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the invention presents a new blocking logic to block unknowns for temporal compactors . the proposed blocking logic can reduce data volume required to control the blocking logic and also improve the number of scan cells that are observed by temporal compactors . control patterns , which describe values required at the control signals of the blocking logic , are compressed by lfsr reseeding . in the inventive method , scan chains are clustered into several groups and the outputs of the scan chains in each group are connected to 2 - input and gates that are controlled by the same control signal before the blocking logic gates . if no scan chains in a group capture unknowns , then the corresponding blocking logic gates are bypassed by the 2 - input and gates . hence no bits need to be specified in the control pattern for that group . this can significantly reduce the number of 0 &# 39 ; s that should be specified to propagate errors for observation . since all the scan cells in the group are observed , bypassing can improve observability . numbers of specified bits in highly specified test patterns are reduced by not observing one or more scan chain groups . the scan chains groups that are not observed are selected such that no decrease in fault coverage results . fig1 describes the lfsr reseeding based unknown blocking scheme used in prior work . every unknown value that is scanned out of the output of a scan chain ( see x &# 39 ; s on the outputs of scan chains h 1 and h n ) in a shift cycle must be blocked to prevent it from corrupting the signature by setting the control input of the corresponding blocking logic gate to a 1 . on the other hand , errors that need to be observed should propagate to the misr through the blocking logic gate . for example , in fig1 , since an error ( denoted by d ) that needs to be observed is scanned out of the output of h 2 in the current cycle , the control input of the blocking logic gate for h 2 is set to a 0 . the lfsr should be loaded with appropriate seeds to block all unknowns and propagate the errors that need to be observed to the misr . these seeds should be stored in the ate memory prior to test application along with test data . hence , if the size of seeds is large , it will increase overall data volume to be stored in the ate memory . ( in this paper , we use a scheme that loads a new seed into the control lfsr for each test pattern .) when test patterns are compressed by lfsr reseeding , normally the size of seeds , i . e ., the number of stages of lfsr , is determined by the number of specified bits in the most specified test pattern among all test patterns . if the number of specified bits in the most specified test pattern is s max , the number of stages of lfsr required is given by s max + m , where m is a margin to ensure that the equations are solvable . hence , it is important to minimize the number of specified bits in the most specified pattern . to minimize volume of control data , control pattern c i that has minimal number of care bits is computed for every test pattern p i . every scan cell that captures an unknown should be assigned 1 &# 39 ; s in c i ( assume that the blocking logic is comprised of only or gates ). the number of specified bits in each control pattern is minimized by minimizing the number of bits that are specified to 0 &# 39 ; s to observe errors . to reduce the number of care bits in c i , we reduce the number of faults that are targeted by test pattern p i . note that if a fault f is detected not only by p i but also by many other test patterns , then even if f is not observed when p i is applied , there is a high chance that fault f will be detected by other test patterns . once a set of faults f i that should be detected by test pattern p i is determined , then the minimum number of scan cells required to observe all faults in f i are selected . fault set f i is called the target fault list of p i . typically , a fault is captured into multiple scan cells and some scan cells capture fault effects for multiple faults . since observing only one fault effect is enough to detect the fault , only one fault effect is selected for observation for every fault in f i . fig2 ( b ) gives control pattern c i obtained by using the procedure described above for the test response shown in fig2 ( a ). the scan cells that capture unknown values are assigned 1 &# 39 ; s in c i . assume that the target fault list of p i contains faults f 1 , f 2 , . . . , f 7 . hence c i is specified to observe fault effects for these 7 faults . only one fault effect is selected for each fault for observation . for example , although fault effects of f 2 are captured into the third scan cell of scan chain h 2 and fifth scan cell of scan chain h 5 , only the third scan cell of scan chain h 2 is selected for observation and assigned a 0 in c i . c i requires 14 specified bits . after a control pattern c i that has minimal number of specified bits is computed for test pattern p i , a seed is computed for c i by using a linear solver . then the lfsr pattern cr i that will be generated by the lfsr / phase shifter from the seed for c i is computed by simulating the lfsr / phase shifter . during the simulation , the lfsr is loaded with the seed for c i and clocked for l cycles , where l is the number of scan cells in the longest scan chain . fig3 depicts a scan design that employs the inventive unknown blocking technique . there are a few differences between the blocking logic of the proposed technique and that of prior work , which is shown in fig1 . note that the blocking logic of the proposed method has an extra 2 - input and gate before each or gate of the blocking logic . one input of each 2 - input and gate is driven by an output of the phase shifter and the other input is driven by an output of the group register . the n scan chains are divided into g groups and all the 2 - input and gates that are connected to the outputs of scan chains that belong to the same group are driven by a common output of the group register . hence if i - th bit of the group register is assigned 0 , then the values captured in all scan cells in i - th group enter the corresponding misr , independent of the output states of the phase shifter . the outputs of scan chains in each group are connected to a separate misr . each group may contain a different number of scan chains although in the example shown in fig3 , every group consists of 4 scan chains . in this paper , all scan chains that can capture unknowns are placed into a few scan chain groups . these scan chain groups , which are assigned 1 &# 39 ; s in the group register such as g g of fig3 , are called unknown capturing scan chain groups or ucgs . on the other hand , scan chain groups that capture no unknowns are called unknown free scan chain groups or ufgs and assigned 0 &# 39 ; s in the group register such as g 1 . the proposed blocking logic can significantly reduce data volume for control patterns and improve observability over the prior art . the control pattern for prior work shown in fig2 ( b ) requires 14 specified bits . in the following , we show that the number of 0 &# 39 ; s in the control pattern for the same test response can be significantly reduced by using the proposed blocking logic . consider computing a control pattern c i for the proposed blocking logic ( see fig2 ( c )) for the test response shown in fig2 ( a ). assume that scan chains are clustered into 4 groups , g 1 , . . . , g 4 . only the scan cells in groups g 3 and g 4 capture unknowns and no other scan cells capture unknowns . hence g 1 and g 2 are assigned 0 &# 39 ; s in the group register and all scan cells in these scan chain groups can be observed without specifying any bit of c i to 0 for them . all the 7 faults except 2 faults f 4 and f 9 in the target fault list of p i can be detected by observing g 1 and g 2 . although the proposed scheme can reduce the number of 1 &# 39 ; s too ( see the next section ), assume that all scan cells that capture unknowns are assigned 1 &# 39 ; s in the control pattern for now . hence , 5 bits are assigned 1 &# 39 ; s to block the unknowns in the control pattern . only two additional bits need to be specified to 0 &# 39 ; s to observe fault effects for f 4 and f 9 . in consequence , total only 7 bits ( 5 1 &# 39 ; s and 2 0 &# 39 ; s ) need to be specified in the control pattern for the proposed blocking logic . as described above , data for the group register are determined according to scan chains that capture unknowns . a simple method to identify scan cells that can capture unknowns is to simulate the design with a set of random patterns . during the simulation , all scan chains that contain scan cells that capture unknown ( s ) in the response to any random pattern are identified . these scan chains are grouped together into 2 - 3 ucgs ( ucgs are assigned 1 &# 39 ; s in the group register ). since the number of groups , i . e ., the number of stages of the group register , is small and the group register need not be updated often with different data ( in most cases , the group register needs to be loaded only once during the entire test session ), data volume for the group register is negligible . in lfsr reseeding , the size of seeds ( or the number of stages of the lfsr ) is normally determined by the number of specified bits in the most specified pattern among all patterns . hence even if there is only one control pattern that has large number of specified bits and all the other responses have very few specified bits , the blocking logic will require large seed size , which in turn results in large control data volume . the numbers of specified bits in densely specified control patterns are reduced as follows . initially , a control pattern that requires minimum number of specified bits is computed for every test pattern . assume that an lfsr with s max + m stages is used to generate control sequences for the blocking logic . first , we select a set of control patterns that have more than s max specified bits . let this set be c d and the set that includes all the other control patterns be c s . next , we compute a seed for every control pattern c i in c s and calculate the lfsr pattern cr i from the computed seed by simulating the lfsr operation as described in section 2 . we apply cr i to the blocking logic and drop all faults that are observed not only from the target fault list of p i but also from target fault lists of all the other test patterns . the signatures of all misrs are updated . hence , many faults will be dropped from target fault lists of test patterns for which control patterns are in c d when processing all control patterns in c s is complete . then the signatures of all misrs are reset . now we start processing control patterns in c d . numbers of specified bits of these control patterns are reduced by unspecifying the bits that are specified for scan cells in one or more ucgs , i . e ., by not observing scan cells in one or more ucgs . the ucg ( s ) for which bits are unspecified in c i are called the unobserved ucgs of c i . for every control pattern c i in c d , we first drop the faults that are captured in scan cells in ufgs , i . e ., unknown free scan chain groups ( these faults are always observed independent of control sequences generated by the lfsr ). the unobserved ucgs are selected to avoid decrease in fault coverage . we first unspecify the specified bits for all the ucgs from c i . the number of remaining target faults of p i that are captured in each ucg is counted . then we select a ucg g m that captures the largest number of target faults of p i , mark the ucg , and specify c i to block all unknowns and observe all target faults of p i that are captured in g m . if the number of specified bits of c i is small enough for the linear solver to find a seed for c i , then we drop the faults from the target fault list of p i whose fault effects are captured in the scan cells that are assigned 0 &# 39 ; s in c i . otherwise we unspecify back the bits that are specified for g m from c i . then we select another ucg among the unmarked ucgs that captures the largest number of target faults of p i . we repeat the procedure described above in this paragraph until all ucgs are marked . when all ucgs are marked , we select the next control pattern and determine the unobserved ucgs for it . this is repeated until a set of unobserved ucgs is determined for every control pattern in c d . if in the response to test pattern p i , an unobserved ucg captures at least one target fault that is captured only in that ucg ( the fault is captured in no other scan chain group ), then not observing the ucg will make some faults undetected . if this is the case for a control pattern c i ( it does not occur often since many faults in the target faults of p i have already been dropped and very few faults remain ), then c i is applied twice during test application . in each of the two applications , a different ucg is selected as the unobserved ucg . this guarantees detection of all target faults of p i . after unobserved ucgs are determined for every control pattern in c d , the control patterns in c d are sorted by their unobserved ucgs such that test patterns for which control patterns have the same unobserved ucgs are consecutively applied during test application . after all test patterns for which control patterns have the same unobserved ucgs are applied , the signatures in all misrs are scanned out and the misrs are reset before the next group of test patterns are applied . fig4 ( a ) shows numbers of specified bits in each control pattern required for the ucgs g a , g b , and g c and the total number of specified bits ( the column “ total ”). for example , control pattern c x - 1 requires respectively 21 , 23 and 30 specified bits for g a , g b and g c and total 74 specified bits . assume that s max = 75 is given for the control lfsr . all control patterns other than c x , c y , and c z require fewer than 75 specified bits . hence c d ={ c x , c y , c z } and c x ={ all control patterns except c x , c y and c z }. an lfsr seed is computed for every control pattern in c s and the faults that are observed are dropped from target fault lists of all test patterns including test patterns for which control patterns are in c d . as more faults are dropped , fewer specified bits are required in each control pattern . after all test patterns except p x , p y , and p z for which control patterns are in c d are applied to the scan chains , the signatures in the misrs are scanned out for comparisons with good signatures . then all misrs are reset . now control patterns in c d are processed to compute seeds for them . control pattern c x is taken first from c d and all specified bits of c x that were specified for the three ucgs are unspecified . the faults that are captured in ufgs are dropped from the target fault list of p x . since g a captures the largest number of faults , 12 ( in fig4 ( a ), the number over the number of specified bits required for each ucg represents the number of target faults captured in the ucg ), the bits for g a are specified to block unknowns and to observe the 12 faults . g a is marked . since the number of specified bits of c x is only 30 ( smaller than s max = 75 ), the linear solver finds a seed for c x . the faults whose fault effects are captured in the scan cells that are assigned 0 &# 39 ; s in c x are dropped from the target fault list of p x . since g c captures more faults than g b , g c is marked next and the bits for g c are additionally specified in c x . since the number of specified bits of c x is only 63 ( the sum of bits that are specified for g a and g c ), the linear solver still finds a seed for c x . the faults whose fault effects are captured in the scan cells that are assigned 0 &# 39 ; s in c x are dropped from the target fault list of p x . since the only unmarked ucg is g b , g b is marked next and the bits for g b are specified in c i . since the number of specified bits of c x now becomes 98 , which is far greater than s max , the linear solver does not find a seed for c x . the bits that are specified for g b are unspecified back and g b is determined as the unobserved ucg of c x . if there are faults in the target fault list of p x that can be detected only by observing g b , then p x will be applied one more time . in the control pattern for the second application of p x , a ucg other than g b is selected as the unobserved ucg . a seed is computed for c x and observed faults are dropped from all target fault lists . since there are no further unmarked ucgs , we take the next control pattern c y from c d and process the ucgs in the order of g b , g c , and g a ( according to the number of faults captured in each ucg ) to determine the unobserved ucgs . since specifying c y for g c after g b makes the number of specified bits of c y 76 , which is greater than s max , the bits of c y that are specified for g c are unspecified back . specifying bits for the remaining unmarked ucg , g a , makes the number of specified bits of c y only 61 . hence g c is determined to be the unobserved ucg of c y . using the same procedure that were used for c x and c y , g b is determined to be the unobserved ucg of c z . control patterns in c d are now sorted into two different groups . for the first group , which includes c x and c z , g b is not observed and for the second group , which includes only c y , g c is not observed . since they are not observed ( compared with good signatures ), the signatures for unobserved ucgs are denoted by xxx in fig4 ( b ). another advantage of the proposed scheme over prior work is better observability . if an lfsr is used to generate control signals for the blocking logic , then on an average only 50 % of scan cells are observed . in contrast , in the proposed scheme , all scan cells in the groups that are assigned 0 &# 39 ; s in the group register are observed . for example , in fig2 ( c ), since all scan cells in ufgs , g 1 and g 2 , are observed , 75 % scan cells can be observed ( assume that approximately 50 % scan cells of g 3 and g 4 are observed ). the invention presents a new blocking logic to block unknowns for temporal compactors . the proposed blocking logic can reduce data volume required to control the blocking logic and also improve the number of scan cells that are observed by temporal compactors . control patterns , which describe values required at the control signals of the blocking logic , are compressed by lfsr reseeding . in the inventive method , scan chains are clustered into several groups and the outputs of the scan chains in each group are connected to 2 - input and gates that are controlled by the same control signal before the blocking logic gates . if no scan chains in a group capture unknowns , then the corresponding blocking logic gates are bypassed by the 2 - input and gates . hence no bits need to be specified in the control pattern for that group . this can significantly reduce the number of 0 &# 39 ; s that should be specified to propagate errors for observation . since all the scan cells in the group are observed , bypassing can improve observability . numbers of specified bits in highly specified test patterns are reduced by not observing one or more scan chain groups . the scan chains groups that are not observed are selected such that no decrease in fault coverage results . experimental results show that control patterns for the proposed blocking logic require very small number of specified bits . the number of scan cells that are observed by the proposed blocking logic is close to that of scan cells that can be achieved by direct observation even under existence of many unknowns in responses . run time of the proposed method is several orders of magnitude shorter than that of prior work . experiments with large industrial designs clearly demonstrate scalability of the proposed method . since only n 2 - input and gates , where n is the number of scan chains in the design , and a small group register are only additional hardware to the blocking logic of prior work , hardware overhead for the proposed blocking logic is very low . the present invention has been shown and described in what are considered to be the most practical and preferred embodiments . it is anticipated , however , that departures may be made therefrom and that obvious modifications will be implemented by those skilled in the art . it will be appreciated that those skilled in the art will be able to devise numerous arrangements and variations , although not explicitly shown nor described herein , embody the principles of the invention and are within their spirit and scope . | 6 |
referring to the drawings , the heat retentive food container 10 is shown as having a vacuum - sealed base section 12 and a vacuum - sealed cover section 14 , each being of linear , non - circular configuration . when closed together , a cavity 16 in the base section 12 is provided in which solid and liquid foods may be stored and kept warm . as more clearly shown in fig3 - 5 a substantially non - slip surface is included on an underside 18 of the base section 12 for restraining movement of the container 10 when placed on a flat surface . as fig3 - 5 illustrate , this substantially non - slip surface may be in the form of a series of non - skid disks 75 of any appropriate material to provide a degree of friction for any accidental motion . fig1 - 4 and 6 also illustrate the food container 10 having a substantially non - slip surface 22 on opposing side surfaces ( as 24 , 26 ) of the base section 12 for supporting the holding of the container 10 when lifted from the flat surface . fig1 - 4 additionally illustrate a substantially non - slip surface 28 on opposing side surfaces ( as 30 , 32 ) of the cover section 14 for easing removal of the cover section 14 from the base section 12 in the opening and closing of the container . although the food container of the invention may be of triangular , rectangular , square , or like parallelogram shape , the rectangular configuration of fig1 - 6 is to be preferred . the base section 12 and cover section 14 of the food container 10 may be hinged together for opening and closing — but in the preferred embodiment of the invention , are removably joined together by a latch system employing a clasp and tab releasable mount . as more clearly seen in fig2 and 3 , individual pairs of clasps 34 and tabs 36 are illustrated extending from correspondingly facing side surfaces ( 24 , 50 ) in removably joining the base and cover sections together . to effectuate any non - leaking , thermal join between the two sections 12 , 14 , the cover section 14 is arranged to have first and second sets of surrounding side surfaces ( 30 , 31 on the one hand , and 50 , 52 on the other hand ), with the first set of surfaces 30 , 31 overlying the second set of surfaces 50 , 52 — such that the second set 50 , 52 align the clasps 34 to removably join with the base section tabs 36 for the releasable securement . gasket seals 91 and 93 are understood as being included at the underside of the cover section 14 and the base section 12 to prevent leakage of the thermos when closed ( fig3 ). as will be appreciated by those skilled in the art , the non - slip surface at the underside 18 of the base section 12 allows the straight - sided thermos to be set down , to remain in place . with the non - slip surface 28 on the cover section 14 , the cover could be easily removed and replaced as a lid . with the non - slip surface 22 , it becomes easier for the lid to then be removed - by similarly holding on to each of their respective non - slip surfaces ; and , once the lid is removed , the non - slip surface 22 provides an easy manner of grasping the base section 12 to either drink from the cavity 16 or eat from the solid food stored therein . by employing the base and cover sections 12 , 14 of a vacuum - sealed construction , the solid and / or liquid foods stored therein can be kept warm . while there have been described what are considered to be preferred embodiments of the present invention , it will be readily appreciated by those skilled in the art that modifications can be made without departing from the scope of the teachings herein . for example , fixed partitions may be provided internal of the cavity 16 for separating one hot food from another — or various clips can be affixed to the inside walls defining the cavity to receive removable partitions in separating one food from another . also , while spanning the opposing side surfaces of the cover section 14 to remove its lid or spanning the opposing side surfaces of the base section 12 to hold the container can be accomplished by a grasping action of the hand where the container is of a small or medium size , only adjacent side surfaces might be able to be grasped where the container is larger . recognizing that the non - slip surfaces 22 and 28 go around the edge surfaces of the straight - sided thermos of the invention , it is to be understood that the words “ opposing side surfaces ” in the claims also encompass the “ adjacent side surfaces ” of the container , and are to be read in this context . and , at the same time , while the teachings of the present invention are particularly attractive in keeping solid and liquid foods warm or hot , the teachings of the invention will be understood to be equally applicable as well for the keeping of solid and liquid foods cold by the inherent nature of the vacuum - sealing provided . for at least such reasons , therefore , resort should be had to the claims appended hereto for a true understanding of the scope of the invention . | 0 |
a better understanding of the multiple endocrine activity of synthetic progestins is required not only for their more rational use in the prevention and therapy of breast and endometrial cancers as well as endometriois and bone loss but also to avoid side effects caused by interaction with steroid receptors unnecessary for the desired beneficial effect . precise analysis of the biological actions of synthetic &# 34 ; progestins &# 34 ; having affinity for many steroidal receptors would ideally require the selection of in vitro models possessing functional receptors for all major classes of steroids . for this purpose , we have chosen the zr - 75 - 1 human breast cancer cell line , which possesses functional receptors for estrogens , androgens , progesterone and glucocorticoids ( vignon et al ., j . clin . endocrinol . metab . 56 : 1124 - 1130 , 1983 ) in order to compare the relative contribution of the different steroid receptor systems in the control of cell proliferation by synthetic progestins . while estrogens are strongly mitogenic in zr - 75 - 1 cells ( poulin and labrie , cancer res . 46 : 4933 - 4937 , 1986 ) and specifically regulate the expression and / or the secretion of several proteins ( dickson and lippman , endocr . rev . 8 : 29 - 43 , 1987 ), androgens ( poulin et al ., breast cancer res . treatm . 12 : 213 - 225 , 1988 ), glucocorticoids ( hatton , a . c ., labrie , f ., unpublished results ) as well as progestins ( poulin et al ., breast cancer res . treatm . 13 : 161 - 172 , 1989 ) inhibit their proliferation through specific interactions with their respective receptors . many progestins have been used in the treatment of breast cancer , including mpa ( blossey et al ., cancer 54 : 1208 - 1215 , 1984 ; hortobayyi et al ., breast cancer res . treatm . 5 : 321 - 326 , 1985 ), mga ( johnson et al ., semin . oncol . 13 ( suppl . ): 15 - 19 , 1986 ; tchekmedyan et al ., semin . oncol . 13 ( suppl . ): 20 - 25 , 1986 ) and norethindrone ( clavel et al ., eur . j . cancer clin . oncol . 18 : 821 - 826 , 1982 ; earl et al ., clin . oncol . 10 : 103 - 109 , 1984 ). using the in vitro system of human breast cancer zr - 75 - 1 cells , i have found that the synthetic progestins or anabolic steroids , nor - testosterone , r1881 , dromostanolone , fluoxymesterone , ethisterone , methandrostanolone , oxandrolone , danazol , stanozolol , calusterone , oxymetholone , cyproterone acetate , chlormadinone acetate and norgestrel , possess androgenic activity at low concentrations . in addition to inhibition of cell growth , the secretion of two glycoproteins , namely gross cystic disease fluid protein - 15 ( gcdfp - 15 ) and gcdfp - 24 is markedly stimulated by androgens ( simard et al ., mol . endocrinol . 3 : 694 - 702 , 1989 ; simard et al ., endocrinology 126 : 3223 - 3231 , 1990 ). measurements of gcdfp - 25 or gcdfp - 24 secretion can thus be used as sensitive parameter or marker of androgen action in these cells . in fact , changes in gcdfp - 15 and gcdfp - 24 secretion are opposite to the changes in cell growth under all experimental conditions examined . all the synthetic progestins or anabolic steroids that i have studied exhibit androgenic activity on zr - 75 - 1 breast cancer growth and secretion of gcdfp - 15 and gcdfp - 24 . identification of the receptors ( estrogen , androgen , progesterone and glucocorticoid ) responsible for the action of the compounds is essential in order to assess the potential actions ( including adverse effects ) of such compounds . it is thus especially important to assess the specific interaction at low concentrations with the androgen receptor since such low concentrations do not interact with the glucocorticoid receptor , thus avoiding or minimizing secondary side effects . one method for inhibiting growth of breast and endometrial cells is activation of the androgen receptor with an effective compound having an affinity for the receptor site such that is binds to the androgen receptor at low concentrations while not significantly activating other classes of steroid receptors linked to potential side effects . it is important to select compounds having maximal affinity for the androgen receptor which have minimal or no virilizing effects in women . in order to minimize interaction of such compounds with the glucocorticoid and estrogen receptors , it is important to use low dose of the compounds . it is also important to choose steroids having androgenic activity at low concentrations which are not metabolized into estrogens under in vivo conditions which , at the low concentrations used , will not lead to significant activation of receptors other than the androgen receptors . my research has shown that the compounds used in the invention , particularly anabolic steroids and synthetic progestins , vary markedly , over different concentrations , in their ability to activate different classes of steroidal receptors . hence , by carefully controlling concentration , it is possible to selectively cause activation of desired receptors while not causing significant activation of undesired receptors . for example , at the low concentrations specified herein , mpa can be utilized to desirably activate androgen receptors while substantially avoiding side effects associated with glucocorticoid activation which have plagued prior art treatments . thus , this invention provides a novel method for prevention and therapy of breast and endometrial cancer as well as other diseases responsive to activation of the androgen receptor , e . g . bone loss and endometriosis . in this invention , the amount of the androgenic compounds administered is much lower than previously used in art for the treatment of breast and endometrial cancer . to help in determining the potential effects of the treatment , blood concentrations of the compound can be measured . for example , measurements of plasma medroxyprogesterone acetate ( mpa ) levels can be made by radioimmunoassay following extraction as follows : antibody 144a was raised in rabbits against 17 - hydroxyprogesterone - 3 - 0 - carboxymethyloxime - bsa . the labeled steroid used in the radioimmunoassay ( ria ) was methyl - 17α - hydroxyprogesterone acetate , 6α - 1 , 2 - 3 h ( n )!- obtained from nen ( cat no : net 480 ) while the reference preparation was medroxyprogesterone acetate ( mpa ) obtained from steraloids . the assay buffer used was 0 . 1 % gelatin in 0 . 1m sodium phosphate , 0 . 15m sodium chloride , 0 . 1 % sodium azide , ph 7 . 2 . the extraction solvent mixture was ethyl ether - acetone ( 9 : 1 , v : v ) eea ! while the lh - 20 chromatography solvent mixture was iso - octane : toluene : methanol ( 90 : 5 : 5 ; v : v : v ) ioth !. one ml of plasma was extracted twice with 5 ml of eea . the extracts were evaporated to dryness with nitrogen and the remaining residue was dissolved in one ml of ioth . the extracts were then subjected to lh - 20 chromatography on 10 × 30 cm columns ( corning cat no : 05 722a ) filled with 2 g of lh - 20 ( pharmacia ). the gel was washed with 30 ml of ioth before addition of one ml of sample and elution with ioth . the first 6 ml were discarded . the following 10 , 16 . 5 and 27 . 5 ml of eluent were fraction i ( progesterone ), ii ( mpa ) and iii ( 17 - lh - progesterone ), respectively . fraction ii was evaporated to dryness and reconstituted in 1 . 5 ml of assay buffer . to each 12 × 75 mm borosilicate test tube was added : 0 . 2 ml containing 25 , 000 dpm of tritiated steroid , 0 . 5 ml of reference preparation ranging from 5 to 5000 pg / tube or 0 . 5 ml of extracted sample fraction ii , 0 . 2 ml of antiserum 144a diluted 1 / 5000 or 0 . 2 ml of assay buffer to account for non specific binding . the tubes were then incubated overnight at 4 ° c . then , 0 . 2 ml 2 % charcoal norit - a , 0 . 2 % dextran t - 70 diluted in water was added . the tubes were then shaken gently and , after 10 min , they were centrifuged at 2000 × g for 10 min . the supernatant was mixed with 8 ml of formula - 989 ( nen : nef - 989 ) and the radioactivity was counted in a β - counter . the lower and upper limits of detection of mpa are 10 and 10000 pg / ml , respectively , while the slope ( logit - log ) is - 2 . 2 and the ed 50 value is 315 pg / ml . non - specific and net binding are 1 . 