 604a , which points to the entry in the point table 605 that is the first point in the stroke , and index wpntlast 604b , which points to the entry in the point table 605 that is the last point in the stroke . the point table 605 contains an entry for each point that comprises the strokes . each entry contains the x 605a and y 605b coordinates for a point . fig7 shows the components of a preferred embodiment of the present invention . application 709 operates in a windowing environment supported by windows 701 . however , one skilled in the art would recognize that the methods of the present invention can be practiced in other windowing and non - windowing environments . a description of the handwriting aspects of windows is contained in &# 34 ; microsoft windows graphical environment for pen computing sdk -- guide to programming &# 34 ; manual ( appendix a ). windows 701 contains a recognition context ( rc ) manager 702 that support handwriting data entry and recognition . the rc manager 702 includes a recognizer 703 , which receives raw handwritten data and converts the data to recognized symbols . application programs requesting recognition of handwritten data receive recognized symbols upon completion of the recognition . windows 701 has a standard keyboard driver 704 and a standard mouse driver 705 . the display surface driver 706 controls the inking of data on a display . the input grid driver 707 controls the input of handwritten data from a tablet . the recognizer hook 708 traps all output from recognizer . the recognizer hook 708 sends the trapped output to the trainer 710 . the trainer 710 controls training . in operation , a user writes data onto the input tablet that is intended as input for the application 709 . the input grid driver 707 receives that data and sends it to the rc manager 702 . the rc manager 702 inks the data on the tablet by sending output data to the display surface driver 706 . the display surface driver 706 sends the data to the display . when the rc manager 702 detects that the user has finished writing , it sends the raw handwritten data to the recognizer 703 . the recognizer 703 returns the recognized symbols , formatted as a symbol graph , to the rc manager 702 . the rc manager 702 invokes the recognizer hook 708 . the recognizer hook sends the symbol graph information to the trainer 710 . the rc manager 702 also sends the recognized symbols to the application 709 . the application 709 would typically display the symbols as printed characters or perform the function indicated by gestures . when a user wants to train , the user selects a training mode in the trainer 710 . training then proceeds as illustrated in fig1 a through 1f . fig8 through 13 are flow diagrams for the trainer and the recognizer hook . fig8 is a flow diagram of the main procedure for the trainer . the procedure performs initialization and enters a standard windows message loop . in block 801 , the procedure initializes data for the trainer windows . this initialization includes registering window classes and creating instances of the windows . in block 802 , the procedure installs the recognizer hook ( described below ). in block 803 , the procedure indicates to the rc manager that it should return a recognized symbol to handwritten data mapping , as shown in fig6 . for performance reasons , the recognizer only creates a mapping when the trainer is operating . in block 804 , the procedure enters a standard windows message loop . fig9 is a flow diagram of the recognizer hook function . the recognizer hook receives the recognized symbol to handwritten data mapping ( as shown in fig6 ) each time the recognizer is invoked , and sends the mapping to the trainer , except for recognition that occurs as a result of handwriting in the correction box of the trainer window . in block 901 , if the function is invoked as a result of recognition of handwritten data in the correction box of the trainer window , then the hook ignores the mapping and returns , else the function continues at block 902 . in block 902 , the function determines which symbols were returned to the application by the rc manager , that is , the path of the symbol graph returned . for example , the rc manager may return the symbols &# 34 ; clear &# 34 ; to the application for the symbol graph &# 34 ;{ cl | d } ear .&# 34 ; in block 903 , the function sends the mapping and the symbols returned to the ink box window and the train box window . in a preferred embodiment , the trainer can maintain a circular list of pointers to previous mappings and symbols . this allows the user to select other than the most recently recognized data for training . in block 904 , the function sends the symbols returned to the character boxes window . the function then returns . fig1 is a flow diagram of the main window procedure for the trainer . the trainer window procedure processes the train button and the close button messages . in blocks 1001 through 1009 , the procedure processes the train button . the procedure ensures that the correction box is not empty , invokes function traincontext , and re - recognizes the handwritten data after training . in block 1001 , if the message indicates that the train button was selected , then the procedure continues at block 1002 , else the procedure continues at block 1010 . in block 1002 , the procedure retrieves the data from the correction box . in block 1003 , if the correction box is empty , then no training can be done and the procedure displays an error message in block 1004 and returns , else the procedure continues at block 1005 . in block 1005 , the procedure initializes data structures for training ( described below ). in block 1006 , the procedure invokes the function traincontext to train the recognizer . in block 1007 , if the training is not successful , then the procedure returns , else the procedure continues at block 1008 . in block 1008 , the procedure sets the success flag . the success flag is used to prompt the user whether to actually save the new prototypes as part of the recognizer . in block 1009 , the procedure re - recognizes the handwritten data and sends the re - recognized symbols to the character boxes window and then returns . in the block 1010 , if the message indicates the close button was selected , then the procedure continues at block 1011 , else the procedure continues with normal message processing as indicated by the ellipsis . in block 1011 , if the success flag is set , then the user may want to update the prototypes and the procedure continues at block 1012 , else the procedure returns . in block 1012 , the procedure prompts the user whether to update the prototypes based on the training . in block 1013 , if the user wants to save the training , then the procedure in block 1014 directs the recognizer to update its prototypes based on the training . the procedure then returns . fig1 is a flow diagram of the ink box window procedure . this procedure controls the display of the handwritten data in the ink box . in block 1101 , if the message indicates to display ink , then the procedure continues at block 1102 , else the procedure continues with normal message processing as indicated by the ellipsis . in block 1102 , if the ink has already been displayed in this window , then the procedure continues at block 1105 , else the procedure needs to initialize data structures for display and continues at block 1103 . in block 1103 , the procedure builds a symbol to handwritten data mapping of the symbols returned to the application . in block 1104 , the procedure determines a bounding rectangle for the handwritten data . the upper - left corner of the bounding rectangle is mapped to the upper - left corner of the ink box . the bounding rectangle is delimited by the uppermost , lowermost , right - most , and left - most points of the handwritten data to be displayed . in block 1105 , the procedure displays the handwritten data and returns . the handwritten data represents the actual raw handwritten data input by the user . fig1 is a flow diagram of the window procedure for the character boxes . the procedure controls the selection and scrolling of the symbols . in block 1201 , if the message indicates that the user tapped ( pen down and pen up ) on a character box , then the procedure continues at block 1202 , else the procedure continues at block 1204 . in block 1202 , the procedure highlights the selected ( tapped on ) box . in block 1203 , the procedure sends a message to the train box to display the handwritten data corresponding to the selected symbol and the procedure returns . in block 1204 , if the message indicates that the user dragged the pen across character boxes , then the procedure continues at block 1205 , else the procedure continues with normal message processing as shown by the ellipsis . in block 1205 , the procedure highlights the symbols dragged across and controls the scrolling of the character boxes . in block 1206 , the procedure sends a message to the train box window to display the handwritten data corresponding to the selected symbols . in block 1207 , the procedure sends a message to the ink box window to display the handwritten data corresponding to the symbols visible in the character boxes and then the procedure returns . the procedure processes the scroll arrows for the character boxes in a similar manner , that is , a message is sent to the ink box window to effect scrolling in tandem . fig1 is a flow diagram of the window procedure for the train box . this procedure displays the handwritten data in the train box that corresponds to the selected symbols . in block 1301 , if the message is to display handwritten data , then the procedure continues at block 1302 , else the procedure continues with normal message processing as shown by the ellipsis . in block 1302 , the procedure determines the bounding rectangle for the handwritten data to be displayed . the bounding rectangle is delimited by the uppermost , lowermost , right - most , and left - most points of the handwritten data to be displayed . in block 1303 , the procedure maps the upper - left corner of the bounding rectangle with the upper - left corner of the train window and displays the handwritten data . the procedure then returns . the function traincontext provides a recognizer independent training interface . in a preferred embodiment , the recognizer supplies this function . the trainer calls this function passing as parameters the symbol graph data structure containing the symbol to raw handwritten data mapping as shown in fig6 an element table containing the symbols from the correction box , and and element to stroke table that delimits the handwritten data in the train box . the index isyc of the element table may be set to null to indicate the trainer does not know how to map the new symbols to strokes . however , the index isyc may point to entries in the passed element to stroke table to indicate suggested segmentation boundaries , that is , the strokes that delimit the symbols in the correction box , to the recognizer . for example , if a user writes &# 34 ; lc ,&# 34 ; which is recognized as &# 34 ; k ,&# 34 ; then the trainer could call function traincontext , with an element to stroke table that points to the handwritten data of the &# 34 ; lc &# 34 ; and two entries , &# 34 ; 1 &# 34 ; and &# 34 ; c ,&# 34 ; in the element table . these two entries would point to the same index into a stroke to element table , indicating that both use the handwritten data that was interpreted as &# 34 ; k .&# 34 ; segmentation errors can be corrected in the other direction as well . for example , if the user writes &# 34 ; k ,&# 34 ; which is recognized as &# 34 ; lc ,&# 34 ; then the trainer could call function traincontext with a single entry &# 34 ; k &# 34 ; in the element table . the stroke to element table would contain an entry corresponding to the handwritten data that the recognizer interpreted as &# 34 ; lc .&# 34 ; although the present invention has been described in terms of preferred embodiments , it is not intended that the invention be limited to these embodiments . modifications within the spirit of the invention will be apparent to those skilled in the art . the scope of the present invention is defined by the claims that follow . | 6 |
although embodiments of the present invention will be described in further detail below with reference to examples , the present invention is not limited only to these examples . the following ingredients were mixed in formulation amounts shown in tables 1 to 3 , while decreasing the pressure in a sealed stirrer , until the mixture became uniform , to thereby prepare adhesives : the polyoxypropylene - based polymer ( i ) containing a dimethoxysilyl group as the hydrolyzable silyl group and polyoxypropylene as a main chain ( number average molecular weight 10 , 000 , viscosity at 25 ° c . 7 , 000 mpa · s , product name silyl est280 manufactured by kaneka corporation ), heavy calcium carbonate ( whiton sb manufactured by shiraishi calcium kaisha , ltd . ), colloidal calcium carbonate ( calfine 200m manufactured by shiraishi calcium kaisha , ltd . ), a silanol condensation catalyst 1 ( dibutyltin bis ( triethoxysilicate ) neostan s - 303 manufactured by nitto kasei co ., ltd . ), a silanol condensation catalyst 2 ( 1 , 8 - diazabicyclo [ 5 . 4 . 0 ] undec - 7 - ene , dbu manufactured by san - apro ltd . ), a silanol condensation catalyst 3 ( dioctyl bis ( triethoxysiloxy ) tin , trade name “ neostan s - 1 ” manufactured by nitto kasei co ., ltd . ), glass balloons ( average particle size 45 μm , true density 0 . 37 g / cm 3 , glass bubbles k37 manufactured by sumitomo 3m limited ), fly ash balloons ( average particle size 130 μm , true density 0 . 75 g / cm 3 , product name “ omega - spheres sg ” manufactured by omega minerals germany gmbh ), shirasu balloons ( average particle size 37 μm , true density 1 . 27 g / cm 3 , product name “ vs light da - 30n ” manufactured by daiken corporation ), flaky talc ( average aspect ratio 60 , average maximum length 25 μm , product name “ ms - ky ” manufactured by nippon talc co ., ltd . ), an aminosilane coupling agent ( n -( 2 - aminoethyl )- 3 - aminopropyl trimethoxysilane , kbm - 603 manufactured by shin - etsu chemical co ., ltd . ), an epoxysilane coupling agent ( 3 - glycidoxypropyl trimethoxysilane , kbm - 403 manufactured by shin - etsu chemical co ., ltd . ), a dehydrating agent ( vinyl trimethoxysilane ), the polyoxypropylene - based copolymer ( ii ) in which one dimethoxysilyl group is contained in one molecule in terms of a number average and a main chain structure is polyoxypropylene ( number average molecular weight 4 , 500 , viscosity at 25 ° c . 400 mpa · s , product name “ sax015 ” manufactured by kaneka corporation ) as a reactive diluent , and a hindered phenol - based antioxidant ( irganox ( registered trademark ) 1010 manufactured by basf ). the adhesives prepared in the above were evaluated for the following evaluations . the results are shown in tables 1 to 3 . in accordance with the above - described procedure , the adhesives were used to form the adhesive layers , and then these adhesive layers were measured for shore a hardness . in accordance with the above - described procedure , the adhesives were used to form the adhesive layers , and 90 ° peel strength of these adhesive layers was measured . also , after the adhesive layers were peeled off from softwood plywood , the failure states of the adhesive layers were visually inspected . in tables 1 to 3 , when the adhesive layer was peeled off from the softwood plywood , “ excellent ” was assigned for cohesive failure of the whole adhesive layer ; “ good ” was assigned for coexistence of cohesive failure and interfacial failure of the adhesive layer ; and “ failure ” was assigned for interfacial failure of the whole adhesive layer . the cohesive failure of the adhesive layer refers to a state where the adhesive layer was failed when peeling off the adhesive layer from the softwood plywood . also , the interfacial failure of the adhesive layer refers to a state where the peeling occurred at an interface between the softwood plywood and the adhesive layer when peeling off the adhesive layer from the softwood plywood . a higher adhesion of the adhesive layer causes more cohesive failure , and a lower adhesion of the adhesive layer causes more interfacial failure . a sub - floor material 70 ( softwood plywood : length 300 mm × width 1800 mm × thickness 20 mm ) was heated at 80 ° c . for one week to thereby be dried . after that , as shown in fig3 , an adhesive 60 ′ was applied to the sub - floor material 70 in a lateral direction in a bead shape ( width 6 mm , thickness 5 mm ) such that six beads are placed with a distance from each other of 6 mm . after that , as shown in fig4 , onto the surface of the sub - floor material 70 where the adhesive 60 ′ was applied , two floor finishing materials 80 ( softwood plywood : length 300 mm × width 900 mm × thickness 12 mm ) were laminated to thereby obtain a layered body . at this time , one end in the lateral direction of one of the floor finishing materials 80 was arranged so as to come into contact with the other end in the lateral direction of the other of the floor finishing materials 80 . next , nails 81 were driven through the floor finishing materials 80 of the layered body at four corners to fix the floor finishing materials 80 to the sub - floor material 70 . after that , the layered body was aged in an atmosphere of a temperature of 23 ° c . and a relative humidity of 55 % for two weeks , so that the adhesive 60 ′ was cured to become an adhesive layer 60 . in this manner , a connection body ( i ) was obtained in which the floor finishing materials 80 were adhesively integrated with the sub - floor material 70 by the intermediary of the adhesive layer 60 . then , this connection body ( i ) was dried in an atmosphere of a temperature of 80 ° c . and a relative humidity of 2 % for one week . the dimension ( mm ) of the joint gap generated between the two floor finishing materials in the dried connection body ( i ) was measured . as shown in fig5 , an adhesive 60 ′ was applied to a sub - floor material 70 ( softwood plywood : length 300 mm × width 450 mm × thickness 20 mm ) in a lateral direction of the sub - floor material in a bead shape ( width 6 mm , thickness 5 mm ) such that two beads are placed with a distance from each other of 300 mm . after that , onto the surface of the sub - floor material 70 where the adhesive 60 ′ was applied , a floor finishing material 80 ( softwood plywood : length 300 mm × width 450 mm × thickness 12 mm ) was laminated , and pressure was applied on the floor finishing material 80 to press and spread the adhesive 60 ′ between the sub - floor material 70 and the floor finishing material 80 . after that , a 10 kg weight was placed on a central region of the floor finishing material 80 to pressure - bond the sub - floor material 70 and the floor finishing material 80 , to thereby obtain a layered body . this layered body was aged in an atmosphere of a temperature of 23 ° c . and a relative humidity of 55 % for two weeks , so that the adhesive 60 ′ was cured to produce an adhesive layer 60 . thus , a connection body ( ii ) was obtained in which the floor finishing material 80 was adhesively integrated with the sub - floor material 70 by means of the adhesive layer 60 . the sub - floor material 70 of the connection body ( ii ) was supported by two supports 90 at both ends in the longitudinal direction as shown in fig6 . then , bending stress was applied on a central region b in the longitudinal direction of the floor finishing material 80 of the connection body ( ii ) toward the lateral direction of the floor finishing material 80 at a speed of 500 mm / min , such that a displacement ( distortion ) of 3 mm is generated . accordingly , the occurrence of floor squeaks caused by the peeling or cracking of the floor finishing material 80 was evaluated . note that “ good ” and “ fail ” in tables 1 to 3 are as follows . an adhesive in a bead shape ( width 6 mm , thickness 5 mm , length 1800 mm ) was applied to a piece of softwood plywood ( length 300 mm × width 1800 mm × thickness 20 mm ). the piece of softwood plywood stood in an atmosphere of a temperature of 23 ° c . and a relative humidity of 50 % for 7 days , to thereby obtain a cured product . then , the cured product was peeled off from the softwood plywood using a scraper from one end toward the other end in the length direction thereof , and a time ( second ) taken for peeling off the whole cured product from the softwood plywood was measured . in the same manner as that in the above - described floor squeak test , there was obtained a connection body ( ii ) in which the floor finishing materials 80 were adhesively integrated with the sub - floor material 70 by means of the adhesive layer 60 . then , the floor finishing material 80 was peeled off from the sub - floor material 70 in this connection body ( ii ) using a crowbar . at this time , “ good ” was assigned when the floor finishing material 80 was able to be peeled off from the sub - floor material 70 without damaging the sub - floor material 70 , and “ fail ” was assigned when at least part of the sub - floor material 70 was peeled off together with the floor finishing material 80 causing the sub - floor material 70 to be damaged while peeling off the floor finishing material 80 from the sub - floor material 70 . the adhesive for floor structure of the present invention is suitably used for the formation of the floor structure in which the floor finishing material is adhesively integrated with the sub - floor material . | 2 |
[ 0020 ] fig1 is plan representation of a tray 10 constructed in accordance with the principles of the invention . as shown , tray 10 has a bottom portion 12 surrounded by a peripheral sloping wall 13 . extending outward from the upper portion of peripheral sloping wall 13 is a flange 15 . the dimensions of bottom portion 12 , peripheral sloping wall 13 , and flange 15 are such as to conform to corresponding dimensions of preexisting trays ( not shown ), whereby tray 10 is nestable with , and therefore , stackable upon , the prior trays . in this manner , therefore , restaurants that purchase tray 10 are not required to dispose of their existing inventory of trays entirely , as a gradual phase - out is enabled . bottom portion 12 is provided with a molded - in pattern , which may be in the form of lines 20 , cross - hatching 21 , roughened surface 22 , or any other surface finish that would enhance frictional communication between the food - carrying containers ( not shown ) and beverages ( not shown ) thereon . of course , such a surface finish is itself optional in the practice of the invention , and any other information may be printed on bottom portion 12 of the tray , such as advertising material or an identifying trademark used by the particular restaurant , as is customary in fast food establishments . at the ends of tray 10 flange 15 is shown to extend further outward to form handle regions 25 and 26 . each of handle regions 25 and 26 has an upper surface on which molded - in information 27 and 28 is presented . the placement of molded - in information on the upper surfaces of handle regions 25 and 26 avoids the problem in the art of providing information on peripheral sloping wall 13 , which required the wall to be enlarged whereby the tray is made non - standard , thereby causing disruptions in the service and operation of the restaurant . molded - in information 27 and 28 need not be identical on both handle regions , as shown in fig1 . instead , each of the handle regions can be provided with different information . moreover , such information need not be molded - in , but may be molded to raised or negative relief on the handle regions . it is an advantage of the present invention that placement of the molded - in information on the upper surfaces of handle regions 25 and 26 produces a multi - sensory presentation of the information in that such information is not only visible , but palpable as the tray is carried by the customer . thus , the customer &# 39 ; s attention is drawn to the information which is immediately felt by the customer . thus , such information may contain material presented in braille for assisting visually challenged customers . [ 0024 ] fig2 is an isometric representation of an insert 40 which is one of a pair of such inserts that would be installed in a mold ( not shown ) during injection molding of tray 10 . as shown in this figure , mold insert 40 is provided with a pair of mounting apertures 42 that facilitate the installation of the mold insert to the mold with the use of fasteners ( not shown ). in this specific illustrative embodiment of the invention , mold insert 10 has a sealing edge 44 that has a curvature that corresponds to the outer contour of handle regions 25 and 26 . mold insert 40 has a mold surface 45 into which is made an engravement 47 in the mirror image form of the variable information that would be presented on handle regions 25 and 26 , such as molded - in information 27 or 28 . of course , the molded - in information need not be in the form of an engravement , but may , as stated hereinabove with respect to other embodiments of the invention , be in the form of a raised relief information , whereby a desired form of relief is made in the handle regions . persons of skill in the art would be able to configure the molded - in information to achieve a presentation on the handle regions of the tray of images , logos , trademarks , foreign language characters , raised braille characters , and the like . in the practice of the invention , the molded - in information has a height characteristic that has been determined empirically to provide excellent ergonomic feel while maintaining a high degree of cleanliness . that is , food particles and other substances , such as grease , must not accumulate on or around the molded - in information . additionally , the determined height characteristic must retain its advantageous tactile response and visibility characteristics after repeated usage and washing . in a practicable embodiment , the height ( or depth ) characteristic of the molded - in information is approximately between 0 . 003 ″ and 0 . 008 ″, and preferably between 0 . 005 ″ to 0 . 007 ″. these height / depth dimensions provide good feel , while the tray material stays clean and the information molded thereon remains visible during extended periods of restaurant service . in addition , it is desirable that the molded - in information have an edge contour that serves to preclude accumulation therealong of food particles , greases , and hand oils . thus , the contour , which ultimately depends on the letters and / or logo that form the molded - in information , should not have a deep ridge or corner . in some embodiments of the invention , the molded - in information is textured , while maintaining the height / depth thereof within the advantageous range set forth above . although the invention has been described in terms of specific embodiments and applications , persons skilled in the art can , in light of this teaching , generate additional embodiments without exceeding the scope or departing from the spirit of the disclosed invention . accordingly , it is to be understood that the drawing and description in this disclosure are proffered to facilitate comprehension of the invention , and should not be construed to limit the scope thereof . | 0 |
referring now to the drawings , which are for purposes of illustrating the exemplary embodiments only and not for purposes of limiting the claimed subject matter , fig1 provides a view of a system into which the presently described embodiments may be incorporated . as shown generally , fig1 is a view illustrating an exemplary structure of a umts 2 as described in the 3gpp specifications . in the drawings , like reference numerals have been used throughout to designate identical elements . the msc server 10 on the originating side of the umts 2 is connected to a mgw 12 via an mc interface . the originating mgw 12 connects to other media gateways via an nb interface . the originating msc server 10 and the originating mgw 12 are connected to a universal mobile telecommunications system radio access network ( utran ) via an iu interface . the originating msc 10 and the originating mgw 12 may be connected to a public switched telephone network ( pstn ) as well ( not shown in fig1 ). here , the utran includes a radio network controller ( rnc ) 14 and cell sites ( node bs ) ( not shown in fig1 ). the user terminal ( or user equipment : ue ) is shown as 16 . the originating msc server 10 uses megaco / itu h . 248 as the protocol for controlling the originating mgw 12 . the mc , nb , and iu interfaces are defined in current 3gpp specifications . similarly , the msc server 20 of the terminating side is connected to a mgw 22 via an mc interface . the terminating msc server 20 and the terminating mgw 22 are connected to a utran via an iu interface . the terminating msc 20 and the terminating mgw 22 may be connected to a pstn as well . here , the utran includes a rnc 24 and cell sites ( node bs ) ( not shown in fig1 ). the user terminal ( or ue ) is shown as 26 . the terminating msc server 20 uses megaco / itu h . 248 as the protocol for controlling the terminating mgw 22 . it is to be understood , however , that additional network components may be present , including intermediate nodes ( e . g ., tandem exchanges , gateway mscs ). the msc servers 10 and 20 are connected via an nc interface , while the mgws 12 and 22 are connected via an nb interface . the msc servers 10 and 20 are generally connected to each other using the session initiation protocol ( sip ) as defined by ietf rfc 3261 and associated extensions , to initiate interactive user sessions that involve the exchange of voice or data . further , the msc servers 10 and 20 control the mgws 12 and 22 and include a visitor location register ( vlr ) function to manage mobility of the terminals . the msc servers 10 and 20 may be connected to each other using bearer independent call control ( bicc ) rather than sip . while this patent describes procedures using sip , it also applies to bicc protocol or any other signaling protocol controlling packet bearers . further , the msc servers 10 and 20 are connected to the rncs 14 and 24 , respectively , via a radio access network application part ( ranap ). ranap represents a radio access network ( ran ) signaling protocol that enables each msc to control its utran . the mgws 12 and 22 perform substantial media functions and bearer interworking ( i / w ) functions for the network . the mgws 12 and 22 may additionally perform functions such as transcoding , echo cancellation , modem , bridging , lawful intercept delivery , and media packet framing interworking . mgws 12 and 22 interwork between their cn bearer and their iu bearer . the iu bearers use ietf framing as an aspect of this invention . the rncs 14 and 24 are connected to their respective ues 16 and 26 via radio access bearers ( and node bs not shown ). two control planes ( 30 a and 30 b ) exist in the standards for call establishment . the first control plane 30 a conveys call information between the msc server , the utran and the ue . the second control plane 30 b goes between the rnc and the mgw and / or msc to establish the ip iu bearer . a user plane 32 includes nodes 12 , 14 , 16 , 22 , 24 , and 26 through which user traffic travels . connections between the ues 16 and 26 and the . rncs 14 and 24 , respectively , are established by means of radio access bearers ( note that nodeb connections have been omitted for clarity ), while connections between the rncs 14 and 24 and the mgws 12 and 22 , respectively , are established through iu bearers . moreover , a connection between the mgws 12 and 22 through a transit network is established by a core network ( cn ) bearer . an end - to - end connection between the ues 16 and 26 may be established through the above - described bearers . referring to fig1 , when a call is established between the two ues 16 and 26 , each mgw ( 12 and 22 ) generates a logical entity referred to as a “ context ” for processing the corresponding call , and provides “ terminations ” for each context , which define each external connection to a context . the terminations on each context define the endpoints associated with iu or cn bearers comprising an end - to - end connection between the two ues 16 and 26 . at this time , the msc servers 10 and 20 must manage information regarding the bearer encoding ( or codec ) and network addresses and ports on each termination of the mgws 12 and 22 , respectively , to establish and maintain the end - to - end bearer path . when both the ingress and egress paths of a mgw use the same codec , transcoding is not necessary at that mgw . if no media gateway in the bearer path performs transcoding so that the ues transparently exchange codec frames along the bearer path , this condition is known as transcoder free operation ( trfo ). if one of the endpoints is required to transcode , for example , when transcoding to pcm for a ue in the pstn , but no other media gateway in the bearer path performs transcoding , the condition is known as remote transcoder operation ( rto ). trfo or rto is desired to minimize the number of transcoding stages performed in the network , thus minimizing the bearer delay and voice quality degradation introduced by each transcoding stage . the establishment of trfo or rto in the network requires the end - to - end negotiation of codec capabilities throughout the network to maximize the number of bearer segments using the same codec . sip uses the session description protocol ( sdp ) defined in ietf rfc 4566 and the corresponding sdp offer / answer negotiation procedures defined in ietf rfc 3264 to perform the end - to - end codec negotiation . the voice packets then traverse through the originating mgw 12 on route toward the destination , for example , the ue 26 on the terminating side . in many cases , the originating mgw 12 does nothing more than convert the type of packetization used for the voice , i . e ., no transcoding of voice to another format is necessary . for example , the originating mgw 12 performs framing conversion between amr / iuup / rtp on the rnc side and amr / rtp / ip on the cn side . the newly reframed packets are then sent on toward the destination ( which can be another mgw , an rnc , an ims system , and so on ). thus , the originating mgw 12 is in bearer paths even when it does not do transcoding , which is one of its main functions . using the originating mgw 12 solely for a reframing function is not efficient from a cost and voice quality viewpoint . the solution to this problem involves eliminating the mgws 12 and / or 22 from the voice path when transcoding is not involved . to accomplish this goal , the rnc framing and vocoding is changed to be the same ( or a subset of ) that used in the cn . the rnc supports amr / rtp and csd bearers as used in the cn ; thus , the mgws 12 and 22 are not needed for framing conversion when carrying these bearers through the network . of course , the mgw 12 or 22 may be added and subtracted from the bearer path as necessary . in this regard , the mgw is only utilized for services such as hard handover , multiparty , call forwarding , tones and announcements , and customized applications for mobile network enhanced logic ( camel ). the mgw is subsequently removed after that service completes ( per fig2 ). this solution applies equally as well to intra - msc and inter - msc calls . iucs is the circuit switched ( cs ) interface between the rnc and the msc . this consists of several protocols and underlying atm or ip hardware with an integrated management entity . with respect to the exemplary embodiment of the invention , the iucs control plane protocol stack ( 3g ts 25 . 413 ) is not modified , i . e ., it remains as ranap / sccp / m3ua / sctp / ip / ethernet , while the iucs user plane protocol stack changes to become rtp / udp / ip / ethernet . the exemplary embodiment of a call processing method 100 for improving network efficiency is set forth in fig2 . the method 100 includes the following steps . initially , a call from a calling party originates at the msc 10 on the originating side or is delivered to the msc 20 on the terminating side ( 102 ). next , the msc 10 or 20 determines if an mgw 12 or 22 is needed immediately ( 104 ). if so , the mgw is allocated and inserted as part of the initial bearer path establishment ( 106 ). else , the call bearer path is set up directly via the rnc 14 or 24 ( 108 ). in this regard , the mgw 12 or 22 is bypassed . once the call bearer path has been set up , any number of call events may occur ( 110 ) at a node that allow the removal of the mgw 12 or 22 that is already in the call bearer path or that require the insertion of the mgw 12 or 22 into the call bearer path . such call events may include call answer , tones and announcements , call conferencing ( e . g . 3 - way or 6 - way calling ), resuming to a 2 - party call , wire tapping ( calea ), handover to another rnc or to a gsm system , services such as call forwarding and multi - party conferencing , etc . this applies to intra - msc and inter - msc calls . thus , when a call event occurs ( 110 ) at a node in the umts 2 , a determination is made as to whether the originating mgw 12 ( or the terminating mgw 22 ) is needed ( 112 ). if it is needed , then the appropriate mgw ( 12 or 22 ) is added to the call bearer path if it is not already present ( 114 ). when the mgw ( 12 or 22 ) is no longer needed , another call event occurs that allows it to be subtracted from the session . of course , if the mgw ( 12 or 22 ) is not needed , then the triggering call event is processed without a mgw or the mgw is removed if currently being used ( 116 ). to further explain the operation of the present invention , two message signaling diagrams are presented in fig3 and 4 . the following two scenarios in fig3 and 4 illustrate two common end - to - end call scenarios and possible methods for removing and inserting cn mgws on an as - needed basis within the scenarios . fig3 and 4 show call scenarios in which either the originating msc or the terminating msc , respectively , generates in - band call progress information towards the calling party . these figures show the establishment of the originating radio access bearer before the establishment of the core network ( cn ) bearer and establishment of the terminating radio access bearer either before or after establishment of the cn bearer . other variations exist for radio access bearer establishment and can be used to achieve the same result . for example , some implementations could choose to establish the cn bearer ( via invite ) before establishing the bearer with the originating rnc . these figs also show the sending of the 180 ringing response as the first sip provisional response message . other variations exist in the sip message sequence ( e . g ., sending the 183 call progress response as the first sip provisional response message ) that can achieve the same result in supporting sdp offer / answer negotiation procedures and progressing the call . additionally , the current flows in this description convey a sequential flow of messages . reasonable implementations could use parallel message exchange to optimize and reduce the time needed to complete the signaling . one example of the latter case is performing mgw “ add ” commands in parallel with the response to the 180 ringing response . sip and 3gpp messaging provide the building blocks with which an msc server brings mgws in and out of the bearer path as needed . these scenarios and procedures also apply to other network types such as cdma . fig3 shows a message signaling diagram when a network subscriber desires to establish a session with another network participant and the call establishment signaling in the network determines that the originating msc is to provide call progress information to the calling party . the procedure begins with a mobile origination triggered by a message from the ue 16 that is not shown in fig3 . after a setup message is received from an originating ue , the originating msc 10 requests media resources to be allocated at the originating rnc 14 . since the peer party ip address is not known at this point , the originating msc 10 sets the ip address to 0 . 0 . 0 . 0 in the rab assignment message ( 201 ). the originating rnc 14 responds to the rab assignment by establishing the radio access bearer and returning an rab assignment complete message ( 202 ) to the originating msc 10 with the ip address / port ( r 1 ) assigned at the rnc 14 for the iu bearer connection . while a radio access bearer assignment message exchange has occurred , the iu bearer is not yet established at this point because the originating rnc 14 does not have the ip address / port of the iu or cn bearer endpoint . the call setup is then continued from the originating msc 10 to the terminating msc 20 . an invite request ( 203 ) is sent from the originating msc 10 to the terminating msc 20 with a list of supported codecs and cn bearer connection information to the remote end . it is desirable to prevent the flow of early media before all necessary resources have been allocated in the bearer path . the method shown in the flow to accomplish this is the use of the unspecified address of 0 . 0 . 0 . 0 for the originating ip address . alternative methods , which are not illustrated in the flow , such as the use of sip preconditions procedures ( per ietf rfc 3312 ) or a separate media line for early media , are also possible . the terminating msc 20 responds by sending a 100 trying response ( 204 ). the terminating msc 20 indicates that the called party &# 39 ; s terminal device or phone is ringing by sending a 180 ringing response ( 205 ) to the originating msc 10 . the coding of the p - early - media header with the “ inactive ” parameter in this message indicates that the terminating msc 20 is not providing call progress tones to the calling party and that it expects the originating msc 10 to provide a ringback tone to the calling party . the ringback is a signaling tone indicating that a called party is being alerted . in parallel , the terminating msc 20 initiates paging and authentication of the called mobile ( which is not shown in the call flows ). the originating msc determines that it needs to insert a mgw in the bearer path to provide the ringback call progress tone to the originator as indicated by the 180 ringing response ( 205 ) to the initial invite request . the originating msc does the following in parallel : responds to the 180 ringing response with a prack request ( 206 ) ( which supports a reliable exchange of the 180 ringing provisional response per ietf rfc 3262 ), and requests an ip address / port assignment from mgw 12 by sending a h . 248 add command ( 208 ) to mgw 12 . the add command includes the codec selected for the ue 16 during the rab assignment procedure ( 201 , 202 ) and the ringback call progress tone indicator ( cg / rt ) to be played to the originating ue 16 . the mgw 12 responds with the ip address / port ( o 1 ) in the addreply message ( 209 ). next , the originating msc 10 completes the establishment of the iu bearer connection between the allocated originating mgw 12 and the originating rnc 14 . it does this by sending an rab assignment message ( 210 ) containing the mgw ip address / port ( o 1 ) to the originating rnc 14 . the rnc 14 confirms the rab assignment message by returning an rab assignment complete message ( 211 ) containing the same rnc 14 ip address / port ( r 1 ). upon receiving the prack request ( 206 ) from the originating msc 10 , the terminating msc 20 responds with a 200 ok ( prack ) response ( 207 ) to complete the sip prack sequence . after the terminating msc 20 receives a paging response from ue 26 , it allocates media resources on the terminating rnc 24 . it forwards a rab assignment message ( 212 ) to the terminating rnc 24 with a remote ip address set to 0 . 0 . 0 . 0 to establish the terminating radio access bearer . in response , the terminating rnc 24 sends an rab assignment complete message ( 213 ) to the terminating msc 20 with the terminating rnc ip address / port ( r 2 ). the terminating msc 20 sets up the terminating iu connection without the remote ip address / port since it does not yet have a valid ip address / port of the originating side . the terminating msc 20 then communicates the terminating rnc 24 media information to the originating msc 10 by sending a 183 session progress response ( 214 ) to the originating msc 10 . the 183 session progress response includes the selected codec ( e . g ., amr ) and the ip address / port of the terminating rnc 14 ( r 2 ). the originating msc 10 responds with another prack request ( 215 ). the terminating msc 20 responds with a 200 ok ( prack ) response ( 216 ) to complete the sip prack sequence . the originating msc saves the remote ip address / port ( r 2 ) and codec received in the 183 session progress response for future use . when the mobile answers , the terminating msc 20 sends a 200 ok ( invite ) response ( 217 ) to the originating msc 10 , which responds with an ack request ( 218 ). the initial codec negotiation is completed , but an end - to - end media path has not yet been established . furthermore , the call answer call event requires the cessation of ringback to the calling party , making the tone generation function of mgw 12 unnecessary . to fully establish an end - to - end media path , the originating msc ( 10 ) sends a re - invite request ( 219 ) with the preferred codec ( e . g ., amr ) received in step 214 . it also includes the rnc 12 ip address / port ( r 1 ) in the re - invite request . in this example , since a common codec is negotiated between the radio access bearer connection and the core network bearer path and the framing protocol is also the same ( rfc 3267 ) between these two interfaces , neither codec transcoding nor framing conversion is necessary . therefore , the originating mgw 12 is no longer needed and the originating msc 10 can remove it from the call bearer path . to remove the originating mgw 12 from the bearer path , the originating msc 10 sends a subtract message ( 220 ) to the originating mgw 12 ( 220 ), which responds with a subtractreply message ( 224 ). in parallel , the originating msc 10 assumes that the remote cn bearer address / port ( r 2 ) will not change and sends an rab assignment message ( 223 ) to the originating rnc 14 containing the terminating rnc ip address / port ( r 2 ). the originating rnc 14 responds with an rab assignment complete message ( 225 ). if the remote cn bearer address / port returned in the subsequent 200 ok response ( 226 ) is not the assumed value ( r 2 ) then the originating msc 10 can update the originating rnc 14 with another rab assignment message ( not shown ). when the re - invite request is received at the terminating msc 20 , the terminating msc 20 sends an rab assignment message to the terminating rnc 24 ( 221 ) with the ip address / port of the originating rnc ( r 1 ) received in the re - invite request , thus connecting the bearer path from rnc 12 to rnc 14 . rnc 14 confirms receipt by returning an rab assignment complete message ( 222 ). finally , the terminating msc 20 sends a 200 ok ( re - invite ) response ( 226 ) to the originating msc 10 with the ip address / port of the terminating rnc ( r 2 ), and the originating msc 10 responds with an ack request ( 227 ). the media now flows between the rnc 14 and rnc 24 without any intervening mgws in the path after call answer . it was shown in fig3 that a media gateway may be necessary during call establishment in order to provide the ringing call progress tone . however , one option to optimize this method even more is that the rnc could be instructed to provide the ringback call progress tone . in this way , the initial call setup does not use a mgw . additionally , the rnc could support and be instructed to play common announcements such as when the terminating party does not answer or is busy . the additional signaling required for the rnc to provide call progress tones is not shown . if at any time a call event occurs at either msc 10 or msc 20 for which it would be desirable to insert or remove a local mgw , the msc can initiate a standard re - invite transaction by sending the re - invite request to its peer msc . the re - invite request will include sdp with codec and address information for the desired local bearer configuration ( with or without the local mgw ). this is a standard mid - call sdp offer / answer scenario so no figure is included to describe the message flow . fig4 represents a message signaling diagram when the call establishment signaling in the network determines that the terminating msc is to provide the call progress information to the calling party . the procedure begins with a mobile origination triggered by a message from the ue 16 that is not shown in fig4 . the initial message flows for fig4 are identical to fig3 through the initial invite request . after a setup message is received from an originating ue , an rab assignment is sent from the originating msc 10 to the originating rnc 14 ( 301 ) with the remote ip address set to 0 . 