5 and 45 %, respectively . antibody 144a is highly specific for mpa since cross - reactivity with progesterone , 20α - oh - prog , pregnenolone , 17 - oh - pregnenolone , dht , androstenedione , testosterone , 3α - diol , estrone , estradiol and cortisol is less than 0 . 1 %. ria data were analyzed using a program based on model ii of roadbard and lewald ( in : 2nd karolinska symposium , geneva , 1970 , pp . 79 - 103 ). plasma mpa levels are usually shown as the means ± sem ( standard error of the mean ) of duplicate measurements of individual samples . statistical significance is measured according to the multiple - range test of duncan - kramer ( kramer , c . y ., biometrics 12 : 307 - 310 , 1956 ). to assist in determining the activity of the potential compounds on the various steroid receptors , androgen , glucocorticoid , progesterone and estrogen - receptor - mediated activities of synthetic progestins and anabolic steroids can be measured in zr - 75 - 1 human breast cancer cells using cell growth as well as gcdfp - 15 and gcdfp - 24 release as parameters of response ( poulin and labrie , cancer res . 46 : 4933 - 4937 , 1986 ; poulin et al ., breast cancer res . treatm . 12 : 213 - 225 , 1988 ; poulin et al ., breast cancer res . treatm . 13 : 161 - 172 , 1989 ; poulin et al ., breast cancer res . treatm . 13 : 265 - 276 , 1989 ; simard et al ., mol . endocrinol . 3 : 694 - 702 , 1989 ; simard et al ., endocrinology 126 : 3223 - 3231 , 1990 ). the following properties permit measurement of progesterone receptor ( pgr ) activity : 1 ) the addition of insulin completely reverses the inhibition due to the interaction of the progestin r5020 with the pgr in zr - 75 - 1 cells ; and 2 ) the antiproliferative effect of r5020 is observed only under e 1 - stimulated conditions . these two characteristics of zr - 75 - 1 cell growth permit study of the extent to which a tested compound &# 39 ; s effects on zr - 75 - 1 cells are attributated to its interaction with pgr by evaluating the effect of insulin and / or estrogen addition on the growth response measured at the end of a 15 - day incubation of zr - 75 - 1 cells with the test compounds . the contribution of the estrogen receptor ( er ), on the other hand , can be directly measured by incubating zr - 75 - 1 cells in the presence or absence of estrogen in the medium . in order to analyze the interactions of synthetic progestins or anabolic steroids with the androgen receptor ( ar ) and glucocorticoid receptor ( gr ) in their inhibitory action on cell growth , one takes advantage of the additivity of the anti - proliferative effects of androgens and glucocorticoids in this cell line ( poulin et al ., breast cancer res . treatm . 12 : 213 - 225 , 1988 ; hatton and labrie , f ., unpublished data ). thus , one can saturate ar with 5α - dihydrotestosterone ( dht ) and then measure the effect on cell proliferation resulting from the addition of a putative glucocorticoid . on the other hand , the effect of a putative androgen can similarly be measured following saturation of gr by dexamethasone ( dex ). the specificity of the growth - inhibitory activity thus observed with the test compound can also be further assessed by its reversibility using the appropriate antagonist ( i . e . antiglucocorticoid or antiandrogen ). thus , in the presence of excess androgen ( 1 μm dht ) in the presence of e 2 and insulin , glucocorticoid effects can be assessed with precision and with no interference by the other receptors . the same applies to study of the role of ar when the cells are incubated in the presence of excess glucocorticoid ( 3 μm dex ), in the presence of e 2 and insulin . as demonstrated by detailed kinetic studies , 1 μm dht and 3 μm dex exert maximal inhibitory effects on the ar and gr , respectively . in addition , the possible antagonistic activities of &# 34 ; progestins &# 34 ; mediated through the ar and gr can be determined by saturating both receptor systems with dht and dex with one ligand being in far greater excess than the other in order to allow reversal through a single chosen receptor at a time . all experiments are performed with zr - 75 - 1 cells grown in e 2 - supplemented media containing insulin in order to prevent the pgr - mediated effect of &# 34 ; progestins &# 34 ; on cell growth . using the foregoing techniques , i have found that numerous androgenic compounds which also activate other receptors ( e . g . glucocorticoid or progesterone receptors ) vary in their relative effects on different receptors as a function of concentration . by staying within concentration ranges defined herein , compounds of the invention may beneficially affect androgen receptors without substantial undesirable effects on other receptors . selection of patients who may benefit from the method &# 39 ; s described herein the appearance of breast cancer is usually detected by self breast examination and / or mammography . endometrial cancer , on the other hand , is usually diagnosed by endometrial biopsy . both cancers can be diagnosed and evaluated by standard physical methods well known to those skilled in the art , e . g . bone scan , chest x - ray , skeletal survey , ultrasonography of the liver and liver scan ( if needed ), cat scan , mri and physical examination . endometriosis can be diagnosed following pains or symptoms associated with menstruations in women while definitive diagnosis can be obtained by laparascopy and , sometimes , biopsy . bone density , on the other hand , can be measured by standard methods well known to those skilled in the art , e . g . qdr ( quantitative digital radiography ), dual photon absorptiometry and computerized tomography . plasma and urinary calcium and phosphate levels , plasma alkaline phosphatase , calcitonin and parathormone concentrations , as well as urinary hydroxyproline and calcium / creatinine ratios . breast or endometrial cancer , osteoporosis or otherwise insufficient bone mass , and other diseases treatable by activating androgen receptor may be treated in accordance with the present invention or prophylactically prevented in accordance herewith . typically suitable androgenic compounds include 6 - alpha - methyl , 17 - alpha - acetoxy progesterone or medroxyprogesterone acetate available , for exemple , from upjohn and farmitalia carlo erba , s . p . a . under the trade names provera , depoprovera or farlutal , and the acronym mpa . other suitable androgenic compounds include those described in labrie et al . ( fertil . steril . 31 : 29 - 34 , 1979 ) as well as anabolic steroids or progestins ( raynaud and ojasso , in : innovative approaches in drug research , elsevier sci . publishers , amsterdam , pp . 47 - 72 , 1986 ; sandberg and kirdoni , pharmac . ther . 36 : 263 - 307 , 1988 ; and vincens , simard and de lignieres , les androgenes . in : pharmacologie clinique , base de therapeutique , 2ieme edition , expansion scientifique ( paris ), pp . 2139 - 2158 , 1988 ), as well as calusterone ( 7β , 17α - dimethyltestosterone ), anabolic steroids ( lam , am . j . sports medicine 12 , 31 - 38 , 1984 ; hilf , r ., anabolic - androgenic steroids and experimental tumors . in : ( kochachian , c . d ., eds . ), handbook of experimental pharmacology , vol . 43 , anabolic - androgenic steroids , springer - verlag , berlin , 725 pp , 1976 ), fluoxymesterone ( 9α - fluoro - 11β - hydroxy - 17α - methyltestosterone ), testosterone 17β - cypionate , 17α - methyltestosterone , pantestone ( testosterone undecanoate ), δ 1 - testololactone and andractim . other typical suitable androgenic compounds are cyproterone acetate ( androcur ) available from shering ag , 6 - alpha - methyl , 17 - alpha - acetoxy progesterone or medroxyprogesterone acetate ( mpa ) available from , among others , upjohn and farmitalia , calbo erba , gestodene available from shering , megestrol acetate ( 17α - acetoxy - 6 - methyl - pregna - 4 , 6 - diene - 3 , 20 - dione ) available from mead johnson & amp ; co ., evanswille , ind ., under the trade name of megace . other synthetic progestins include levonorgestrel , norgestimate , desogestrel , 3 - ketodesogestrel , norethindrone , norethisterone , 13α - ethyl - 17 - hydroxy - 18 , 19 - dinor - 17β - pregna - 4 , 9 , 11 - triene - 20 - yn - 3 - one ( r2323 , gestrinone ), demegestone , norgestrienone , gastrinone and others described in raynaud and ojasso , j . steroid biochem . 25 : 811 - 833 , 1986 ; raynaud et al ., j . steroid biochem . 25 : 811 - 833 , 1986 ; raynaud et al , j . steroid biochem . 12 : 143 - 157 , 1980 ; raynaud , ojasoo and labrie , steroid hormones , agonists and antagonists , in : mechanisms of steroid action ( g . p . lewis and m . ginsburg , eds ), mcmillan press , london pp . 145 - 158 ( 1981 ). any other progestin derivative having the above - described characteristics could also be useful for the invention . the androgenic compound is preferably administered as a pharmaceutical composition via topical , parenteral or oral means . the compound can be administered parenterally , i . e . intramuscularly or subcutaneously by injection of infusion by nasal drops , by suppository , or where applicable intravaginally or transdermally using a gel , a patch or other suitable means . the androgenic compound may also be microencapsulated in or attached to a biocompatible , biodegradable polymer , e . g . poly ( d1 , 1 - lactide - co - glycolide ) and subcutaneously or intramuscularly injected by a technique called subcutaneous or intramuscular depot to provide continuous , slow release of the compound over a period of 30 days or longer . in addition to the oral route , a preferred route of administration of the compound is subcutaneous depot injection . depoprovera can be released at a relatively constant rate for approximately 3 months after intramuscular administration of an aqueous suppression . the amount of each compound administered is determined by the attending clinician taking into consideration the patient &# 39 ; s condition and age , the potency of each component and other factors . in the prevention of breast and endometrial cancer , as well as bone loss , according to this invention , the following dosage ranges are suitable . the androgenic composition is preferably administered in a daily dosage which delivers less than 25 mg of active androgenic steroid per 50 kg of body weight . a dosage of 1 - 10 mg per 50 kg of body weight , especially 3 - 7 mg ( e . g . 5 mg ) is preferred . the dosage selected preferably maintains serum concentration below 50 nanomoles per liter , preferably between 1 . 0 nanomoles per liter and 10 , 15 or 25 nanomoles per liter depending on patient &# 39 ; s response . the dosage needed to maintain these levels may vary from patient to patient . it is advisable for the attending clinical to monitor levels by the techniques described herein and optimize dosage accordingly . for prophylactic purposes , administration of the androgen is preferably started in the perimenopausal period for the prevention of breast and endometrial cancer and bone loss in normal women . the androgen may be associated with an accepted dose of an estrogen used to prevent other signs and symptoms of menopause . in women , when estrogen formation and / or action has been blocked for treatment of endometriosis , leiomyomata , breast cancer , uterine cancer , ovarian cancer or other estrogen - sensitive disease , administration of the androgen can be started at any time , preferably at the same time as blockade of estrogens . the androgen for intramuscular or subcutaneous depot injection may be microencapsulated in a biocompatible , biodegradable polymer , e . g ., poly ( d , 1 - lactide - co - glycolide ) by , among other techniques , a phase separation process or formed into a pellet or rod . the microspheres may then be suspended in a carrier to provide an injectable preparation or the depot may be injected in the form of a pellet or rod . see also european patent application epa no . 58 , 481 published aug . 25 , 1982 for solid compositions for subdermal injection or implantation or liquid formulations for intramuscular or subcutaneous injections containing biocompatible , biodegradable polymers such as lactide - glycolide copolymer and active compounds . these formulations permit controlled release of the compound . the androgens useful in the present invention can be typically formulated with conventional pharmaceutical excipients , e . g ., spray dried lactose and magnesium stearate into tablets or capsules for oral administration . the active substance can be worked into tablets or dragee cores by being mixed with solid , pulverulent carrier substances , such as sodium citrate , calcium carbonate or dicalcium phosphate , and binders such as polyvinyl pyrrolidone , gelatin or cellulose derivatives , possibly by adding also lubricants such as magnesium stearate , sodium lauryl sulfate , &# 34 ; carbowax &# 34 ; or polyethylene glycol . of course , taste - improving substances can be added in the case of oral administration forms . as further forms , one can use plug capsules , e . g ., of hard gelatin , as well as closed soft - gelatin capsules comprising a softener or plasticizer , e . g . glycerine . the plus capsules contain the active substance preferably in the form of granulate , e . g ., in mixture with fillers , such as lactose , saccharose , mannitol , starches , such as potato starch or amylopectin , cellulose derivatives or highly dispersed silicic acids . in soft - gelatin capsules , the active substance is preferably dissolved or suspended in suitable liquids , such as vegetable oils or liquid polyethylene glycols . in place of oral administration , the active compound may be administered parenterally . in such case , one can use a solution of the active substance , e . g ., in sesame oil or olive oil . the active substance can be microencapsulated in or attached to a biocompatible , biodegradable polymer , e . g . poly ( d , 1 - lactide - co - glycolide ) and subcutaneously or intramuscularly injected by a technique called subcutaneous or intramuscular depot to provide continuous slow release of the compound ( s ) for a period of 2 weeks or longer . the invention also includes kits or single packages containing the pharmaceutical composition active ingredients or means for administering the same for use in the prevention and treatment of breast and endometrial cancer as well as bone loss and treatment of endometriosis as discussed above . the kits or packages may also contain instructions on how to use the pharmaceutical compositions in accordance with the present invention . following the above therapy using the described regimen , tumor growth of breast and endometrial cancer as well as bone loss and endometriosis can be relieved while minimizing adverse side effects . the use of the described regimen can also prevent appearance of the same diseases . prevention of mammary carcinoma induced by dimethylbenz ( a ) anthracene ( dmba ) in the rat , by low dose medroxyprogesterone acetete (&# 34 ; mpa &# 34 ;) to illustrate the efficacy of the present invention in reducing the incidence of mammary carcinoma , fig1 illustrates the effect of a single subcutaneous injection of depo - provera ( medroxyprogesterone acetate ( mpa ) ( 30 mg )) one week before inducing carcinoma with dimethylbenz ( a ) anthracene . fig1 shows the period from 30 to 85 days following administration of dmba . one curve in fig1 shows the average number of tumors per animal in the group protected by depo - provera while the other curve shows the average number of tumors per animal in the unprotected group . it is estimated that the 30 mg . injection of depo - provera would release approximately 0 . 17 mg . of active medroxyprogesterone acetate per day over a six - month period . as may be seen by comparing the two graphs in fig1 the depo - provera - treated group showed much greater resistance to the development of tumors than did the unprotected group . after 85 days an average of 1 . 89 tumors per rat was observed in the unprotected group , while only 0 . 30 tumor per rat was observed in the depo - provera protected group . tumor number and size measured with calipers were determined weekly . treatment of mammary carcinoma induced by dimethylbenz ( a ) anthracene in the rat , by low dose medroxyprogesterone acetate fig2 illustrates the inhibition of mammary carcinoma growth which may be achieved in accordance with the methods of the invention . tumors were induced in ovariectomized rats using dimethylbenz ( a ) anthracene . estradiol was used to stimulate growth in both a treatment and control group of rats . each animal in the treatment group received a single subcutaneous administration of 30 mg of depo - provera ( which is estimated to release approximately 0 . 17 mg . per day of active medroxyprogesterone acetate for a period of about six months ). this figure illustrates the average estradiol - stimulated change in total tumor area in each group following treatment . as may be seen in fig2 the group treated with depo - provera exhibited significantly less tumor growth than the untreated group . the terms and descriptions used herein are preferred embodiments set forth by way of illustration only , and are not intended as limitations on the many variations which those of skill in the art will recognize to be possible in practicing the present invention as defined by patent claims based thereon . | 0 |
a pressure regulating valve in accordance with the present invention is shown in fig1 a and 1 b and identified with reference numeral 10 . it has a magnetic part 12 and a valve flange 14 which is connected to the latter . the magnetic part 12 includes a hollow - cylindrical coil 16 , a sleeve - shaped coil core arranged in the interior of the coil 16 , and a movably guided armature 20 . the latter is arranged at the end side of the coil 16 which faces the valve flange 14 and overlaps it . for its axial guidance , the armature 20 has a pin 24 which is mounted in a central opening 22 extending through the armature . it extends into a sliding bushing 26 which is anchored in the coil core 18 . the sliding bushing 26 is inserted in a blind hole - shaped recess of a plug 28 which is screwed in the sleeve - shaped coil core 18 and closes the same from outside . the plug 28 is changeable in its relative position relative to the coil core 18 . a spring 30 which is centered by the pin 22 is supported on it . with its second end it abuts against the armature 20 . the pre - tensioning of the spring 30 is adjustable via the relative position of the plug 28 relative to the coil core 18 during the mounting of the pressure regulating valve . the function of the spring 30 is to provide a restoring force which brings the armature 20 in powerless condition of the coil 60 to the illustrated base position of the pressure regulating valve 10 . the magnetic part 12 is injection - molded with a synthetic plastic casing 34 with embedding of an element 32 which conducts the magnetic flux . contact tongues 36 extend outwardly from the synthetic plastic casing 34 . electrical contacting of the coil 16 with a not shown control electronic system is provided through the contact tongues 36 . the armature 20 of the magnetic circuit is disc - shaped and has a central portion 38 with a reduced outer diameter . it extends in direction of the coil 16 and also in direction of the valve flange 13 . an elastic guiding disc 40 is anchored at the end of the central portion 38 which faces the valve flange . it is fixed with its outer periphery with a magnetic flux conducting element 32 and the valve flange 14 . the guiding disc 40 together with the pin 22 guarantees the exact guidance of the armature 20 . the armature 20 moreover is provided with throughgoing openings 42 in the region between its outer diameter and the diameter of the central portion 38 . one of such openings is shown in fig1 a , 1 b . the throughgoing openings 42 are distributed uniformly around the circumference of the armature and connect the part of the armature chamber 44 located about the armature 20 with its part located below . identical conditions which are thereby provided in the both parts of the armature chamber 44 guarantee the undampened movement of the armature 20 . it should be mentioned that the above shown design of the magnetic part 12 is purely exemplary and is not limiting for the scope of the present invention . the design of the magnetic part 12 as such does not constitute the inventive features . any other magnetic circuit design or armature support which can not be provided for the realization of the invention can be utilized . for the operation of the invention an undamped movement of the armature 20 in the magnetic part 12 must be however guaranteed . the armature 20 cooperates with the piston 46 which is guided in the valve flange 14 in a force - transmitting manner . for this purpose the valve flange 14 is formed for example as a pressure cast part which is flanged in the magnetic part 12 . the valve flange 14 is provided with a guiding opening 44 which extends in direction of its longitudinal axis and receives the piston 46 . the guiding opening 44 opens at the end of the valve flange 14 which faces the magnet , into an opening 56 which opens toward the magnetic part 12 . the recess 50 is expanded in its diameter relative to the guiding opening 48 and forms a mounting space for a diaphragm element 52 . the diaphragm element 52 separates the recess 50 in two pressure chambers 50 a and 50 b which are separated from one another and seals the magnetic part 20 relative to the valve part 14 . for this purpose the diaphragm element 52 is ring - shaped and is mounted on its diameter in a slot 54 on the periphery of the piston 46 . the outer diameter of the diaphragm element 52 is received in a groove 56 which is formed on the valve flange 14 . it is fixed there by a holding ring 58 which is clamped in the recess 50 . the diaphragm element 52 has such dimensions that it can follow an axial movement of the piston 46 within the control of the coil 16 . the hydraulic connections 61 , 62 , 64 , of the pressure regulating valve 4 are formed on the valve flange 14 . a not shown hydraulic consumer is connected with the connection 61 , which in the preferable embodiment of the pressure regulating valve 10 , is a following valve over a coupling . the connection 62 is connected with a not shown pressure generator and acts as a supply of the pressure regulating valve 10 . the connection 64 is connected with a not shown pressure medium supply container and acts as a return . moreover , a contact connection 64 schematically shown in fig1 a , 1 b is provided between the connection 61 at the side of the consumer and a connection 60 at the end of the guiding opening 48 which is opposite to the magnetic part 12 . the end surface of the piston 46 is loaded with a working pressure through the connection 60 , to guarantee its abutment against the armature 20 . the connection 61 is formed as a ring groove 61 a on the periphery of the valve flange 14 and opens through a radially extending working passage 61 b into the guiding opening 48 . therefore the opening section of a first control cross - section 68 is formed . the connection 62 is arranged between the connection 60 and 61 on the pressure regulating valve 10 . it is also formed as a ring groove 62 a and is connected through radial supply passages 62 b with the guiding opening 48 . therefore this opening part forms the second control cross - section 70 of the pressure regulating valve 10 . a return - side connection 64 is provided in direction of the magnetic part 12 above the connection 61 of the pressure regulating valve 10 . it opens through a return passage 64 b into the guiding opening 48 . for the operation of the above described pressure regulating valve 10 it is important that the connection 64 is located deeper than the pressure medium level in the connected supply container since only in this way the return passage 64 b is reliably filled with pressure medium under low pressure . the passages 61 b , 62 b , and 64 b of the pressure regulating valve 10 through which the pressure medium flows are separated by a wall 72 from the pressure chamber 50 a . however , a connecting opening 74 is provided in the valve 72 and couples the pressure chamber 50 a hydraulically with the return passage 64 b . thereby the pressure chamber 50 a is always filled with pressure medium . as shown in fig1 a , a throttling device 76 is anchored in accordance with the present invention in the connecting opening 74 . in the shown example it is integrated in a separate hat orifice . the hat orifice is pressed with its circumferential edge up to the abutment in the connecting opening 74 . it has at least one orifice opening 81 at its part which covers the cross - section of the connecting opening 74 . with dimensioning of the cross - section of the orifice opening by the material thickness of the hat orifice , the latter can be formed in a simple way as an ideal orifice in accordance with a flow technique . the dampening characteristic of ideal orifices is preferably , in the temperature region under consideration , substantially independent from temperature changes . a narrowing 78 is provided in the substantially cylindrical piston 46 for controlling the pressure of the connection 61 of the pressure regulating valve 10 which is connected to the consumer . at the beginning and at the end of the narrowing 78 , two control edges 80 , 82 are formed on the piston 46 . they cooperate in alternating action with both control cross - sections 68 and 70 of the valve flange 14 . in the shown base position of the pressure regulating valve 10 the second control valve 82 which is located facing away from the magnetic part 12 releases a pressure medium connection between the connection 61 associated with a consumer and the connection 62 of the valve flange 14 associated with a supply . simultaneously the first control edge 80 of the piston 46 closes the pressure medium connection between the consumer - side connection 61 and the return - side connection 64 of the pressure regulating valve . the consumer is thereby supplied from the pressure generator with pressure medium until the required working pressure is built up and the control edge 82 no longer closes . with the electrical control of the coil 16 , the armature 20 is moved due to the produced magnetic force against the restoring force of the spring 30 in direction of the coil 16 . the piston 46 follows because of the loading of its end surface which faces away from the magnetic part 12 with the working pressure of this stroke movement . the free flow cross - section between the control cross - section 68 and the control edge 80 opens , so that the pressure at the consumer - side connection 61 of the pressure regulating valve 12 reduces , until finally the piston 46 completely interrupts the pressure medium connection . due to the anchoring at the piston 46 , the diaphragm element 52 follows the stroke movement of the piston . the volumes of the pressure chambers 50 a and 50 b which are separated from one another by the diaphragm element 52 change . with corresponding movement direction of the piston 46 the pressure medium is displaced by the diaphragm element 52 through the connecting opening 74 with the inserted throttling device 66 into the return 64 . the diaphragm element 52 performs in addition to its sealing function also a pumping function . the throttling action produced by the throttling device 76 in the connection passage 34 maintains , depending on the speed , the stroke movement of the piston 46 and acts in a stabilizing way on the regulating properties of the pressure regulating valve 10 . short - term pressure fluctuations in the pressure regulating circuit , for example mechanically caused vibrations in the magnetic circuit 12 which are transmitted through the armature 20 to the piston 46 remain due to the dampening properties without influencing the pressure level at the consumer . an adaptation of the dampening properties to the corresponding applications of the pressure regulating valve 10 is performed by the number of the throttling devices 76 , their geometrical construction and / or dimensions . it is to be understood that it is also possible to dispense with the connecting passage 74 with the inserted throttling device 76 , and to provide between the piston 46 and the wall of its guiding opening 48 in the region between the pressure chamber 50 a and the return passage 64 b a gap 80 as the throttling device 76 , as shown in fig1 b . regardless of this it is advantageous when the connecting passage 74 is formed as the throttle device 76 and therefore a separate hat orifice can be dispensed with . in order to exclude the temperature dependency of the throttling condition , the throttle device 76 can be formed so that in the throttle gap a turbulent stream is introduced . it is achieved with so - called ideal orifices , whose length / diameter ratio is maintained in a predetermined value . furthermore , it is also proposed in the case of the formation of the throttling device 76 in the connecting passage 74 , to design the gap between the piston 46 and its guiding opening 48 in the region between the pressure chamber 50 a and the return passage 64 b so that , a pressure medium leakage from the pressure chamber 50 a via the gap is excluded . this is achieved through the absolute gap dimension and a correspondingly determined gap length . fig2 shows a second embodiment of an inventive pressure regulating valve 10 with integrated dampening device . components which are functionally identical to those shown in the preceding figures are identified with the same reference numerals . the pressure regulating valve 10 of fig2 in contrast to the pressure regulating valve of fig1 is formed as a so - called flat seat pressure regulator . it has a valve flange 14 with three hydraulic connections 61 , 62 and 64 . the working passage - side connection 61 of the pressure regulating valve 10 is now connected with the return - side connection 64 through a valve seat 84 . the third , supply - side connection 62 is arranged between the connection 61 and 64 . it extends perpendicularly to the plane of the drawings , so that in fig2 only its opening cross - section into the working passage 61 b is recognizable . the connection 64 merges into the return passage 64 b and opens into the working passage 61 b , while it is located at the opening point of the valve seat 84 . it is designed in form of metallic seat plate 86 , which is injection molded in the valve flange 14 . in the shown base position the valve seat 84 of the pressure regulating valve 10 is closed by a closing member 88 . the closing member 88 in this case is formed of one piece with the armature 20 . the valve flange 14 is formed as a synthetic plastic injection molded component , and a sleeve - shaped deep drawn part 90 locally is surrounded by this synthetic plastic injection molded component . the deep drawn part 90 extends outwardly beyond the valve flange 14 and with its outwardly extending end locally engages the magnetic part 12 . moreover , a throughgoing passage 92 is provided on the deep drawn part 90 in the region of its portion which is surrounded by the valve flange 14 . the throttling device 76 in form of a hat orifice with at least one orifice opening which is not shown in fig2 is inserted in the throughgoing opening 92 . the throttling device 76 is located also in a connecting passage 74 of the valve flange 14 , between the return passage 64 b and the pressure chamber 50 a which is limited by the diaphragm element 52 . the deep drawn part 90 is injection molded only on the outer side of its inserted end . its inner side is free from synthetic plastic and forms a guide for the part of the armature 20 which forms the valve piston . with respect to its dampening properties , the second embodiment is identical to the first embodiment , so that the corresponding explanations are dispensed with . it should be mentioned that in the second embodiment the coil core 18 and the armature 20 of the magnetic part 12 extend locally into the interior of the hollow - cylindrical coil 16 . this construction of the magnetic part 12 is typical for the pressure regulating valve 10 with proportional regulating functions . in proportional valves the armature 20 between its end positions is bringable to any intermediate positions , whereby a pressure regulation is constantly regulatable by variation of the control voltage of the coil 16 . in the pressure regulating valve 10 of fig2 the armature 20 is voluminous . it is a rotation - symmetrical component , with collar 20 a which covers the coil 16 at the end side . the collar 20 a extends in direction of the valve flange 14 into an armature plunger 20 b , at whose end the closing member 88 is formed . the collar 20 a in direction of the magnetic part 12 transits into an armature dome 20 c which is placed inside the coil 16 . a blind - hole - shaped central opening 22 is formed in the armature dome 20 c and receives the pin 24 . the pin 24 on the one hand centers the spring 30 which returns the pressure regulating valve 10 to its base position and on the other hand provides the pin 24 with armature guidance , since the end extending beyond the armature 20 is inserted in the sliding bushing 26 of the plug 28 that closes the coil core 18 . it is to be understood that further changes or additional features are possible without departing from the spirit of the present invention . for example in a pressure regulating valve 10 with pressure medium - free magnetic part 14 a cost favorable damping device 76 can be integrated without increasing the dimensions or the number of the components . it will be understood that each of the elements described above , or two or more together , may also find a useful application in other types of constructions differing from the types described above . while the invention has been illustrated and described as embodied in hydraulic pressure regulating valve , it is not intended to be limited to the details shown , since various modifications and structural changes may be made without departing in any way from the spirit of the present invention . without further analysis , the foregoing will so fully reveal the gist of the present invention that others can , by applying current knowledge , readily adapt it for various applications without omitting features that , from the standpoint of prior art , fairly constitute essential characteristics of the generic or specific aspects of this invention . | 5 |