0 . 0 . 0 to establish the radio access bearer . the originating rnc 14 responds by sending an rab assignment complete message ( 302 ) with the ip address / port r 1 assigned at the rnc to be used for this session . an invite request ( 303 ) is then sent from the originating msc 10 to the terminating msc 20 with the codec list and ip address set to 0 . 0 . 0 . 0 . when the terminating msc 20 receives the invite request , it responds with a 100 trying response ( 304 ). also , the terminating msc 20 , because it determines that it will provide the call progress tone , needs to insert a mgw in the media path to do so . terminating msc 20 sends an add request ( 305 ) with the remote ip address / port received in the invite request , the selected codec and the ringback call progress tone indicator ( cg / rt ) to the terminating mgw 22 , though the call progress media can not flow until the bearer path is fully established with an exchange of valid address information . the selected codec is usually the first codec in the offered list , if supported by the terminating mgw 22 , to avoid any transcoding at the originating mgw 12 . the terminating mgw 22 responds with an addreply message ( 306 ) including the ip address / port ( t 1 ) assigned by the mgw 22 . the terminating msc 20 then sends a 180 ringing response ( 307 ) to the originating msc 10 with the terminating mgw ip address / port ( t 1 ) and selected codec ( e . g ., amr ). it also includes the p - early - media header coded with “ sendonly ” indicating that the terminating msc 20 is providing the call progress tone . in parallel , the terminating msc 20 initiates paging and authentication of the called mobile ( which is not shown in the call flows ). the originating msc 10 needs to establish the bearer path between rnc 14 and the remote network endpoint ( mgw 22 ) and therefore sends an rab assignment ( 308 ) to the originating rnc 14 with remote ip address / port set to t 1 . rnc 14 returns an rab assignment complete message ( 309 ) to the originating msc 10 . the originating msc 10 sends a prack request ( 310 ) to the terminating msc 20 with ip address / port of originating rnc 14 ( r 1 ) and the selected codec . the terminating msc 20 then sends a h . 248 modify message ( 311 ) to the terminating mgw 22 with remote ip address / port of r 1 . mgw 22 responds with a modifyreply message ( 312 ). in parallel with 311 the terminating msc 20 sends a 200 ok ( prack ) response ( 313 ) to the originating msc 10 . at this point , the bearer path is connected between the originating rnc 14 and the terminating mgw 22 to provide call progress tone to the originating ue 16 using the selected codec ( e . g ., amr ). therefore , in this scenario no transcoding is needed so far . upon receiving a page response message ( not shown ) from the terminating ue 26 , the terminating msc 20 establishes the radio access bearer connection between the terminating rnc 24 and the terminating ue 26 . ( the page response provides an indication to the terminating msc which rnc to use for the call .) msc 20 sends an rab assignment message ( 314 ) with an unspecified address ( 0 . 0 . 0 . 0 ) to the terminating rnc 24 to prevent any backward media flow from the terminating rnc 24 . the terminating rnc 24 responds with an rab assignment complete message ( 315 ) including the rnc ip address / port r 2 to be used for this call . when the terminating ue 26 answers , the terminating msc 20 establishes the bearer path directly between the originating and terminating rncs by sending an update request ( 316 ) to the originating msc 10 with the rnc 24 ip address / port r 2 and the selected codec ( e . g ., amr ). because no transcoding is required ( as amr was negotiated as a common codec ) and the framing protocol ( rfc 3267 ) is the same on the originating rnc 14 and on the terminating rnc 24 it is possible to remove all mgws from the bearer path between the originating rnc 14 and the terminating rnc 24 . since the call progress tone is no longer needed at this point , the terminating mgw 22 may now be removed . the terminating msc 20 sends a subtract message ( 317 ) to the terminating mgw 22 , which responds with a subtractreply message ( 318 ) and removes itself from the bearer path . upon receiving the update request , the originating msc 10 sends an rab assignment message ( 319 ) with the ip address / port r 2 to the originating rnc 14 , which responds with an rab assignment complete message ( 320 ) with r 1 as the ip address / port to use on rnc 14 . the originating msc 10 then sends a 200 ok ( update ) response ( 321 ) to the terminating msc 20 with the ip address / port of rnc 14 ( r 1 ). the terminating msc 20 then sends an rab assignment message ( 322 ) to the terminating rnc 24 with the far end ip address / port r 1 . the terminating rnc 24 responds with an rab assignment complete message ( 323 ). this completes the establishment of the end - to - end bearer path . the terminating msc 20 sends a 200 ok ( invite ) response ( 324 ) to the originating msc 10 , which responds with an ack request ( 325 ) to complete call setup . at this point media flows directly between rnc 1 and rnc 2 . since no transcoding is required , a mgw is not needed in the path . as in the scenario of fig3 , if at any time a call event occurs at either msc 10 or msc 20 for which it would be desirable to insert or remove a local mgw , the msc can initiate a standard re - invite transaction by sending the re - invite request to its peer msc . the re - invite request will include sdp with codec and address information for the desired local bearer configuration ( with or without the local mgw ). this is a standard mid - call sdp offer / answer scenario so no figure is included to describe the message flow . this invention does not apply to intermediate mscs and mscs that interface to other networks ( e . g . tandems , gateway mscs ) since they do not involve a radio access network . insertion and removal of mgws at call setup and as the result of call events at these nodes ( not shown in any figures ) can be realized using sip third party call control procedures as described in prior art . the detailed description presented above is represented largely in terms of processes and symbolic representations of operations performed by conventional computer components , including a central processing unit ( cpu ), memory storage devices for the cpu , and connected display devices . these operations include the manipulation of data bits by the cpu , and the maintenance of these bits within data structures that reside in one or more of the memory storage devices . such data structures impose a physical organization upon the collection of data bits stored within computer memory and represent specific electrical or magnetic elements . these symbolic representations are the means used by those skilled in the art of computer programming and computer construction to most effectively convey teachings and discoveries to others skilled in the art . for the purposes of this discussion , a process is generally conceived to be a sequence of computer - executed steps leading to a desired result . these steps generally require physical manipulations of physical quantities . usually , though not necessarily , these quantities take the form of electrical , magnetic , or optical signals capable of being stored , transferred , combined , compared , or otherwise manipulated . it is conventional for those skilled in the art to refer to these signals as bits , values , elements , symbols , characters , terms , objects , numbers , records , files or the like . it should be kept in mind , however , that these and similar terms should be associated with appropriate physical quantities for computer operations , and that these terms are merely conventional labels applied to physical quantities that exist within and during operation of the computer . in addition , it should be understood that the programs , processes , methods , etc . described herein are not related or limited to any particular computer or apparatus . rather , various types of general purpose machines may be used with programs constructed in accordance with the teachings described herein . similarly , it may prove advantageous to construct specialized apparatus to perform the method steps described herein by way of dedicated computer systems with hard - wired logic or programs stored in nonvolatile memory , such as read only memory . the above description merely provides a disclosure of particular embodiments of the invention and is not intended for the purposes of limiting the same thereto . as such , the invention is not limited to only the above - described embodiments . rather , it is recognized that one skilled in the art could conceive alternative embodiments that fall within the scope of the invention . | 7 |
preferred compounds of the invention are dcnbs sodium salt and dmnbs sodium salt . however , other salt forms are contemplated , and which retain the essential features of the invention . dcnbs and dmnbs may be formulated and used in the same manner as dbnbs . dcnbs and dmnbs , and their respective salts , may be isotopically labelled using the isotope 2 h or 15 n . the synthesis and utility of dcnbs and dmnbs are described below . for example , a compound of the invention may be used in assaying any suitable sample for the presence of sulphite radical anion , nitric oxide , alkyl free radicals or superoxide . a compound of the invention may also be used in an assay for an oxidant from the dialysate of a uremic patient . see also british patent application no . 0024938 . 3 . in an assay of the invention , radicals may be detected by esr spectroscopy . in a particular embodiment of the invention , dmnbs may be used instead of hhtio in the elisa - esr assay described above . based on the same principles , the dmnbs - so 3 − adduct can be formed from a reaction mixture of sulphite , hydrogen peroxide and dmnbs by the action of hrp ( fig2 ). many hrp - labelled antibodies are widely available . preliminary results suggest that the dmnbs assay is superior to the hhtio assay , indicating that a compound of the invention may be used as a detector molecule for the presence of antibody - peroxidase complexes in elisas with esr detection . the following examples illustrate the preparation of compounds of the invention . the subsequent tests illustrate their utility . dcnbs was synthesised in two steps from 2 , 6 - dichloroaniline ( aldrich chemical co .) as described below . for reference , dbnbs was synthesised from 3 , 5 - dibromosulphanilic acid , sodium salt ( aldrich chemical co .) by the method of kaur et al , supra . horseradish peroxidase ( type vi ), phosphate buffered saline tablets , hydrogen peroxide and dipotassium sulphite were all purchased from sigma chemical company , poole , dorset , u . k . 2 , 6 - dichloroaniline ( 22 . 0 g ; 0 . 136 mol ) was added cautiously to concentrated sulphuric acid ( 50 ml ) under nitrogen , with cooling and stirring . when addition was complete the reaction mixture was heated under nitrogen at 170 ° c . for 5 hr , then allowed to cool to 50 ° c . before pouring into cold water ( 4 ° c .). the precipitate was filtered and then heated with decolourising charcoal ( 2 g ) in boiling water ( 500 ml ) for 15 min . after filtration the solvent was removed and the crude product was recrystallised from water to give a crystalline solid , which was dried over silica gel overnight , to give 3 , 5 - dichlorosulphanilic acid as a white powder . yield 13 . 7 g ( 42 %). 3 , 5 - dichlorosulphanilic acid ( 2 . 0 g ; 8 . 26 mmol ) and 30 % hydrogen peroxide ( 5 . 9 ml ; 0 . 058 mol ) were added to a solution of sodium acetate ( 0 . 68 g ; 8 . 26 mmol ) in glacial acetic acid ( 14 ml ) and stirred until the solid was completely dissolved . the resulting solution was left to stand at room temperature for 14 days , after which time a portion of the solvent was removed on the rotary evaporator ( water bath temperature 40 - 50 ° c .) until a solid product was just observed . the reaction mixture was then left to stand overnight at 4 ° c . the product was filtered and washed with glacial acetic acid ( 5 ml ), absolute ethanol ( 10 ml ), dioxane / diethyl ether ( 1 : 1 ) ( 10 ml ) and absolute ethanol ( 10 ml ). the product was dried over silica gel overnight , to give 3 , 5 - dichloro - 4 - nitrosobenzenesulphonate , sodium salt as a cream powder . yield 0 . 92 g ( 40 %). peaks observed at 254 , 256 , 258 a . m . u . ( 14 %, 10 %, 4 %) which is consistent with m + - na for dcnbs . freshly distilled 2 , 6 - dimethylaniline ( 25 ml ; 0 . 20 mol ) was added cautiously to concentrated sulphuric acid ( 37 . 5 ml ) with cooling and stirring . when addition was complete , the reaction mixture was heated at 170 ° c . for 5 hr , then allowed to cool to 70 ° c . before pouring into cold water ( 4 ° c .). the precipitate was filtered after standing for 15 min . it was then dissolved in 2m sodium hydroxide ( 600 ml ) and heated with decolourising charcoal for 15 min . the mixture was filtered and allowed to cool . it was then acidified to ph 3 ( with caution ) using 2m hydrochloric acid . upon cooling to 4 ° c ., the product crystallised as a white solid . this was filtered and dried over silica gel under vacuum . yield 18 . 4 g ( 45 %). aqueous sodium hydroxide ( 2m ) was added dropwise to a suspension of 3 , 5 - dimethylsulphanilic acid ( 8 . 3 g ; mmol ) in water ( 50 ml ) until all the acid had dissolved and the solution was just basic ( ph 11 ). the solution was refluxed for 1 hr , the solvent was removed under reduced pressure to give a white solid which was dried over p 2 o 5 under vacuum . yield 8 . 0 g ( 87 %). i . r . 1167 cm − 1 ( s ) ( so 3 − ). literature states 1200 - 1145 cm − 1 ( so 3 − ). anhydrous sodium acetate ( 3 . 09 g ; 37 . 7 mmol ) was dissolved in glacial acetic acid ( 84 . 6 ml ) with stirring . to this solution was added 3 , 5 - dimethylsulphanilic acid , sodium salt ( 8 . 39 g ; 37 . 7 mmol ) and hydrogen peroxide ( 30 % w / v , 30 . 2 ml ; 0 . 294 mol ). the reaction mixture was heated at 60 ° c . for 1 hr and then stirred at room temperature for 2 hr . the reaction mixture was left to stand at room temperature overnight to give a crystalline product . the product was filtered and washed with glacial acetic acid ( 40 ml ), ethanol ( 40 ml ), dioxane / diethyl ether ( 1 : 1 ) ( 40 ml ) and ethanol ( 40 ml ) to give a pale yellow solid . fab - ms ( negative ion mode , using 3 - nba as the matrix ). peak observed at 214 ( m + - na , 24 %). 1 h nmr ( 400 mhz , d 2 o ) 2 . 42 ( 6h , s , 2 ×— c h 3 ) and 7 . 68 ( 2h , s , 2 - h and 6 - h ). 13 c nmr ( 400 mhz , d 2 o ) 18 . 2 ( 2 ×— ch 3 ), 126 . 8 ( c - 2 and c - 6 ), 134 . 6 ( c3 and c - 5 ), 142 . 0 and 145 . 5 ( c - 1 and c - 4 ). esr spectra were obtained using a prototype spectrometer ( jeol ( u . k ) ltd ., welwyn garden city , england ) equipped with a te 011 cylindrical cavity . samples were analysed at room temperature in a wg - lc - 11 quartz flat cell ( wilmad - glass , buena , n . j .). in general the instrument parameters were : microwave frequency 9 . 2 ghz , microwave power 4 mw , centre field ( cf ) 336 . 7 mt , sweep width ( sw ) ± 5 mt , number of data points 4095 , modulation frequency 100 khz . for the spin traps reacted with horseradish peroxidase / h 2 o 2 / sulphite : sweep time 200 s , time constraint 0 . 1 s , modulation width 0 . 05 . for the spin traps reacted with the oxidant and no ; sweep time 150 s , time constraint 0 . 3 s , modulation width 0 . 2 mt . a jeol es - dm1 digital manganese oxide marker ( 0 . 03 mm of the glass tube inserted per unit on the dial setting ) with a dial setting of 500 was used to ensure the reproducibility between samples and to identify the position of the signals in the microwave field . reaction of so 3 − ( horseradish peroxidase / h 2 o 2 / sulphite ) solutions of the spin traps dbnbs , dcnbs and dmnbs ( 40 mm ) ( 25 , 50 , 91 , 75 , 110 . 75 , 125 and 156 . 25 μl for final concentrations of 4 , 8 , 14 . 68 , 17 . 72 , 20 and 25 mm in pbs ) were added to 8 μl horseradish peroxidase ( 91 μm in pbs ), 8 μl k 2 so 3 ( 100 mm in water ) and 12 . 5 μl h 2 o 2 ( 5 mm in pbs ). the difference in the volume comprised pbs ( ph 7 . 4 ). the final volume of the reaction mixture was 250 μl . the reaction mixture was mixed thoroughly and analysed by esr spectroscopy after 25 min incubation at room temperature . controls were run using individual reactants as well as the reaction mixture above in the absence of the spin traps . the extent of formation of radicals by dbnbs and dcnbs was tested in the so 3 − system . when dbnbs was reacted with horseradish peroxidase / h 2 o 2 / sulphite , a triplet of doublets was observed under the esr conditions specified above . the triplet was due to the nitrogen hyperfine splitting at position 4 of the benzene ring in the dbnbs molecule and the doublet was due to the hydrogen hyperfine splitting at the 2 and 6 positions of the benzene ring . when dbnbs is replaced by dcnbs , the large bromine atoms are replaced by the smaller chlorine atoms , which causes a reduction in the line width of the signal from 0 . 087 to 0 . 085 mt . in this so 3 − system , dbnbs reached an optimal concentration at 17 . 72 mm and dcnbs at 20 - 25 mm . therefore the sensitivities of the spin traps were compared at these concentrations . the respective signal / marker ratios were 3 . 33 and 10 . 62 , indicating that dcnbs has 3 times greater sensitivity than dbnbs . when the water - soluble spin traps dmnbs , dcnbs , dbnbs , dbnbs - d 2 , dbnbs - 15 n and dbnbs - d 2 - 15 n were compared as traps for the sulphite radical anion ( so 3 − ) ( generated from hrp , h 2 o 2 , so 3 2 − ), dmnbs was found to give the largest esr signal . the signal height was found to be more than twenty times that obtained for dbnbs . it was also found to be more than three times that obtained for the isotopically labelled dbnbs analogue dbnbs - d 2 - 15 n . thus dmnbs is a particularly useful spin trap for the sulphite radical anion . the apparatus shown in fig1 was flushed with nitrogen for 15 min . the vacutainer containing deionised water ( 4 ml ) was then connected to the system and flushed with nitrogen for a further 15 min , to remove any oxygen present in the system , and therefore to prevent the formation of nitrogen dioxide . the no gas was bubbled through the deionised water via the system for 45 min . the small amount of nitrogen dioxide present in the pressurised no container was removed by bubbling through two bottles of 5m naoh . the gas was then bubbled through a scrubbing bottle containing deionised water to remove any alkaline aerosol contamination . any excess of no after the deionised water step was bubbled through a scrubbing bottle containing 1m potassium permanganate / 1m naoh to prevent excess no escaping from the fume hood . the concentration of no in the resulting no - saturated water was taken to be 2 . 0 mm . samples of dbnbs , dcnbs and dmnbs were weighed into vacutainers and evacuated . tris - hcl buffer , 0 . 01m , ph 7 . 4 , was deoxygenated by bubbling with nitrogen gas for 15 min . the deoxygenated buffer was added to the spin traps by a gas tight syringe to give a final spin trap concentration of 0 . 30m . the spin trap solution was briefly flushed with nitrogen and was then ready for use . no - saturated water ( 1 ml ) was added to 1 ml of each of the spin trap solutions ( dbnbs , dcnbs and dmnbs ). the final concentrations of the spin traps were 0 . 15m and no 1 mm . parallel blanks were carried out by adding 1 ml of deoxygenated water to the spin trap solutions . at each time point samples were taken from test solutions and blanks for esr spectroscopic analysis and the blank was substracted from the spectra . the time course experiment showed that dbnbs ( 0 . 15m ) reacted with no ( 1 . 0 mm ) very slowly under the conditions used . the reaction of dbnbs with no was found to reach a maximum at approximately 50 hr . the reaction of dmnbs with no was found to reach a maximum at 24 - 28 hr . the reaction of dcnbs with no was found to proceed fastest , with a maximum being reached between 20 - 24 hr . the spin trap solutions were prepared as above to give final concentrations of 0 . 05 , 0 . 1 , 0 . 15 , 0 . 2 and 0 . 25m in the reaction mixtures and the parallel blanks . the saturated no solution ( 0 . 5 ml , final concentration 1 mm ) was added to the test solutions and the deoxygenated water ( 0 . 5 ml ) was added to the blanks . the reaction mixtures with dbnbs were incubated for 26 hr . while those with dcnbs were incubated for 22 hr . before analysis by esr spectroscopy . the blanks were subtracted from their parallel test spectra respectively . the maximum signal intensity for dbnbs reacting with no was obtained at a concentration of 0 . 15m dbnbs . for dcnbs reacting with no , a plateau is observed from 0 . 05 - 0 . 40m dcnbs . thus the concentration at which to assess the sensitivity of dbnbs and dcnbs reacting with no was chosen as 0 . 15m . the concentration of no in no saturated water is taken to be 2 . 0 mm . this no solution was diluted with deoxygenated water to give final concentrations in the reaction mixture of 0 , 0 . 25 , 0 . 5 , 1 , 2 . 5 , 5 , 10 , 50 and 100 μm . the no solution was added to dbnbs and to dcnbs to give a final spin trap concentration of 0 . 15m . the blank ( or zero point ) was ran by adding 0 . 5 ml of deoxygenated deionised water to the spin trap solutions . the reaction mixture containing dbnbs was incubated for 50 hr , and that containing dcnbs was incubated for 20 hr . the signal to noise ratio was calculated from each spectrum . all withdrawals and additions of solutions were carried out using a gas - tight syringe . the limit of detection ( s / n ratio equals 3 ) and limit of quantitation ( s / n ratio equals 10 ) were calculated from the linear part of the curve from 0 to 10 μm . the limit of detection and limit of quantitation for dcnbs were found to be 4 . 06 μm and 17 . 30 μm respectively . the limit of detection for dbnbs was found to be 0 . 23 μm and the limit of quantitation was 0 . 92 μm . hence dbnbs was found to be a more sensitive spin trap than dcnbs for nitric oxide while dcnbs was found to react more quickly with no than dbnbs . dialysate from a patient with renal failure on continuous ambulatory peritoneal dialysis ( capd ) was used for this study . the dialysate was collected when the dialysate bag was changed . solutions of 10 mm dbnbs and dcnbs ( 5 , 8 , 12 , 25 and 30 μl for final concentrations of 0 . 5 , 0 . 8 , 1 . 2 , 2 . 5 and 3 . 0 mm ) were added to 60 μl of the dialysate . the difference in volume comprised pbs . the reaction mixture was mixed thoroughly and analysed by esr spectroscopy after 25 min incubation at room temperature . when dbnbs and dcnbs were reacted with the oxidant , a typical three - line esr signal was obtained . a reduction in peak width from 0 . 495 to 0 . 306 mt was observed when dbnbs was replaced by dcnbs . a reduction in peak width in esr spectroscopy is generally regarded as beneficial , as it may lead to increased sensitivity . to compare the sensitivity of dbnbs and dcnbs , the spin trap should be used in excess . dose - response experiments showed that in the oxidant system dbnbs reached an excess at a final nominal concentration of ca . 1 . 2 mm , while dcnbs reached an excess at a final nominal concentration of 2 . 5 mm . therefore the sensitivities of dbnbs and dcnbs were compared at 1 . 2 mm and 2 . 5 mm respectively . they were found to give almost identical results , viz respective signal / marker ratios of 0 . 516 and 0 . 521 . dcnbs has the advantage that it is more soluble than dbnbs and consequently no turbidity problems have been encountered with dcnbs . thus dcnbs is the preferred spin trap for analysis of the oxidant from the dialysate of uremic patients . | 8 |