according to the present invention , it has now unexpectedly been found that the time required for dissolution of waste solids is significantly decreased if the solvent contacting the bed can help create or release a gas in the bed . the pores of the solid waste are kept open by the emission of the gas and the furthering of the solvent encroachment results in reduced time for cleaning the filter bed and preparing it for use . in the process of the present invention , a filter bed is used to filter a solution of the desired products such as photographic couplers , hardeners , dyes and the like from waste materials . the waste materials are generally formed as by - products of the chemical reactions carried out to form the desired product . the product passes through the filter bed in solution ( filtrate ) leaving the waste . the filter bed is made up of the by - products of the reaction and remains as waste . the filter is generally of a type comprising a simple cloth as the filtering surface such as polypropylene or cotton duck . for example , fig1 shows a typical filter bed at the start of a cleaning operation . fig2 shows the action of the solvent dissolution of the bed of waste ( such as salt ). fig3 shows the use of dissolution as in fig2 but with the generation or release of a gas with the solvent on contact , which opens the pores of the waste material to facilitate fast dissolution of the waste material . fig4 depicts the final filter which is now free of solid waste material and ready for reuse . in the preferred embodiment , the salt is deposited in a deep bed ( 1 ) such as a filter box during the removal of the product from a slurry fed to the box . the filter box is then subjected to a bottom feed of a hot water stream ( 3 ). the water can be heated from 20 ° c . to 100 ° c . this releases carbon dioxide gas . the carbon dioxide opens the cake up by bubbling out of it , creating a path for the water to rapidly penetrate the whole cake and increase the dissolution rate . the rate is much slower if no gas evolution is available ( fig2 ). at the end , the cake is completely dissolved from the filter box and the box is ready for the next batch of material . the filter is designed to capture waste products and pass desirable products out in the filtrate . the products to be filtered can be couplers , dyes , hardeners , or the like . when the above slurries are filtered , the packed beds preferably comprise waste solids such as inorganic salts , insoluble organics , and the like . the filtrate contains the product . solvents used to dissolve these waste products in the filter beds comprise water , solvent for the insoluble organics , and the like . the amount of solvent used can be varied and is generally enough to saturate a dilute solution . the amount of gas or gas forming material is a function of the reaction or added in quantities to form cracks in the filter cake on activation . if additional material is added to the filter bed with the solvent it is designed to react on contact with the solvent to form an emitted gas . generally materials which react with various solvents , and the solvents reactable with these materials on contact to produce emitted gas are shown in table 1 below . table 1______________________________________materials added solvent gaseous product______________________________________sodium bicarbonate low ph water co . sub . 2sodium carbonate low ph water co . sub . 2sodium sulfite low ph water so . sub . 2______________________________________ the gas could also exist in a saturated solution and be released by an increase in temperature . the gas that is emitted is sufficient to break up thick cakes of solid waste and allows the solvent to dissolve the solid waste in a decreased period of time . the gas could also be released during the chemical reaction to form the solid by - product and be trapped or occluded in the by - product structure . in order to further illustrate the present invention and the advantages thereof , the following examples are given , it being understood that it is intended only as illustrative and in no way limiting . a chemical slurry containing dissolved product and unwanted salts plus sodium bicarbonate and some trapped carbon dioxide gas , for example , is filtered in a large filter box . the depth of the cake can be over 3 foot high . after the product solution is removed by vacuum , the remaining salts contain trapped gas plus a material capable of gas formation on contact with the solvent for the majority of the salts . in the simple example , water is added to a sodium chloride / sodium bicarbonate salt cake . the cake is formed into a deep bed from a non - solvent salt slurry . in an acid environment , the bicarbonate internal to the cake will decompose to carbon dioxide and water . the carbon dioxide in the cake will form channels to allow the water to rapidly penetrate into the cake and dissolve the large salt deposit . without internal channeling the water penetrates much slower and the time to dissolve the cake becomes longer . in the first comparative example whose flow is depicted in fig2 a 13 &# 34 ; sodium chloride cake was prepared in a 3 &# 34 ; diameter pressure filter by pouring in 1765 g of nacl . two washes of two liters each were added to the pressure filter ( acetone + 100 g of 36 % hcl ( ph & lt ; 1 ). this was pressure filtered through the cake using 15 psig nitrogen . this mimics the removal of mother liquor in a chemical process and the washing of the cake to remove product . after most of the acetone / water was removed with the 15 psi nitrogen , water was added backflushing through the cake . after 53 / 4 minutes all of the cake was dissolved . the same procedure was used as above except 1 % by weight of sodium bicarbonate was dry mixed into the nacl before loading into the column . the cake was dissolved in 41 / 4 minutes with the aid of the internally generated gas bubbles from the bicarbonate breaking up the cake . a sample containing process chemicals and salt in acetone was washed with acetone and backflushed with water . despite the fact that a portion of the tacky product remained with the salt , the water was able to break up cakes of thickness &# 39 ; up to 2 feet rapidly due to internal generation of air bubbles . an analine derivative is converted to a hydrazine hydrochloride . the process results in the formation of mixed sodium salts which include sodium sulfite . in an acid medium the sulfite breaks down to sulfur dioxide gas which remains trapped in the salt matrix as a gas or a crystal occlusion ( gas trapped in the crystal structure during or post crystal formation ). when the salt is dissolved in water the sulfur dioxide bubble help break up the salt cake and enhance cake dissolution . while the invention has been described in terms of various preferred embodiments , the skilled artisan will appreciate that various modifications , substitutions , omissions , and changes may be made without departing from the spirit thereof . accordingly , it is intended that the scope of the present invention be limited solely by the scope of the following claims , including equivalents thereof . | 1 |
the process of the subject invention generally comprises the addition of a direct heating unit ( dhu ) in parallel to a reheater located between two or more of the serial eb dehydrogenation reactors . utilizing the ethylbenzene to styrene dehydrogenation reaction as a non - limiting example , generally the energy needed for the reaction to convert ethylbenzene to styrene is supplied by superheated steam ( at about 1000 ° f . to 1650 ° f .) that is injected into a vertically mounted fixed bed catalytic reactor with vaporized ethylbenzene . the catalyst is typically iron oxide - based and contains one or more potassium compounds ( k 2 o or k 2 co 3 ), which act as reaction promoters . typically , 1 - 2 pounds of steam is required for each pound of ethylbenzene to ensure sufficiently high temperatures throughout the reactor . the superheated steam supplies the necessary reaction temperature of about 1000 - 1200 ° f . throughout the reactor . ethylbenzene conversion is typically 60 - 70 %. the system is generally operated under vacuum . because of the endothermic nature of the dehydrogenation reaction , conventional eb processes require the addition of heat to the process to maintain the dehydrogenation reaction at economic levels . this , in turn , necessitates the use of multiple reactors in order to provide opportunity to add heat during the process , which the prior art accomplished by utilizing heaters , commonly referred to as reheaters , located between each of the serial reactors . fig1 illustrates a conventional multiple reactor dehydrogenation system having a steam reheater located between the first and second reactor and between the second and third reactor . fig2 illustrates an embodiment of the invention where a dhu is added and operated in parallel to the steam reheater located between the first and second reactor . although not shown , a dhu can also be added in parallel with a steam reheater located between the second and third reactor ( or any additional reactors ), or prior to the first reactor . fig3 further illustrates an embodiment wherein a dhu is operated in parallel to a steam reheater . the combination of the reheater and the dhu in a parallel arrangement can enable the input of more heat into the reactant stream than can be accomplished by a reheater or a dhu alone . the feed to the primary reactor is comprised of primarily of ethylbenzene and steam . the primary reactor effluent stream from the first reactor and can comprise a mixture of ethylbenzene , styrene , hydrogen , steam , and may contain small amounts of other components exiting the first stage ( primary ) reactor . a first portion of the primary reactor effluent enters the reheater where it is heated by cross exchange with a steam supply , which can be a superheated steam supply . a second portion of the primary reactor effluent enters the dhu rather than the reheater . the second portion of the primary reactor effluent is heated by heat exchange with the heat of combustion from the dhu . the first portion of the primary reactor effluent exiting the reheater combines with the second portion of the primary reactor effluent exiting the dhu to form the feed stream to the second stage ( secondary ) reactor . the steam supply to the reheater can be superheated steam that is heated above the saturation temperature . the superheated steam return will be cooler steam as it has transferred heat to the process in the reheater . the fuel stream to the dhu can be of any combustible fuel suitable for the application , such as for example natural gas , butane or hydrogen extracted from the dehydrogenation process . other hydrocarbons extracted from the dehydrogenation process can also be used as a fuel source . combinations of one or more of the fuel sources listed above , or other sources can also be used . air is provided for the combustion of the fuel within the dhu . the air for the dhu can be heated or cooled as needed to increase the thermal efficiency of the dhu or to reduce emissions such as co 2 or nox . fig4 illustrates one embodiment of a dhu that has a fuel supply tube capable of having multiple fuel injection points . the fuel supply tube is located within a reaction zone tube wherein the fuel is combusted . the fuel supply tube and the reaction zone tube are in a concentric arrangement . air is input into the exchanger and heated above the fuel &# 39 ; s auto ignition temperature . the injection of fuel into this stream results in a reaction between the fuel and the oxygen contained in the air . the air is supplied by an air supply tube that is concentrically positioned around the reaction zone tube . the air supply tube is sealed on its end such that the air is forced to flow through the reaction zone tube . heat from the fuel combustion is transferred through the air stream to the process stream as shown . the concentric tubes comprising the fuel tube , reaction tube and air supply tube can be referred to as a three - tube configuration or a three - tube dhu . there of course can be additional configurations of the air , fuel , exhaust streams using more or fewer tubes , and this invention also covers the contemplated use of other tube arrangements and more or fewer tubes . fig5 illustrates one embodiment of a dhu in the form of a flameless oxidation burner that is described in u . s . pat . no . 7 , 293 , 983 to butler , which is fully incorporated by reference herein . flameless oxidation can occur within the burner , which then dissipates heat to the process flow stream . other designs of types of direct heating units that can be used within the present invention include , but are not limited by , those disclosed in u . s . pat . no . 7 , 025 , 940 to shaw , et al . ; u . s . pat . no . 6 , 588 , 416 to landais , et al . ; u . s . pat . no . 6 , 321 , 743 to khinkis , et al . ; u . s . pat . no . 6 , 007 , 326 to ryan et al . ; u . s . pat . no . 4 , 705 , 022 to collier ; and u . s . pat . no . 4 , 298 , 333 to wunning , the contents of which are fully incorporated by reference herein . the illustrations of fig3 , 4 and 5 are shown wherein the process flow is generally parallel to the dhu , but the dhu may also be configured wherein the process flow can flow generally perpendicular to the dhu or in other configurations wherein the process flow can flow other than parallel or perpendicular relative to the dhu . the illustrations of a single dhu should also not be limiting as multiple dhus may be utilized , for example two or more dhus located in parallel or series arrangement with one or more reheaters that are located between two dehydrogenation reactors . utilizing a dhu and reheater to add heat to a dehydrogenation reaction system may reduce the quantity of steam needed for the process as described herein . this may reduce the total quantity of fuel that is combusted within the process , thus reducing the amount of combustion products , such as co 2 and nox that are emitted . certain dhu designs may be more efficient than the corresponding design of the steam boilers and therefore may have the capability to decrease the fuel usage for the process . reductions in the fuel to hydrocarbon ratios of from 0 . 1 % to 15 % or greater may be achieved . the quantity of heat that can be added to the system at a particular location may be limited by the metallurgy used within the process . for example , if a reheater has a temperature limit that is less than the temperature of the superheated steam , then the quantity of superheated steam being sent through the reheater will have to be controlled and possibly limited in order to maintain the reheater temperature below its limit . the use of one or more dhus as described herein can enable the reheater to operate within its temperature limitations while the total amount of heat added between the reactors can be increased . the use of one or more dhus as described herein in conjunction with a reheater can enable the total amount of heat added between dehydro reactors to be increased more uniformly so that undesirable “ hot spots ” of temperature do not occur within the heating units . hot spots can cause difficulties such as coking , degradation or unwanted reactions of a reactant or product . various types of dhus can be used within the present invention and the invention should not be limited by the use of a certain dhu type . the concept of utilizing a dhu in conjunction with a reheater for the purpose of adding heat to an endothermic dehydrogenation process is not therefore limited by the particular design of either the dhu or the reheater . one illustrative example involves an existing system used for eb dehydrogenation that produces approximately 1 . 5 billion pounds / year of styrene . the existing system had an existing reheater , and a dhu was added to the system . the dhu and the reheater were positioned in a parallel arrangement in the system after the first reactor , and approximately 2 % to 5 % of the first reactor effluent was diverted to a dhu rather than being fed with the remainder of the first reactor effluent stream ( 95 % to 98 %) into the reheater for heating . the dhu was found to consume 28 pounds / hour of fuel gas , and the overall steam to hydrocarbon / oil ratio was reduced by approximately 0 . 1 , which translated into about a 1 . 6 % cost savings on steam used in the overall process . as used herein , “ between ” is defined to mean that the components are arranged in series process flow rather than parallel process flow and that the component referred to is situated after the process flow through one of the reference items and before the process flow through the other reference item . as such , the components do not have to be aligned in a particular physical location with respect to each other . as used herein , “ parallel ” or “ parallel arrangement ” is defined to mean that the components are not arranged in series and that each component separately processes a portion of the stream . as such , the components do not have to be aligned in a true physical parallel manner with respect to each other . while the foregoing is directed to embodiments , versions and examples of the present invention , which are included to enable a person of ordinary skill in the art to make and use the inventions when the information given herein is combined with available information and technology , the inventions are not limited to only these particular embodiments , versions and examples . other and further embodiments , versions and examples of the invention may be devised without departing from the basic scope thereof . | 1 |
fig1 -- an embodiment of an apparatus in the form of a linear prime mover for the conversion of microscopic movements of piezo elements into macroscopic linear displacement of a piston capable of performing a mechanical work fig1 is a longitudinal sectional view of an apparatus of the invention in the form of a linear prime mover for the conversion of microscopic movements of piezo elements into macroscopic linear displacement of a piston capable of performing a mechanical work . the apparatus , which is generally designated by reference numeral 20 , consists of a housing 22 which is sealingly closed at one end by a first cover 24 and at another end by a second cover 26 . covers 24 and 26 are attached to housing 22 by bolts , which are not shown in the drawings . it is understood that appropriate seals , which also are not shown in the drawings , are placed between respective covers and housing 22 . housing 22 is divided into two chambers , i . e ., a first chamber 28 and a second chamber 30 , by a transverse partition 32 . first chamber 28 is preferably of a cylindrical shape and contains a piston 34 slidingly moveable in chamber 28 and dividing it into an upper chamber 36 , which is filled with a liquid 38 , and a lower chamber 40 which is sealed from liquid 38 by a piston head or piston 34 of a substantial diameter . it is understood that the terms &# 34 ; upper &# 34 ; and &# 34 ; lower &# 34 ; are conventional and that the apparatus may have different orientation than the one shown in fig1 . second chamber 30 is filled with a dielectric liquid 31 such as a transformer oil . partition 32 has a central hub 42 with an opening 44 which slidingly receives a piston rod 46 of piston 34 . a through opening 48 passes through the central part of piston 34 . a valve , e . g ., an electrically controlled solenoid valve 50 , is installed at the end of opening 48 opposite to the piston . valve 50 can open or close the above - mentioned through opening 48 from an external command . a tube 52 made of a relatively resilient material , such as bronze , spring steel or the like , is installed between the lower end of central hub 42 and the inner surface of second cover 26 . a space 54 formed underneath piston rod 46 inside tube 52 is filled with liquid 54a and is isolated from the rest of second chamber 30 . a reinforcement perforated sleeve 56 is located inside tube 52 in order to restrict its inward motion under the effect of pressure developed in second chamber 30 , as will be described later . extensions or piston heads 58 and 60 of a diameter substantially smaller than that of piston 34 protrude downward from the lower end face 62 of piston 34 . extensions 58 and 60 are slidingly fitted in openings 64 and 66 of partition 32 . for stability of extensions 58 and 60 during their axial motion , they can be guided by guide rods 68 and 70 which pass through openings 64 and 66 and are rigidly fixed in the housing between first cover 24 and second cove 26 . first cover 24 can be connected to a pneumatic power cylinder 72 which consists of a cylinder housing 74 rigidly attached to first cover 24 by bolts ( not shown ) and a working piston 76 with a piston rod 78 . a lower end 75 of the piston rod of working piston 76 extends into upper chamber 36 . seal rings 77 are used for sealing liquid 38 of upper chamber 36 from the cavity of pneumatic cylinder 72 . piston rod 78 can be connected to a tool , actuator or any other member ( not shown in the drawings ) designed to fulfil a mechanical work . piston 76 divides cylinder house 74 into an upper pneumatic chamber 79 and a lower pneumatic chamber 79a . the latter is connected to the atmosphere via a bleeding hole 85 . now an essential feature of the present invention , i . e ., a piezoelectric conversion unit 80 will be described . in the embodiment of fig1 unit 80 consists of piezoelectric plates 82a through 82f arranged longitudinally between the inner surface 84 of partition 32 and inner surface of second cover 26 . for stability , both ends of respective piezoelectric plates 82a through 82f can be inserted into recesses 86 and 88 made in partition 32 and second cover 26 , respectively . in order not to complicate the drawing , only two such recesses are designated by reference numerals 86 and 88 . piezoelectric plates 82a through 82f can be made of a piezocrystals or piezoceramic , such as those described in entziklopediya neorganicheskikh materialov ( encyclopedia of inorganic materials , vol . 2 , head editors of the ukrainian soviet encyclopedia , kiev , 1977 , p . 268 ). since these materials are brittle , resilient pads 90 are placed onto the bottoms of respective recesses 86 . electrodes 94 and 96 are applied to opposite side surfaces of each piezoelectric plate ( 82a through 82f ). each electrode is electrically connected to external terminal 98 and 100 . in order not to complicate the drawing , only two electrodes , i . e ., 94 and 96 , and only two external terminals , i . e ., 98 and 100 , are designated with reference numerals . it is understood , however , that each piezoelectric plate has a pair of electrodes connected to a pair of respective external terminals , i . e ., the device has electrodes 94a through 94f and 96a through 96f , as well as external terminals 98a through 98f and 100a through 100f . although , depending on the orientation of crystallographic axes , piezoelectric elements can either expand or contract under the effect of electric current , plates 82a to 82f have crystallographic axes oriented so that the plates can only expand . in operation , a high - voltage direct current is applied to electrodes 94a through 94f from an external d . c . source ( not shown in the drawing ) via external terminals 98a to 98f and 100a to 100f . under the effect of electric current , piezoelectric plates 82a to 82f expand radially outwardly so that the volume occupied in second chamber 30 by liquid 31 is reduced , and the pressure of liquid 31 in second chamber 30 is increased . as a result , the pressure applied to piston extensions 60 also increases and pushes these extensions and , hence 34 in an upward direction . during its motion , piston 34 over guide rods 68 and 70 . the upward movement of piston 34 compresses liquid 38 in upper chamber 36 . the of this liquid is applied to the lower end 75 of piston rod of working piston 76 . as a result , piston 76 and its piston rod 78 are moved in the upward direction together with a working tool ( not shown ) which is attached to the upper end of piston 78 . upon completion of the working stroke , piston 76 hence , the working tool are returned to the initial position by air compressed in upper pneumatic chamber 79 . the following will explain how apparatus 20 of the converts microscopic movements ( in the order of microns ) of piezoelectric plates into macroscopic movements ( in the order of dozens of centimeters ) of the working tool . when high - voltage d . c . current is applied to electrodes 94 and 96 of piezoelectric plates 82a and 82b , their volume is increased by several cubic millimeters . since second chamber 30 contains a plurality of conversion units 80 , an increase in the volume of each unit is multiplied by the number of such units . for example , six conversion units 80 are shown in the illustrated embodiment ( fig1 ). therefore , the total decrease in the volume of liquid 31 in second chamber 30 will correspond to sixfold increase in the volume of elementary conversion unit 80 . however , piston 34 has a diameter several times greater than that of extensions 58 and 60 , so that a coefficient of multiplication of displaced liquids , which is a ratio of cross - sectional area of piston 34 to total cross - sectional area of extensions 58 and 60 , may be in terms of hundreds or thousands . for example , in case piezoelectric plates 82a and 82b have dimensions of 10 × 50 × 100 mm , are made of a piezoelectric material such as an artificial crystal of dislocation - free quartz having a piezo module of about 10 - 9 m / v , and operate with a d . c . voltage equal to 10 6 v , each plate will have a linear expansion of about 10 - 4 m ( 0 . 01 mm ). taking into account the dimensions of each plate , its volume can be increased by 50 mm 3 . in case ten such plates are used , the total increase in volume will be equal to 500 mm . this is the initial volume for multiplication . with the cross - sectional area of both extensions 58 and 60 equal to 100 mm 2 and the cross - sectional area of piston 34 equal to 10 . 000 mm 2 , the displaced volume of liquid 38 in first chamber 28 ( with a 5 mm stroke of extensions 58 and 60 ) will be equal to 50 , 000 mm 3 . in other words , changes in the volume of plates 82a through 82f increases the volume of liquid 38 in first chamber 28 by 100 times . in fact , extensions 58 and 60 function as multiplicator means which can multiply changes in the volume of one hydraulic chamber into 10 to 100 times greater changes in the volume of another chamber . extensions 58 and 60 are rigidly connected to piston rod 46 , the cross - sectional area of which is always smaller than the cross - sectional area of piston 34 . piston rod 46 is an element of the unloading system , which significantly lowers the pressure in the second chamber 30 . in case piston rod 78 has a cross - sectional area of 50 mm 2 , its axial displacement together with the working tool will be equal to 1000 mm ( 1 m ), and the working tool will develop a force of 50 kg , provided the piezoceramic material ( which is the weakest point of the system ) can withstand 100 kg / mm 2 . when the apparatus is maintained under load , solenoid valve 50 is closed , so that through opening 48 of piston 34 is closed and the load is not transmitted to piezoelectric plates 82a and 82b , but is received by the column of liquid 54 in a closed space within tube 52 . as tube 52 is made of a resilient material such as bronze , it expands radially outward , so that the volume of liquid 31 in chamber 30 is increased at the expense of resilient tube 52 , rather then piezoelectric plates 82a and 82b . in other words , the piezoelectric loads are unloaded , and the load is taken by liquid 54 and tube 52 . deformation of tube 52 in the inward direction is limited by reinforcement perforated sleeve 56 . although piezoelectric units 80 were shown in fig1 in vertical positions , it is understood by those skilled in the art that they may have a horizontal or inclined positions without the departure from the principle of the present invention . thus it has been shown that apparatus 20 of the invention converts microscopical movements of piezoelectric plates 82a and 82b into macroscopic movements of piston rod 78 . fig2 to 6 -- an embodiment of an apparatus with piezoelectric elements arranged in cartridges fig2 is a view of an apparatus 200 similar to apparatus 20 shown in fig1 but with piezo elements arranged in cartridges . elements and parts which are identical with those of the embodiment of fig1 will be designated by the same reference numerals , but with addition of 100 . for example , piston 34 of fig1 will corresponds to piston 134 in fig2 etc . since in both embodiments the identical parts operate in the same manner , in the second embodiment their description will be omitted . it is shown in fig2 that each piezoelectric unit is made in the form of a replaceable cartridge 300 . eight such cartridges 300 are shown in the embodiment of fig2 . these cartridges may have different constructions , examples of which are shown in fig3 , 5 , 6 , and 7 and will be described and considered separately . what is common for all cartridges is that each cartridge is a self - contained unit with a sealed interior . since all the remaining parts of apparatus 200 of the second embodiment of the invention ( fig3 ) operate in the same manner as respective parts of apparatus 20 and since each cartridge 300 , 400 , and 500 ( fig3 through 5 ) functions as conversion element 80 of apparatus 20 , the operation of the above - mentioned parts and each cartridge as a whole will be omitted . consideration will be given only to the construction and interaction of the internal parts of each cartridge . this is because similar to element 80 the function of each cartridge is to merely increase its volume and thus to develop a pressure in liquid 131 . since , as will be shown below , each cartridge is a sealed unit , liquid 131 is not necessarily a dielectric liquid . fig3 is a sectional view of a piezoelectric cartridge 300 used in the apparatus of fig2 and designed for operation from direct current . cartridge 300 consists of an inner casing 302 telescopically and sealingly fitted into an outer casing 304 . seal rings 306 can be placed between inner casing 302 and outer casing 304 . as shown in fig3 both casings have cup - shaped configurations ( or boxlike configurations with each box being open from one side ) with cups or boxes inserted one into another with their bottoms facing outward so that they form a sealed chamber 307 . inner casing 302 contains a number , e . g ., three piezoceramic columns 308a , 308b , and 308c . each such column is composed of a plurality of piezoceramic elements 310 arranged in series and forming the above - mentioned column . the construction and manufacture of each such element will be described later in connection with fig6 and after consideration of each embodiment of the cartridge . each column is compressed between facing bottoms 312 and 314 of inner casing 302 and outer casing 304 , respectively , under the effect of expansion springs 316 and 318 located between the outer end face 320 of inner casing 302 and inner surface 322 of outer casing 304 opposite to bottom 314 . in order to unload piezoceramic columns 308a , 308b , and 308c from external loads , cartridge 300 is provided with an unloading mechanism which consist of wedge - like seats 324 and 326 , which are attached to inner casing 302 , and prismatic blocks 328 and 330 . blocks 328 and 330 engage respective seats 324 and 326 and are maintained in tight contact with the latter by screws 332 and 334 threaded into the bottom wall of outer casing 304 . when high - voltage d . c . current is applied to electrodes ( not shown ) of piezoceramic columns 308a , 308b , and 308c , they expand linearly and thus push inner casing 302 telescopically with respect to outer casing in the direction of arrow a . since outer end face 320 of inner element 302 is in contact with liquid 131 , the pressure in this liquid will be decreased , and the sequence of operations described in connection with the embodiment of fig1 will be repeated . fig4 is a sectional view of a piezoelectric cartridge 400 used in the apparatus of fig2 and designed for operation from alternating current . cartridge 400 has a stationary outer casing 402 and an inner casing 404 telescopically fitted in outer casing 402 . seal rings 406 are placed between the mating side surfaces of both casings . similar to the embodiment of fig3 both casings form a sealed chamber 408 which is filled with liquid 410 , e . g ., water . an annular piston 412 is sealingly inserted into an annular slot formed in a bottom wall 416 of inner casing 404 . a piezoceramic column 420 of the type shown in fig3 ( 308a , 308b , 308c ) is rigidly connected to the external surface 415 of bottom wall 416 . if liquid 131 is a non - dielectric liquid , piezoceramic column 420 has to be sealed in a telescopically expandable and contractible covering which is generally designated by reference numeral 422 ( fig4 ). reference numeral 424 designates an external surface of inner casing 404 which is exposed to liquid 131 , and reference numeral 426 designates an external surface of annular piston 412 exposed to the same liquid 131 . it is understood that the piezoceramic column is connected to an a . c . current source through respective electrodes ( not shown ). in operation , application of a . c . current to piezoceramic column 420 will cause its cyclic expansion and contraction . when column 420 expands , it compresses liquid 410 in chamber 408 , whereby annular piston 412 is pushed out in the direction of arrows b and into position indicated by broken lines . when at the next moment the column contracts , it will carry inner casing 404 , which is rigidly connected thereto at its bottom , in the direction of the same arrow b . with the next expansion and contraction cycle , the operation will be repeated . as a result , inner casing 404 and ring piston 412 , will perform translatory motion in the same direction , i . e ., in the direction of arrow b . in order to provide uniformity of step - like motions of inner casing 404 and , hence , piston rod 178 , the volume of liquid 131 displaced by external surfaces 426 of annular piston 412 should be equal to the volume of liquid 131 displaced by the external surface 424 of moveable inner casing 404 . in case unit 400 works in an electric - motor mode , surface 426 should be smaller than surface 424 , while in case the unit works in a generator mode , surface 426 should be greater than surface 424 . fig5 is a sectional view of a piezoelectric cartridge 500 with a hydraulic multiplicator and a camming mechanism . similar to all previous embodiments , cartridge 500 consists of two telescopically connected casings , i . e ., an outer casing 502 and an inner casing 504 which define a closed and sealed space . outer casing 502 is moveable and inner casing 504 is stationary . connected to the inner surface of bottom wall 508 is a cup - shaped housing 510 which has a centrally arranged main cylinder 512 and a number of peripheral cylinders 514 and 516 . although only two such peripheral cylinders are shown in fig5 it is understood that a greater number of such peripheral cylinders can be uniformly spaced and arranged circumferentially around main cylinder 512 . a main piston 518 is slidingly fitted in main cylinder 512 and its piston rod 520 is made of a piezoceramic material . the lower end of piston rod 520 is rigidly connected to main piston 518 , while the upper end of piston rod 520 is rigidly connected to inner casing 504 at 522 . each peripheral cylinder ( 514 , 516 ) receives an auxiliary piston ( 524 , 526 ) having a piston rod 528 and 530 . each piston rod carried on its free end a camming or wedging element ( 532 , 534 ). chamber of peripheral cylinders 514 formed beneath pistons 524 and 526 are connected to the chambers formed in main cylinder 512 beneath main cylinder 518 via ports 536 and 538 which can be closed or opened by solenoid valves 540 and 542 . these valves are can be remotely controlled from an external source , or a program device ( not shown in fig5 ), so that peripheral cylinders 514 and 516 can operate sequentially . attached to an inner side wall 544 of inner casing 504 are stands 546 and 548 which extend radially inwardly into the cavity of inner casing 504 . stands 546 and 548 rotatingly supports gear wheels 550 and 552 which are in mesh with a central gear wheel 554 . the latter also is supported by stands 546 and 548 so that it can freely rotate but is protected by the above - mentioned stands from axial displacement . central gear wheel 554 has a central hole 556 to provide unobstructed passage of piezoceramic piston rod 520 . each gear wheel 550 and 552 has a threaded opening 556 and 558 , respectively , which engages a thread pin 560 and 562 . on the side which faces piston rods 528 and 530 , central gear wheel 554 has a camming surface 564 which engages the above - mentioned camming elements 532 and 534 on piston rods 528 and 530 . when a high - voltage d . c . current is applied to piezoceramic piston rod 520 , the latter linearly expands for a microscopic value . however , as main piston 518 has a large surface area , this microscopic motion is multiplied into macroscopic displacements of pistons 524 and 526 which have much smaller surface areas . communication between main cylinder 512 and peripheral cylinders 514 via valves 540 and 542 is controlled from the above - mentioned program device ( not shown ) so that piston rods 528 and 530 and , hence , camming elements 532 and 534 will be activated sequentially and thus will engage camming surface 564 of central gear wheel 554 with the same sequence . the profile of the camming surface is made so that this sequential engagement will cause uniform rotation of gear wheel 554 . since the latter is in mesh with gear wheels 550 and 552 , rotation of these gears will cause axial displacement of threaded pins 560 and 562 . these pins will contact the inner side of moveable outer casing 502 and will push it in the direction of expansion of cartridge 500 . the rest of the operation is the same as in connection with the description of fig2 . it is understood that under the control of the program device , the cartridge can be expanded or contracted in any sequence required by specific conditions . fig6 is a sectional view of an elementary piezoceramic element 310 used for assembling piezoceramic columns employed in all the above - described embodiments . this element has a conventional construction [ described , e . g ., by i . a . glozman in &# 34 ; piezokeramika &# 34 ; ( piezoceramics ), moscow , &# 34 ; energiya &# 34 ; publishers , 1972 ] with the exception that a piezoceramic body 566 is press - fitted into a ferrule 568 made of a hard material , such as steel , and that after grinding the end faces of piezoceramic body 566 has to be polished to remove a friable layer formed as a result of grinding . this is important because microscopic linear expansions are absorbed by the above - mentioned friable layer . it is understood that after polishing , electrodes 570 and 572 are applied onto the polished surfaces of body 566 , e . g ., by vapor deposition in vacuum . electrodes 570 and 572 are connected to lead wires 574 and 576 in a manner known in the art . thus it has been shown that the invention provides a method and apparatus for converting microscopic movements into a macroscopic motion with power capable of performing mechanical work . the apparatus has low momentum of inertia during reversion of movement , low weight per unit power , is simple in construction , inexpensive to manufacture , uses low - cost materials , is capable of stopping in an accurate position , and has low energy losses . although the apparatus has been described and illustrated with reference to specific practical embodiments , it is understood that these embodiments were given only as examples and that many modifications of the device are possible . for example , the length of the linear expansions of piezoceramic elements can be increased by forming a piezoceramic column into a spiral body , or by sequentially connecting a series of mechanisms containing piezoelectric columns into a chain . the piezoceramic columns can be unloaded by various mechanisms such as wedging mechanisms . the shapes , materials , quantities , and dimensions of various parts and units of the apparatus can be different from those shown in the illustrated embodiments . piezoceramic may be comprised of a piezosegnetic salt . it is also understood that magnetostrictive materials can be used instead of piezoceramics . the output element of the apparatus may have any configuration and can be connected to any known motion conversion mechanism , e . g ., for the conversion of a linear motion to a rotary motion . it is also understood that cartridges can be expanded or contracted under the effect of heat energy , e . g ., due to thermal expansion . each unit or cartridge can operate in an electric - motor or a generator mode . therefore the scope of the invention should be determined , not by the examples given , but by the appended claims and their legal equivalents . | 7 |
in the operation of the separation process of this invention , the carbon dioxide containing feed gas is preferably introduced into the low pressure section of the column and the total pressure in this section is maintained below the critical pressure of carbon dioxide , the primary component of the liquid bottoms . by maintaining a pressure well below the critical pressure of carbon dioxide phase separation of liquids readily occurs within this section of the column . suitably , the temperature within the uppermost stage of the low pressure section of the column is maintained above about - 100 ° f ., and the temperature at the uppermost stage and the lowermost stage of the column , respectively , ranges from above about - 100 ° f . to below about + 85 ° f ., preferably from above about - 80 ° f . to below about + 45 ° f . the gas from the low pressure section , prior to or at the time of its introduction into the high pressure section of the distillation or fractionation column , is cooled . suitably , the temperature within the uppermost stage of the high pressure section of the column is maintained above about - 170 ° f . and the temperature at the uppermost stage and the lowermost stage of the column , respectively , ranges above about 170 ° f . to less than about - 80 ° f ., preferably from above about - 145 ° f . to below about - 85 ° f . in accordance with such process it becomes feasible to effect almost complete separation of carbon dioxide and other acid gas components from a methane - containing feed gas such as natural gas or synthesis gas . in copending application ser . no . 833 , 937 , filed sept . 16 , 1977 by james m . eakman and harry a . marshall , now u . s . pat . no . 4 , 149 , 864 , there is also described a process for the separation of carbon dioxide and other acid gas components from methane feeds by low temperature high pressure distillation . this process , which utilizes a simple distillation column to effect such separation , is an improvement over prior art processes used to effect acid gas separation from hydrocarbons . it is superior , inter alia , in that carbon dioxide separation above 90 mol percent and even on the order of about 95 to 99 mol percent and higher is achieved . it is entirely feasible , in fact , to provide products which contain carbon dioxide levels of only about 5 to about 1 mol percent and less . whereas this process has proven admirably effective for carbon dioxide separation from methane , it is nonetheless necessary to maintain close control of the conditions of operation to assure adequate methane and carbon dioxide phase separation at the bottom of the column . thus , at the high total pressure required to effect maximum removal of the carbon dioxide from the effluent taken from the upper stages of the column , the increased pressure at the bottom of the column approaches the critical pressure of carbon dioxide , the primary component leaving the bottom of the column , which makes it difficult to effect the phase separation required . this problem is avoided and all of the other advantages of the simple column approach are retained . essentially complete removal of the carbon dioxide can be effected in accordance with the present process by use of a compound distillation column or column having a section which is operated at relatively low pressure at the location where a carbon dioxide - rich product is removed and a section which is operated at relatively high pressure at the location wherein a methane - rich product is removed . the distillation is carried out in conventional vapor - liquid contacting apparatus comprising a single column with associated high pressure and low pressure sections or in separate associated columns , one of which is operated at high pressure and the other of which is operated at low pressure . referring to fig1 there is shown fractionating columns 10 , 20 , each of the vapor - liquid contact type constituted generally of an outer metal shell within which is provided a plurality of vertically separated bubble cap trays . column 10 is a low pressure column , or column operated at lower pressure than column 20 . hence , column 10 is designated in the figure as the low pressure column and column 20 as the high pressure column . in an operation , a gaseous feed which contains carbon dioxide , methane and hydrogen and which may also contain nitrogen , carbon monoxide and other components , after passage through a heat exchanger ( not shown ), is introduced via line 11 into about the middle or upper portion of column 10 . in the lower column , in order to maintain two phases , the total pressure must be maintained below the critical pressure for co 2 this is because there is essentially pure co 2 in the bottom part of the column . also in the lower column , the sum of the partial pressures of co 2 and ch 4 at all points must be greater than the pressure expressed by the following relationship to avoid co 2 freeze - out : where pressures are expressed in psia and temperatures in degrees fahrenheit . this relationship applies over the temperature range from - 100 ° f . to the co 2 triple point temperature or - 69 . 9 ° f . in practice this limitation would only effect the conditions in the top stage or partial condenser of the lower column . alternatively , this may be expressed as : ## equ1 ## where y ch . sbsb . 4 , 1 and y co . sbsb . 2 , 1 are the mol fractions of ch 4 and co 2 in the vapor leaving the lower column 10 . the specific values of these mol fractions will be affected by the temperature , flow rate and composition of the feed , and by the flow rate and composition of the bottoms stream 23 from the high pressure column . the specific values may be computed by the usual stage - to - stage computation procedures used for predicting the performance of a distillation column . the primary function of the lower pressure column 10 is to reduce the quantity of methane and other more volatile constituents leaving the bottom of the column with the liquid acid gas components . as previously indicated , column 10 is necessarily maintained at a pressure less than about 1073 psia , the critical pressure of carbon dioxide , which is the primary component of the liquid leaving the column . preferably , however , the total pressure is maintained from about 200 psia to about 700 psia . the upper stage of the low pressure column 10 is operated such that no solid carbon dioxide formation can occur . for best results this requires , in column 10 , a top stage temperature above about - 100 ° f ., preferably above about - 80 ° f ., and a vapor composition of approximately 10 mol percent carbon dioxide or greater . product of highly concentrated acid gas components is withdrawn as a liquid via line 12 after recirculation of a portion of the product through a reboiler - type heat exchanger 13 . a portion of the vapor from the top stage of the low pressure column 10 is recirculated through a condenser 9 , which can be an external condenser ( as shown ) or an internal condenser and condensed for the return of liquid as reflux . uncondensed vapor from the top stage of the low pressure column 10 is compressed and preferably cooled before feeding it to the high pressure fractionation column 20 . suitably , effluent vapors from column 10 are passed via line 14 to a compressor 15 and then passed via line 16 through a heat exchanger 17 , cooled and then injected into the column at some suitable location , e . g ., at the bottom of column 20 . in order for co 2 freeze - out to be prevented in the upper stages of the higher pressure upper column the total pressure in the upper stages at this column must be : ## equ2 ## where y ch . sbsb . 4 , 2 and y co . sbsb . 2 , 2 are the local mol fractions in the vapor . in terms of the reflux ratio ( l / d = mols liquid reflux / mols vapor distillate ) and feed composition . this pressure may be expressed more generally as : ## equ3 ## where : z n . sbsb . 2 = mol fraction n 2 in feed ( when present ) the total mols of feed to the column are f mols / hour , hence the feed rate of an individual component , e . g ., co 2 , is given by again , in order to maintain liquid and vapor phases in the upper stages of the column , it is necessary to keep the total column pressure below the mixture critical pressure . for the ch 4 -- h 2 binary this is defined by : z n . sbsb . 2 = mol fraction n 2 in feed ( when present ) z ch . sbsb . 4 = mol fraction ch 4 in feed however , there is no limitation on the total pressure in this column being maintained below 1073 psia as there is in the single column case . that is , use of the compound column has removed the restriction of staying below the co 2 critical for the second column , since pure co 2 does not exist at any point in the second column . the primary function of the higher pressure column 20 is to reduce the quantity of acid gas components in the overhead gas . this column is maintained at a pressure greater than 600 psia and generally at least 50 psia above the pressure of low pressure column 10 . column 20 is designed and operated to reduce the carbon dioxide to a desired level by control of temperature and the rate of the reflux liquid , by virtue of which the carbon dioxide content can be reduced to a level below one mol percent . the formation of solid carbon dioxide is prevented , even at reflux temperatures well below - 80 ° f ., by maintaining the column pressure at a suitable level above approximately 600 psia . in the presence of hydrogen , gas and liquid phases will be present in the fractionator at these higher pressures , which are above the critical pressure of methane ( 673 psia ). the range of satisfactory operating conditions for this column will depend to some extent on the number of trays employed , on the composition of the particular feed gas that is processed and on the desired level of carbon dioxide desired in the product . overhead vapors consisting primarily of methane or methane and carbon monoxide and hydrogen are removed via line 21 since the primary function of the upper stages of column 20 is to reduce the quantity of carbon dioxide and other acid gas components leaving the top of the column . a portion of the vapors is recirculated through an external condenser 22 . the condenser , however , can be internal or external but is illustrated for convenience as an external condenser . uncondensed effluent is withdrawn via line 21 from column 20 and stored . the level of carbon dioxide contained in the overhead product from column 20 is controlled by a combination of staging , temperature and rate of reflux liquid . the upper stage temperature is maintained above about - 170 ° f . but for best results the temperature is maintained above about - 145 ° f . suitably , the molar ratio of liquid : distillate used as reflux ranges about 1 . 25 : 1 , and higher and preferably about 1 . 3 : 1 and higher . the process is particularly suitable for the separation of carbon dioxide from admixtures of methane ( ch 4 ) and synthesis gas ( h 2 + co ) at molar ratios of ch 4 :( h 2 + co ) of about 1 : 1 to about 5 : 1 , and gas feed not of this composition can be readily adjusted in situ or ex situ by the addition of components to provide such mixture . with some feed gases it may thus be desirable or preferred to add methane or hydrogen or carbon monoxide or both to either the feed gas or to the gas entering the higher pressure column in order to adjust the gas composition to the preferred range . the liquid phase from the bottom of the high pressure column 20 can be returned to the low pressure column and introduced at some suitable location either by expansion , as through line 23 containing , e . g ., a joule - thompson valve , or by heat exchange with the higher temperature compressed gas from the low pressure column followed by expansion through a turbine , or by some combination of the two techniques . in the latter instance the expansion turbine can be used to help drive the compressor thus reducing the total energy requirement of the system . referring to fig2 there is graphically described an essential relationship between temperature in ° f . and the partial pressure of carbon dioxide and methane ( co 2 + ch 4 ), expressed in pounds per square inch absolute , if solid formation is to be avoided in such systems . it will be observed that in order to avoid the formation of solids , operation of the column at temperatures ranging from about - 170 ° f . to about - 84 ° f . as shown on the x - axis requires higher and higher partial pressures of carbon dioxide and methane as shown on the y - axis ranging from about 200 psia to about 710 psia at the higher temperature . thereafter , up to about - 70 ° f ., the partial pressure that is required declines . the relationship expressed in the graph which is required to avoid the solids formation region is tabulated for convenience as follows : ______________________________________temperature , partial pressure of ° f . ( co . sub . 2 + ch . sub . 4 ), psia______________________________________ - 170 & gt ; 200 - 150 & gt ; 280 - 130 & gt ; 420 - 110 & gt ; 550 - 90 & gt ; 700 - 84 & gt ; 710 - 70 & gt ; 75______________________________________ in sharp contrast to prior art distillation processes for effecting such separations which remove only about 90 mol percent of the carbon dioxide it has been found feasible to remove carbon dioxide to a level of 1 mol percent or less in the admixture of carbon dioxide and methane , or methane in admixture with other hydrocarbons and hydrogen , e . g ., methane and synthesis gas , in a compound column utilizing generally 20 to 30 theoretical stages . this is conveniently illustrated by reference to the following example which presents data taken from a computer - simulated run conducted as described . two columns are employed ; a high pressure column having two theoretical trays and a low pressure column having twenty theoretical trays interconnected and fitted generally as described by reference to fig1 except that the heat exchanger 17 is not employed ; and a valve is employed instead of an expansion turbine . the columns are operated at conditions well within the parameters represented in the foregoing discussion . the high pressure column is operated at a pressure of 1100 psia and the low pressure column is operated at a pressure of 465 psia . the uppermost stage of the high pressure column ( stage 2 ) is operated at - 113 ° f . and the lowermost stage ( stage 1 ) at - 87 ° f . the uppermost stage of the low pressure column ( stage 20 ) is operated at - 93 ° f ., which represents the equilibrium temperature of the product stream from the top of the low pressure column after compression , the reflux of product from the bottom stage of the high pressure column after passage through the valve , and the influx of gases and vapors from the lower stages of the low pressure column . the lowermost stage of the low pressure column ( stage 1 ) is operated at + 25 . 4 ° f . a feed in the amount of 84 . 53 mols of the mol composition given in column 1 of table 1 at - 55 ° f ., is introduced into stage 12 of the low pressure column . the mol composition of the product taken from the top of the low pressure column and injected into stage 1 of the high pressure column is given in column 2 of table 1 and the mole composition of the product taken from the bottom of the high pressure column and injected into stage 20 of the low pressure column is given in column 3 of table 1 . table 1______________________________________ mols______________________________________hydrogen 20 . 09 20 . 59 0 . 52carbon monoxide 5 . 72 6 . 32 0 . 60methane 36 . 93 48 . 00 11 . 09carbon dioxide 21 . 38 8 . 36 7 . 79hydrogen sulfide 0 . 41 0 . 00 0 . 00 84 . 53 83 . 27 20 . 00______________________________________ the molar ratio of liquid : distillate in the reflux which is returned to stage 2 of the high pressure column is maintained at 1 . 47 . the product streams from the high pressure and low pressure columns are 63 . 27 mols and 21 . 23 mols , respectively . the composition of the components in the two streams are : ______________________________________ mols vapor liquid overhead bottoms______________________________________hydrogen 20 . 07 0 . 02carbon monoxide 5 . 72 0 . 00methane 36 . 91 0 . 02carbon dioxide 0 . 57 20 . 81hydrogen sulfide 0 . 00 0 . 40 63 . 27 21 . 23______________________________________ these data show that it is quite feasible to remove carbon dioxide to a very low level , considerably below about 1 mol percent carbon dioxide present in the vapor phase mixture . it is apparent that various modifications can be made in the process without departing the spirit and scope of the present invention . | 5 |
the success of biosdi in making the data available to its participants will be based on the classification of the data in its database . the proposed interchange will attach a number of keywords to each set of data in consultation with the disclosing party . these keywords will assist in storing as well as retrieving the data . in addition to attaching the keywords , the data may be stored in various classes to begin with . these classes could be the various systems of study by the participants , the techniques used in obtaining the data , or the class of the data obtained itself . for example , the techniques used could provide data which may be probabilistic or deterministic in nature . such classes could also assist the recipient in knowing if the data he / she is looking for would be useful to him / her or not . criteria for acquisition of data through the interchange may be performed either via manual or automated techniques ( i . e ., as a persistent set of queries ) which in the latter case sdi also acts separately on behalf of the present recipient to seek out and identify available data as currently possessed by the interchange &# 39 ; s pool of participants which is determined to be able to add potential value to the recipient , which , in turn , can be achieved in a plethora of different manual and automatic ways . in one example scenario , in the sharing of interaction parameter data , the potentially complementary data may : 1 . match the criteria for statistical similarity as measured by statistical similarity of the newly identified data to that of the present entity &# 39 ; s preexisting data , thus representing the ability to improve or refine the quality of existing data possessed by that entity ; for example , such improvements could quantifiably enhance the quality and rigor of the methods used in the supporting research work substantiating the model of that data , or the quantity of relevant data statistics as collected which were used in the creation of the models for that data . 2 . or , complementarily “ adds to ” the detail or completeness of the present entity &# 39 ; s ( prospective recipient &# 39 ; s ) data model used to achieve its desired objectives . 3 . data needs which represent active research endeavors of present interest and priority for the present entity &# 39 ; s current laboratory research projects ( perhaps which may be explicitly defined and submitted to sdi ). the techniques used for identifying complementary data from among the plethora stored within sdi ( as would be applicable to items 1 and 2 above ) may often be able to be performed based upon a methodology which is very similar to that of pattern matching techniques in which the search and matching process used to identify data “ similarity ” may be automatically adjudged in accordance with multiple similar and accordingly similarly weighted attributes ( occurring among two or more disparate data sets ) whose relevancy ( relative weighting ) value of each attribute is determined by particulars of the specific data of interest which is associated with the statistical model . ( sdi can efficiently perform this task as it possesses both data parameters and the specific tools / modeling techniques used in the formulation and processing of those data parameters ). depending on the type of data being shared , the disclosing user may place a series of preconditions on how data is to be given out . it will often be the case that parts of the data will be obscured such that proprietary aspects of the disclosers &# 39 ; own work will not be revealed . biosdi will contain statistical tools capable of analyzing and reporting back to the discloser how risky a given level of obscurity will be , before the discloser actually releases the data to the network . several examples of potentially relevant parameters which may be useful predictors of the various data obscurity parameters are suggested below under “ methodology ”. accordingly , one preferred implementation prescribes , well in advance of disclosure , certain desired thresholds which define quantitatively a level of risk ( i . e ., for purposes of the present system , a quantitative measure of “ indistinguishability ” from other “ similar ” biological systems ) ( e . g ., relating to the present molecule , metabolic pathway , cell type or class of physiological effects to which the presently disclosed data relates ). in this latter application , the discloser may pre - specify data security conditions for disclosure . ( the term “ indistinguishability ” may be used interchangeably with “ obscurity ”). suppose that a data - providing user specifies and releases complete atom - atom interaction data for a part of a molecule “ a ” in a cell target “ b ” participating in a metabolic pathway “ c ”. taking into account currently available models , the most that a recipient might be able to infer about the overall structure would be that it contains a specified number of atoms in the disclosed portion of the molecule or unrelated part of the molecule ( for example ) and that these atoms may relate to a w number of currently known molecules participating in x other significant molecular pathways , and that there may exist y number of further “ significantly ” recognized reactions for each of these pathways and that there are z number of other potential significantly recognized protein molecules to which that molecular segment could just as easily constitute a portion of . certainly , it is easy to assume that if the length of a particular molecular segment is shortened ( e . g ., by even only one atom ) that the indistinguishability ( obscurity ) of that segment will increase significantly ( non - linearly ) to the percent reduction of the segment . of course , by far the most significant obscurity enhancing effect is achieved by removal of the relatively unique portions of a molecule , which are most prevalent parts of a biochemical reaction . although other relevant variables are applicable such as which portion of the molecule , its structural uniqueness ( within all plausible or likely other possibilities in light of the total data possessed by the recipient , etc .) thus this latter technique constitutes an important part of the role of bio sdi in maximizing shared value exchange while attempting to greatly minimize the effect of enhancing the dissemination of data which could be used as an end objective by the recipients which are potentially directly competitive to the disclosing organization for potentially directly competitive end - objectives . in addition , as the range / variety and total pool of bioinformatic information continues to grow ( and at an ever accelerating rate the inherent indistinguishability ( obscurity ) of any given piece of data will also increase plausibly according to a relatively linearly correlated relationship ) given the presently known range of pathways , protein structures and potential interactions of significance , the discloser &# 39 ; s ultimate objective is to achieve a quantified set of prescribed ( or pre - disclosed ) conditions ( a minimum level of satisfaction ) such that outside of such quantified conditions or constraints it is impossible for the recipient to make statistical inference as to presence of statistical likelihood of that segment or parameter ( s ) to be associated with ( or part of ) a particular parameter , a particular pathway or a protein molecule with which the present segment is associated by making it indistinguishable from x number of potential alternatives ( within a maximum limit of statistical probability ). selection of the particular parameters which are truly relevant reasonably reliable predictors of indistinguishability ( or obscurity ) parameters are at best tricky involving complexity in the parameters and are likely to be variable depending upon the type of structural and interaction - based parameters associated with the specific data contained within the present data model . a few suggested ( reasonably plausible ) possible parameters are disclosed in the following section (“ methodology ”). accordingly from the standpoint of the methodology itself which is used to estimate these various obscurity values because the data modeling algorithm of choice by the discloser also utilized for the modeling / creation of the actual data as disclosed , it is reasonable to certainly use the same statistical algorithm as well as other modeling algorithms ( which may possess other strengths / advantages in determining accuracy of the various parameters ) provided that the algorithm is based upon a core statistical / earning technique . in this regard , the “ unknown ” parameters are the indistinguishability parameters ( as above explained ) and the input parameters are , of course , those known descriptive parameters relating to the structural / functional characteristics of the molecule , its interaction - based moieties and / or its associated as well as the parameters which are “ predictors ” of indistinguishability ” ( such as those suggested in items a - g in the following section ), which may in some cases require the additional capture and correlation of parameters to the basic modeling parameters and which are not typically critically required within the data modeling scheme which is used for the present experimental objectives . in some cases , rather than simply hiding information , a user may wish to make use of “ randomized aggregates ” to add noise to the data being disclosed . in such a case , the aggregate properties of a collection of objects will be preserved ( for example , mean value ), but individual items within the collection will not be fully