the present invention provides fibers comprising poly ( trimethylene terephthalate ), and processes for making dyed poly ( trimethylene terephthalate ). fibers made according to the processes disclosed herein can have lightfastness ratings of at least 4 after exposure to 488 kj of uv radiation under standardized testing conditions , and even after exposure 779 kj of uv radiation when certain disperse dyes are used . it has been surprisingly found that with the use of the processes disclosed herein , poly ( trimethylene terephthalate ) fibers dyed at temperatures and pressures higher than even the highest temperatures disclosed in some prior publications , such as jp 2000 192375a and jp 2002 180384a , have improved colorfastness in comparison with poly ( trimethylene terephthalate ) fibers dyed using conventional processes . while it is not intended that the invention be bound by any particular theory , it is believed that the processes disclosed herein allow relatively deeper penetration of the fibers by dye molecules , which improves colorfastness . fibers made according to the processes disclosed herein can also be referred to as “ fiber - dye combinations ”, indicating the presence of dye molecules with the fibers . a process for making dyed poly ( trimethylene terepthalate ) s according to the present invention comprises : a . providing a poly ( trimethylene terephthalate ) fiber ; b . combining at room temperature in an aqueous medium about 0 . 50 weight percent of an alcohol ethoxylate surfactant , about 0 . 25 weight percent of a sequestering agent , 3 . 00 weight percent of a benzotriazine derivative uv absorber , 0 . 5 weight percent of a disperse dye , and sufficient water to provide a water : fiber ratio from about 2 : 1 to about 40 : 1 , all weight percents on weight of fiber , to form a dyebath ; c . adjusting the ph of the dyebath to about 4 . 0 to about 5 . 0 ; d . heating the dyebath at a rate of at least about 1 ° c . per minute to a temperature of 132 - 145 ° c . ; e . immersing the poly ( trimethylene terephthalate ) fiber in the dyebath ; f . maintaining the dyebath temperature for at least about 30 minutes to produce a dyed poly ( trimethylene terephthalate ) fiber ; g . allowing the dye bath to cool ; and h . rinsing the dyed poly ( trimethylene terephthalate ) fiber . all percentages in the foregoing process are weight percents “ on the weight of fiber ” ( owf ). the processes disclosed herein provide poly ( trimethylene terephthalate ) fibers having desirable lightfastness with a rating of 4 or higher , more particularly from 4 to 5 , under 488 kj uv exposure by aatcc method number 16 - 1998 with certain disperse dyes , especially such dyes suitable for dyeing automotive fabrics , particularly color index (“ ci ”) disperse red 86 , ci disperse red 91 , ci disperse red 161 , ci disperse red 279 , ci disperse yellow 42 , ci disperse yellow 96 , ci disperse yellow 160 , ci disperse blue 27 , ci disperse blue 60 , and ci disperse blue 77 , at 0 . 5 % on weight of fibers ( owf ) dyeing depths . according to aatcc method number 16 - 1998 , ratings of lightfastness range from 1 to 5 , 5 being the highest rating . thus , a lightfastness of 4 to 5 is highly desirable . in some preferred embodiments , the processes disclosed herein provide poly ( trimethylene terephthalate ) fibers having desirable lightfastness with a rating of 4 or higher at 779 kj uv exposure with certain disperse dyes , particularly ci disperse red 86 , ci disperse red 161 , ci disperse yellow 42 , ci disperse yellow 96 , ci disperse yellow 160 , ci disperse blue 60 and ci disperse blue 77 at 0 . 5 % owf dyeing depths . percentage quantities of dyes are disclosed herein as “% owf ”, which means weight percent dye based on the weight of fiber . ci disperse dyes are known to those skilled in the art , and appropriate disperse dyes for use in dyeing polyester fibers , particularly poly ( trimethylene terephthalate ) fibers , can be selected by the skilled person . examples of commercially available disperse dyes suitable for use in dyeing fibers , particularly fibers suitable for automotive uses , produced according to the processes disclosed herein include : terasil ® pink 2gla - 01 ( ci disperse red 86 ), disperseriteg pink rel ( ci disperse red 91 ), dorospers ® red kffb ( ci disperse red 161 ), dorospers ® red kffn ( ci disperse red 279 ), terasil ® yellow gwl ( ci disperse yellow 42 ), dorospers ® golden yellow r . conc ( ci disperse yellow 96 ), dianix ® yellow sg ( ci disperse yellow 160 ), terasil ® blue glf ( ci disperse blue 27 ), terasil ® blue bge - 01 ( 200 ) ( ci disperse blue 60 ) and dorospers blue blfr ( ci disperse blue 77 ). newly developed disperse dyes having the colorfastness characteristics and suitable for use under the conditions disclosed herein for dyeing poly ( trimethylene terephthalate ) fibers are intended to be within the scope of the present invention . one skilled in the art will recognize that such dyes can be tested using the standard conditions disclosed herein , on commercially available poly ( trimethylene terephthalate ) s such as , for example , sorona ® 3gt polymer . unless otherwise stated , the terms “ poly ( trimethylene terephthalate )”, “ 3gt ” and “ ptt ”, as used herein , include homopolymers and copolymers containing at least 70 mole % trimethylene terephthalate repeat units , and polymer blends containing at least 70 mole % of trimethylene terephthalte homopolymers or copolyesters . preferred poly ( trimethylene terephthalate ) s , including copolymers and blends , contain at least 85 mole %, more preferably at least 90 mole %, even more preferably at least 95 mole %, still more preferably at least 98 mole %, and most preferably about 100 mole %, trimethylene terephthalate repeat units . for convenience , poly ( trimethylene terephthalate ) s are also referred to herein as “ 3gts ”. the term “ mole percent ”, as used herein , means the percent of a particular component , in moles , based on the total number of moles of , for example , monomer units in a polymer . examples of poly ( trimethylene terephthalate ) copolymers include copolyesters made using 3 or more reactants , each having two ester forming groups . for example , a copoly ( trimethylene terephthalate ) can be made using a comonomer selected from linear , cyclic , and branched aliphatic dicarboxylic acids having 4 - 12 carbon atoms , such as butanedioic acid , pentanedioic acid , hexanedioic acid , dodecanedioic acid , and 1 , 4 - cyclo - hexanedicarboxylic acid ); aromatic dicarboxylic acids other than terephthalic acid and having 8 - 12 carbon atoms , such as isophthalic acid and 2 , 6 - naphthalenedicarboxylic acid ; linear , cyclic , and branched aliphatic diols having 2 - 8 carbon atoms , other than 1 , 3 - propanediol , such as ethanediol , 1 , 2 - propanediol , 1 , 4 - butanediol , 3 - methyl - 1 , 5 - pentanediol , 2 , 2 - dimethyl - 1 , 3 - propanediol , 2 - methyl - 1 , 3 - propanediol , and 1 , 4 - cyclohexanediol ); and aliphatic and aromatic ether glycols having 4 - 10 carbon atoms , such as hydroquinone bis ( 2 - hydroxyethyl ) ether . alternatively , a copoly ( trimethylene terephthalate ) can be made using a poly ( ethylene ether ) glycol having a molecular weight below about 460 , such as diethyleneether glycol . the comonomer typically is present in the copolyester at from about 0 . 5 mole % to about 15 mole %, and can be present in amounts up to 30 mole %. the poly ( trimethylene terephthalate ) can contain minor amounts , e . g ., about 10 mole % or less , in some embodiments about 5 mole % or less , of one or more comonomers other than trimethylene terephthalate , and such comonomers are usually selected so that they do not have a significant adverse affect on properties . exemplary comonomers that can be used include functional comonomers such as 5 - sodium - sulfoisophthalate , which is preferably used at an amount within the range of about 0 . 2 to 5 mole %. very small amounts , about 5 mole % or less , even 2 mole % or less , of trifunctional comonomers , such as , for example trimellitic acid , can be incorporated for viscosity control . a poly ( trimethylene terephthalate ) homopolymer or copolymer can be blended with one or more other polymers . preferably , if blended , the poly ( trimethylene terephthalate ) is blended with about 30 mole percent or less of one or more other polymers . examples of polymers suitable for blending with a poly ( trimethylene terephthalate ) homopolymer or copolymer are polyesters prepared from other diols , such as those described above . preferred poly ( trimethylene terephthalate ) blends contain at least 85 mole %, more preferably at least 90 mole %, even more preferably at least 95 mole %, still more preferably at least 98 mole %, poly ( trimethylene terephthalate ) polymer . in certain highly preferred embodiments , blends contain substantially about 100 mole % poly ( trimethylene terephthalate ) homopolymer or copolymer . for some applications , blends are not preferred . the intrinsic viscosity of the poly ( trimethylene terephthalate ) is at least about 0 . 70 dl / g , preferably at least about 0 . 80 dl / g , more preferably at least about 0 . 90 dl / g and most preferably at least about 1 . 0 dl / g . also , the intrinsic viscosity is preferably not greater than about 2 . 0 dl / g , more preferably not greater than about 1 . 5 dl / g , and most preferably not greater than about 1 . 2 dl / g . the number average molecular weight ( m n ) of the poly ( trimethylene terephthalate ) is preferably at least about 10 , 000 , more preferably at least about 20 , 000 , and is also preferably about 40 , 000 or less , more preferably about 25 , 000 or less . the preferred m n depends on the components of the poly ( trimethylene terephthalate ), and also can be affected by the nature and amount of any additives or modifiers used that affect the physical properties of the poly ( trimethylene terephthalate ). poly ( trimethylene terephthalate ) and methods for making poly ( trimethylene terephthalate ) are known and are described , for example , in u . s . pat . nos . 5 , 015 , 789 , 5 , 276 , 201 , 5 , 284 , 979 , 5 , 334 , 778 , 5 , 364 , 984 , 5 , 364 , 987 , 5 , 391 , 263 , 5 , 434 , 239 , 5 , 510 , 454 , 5 , 504 , 122 , 5 , 532 , 333 , 5 , 532 , 404 , 5 , 540 , 868 , 5 , 633 , 018 , 5 , 633 , 362 , 5 , 677 , 415 , 5 , 686 , 276 , 5 , 710 , 315 , 5 , 714 , 262 , 5 , 730 , 913 , 5 , 763 , 104 , 5 , 774 , 074 , 5 , 786 , 443 , 5 , 811 , 496 , 5 , 821 , 092 , 5 , 830 , 982 , 5 , 840 , 957 , 5 , 856 , 423 , 5 , 962 , 745 , 5 , 990 , 265 , 6 , 235 , 948 , 6 , 245 , 844 , 6 , 255 , 442 , 6 , 277 , 289 , 6 , 281 , 325 , 6 , 312 , 805 , 6 , 325 , 945 , 6 , 331 , 264 , 6 , 335 , 421 , 6 , 350 , 895 , and 6 , 353 , 062 , ep 998 440 , wo 00 / 14041 and 98 / 57913 , h . l . traub , “ synthese und textilchemische eigenschaften des poly - trimethyleneterephthalats ”, dissertation universitat stuttgart ( 1994 ), s . schauhoff , “ new developments in the production of poly ( trimethylene terephthalate ) ( ptt )”, man - made fiber year book ( september 1996 ), and u . s . patent application ser . no . 10 / 057 , 497 , all of which are incorporated herein by reference . poly ( trimethylene terephthalate ) s are commercially available from e . i . du pont de nemours and company , wilmington , del ., as soronag 3gt polymer . other polymeric additives can be added to the poly ( trimethylene terephthalate ) polymers , copolymers or blends to improve strength , to facilitate post extrusion processing or provide other benefits . for example , hexamethylene diamine can be added in minor amounts of about 0 . 5 to about 5 mole % to add strength and processability to the polymers . polyamides such as nylon 6 or nylon 6 - 6 can be added in minor amounts of about 0 . 5 to about 5 mole % to add strength and processability to the polymers . a nucleating agent , preferably 0 . 005 to 2 weight % of a mono - sodium salt of a dicarboxylic acid selected from the group consisting of monosodium terephthalate , mono sodium naphthalene dicarboxylate and mono sodium isophthalate , as a nucleating agent , can be added as disclosed in u . s . pat . no . 6 , 245 , 844 , which is incorporated herein by reference . the poly ( trimethylene terephthalate ) polymers and blends can , if desired , contain additives , e . g ., delusterants , nucleating agents , heat stabilizers , viscosity boosters , optical brighteners , pigments , and antioxidants . tio 2 or other pigments can be added to the poly ( trimethylene terephthalate ) s and blends , or in fiber manufacture . additives suitable for use with the poly ( trimethyene terephthalate ) s are disclosed , for example , in u . s . pat . nos . 3 , 671 , 379 , 5 , 798 , 433 and 5 , 340 , 909 , ep 699 700 and 847 960 , and wo 00 / 26301 , which are incorporated herein by reference . in some embodiments , the poly ( trimethylene terephthalate ) fiber is provided in the form of a fabric , e . g ., a woven fabric or a nonwoven fabric . also , in some embodiments , the fiber , optionally as a fabric , is immersed in water prior to the addition thereto of the surfactant , the sequestering agent , the uv absorber , and / or the dye . preferably , the process is initiated , i . e ., the fiber and dyebath components are combined , at room temperature , which can be , for example , about 22 to 28 ° c . also preferably , the process is carried out at autogenous pressure in a sealed vessel . because the vessel is sealed , during the process , the pressure within the vessel rises . about 0 . 50 weight percent of an alcohol ethoxylate surfactant , about 0 . 25 weight percent of a sequestering agent , 3 . 00 weight percent of a benzotriazine derivative uv absorber , and 0 . 5 weight percent of a disperse dye , are combined in an aqueous medium to provide a water : fiber ratio from about 2 : 1 to about 40 : 1 . preferably , the water : fiber ratio is at least about 6 : 1 . the water : fiber ratio can vary depending upon the equipment being used in the process , which depends in part upon the volume of materials being used in the process . in some applications of the process , particularly larger scale production , a water : fiber ratio of about 8 : 1 to about 12 : 0 may be preferred , even more preferably about 10 : 1 . when the fiber is used in the form of a fabric , the same ratios apply , i . e . based on weight , the ratio is a water : fabric ratio . however a range of such ratios can be used . the appropriate ratio for a particular application can be selected by one skilled in the art . in the process , the dyebath and components thereof and the fiber are heated at a rate of at least about 1 ° c . per minute , and slower than 8 ° c . per minute . preferably , the heating rate is about 5 ° c . per minute or slower , more preferably about 4 ° c . per minute or slower , most preferably about 3 ° c . or slower . in highly preferred embodiments , the heating rate is about 2 ° c . per minute . the dyebath and components are heated to a temperature of 132 - 145 ° c ., preferably 132 - 140 ° c ., more preferably 132 - 135 ° c ., and in highly preferred embodiments , to about 132 ° c . once the dyebath has reached the desired temperature , it is maintained at that temperature for at least about 30 minutes , preferably at least about 45 minutes . typically , maintaining the dyebath at the desired temperature for about 60 minutes will ensure adequate dyeing ; however , shorter or longer periods of time may be desirable for certain dye formulations and depending upon the shade and intensity of color desired in the dyed fiber . the process uses a benzotriazine derivative uv absorber . such absorbers are commercially available from , for example , ciba geigy , inc . a preferred benzotriazine derivative uv absorber is cibafast usm ® uv absorber . the amount of uv absorber is preferably at least about 2 weight percent , and more preferably at least about 3 weight percent . although higher uv absorber amounts than , for example , about 4 weight percent , can be used , the use of such higher levels is not required and may not be cost effective for some applications . the ph of the dyebath can be adjusted by adding a suitable acid . acetic acid is preferred , although other organic or inorganic acids , including propionic acid and formic acid , can be used . preferably , the ph of the dyebath is adjusted to within the range of 4 . 2 to about 4 . 85 , preferably from about 4 . 25 to 4 . 7 , more preferably 4 . 50 to 4 . 75 . alcohol ethoxylate surfactants are known and are commercially available . an exemplary alcohol ethoxylate surfactant is surfactant lf - h , available from dupont specialty chemicals , wilmington , del . the processes disclosed herein use a sequestering agent . sequestering agents , also known as chelating agents , remove undesired or excess ions from solutions . examples of sequestering agents are ethylene diamine tetraacetic acid ( edta ) and derivatives thereof , including nitrilo triacetic acid ( nta ), diethylene triamine pentaacetic acid (( dtpa ) and salts thereof . edta is a preferred sequestering agent . sequestering agents are well known and commercially available . edta is commercially available , for example , as versene ® 100 edta from dow chemical co ., midland , mich . after the fiber has been immersed in the dyebath and the dyebath maintained at the desired temperature for the desired period of time , the dyebath is allowed to cool before the fiber is rinsed . the dyebath can be allowed to return to room temperature without the use of any external cooling methods or devices , or , if desired , cooling can be facilitated by , for example , the application of cooling water . also , upon cooling , the dyebath depressurizes , preferably to atmospheric pressure . it is advantageous to precede the foregoing process with a prescour to remove dirt , particles , and other impurities that could impede dyeing . a prescour can be carried out , for example , by maintaining the poly ( trimethylene terephthalate ) fiber at about 60 ° c . for about 20 minutes in a bath containing : 0 . 50 % surfactant , 0 . 25 % sequestering agent , and 0 . 50 % tspp ( tetrasodium pyrophosphate ). it is also advantageous to follow the dyeing process with a reductive after - scour , to remove loose dye molecules and residual chemicals , which aids in maximizing lightfastness . the after - scour preferably includes : providing a scour bath by adding , at room temperature , 2 . 0 g / l sodium hydrosulfite and 2 . 0 g / l soda ash ; raising the temperature , e . g ., at a rate of about 1 - 22 ° c . per minute to about 60 ° c . or higher , but less than 180 ° c . ; holding at temperature 60 ° c . for 20 minutes ; and rinsing and neutralizing the fiber . neutralization can be accomplished , for example , with a final rinse in a bath having a ph adjusted to 6 . 0 - 7 . 0 by addition of a suitable organic acid such as acetic acid . the present processes provide dyed fibers , e . g ., colored fibers that perform desirably using standard lightfastness testing . lightfastness testing procedures are known to those skilled in the art , and are described in publications of the american association of textile chemists and colorists ( aatcc ). poly ( trimethylene terephthalate ) fibers , including fibers made from blends and compolymers , made according to the processes disclosed herein have been found to show no color break worse than a 4 break , i . e ., no lower than a 4 on the aatcc greige scale , after exposure to 488 kj of uv light according to standard test method aatcc 16 - 1998 . in some embodiments , a color break no worse than 4 has been observed following 779 kj uv light exposure ( using the same testing procedure but effectively using a more stringent testing than a test using 488 kj of uv light ) when certain disperse dyes are employed in the dyeing process . further , fibers are obtained that demonstrate desirable retention of physical properties besides color . tests of tenacity before and after extensive uv exposure indicate little loss in tenacity . preferably , the tenacity of dyed poly ( trimethylene terephthalate ) fibers prepared according to the processes disclosed herein exhibit a loss of tenacity of about 10 % or less , following exposure to at least 481 kj of uv radiation . more preferably , the tenacity of dyed poly ( trimethylene terephthalate ) fibers prepared according to the processes disclosed herein exhibit a loss of tenacity of about 10 % or less , following exposure to at least 779 kj of uv radiation . for testing color fastness and strength under uv exposure , candidate fibers are typically knitted to test forms in the shape of tubing , or wrapped on cards . testing can be carried out , for example , in a weather - o - meter ® uv exposure device . physical properties that can be tested include tenacity and elongation , and color fastness under rigorous uv light exposure / high temperature conditions . the following examples are presented for the purpose of illustrating the invention , and are not intended to be limiting . all parts , percentages , etc ., are by weight unless otherwise indicated . the tenacity of the poly ( trimethylene terephthalate ) yarns reported in the following examples was measured using an instron corp . tensile tester , model no . 1122 . tenacity was measured according to astm d - 2256 . the xenon light fastness testing was done using an “ atlas ” weatherometer ( atlas material testing technology llc , 4114 n . ravenswood ave ., chicago , ill . 