accurate representations of the underlying data . the technical details explaining the mathematical theory of randomized aggregates is disclosed in co - pending patent application entitled “ secure data interchange .” among many useful applications for randomized aggregates within the present system context is the use of the presently described statistical framework or “ interaction moieties ” in which it may be desirable to obscure not only the individual directly interacting atoms or “ interaction moieties ”, but rather also the associated indirect multiple ( neighboring ) atoms ( or molecular segment ( s ) associated with that interaction . invariably , the vast majority of the distinguishing structurally “ unique ” features of any given sequence in a molecule when compared to the sum of all other very similar sequences found in other molecules ( most likely ) have very little functional influence on a given interaction in and of themselves . the square of the number of these unique features ( roughly the length of a given molecular segment , which is disclosed ) is inversely proportional to the level of overall obscurity . as a consequence , in yet another ( third ) variation of randomized aggregates , it could be advantageous to the disclosing party to limit the information disclosure to a particular segment by excluding or subtracting the indirectly induced interaction effect emanating from any additional atoms outside of that segment whose ( indirect ) interaction parameters could be revealing of associated information about specifics of those atoms inducing those secondary interaction effects . methodology for deriving and implementing statistical measures of obscurity of disclosed data the proposed methodology for deriving various critically important parameters in order to determine a variety of key measures of statistical obscurity , can only function with some predictable and reliable level of accuracy , if and only if a ) a plethora of attributes are tested repetitively across a variety of types of actual biochemical data and against a “ hacker ” using a statistical model to derive the actual data the discloser is attempting to conceal by virtue of the proposed methodology &# 39 ; s steganographic and cryptographic advantages . b ) these attributes are deliberately selected by human experts knowledgeable in the field . in the following we provide a number of attributes , which determine the degree of obscurity of the disclosed data from the data on hand . the attributes provided are described using a particular kind of data , however , these attributes are not limited to a particular style of data . in fact , a similar set of attributes could be determined which would be applicable to an altogether new class of biochemical data . several examples of attributes , which may statistically relate and thus be predictive of some of the useful and important obscurity parameters as suggested in the above example include the following ( note the pre - qualifying terms “ directly proportional to ” and “ inversely proportional to ” are stated simply for exemplification purposes ): 1 . the degree of obscurity is likely to be inversely proportional to the following parameters : a ) data quantity within the domain of that particular biochemical pathway and its degree of similarity to that possessed by the recipient prior to receipt , specifically : i . the amount of existing data that the disclosee ( recipient ) has in its possession a priori regarding that type of molecular interaction as well as : ii . the degree of “ similarity ” that these data models share with the present data model being disclosed . ( in this latter , regard , sdi may be able to act as a trusted “ auditor ” in terms of verifying all of the information which it had previously disclosed to that receiving party and possibly the data , which that party had independently created , so as to appropriately adjust the degree of obscurity relative to the recipient prior to disclosure of the data in this manner ). i . the number and degree of precision ( e . g ., quantifiable numerical value ) of the physical and chemical parameters associated with the atomic interaction model . ii . the degree of novelty or uniqueness of the associated physical and chemical parameters ( more precisely , the novelty of the combinatorial pattern of these parameters ) assuming that the recipient &# 39 ; s data model correlations of these parameters inherently possesses “ statistical confidence ”. iii . the degree of “ commonality ” of the physical and chemical parameters ( i . e ., their combinatorial patterns ) assuming statistical confidence in the above correlation are absent . iv . the present degree of popularity within the field &# 39 ; s overall research initiatives and degree of precision ( e . g ., quantifiable numerical value ) of the chemical parameters associated with the atomic interaction model . i . the number and degree of precision ( e . g ., quantifiable numerical value ) of the interaction parameters associated with the molecular / molecular interaction model . ii . the degree of novelty or uniqueness of the associated interaction parameters ( more precisely , the novelty of the combinatorial pattern of these parameters ) assuming that the recipient &# 39 ; s data model correlations of these inherently possesses “ statistical confidence ”. iii . the degree of “ commonality ” of the interaction parameters ( i . e ., their combinatorial patterns ) assuming statistical confidence in the above correlation is absent . d . quantity of data describing molecular structures within a biochemical pathway and degree of structural transformation of a molecule &# 39 ; s precursors within a pathway specifically : ii . the degree of net structural change , which occurs within the molecule and / or its target . iii . the degree of statistical novelty ( relative to the recipient &# 39 ; s collective data ) of the structural features , which characterize these disclosed molecule segments . e . number / complexity of molecular structure ; specifically : the number of additional “ neighboring ” atoms ( in their proper structural orientation / relationship ), which are disclosed in conjunction with each single atom - atom interaction parameter ( and , if relevant , associated physical and chemical parameters ). f . assuming that both the prospective recipient and the data slated for delivery relate to the cell target ( as opposed to a proposed targeting molecule ), the number , of related cell targets ( within a family ) which are molecularly similar enough so as to be likely to interchangeably interact biochemically with an associated targeting molecule designed to target one of them . g . the number , of related cell targets ( within a family ) for which only one interacts with the associated targeting molecule . the number of biochemically / structurally similar targets which are known and modeled by the prospective data recipient as well as among these , the number of structurally similar targets which are presently known to be similar to those with which the ultimately desired targeting molecule under development is designed to interact ( these of course would necessarily be entrusted with sdi ). 2 . the degree of obscurity is directly proportional to : a ) the degree of error , which is selectively added to the molecular interactions or the correlations between the molecular interactions and the chemo - physical parameters ( as exemplified above ). ( so as to ultimately minimize degree of error while maximizing degree of obscurity . b ) the number , of related cell targets ( within a family ) for which these multiple targets each interact ( to some desirable extent ) with the associated targeting molecule . it is worth emphasizing that it is extremely advantageous for optimizing this degree of obscurity to only reveal individual atom - atom interactions whose direct interaction parameters are influenced by other neighboring atoms but whose associated identities are concealed ; it could , for example , be possible to state along with the disclosure the isolated individual atom - atom interaction parameters ( as if in a vacuum ) and only if the recipient is working with those atoms within the context of the same neighboring atomic structures would the appropriately modified interaction parameters become revealed ( inasmuch as they , in turn , also affect and are affected by these neighboring similar structures ). of course , even so , this more extensive data revelation is predicated upon the condition that the totality of recipient data following disclosure results in the recipient remaining within the obscurity threshold as prescribed by the original discloser as exemplified in the above example . once biosdi detects useful correlations between particular sets of data , it contacts those users who might benefit from the information . if they are interested in making use of the offered data , and agree to the terms of disclosure ( which determine the final form of the data that they will receive ), the system brokers an exchange . in short , the receivers get the data and the provider gets a payment . there are obviously many different ways that the price for this exchange could be determined and it is likely that a variety of modalities for the exchange which co - exist together ( or even could be used to create hybrid forms of payment for a given transaction ) would provide an overall advantage to the system : 1 ) swaps — if both parties own data that is potentially useful to the other , they can simply trade the data with each other . 2 ) fixed payment — the provider assigns a pre - determined price to the data before it is submitted to the system . the provider then receives this amount each time a user accesses the data . 3 ) value - based pricing — biosdi uses its proprietary knowledge of a potential purchaser in conjunction with statistical models to forecast the marginal benefit of a given piece of data . because biosdi serves as an impartial marketplace , it splits the surplus between the buyer and the seller . 4 ) auction - based pricing — in situations in which it is preferable for only one user to receive the data , biosdi serves as an electronic auction house : it alerts users of the data &# 39 ; s potential benefits , holds an auction , and sells the data to the highest bidder . the specific technical details explaining how an auction - based trading system is designed when the traded assets are clearly of a multi - dimensional nature ( as they are in the present application ) is disclosed in the ph . d . thesis , “ iterative combinatorial auctions ”, of david c . parkes of the computer information science department at the university of pennsylvania . bioshared data interchange would obviously offer to exchange data of various kinds which are important in the pharmaceutical and biotechnology industry community . the above example is one such kind . in the following we give a few examples of important classes of data which can easily be obscured enough to keep their proprietary value to the discloser . a ) structural and proteomics data : over the last three decades , the pharmaceutical and biotech industries have benefited greatly from advances made in x - ray crystallography , nmr techniques , mass spectrometry , and micro array techniques . advances in computational methods have particularly helped in areas where it has been difficult to obtain reliable results from experimental work . this is especially true in the fields of computational biochemistry and biology . in spite of the enormous success of these new techniques in generating useful data , there are significant number of areas where the biochemical data sharing could be advantageous to the pharmaceutical industry . sdi provides a framework under which such information could be safely shared . b ) interaction parameters : starting with the pioneer simulation of hard spheres , computer simulations of atoms and molecules have been important tools for almost four decades . they are now commonplace in the physical sciences , particularly in the fields of chemistry , biochemistry and biology . by simulating molecules of biological importance , scientists are able to study various biological reactions and predict various properties of individual biomolecules . because these studies are hard to conduct experimentally , the computer simulations are especially important . in spite of a history of scientific success , these methods are still marked by certain inherent problems . for example , the underlying database used to simulate the atomic - level interactions between participating atoms still needs improvement . because this set of interaction parameters is not entirely accurate , many of the molecular properties estimated by the simulations are not comparable to experimentally observed values . in this disclosure , we suggest that a secure data interchange could compare interaction parameters derived from a wide variety of different sources , combining them into more reliable estimates that could then be compared against experimentally derived values . c ) protein structures and prediction methods : in addition to direct molecular simulations , there are various other computational techniques popular among biochemists and biologists . the method for predicting the tertiary structure of proteins is such an example . homology modeling uses the primary sequence of proteins to predict their tertiary structures . neural networks are often used to accomplish this task . we suggest that if a large set of predictive methods and a large set of unpublished protein structures are shared in the interchange , it might lead to better predictive schemes as well as predicted structures for yet unsolved proteins . many institutions should be able to share the unpublished data on protein structures without fearing a loss of proprietary value . d ) drug binding : drug molecules bind to protein molecules ; however , some of them bind to dna as well . it is very important to understand the various aspects of this binding mechanism . one such aspect is the binding energy involved in the reaction of drug molecules to proteins . in this disclosure , we suggest that the secure data interchange provides a framework for storing and sharing data about drug molecules and the proteins they bind to . e ) mass spectrometric data : sharing mass spectrometric data obtained from various cell studies could assist in the determination of the secondary and tertiary structures of the hundreds of protein molecules involved in whole cells ( as opposed to individual protein structures , which are determined in the laboratory by x - ray crystallographic methods ). the thousands of pieces of information obtained from mass spectrometric methods applied to the cell components could be gathered at the shared data interchange , allowing more light to be shed on the regulatory functions of various proteins in the cells . more macro - level data modeling techniques and especially those which additionally choose to incorporate protein structure models could be particularly benefited by complementary share of these two types of data . in this type of model , integrating the presence of both types of parameters may often result in an overall enhancement ( mutually ) to all parameters of both types ( i . e ., secondary and tertiary structural and individual protein structural ) parameters . although the biosdi system framework addresses a significant need within the field of bio - informatics , there will be nonetheless from a practical implementation standpoint admitted imperfections which once successfully addressed over time through improvements could eventually provide much greater efficiencies of scale such as more dynamical and more complex querying in a completely automated fashion the distributed data sharing paradigm which could be achieved through such system refinements as a common data format ( among currently disparate heterogeneous data formats ), common semantic protocols ( as well as computer - mediated generation of the semantic representation of data created ). certainly the industry - wide agreement and associated acceptance of unified industry - wide common protocols relating to this presently proposed data sharing scheme would improve the efficiency and responsiveness of the system at a variety of levels in the data sharing process . biosdi may ( particularly in the interim ) in addition , achieve certain ( perhaps most ) of these objectives through the use of similarly functioning middleware software in order to mediate these data conversions for purposes of communications between sdi and its associated participating constituent data sharing entities . one particularly intriguing future emergent paradigm in the field of bioinformatics for which these common data exchange protocols if used in conjunction with sdi could prove most valuable is the integration of embedded systems technology into the actual in vitro ( and potentially even in vivo laboratory testing environments and associated data measurement and data collection instrumentation . significant gains could effectively be achieved at a variety of levels including much faster data collection recording and processing as well as a significantly greater quantity of data most of which is currently either uncollected or discarded by presently used methodologies . however , by contrast , within the biosdi framework the free flow of this data into biosdi could enable real time centralized monitoring and dynamic detection of any and all useful pieces of data within the scope and context of the present ( and continually updated ) “ needs criteria ” for the overall data collection and processing needs of biosdi in as much as it is able to be instead represented as such as a singular collective entity . dr . ed lazowska , department of computer science , university of washington , in his science forum lecture series describes and refers to current research initiatives within this area of embedded systems for use within biotechnology research , which is of noteworthy potential use and applicability to a biosdi common data protocol based framework . an additional value added benefit and opportunity which biosdi enables is the opportunity to act in a “ match making ” capacity whereby , for example , substantially large data sharing procedures occurring through sdi may also suggest that the human experts involved in the original creation of such data may potentially also share in common a potential need and thus opportunity to collaborate in a direct literal sense on active research endeavors which they mutually share in common . furthermore , if desired , such human experts may even wish to submit cvs of both present and past research activities and experience such that , subject to the proper conditions ( of pricing and data disclosure policies ), these additional professional profile based features may be further incorporated into the matching scheme in order to further improve the system &# 39 ; s performance accuracy and range of matchmaking opportunities , thus more readily harnessing the value of such mutual opportunities where ever or whenever they happen to exist among various disparate entities . the issued grandparent application ( u . s . pat . no . 5 , 754 , 938 ) as well as the parent application ( pending ) entitled “ secure data interchange ” explains in significant technical detail how such a “ match maker ” system is designed as well as the types of applications and autonomous communication functions it may be able to perform . although the presently disclosed preferred methodologies of the preferred embodiment ( constituting the system and methods for bioinformatics secured data exchange are potentially extremely important within the context of facilitating the speed , efficiency and cost savings of bioinformatics in its crucial role towards the growth of the biotechnology field as a whole , there are nonetheless other application domains for which very similar methodologies and conceptual objectives of the presently disclosed system could be readily and very advantageously adopted ( and which would be reasonably obvious to those skilled to the relevant particular domains to which the above methods could be adopted ). it can be appreciated that although the chemical structures and lengths of pathways may differ from that of the primary embodiment of biosdi as herein disclosed in detail , those skilled in the art within each of the various respective alternative fields of use could readily extend the methods used in the presently detailed bioinformatics exemplary application and the associated novel methods of biosdi for confidentially disclosing , detecting and selectively sharing that portion of the modeled data which does not threaten to compromise the proprietary nature of sensitive data portions of those data models . accordingly , it is abundantly clear to those skilled in the relevant parallel alternative fields of art that the presently proposed methodology is readily and reasonably extensible to these same parallel related fields without substantially departing from the novel and paradigmatically exemplified teachings of the presently disclosed primary embodiment of biosdi . some examples of these fields include : 1 . genomics and genetic engineering , 2 . biochemical ( as well as chemical ) engineering , ( including the related field of industrial enzymatics ), 3 . nanotechnology ( including nanomolecular engineering ), 4 . materials science 5 . general purpose research data sharing — although it is an extremely ambitious goal , within the framework of the presently discussed techniques for common data classification / metadata , data format and semantic protocol development and evolution as above suggested , as well as the development of middleware designed to achieve similar end objectives , it is certainly a reasonable goal to eventually develop a general purpose research application domain for sdi in which researchers within disparate laboratory environments could use sdi to find other potentially complimentary research data to that which they are currently working on and either automatically share that data within the data disclosure constraints of the prospective disclosers or to identify the existence of such complementary data and , in turn , notify the associated disclosers and recipients of these complementary assets and thus prompt a negotiation process between the prospective discloser and recipient based upon price offered by the recipient against the amount and detail of data provided by the associated discloser ( or such process with sufficient critical mass could be automated through the above suggested market based techniques used within biosdi ). certainly in order for these negotiations to be most efficiently performed , it is most useful to utilize the totality of data disclosed compared to data received of each entity into the exchange in order to arrive at a “ net balance ” of asset value which each entity is able to provide to the exchange in the form of “ credit ”. in addition , it is worthy to note that depending upon the degree of value which an entity which a particular data asset is worth to a given recipient , and if a portion of this value as determined by sdi is presently withheld in accordance with the disclosers data disclosure policy , this additional marginal value as it would exist relative to the prospective recipient could accordingly be appraised and estimated by sdi . based upon a detailed pricing policy provided by the prospective recipient beforehand most ( or all ) of the steps in the data exchange process including frequently matching , in addition to negotiation and transaction may occur in automated fashion . this negotiation process requires determination of the maximum price that the recipient would be willing to pay for data of a certain type . this pricing policy may be based upon such pricing policy criteria as such information regarding the particular pathway , receptor site and molecule ) data quality ( e . g ., soundness of the techniques used in the experimentation / modeling procedures ) and nature of the prospective recipient ( e . g ., is the recipient a present or possibly a potential competitor and if so , with relation to what specific type / domain of bioinformatics data . this information may be based upon biosdis privileged access to information about the specific activities and focused areas of effort of the prospective recipient ( e . g ., via explicit knowledge or as determined and estimated by the quantity of data actually produced and submitted to biosdi within each family of molecules receptors , pathways , etc ., and perhaps more indirect knowledge of the same as inferred indirectly from the specifics of pricing polices of the recipient for data disclosure and receipt . of additional relevance in many cases to the recipient is the value that that particular data provides relative to that particular recipient itself . the measurement of this parameter is a bit tricky , but could likely be modeled and predicted with some reasonable degree of reliability and accuracy ( e . g ., via a multi - dimensional predictive statistical model such as k - means clustering . for example , 100 % of the potential value to recipient is invariably based upon the relevancy of the very specific nature of the data relative to the collective commercial investment in research and development initiatives relating directly ( and indirectly ) to research objectives requiring the application of such data . what percentage of this overall potential value is realizable depends upon such variables ( possibly the product thereof ) as to what degree is the present data to be received relevant to such overall objectives and to what ( percentile ) degree does the addition of the present prospective data disclosure actually quantitatively constitute the overall potential value that this type of data is able to provide relative to the recipient . it is worthy to note that the quantity of pre - existing data specifically relevant to the particular item of specific interest ( e . g ., structure , pathway , etc .) reduces the marginal increased value to the overall “ data value ” of the system by approximately the inverse of the square of this quantity of pre - existing data ( assuming both new and existing data are of equal quality . in addition , the degree of “ remoteness ” of the portion of data to be disclosed to the primary objective item ( s ) of value / interest to the recipient also has an exponentially diminishing effect on the value of any such associated data as well ( which may be considered for “ sale ” to that recipient ). given all of the relevant parameters ( which may include but is in no way limited per se to those suggested above ) as indicated , it should be possible to reasonably predict the approximate value to a recipient that a given piece of data slated for prospective acquisition is likely to provide to recipient . thus it is possible to determine ( e . g ., automatically via biosdi ) an appropriate pricing policy that is adaptive to not only the needs of the recipient but also the context of the margin of value that a given piece of data is able to provide in addressing that specific need . as such with the resulting capability to manage and implement not only data disclosure polices , but also pricing polices for both prospective disclosers and recipients in automated fashion , biosdi is positioned to also perform automated negotiation procedures . the details of how such an automated negotiation process could be designed to function within the context of the present system ( using either a single intermediary , i . e ., biosdi or two separate intermediaries , i . e ., assigned representative agents of each of the negotiating entities ) are disclosed in detail in the parent ( pending patent application entitled “ secure data interchange ” and are generally well understood within the relevant field of art . dr . david croson and rachel croson ( professors at the wharton school , university of pennsylvania ) have also done a substantial amount of research work and publications in this general area of agent - based automated negotiations and intermediary - based negotiations . based upon a detailed pricing policy provided by the prospective recipient matched against additional data disclosure policy parameters which are “ negotiable ” subject to price by the prospective discloser , it may be possible for sdi to mediate further higher additional value based trades involving the revelation of data of a somewhat more explicit nature to potential beneficiaries than would otherwise occur without these additional qualifying criteria to the pricing policies of the discloser and recipient and the data disclosure policy of the discloser . as consistent with the general framework &# 39 ; s preferred implementation across its various potential domains , the prospective recipient could also be introduced to the prospective discloser , if desired provided that such an introduction is compatible with the prescribed data disclosure policy of the data discloser . the advantage of such introduction being more detailed exchange of data at a conceptual and creative level as well as identifying the potential mutually advantageous opportunities which may inherently exist between the parties for collaborative research . | 6 |
the present invention will now be described more fully hereinafter with reference to the accompanying drawings , in which preferred embodiments of the invention are shown . the present invention relates to a rear bumper protection device for a vehicle . the device is particularly suited for any size vehicle having a trunk located in the rear portion of the vehicle . the protective portion of the device is a base layer of hanging flexible material . the base layer can be of any desired size , preferably capable of covering the entire rear bumper of a vehicle . the base layer has a top portion , side portions , and a bottom portion , each of which portions are independently any desired shape or contour . the top portion of the base layer is the portion having a closer proximity to the trunk of the vehicle , whereas the bottom portion of the base layer is the portion having a closer proximity to the ground when the device is installed onto a vehicle . the base layer also has a front portion facing away from the vehicle and a back portion immediately adjacent to the vehicle . the size , shape , thickness , and construction of the base layer must be such as to provide protection to the rear portion of a vehicle . more particularly , the base protective layer is of a sufficient thickness and construction so that it can effectively protect the rear of the vehicle from scratches , dents , and marring caused by vehicle - to - vehicle contact , repair work , collision with an object , weathering , and the like . the base layer is to be distinguished from a sheet or tarpaulin , which are typically too thin to prevent damage due to impact , rubbing , scratching , or abrading . the base protective layer is preferably constructed of a flexible plastic or rubber composition . a polyvinylchloride ( pvc ) construction is particularly preferred . the base layer can be constructed of a single flexible material or a composite of different flexible materials . the thickness of the base protective layer required to make it effective at preventing damage is dependent on the composition and construction of the base layer . the thickness is adjusted according to the composition to make the base layer effective at protecting a vehicle . preferably , the protective layer is a flexible plastic or rubber composition with a minimum thickness of about 3 or 4 millimeters . more preferably , the base layer of such a composition has a minimum thickness of about 6 millimeters . in other embodiments , the base layer can have a minimum thickness of about 8 millimeters or 1 centimeter depending on the size of the vehicle and the type of damage to be prevented . additional padding may be permanently , semi - permanently or temporarily affixed to the back portion of the base protective layer . the bumper protection device contains one or more stabilizing blocks positioned on the top portion of the base layer of the hanging protective material . for most applications , the bumper protection device preferably contains a single stabilizing block . however , in some embodiments it can be preferred to use more than one stabilizing block . in a preferred embodiment , the stabilizing block is in the form of a protrusion or raised edge directed colinearly with or along a contour edge of the top portion of the base layer spanning from one side portion to another side portion of the base layer , and is of sufficient rigidity , thickness , width , and length to reduce curling of the rear bumper protective cover . the stabilizing block is particularly effective in reducing lateral curling or rolling , i . e ., curling , rolling , or flapping roughly parallel with the sides of the vehicle . for example , in one embodiment , a stabilizing block protrudes at least about 8 millimeters above the base layer and has a width of at least about 20 millimeters . in other embodiments , the stabilizing block protrudes at least about 10 , 12 , or 14 millimeters above the base layer and has a width of at least about 20 , 25 , or 30 millimeters . in a preferred embodiment , a stabilizing block protrudes at least about 8 millimeters above the base layer and has a width of at least about 25 millimeters . in one embodiment , the thickness , width , and length is each independently uniform throughout the stabilizing block . in another embodiment , the thickness , width , and length of the stabilizing block is independently variable in order to maximize an anti - curling or other beneficial effect . the stabilizing block can be flush with an upper edge of the top portion of the base layer , and / or flush with the side portions of the base layer . alternatively , there can be a spacing between the upper edge of the top portion of the base layer or the edges of the side portions with the stabilizing block . in a preferred embodiment , the stabilizing block is of the same material as the base layer and is formed of a continuous mold with the base layer . for example , the protective device can include a rubber base layer and rubber stabilizing block constructed from a single mold . alternatively , the stabilizing block can be of the same or a different material than the base layer and be bonded , affixed , or attached by any suitable means to the base layer . in one embodiment , the stabilizing block is uninterrupted by gaps . in another embodiment , the stabilizing block is interrupted by one or more gaps . preferably , a gap in the stabilizing block retains the base layer within the gap . however , the gap in the stabilizing block can also include a gap in the base layer . in particular embodiments , it may be advantageous to increase the thickness and decrease the width , or decrease the thickness and increase the width of the stabilizing block in order to optimize resistance to curling . one or more gaps may be included and positioned appropriately for a similar purpose . the bumper protective device requires the use of one or more securing means to attach the device to the rear portion of a vehicle . in one embodiment , the securing means are part of the final assembled device , while in another embodiment , the securing means are not part of the final assembled device . in either case , the securing means can be either permanently attached to the protective device , or alternatively , an attachable / detachable type of securing means . the securing means can be any securing means known in the art capable of attaching a rear bumper protective cover to a rear portion of a vehicle . the securing means attaches the protective device to any convenient portion of the rear portion of the vehicle so that the protective layer can fit over the rear bumper . for example , the securing means can be made to attach the protective device to a trunk element , door hinge , or wheel well . the securing means may also function by wrapping around some portion of the rear of the vehicle . some examples of suitable non - permanent securing means include latches , clamps , 10 straps , hooks , mechanical fasteners , fabric hook - and - loop fasteners ( e . g ., velcro ), and magnets , as well as elastic , metallic , or fabric bands , loops , or strings . the foregoing examples can also be modified to be permanent . some well - known suitable permanent securing means include use of screw - bolt fasteners , chemical bonding , or gluing . in a preferred embodiment , the securing means include one or more straps extending from the top portion of the bumper protective 15 device . the straps or extensions can be designed by a suitable thickness or with suitable promontories or apertures to render them fixed , wedged , or otherwise immobilized onto the rear of the vehicle when closing the trunk . for example , one or more extensions can include an aperture suitable for securing the device onto a trunk latch . in a preferred embodiment , the securing means is attached to a top portion of the bumper protective device . attachment of the securing means to the top portion of the device can allow for more facile securing of the device to a trunk element of the vehicle . for example , the securing means can attach to an edge or hinge of the trunk lid , or to any suitable edge , hinge , or protrusion inside or outside of the trunk . the bumper protective device may also be attached to a vehicle so as to protect a front bumper without departing from the inventive aspects of the invention disclosed . the invention will now be described by referring to fig1 and 2 . the bumper protective device is generally designated as numeral 1 . fig1 depicts a preferred embodiment of the bumper protective device 1 . a base layer of protective flexible material 2 is preferably attached to securing means 3 along its top portion . one or more stabilizing blocks 4 are attached to the upper portion of the base layer . each block can optionally include one or more gaps , as depicted by the dashed lines within 4 . the base layer can optionally be inscribed , recessed , or cut out according to any suitable shape 5 . the inscription , recess , or cut - out can be useful for holding an item of interest , such as , for example , a license plate or advertisement . the base layer can optionally also include any number of raised portions 6 having any suitable shape . the raised portions can be useful as , for example , locations onto which reflectors , advertisements , or adornments can be affixed . fig2 depicts the bumper protective device 1 installed onto the rear bumper 8 of a vehicle . as shown , the securing means 3 are preferably attached by any suitable means onto or into the trunk portion 7 of the vehicle . while the present invention is illustrated with particular embodiments , it is not intended that the scope of the invention be limited to the specific and preferred embodiments illustrated and described . | 1 |
the apparatus shown in fig1 comprises an electric motor driven fan assembly 10 having a motor housing 11 , a fan housing 12 and an end plate 13 which is formed with upwardly extending walls 14 defining a rectangular aperture which serves as an air inlet and across which is disposed a perforated plate 15 . a cable c for connection of the motor of the fan assembly 10 to a source of electric current ( not shown ) enters the motor housing 11 through an aperture provided for the purpose . two toggle switches 16 and 17 are mounted in apertures provided on the front of the motor housing 11 , switch 16 being provided for switching on and off of the electric motor and switch 17 being provided for switching on and off of a heater the purpose of which is mentioned below . a track 18 is secured to the rear of the motor housing 11 and extends vertically to a point some distance above the perforated plate 15 . a frame 19 is mounted by means ( not shown ) for vertical movement on the track 18 and means ( also not shown ) are provided to enable the frame 19 to be secured in fixed position of the track 18 . the frame 19 comprises an upper frame member 20 and a lower frame member 21 , the two being hinged together by conventional hinges ( not shown ) provided between opposing faces of each frame member 20 , 21 , at the left - hand side ( as viewed in fig1 ) of the frame 19 so that the two frame members can be parted by movement in the direction shown by the arrow a . two handles 22 and 23 are provided on the right - hand side ( as viewed in fig1 ) of the frame 19 to assist in parting the two frame members 20 and 21 . a conventional screw clamp 24 is provided on the front of the frame 19 to secure the two frame members together in use . a heater assembly 25 is secured to an upper part of the track 18 above the frame 19 . the heater assembly 25 is mounted so as to be vertically fixed but so as to be movable from side - to - side ( in the directions of the arrows b ) to enable easy access to the frame 19 . a knob 26 is provided on the front of the heater assembly 25 to assist in such side - to - side movement . the heater assembly 25 comprises a parallelepipedic housing 27 closed on its four sides and its top but open at its base 28 . housed in the housing 27 is an electrical resistance heating element ( not shown ) connected to a source of electrical current ( not shown ) through the switch 17 by means of electrical wiring concealed by the track 18 in the view shown . use of the apparatus just described for making a mould for use in making an ear insert will now be described . the frame 19 is moved to its lowest position on the frame 18 , in which position the track 19 is supported by the top of the fan assembly 10 , and the heater assembly 25 is moved to one side . using the handles 22 and 23 , after unfastening the clamp 24 , the two frame members 20 and 21 of the frame 19 are parted and a sheet of plastics film is placed on the upper surface of the lower frame member 21 . the two frame members 20 and 21 are then brought together and secured by means of the clamp 24 and the heater assembly is moved back to its previous position . an impression or a number of impressions are then placed on the upper surface of the perforated plate 15 of the fan assembly 25 , after raising the frame 19 to , and securing it at , a desired position a short distance below the heater assembly 25 . the heater assembly , supplied with current by earlier operation of the switch 17 , is then allowed to heat - soften the plastics film in the frame 19 . when softened to the desired degree , the motor of the fan assembly 10 is switched on and the frame 19 is lowered to its maximum extent on the track 18 in which position the lower frame member 21 is sealingly engaged over the air inlet 14 of the fan assembly 10 . the suction of the fan of the fan assembly causes the heat softened plastics film in the frame 19 to be drawn down over the impression ( s ) on the perforated plate 15 and to be deformed to their shape . when so deformed and the film has cooled , the frame 19 is raised , the heater assembly 25 moved to one side , the fan motor switched off , the frame 19 opened and the film removed from the frame 19 together with the impressions which are temporarily retained by the film . the impressions are then pressed out manually leaving cavities in the film which accurately reproduce the shape ( s ) of the impression ( s ). manufacture of an ear insert by a process according to the invention will now be described , by way of example only . an impression of the ear canal of a patient was formed by direct moulding in the patient &# 39 ; s ear using a proprietary rubbery material well - known for use for this purpose ( e . g . &# 34 ; panasil a &# 34 ;). four further identical impressions were taken from the same patient , the five impressions then being placed on the perforated plate 15 of the apparatus shown in the accompanying drawing . the heater assembly 25 of the apparatus was then switched on for 10 minutes . a sheet of polycarbonate resin ( 0 . 060 mm thick ) was then fixed in the frame member 21 and the sheet brought up to the pre - heated assembly 25 . after approximately 3 minutes , the polycarbonate sheet was sufficiently thermosoftened , sagging at its middle by an amount of approximately 1 . 25 cm . the frame 19 was then lowered onto the perforated plate 15 to bring the thermo - softened sheet into contact with the impressions . vacuum drawing resulted causing the sheet of plastics material to be drawn down tightly over the impressions accurately conforming to the shape of each . the frame and sheet were retained in this lowered position and the vacuum applied for a few seconds until the sheet of polycarbonate resin had set . the frame 19 was then raised , the deformed sheet was removed from the apparatus and each impression pressed out of the vacuum - formed sheet of polycarbonate resin to leave five mould cavities . one of the so - formed cavities was cut from the sheet to form a mould which was then filled with a self - curing acrylic resin , e . g . &# 34 ; duro &# 34 ; ( trade mark of eden vale laboratories ) self curing denture base acrylic material . a piece of wire which retained its shape when bent was then inserted into a tube . the wire and tube were then bent to conform to a desired configuration and were then inserted vertically into the resin until they reached the base of the cavity . a tubular plastics barb was then threaded onto the upper end of the wire so as to be partially embedded in the resin . the purpose of these measures is to provide in the finished insert a meatal passage ( when the wire or wire and tube are subsequently removed ) and a barb , connected to the passage , to the projecting end of which barb can be connected a tube for connection to the acoustic output of a hearing aid . the mould was then placed in a warm glycerine bath maintained at approximately body temperature and a suitable pressure , typically 3 . 5 kg / cm 2 ( gauge ), applied . the mould was left to cure in this condition for at least 5 minutes , e . g . 10 minutes , and then the cured acrylic resin material was manually removed from the mould . the resulting moulded insert was found to be highly polished and needed no trimming or further polishing on the surfaces which , in use , contact the ear . the flat surface not in contact with the polycarbonate sheet when insert is in the mould was polished by means conventional in the art . the ear insert was found to fit snugly in the patient &# 39 ; s ear and in use not to give rise to any acoustic feedback . it was also found that , to avoid any possible allergenic response from the patient , the patient &# 39 ; s ear could be protected from contact with the ear insert by first placing the ear insert back in one of the moulds produced by the suction - forming operation , and it was found that when used in this manner the ear insert was equally satisfactory , still providing a snug fit and resulting in no acoustic feedback . fig2 shows the completed insert . the earcontacting surface being uppermost , the meatal passage is indicated at 30 and the tubular barb at 31 . the aperture 32 is formed to reduce the overall weight of the insert and is normally formed by cutting - away a central part of the impression before it has been moulded . alternatively the aperture 32 may be cut out after the ear insert has been moulded , or a former can be placed in the mould cavity prior to moulding . in other embodiments of the invention the pressure deformable sheet of material may be deformed over the impression of the ear canal by the application of an over pressure instead of by the application of a suction . furthermore the ear insert could be drilled after moulding to provide the meatal passage or to enable tubing and / or a tubular barb to be glued into the drilled passage . however it should be realised that it is preferred to mould as opposed to drilling the meatal passage since the meatal passage can be moulded to change directions by gently curving the passage . if the meatal passage is drilled a change of direction can only be made by drilling bores from two different directions , the two drilled bores meeting at an angle . it will of course be appreciated that a gently curving meatal passage is preferred acoustically to an angled meatal passage . the suction generated by the electric motor driven fan assembly 10 for vacuum - drawing the pressure deformable sheet over the impressions could be generated instead by other means . for example if a straight main tube was provided having a branch tube extending at right angles to the main tube , sufficient suction could be generated at the outlet of the branch tube by running tap water through the main tube at a sufficient pressure , e . g . 3 kg / cm 2 ( gauge ). finally it should be realised that any form of insert may be moulded , e . g . solid , shell or skeleton . the insert may be moulded from different materials to have a soft tip or tips with the rest of the material moulded from harder material . alternatively the insert may be moulded completely from soft , semi - soft or semi - hard material . in addition the solidified moulding material may be retained in the mould cavity formed in the sheet material to act as a protective packaging or as a covering , e . g . a non - allergenic covering , in use of the insert . the dashed line in fig2 schematically indicates the sheet material , the insert being retained in the mould cavity formed in the sheet material . the small circles on the sheet in fig2 represent where the sheet material has been drawn into the perforations of the perforated plate 15 during application of the suction to draw the softened sheet material over the impression ( s ) on the plate 15 . although the invention has been described with reference to a particular embodiment thereof , it will be understood by those skilled in the art that various changes in the method and construction of the body insert may be made without departing from the spirit or the scope of the present invention . | 7 |
no fluid flow is ever perfectly homogenous . small variations in the flow are present that are being transported by the flow at the flow velocity . these small variations , such as localized changes in density , and the characteristics of light absorption and reflectivity , can be detected optically by passing light through the flowing medium and observing the changes in the light intensity . some prior art velocimeters have structure for creating disturbances , such as vortices , then they count vortices passing a reference point ; the number passing in a determined interval of time being indicative of the flow velocity . some instruments of the &# 34 ; time - of - flight &# 34 ; type utilize doppler shift techniques . the instrument disclosed herein is considered to be in the &# 34 ; time - of - flight &# 34 ; category however it functions by the spatial convolution of the light intensity pattern established by an artificially - introduced transfer function co - acting with the variations in the light intensity due to the nonhomogeneities which are transported by the flow medium . this convolution generates a new intensity response function which is periodic and whose base frequency is directly proportional to the flow velocity . fig1 is a pictorial view of a typical embodiment of the invention . in this particular operating embodiment , the flow channel 21 through which the flowing medium 22 is contained as it passes was approximately one square inch in cross section . the absolute dimensions of apparatus of this invention are not critical . those practicing the invention will understand from the following descriptions of embodiments the relative relationships of dimensions with respect to the output characteristics of the devices . in addition they will readily comprehend the light spectral and intensity requirements in connection with the sensitivities of the photodetection means employed and the light transmissibility and reflection characteristics of the medium from which the flow characteristics are being obtained . the output signal on line 23 from the electrical processor unit 24 is an alternating current signal whose frequency is proportional , and linearly related , to the velocity of the flow 22 . this frequency may be read out in a conventional electronic counter display unit 25 in cycles per second or the appropriate time base may be used so that the read - out is directly in feet per second of flow velocity . the counter may be set to up - count for a determined time interval and then down - count for the same time interval and display the difference , which is the change in velocity per unit of time , which is the acceleration of the flowing medium . this usage of electronic counters is conventional and well known . obviously , the frequency of the signal on line 23 may be displayed by instruments other than an electronic counter . any of the well known electrical frequency indicating devices may be used . acceleration characteristics may also be obtained by differentiating a dc analog voltage ( such as obtained from a discriminator circuit ) of the velocity by a conventional electronic differentiator . the details of such display units are well known and are not a part of this invention . the read - out display unit is , however , a component of the combination comprising the invention to provide a complete utilitarian system . this particular embodiment illustrated in fig1 has a heater element 26 which may be used to heat the flowing medium before the medium passes the optical part of the system . with normally very nearly perfectly homogenous flows heating the flow will accentuate the small nonhomogeneities present and decrease the sensitivity required of the optical system . it is to be observed that the system does not utilize turbulence , vortices , or any temperature gradients created by the heater . in the majority of flows , heating will not be required with optical and electronic systems of normal sensitivity . the heating of the flow is not critical , but may be desirable . both ac and dc currents have been used successfully . in the particular embodiment being illustrated and described a conventional nichrome wire heating element dissipating approximately 2 watts of electrical power at five volts 60 hz has proven very satisfactory . the conventional power source 27 supplies the energy requirements of the electronic processing unit 24 and the heater element 26 . a requirement of the optical system of the invention is that it includes an element to provide an artificially - introduced transfer function which intercepts the collimated light traversing the flowing medium . generally the preferred embodiments of the invention comprise a double - faced mirror providing this transfer function , and two photodetectors whose outputs are subtracted to provide a differential light detector system . the optical system of an embodiment having this structure is illustrated schematically in fig2 . a cross - section side view of the mechanical structure is shown in fig3 and an end view of the structure represented by fig3 is shown in fig4 . embodiments having a double - faced mirror are the most compact physically , and embodiments having two photodetectors differentially connected are much less susceptible to extraneous noise components ( from stray light , for example ), thus embodiments having these combinations of elements are generally preferred . referring to fig1 through 4 , the fluid flow 22 , which in a typical instance is the air through which an aircraft is passing , passes first over the heater element 26 which can be energized if necessary , such as might be desirable at high altitudes . generally it is preferable to have the heater element 26 positioned with respect to the rest of the apparatus as shown in fig1 and 4 . it may be placed at right angles to this position as the heater element 26 is shown in fig2 . configuration of the heating element is not critical . a light source 30 ( such as a type mled 910 is suitable ), provides the necessary illumination . the light must be collimated by a lens system 31 so that parallel rays of light 32 traverse the fluid flow 22 substantially at right angles to the direction of flow . in these generally preferred embodiments the lens system 31 simultaneously serves two functions , it collimates the light from the light source 30 into parallel rays , and then it refocuses the light returning from the double - faced mirror 33 onto the two photodetectors 34 and 35 . suitable photodetectors for use with the previously enumerated light source are type ls 400 phototransistors . ( type fpt 102 photodiodes with appropriate preamplifiers may be used .) a typical double - faced mirror may easily be constructed as shown in fig1 a , 13b , 14a , 14b , and 15 . two interdigitated strips of substantially totally reflecting surfaces , with the parallel reflective strips of one surface slightly angled to the parallel reflective strips of the other surface are required . in a typical embodiment the reflective elements are fabricated by conventionally depositing gold on conventional microscope slide glasses . with the previously enumerated light source and photodetectors , gold is the preferred reflecting material due to its spectral characteristics . with other light sources and photodetectors , other surface materials such as silver may be more appropriate to match the spectral characteristics of the particular light used . fig1 a is a front view of the front mirror having a set of parallel , planar , reflective gold strips 131 deposited on a glass microscope side . the equal parallel strips are equally spaced apart a distance equal to their width . fig1 b is a top or edge view of the glass microscope slide 132 showing the front deposited reflective strips 131 . the second set of parallel , planar , strips may be easily , effectively , formed by depositing a gold reflective surface 141 completely over the surface of a second mircoscope glass side 142 and positioning it behind the first slide as shown in fig1 . fig1 b is a top edge view of the coated slide as shown in the front view on fig1 a . any substantially flat transparent medium ( transparent to the light from the source 51 ) may be used in place of the front glass slide . obviously , the rear mirror surface need not be placed on a transparent medium . a thin wedge 151 is placed along one edge between the glass slides to provide an angle of separation 152 . a wedge sufficient to provide approximately 0 . 4 ° of angle has been found to be suitable for the particular embodiments being described in detail . the absolute value of the angle is not critical , only that the correct alignment with the other elements is required . the angle formed between the two reflective surfaces cooperates with the spacing between the photodetectors 34 and 35 , and the lens 31 , such that the light reflected from one surface of strips is brought to focus on one photodetector , by the lens system 31 and the light reflected from the other surface of strips is brought to focus by the lens 31 on the other photodetector . a thin , narrow , strip of gold foil provides a suitable wedge . conventional adhesive bonding of the foil to the microscope slides at the location shown in fig1 has been found satisfactory for maintaining the proper alignment . the foregoing description of a doubly - reflective mirror provides a simple , economical , satisfactory element . it is not required that it be fabricated in this exact form . the requirements of the doubly - reflective mirror are that a first set of a plurality of equally spaced planar reflective elements be interleaved with a second set of a plurality of equally spaced planar reflective elements such that the parallel perpendicular reflections from the first reflective elements make an angle with the parallel perpendicular reflections from the second , such that the reflections may be separately detected . in the operation of the doubly - reflective mirror in this invention , it is to be understood that the doubly - reflective mirror is positioned such that the collimated light rays impinging on the mirror are reflected back , with the angle of incidence equal to the angle of reflection and the angles of reflection are such that the light is brought to focus from one mirror set on one photodetector and the light from the other mirror set is focused on the other photodetector . ( the light rays neither strike or leave the mirror surfaces perpendicularly to the reflective surfaces .) generally , it is desirable to shield the photodetectors 34 and 35 from stray light rays from the light source 30 by positioning a light shield 40 around the light source as shown in fig3 and 4 . the frequency in hz of the output signal on line 23 may be expressed by the relationship f ≈ v / d , where v is the velocity of the flowing medium and d is spacing of the effective sampling period . in the typical embodiment being described the widths of the reflective strips were approximately 0 . 04 inch , which provides approximately 25 pulses per inch of flow travel . this provides a device having a typical calibration characteristic as shown in fig1 . thus in this typical embodiment the period d in feet per cycle is approximately 0 . 08 / 12 , and the velocity of the flowing medium may be expressed as v = hz ( 0 . 0066 ). for example , a 3 khz signal is indicative of approximately a 20 - feet per second flow velocity . fig5 shows schematically in cross section typical mechanical structure for embodiments of the invention using a single photodetector . in these embodiments the light flow is from the light source 51 through the collimating lens 52 , which forms the light into parallel rays 53 traversing the flowing medium 54 , and then through the artificially - introduced transfer function element 55 , then the light rays are focused by the lens 56 on the single photodetector 57 . the electronic processor unit for these embodiments is generally contained in the compartment 58 . the fundamental relationships previously stated for the earlier described embodiments generally apply except for the structure of the transfer function element 55 , and separate individual lens systems are used for the collimating lens and the focusing lens . the physical structures involved in the lens systems are not critical provided the functions of collimating and focusing are obtained . it is generally desirable to include a heater element 59 in these embodiments for the same reason as previously explained . these embodiments do not have a differential photodetecting system hence they are more susceptible to extraneous noise signals . a schematic diagram of a typical optical system for embodiments represented by fig5 is shown in fig6 . the collimating lens system 62 and the focusing lens system 66 are represented schematically as previously by simple lens elements . in this embodiment the artificially - introduced optical transfer function element 67 is a conventional ronchi grating . for embodiments using this structure and having the range of response characteristics that the earlier described embodiments have , the ronchi grating has equal opaque and transparent elements of approximately 0 . 04 inch widths . ( different widths would result in a different calibration .) instead of using a ronchi grating to provide the artificially - introduced transfer function an optical element with a determined variation in optical density may be used . fig7 shows schematically such an optical system . it is similar to the ronchi grating system shown in fig6 except the ronchi grating 67 is replaced with the optical element 77 as shown in fig7 . the requirement on this optical element is that it has a determined pattern in its light transmissibility characteristics that will provide a known light intensity response characteristic . this known light intensity response then is convoluted with the intensity response of the non - homogeneities in the flowing medium to provide a resultant response from which the electronic processor unit derives a signal whose base frequency is proportional to the flow velocity . typical examples of this optical element are variable density optical filters in which the variable density is in the form of a step function , a cosine function , and a pulse train function . the optical density cannot be a constant as a function of distance in the element along the direction of flow , but must have a known variation in density as a function of x , the distance along the element in the direction of flow . the artificially - introduced transfer function may also be generated by an array of photodetectors 87 , as shown schematically in fig8 having alternate detectors connected in parallel such that two signals , one signal on line 81 and one signal on line 82 , are provided to the differential amplifier 88 . the differential amplifier provides an output signal on line 83 to the electronic processor unit which is proportional to the instantaneous differences between the two signals . the signal on line 83 is the effective convolution response of the changes in light intensity due to the nonhomogeneities in the medium and the step function introduced by the detector array and differential amplifier system . element 89 merely represents a thin transparent wall section in the flow channel . a similar functioning embodiment may be provided as shown in fig9 . in these embodiments as represented by this figure fiber optic members 91 are interleaved , along the flow direction , with fiber optic members 92 . each set of fiber optics conduct light to a respective photodetector , i . e ., set 91 to photodetector 93 , and set 92 to photodetector 94 . the other ends of the fiber optic member are extended through the flow channel wall 95 and are flush with the inner wall surface to provide a smooth channel surface for the flowing medium . alternatively , wall member 95 may be a transparent member and the ends of the fiber optic members may be positioned adjacent the transparent wall . fig1 shows a representative block diagram illustrating in block form the major components of the invention . as previously indicated the collimator 101 and the focusing lens system 102 may be one structure providing both functions . the heater 103 , while generally not required for normal operation of the embodiments , is generally desirable for improved operation with some flows . heat may either or not be applied to the medium by activation of switch 104 . the display unit 105 as previously discussed may read either or both velocity and acceleration . fig1 is an electronic schematic diagram of a typical electronic processor unit , ( the light source and photodetectors are also shown for clarity ), that may be used with embodiments of the invention that operate in a differential detection mode . it is applicable to the embodiments illustrated in fig1 , 3 and 4 . it is also suitable for the embodiment illustrated in fig9 with the photodetectors 34 and 35 replaced by those represented at 93 and 94 in fig9 . the operation of the system may readily be understood from the schematic diagram . briefly , the phototransistors 34 and 35 are differentially connected to the conventional difference amplifier 111 . the difference signal from this amplifier is passed through the conventional high pass rc filter 112 to remove low frequency variations and noise from the signal . the conventional phase - lock - loop circuit 113 is used to present a clean uniform alternating current signal to the display unit . the use of a phase - lock - loop circuit is not mandatory but highly desirable . such circuits are well known and in wide usage . a type lm 208 module for amplifier 111 , and a type lm 565 module for the phase locked loop circuit 113 are typical and have proven generally suitable . fig1 is an electronic schematic diagram of a typical electronic processor unit ( included also is the light source and photodetector ) suitable for the embodiments illustrated in fig5 and 7 . by taking the signal on line 83 of the embodiment illustrated in fig8 and feeding it into the amplifier 121 instead of the circuits shown it may also be used with the embodiments illustrated by fig8 . as in the previous electronic schematic diagram , a type ls 400 phototransistor or a type fpt 102 photodiode with a conventional preamplifier may be used for the photodetector 122 . the amplifier 121 is a conventional amplifier . it may also be a type lm 208 as in the previous schematic diagram with the unused input grounded . the light source 123 is typically a type mled 910 light emitting diode . the filter circuit 112 and the phase locked loop circuit 113 are the same and provide the same function as in the previous schematic diagram . in embodiments of this invention the excitation current for the light source is not critical . generally , either ac or dc may be used . with embodiments having a differential mode of operation such as represented by the schematic diagram of fig1 . the frequency of the excitation for the light source is automatically removed from the output by the differential action of the electronic circuit . for the embodiments of the invention having a photodetector input as represented by the schematic diagram of fig1 it is preferable when an alternating current excitation voltage is used for the light source that the frequency of the excitation voltage be outside the normal operating range of output frequencies of the devices . thus for some low velocity embodiments it will be desirable to use a direct current source of excitation voltage for the light source of these embodiments . fig1 is a copy of an oscilloscope trace 161 of the signal on the output line from the electronic processor unit of a typical operating embodiment of the invention when the velocity of a flowing medium was being measured . fig1 shows the calibration response 171 of this same typical operating embodiment . | 6 |