60613 ) following the established testing procedures of aatcc method 16 - 1998 and blue wool light fastness standard l - 4 ( lot 5 ). visual ratings were made on all samples after exposure to uv light utilizing the aatcc greige scale rating system of 1 through 5 , wherein 5 indicates “ no visible change ” and 1 indicates “ severe color change ”. the rating of one half unit was considered not to be a significant variation between polymer substrates , and a 4 rating or greater was judged to be excellent fading performance after extended exposure to ultraviolet light . the impact of extended exposure to ultraviolet light on the tensile properties of yarns of sorona ® ptt was tested . the baseline tenacity was obtained from measurements on “ mock dyed ” knit tubing of the textured yarns of soma ® ptt . “ mock dyeing ” means that all components of a dyebath other than a colored dye are used , and all of the steps in the dyeing process , including temperature , pressure etc . are included . mock dyeing is used to provide a baseline for strength retention testing of the polymer . the reported data is an average of 10 individual instron measurements . the dyed knit tubing , prepared with cibafast ® usm ultraviolet absorber in the dyebath , was tested after exposure in the atlas weather - o - meter ® device at 481 , 486 . 5 , and 496 kj . the tenacity of the yarns from the dyed knit tubing from the ptt after extended uv exposure was compared to the initial mock dyed ( before exposure ) baseline data , and the loss in tenacity due to uv exposure was determined . all materials used herein are available commercially . sorona ® poly ( trimethylene terephthalate ) fiber was obtained from dupont ( wilmington , del .). dacron ® poly ( ethylene terephthalate ) fiber ( pet ) was obtained from invista , inc . chemical reagents used were as follows : dianix ® dyes ( dystar l . p ., 9844 - a southern pine blvd ., charlotte , n . c . 28274 ); dispersrite ® dyes ( rite industries , inc ., highpoint , n . c . ); dorospers ® dyes ( m . dohmen usa inc ., 25 ellwood conn ., greenville , s . c . 29607 ); terasil ® dyes and cibafast ® usm ( ciba specialty chemicals , colors div ., 4050 premier dr ., high point , n . c . 27265 ); versene ® 100 ( dow chemical co ., po box 1206 , midland , mich . 48642 ); surfactant lf - h ( dupont specialty chemicals , wilmington , del . 19898 ); burco reduct t ® ( burlington chemical co ., po box 111 , burlington , n . c . 27216 ). testing was conducted on false twist yarns of textured dacron ® poly ( ethylene terephthalate ) homopolymer ( control ) and yarns of sorona ® poly ( trimethylene terephthalate ) homopolymer ( test ) that were knit into tubing on a lawson - hempill fak circular knit machine ( lawson hemphill sales inc ., p . o . drawer 6388 , spartanburg , s . c . 29304 ). test yarns of textured sorona ® poly ( trimethylene terephthalate ) fiber were tested along with a control yarn of textured dacron ® poly ( ethylene terephthalate ) utilizing the same dyeing auxiliaries and conditions . in addition to the evaluation of a variety of disperse dyes that were found to exhibit good fastness to light after extended exposure to uv light , the resistance of textured test yarns of sorona ® ptt vs . dacron ® pet control yarns to degradation of tensile properties due to the exposure to uv light was examined . all percentages of dyes and chemicals are weight percents based on the weight of the fabric ( owf ). pre - scour , dyeing , and after - scour were conducted in a mathis labomat ® bfa 16 test unit ( werner mathis u . s . a . inc ., 2260 hwy 49 ne / p . o . box 1626 , concord , n . c . 28206 ). knit tubing of test and control samples was pre - scoured at 60 ° c . for 20 minutes in a bath containing : 0 . 50 % surfactant lf - h ® surface active agent 0 . 25 % verseneg 100 ( sequestering agent ) 0 . 50 % tetrasodium pyrophosphate a dye bath was prepared in a vessel at room temperature , containing : 0 . 50 % “ surfactant ” lf - h 0 . 25 % “ versene ” 100 ( sequestering agent ) 3 . 00 % “ cibafast ” usm ( uv absorber ) disperse dye ( quantities and dyes are shown in table 1 ) acetic acid as needed to adjust ph to 4 . 50 - 4 . 75 the fabric for testing was immersed in the dyebath , and the vessel was sealed . the temperature was raised at a rate of 2 ° c . per minute , to 132 ° c . ( 270 ° f . ), then held at 132 ° c . for 45 minutes . the dyebath was cooled and depressurized , and the fabric sample was removed and well rinsed . an afterscour bath was prepared , at room temperature , containing : 2 . 0 g / l burco reduct t ® sodium hydrosulfite and 2 . 0 g / l soda ash . the temperature was raised at 2 ° c . per minute to 60 ° c . ( 140 ° f .). the fabric was immersed in the afterscour bath , held at 60 ° c . for 20 minutes , rinsed well , and neutralized with a final rinse in a bath with ph adjusted to 6 - 7 with acetic acid . lightfastness results for fabrics dyed using various dyes and tested at different times of uv exposure are presented in table 1 . table 2 shows the effect of extended exposure to uv light on the tenacity of textured yarns of sorona ® ptt . the loss of tenacity of the exposed yarns was calculated by comparing the tenacity of the exposed dyed knit tubing to that of the “ mock dyed ” knit tubing that provided the baseline for the calculations . the high resistance of yarns of sorona ® ptt to the degradation caused by extended exposure to uv light is apparent . the foregoing disclosure of embodiments 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 forms disclosed . many variations and modifications of the embodiments described herein will be obvious to one of ordinary skill in the art in light of the disclosure . | 3 |
generally stated the present invention is concerned with the simulation of human locomotion . fig1 schematically illustrates the mechanical components of a human locomotion simulator 20 according to an illustrative embodiment of the present invention . the human locomotion simulator 20 is mainly concerned with locomotion patterns of the human body by the fully coordinated simulation of the pelvic structure , the hip joint and the thigh segments with longitudinal displacement of the ground including 3 - d mobility of the ground . this mechanical framework is completed by the connection of an above knee leg prosthesis equipped with at least a motorized knee joint and a motorized or a passive ankle joint in order to complete the simulation of the locomotion movements with the knee joint and the ankle joint motions . of course other uses of the human locomotion simulator described herein are possible , such as , for example , the testing of footwear . it is to be understood that in the foregoing the words “ vertical ” and “ horizontal ” are to be construed broadly . for example , generally orthogonal orientations would be encompassed thereby . the human locomotion simulator 20 consists of a five degrees of freedom ( dof ) system which are actively controlled by a controller or a computer network running a control software ; the vertical and the horizontal linear axes of the pelvic structure , the hip - thigh mechanism ( hip joint and the thigh segment ) of the simulator itself , the knee joint of the motorized leg prosthesis and longitudinal displacement of the ground . optionally , the human locomotion simulator 20 could also include the four vertical displacement pistons of the treadmill to allow for the 3 - d variable positioning of the ground and a controlled ankle joint in the case where the leg prosthesis includes a active ankle joint . referring to fig1 , the mechanical components of the human locomotion simulator 20 include a base 22 onto which is mounted a conventional treadmill 24 , a vertical post 26 mounted to the base 22 , a pelvic structure 29 composed of a vertically movable support 28 mounted to the vertical post 26 as to produce the vertical displacement of the pelvic structure 29 and a horizontally movable support 30 so mounted to the vertically movable support 28 as to move the pelvic structure 29 horizontally , a hip - thigh mechanism 33 including a hip joint 40 represented by a pivot pin and a thigh segment assembly 38 ( schematically illustrated in fig1 ) mounted on the horizontally movable support 30 of the pelvic structure 29 providing the rotational mobility at the hip joint 40 of the thigh segment assembly 38 . fig1 also illustrates a schematic prosthesis leg 32 provided with a knee joint , a shank segment , a ankle joint and a foot mounted to the thigh segment assembly 38 . the hip - thigh mechanism 33 is illustrated in fig3 . it is designed to allow easy installation and maintenance of all it &# 39 ; s components . the unit can be completely assembled before attaching to the rest of the system . and all it &# 39 ; s sub - assemblies can be assembled or disassembled individually . calculations have been done to ensure that the hip - thigh mechanism 33 can provide the required level of torque and speed with the torque and speed range of the motor . the calculation ( equation 1 ) is also used in the control software to translate the hip angle into linear displacement along the motor axis . the variables used in equation 1 are shown in fig2 . ρ =√{ square root over (( l 2 + l 4 · sin θ ) 2 +( l 4 · cos θ − l 1 ) 2 )} equation 1 returning to fig3 , the hip - thigh mechanism 33 includes a hip frame assembly 34 , a hip joint motor assembly 36 and a thigh segment assembly 38 with a connector or attachment member 39 for mounting the prosthesis leg 32 . the hip frame assembly 34 is configured and sized to be mounted to the horizontally movable support 30 of the pelvic structure 29 as will be described hereinbelow . the hip joint motor assembly 36 shown in fig4 is pivotally mounted to the hip frame assembly 34 . the hip joint motor assembly 36 and the thigh segment assembly 38 are interconnected by a hip joint ball - nut assembly 42 shown in fig5 . similarly , the thigh segment assembly 38 is pivotally mounted to the hip frame assembly 34 via a hip pivot pin 40 ( fig3 ) that simulates the biomechanical axis of the human locomotion structure at the hip . fig4 illustrates the hip joint motor assembly 36 in an exploded view . the hip joint motor assembly 36 includes a hip motor 44 , a hip joint ball - screw holder 46 and a ball screw 48 . the hip motor 44 is fixedly mounted to the hip joint ball - screw holder 46 that is itself pivotally mounted to the hip frame assembly 34 of fig3 via bearings 54 and a fastener 52 ( see fig3 ). the ball screw 48 is mounted to the hip motor 44 to rotate therewith , passing through the angular - contact bearings set 55 . the hip joint ball - nut assembly 42 is shown in an exploded view in fig5 . it includes a body 50 that is pivotally mounted to the thigh segment assembly 38 via bearings 57 and a threaded element 52 fixedly mounted to the body 50 . the threaded element 52 is so internally threaded as to receive the externally threaded ball screw 48 . the hip joint motor assembly 36 provides a linear motion to the hip joint ball - nut assembly 42 , which induces a rotational movement to thigh segment assembly 38 around the hip pivot pin 40 . the ball - screw 48 is inserted into the hip joint ball screw holder 46 with angular - contact bearings set 55 in a back - to - back arrangement ( see fig4 ). because this arrangement provides a stiff linkage between the ball screw 48 and the hip joint ball - nut assembly 42 , it is necessary to have an accurate alignment between the ball screw 48 and the hip joint ball - nut assembly 42 . the thigh segment assembly 38 is illustrated in an exploded perspective view in fig6 . the thigh segment assembly 38 makes the link between the prosthesis leg 32 ( fig1 ) and the horizontally movable support 30 . the thigh segment assembly 38 includes two parallel plates 56 and 58 interconnected by a spacer 60 and a bracket 62 configured and sized to mount the prosthesis leg thereto . two toller bearings 64 are provided to pivotally mount the thigh segment assembly 38 to the hip frame assembly 34 . a hip joint position sensor assembly 66 is located between the two plates 56 and 58 . the position measurement of the thigh segment assembly 38 is achieved via the hip joint position sensor assembly 66 illustrated in a perspective view in fig7 . angular position measurement of the thigh segment assembly 38 is supplied by rotational optical sensor disk 68 installed on the hip pivot pin 40 and read by an encoder module 70 . the hip joint axis sleeve 72 and hip joint sensor hub 74 receive the hip pivot pin 40 that pivotally mount the thigh segment assembly 38 to the hip frame assembly 34 . without limiting the present description , it has been found that the sensor model heds - 9040 - t00 e3 - 2048 - 1000 - ihub made by us digital is adequate to be used as the hip position sensor assembly 66 . turning now to fig8 to 11 of the appended drawings , the pelvic structure 29 , its vertically movable support 28 , its horizontally movable support 30 , its attached vertical and horizontal axis movement generator assemblies and the bumper structure will be described . as can be seen from fig9 , the vertically movable support 28 includes a generally triangular body defined by two triangular plates 76 and 78 , maintained at a predetermined spacing by spacers 80 ( only one shown ), and both a vertical plate 82 and a horizontal plate 84 . a vertical axis movement generator 86 is mounted to the vertical plate 82 and a horizontal axis movement generator 88 is mounted to the horizontal plate 84 . the vertical and horizontal axis movement generators 86 and 88 are identical . accordingly , for concision purposes , only the vertical axis movement generator 86 will be described hereinbelow with respect to fig1 . the vertical axis movement generator 86 includes a motor 94 to which is associated a ball screw 92 . a pair of linear slides 95 are mounted to the fixed portion of the motor 94 . a mobile unit 96 is slidably mounted to the pair of slides 95 via linear bearings 97 . the mobile unit 96 includes a carriage portion 98 and secondary portions 100 . both portions 98 and 100 being slidably mounted to the slides 95 via the linear bearings 97 . a ball nut 102 is mounted to the carriage portion 98 of the mobile unit 96 and is engaged by the ball screw 92 . accordingly , rotation of the ball screw 92 by the motor 94 causes a linear movement of the mobile unit 96 on the slides 95 . four springs 104 are provided between the carriage portion 98 and the secondary portions 100 of the mobile unit 96 . these springs 104 are used as a suspension between the carriage portion 98 and the secondary portions 100 . this suspension is interesting in the simulation of human locomotion because this type of mechanism provides the expected damping effects of the mobility of the vertical movable support 28 of the pelvic structure 29 , as will easily be understood by one skilled in the art . the four springs 104 are part of the series elastic actuators ( sea ) that are used to control the force applied on the corresponding vertical and horizontal movable supports 28 or 30 . these springs 104 allow the simulation of various persons weight and to separate the inertia of the actuator from the inertia of the vertical and horizontal movable supports 28 and 30 . in other words , the linear slides 95 and linear bearings 97 guide the movement and the actuation is provided by a combination of motor 94 , ball - screw 92 and ball - nut 102 . the vertical and horizontal axis movement generators 86 and 88 are controlled in position and force and use a special mechanism and sensors to perform this task as will be described hereinbelow . the position control loop utilizes position sensors 99 to get position feedback on both vertical and horizontal axes . without limiting the present disclosure , table 1 presents the technical information on linear optical sensors that have been found suitable to be used as position sensors 99 . force sensors are used to measure the force levels applied on the vertical and horizontal axes . those sensors measure the displacement between the carriage portion 98 and the secondary portions 100 of the mobile unit 96 for each axe . the secondary portions 100 being linked to the carriage portion 98 with springs 104 , the applied force is a function of the displacement between the two portions ( 98 , 100 ) and of the known strength of the springs 104 . force sensors advantageously require fine position measurement accuracy . therefore , magnetic stripe technology was selected . without limiting the present disclosure , table 2 presents the technical information on linear magnetic sensors that have been found adequate for this application . along with the linear magnetic sensors , an index sensor is used to determine the reference position . turning now to fig1 to 13 , the linear magnetic sensors will be described . fig1 illustrates , in a perspective view , the mobile unit 96 of the vertical axis movement generator 86 without the slides 95 and the motor 94 . a magnetic stripe 106 is attached to the carriage portion 98 and a linear magnetic sensor 108 is in close proximity to the magnetic stripe 106 and is designed to be rigidly connected to the secondary portions 100 . more specifically , as can be better seen from fig1 , the linear magnetic sensor 108 is secured to a bracket 101 itself mounted to a plate 103 that connects to the secondary portions 100 . therefore , relative displacement of the carriage portion 98 with respect to the secondary portions 100 is detected and measured by the linear magnetic sensor 108 . an optical index sensor 110 is also mounted to the carriage portion 98 . the optical index sensor 110 serves as a means to determine the absolute home position of the linear magnetic sensor 108 . as can be better seen from fig1 , the index sensor 110 includes a thin opaque mask 111 attached to the carriage 98 that moves between the emitter and the receptor of a photo sensor 113 attached to the plate 103 of the mobile unit 96 . for example , and without limiting the present disclosure , it has been found that a transmissive photomicrosensor made by omron under model number ee - sx1042 has been found suitable for the present application . the actuators used to move the mobile units of the vertical and horizontal axis movement generator 86 and 88 are series elastics actuators ( sea ). these actuators are mechanisms that allow to control position and force while eliminating undesired inertia of the drive system . since sea actuators are believed well known in the art they will only be briefly discussed herein . referring to fig1 , the present implementation of the sea consists of a motor 94 and a motor drive transmission ( ball - screw 92 and ball - nut 102 ) connected at the output of the motor 94 . an elastic element , in the form of the four springs 104 , is connected in series with the motor drive transmission , and this elastic element is positioned to alone support the full weight of any load connected at an output of the actuator . referring to fig1 , a position sensor , in the form of the linear magnetic sensor 108 positioned between the carriage 98 and the mobile unit 96 generates a signal proportional to the deflection of the elastic element and indicates the force applied by the elastic element to the output of the actuator . referring now to fig8 and 14 of the appended drawings , the bumper structure will be described . the bumper structure is so designed that each axis is completely independent . the bumper structure includes an upper vertical bumper assembly 112 , a lower vertical bumper assembly 114 , a front horizontal bumper assembly 116 , a back horizontal bumper assembly 118 , a back thigh bumper bracket 120 and a front thigh bumper bracket 122 . it is to be noted that even though only one of each bumper assembly 112 , 114 , 116 and 118 is illustrated in fig8 , two of each of these assemblies are present , one for each side of the simulator . the upper vertical bumper assembly 112 includes a bumper 112 a mounted to the triangle plate 76 of the vertically movable support 28 and a stop bracket 112 b , mounted to the vertical post 26 ( see fig1 ) and vertically aligned with the bumper 112 a to upwardly stop the course of the vertically movable support 28 . similarly , the lower vertical bumper assembly 114 includes a bumper 114 a mounted to the triangle plate 76 of the vertically movable support 28 and a stop bracket 114 b , mounted to the vertical post 26 and vertically aligned with the bumper 114 a to stop the course of the vertically movable support 28 at the lowers desired position . the front horizontal bumper assembly 116 includes a bumper 116 a and the back horizontal bumper assembly 118 includes a bumper 118 a where the both bumper 116 a and 118 a are positioned on the mobile unit of the horizontal axis movement generator 88 . the front and back horizontal bumpers assembly 116 , 118 share a common stop bracket screwed on the triangle plate 76 of the vertically movable support 28 providing the front stop bracket 116 b and the stop bracket 118 b . front and rear movement of the hip - thigh mechanism 33 is stopped by the contact of the bumpers 116 a , 118 a with the stop bracket portions 116 b and 118 b , respectively . referring to fig1 , the back thigh bumper bracket 120 includes a bumper 124 and a bracket 126 positioned to the hip frame assembly 34 . similarly , front thigh bumper bracket 122 includes a bumper 128 and a bracket 130 positioned to the hip frame assembly 34 . the thigh bumper brackets 120 and 122 limit the movement of the thigh segment assembly 38 . the bumpers were selected such that the system &# 39 ; s kinetic energy can be absorbed by the bumpers . all bumpers are the same , simply for standardization . the worst case condition that produces the highest kinetic energy level is when the system stands at the highest point and is let down in free - fall . the motor of the vertical axis movement generator 86 could also add to the total energy , but its contribution is negligible compared to the free - fall . both bumper 114 a of the lower vertical bumper assembly 114 b and the bumper 128 of the front thigh bumper bracket 122 shall be able to sustain the free - fall drop . the condition where the bumper 128 can be solicited is when the foot enters in contact with the floor before the said bumper 114 a hits its respective stop bracket 114 b . the total energy is calculated as follow : therefore , each bumper should be able to sustain about 1700 lb . in . miner &# 39 ; s gba - 5 bumpers or one gba - 9 meet this requirement . one skilled in the art will understand that the range of motion of the vertically movable support 28 can be adjusted by changing the position of respective stop brackets 112 b , 114 b , 116 b , 118 b , 120 and 122 or their corresponding bumpers 112 a , 114 a , 116 a and 118 a . from the kinetics standpoint , all joints provide enough force / torque to simulate the locomotion activities characterizing a human subject , which mass is corresponding to the mechanical simulator lower - limb linkage ( i . e ., about 72 . 