the present application provides an atm communication network architecture which includes a network interface to multiplex and demultiplex composite information streams onto a single logical connection independent of the host processors connected to the network . fig2 illustrates an exemplary atm communication network 20 incorporating network interfaces 22 between atm switches 24 and a plurality of processors 26 , 28 , 30 and 32 . the atm switches are known in the art . an example of a suitable atm switch is the at & amp ; t univercell . processors 26 , 28 , 30 and 32 may be isochronous information processors , such as digital signal processors and video coders / decoders , or non - isochronous information processors , such as the intel x86 processor line running standard operation systems , such as microsoft windows ®. fig3 illustrates an expanded view of a single network interface connection to the atm based communication network shown in fig2 . in this configuration , there are four processors connected to the network interface 22 . two of the processors are non - isochronous data processors 34 and two are isochronous processors 36 . as shown in fig1 and described above , current atm network technology utilizes a host processor to initiate and manage communications between isochronous data processors connected to the network , as well as managing nonisochronous data communications by the host . utilization of the host processor for such network communication reduces the number of cpu cycles allotted to the host &# 39 ; s data application programs . the network interface of the present invention overcomes the drawback of current atm networks by relieving the host processor of the task of managing isochronous data communications . this is accomplished by connecting the host and isochronous processors to the network interface which then multiplexes and demultiplexes the communications over a single logical connection . referring to fig3 and 5 , the network interface 22 resides between atm switch 24 and the various processors 34 and 36 . the network interface 22 has a multiplexer portion 40 and a demultiplexer portion 42 . the multiplexer portion 40 preferably includes a cell multiplexer controller 48 and buffer memories 50 and 52 . preferably , cell multiplexer controller 48 utilizes a processor 60 , such as the intel model 960 microcontroller or equivalent processor circuitry having similar processing characteristics , and associated memory 62 for storing system and application programs . multiplexing communication circuitry 64 is coupled to the processor 60 to combine the nonisochronous data with the isochronous data and to transfer the data along a single logical connection via an atm based communication network , such as an atm based b - isdn network . such multiplexing communication circuitry is known in the art . fig6 illustrates an exemplary flow diagram for the multiplexing operation according to the present invention . prior to sending data on or receiving data from the atm network , a host processor at the sending end of the network creates a logical connection with the host processor at the receiving end . typically , when transferring data along a communication network , the network defines the parameters on how data is transferred , e . g ., the bandwidth and bit or baud rates . the atm based b - isdn network utilized with the present invention defines the bandwidth for data flow , that is , the network defines how many atm cells may be transferred per second so that the audio and video portions of the isochronous data stream remain synchronized . once the logical connection is established , the host processor is relieved of managing isochronous data flow and the isochronous processors can transmit data therebetween without host processor intervention using the network interface . the network interface 22 receives and stores the isochronous and nonisochronous data for subsequent multiplexing . numerous methods may be utilized to transfer data from the host or isochronous processors 34 and 36 to the network interface . for example , the network interface 22 may periodically poll each processor for data , or the processors could continue to send data to the network interface 22 until the interface transmits a buffer full interrupt to the processor . as data is loaded into the buffer memories 50 and 52 , the network interface 22 at the transmitting end interrogates the isochronous transmit data buffer 50 to determine if the buffer is either full or has reached a predetermined threshold ( steps 610 and 620 ). if the buffer 50 is full , the multiplexer controller 48 retrieves the isochronous data from the buffer and creates an atm cell ( step 630 ). techniques for creating an atm cell are known in the art . when creating the cell , multiplexer controller 48 incorporates cell header information including the channel identifier . the channel identifier is used by the receiving network interface 22 to transfer the payload of the atm cell to the appropriate host or isochronous data processor . once the cell is created the isochronous data can be transferred to the remote processor via the b - isdn network ( step 640 ). alternatively , timing or bandwidth constraints may require the isochronous data cell to be temporarily stored in memory and retrieved and transferred along the network at an appropriate interval . for example , if the bandwidth of the network permits the transfer of five cells per second and every fifth cell is reserved for the isochronous data cell , then the isochronous data cell may have to be stored in memory until the fifth cell is to be transferred along the network . continuing to refer to fig5 and 6 , if the isochronous data transmit buffer 50 is not full , multiplexer controller 48 retrieves nonisochronous data from frame segmentation buffer 52 and segments the data to create a nonisochronous data cell ( step 650 ). once the cell is created , it may be transferred along the atm based b - isdn network ( step 660 ). alternatively , as with isochronous data cells , the nonisochronous data cells may have to be temporarily stored and retrieved as network bandwidth requirements dictate . referring again to fig5 the demultiplexer portion 42 is constructed similar to the multiplexer portion and preferably includes a cell demultiplexer controller 54 which has a processor and associated memory for storing system and application programs , and buffer memories 56 and 58 . cell demultiplexer controller 54 preferably utilizes processor 60 and memory 62 . however , one skilled in the art will recognize that independent processing circuitry may be utilized for each controller 48 and 54 . cell demultiplexer controller 54 also includes demultiplexing communication circuitry 66 coupled to the processor . the communication circuitry 66 extracts the payload and header information from the isochronous and nonisochronous atm cells received from the atm based b - isdn network . as noted , the header information includes the channel identifier . communications received from the b - isdn network are directed to the appropriate isochronous or non - isochronous data processors utilizing the channel identifier . typically , upon creation of the logical connection , a cross - reference table relating to the channel identifier and associated processor is generated by the host processor establishing the virtual channel . the table is stored in memory 62 of the corresponding network interface 22 . once the destination of the isochronous or nonisochronous data is ascertained by the network interface , the data may be transferred to the appropriate processor 34 or 36 using , for example , standard communication backplanes . a suitable backplane configuration is a peripheral component interconnect ( pci ) bus 44 and shared pci bridge 46 , shown in fig5 . fig7 illustrates an exemplary flow diagram for the demultiplexing operation according to the present invention . as noted above , before any communications between processors can occur , a logical connection must be created . data is received from the atm based b - isdn network by the demultiplexer controller 54 which demultiplexes the incoming stream of atm cells , by extracting payload and header information from each cell ( step 710 ). the controller determines which processor 34 or 36 is designated to receive the data using the channel identifier . if the data is isochronous , the controller directs the data to the isochronous data receive buffer 56 ( steps 730 and 740 ). if the data is nonisochronous , the controller directs the data to the frame reassembly buffer 58 ( steps 730 and 750 ). once the data is transferred to the appropriate buffer , the data is then transferred to the appropriate processor ( step 760 or 770 ). numerous methods may be implemented to transfer the data within the buffer to the appropriate processor . for example , the individual processors 34 and 36 may periodically poll the network interface 22 for buffer data designated for that particular processor . however , other known communication techniques may be utilized to transfer the data to the appropriate processor . what has been described is merely illustrative of the application of the principles of the present invention . other arrangements and methods can be implemented by those skilled in the art without departing from the spirit and scope of the present invention . | 7 |
while this invention is susceptible of embodiments in many different forms , there is shown in the drawings and will herein be described in detail preferred embodiments of the invention with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the broad aspect of the invention to the embodiments illustrated . the present invention and the embodiments described and disclosed within this document , propose to solve the same problems relating to yard waste handling and containment as addressed by the prior art . however , this is accomplished by reinventing the actual bag and handling system verses adding attachments or peripherals to a poorly designed standard yard waste bag . the present invention allows a sole individual to collect or rake leaves and other lawn waste into a novel , reconfigured and conducive to be laid ( horizontally ) on the ground , yard waste bag . this is accomplished by two main features . the first feature or component is the combination lid and raking ramp 1 . the ramp / lid 1 runs the length and parallel to the long side of a traditional shaped yard waste bag , again when in the horizontal position and on the ground , where this bag / container is designed to remain until it is filled completely and ready to be moved to a desired location . the second main feature is the location of the bag / opening 2 . the opening / lid 2 is on the container top and extending the length or a large portion of the upper most horizontal surface parallel to the ramp 1 . this ramp 1 to bag opening 2 configuration allows a sole individual to rake , broom or shovel the desired waste material up and into the four sided bag or box containment area 3 . since the container opening 2 is on the top , not the side , as the debris is added to the container via the ramp 1 or by hand , it may easily be arranged and compacted as the filling process continues . the compacting procedure is simply achieved by stepping down with one &# 39 ; s foot and body weight to compress the leaves , twigs , brush , etc ., once again until the bag / container is filled to its capacity . furthermore , the large opening 2 and access to the containment area allows longer debris such as branches , stalks , etc . to be efficiently loaded and compacted . in one embodiment , after the bag / container is filled , the ramp 1 is collapsed and flipped up 4 ( see fig1 - 3 ) along its living hinged side to now become the lid / top and a means for neatly sealing the bag / container &# 39 ; s contents in and the potential adverse weather conditions out . adverse weather such as wind blowing the loaded debris around or more importantly rain , which could saturate the bag material , along with its contents . this scenario would add significantly more weight , along with the chance of the bag / container falling apart or decomposing before its desired time . additionally , a half filled bag could be closed and stored for further filling at a later date . the lid / top would be secured in its closed position by a number of methods , all commonly known . examples of temporary and permanent sealing methods would be : flaps that fold and tuck into a slit opening 11 as illustrated in fig6 , slits 14 , 15 as illustrated in fig7 , or behind a paper strap as double stick tape or opposing bent surfaces . once the bag / container is filled and the lid / top / cover is closed , carrying handles 5 are now exposed and ready for use . as per the preferred embodiment , these carrying handles would be constructed of the same material as found on a common paper grocery bag , whereas the paper material is doubled up for added strength or they may be constructed of a biodegradable twine or the like . furthermore , the two handles 5 could be joined together and held that way by the addition of a section of tape or a community yard waste sticker 12 , which are sometimes required . when filled , a typical yard waste bag is awkward to handle or carry . the addition of handles 5 would be extremely useful not only to the homeowner while filling the bag , but also to the yard waste hauler when depositing the filled bags into the truck or vehicle . the bag / container itself would be constructed of common to the industry materials used for a typical yard waste bag to compost scenario . the most common being doubled up grocery bag weight paper , but not limited to . in order to add strength and rigidity to the bag / container &# 39 ; s structure , a small amount of very light weight biodegradable cardboard may be required in some key structure locations . the objective would be to construct the most economical yet effective bag / container for this type of recycling application . another embodiment shows a ramp 6 as a separate structure from the containment bag . this application may be desired for a number of reasons . one being if the cost of manufacturing the combination lid and ramp became cost prohibited as a recyclable product . in this case , the ramp 6 alone would be constructed of either a sturdy weather - resistant cardboard or some form of plastic etc ., whereas the recyclable bag with lid would be situated next to the more “ permanent product ” ramp . the ramp 6 would obviously be used repeatedly as intended for this particular application . the ramp 6 would certainly fold and collapse for convenient storage . additionally , when used alone with the disposable lid / ramp , the added ramp 6 would add rigidity to the bag attached lid / ramp , also providing a space for one &# 39 ; s foot to help stabilize the bag while the containment area is being loaded ( see fig8 ). another embodiment , fig5 , shows a traditional shaped yard waste bag with its typically located opening at one end or short side of the elongated bag . the integrated chute / ramp / lid 8 is novel in that it would also be made of the same biodegradable material as the bag itself and would be manufactured along with each bag . as per the drawing , chute / ramp / lid 8 would fold out and open to form a slight ramp with a curb 9 for debris containment . when the desired waste material was swept in and the bag stood up , the ramp 8 would fold up and collapse to form a bag lid or cover , ready for disposal ( see fig7 ). furthermore , the embodiment shows a permanently attached biodegradable handle 5 constructed as previously described in another embodiment , only located differently . one of ordinary skill in the art would appreciate that the terms “ first ,” “ second ,” “ upper ,” “ lower ,” etc . are used for illustrative purposes only and are not intended to limit the embodiments in any way . the term “ plurality ” as used herein is intended to indicate any number greater than one , either disjunctively or conjunctively as necessary , up to an infinite number . the terms “ joined ” and / or “ connected ” as used herein are intended to put or bring two elements together so as to form a unit , and any number of elements , devices , fasteners , etc . may be provided between the joined or connected elements unless otherwise specified by the use of the term “ directly ” and / or supported by the drawings . while the specific embodiments have been illustrated and described , numerous modifications come to mind without significantly departing from the spirit of the invention , and the scope of protection is only limited by the scope of the accompanying claims . while some of the prior art may contain some similarities relating to the present invention , none of them teach , suggest or include all of the advantages and unique features as the invention disclosed within this document . | 1 |
referring to fig1 , a side view of a first preferred embodiment of the wheel with flexible spokes of the present invention is shown and generally designated 100 . in fig1 , the side of wheel 100 facing the viewer can be referred to as the right side of the wheel 100 . the side of wheel 100 opposite the right side can be referred to as the left side of the wheel 100 . the wheel 100 has a wheel axis 104 , and a rim 110 which has an inner perimeter 112 and an outer perimeter 114 . still referring to fig1 , with reference to fig3 , distributed symmetrically along inner perimeter 112 are spoke holes 120 . each spoke hole 120 has a spoke hole width 122 . along the outer perimeter 114 are nipple access holes 124 ( not visible in fig1 ), one nipple access hole 124 adjacent each spoke hole 120 . wheel 100 further includes a hub 130 having a right flange 132 and a left flange 134 ( not visible , behind right flange 132 ). each flange 132 and 134 has an inner surface 136 and an outer surface 138 . in each flange 132 and 134 are flange holes 140 , each flange hole 140 corresponding to a unique spoke hole 120 . each flange hole 140 has an inner opening 142 in the corresponding inner surface 136 , and an outer opening 144 in the corresponding outer surface 138 . hub 130 also has a barrel 148 which receives an axle of a bicycle . wheel 100 further includes non - rigid spoke members , or spokes 150 . each spoke 150 has non - rigid fibers 152 ( not visible this figure ) covered by a jacket 154 having an inner diameter 156 ( not visible ) and an outer diameter 158 which is also the width 158 of spoke 150 . each spoke 150 has a length 160 . fibers 152 are substantially continuous along the length 160 of spoke 150 . alternatively , one or more of fibers 152 may be less than continuous along the length of spoke 150 . each spoke 150 has an inner end 162 adjacent hub 130 , and an outer end 164 adjacent rim 110 . each spoke 150 has a tube 170 about its outer end 164 , and each tube 170 is formed with a tapered bore 171 opening away from the midpoint of the spoke . each tube 170 is affixed to its corresponding outer end 164 by inserting the fibers into the tube , and filling the tube with epoxy 175 . once hardened , the epoxy 175 and fibers 152 form a wedge within the tapered bore 171 such that any tension on the spoke draws the hardened wedge against the taper thereby securing the fiber within the tube . alternatively , tube 170 may be affixed to outer end 164 by any other material of similar strength . tube 170 may be equipped with a hexagonal , reinforced head 165 which provides for added strength at the hub - end of the tube 170 . this is helpful in preventing breakage for a non - axial tension on spoke 150 , and facilitates the tightening of spoke 150 . each tube 170 has a tube axis 172 and external spoke threads 174 . each spoke 150 also has an anchor ( or eyelet or ferrule ) 180 about its inner end 162 . each anchor 180 is formed with a tapered bore 181 opening away from the midpoint of the spoke . each anchor 180 is affixed to its corresponding inner end 162 by inserting the fibers into the anchor , and filling the tapered bore 181 with epoxy 163 . once hardened , the epoxy and fibers form a wedge within the tapered bore 181 formed in the anchor 180 such that any tension on the spoke draws the hardened wedge against the taper thereby securing the fiber 150 within the anchor 180 . alternatively , anchor 180 may be affixed to inner end 162 by any other material of similar strength . each flange hole 140 is wider than spoke 150 but narrower than anchor 180 , such that tube 170 about outer end 164 can be passed into inner opening 142 and out of outer opening 144 , and such that the rest of spoke 150 can then be passed through flange hole 140 until anchor 180 comes into contact with inner surface 136 around inner opening 142 , which causes inner end 162 to be retained in flange hole 140 by anchor 180 . wheel 100 also includes nipples 190 . one nipple 190 is shown in fig1 in broken line , inside rim 110 . there is a nipple 190 between each spoke hole 120 and its corresponding nipple access hole 124 . each nipple 190 has a nipple opening 192 , nipple threads 194 inside nipple opening 192 , a collar 196 , and a nipple head 198 . once each spoke 150 is passed through flange hole 140 until anchor 180 comes into contact with inner surface 136 around inner opening 142 , tube 170 is positioned and threaded into the corresponding nipple 190 via inter - engagement of spoke threads 174 with nipple threads 194 . this causes tube 170 to be retained in nipple 190 such that tube axis 172 is perpendicular to wheel axis 104 ( shown in fig1 ). the retention of tube 170 in nipple 190 , and of inner end 162 in flange hole 140 by anchor 180 , causes spoke 150 to be held taut between rim 110 and hub 130 . fig1 shows eight ( 8 ) spokes 150 attached to right flange 132 , and eight ( 8 ) spokes 150 attached to left flange 134 ( not visible , behind right flange 132 ), for a total of sixteen ( 16 ) spokes 150 . wheel 100 may alternatively have more or fewer than sixteen ( 16 ) spokes 150 . for example , wheel 100 may have twelve ( 12 ) spokes 150 , six ( 6 ) spokes 150 attached to each of flanges 132 and 134 . while it is also possible to have different numbers of spokes 150 attached to each of flanges 132 and 134 , having the same number of spokes attached to each of flanges 132 and 134 balances the load on the flanges 132 and 134 . fig2 is a rear view of hub 130 . fig2 shows the angle that one of the spokes 150 is attached to right flange 132 , and the angle that one of the spokes 150 is attached to left flange 134 . in fig2 , the right side of wheel 100 is on the right side of fig2 , and the left side of wheel 100 is on the left side of fig2 . broken line 230 in fig2 represents a plane 230 that bisects wheel 100 between the right side and left side of wheel 100 . plane 230 is perpendicular to wheel axis 104 . each outer surface 138 has the shape of a conical section that has an angle 240 to wheel axis 104 . each spoke 150 extends perpendicularly from the corresponding outer surface 138 . therefore , each spoke 150 extends from outer surface 138 at an angle 250 to plane 230 . this means that the magnitude of angle 260 between spoke 150 attached to right flange 132 and spoke 150 attached to left flange 134 , is twice the magnitude of angle 250 . fig3 shows a partial cross - sectional detail view of a spoke 150 with its inner end 162 retained in flange hole 140 by anchor 180 , and tube 170 about to be received in nipple 190 in rim 110 . fig3 shows how nipple 190 is retained in spoke hole 120 . spoke hole width 122 allows the portion of nipple 190 around nipple opening 192 to pass through spoke hole 120 , but does not allow collar 196 to pass through spoke hole 120 , such that nipple is retained in spoke hole 120 by the tension of spoke 150 on nipple 190 once tube 170 is threaded into nipple 190 . fig3 also shows spoke threads 174 which inter - engage with nipple threads 194 to thread tube 170 into nipple 190 . with tube 170 retained in nipple 190 , tube axis 172 is perpendicular to wheel axis 104 ( not shown ) and intersects the corresponding spoke hole 120 . spoke holes 120 lie in plane 230 . while spoke holes 120 may alternatively be adjacent plane 230 , spoke holes 120 being in plane 230 causes the forces of spokes 150 to be placed on rim 110 where plane 230 intersects rim 110 , which is the middle of the inner perimeter 112 of rim 110 . with spoke holes 120 in plane 230 , and each tube 170 received in the corresponding nipple 190 , tube axis 172 also lies in plane 230 . in fig3 , tube axis 172 coincides with the broken line representing plane 230 . however , because each spoke 150 extends at angle 250 to plane 230 , each spoke 150 extends from its tube 170 at angle 250 to tube axis 172 . this means that there is a bend in spoke 150 at an angle 250 at the point 320 where spoke 150 protrudes from tube 170 . with steel spokes , such a bend would weaken the spoke and ultimately cause the spoke to fail . however , with spokes 150 , such a bend does not damage spokes 150 , because fibers 152 are flexible and resilient yet strong such that spokes 150 retain their integrity and strength even when bent under tension in the manner described . therefore , spokes 150 can bend without weakening or failing . furthermore , each of spokes 150 is three times as strong , and weighs half as much , as a steel spoke that would otherwise be used in its place . this allows the width 153 of each of spokes 150 to be greater than that of a steel spoke that would be used in its place . in the alternative , the width 158 of each spoke 150 may be less than or equal to the width of a steel spoke that would be used in its place ; the strength of each of spokes 150 may be greater or less than three times that of a steel spoke that would be used in its place ; and the weight of each of spokes 150 may be greater or less than half that of a steel spoke that would be used in its place . rim 110 , hub 130 , tube 170 , anchor 180 and nipple 190 , in a preferred embodiment , are made of aluminum . alternatively , any of rim 110 , hub 130 , tube 170 , anchor 180 or nipple 190 may be made of any other material of comparable strength . in a preferred embodiment of the present invention , fibers 152 are a bundle of thermotropic liquid crystal fibers that exhibit high strength , low creep , and weather resistance . for instance , the fibers could be a peso fiber such as zylon ®, a strong yet lightweight fiber , available from toyobo . alternatively , fibers 152 may be made of any other material having comparable weight and strength . jacket 154 is made of rilsan ®, a high - performance polyamide . alternatively , jacket 154 may be made of any other material having comparable weight and strength . each nipple access hole 124 allows access to nipple head 198 so that it can be turned to facilitate the threading of nipple 190 onto tube 170 . for instance , a hexagonal head nut - driver may be positioned over nipple 190 and rotated to tighten spoke 150 in place . fig4 shows a cross - sectional detail view of the inside of a spoke 150 , showing the fibers 152 , and inner diameter 156 of jacket 154 . fibers 152 are gathered in forty - four ( 44 ) bundles 410 of nine - hundred ninety - six ( 996 ) filaments each bundle , for a total of 43 , 824 filaments in spoke 150 . this great number of filaments is one factor contributing to the great strength of spoke 150 , while minimizing the weight of spoke 150 . spoke 150 has a breaking strength of 3 , 600 pounds . alternatively , the number of bundles 410 may be greater or less than 44 ; the number of filaments in each bundle 410 may be greater or less than 996 ; and the breaking strength of spoke 150 may be greater or less than 3 , 600 pounds . referring to fig5 , a cross - sectional view of the first preferred embodiment of the wheel with flexible spokes of the present invention showing cross - sectional portions of the rim and hub is shown . as can be appreciated from fig5 , the width of rim 110 is just slightly wider than the width of nipple 190 . as a result , it is necessary that the nipple be aligned so that the tube extends radically inward from rim 110 . because of this positioning , it is important that spoke 150 be flexible as it leaves tube 190 so as to accommodate angle 250 without any decrease in strength and durability . due to the number of fiber strands contained within spoke 150 , there is no noticeable decrease in strength despite the off - axis tension . when tension is applied to spoke 150 , collar 196 strikes the inside surface of rim 110 and maintains the nipple , and corresponding sleeve , in its perpendicular arrangement . referring now to fig6 through 9 , a number of alternative embodiments of the wheel with high strength flexible spokes of the present invention are shown and include variations on the nipple and rim . referring initially to fig6 , the wheel with high strength flexible spokes of the present invention is shown and includes a shortened nipple generally designated 450 . shortened nipple 450 is sized to be fully received within the rim 110 . nipple 450 includes a nipple head 452 and a collar 460 sized to rest against the interior of the rim 110 and allow nipple opening 456 to pass through spoke hole 120 . shortened nipple 450 is formed with a threaded bore 454 passing longitudinally along axis 172 from nipple opening 456 . threaded bore 454 is sized to threadably receive head tube 170 . shortened nipple 450 is formed with a keyway 462 to receive a key when secured during assembly of the wheel . more specifically , nipple head 452 is formed with a pattern of keyways 462 to receive a correspondingly shaped key to maintain the rotational position of nipple 450 along axis 172 during the installation of spoke 150 . by inserting a key into keyways 462 , the nipple 450 may be held in place while head tube is rotated such that head tube threads 174 enter nipple 450 . as shown in fig6 , spoke 150 may extend away from axis 172 by an angle 250 as described in conjunction with alternative embodiments . referring now to fig7 , a cross - sectional view of an alternative embodiment of the wheel with high strength flexible spokes of the present invention is equipped with a shouldered nipple generally designated 480 . shouldered nipple 480 includes an insert 482 having a diameter 484 which is slightly less than the diameter of spoke hole 120 of rim 110 . shoulder 484 is larger in diameter than insert diameter 484 such that the insert shoulder 484 rests on the inside surface of rim 110 . shouldered nipple 480 is formed with a threaded bore 488 which passes from nipple opening 483 through to nipple head 486 , and includes threads 492 matching threads 174 . threaded bore 488 is sized to threadably receive threads 174 on tube head 170 during the assembly of the wheel with high strength flexible spokes of the present invention . from fig7 it can been seen that shoulder 484 is rounded and corresponds with a mating surface 494 on rim 110 such that the axis 172 of nipple 480 may vary slightly within rim 110 . specifically , the mating surface 494 allows the shouldered nipple 480 to pivot slightly within the rim 110 to accommodate slight angular adjustments within the rim , such that the spoke 150 can extend away at an angle 250 from the nipple 480 and rim 110 . a number of keyways 490 are formed in nipple head 486 such that a corresponding key ( not shown ) can be inserted into keyways 490 to maintain the rotational position of nipple 480 during the threading of tube head 170 into threaded bore 488 , and when tightening the spoke 150 using hexagonal head 165 . also , nipple 480 is sized to be fully received within access hole 124 in rim 100 . referring now to fig8 and 9 , cross - sectional views of an alternative embodiment of wheel with high strength flexible spokes of the present invention showing cross - sectional portions of the rim and hub , and showing a spherical , or rounded , nipple generally designated 500 . rounded nipple 500 is formed with a spherical or near spherical body 502 having a bore 506 along axis 172 and formed with threads 504 from inlet 506 through end 510 . rim 110 is formed with nipple seat 508 that is shaped to receive rounded nipple 500 to retain nipple 500 in position along axis 172 of rim 100 . fig9 depicts the insertion of a spoke 150 into rounded nipple 500 by threadably rotating spoke 150 along axis 518 and advancing the spoke 150 in direction 514 . rounded nipple 500 is formed with a number of keyways 512 sized to receive a key , such as the key 550 shown in fig1 , having a handle 552 and a shaft 554 leading to a head 556 formed with keys 558 positioned and sized to correspond to keyways 512 on rounded nipple 500 . it is to be appreciated that the number , size , positioning of the keys 558 may vary to accommodate keyway size , shapes , and patterns of nipples described herein . head 556 of key 550 is formed to have a diameter 560 that is less than the diameter of access hole 124 . accordingly , key 550 can be inserted into rim 110 during the wheel assembly process to engage keys 558 into keyways 512 to maintain the rotational position of rounded nipple 500 as head tube 170 is threaded into nipple 500 . also from fig9 , the rotation of rounded nipple 500 within rim 110 is shown . rounded nipple 500 rotates within the rim 110 to accommodate the angular positioning of a spoke 150 extending away from the rim 110 with lithe or no angular change with the tube head and spoke . specifically , rounded nipple 500 rests against nipple seats 508 and can rotate about a center of rotation 522 such that the axis 518 of tube head 174 can move within range 520 . this range 520 allows the spoke 150 to maintain a relatively straight line between tube head 174 and anchor 180 of hub 130 . this straightness along axis 518 provides additional strength as all fibers 152 within spoke 150 are stressed similarly along the longitudinal axis of the spoke . referring now to fig1 , an exemplary embodiment of a key tool for tightening the high strength flexible spokes of the present invention is shown and generally designated 550 . key tool 550 includes a handle 552 having a shaft 554 leading to a head 556 formed with a number of keys 558 sized and positioned to cooperatively engage the keyways on nipples of the present invention . the diameter 560 of head 556 is intended to be sized to be insertable through the access hole 124 in the rim 110 as disclosed herein to engage the nipples described to facilitate the high strength flexible spokes of the present invention . it is to be appreciated that the key tool 550 is shown in fig1 to have four keys 558 which , in a preferred embodiment , correspond to the inserts shown to have four keyways . it is to be appreciated further , that the number , size and positioning of keys 558 can vary to accommodate a nipple formed with different configurations of keyways . while the wheel with high strength flexible spokes of the present invention as herein shown and disclosed in detail is fully capable of obtaining the objects and providing the advantages herein before stated , it is to be understood that it is merely illustrative of preferred and alternative embodiments of the invention and that no limitations are intended to the details of construction or design herein shown other than as described in the appended claims . | 1 |