5 kg in the illustrated embodiment ) by adequately mobilizing the vertically and horizontally movable supports 28 and 30 of the pelvic structure 29 , the hip - thigh mechanism 33 and the thigh segment assembly 38 . another aspect of the present invention is concerned with the simulation of human locomotion in stairs . in order to simplify the simulation approach , limit the number of subsystems required , minimize modifications to the actual platform design , and facilitate integration with the actual level - walking simulation capabilities of the platform , the implementation of a complete stance phase simulation with a modified swing phase using the treadmill was proposed over the use of an approach requiring the use of a stepmill - like device . in the proposed approach , the treadmill moving surface is used to simulate the step tread as well as the velocity corresponding to the horizontal progression speed of a normal human subject climbing or descending stairs . this approach allows to correctly simulate the pelvic , the hip and the knee joint mobility during both stairs ascent and descent tasks stance phase , while the swing phase needs to be modified to account for the limited motion range available on the platform and in order to generate coherent stance initial conditions . the swing phase trajectories modifications mostly affect the vertical and horizontal degrees - of - freedom and do not harm the overall simulation validity in a significant manner of this type of locomotion and more specifically the respective stance phase . the range of motion provided by the vertical , horizontal displacement of the pelvic structure 29 and the rotational displacement of the thigh segment assembly 38 , combined with the constant treadmill 24 movement , allows the simulation of the desired tasks : level walking , ascending and descending stairs . the trajectory of the vertical axis of the pelvic structure 29 has been modified ( as can be seen in fig1 and 16 ) for the stair ascent and descent to address the fact that the simulator &# 39 ; s 20 flat treadmill 24 approach doesn &# 39 ; t allow natural kinematics during those tasks . for example , at the end of the stance phase of a step during stair ascent , the pelvic structure 29 would normally continue going up until the next step , but due to the limited vertical freedom of movement on the simulator 20 , the body of the simulator 20 will go down during the swing phase and ensure that the foot is placed properly on the treadmill 24 for the next step . fig1 and 16 show an example of how the vertical axis motion of the pelvic structure 29 is modified for the stairs ascent . the graph of fig1 displays the modified displacement 142 during the stair ascent simulation whereas the fig1 displays the force level 144 required on the vertical axis to follow the desired trajectory . the trajectory displacement 142 and the exerted vertical force 144 represent the kinematics and the kinetics respectively of the vertical mobility of the pelvic bone of the human body . it is to be noted that the forces displayed in fig1 represent the vertical forces to be applied in order to precisely follow the given trajectory , with the assumption that there is no ground contact . this assumption provides force levels that are at least as high as with ground contact condition . it is obvious that the highest force peaks originate from the modification of the trajectory instead of the original gait motion itself ( high acceleration level at the end of the modified trajectory ). all three axes of the simulator 20 are driven by drive systems that allow following their respective trajectories while providing the required level of forces and accelerations . the range of motion was established directly from the trajectory to follow , and the required motor forces are computed from acceleration levels to reach and from the masses / inertias of the moving bodies . to select the different components of a drive system ( electric drive / motor / screw ), the motor torques and speeds are computed and compared with the capacity chart of the drive system . without limiting the present disclosure , we present here below an example of dimensions and specifications that could be used to build the simulator 20 . referring to fig2 , the following dimensions have been used : the distance between the hip joint 40 and the prosthesis knee axis was selected as 403 . 34 mm . table 3 position and force feedback sensors characteristics force feedback sensor position feedback sensor axis type model resolution type model resolution vertical linear siko 4 μm linear us digital 1 / 250 inch magnetic msk200 / 1 optic emi - 0 - 250 ( 0 . 1 mm ) mb200 lin - 250 - 16 - s2037 horizontal linear siko 4 μm linear us digital 1 / 250 inch magnetic msk200 / 1 optic emi - 0 - 250 ( 0 . 1 mm ) mb200 lin - 250 - 16 - s2037 hip n / a n / a n / a rotational us digital 1 / 2048 turn optic heds - 9040 - ( 0 . 18 °) t00 e3 - 2048 - 1000 - ihub the vertical and horizontal axes of the pelvic structure 29 are controlled in position and force ( see fig1 ). position control is conventional , and relatively straightforward . force control is utilized to eliminate the appearance of inertia induced by the drive system . in the case of the vertical axis of the pelvic structure 29 , the mass of the system is about 75 kg , but for the reason that the motor / ball screw system rotates when the mass moves vertically , the apparent mass when accelerations are induced would increase to about 85 kg ( apparent inertia ). the force control mechanism allows eliminating the additional apparent inertia of the drive system . this system also allows simulating weights different than the system &# 39 ; s weight by requesting the desired level of force on the force control loop . although the present invention has been described by way of particular embodiments and examples thereof , it should be noted that it will be apparent to persons skilled in the art that modifications may be applied to the present particular embodiment without departing from the scope of the present invention . | 0 |
as shown in fig1 and 2 , the apparatus comprises a support frame 1 , formed by various sections assembled by welding , and of which the base portion 2 , larger so as to obtain a rigid support of the unit , rests on casters 3 which facilitates , if need be , the relocation of the apparatus . a pivotable frame 4 made of two vertical uprights 5 and 6 and of four horizontal beams 7 , 8 , 9 and 10 , is mounted on two half - shafts 11 , 12 borne by the support frame 1 and in turn supports the various elements for effecting the assembly and pressing operation . a plurality of lower wheels 13 are mounted on axes 14 supported by forks 15 extending from threaded rods 16 which , screwed into the lower beam 7 and supported by beam 8 , regulate the height of the wheels and their placement with regard to one another so that their upper surfaces cumulatively assume a curvature substantially identical to the average transverse curvature of the lower surface of the glazing to be manufactured . the apparatus comprises about twenty lower wheels , each having a diameter of about 25 centimeters . several of these wheels 17 are connected to gears 18 linked by chains 19 to cogwheels 20 of a horizontal rotating shaft 21 displaced toward the back part of the apparatus with regard to the horizontal beam 8 . the rotating shaft 21 is itself supported by bearings 22 fixed to the frame 4 . the other lower wheels 13 are freely rotatable on their axes 14 . the metallic core of each lower wheel is covered on its periphery with at least one layer of a flexible and wear resistant material , such as vulcanized rubber . a cylindrical pressure roller 23 is mounted above the upper surfaces of the lower wheels . the pressure roller 23 has a diameter of about 10 centimeters and is preferably made of vulcanized rubber with inner and outer layers , for example an outer layer of shore hardness of 70 and of an inner layer of shore hardness of 40 forming the core of the roller . the pressure roller 23 is deflected into a curved configuration conforming to the upper surface of the glazing assembly by the action of a series of upper or roller bending wheels 24 . these wheels are mounted for free rotation on axes 25 supported by forks 26 extending from the threaded rods 27 screwed into an upper horizontal brace 28 and passing through the center part 29 of the beam 9 formed by three parts . this center part 29 is parallel to the upper horizontal brace 28 and slightly displaced about 15 millimeters upstream ( to the left in fig2 and 4 ) with regard to the two end parts 30 and 31 of the beam 9 , therefore also with regard to the plane of the pivoting frame . the threaded vertical rods 27 may be adjusted to regulate the height of the roller bending wheels 24 and accordingly their deflection of the pressure roller 23 , since the wheels bear upon its upper upstream portion . the roller bending wheels 24 , numbering around 10 and having a diameter of about 10 centimeters , are made of steel and covered on their periphery with at least one layer of flexible and wear resistant material , such as rubber . in the illustrated embodiment the wheels 24 are vertical and their width varies according to their position above the roller , the wheels at the center being wider than those at the extremities . this is justified by the fact that the acting part of the wheels , given the curvature of the roller , is narrower at the edges of the roller than at its center . therefore the distance between the wheels varies according to their location . these wheels preferably have rounded edges . the wheels 24 can also be mounted on a more or less inclined plane with regard to the plane of symmetry of the apparatus , as a function of their position and of the curvature to be given to the roller , so that their action on the roller is perpendicular to its axis . the cylindrical pressure roller can have a length of 1 meter and more as required by the dimensions of the glazing to be manufactured . to avoid potential edge effects due to its means of support and rotational drive , it should exceed the boundaries of the glazing by at least 10 centimeters on each side . to increase the flexibility of the pinching elements of the apparatus with respect to the curvature change of a given glazing , a flexible spring - loaded mounting system , not shown , can be mounted on the rods of the upper running wheels and / or on that of the lower running wheels . for example , calibrated springs can be mounted on the rods of the running wheels between the small beam part 29 of the beam 9 and also between the two beams 7 and 8 . the upper horizontal beam 28 is supported by the intermediary plates 32 above the center part 29 of the horizontal beam 9 . this beam 9 is fixed on each side to a plate 33 bearing four rings 34 sliding around two cylindrical rods 35 and 36 forming the upper part of each of the two uprights of the pivotable frame 4 . beam 9 is connected to the piston rods 37 of two vertical piston - cylinder assemblies 38 of which the cylinders are fixed to the upper horizontal beam 10 of the frame . these two cylinders 38 enable the lifting of the upper part of the pressing unit , that is to say , the pressure roller 23 , the upper running wheels 24 and a support roller 39 described herebelow , and by so doing to create a space between the pressure roller and the lower running wheels . in this way , one can intervene easily and rapidly to free , if need be , a misdirected or defective glazing which could become jammed between the pressure roller and the lower running wheels , all while avoiding the need to raise the upper running wheels and by that to deregulate the curvature of the roller in its operational position . the raising also facilitates the initial regulating of the position of the lower running wheels . preferably , the cylinders 38 are of the hydropneumatic type , the movement of which can be accurately controlled . a support roller 39 is mounted at each of its extremities on a hinge 40 connected on one side to a vertical holding rod 41 attached to a right - angled brace 42 on the beam 9 . the hinge 40 is connected on the other side to an inclined rod 43 formed by two halfrods with reversed thread channels , connected by a threaded ring suitable for bringing them closer together or farther apart , therefore changing the length of the inclined rod 43 . this type of mounting of the support roller enables the regulation of its height and position with regard to the pressure roller as well as its pressure against the roller . the support roller is applied against the upper part of the pressure roller on the downstream side thereof . the pressure roller is rotatably supported at its extremities by rotating half - shafts 44 and 45 mounted on forks 46 and 47 having double oscillating and sliding ball bearings . the forks are supported and regulated in height by threaded rods 48 and 49 screwed to right - angled braces 50 and 51 attached to the horizontal beam 9 . the mounting on double ball bearings ( this mounting will be described in detail herebelow with reference to fig3 ) gives great freedom of movement to the roller and in no way hinders its action on the glazing . the two half - shafts 44 and 45 are respectively connected by homokinetic joints 52 and 53 to two horizontal half - shafts 54 and 55 mounted on the uprights 5 and 6 of the frame 4 . borne by the two horizontal half - shafts 54 and 55 , two cogwheels 56 and 57 are connected by chains 58 and 59 to two other cogwheels 60 and 61 , carried by axes concentric with the pivoting half - axes 11 and 12 of the frame 4 . the extremities of these outermost half - axes 11 and 12 of the apparatus bear cogwheels 62 and 63 connected to a motor apparatus 65 , one by a chain 64 and the other by a chain 66 and a shaft 67 . the other extremity of the half - axis 11 bears a first gear wheel 68 connected to a second gear wheel 69 integral to a half - shaft 70 borne by the upright 5 . a cogwheel 71 is mounted on this half - shaft 70 . this cogwheel is connected by a chain 72 to a cogwheel 73 connected to the shaft 21 driving the lower motorized wheels 17 . the cogwheels and chains of the transmission system are protected by housings 74 , 75 , 76 and 77 . the present apparatus also provides two counterweight systems 78 and 79 which facilitate the pivoting of the frame around the half - axes 11 and 12 as described below . fig3 represents the mounting of the pressure roller 23 at one of its extremities on the half - shaft 44 . the extremity of the rubber roller 23 , previously bored out , contains a threaded ring 80 into which the extremity 81 of the half - shaft 44 is screwed . this threaded connection is secured by a lock nut 82 . the half - shaft 44 is mounted in two spherical ball bearings 83 and 84 enabling an oscillating movement of the half - shaft with regard to the two arms 85 and 86 of the fork 46 which supports the ball bearings . two rings 87 and 88 fixed by screws 89 to the arm 85 maintains the position of the bearing 83 . the arm 86 is formed from two bored out parts 90 and 91 which , when they are assembled , form a vertical guide in which the oscillating ball bearing 84 can slide freely . the outer end 93 of the half - shaft 44 is connected to the half - shaft 54 , not shown , by homokinetic joint 52 comprising a double universal joint of which only part is shown in fig3 . fig4 shows in a cross - sectional view the position of the principal elements involved in the pressing of the laminated glazing . regardless of the degree of curvature of the pressure roller 23 produced by the roller bending wheels 24 , the pressure roller 23 is disposed in a vertical plane 95 ( fig4 ) passing through the axes of the lower wheels 13 . the wheels 24 bear against the pressure roller slightly upstream , for example about 15 mm . off the vertical plane 95 , while the support roller 39 bears against an upper downstream portion of the pressure roller . due to this arrangement , the pressure roller , or at least its two extremities , cannot move longitudinally during calendering . the cylindrical pressure roller shown is made of two layers of vulcanized rubber : for example an outer layer 96 , being 20 millimeters thick and of shore hardness 70 , and a softer inner layer 97 , of shore hardness 40 for example which forms the core of the roller . this structure provides a great flexibility of the roller and enables it to bear constantly on the upper element to be assembled with the rigid substrate in order to make the glazing , while conforming to all or most of the changes of the transverse curvature of the glazing . to increase this ability to adapt to the variations of curvature of a given glazing , the lower wheels , as well as the roller bending wheels , can be mounted on a resilient spring - loaded mounting system . they can also have a peripheral structure with two layers of rubber of different hardnesses . thus their steel core can be covered on its periphery by an inner layer 98 and 99 respectively , of about 20 millimeters thick , made of a sufficiently soft rubber , and by a second outer layer , 100 and 101 respectively , of about 20 millimeters thick , made of harder rubber which is more resistant to wear . the steel support roller 39 is also covered with a layer of rubber 94 . the operation of the apparatus is described hereafter with reference to fig5 and 7 and with respect to the manufacture by calendering of a double - curvature safety glazing , comprising a monolithic or laminated rigid substrate 102 made of glass and / or plastic material which is covered with a sheet of flexible plastic material 103 . for example , a sheet such as the one described in belgian pat . no . 856 , 398 , already cited , is utilized , made essentially of a layer of thermosetting polyurethane presenting anti - lacerative and self - heating properties and of a layer of a thermoplastic polymer having adhesive properties with the substrate to be covered . in fig5 and 7 the apparatus is shown in an assembly line , placed between an upstream conveyor 104 , with rollers or belts which carry the substrate to be covered , and a downstream conveyor 105 which receives and removes the covered substrated . the final section 106 of the upstream conveyor is inclined with regard to the horizontal plane so as to lead the edge of the substrate to be covered perpendicularly to the common plane of the lower wheels and the pressure roller ( that is to say perpendicularly to the pinching plane ) without it being necessary to greatly incline the pivoting frame which carries these elements . the sheet of plastic material which must cover the substrate is part of a strip of indefinite length . it is lead from above the apparatus while being constantly kept taut by an upper tension roller 107 . the position of the lower wheels is regulated with the threaded rods to give the unit the desired curvature which is generally the average transverse curvature of the glazing . an identical curvature is given to the pressure roller by bending it with the roller bending wheels , the position of which is regulated by means of their threaded rods . the distance from the pressure roller to the lower wheels being slightly less than the thickness of the glazing to be manufactured , or even null , the pressure roller then being in contact with the lower wheels , the support roller is adjusted so that it exercises its action on the pressure roller . the motor apparatus is activated and the pressure roller and the lower motorized wheels are driven in a rotational movement , at the linear speed of about 3 meters per minute or more , if need be . this speed may vary during the passage of a given assembly , as a function of the sequence : approach of the glazing , the actual assembly , etc . the roller bending wheels and the support roller are driven in rotation by the pressure roller . the rotational direction is that of the arrows shown in fig4 . when the substrate 102 to be covered arrives on the inclined , upstream conveyor 106 , the balanced frame 4 , which carries in particular the pressing elements , is manually or automatically pivoted in order to incline the upper part of the frame upstream . the edge of the substrate to be covered is presented perpendicularly to the pinching plane . in contact with the lower motorized wheels , this substrate is entrained between these running wheels and the pressure roller which , itself , entrains the sheet of plastic materials and presses it at all points onto the substrate . as the substrate advances between the pressure roller and lower motorized and freely moving wheels , these latter entrained in rotation by the bottom side of the substrate , and as the sheet of plastic materials covers the latter , the frame 4 pivots around the two horizontal half - axes 11 and 12 to reach the vertical position at the time when the assembly is half finished ; then it is inclined with its upper portion leaning toward the downstream conveyor , on the inclined section 108 of which the substrate covered with the sheet of the plastic material is deposited . during the calendering operation , the pressure roller exerts the required pressing force on the glazing which can be relatively equal at all points . this force can be adjusted through a wide range according to the glazing manufactured and can vary , for example , from one to several hundreds of newtons per linear centimeter . although the pressure roller and the lower running wheels are initially regulated to the average transverse curvature of the glazing , the great flexibility of the pressure roller , associated if need be to that of the damping devices on which the upper and roller bending wheels can be mounted , enables the absorption of the possible variations in the transverse curvature encountered during the movement of the glazing . when the glazing assembly emerges from the apparatus , the sheet of plastic material is perfectly applied to the substrate and no bubbles appear between the two . the adherence obtained is generally improved for an automobile windshield by submitting the glazing to an autoclave cycle , for example at 120 ° c . under a pressure of 10 bars for one hour . if need be , in order to increase the adhesion produced during calendering , the sheet is heated before assembly to a temperature of about 60 ° c . so as to activate the adhesive layer . this heating can be done with an additional apparatus such as infrared tubes placed opposite the sheet . the substrate can also be heated beforehand . when the assembly is completed , the edges of the sheet of plastic material are cut to correspond to the shape of the glazing by known means such as a heated knife . the degree to which the pressure roller deforms in the direction of the displacement of the glazing is dependent upon the extent of contact with and hence the support provided by the supporting roll which is a function of the amount of curvature given the pressure roll . all sorts of laminated safety glazing may thus be manufactured , of very diverse sizes and curvatures , particularly for motor vehicle windshields , and the manufacture may be carried out at a rapid rate . for example , about two hundred glazings and more can be manufactured in an hour . the apparatus can also be advantageously utilized for the manufacture of lenses or other assemblages of elements for which the curvatures of the two opposite sides are different . it suffices to regulate the pressure roller to the curvature of the top side of the laminate to be obtained , and the lower pinching means such as the lower wheels , to the curvature of the bottom side of the laminate . the great flexibility of the apparatus permits its use , if need be , to assemble various types of glazings having different curvatures and thicknesses , without it being necessary to readjust the respective positions of the pinching means . it is in such cases important that the said pinching means are adjusted to correspond to the most accentuated curvature so that the extremities of the lower pinching means , for example the lower wheels placed at the extremities , always support the glazing . | 1 |
a food processor 1 is illustrated and described -- first of all with reference to fig1 -- which has an agitator drive 2 , not illustrated in any more detail , in the form of an electric motor . a mixing vessel 4 , which has a handle 5 , is received in a mixing - vessel mount 3 . as can be seen from the plan view according to fig2 a cutter mechanism 6 is located in the mixing vessel 4 . the cutter mechanism 6 may also be exchanged and replaced by another cutter mechanism . it can be seen from the illustration according to fig1 but also from the end view according to fig3 that , at its upper rim 7 , the mixing vessel 4 is formed such that it widens by way of a conical shoulder 8 . a mixing - vessel lid 9 is illustrated in plan view in fig4 . it has a substantially circular opening 10 . the circular opening 10 has a centre point 11 which is offset with respect to a geometrical centre point 12 of the mixing - vessel lid 9 . the mixing - vessel lid 9 has an elliptical surface area . formed at the ends of the mixing - vessel lid 9 which are associated with the greater axis of the surface area , is , on one side , a hand grip 13 and , opposite this , a protrusion grip 14 , which is explained in detail hereinbelow . as can also be seen from the side view according to fig5 a locking hook 16 is formed on the underside of the hand grip 13 and , when the mixing vessel lid has been attached onto the mixing vessel , engages in a corresponding locking opening in the mixing vessel 4 . furthermore , it can also be seen that the opening 10 is adjoined by a downwardly projecting cylindrical continuation 15 which , when the lid has been attached , projects into the interior of the mixing vessel 4 . the protrusion grip 14 has a downwardly projecting spigot 17 . the latter interacts with the securing device , as is explained in more detail hereinbelow . fig6 shows the end view of the mixing - vessel lid 9 , on the side of the protrusion grip 14 . taking fig5 and 6 together , it is possible to see , specifically , a peripheral centring edge 70 which , in the inserted condition , is located in the interior of the mixing vessel 4 . furthermore , it is possible to see , specifically , from fig8 that the centring edge 70 consists of a relatively pliable plastics which is either moulded on in the two - component process or , as a ring , is fitted onto the structure of the mixing - vessel lid 9 or is inserted into the recess illustrated . specifically , the centring edge 70 has a protruding lip 71 which protrudes in the form of a v with respect to a solid region 72 of the centring edge 70 . if a liquid is in contact with the seal , then this pushes against the inside of the sealing lip 71 , thus increasing the contact - pressure force against the mixing vessel 4 . it can be seen from the bottom view of the mixing - vessel lid 9 illustrated in fig7 that the centring edge 70 has a geometrically identical progression , although on a smaller scale , to the surface area of the mixing - vessel lid 9 . it is thus also adapted to an opening cross - section of the mixing vessel 4 in the upper region , as is illustrated in detail hereinbelow . fig8 shows a section through the mixing - vessel lid in the direction of the greater axis of the elliptically - shaped surface area . fig9 shows a cross - section according to the illustration of fig8 although the section plane is offset by 90 ° with respect to the section plane of fig8 . as in fig4 it can also be seen here that an -- inner -- termination surface 73 provided on the narrow sides runs in a rectilinear manner , unlike the rest of the inner surface of the mixing - vessel lid 9 , which is curved to a relatively pronounced extent ( in the edge region ) or shallow extent . from the detail of fig1 , the spigot 17 can be seen , which interacts with the securing device , as is now explained in detail hereinbelow . it is disposed centrally with respect to the protrusion grip 14 , the latter also forming a protrusion edge 74 which projects downwards in the direction of the spigot 17 . from the cross - sectional detail of fig1 , it is also possible to see , in particular , an attachment edge 75 which is formed at the bottom of the upper cover periphery 76 , the outer surface of which connects with the mixing vessel 4 as a continuation thereof . it can be seen from the side illustration of the mixing vessel 4 according to fig1 that the mixing vessel 4 can be divided up essentially into three regions a , b and c . the lower region a is of substantially cylindrical construction . the region b adjoining it is of substantially conical construction . further , a region c connects with this in the upward direction , which defines a protruding portion extending away from the handle 5 , region c leading to a curved front contour line 18 -- on the side opposite the handle 5 . this contour line 18 also corresponds to an inner contour line . the end view of the mixing vessel 4 according to fig1 shows that the curved contour line 18 is not formed in the side regions of the mixing vessel 4 . it can be seen from the plan view according to fig1 that a centre point 19 of a circular opening cross - section of the lower region a , which centre point 19 coincides with an axis of rotation of the cutter mechanism , is located offset with respect to a centre point 19 &# 39 ; of the elliptically - shaped upper opening cross - section of the region c . the offset section v is formed in the direction of a greater longitudinal axis x of the upper elliptically - shaped opening cross - section , pointing away from the handle 5 . in addition , the bottom view of the mixing vessel 4 according to fig1 shows , in particular , a star - shaped coupling insert 20 for driving , for example , the cutter assembly 6 , which is described in more detail hereinbelow . it can further be seen from the cross - sectional illustration according to fig1 that an inwardly protruding step 21 is provided in the interior of the mixing vessel 4 . the step 21 is part of an overall wedge - shaped structure which extends in the region of the central section b and of the upper section c of the mixing vessel . the step 21 is provided on one side in the mixing vessel , as can also be gathered , in particular , from the illustration of fig1 . the step 21 proceeds further at a small angle to merge , via a surface 22 , into the inner wall 23 of the mixing vessel . the centre point of curvature for the surface 22 is in this connection the centre point 19 . the step 21 is arranged such that the material being stirred or mixed passes over it as it is subjected to a pronounced rotary movement , the cutter mechanism or a stirring insert thus not engaging against the step 21 . moreover , as can also be seen from the illustration shown , the step 21 is of an angled configuration , an upper step surface running approximately at and along the lower edge of the shoulder 8 . the other step surface runs approximately perpendicular thereto , with the curved transition in the right angle . the largest step shoulder can also be seen in the curved , substantially right - angled transition . towards the bottom , in the vertical region , the step surface is fully curved to a slight extent such that in detail , no right angle is formed , but rather an acute angle which is defined by the upper and vertical step surfaces . towards the bottom , the step shoulder is also reduced to an increasing extent until it terminates substantially in the region of an upper boundary of the region a of the mixing vessel 4 . overall , the upper surface 22 , which is parallel to the wall or is integrated into the circular shape of the wall , extends approximately over a quarter - circle of the surface area of the mixing vessel 4 . a securing device 24 is provided in the handle 5 of the mixing vessel 4 . the securing device 24 specifically comprises a hand lever 25 which is connected fixedly to a bush 26 formed as a coupling rod . a securing pin 27 is received in an upper region in the bush 26 . the securing pin 27 can only be moved vertically in the bush 26 , i . e . against the force of a spring 28 . by attaching the mixing - vessel lid 9 , the securing pin 27 is pushed downwards , i . e . by the spigot 17 ( see fig8 and 10 ). by this , specifically , a securing continuation 28 which is connected to the securing pin 27 is moved vertically downwards out of a slot 29 &# 39 ; of the bush 26 . the securing continuation 28 thus passes into a groove - like , at least partially circular , recess 29 , so that a rotation of the bush 26 by means of the hand lever 25 together with the securing pin 27 is enabled . a securing lug 30 is also formed on the hand lever 25 ( see also fig1 ) which engages in a securing groove 31 of the mixing - vessel lid 9 . by rotation of the hand lever 25 , the attached mixing - vessel lid 9 is thus simultaneously locked on the mixing vessel . however , due to the necessary vertical movement of the securing pin 27 , it is not possible to rotate the hand lever 25 unless the mixing - vessel lid 9 has been attached correctly . it is essential that the hand lever 25 , the securing pin 27 and the bush 26 are located outside the actual mixing vessel 4 , i . e . outside a mixing - vessel wall 32 . a through - passage in the wall 32 of the mixing vessel 4 is neither provided nor necessary for actuating the securing means and for providing the securing arrangement . a circumferential attachment edge 33 is provided on the outside of the mixing vessel 4 at the transition between the region a and the region b of the said mixing vessel 4 . a second wall 34 which terminates in the attachment edge 33 is also provided in the lower region of the mixing - vessel wall . the diameter of this attachment edge 33 increases towards the side at which the handle 5 is provided . the attachment edge 33 also secures at the same time the handle to the mixing vessel 4 in its lower region . in the upper region ( see fig1 ), the handle 5 is screwed to the mixing - vessel wall 32 by means of a screw - connection 77 . the securing of the handle 5 on the mixing vessel 4 is , in detail , arranged such that , as has been mentioned above , the handle 5 is screwed to the mixing - vessel wall 32 in the upper region and , in the lower region , is connected at the attachment edge 33 , for example , by hooking in . if , when the mixing vessel 4 has been inserted , any food or liquid should run down the outer wall of this mixing vessel , then the attachment edge 33 deflects this food or liquid around the mixing - vessel mount 3 , with the result that a heating device or the like provided there is not soiled . this could result in the mixing vessel 4 &# 34 ; sticking fast &# 34 ; in the mount 3 , whereupon removal of the vessel 4 from the mount is at least rendered more difficult . rather , the food or liquid trickling off runs off the housing . a free end 35 of the bush 26 has a positive - lock opening 36 level with the attachment edge 33 . the positive - lock opening 36 interacts with a coupling part 38 in the mixing - vessel mount 3 . this coupling part 38 is indicated schematically in the upper region of fig1 , one end of the bush 26 being illustrated here only by dashed lines . the coupling part 38 has a transverse pin 39 which engages in the positive - lock recess of the bush 26 . correspondingly , the mixing vessel can only be inserted into the mixing - vessel mount 3 when the hand lever 25 is located in a position corresponding to the open position . connected to the coupling part 38 , in axial extension of it , is an expansion toggle 40 , fig1 illustrating the non - actuated disposition and the actuated disposition of the expansion toggle . furthermore , these actuated and non - actuated positions can also be seen in the cross - sectional illustrations of fig2 to 23 . specifically , the expansion toggle 40 acts , via the spreading jaws 41 and 42 , on a retaining sleeve 43 which , in the non - stressed state ( see fig2 and 23 ), retains the inserted mixing vessel 4 in the lower region a in a positively locking manner . in the expanded state of the expansion toggle 40 ( see fig1 , 20 and 21 ), the sleeve 43 is biased against the action of the u - shaped spring 44 which acts on the spreading jaws 41 and 42 . it can also be seen from fig1 that a securing lever 45 is provided at a lower end of the coupling part 38 , the securing lever being illustrated in more detail in fig2 and 25 . the securing lever 45 turns with a rotational movement of the coupling part 38 . in this , it runs over a contact switch 46 and moves into the region of a plate 47 . the action of running over the contact switch 46 and moving in the region of the plate 47 further causes a securing pin 48 to move out upwards ( see also fig1 ), which mechanically secures the disposition of the securing lever 45 on the far side of the securing pin 48 and thus in the region of the plate 47 . without moving the securing pin 48 back , it is not possible to release and thus remove the mixing vessel 4 from the mixing - vessel mount 3 in the food processor 1 . also associated with this is the fact that it is only when the securing pin 48 is moved out that the agitator or the heating device can be freed for activation . correspondingly , the mixing vessel 4 cannot be removed without the agitator and the heating device being deactivated . if the food processor is put into operation by means of the speed regulator , then the securing pin 48 moves out and locks the securing lever 45 . this can take place purely mechanically or else electromechanically . the securing pin 48 only moves back when the drive motor and thus the cutter mechanism 6 have come to a standstill . it is only after this that it is possible to unlock the mixing - vessel lid and remove the mixing vessel 4 from the mount 3 . it is thus ensured that the cutter mechanism 6 is at a stand - still before the mixing vessel 4 is opened . any risk to the user is thus ruled out . fig2 to 31 illustrate a cooking insert 50 which is advantageous , in particular , for use in the interior of the mixing vessel 4 beneath the mixing - vessel lid 9 . the cooking insert 50 has a perforated , substantially conical or , optionally , also cylindrical side wall 51 and a perforated base 52 . furthermore , it has an upper peripheral collar 53 which has an elliptical surface area . here , in a manner comparable with the mixing vessel 4 , the elliptical surface of the collar 53 is offset with respect to a centre point of the base 52 . the point 54 can be regarded as the centre point of the base 52 , while the point 55 can be regarded as the geometrical centre point of the elliptical configuration of the collar 53 . this results in the collar 53 having a larger extent of projection y on one side -- the front side -- than to the rear -- z . the lateral extent of projection -- t -- is , in turn , smaller than the rear extent of projection z . in the front region of the collar 53 , there are likewise provided slot - like through - passages 56 , these also being provided in the conical wall and in the base . furthermore , in its front region , the cooking insert has a pouring spout 57 cut into it , which has a crossbar 58 gripping over it . the crossbar 58 may thus act in the manner of an eyelet for receiving a hook in a seating manner . the incorporated of the cooking insert into the mixing vessel is illustrated in fig3 . fig3 shows a plan view of the mixing - vessel mount 3 . this is formed in the manner of a bowl . provided in the base of the mixing - vessel mount 3 is a discharge opening 59 , in regard to which reference is also directed to fig3 . furthermore , it is possible to see a star - shaped coupling recess 60 which transmits the motor power to the agitator and / or the cutter assembly 6 . the star - shaped coupling insert 20 ( see fig1 ) engages in the coupling recess 60 . the three - pointed star configuration of the one side of the coupling and the six - pointed star construction of the other side of the coupling means that , on the one hand , the coupling position can be easily obtained when the mixing vessel 4 is inserted and , on the other hand , a secure , positively locking coupling connection is also achieved . it can be seen from the sectional illustration according to fig3 that the discharge opening 59 engages in a connection piece 62 which projects upwards from a base 61 of the food processor 1 , with the result that any liquid or the like which has run over into the mount 3 can run out in its entirety , from the food processor 1 , through the discharge opening 59 . a mixing - vessel spatula 78 is illustrated in fig3 . the essential feature of the mixing - vessel spatula 78 is a hook - like formation 79 . this is suitable , in particular , for interacting with the eyelet ( crossbar 58 ) on the cooking insert 50 . as a result , the cooking insert 50 can be held down in the mixing vessel 4 , for example , when liquid is being poured out . the vessel may be configured in the form of a bowl . in fig1 , a cream - whipping device 64 inserted in the mixing vessel 4 is illustrated . said cream - whipping device 64 has two blades 66 which are moulded radially onto a cylindrical coupling mount 65 . the blades 66 have regular through - passages and , at least in their lower regions , have an outer contour which corresponds to the mixing - vessel base 67 . the cream - whipping device 64 is positioned on the cutter mechanism 6 , for example on a nut which secures the cutter mechanism 6 , by means of its coupling mount 65 . a second embodiment of the cream - whipping device 80 is illustrated in fig3 to 38 . corresponding to the first exemplary embodiment in fig1 , this cream - whipping device 80 has a cylindrically shaped coupling mount 81 from which there extend two mutually opposite , radially outwardly directed whipping blades 82 . these whipping blades 82 are essentially formed in the manner of a skeleton and , in their regions remote from the mount 81 , have cross - pieces 83 which are aligned perpendicularly with respect to the axis of rotation of the cream - whipping device 80 . as can be seen from fig3 , said cross - pieces are offset at an angle with respect to a horizontal , the cross - pieces 83 being alternately offset in the positive and negative directions with respect to the horizontal . a handle - like grip 84 is moulded on at the top of the coupling mount 81 , by means of which the cream - whipping device 80 can be positioned in the mixing vessel 4 or on the cutter mechanism 6 , or removed from the actor mechanism , in an extremely simple manner . in fig3 , there is illustrated the inserted condition of cream - whipping device 80 in the mixing vessel 4 . it can be seen that the cream - whipping device 80 is plugged onto a driver 85 of the cutter mechanism 6 by means of its coupling mount 81 . the arrangement here is such that the whipping blades 82 are located in a wedge of the cross - form cutter assembly 6 . a second embodiment of the securing device 24 is also illustrated in fig3 . the rotatable hand lever 25 attached on the handle 5 has a u - shaped configuration in cross - section . a coupling rod 86 is actuated by means of this hand lever 25 , as is also the case in the first exemplary embodiment . said coupling rod is connected in a rotationally fixed manner to the hand lever 25 and has a curved extent within the handle 5 . a first section of curvature of the coupling rod 86 is located in an upper region of the handle 5 , the curvature running substantially towards a centre axis z of the mixing vessel 4 . a further , second section of curvature of the coupling rod is effected in the lower region of the handle 5 before the coupling rod 86 passes out of the handle 5 to bring the coupling rod 86 into a vertical position again . this configuration makes it possible to displace the handle 5 or the handle region in the direction of the centre axis z of the mixing vessel 4 such that the lever forces are kept low when the mixing vessel 4 is full . the coupling rod 86 passes through the handle 5 in the region of an opening 87 . the coupling end 88 which projects from the bottom of the handle 5 is in the form of a hammer head . the opening 87 has a contour which corresponds to the hammer head ( see fig4 ). in the region of the coupling rod 86 which is associated with the hand lever 25 , the coupling rod is associated , in a rotationally fixed manner , with a securing pin 89 which is aligned parallel , but in a radially offset manner , to the coupling rod 86 in this region . the securing pin 89 is fastened on the coupling rod 86 by means of a spring 90 . this spring 90 always forces the securing pin in the direction of the hand lever 25 and towards the handle cover 91 provided there . furthermore , the securing pin 89 is retained on a disc 92 located in a rotationally fixed manner on the coupling rod 86 , which disc has a bore 93 for the passage of the securing pin 89 . in the partial representation in fig3 a , the blocking position of the securing device 24 is illustrated . it can be seen that the securing pin 89 passes , by means of the spring 90 , through the bore 93 of the disc 92 into a blocking opening 94 of the handle cover 91 . this blocking opening 94 is open upwardly , that is to say in the direction of the hand lever 25 . the mixing - vessel lid 9 which is to be attached has a downwardly directed spigot 95 which , when the lid 9 has been attached , enters into the blocking opening 94 from above . this results in a displacement of the securing pin 89 into an unblocked disposition according to fig3 . after this , a pivoting of the hand lever 25 can be effected . a rotation or pivoting of the hand lever 25 results in corresponding pivoting of the hammer - head - formed coupling end 88 . pivoting through approximately 67 ° is preferred here . this construction has proved to be particularly advantageous , since there are no relative movements between the actuating elements and no wear thus occurs . the entire securing device 24 can be removed from the handle 5 and inserted into it again in an extremely simple manner . the entire device is fastened on said handle cover 91 which , in turn , can be fastened on the handle 5 , for example by means of a rear - engagement fastening and a fixing screw 96 . a third embodiment of the securing device 24 is illustrated in fig4 , 40a and 40b . in the region of the coupling rod 86 which is associated with the hand lever 25 , a locking protrusion 150 is moulded on this coupling rod 86 , beneath the handle cover 91 , which protrusion , in a blocking position according to fig4 a and 40b , is oriented in the direction of the centre axis z of the mixing vessel 4 . in the blocking position , this locking protrusion 150 is located in a blocking pocket 151 of a locking link 152 . the latter is essentially made up of a plate , which is aligned perpendicularly with respect to the coupling rod 86 and has the blocking pocket 151 , and of an angled leg which extends from this plate . by way of this leg , the locking link 152 is mounted on the underside of the handle cover 91 such that it can be pivoted via a pin 153 . the plate 154 has a central bore 155 for the passage of the coupling rod 86 . the radially aligned blocking pocket 151 extends from this bore 155 on the side facing the handle cover 91 . provided on that side of the bore 155 which is directed away from the blocking pocket 151 is a further through - passage 156 , through which a bolt 157 on the handle cover passes . in the region of its free end , this bolt is provided with an annular collar on which there is mounted a compression spring 158 which engages around the bolt 157 . said compression spring acts on the underside of the locking link 152 by means of its end directed away from the annular collar , with the result that said locking link is spring - loaded in the direction of the underside of the handle cover 91 . this means that the locking link 152 is always biassed in the direction of a position in which the locking protrusion 150 is blocked . as can be seen from fig4 a and 40b , it is not possible , in this position , for the coupling rod 86 to be rotated by means of the hand lever 25 since the locking protrusion 150 is located in the blocking pocket 151 , which is the very thing which prevents this rotation . in order to permit rotation of the coupling rod 86 , the mixing - vessel lid 9 has to be attached . the latter is provided on its underside , in the region of its protrusion grip 14 , with two actuating protrusions 159 which , when the mixing - vessel lid 9 is attached , pass through corresponding bores 160 in the region of the handle cover 91 and act on the locking link 152 . as a result , the locking link 152 is pivoted around the pin 153 against the spring force of the compression spring 158 , with the result that the blocking pocket 151 releases the locking protrusion 150 for turning ( see fig4 ). unlike the exemplary embodiments described above , in this case it is not the securing pin or the locking protrusion which is displaced into a position for turning - action release , but rather the locking link which blocks the locking protrusion . as was also the case in the first exemplary embodiment , the coupling rod 86 or its coupling end 88 acts on a coupling part 38 when the mixing vessel 4 has been inserted into the mixing - vessel mount 3 . in fig4 and 43 , this coupling part 38 is illustrated in more detail in a second embodiment . it can be seen that the coupling part 38 comprises a coupling bush 98 which is pushed onto the top of a camshaft 97 , it being possible for the coupling bush 98 to be displaced vertically against a spring 99 on the camshaft 97 . coupling bush 98 and camshaft 97 are always connected to one another in a positively locking manner irrespective of the vertical displacement position of the coupling bush 98 , with the result that rotational movements of the coupling bush 98 are transmitted to the camshaft 97 . as in the first exemplary embodiment , the camshaft 97 carries an expansion toggle 40 for spreading apart two spreading jaws 41 and 42 of a retaining sleeve 43 . in its upper region , the coupling bush 98 has a peripheral edge 100 . for positively locking coupling to the coupling end 88 of the coupling rod 86 , the coupling bush 98 has a slot - like receiving means 101 located at the top . latched on to the peripheral edge 100 is a blocking sleeve 102 which has a keyhole - like through - opening 103 corresponding to the cross - section of the hammer - head - formed coupling end 88 . the blocking sleeve 102 is preferably moulded as a plastics injection moulding and provides a frustoconical sealing bead 104 at the top . the blocking sleeve 102 has two radially aligned pairs of jaws 105 , between which pairs of jaws 105 there engage pins 106 which are secured to the housing ( see fig4 ). this arrangement prevents the blocking sleeve 102 from rotating , but permits a vertical movement of the blocking sleeve 102 . the hammer - head - formed coupling end 88 passes through the housing 107 of the food processor 1 in the region of a circular through - opening 108 which has at the bottom , that is to say facing the blocking sleeve 102 , a frustoconical contour corresponding to the sealing bead 104 . when the mixing vessel 4 is inserted into the mixing - vessel mount 3 , the coupling end 88 passes through the through - opening 108 of the housing 107 and , after this , through the keyhole - like opening 103 of the blocking sleeve 102 until the coupling end 88 is located in the receiving slot 101 of the coupling bush 98 . after this , there is effected a vertical displacement of the coupling bush 98 together with the blocking sleeve 102 against the pressure of the spring 99 , the coupling bush 98 and blocking sleeve 102 being moved away from the housing through - opening 108 . after insertion of the mixing vessel 4 into the mount 3 has been completed , the above - described pivoting of the hand lever 25 takes place , which results in the coupling rod 86 , and thus the coupling end 88 , being rotated . likewise due to the positive lock , this rotation causes a rotation of the coupling bush 98 , and , as a result , a rotation of the camshaft 97 into the position in which the mixing vessel 4 is clamped in . the blocking sleeve 102 accompanies the vertical movement , but does not rotate . the blocking - sleeve opening 103 and the hammer - head - formed coupling end 88 are oriented offset with respect to one another in this position ( see fig4 ). accordingly , the coupling end 88 is arrested in the vertical direction in this position . should the user wish to remove the mixing vessel 4 , then a reverse displacement into the basic position by means of the hand lever 25 is first of all imperative in order that the receiving slot 101 and the keyhole opening 103 or the coupling end 88 and the keyhole opening 103 are made to coincide . it is only after this , that the hammer - head - shaped coupling end 88 can be pulled vertically out of the coupling part 38 . this precludes the risk of the user spreading apart the retaining sleeve 43 to such an extent that the mixing vessel 4 can indeed be removed , but the retaining sleeve 43 does not latch into its end position . in this case , during removal of the mixing vessel 4 , the coupling end 88 would be pulled out of the coupling part 38 , so that the u - spring 44 allows the retaining sleeve 43 to grip again and clamps the mixing vessel 4 in . since , in this position , the coupling would already have been disengaged , it would no longer be possible for the user to remove the mixing vessel 4 . this malfunctioning is avoided by the invention specified since it is only in a stop position in which the slots and openings of the blocking sleeve 102 and coupling bush 98 are located one above the other that the coupling rod 86 can be pulled out . in the locking position shown in fig4 , the seal in the region of the housing through - opening 108 is deactivated . the seal only takes effect when the mixing vessel 4 has been removed . in this case , the sealing bead 104 of the blocking sleeve 102 seals the region of the housing through - opening 108 in this region . the cones of the sealing bead 104 and of the opening 108 grip one inside the other and thus provide an effective seal . the receiving slot 101 , formed as a driver pocket , of the coupling bush 98 is closed towards the bottom , with the result that it is not possible for any water or the like to penetrate in there either . furthermore , it has proved to be advantageous here that , when the mixing vessel 4 has been inserted , the coupling part 38 and also the coupling end 88 passing through the housing 107 do not come into contact with the housing 107 . manufacturing tolerances in the vertical direction are compensated for by the coupling part 38 penetrating into the housing 107 . tolerances in the horizontal direction do not result in any contact between the coupling rod 86 and housing 107 , since the through - opening 108 is arranged to be considerably larger than the diameter of the coupling rod 86 . furthermore , the weighing result is not influenced by the coupling part 38 being decoupled from the housing 107 . fig4 to 49 illustrate a second embodiment of the cutter - mechanism fastening , in detail and assembly views . the cutter assembly 6 is made up essentially of four cutters 110 which are arranged radially around a drive shaft 109 and in each case enclose an angle of 90 ° with one another , two mutually opposite cutters 110 , starting from the drive shaft 109 , first of all extending perpendicularly with respect to the drive shaft 109 and being then curved downwards , in the direction of the mixing - vessel base 67 in the installed position . the other two cutters 110 run essentially in a horizontal direction . the cutters 110 or the cutter assembly 6 is / are fastened on the drive shaft 109 by means of a screw - member 111 . furthermore , the screw - member 111 carries the abovementioned driver 85 at the top . the drive shaft 109 is mounted rotatably in a cutter bearing 112 and the bottom of the cutter bearing 112 continues in the abovementioned coupling insert 20 . the cutter assembly 6 is operationally connected in non - releasable manner to the cutter bearing 112 . this structural unit is inserted into the mixing vessel 4 from above , the cutter bearing 112 passing through the mixing - vessel base 67 in the region of a correspondingly shaped retaining opening 113 . for engaging against the edge region of the retaining opening 113 , the cutter bearing 112 has a supporting shoulder 114 . in the region which is located beneath the supporting shoulder 114 , which tapers in cross - section , the cutter bearing 112 , which has a substantially circular shape , has two diametrically opposite flattened portions 115 . outwardly directed spigots 116 are provided so as to be offset by 90 ° with respect to these flattened portions 115 . the retaining opening 113 of the mixing - vessel base 67 has a corresponding contour . flattened opening regions 117 and passage regions 118 for the spigots 116 are thus also provided here . fig4 illustrates a stand 119 in section . this stand 119 is preferably a plastics part . the outer contour of the stand 119 corresponds substantially to the shaping in the region of the mixing - vessel base 67 . the stand 119 has a central , circularly shaped , through - opening 120 which , in two mutually opposite regions , has radially outwardly extending through - passages 121 . at the top , the through - opening 120 is surrounded by a collar 123 . at the bottom , the through - opening 120 is provided with a downwardly directed wall 122 which has a larger diameter than the through - opening 120 . said wall 122 has two mutually opposite recesses 124 with open edges . the residual wall regions remaining between these recesses 124 have inwardly projecting latching lugs 125 . these latching lugs 125 hold a retaining ring 126 which , as seen in the vertical direction , is mounted between the latching lugs 125 and the underside of the through - opening 120 . the retaining ring 126 is retained in a rotationally fixed manner since the retaining ring 126 has , on its outer wall , two mutually opposite protrusions 127 which engage in the abovementioned recesses 124 of the wall 123 . a wavy spring 128 located in the region between the retaining ring 126 and the underside of the through - opening 120 forces the retaining ring 126 in the direction of the latching lugs 125 . as already mentioned , the cutter bearing 112 along with the cutter mechanism 6 is plugged through the retaining opening 113 of the mixing - vessel base 67 , after which , due to the flattened formations , it is no longer possible for the cutter bearing 112 to be rotated . provided between the supporting shoulder 114 and the mixing - vessel base 67 is a sealing ring 129 which seals axially between the cutter bearing 112 and the mixing vessel 4 so that it is not possible for any liquid to pass out of the mixing vessel 4 . in order to fasten the cutter bearing 112 on the mixing - vessel base 67 , the stand 19 is then positioned against the cutter bearing 112 from beneath such that the spigots 116 pass through the through - passages 121 in the region of the through - opening 120 . the retaining ring 126 has correspondingly formed recesses 130 . when the stand 119 is turned through approximately 180 °, the spigots 116 engage behind correspondingly formed annular shoulders 131 , which define run - on slopes . a stop projection 132 is provided at the end of each run - on slope . the seal 129 is given a defined bias by the stand 119 , which , at two laterally projecting spigots 116 of the cutter bearing 112 , pushes the latter downwards against the mixing - vessel base 67 . in this case , the stand 119 is supported against the underside of the mixing - vessel base 67 . in order to render the contact - pressure force virtually independent of tolerances , the spring - biassed latching ring , which is made up of the retaining ring 126 and the wavy spring 128 , is fastened in the stand 119 . this latching ring is in positively locking contact with the spigots 116 on the cutter bearing 112 . in order to provide improved support of the cutter bearing 112 on the mixing - vessel base 67 , it may also be provided that the cutter bearing 112 has a radial collar by means of which the cutter bearing 112 engages fixedly against the mixing - vessel base 67 . in this case , the biassing of the seal 129 depends on the vertical extent of the collar . as already mentioned , the stand 119 is produced from plastics and serves simultaneously as a set - down surface of the mixing vessel 4 . in all cases , the temperature of the stand 119 is considerably lower than that of the mixing vessel 4 , thus also making it possible for the hot mixing vessel 4 to be positioned on surfaces which are not heat - resistant , such as , for example , wood . a cooking insert 50 in a second embodiment is illustrated in fig5 to 52 . this differs from the first exemplary embodiment shown in fig2 to 31 essentially in the eyelet - like configuration for mounting reception of a hook . as can be seen , in particular , from the partial section of fig5 , a dovetail - like receiving eyelet 133 is provided here , which is located , as a sheet - metal part , in the region of the pouring spout 57 . the receiving eyelet 33 is upwardly open . the through - passages 56 of the cooking insert 50 serve , inter alia , for rinsing foods , such as , for example , rice , with boiling water . furthermore , when liquid is poured out , solid constituents contained therein are retained by the cooking insert 50 . if the cooking insert 50 is inserted into the mixing vessel 4 before fruit , for example , is chopped up , then this results in an increased amount of juice being produced , since the fruit cannot pass into the upper part of the mixing vessel 4 and is thus subjected to more intensive processing by the cutters 110 . in fig5 to 55 the mixing vessel 4 , the cooking insert 50 and the mixing - vessel lid 9 in a second embodiment are illustrated , in each case in a side view . it can be seen here that , instead of the locking hook 16 provided in the first exemplary embodiment , the mixing - vessel lid 9 now has a cross - member 134 . this cross - member 134 is provided with a slot 135 in which a tongue 136 of the mixing vessel 4 engages when the mixing - vessel lid 9 has been attached . after the mixing - vessel lid 9 has been removed , the tongue 136 also serves as a pouring spout . dual securing is thus provided for the attached mixing - vessel lid , on the one hand by the engagement of the tongue 136 in the slot 135 and on the other hand by a u - leg of the hand lever 25 gripping over the protrusion grip 14 ( see fig3 in this context ). a mixing - vessel spatula 78 in a second embodiment is illustrated in fig5 to 58 . said spatula is made up essentially of a spatula handle 137 and a spatula portion 138 . spatula handle 137 and spatula portion 138 are formed separately , the spatula portion 138 preferably consisting of a more pliable plastics than the spatula handle 137 . the spatula portion 138 is pushed onto the spatula handle 137 by way of a groove - tongue connection . the spatula handle 137 has a plate - like handle - region boundary 139 . furthermore , in the region of the spatula portion 138 , the mixing - vessel spatula 78 has a removal protrusion 140 which is configured in the form of a dovetail , for interacting with an insert vessel , for example , with the cooking insert 50 . in order to remove the cooking insert 50 from the mixing vessel 4 , use may then be made of the mixing - vessel spatula 78 , in that the dovetail - like removal protrusion 140 is pushed into the receiving eyelet 133 , which is likewise in the form of a dovetail . such a removal position is illustrated in fig5 . furthermore , this configuration may also serve to hold down the cooking insert 50 when the mixing vessel 4 is being emptied . furthermore , use is made of the mixing - vessel spatula 78 during mixing operation , in particular for preparing a dough , mix or batter . for this purpose , the mixing - vessel spatula 78 is passed through the mixing - vessel lid 9 and held , in the region of its opening 10 , in the dough , mix or batter which is to be mixed . a further configuration of the safety lock according to fig2 and 25 is illustrated in fig6 to 61a . in this case , a radially outwardly projecting securing lever 45 &# 39 ; is likewise disposed at the lower end of the camshaft 97 , a blocking link 161 being moulded on in its free end region . said blocking link is formed as an extension to the securing lever 45 &# 39 ; and , in plan view , has a contour in the form of part of a ring . as can be seen , in particular , from fig6 a , the blocking link 161 is moulded on on the underside of the securing lever 45 &# 39 ;. a lever - like momentary - contact switch 162 , which is mounted pivotably on a housing wall 163 , is also provided . the switch is mounted via a pivot pin 164 , on which a leg spring 165 is also located . one end of said leg spring is supported on the housing wall 163 and its other end is supported on the inner side of the momentary - contact switch 162 , as a result of which the latter is biassed in a direction which is oriented away from the securing lever 45 &# 39 ;. at its free end , the momentary - contact switch 162 has an l - shaped blocking shoulder 166 , one l - leg 167 being oriented in the direction of the securing lever 45 &# 39 ;. an actuating protrusion 168 which is likewise oriented in the direction of the securing lever 45 &# 39 ; is provided beneath this blocking shoulder 166 . to be specific , this actuating protrusion 168 is oriented in the direction of a safety switch 46 &# 39 ;, which is likewise secured on the wall 163 . on the side directed away from the safety switch 46 &# 39 ;, the momentary - contact switch 171 is supported by a push rod 169 of an electromagnet 170 . this electromagnet 170 is likewise secured on the housing . in fig6 and 60a , a basic position is illustrated , i . e . a position in which the safety device has not yet been activated , for example when the mixing vessel 4 has not yet been inserted into the mount 3 and / or the mixing vessel lid 9 has not yet been attached to the mixing vessel 4 . in this position , the agitator drive 2 or the heating device should be prevented from being activated . this is prevented by the momentary - contact switch 162 , which is to activate the safety switch 46 &# 39 ;, being blocked , in the direction of the safety switch 46 &# 39 ;. in this way , the l - leg 167 of the blocking shoulder 166 is supported against the blocking link 161 ( see fig6 a ). if , in this position , an attempt is made to switch on the agitator drive , then the electromagnet 170 is activated . the push rod 171 tends to move out and displace the momentary - contact switch 162 in the direction of the safety switch 46 &# 39 ;. however , as already mentioned , this is prevented by the blocking link 161 . operation of the agitator drive 2 is thus not possible without first of all inserting the mixing vessel 4 and providing this with the lid 9 . it is only after actuation of the securing device 24 and associated pivoting of the securing lever 45 &# 39 ;, mounted on the camshaft 97 , into the position illustrated in fig6 and 61a that the drive 2 can be switched on . the blocking link 161 leaves the region of the momentary - contact switch 162 , the latter thus pivoting about the pivot pin 164 as a result of the rearward action of the push rod 171 . this pivoting causes actuation of the safety switch 46 &# 39 ; by means of the actuating protrusion 168 . the safety switch 46 &# 39 ; may , for example , be a break - contact element which , upon actuation , closes the circuit to the drive 2 . it is , however , also possible to provide a safety switch 46 &# 39 ; which , for the purpose of releasing the drive , merely sends a pulse to an electronics unit inside the appliance . when the momentary - contact switch 162 is in the pivoted position , locking of the securing lever 45 &# 39 ; in its securing position is effected according to fig6 . it is thus possible to move the securing lever 45 &# 39 ;, by means of the securing device or by the camshaft 97 , into its initial position again only when the momentary - contact switch 162 has been moved back . in this exemplary embodiment , blocking of the securing lever 45 &# 39 ; takes place at two points . on the one hand , the l - leg 167 of the blocking shoulder 166 of the momentary - contact switch 162 blocks the securing lever 45 &# 39 ; in the region of its blocking link 161 and , on the other hand , the other l - leg of the blocking shoulder 166 blocks the securing lever 45 &# 39 ; in the region of the end portion of the latter which projects beyond the blocking link 161 . in order to release the securing lever 45 &# 39 ;, the momentary - contact switch 162 can only be pivoted into a release position when the electromagnet 170 is demagnetized and the leg spring 145 thus becomes effective . for this purpose , it is necessary first of all to switch off the drive 2 and , if appropriate , the heating device . however , the electromagnet 170 is only demagnetized after the cutter mechanism 6 is at a complete standstill . for this purpose , there may be provided , on the agitator drive 2 or in the region of the cutter mechanism , a speed sensor which only interrupts the power supply to the electromagnet 170 when the cutters are at a complete standstill . the push rod 171 is no longer moved in the direction of the momentary - contact switch 162 . the leg spring 165 causes the momentary - contact switch 162 to be moved back , the actuating protrusion 168 leaving the safety switch 46 &# 39 ; and the blocking shoulder 166 leaving the region of the securing lever 45 &# 39 ;. it is then possible to rotate the latter , as a result of which it is also possible to expand the sleeve retaining the mixing vessel 4 . also conceivable is a configuration in which the electromagnet 170 is always activated when the food processor 1 is in the basic switched - on state and , in a basic position , the momentary - contact switch 162 always engages against the blocking link 161 . in this case , it is necessary to switch off the food processor 1 fully in order to release the securing position of the securing lever 45 &# 39 ; shown in fig6 and 61a , this demagnetizing the electromagnet 170 in order to release the momentary - contact switch 162 . finally , a lid cap 141 is provided , which is illustrated in fig6 and 63 . this lid cap is formed as a cylindrical hollow body and is provided with a top 142 . approximately halfway up , the lid cap 141 is provided , on its outside sleeve surface , with an annular collar 143 which has an approximately triangular cross - section . the external diameter of the annular collar 143 is somewhat larger than the diameter of the opening 10 of the mixing - vessel lid 9 . also provided in the region of the annular collar 143 are three supporting protuberances 144 which are distributed uniformly on the circumference , each protuberance 144 extending uniformly above and beneath the annular collar 143 . the radial depth of each supporting protuberance 144 corresponds to that of the annular collar 143 . the lid cap 141 serves for insertion into the opening 10 of the mixing - vessel lid 9 . the lid cap 141 is supported by this in the region of its the supporting protuberances 144 by these protuberances in the edge region of the opening 10 , as a result of which an annular slot 145 remains for the passage of vapour ( see fig6 ). | 0 |
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