according to the first aspect of the present invention , successive bits of data which are to be encoded are cyclically divided into a plurality of groups , and the data in the plurality of groups are input in a plurality of shift registers , respectively . each of the plurality of shift registers simultaneously supplies a part of the m bits of the input to the encoder , synchronizing with the second clock . the above n bits of the output of the encoder is received in parallel in another shift register , and are serially output from the shift register , synchronizing with the first clock . since the m bits of the input to the encoder are supplied from the plurality of shift registers in parallel , the frequency of the clock controlling the operation for supplying the input to the encoder , may be lowered due to the plurality . in addition , since the circuitry in the input side of the encoder can be operated at a low frequency , the cost for constructing the circuitry and the power consumption in operating the construction can be reduced . according to the second aspect of the present invention , successive bits of coded data which are to be decoded are serially input into a serial input circuit synchronizing with the first clock , and the n bits of the input to the decoder are supplied in parallel from the serial input circuit to the decoder . the m bits of the output of the decoder are cyclically divided into a plurality ( r ) of shift registers synchronizing with the second clock , and the original data is obtained in parallel from the plurality of shift registers . since the m bits of the input to the encoder are supplied from the plurality of shift registers in parallel , the frequency of the clock controlling the operation for supplying the input to the encoder , may be lowered due to the plurality . in addition , since the circuitry in the output side of the decoder can be operated with a low frequency , the cost for constructing the circuitry and the power consumption in operating the construction can be reduced . further , both the provisions of the first and second aspects of the present invention are included in the third aspect of the present invention . thus , a high transfer speed is realized in inputting data to be encoded / decoded and outputting encoded / decoded data using a variable frequency oscillator generating a system clock having a low frequency , and therefore , circuitry including the variable frequency oscillator , can be constructed with a low cost , can be operated with a small power consumption , and is stable without complex construction . fig7 shows the construction of an encoding circuit which is used for the first and second embodiments of the present invention . in fig7 reference numeral 40 denotes a clock generator , 41 denotes a variable frequency oscillator , 42 denotes a 1 / 3 frequency divider , 43 and 44 each denote a data buffer , 45 and 46 each denote a shift register , 47 denotes an encoder , 48 denotes a coding table , and 49 denotes a shift register . the variable frequency oscillator 41 generates a coded data shift clock clk1 having a frequency of 54 mhz , and the 1 / 3 frequency divider generates a two - bit shift clock clk2 having a frequency of 18 mhz by dividing the frequency of the coded data shift clock clk1 . fig8 shows timing of the clock signals clk1 and clk2 of 54 mhz and 18 mhz which are generated in the clock generator 40 in fig7 . each of even - numbered bytes of data which is to be written in the rotating disc medium is held in the data buffer 44 , and each of odd - numbered bytes of data which is to be written in the rotating disc medium is held in the data buffer 43 . the outputs of the data buffers 43 and 44 are applied to the shift registers 45 and 46 . the shift registers 45 and 46 each contains eight bits . the connection between the output bits of the buffer registers 43 and 44 and the input bits of the shift registers 45 and 46 in the construction of fig7 are shown in fig9 . in fig9 the output bits of the buffer register 43 are numbered as 15 to 08 from the most significant bit to the least significant bit , and the output bits of the buffer register 44 are numbered as 07 to 00 from the most significant bit to the least significant bit . as shown in fig9 all the even - numbered bits of data which is held in the data buffers 43 and 44 are applied to the shift register 45 , and all the odd - numbered bits of data which is held in the data buffers 43 and 44 are applied to the shift register 46 . the data bits which are applied to the shift registers 45 and 46 , are loaded in parallel in the shift registers 45 and 46 at the timing of the multiplexer control signal ( parallel load signal ). the multiplexer control signal ( parallel load signal ) has a frequency of 2 . 25 mhz ( 1 / 8 of 18 mhz ). the content of each bit of the shift registers 45 and 46 is shifted by one bit in the direction from the most significant bit to the least significant bit , synchronized with the above two - bit shift clock clk2 of 18 mhz . the respective least significant bits in both the shift registers 45 and 46 , which are respectively denoted by b00 and b01 , and the respective second bits from the least significant bits in both the shift registers 45 and 46 , which are respectively denoted by b02 and b03 , are applied to the coding table 48 . the coding table 48 is constructed by a hardware logic circuit , and the above output bits from the shift registers 45 and 46 are applied as an input of the hardware logic circuit . the hardware logic circuit 48 outputs coded data s0 , s1 , and s3 corresponding to the input bits b00 , b01 , b02 , and b03 in accordance with the relationships of fig1 where the above bits b00 , b01 , b02 , and b03 respectively correspond to the bits b0 , b1 , b2 , and b3 in fig1 . the coding table which carries out the conversion in accordance with the relationships of fig1 is explained in the u . s . pat . no . 4 , 488 , 142 to p . a . franaszek and u . s . pat . no . 4 , 866 , 544 to s . hashimoto . the description of the coding tables in u . s . pat . no . 4 , 866 , 544 to s . hashimoto is hereby incorporated by reference herein . the output comprised of the bits s0 , s1 , and s3 of the coding table 48 is loaded in parallel in the shift register 49 , where the shift register 49 contains three bits . the content of the shift register 49 is serially output therefrom synchronized with the coded data shift clock clk1 of 54 mhz , which is also denoted as a coded data shift clock in fig7 . fig1 shows the construction of the shift registers 45 and 46 of fig7 which are used in the first embodiment of the encoding circuit according to the present invention . in fig1 , reference numeral 50 - 0 , 50 - 1 , 50 - 2 , 50 - 3 , 50 - 4 , 50 - 5 , 50 - 6 , 50 - 7 , 50 - 8 , 50 - 9 , 50 - 10 , 50 - 11 , 50 - 12 , and 50 - 13 each denote a multiplexer , 52 - 0 , 52 - 1 , 52 - 2 , 52 - 3 , 52 - 4 , 52 - 5 , 52 - 6 , 52 - 7 , 52 - 8 , 52 - 9 , 52 - 10 , 52 - 11 , 52 - 12 , 52 - 13 , 52 - 14 , and 52 - 15 each denote a flip - flop circuit , and the coding table 48 is the coding table of fig7 . the shift register 45 comprises the multiplexers 50 - 0 , 50 - 2 , 50 - 4 , 50 - 6 , 50 - 8 , 50 - 10 , and 50 - 12 , and the flip - flop circuits 52 - 0 , 52 - 2 , 52 - 4 , 52 - 6 , 52 - 8 , 52 - 10 , 52 - 12 , and 52 - 14 , and the shift register 46 comprises the multiplexers 50 - 1 , 50 - 3 , 50 - 5 , 50 - 7 , 50 - 9 , 50 - 11 , and 50 - 13 , and the flip - flop circuits 52 - 1 , 52 - 3 , 52 - 5 , 52 - 7 , 52 - 9 , 52 - 11 , 52 - 13 , and 52 - 15 . all the flip - flop circuits 52 - 0 , 52 - 1 , 52 - 2 , 52 - 3 , 52 - 4 , 52 - 5 , 52 - 6 , 52 - 7 , 52 - 8 , 52 - 9 , 52 - 10 , 52 - 11 , 52 - 12 , 52 - 13 , 52 - 14 , and 52 - 15 receives the above - mentioned two - bit shift clock clk2 at their edge - triggered input terminals . the flip - flop circuit 52 14 receives the output of the bit of no . 14 from the data buffer 43 . the multiplexer 50 - 12 receives the output of the flip - flop circuit 52 - 14 and the output of the bit of no . 12 from the data buffer 43 , and its output is applied to the flip - flop circuit 52 - 12 . the multiplexer 50 - 10 receives the output of the flip - flop circuit 52 12 and the output of the bit of no . 10 from the data buffer 43 , and its output is applied to the flip - flop circuit 52 - 10 . the multiplexer 50 - 8 receives the output of the flip - flop circuit 52 - 6 and the output of the bit of no . 08 from the data buffer 43 , and its output is applied to the flip - flop circuit 52 - 8 . the multiplexer 50 - 6 receives the output of the flip - flop circuit 52 - 8 and the output of the bit of no . 06 from the data buffer 44 , and its output is applied to the flip - flop circuit 52 - 6 . the multiplexer 50 - 4 receives the output of the flip - flop circuit 52 - 6 and the output of the bit of no . 04 from the data buffer 44 , and its output is applied to the flip - flop circuit 52 - 4 . the multiplexer 50 - 2 receives the output of the flip - flop circuit 52 - 4 and the output of the bit of no . 02 from the data buffer 44 , and its output is applied to the flip - flop circuit 52 - 2 . the multiplexer 50 - 0 receives the output of the flip - flop circuit 5 - 2 and the output of the bit of no . 00 from the data buffer 44 , and its output is applied to the flip - flop circuit 52 - 0 . similarly , the flip - flop circuit 52 - 15 receives the output of the bit of no . 15 from the data buffer 43 . the multiplexer 50 - 13 receives the output of the flip - flop circuit 52 - 15 and the output of the bit of no . 13 from the data buffer 43 , and its output is applied to the flip - flop circuit 52 - 13 . the multiplexer 50 - 11 receives the output of the flip - flop circuit 52 - 13 and the output of the bit of no . 11 from the data buffer 43 , and its output is applied to the flip - flop circuit 52 - 11 . the multiplexer 50 - 9 receives the output of the flip - flop circuit 52 11 and the output of the bit of no . 09 from , the data buffer 43 , and its output is applied to the flip - flop circuit 52 - 9 . the multiplexer 50 - 7 receives the output of the flip - flop circuit 52 - 9 and the output of the bit of no . 07 from the data buffer 44 , and its output is applied to the flip - flop circuit 52 - 7 . the multiplexer 50 - 5 receives the output of the flip - flop circuit 52 - 7 and the output of the bit of no . 05 from the data buffer 44 , and its output is applied to the flip - flop circuit 52 - 5 . the multiplexer 50 - 3 receives the output of the flip - flop circuit 52 - 5 and the output of the bit of no . 03 from the data buffer 44 , and its output is applied to the flip - flop circuit 52 - 3 . the multiplexer 50 - 1 receives the output of the flip - flop circuit 52 - 3 and the output of the bit of no . 01 from the data buffer 44 , and its output is applied to the flip - flop circuit 52 - 1 . the aforementioned multiplexer control signal ( parallel load signal ) of 2 . 25 mhz is applied to the multiplexers 50 - 0 , 50 - 1 , 50 - 2 , 50 - 3 , 50 - 4 , 50 - 5 , 50 - 6 , 50 - 7 , 50 - 8 , 50 - 9 , 50 - 10 , 50 - 11 , 50 - 12 , and 50 - 13 as their control inputs . when the multiplexer control signal ( parallel load signal ) is active , all the multiplexers select their inputs from the data buffers 43 and 44 as their outputs to load the outputs of the data buffers 43 and 44 in parallel in the flip - flop circuits 52 - 0 , 52 - 1 , 52 - 2 , 52 - 3 , 52 - 4 , 52 5 , 52 - 6 , 52 - 7 , 52 - 8 , 52 - 9 , 52 - 10 , 52 - 11 , 52 - 12 , 52 - 13 , 52 - 14 , and 52 - 15 . when the multiplexer control signal ( parallel load signal ) is inactive , all the multiplexers select their inputs from the flip - flop circuits being connected thereto as their outputs so that all the flip - flop circuits 52 - 0 , 52 - 2 , 52 - 4 , 52 - 6 , 52 - 8 , 52 - 10 , 52 - 12 , and 52 - 14 in the shift register 45 are serially connected , and all the flip - flop circuits 52 - 1 , 52 - 3 , 52 - 5 , 52 - 7 , 52 - 9 , 52 - 11 , 52 - 13 , and 52 - 15 in the shift register 46 are serially connected . in the inactive state of the multiplexer control signal ( parallel load signal ), the content of each flip - flop circuit is shifted by one bit in the direction from the flip - flop circuit 52 - 14 to flip - flop circuit 52 - 0 in the shift register 45 , and in the direction from the flip - flop circuit 52 - 15 to flip - flop circuit 52 - 1 in the shift register 46 , when receiving a rising edge of the two - bit shift clock clk2 of 18 mhz . the outputs of the flip - flop circuits 52 - 0 to 52 - 3 , which are the aforementioned bits b00 to b03 , are applied to the coding table 48 . further , in the first embodiment of the present invention , the coding table 48 receives bits b00 and b01 in the next one byte data which is to be written in the rotating disc medium for use in encoding the last pair of bits in the data buffers 43 and 44 respective least significant bits in both the shift registers 45 and 46 . fig1 shows the timing of the first embodiment of the encoding circuit shown fig7 and 10 . in the example shown in fig1 , the data which is expressed by the sixteen bits which are first held in the data buffers 43 and 44 , is &# 34 ; 9222 &# 34 ; in hexadecimal notation . that is , &# 34 ; 1010100100000010 &# 34 ; in binary notation is first held in the data buffers 43 and 44 . the multiplexers 50 - 0 , 50 - 1 , 50 - 2 , 50 - 3 , 50 - 4 , 50 - 5 , 50 - 6 , 50 - 7 , 50 - 8 , 50 - 9 , 50 - 10 , 50 - 11 , 50 - 12 , and 50 - 13 in the shift registers 45 and 46 respectively select their inputs from the data buffers 43 and 44 when the above - mentioned multiplexer control signal ( parallel load signal ) becomes active at the time t0 . the multiplexer control signal ( parallel load signal ) is denoted by parallel load 1 ( mpx control signal 1 ) to distinguish this signal from another multiplexer control signal ( parallel load signal ) which is denoted by parallel load 2 ( mpx control signal 2 ) in the second embodiment . thus , each output bit of the data buffers 43 and 44 is entered in the corresponding flip - flop circuit through the corresponding multiplexer in the shift registers 45 and 46 ( i . e ., the data held in the data buffers 43 and 44 is loaded in parallel in the shift registers 45 and 46 at the time t1 ). from the time t2 to t9 , the content of each flip - flop circuit is shifted by one bit in the direction from the no . 14 bit to the no . 00 bit in the shift register 45 , and the content of each flip - flop circuit is shifted by one bit in the direction from the no . 15 bit to the no . 01 bit in the shift register 46 every time the two - bit shift clock clk2 rises . thus , from the time t2 to t8 , the bit of no . 2i ( i = 0 to 6 ) held in the data buffers 43 or 44 , is applied to the input port b00 of the coding table 48 , after being shifted through the flip - flop circuits 52 - 2i to 52 - 0 . at the same time , the next bit of no . 2 ( i + 1 ) is applied to the input port b02 of the coding table 48 after being shifted through the flip - flop circuits 52 - 2 ( i + 1 ) to 52 - 2 . the bit of no . 2i + 1 ( i = 0 to 6 ) held in the data buffers 43 and 44 , is applied to the input port b01 of the coding table 48 , after being shifted through the flip - flop circuits 52 - 2i + 1 to 52 - 1 . at the same time , the next bit of no . 2 ( i + 1 )+ 1 is applied to the input port b03 of the coding table 48 after being shifted through the flip - flop circuits 52 2 ( i + 1 )+ 1 to 52 - 3 . from the time t8 to t9 , the bit of no . 14 held in the data buffers 43 and 44 , is applied to the input port b00 of the coding table 48 , after being shifted through the flip - flop circuits 52 - 14 to 52 - 0 , and the bit of no . 15 held in the data buffers 43 and 44 , is applied to the input port b01 . of the coding table 48 , after being shifted through the flip - flop circuits 52 - 15 to 52 - 1 . as mentioned before , for decoding the above last pair of bits of nos . 14 and 15 , the bits of nos . 00 and 01 in the next two data bytes which are to be written in the rotating disc medium , are also supplied to the coding table 48 . as shown in fig1 , the next two byte - data &# 34 ; 88cb &# 34 ; in hexadecimal notation is held in the data buffers 43 and 44 between the times t3 and t4 . the multiplexers 50 - 0 , 50 - 1 , 50 - 2 , 50 - 3 , 50 - 4 , 50 - 5 , 50 - 6 , 50 - 7 , 50 - 8 , 50 - 9 , 50 - 10 , 50 - 11 , 50 - 12 , and 50 - 13 in the shift registers 45 and 46 respectively select their inputs from the data buffers 43 and 44 again when the above - mentioned multiplexer control signal 1 ( parallel load signal 1 ) becomes active at the time t8 . thus , each output bit of the data buffers 43 and 44 is entered in the corresponding flip - flop circuit through the corresponding multiplexer in the shift registers 45 and 46 ( i . e ., the data held in the data buffers 43 and 44 is loaded in parallel in the shift registers 45 and 46 at the time t9 ). fig1 shows the construction of the shift registers 45 and 46 of fig7 which are used in the second embodiment of the encoding circuit according to the present invention . since the constructions of the shift registers in fig1 are different from the constructions of the shift registers of fig1 , different reference numerals 45 &# 39 ; and 46 &# 39 ; are used for the shift registers in fig1 . the constructions shown in fig1 and 12 are the same except explained below . in the construction of fig1 , no additional input port is provided in the coding table 48 for receiving the first and second bits in the next byte data , and in the shift registers 45 &# 39 ; and 46 &# 39 ;, the multiplexers 60 - 2 and 60 - 3 the outputs of which are respectively applied to the flip - flop circuits 62 - 2 and 62 - 3 , are each a multiplexer receiving three inputs , where two of the three inputs are the same as the aforementioned two inputs of the multiplexers 50 - 2 and 50 - 3 in the construction of fig1 , the bit of no . 00 is applied as the other input of the multiplexer 60 - 2 , and the bit of no . 01 is applied as the other input of the multiplexer 60 - 3 . the multiplexers 60 - 2 and 60 - 3 are respectively controlled to select the inputs of the bits of nos . 02 and 03 from the data buffers 43 and 44 when receiving an active multiplexer control signal 1 ( parallel load signal 1 ), and are respectively controlled to select the inputs of the bits of nos . 00 and 01 from the data buffers 43 and 44 when receiving an active multiplexer control signal 2 ( parallel load signal 2 ). the multiplexer control signal 2 ( parallel load signal 2 ) is also a periodic signal having a frequency of 2 . 25 mhz , and becomes active one cycle before the multiplexer control signal 1 ( parallel load signal 1 ) becomes active . fig1 shows the timing of the second embodiment of the encoding circuit shown fig7 and 12 . in the example shown in fig1 , the data which is first held in the data buffers 43 and 44 , is again &# 34 ; 9222 &# 34 ; in hexadecimal notation . that is , &# 34 ; 1010100100000010 &# 34 ; in binary notation is first held in the data buffers 43 and 44 . the multiplexers 60 - 0 , 60 - 1 , 60 - 2 , 60 - 3 , 60 - 4 , 60 - 5 , 60 - 6 , 60 - 7 , 60 - 8 , 60 - 9 , 60 - 10 , 60 - 11 , 60 - 12 , and 60 - 13 in the shift registers 45 &# 39 ; and 46 &# 39 ; respectively select their inputs from the data buffers 43 and 44 when the above - mentioned multiplexer control signal 1 ( parallel load signal 1 ) becomes active at the time to in the same manner as the first embodiment . thus , each output bit of the data buffers 43 and 44 is entered in the corresponding flip - flop circuit through the corresponding multiplexer in the shift registers 45 &# 39 ; and 46 &# 39 ; ( i . e ., the data held in the data buffers 43 and 44 is loaded in parallel in the shift registers 45 &# 39 ; and 46 &# 39 ; at the time t1 . from the time t2 to t9 , the content of each flip - flop circuit is shifted by one bit in the direction from the no . 14 bit to the no . 00 bit in the shift register 45 &# 39 ;, and the content of each flip - flop circuit is shifted by one bit in the direction from the no . 15 bit to the no . 01 bit in the shift register 46 &# 39 ; every time the two - bit shift clock clk2 rises . thus , from the time t2 to t8 , the bit of no . 2i ( i = 0 to 6 ) held in the data buffers 43 or 44 , is applied to the input port b00 of the coding table 48 , after being shifted through the flip - flop circuits 62 - 2i to 62 - 0 . at the same time , the next bit of no . 2 ( i + 1 ) is also applied to the input port b02 of the coding table 48 , after being shifted through the flip - flop circuits 62 - 2 ( i + 1 ) to 62 - 2 . the bit of no . 2i + 1 ( i = 0 to 6 ) held in the data buffers 43 and 44 , is applied to the input port b01 of the coding table 48 , after being shifted through the flip - flop circuits 62 - 2i + 1 to 62 - 1 . at the same time , the next bit of no . 2 ( i + 1 )+ 1 is also applied to the coding table 48 through the flip - flop circuits 62 2 ( i + 1 )+ 1 to 62 - 3 , and the input port b03 of the coding table 48 . from the time t8 to t9 , the bit of no . 14 held in the data buffers 43 and 44 , is applied to the input port b00 of the coding table 48 , after being shifted through the flip - flop circuits 62 - 14 to 62 - 0 , and the bit of no . 15 held in the data buffers 43 and 44 , is applied to the input port b01 of the coding table 48 , after being shifted through the flip - flop circuits 62 15 to 62 - 1 . on the other hand , the next two byte - data &# 34 ; 88cb &# 34 ; in hexadecimal notation is held in the data buffers 43 and 44 between the times t3 and t4 . as mentioned above , the multiplexer control signal 2 ( parallel load signal 2 ) becomes active at the time t7 , which is one cycle before the multiplexer control signal 1 ( parallel load signal 1 ) becomes active . corresponding to the above active multiplexer control signal 2 ( parallel load signal 2 ), the bit of no . 00 in the above next data byte is applied through the multiplexer 60 - 2 to the flip - flop circuit 62 - 2 , and the bit of no . 01 in the above next data byte is applied through the multiplexer 60 - 3 to the flip - flop circuit 62 - 3 . then , at the time t8 , the above bits of nos . 00 and 01 are respectively loaded in the flip - flop circuits 62 - 2 and 62 - 3 . thus , at the same time as the above bits of nos . 14 and 15 from the flip - flop circuits 62 - 0 and 62 - 1 , the above bits of nos . 00 and 01 in the next data byte are respectively supplied to the coding table 48 from the flip - flop circuits 62 - 2 and 62 - 3 . all the other operations of the construction of fig1 is the same as the operations of fig1 . fig1 shows the construction of a decoding circuit as the third embodiment of the present invention . in fig1 , reference numeral 80 denotes a clock generator , 81 denotes a variable frequency oscillator , 82 denotes a 1 / 3 frequency divider , 83 denotes a decoder , 84 , 87 , and 88 each denote a shift register , 85 denotes a decoding table , and 89 - 0 to 89 - 7 each denote a flip - flop circuit . the variable frequency oscillator 81 generates a coded data shift clock clk1 having a frequency of 54 mhz , and the 1 / 3 frequency divider generates a two - bit shift clock clk2 having a frequency of 18 mhz by dividing the frequency of the coded data shift clock clk1 . the timing of the clock signals clk1 and clk2 of 54 mhz and 18 mhz which are generated in the clock generator 80 in fig1 , are the same as shown in fig8 . coded data . . . s0 , s1 , s2 , . . . which has been read from a magnetic disc , is serially input into the shift register 84 in the decoder 83 synchronized with the above coded data shift clock clk1 of 54 mhz . the shift register 84 contains three bits , and the parallel output of three bits from the shift register 84 is applied to the decoding table 85 . the decoding table 85 is constructed by a hardware logic circuit , and the above output bits from the shift register 84 are applied as an input of the hardware logic circuit . the hardware logic circuit 85 outputs decoded data b0 and b1 corresponding to the above input bits s0 , s1 , and s3 , using three bits of coded data s - 3 , s - 2 , and s - 1 preceding the above bits s0 , s1 , and s3 , and further three bits s4 , s5 , and s6 following s0 , s1 , and s2 , in accordance with the relationships of fig4 . the decoding table which carries out the conversion in accordance with the relationships of fig4 is explained in the u . s . pat . no . 4 , 488 , 142 to p . a . franaszek and u . s . pat . no . 4 , 866 , 544 to s . hashimoto . the description of the decoding tables in u . s . pat . no . 4 , 866 , 544 to s . hashimoto is hereby incorporated by reference herein . fig1 shows the timing of the decoding circuit as the third embodiment of the present invention . as shown in fig1 , although the input of the decoding table 85 changes synchronized with the coded data shift clock clk1 of 54 mhz , the output bits b0 and b1 are respectively latched in the flip - flop circuits 89 - 7 and 89 - 6 synchronized with the two - bit shift clock clk2 of 18 mhz . the above output bit b0 is serially input into the shift register 87 synchronized with the above two bit shift clock clk2 of 18 mhz , and at the same time , the above bit b1 is serially input into the shift register 88 . in each of the shift registers 87 and 88 , the above bit which is serially input therein is shifted by one bit in the direction from the flip - flop circuit 89 - 7 or 89 - 6 to the flip - flop circuit 89 - 1 or 89 - 0 when the two - bit shift clock clk2 rises . thus , the odd - numbered bits of the decoded data appear in the parallel output of the shift register 87 , and the even - numbered bits of the decoded data appear in the parallel output of the shift register 88 , as shown in fig1 . in the example shown in fig1 , after one byte data is loaded in the shift registers 87 and 88 at the time t4 , the one byte data is latched at the time t5 for being read out . fig1 shows the construction of an encoding and decoding circuit as the fourth embodiment of the present invention . the construction of fig1 functions as an encoding circuit and as a decoder . in fig1 , reference numeral 110 denotes a clock generator , 111 denotes a variable frequency oscillator , 112 denotes a 1 / 3 frequency divider , 113 and 114 each denote a data buffer , 116 and 117 each denote a shift register , 119 denotes an encoding table , 120 denotes a decoding table , and 121 denotes a shift register . the construction of fig1 except the decoding table 120 corresponds to the encoding circuit of fig7 when writing data in the rotating disc medium , the data flows in the direction from the left to the right in fig1 . the construction of fig1 except the encoding table 119 operates in basically the same manner as the decoding circuit of fig1 , except that the shift registers 116 and 117 for loading odd - numbered bits and for loading even - numbered bits respectively contains eight bits as explained later with reference to fig1 and 18 , and the outputs of the shift registers 116 and 117 are held in the data buffers 113 and 114 in the manner as explained later with reference to fig1 . when reading data in the rotating disc medium , the data flows in the direction from the right to the left in fig1 . fig1 and 18 respectively show the constructions of the shift registers 117 and 116 of fig1 . in fig1 , reference numeral 130 - 0 , 130 - 2 , 130 - 4 , 130 - 6 , 130 - 8 , 130 - 10 , 130 - 12 , 131 - 0 , 131 - 2 , 131 - 4 , 131 - 6 , 131 - 8 , 131 - 10 , 131 - 12 , 131 - 14 , 134 - 6 , 134 - 14 , and 135 - 2 each denote an and gate , 132 - 0 , 132 - 2 , 132 - 4 , 132 - 6 , 132 - 8 , 132 - 10 , 132 - 12 , and 132 - 14 each denote an or gate , and 133 - 0 , 133 - 2 , 133 - 4 , 133 - 6 , 133 - 8 , 133 - 10 , 133 - 12 , and 133 - 14 each denote a flip - flop circuit . in fig1 , reference numeral 130 - 1 , 130 - 3 , 130 - 5 , 130 - 7 , 130 - 9 , 130 - 11 , 130 - 13 , 131 - 1 , 131 - 3 , 131 - 5 , 131 - 7 , 131 - 9 , 131 - 11 , 131 - 13 , 131 - 15 , 134 - 7 , 134 - 15 , and 135 - 3 each denote an and gate , 132 - 1 , 132 - 3 , 132 - 5 , 132 - 7 , 132 - 9 , 132 - 11 , 132 - 13 , and 132 - 15 each denote an or gate , and 133 - 1 , 133 - 3 , 133 - 5 , 133 - 7 , 133 - 9 , 133 - 11 , 133 - 13 , and 133 - 15 each denote a flip - flop circuit . in the construction of fig1 , the flip - flop circuits 133 - 2i ( i = 0 to 7 ) respectively receive as their inputs the outputs of corresponding or gates 132 - 2i . the or gates 132 - 2i ( i = 0 to 6 ) respectively receive as their inputs the outputs of corresponding two and gates 130 - 2i and 131 - 2i , and the or gate 132 - 14 receives the outputs of the and gates 131 - 14 and 134 . 14 . the and gates 131 - 2i ( i = 0 to 7 ) receives a parallel load signal a in their one input terminal . when the output bits of the data buffer 113 are numbered as nos . 15 to 08 from its most significant bit to its least significant bit , and the output bits of the data buffer 114 are numbered as nos . 07 to 00 from its most significant bit to its least significant bit , the output bits no . 2i ( i = 0 to 7 ) of the data buffers 113 and 114 are respectively applied to the other input terminals of the and gates 131 - 2i . when the output bits of the data buffer 113 are numbered as nos . 15 to 08 from its most significant bit to its least significant bit , and the output bits of the data buffer 114 are numbered as nos . 07 to 00 from its most significant bit to its least significant bit , the output bits no . 2i ( i = 0 to 7 ) of the data buffers 113 and 114 are respectively applied to the other input terminals of the and gates 131 - 2i . similarly , in the construction of fig1 , the flip - flop circuits 133 - 2i + 1 ( i = 0 to 7 ) respectively receive as their inputs the outputs of corresponding or gates 132 - 2i + 1 . the or gates 132 - 2i + 1 ( i = 0 to 6 ) respectively receive as their inputs the outputs of corresponding two and gates 130 - 2i + 1 and 131 - 2i + 1 , and the or gate 132 - 15 receives the outputs of the and gates 131 - 15 and 134 . 15 . the and gates 131 2i + 1 ( i = 0 to 7 ) receive a parallel load signal a in their one input terminal . the output bits no . 2i + 1 ( i = 0 to 7 ) of the data buffers 113 and 114 are respectively applied to the other input terminals of the and gates 131 - 2i + 1 . in addition , in the constructions of fig1 and 18 , the and gates 131 - 2i ( i = 0 to 6 ) receives the output of the flip - flop circuit 133 - 2 ( i + 1 ) ( i = 0 to 6 ) in their one input terminal , and the and gates 131 - 2i + 1 ( i = 0 to 6 ) receives the output of the flip - flop circuit 133 2 ( i + 1 )+ 1 ( i = 0 to 6 ) in their one input terminal . the and gates 130 - 13 to 130 - 8 further receive a shift a signal in their other input terminals , the and gates 130 - 0 , 130 - 1 , 130 - 4 , and 130 - 5 further receive a shift b signal in their other input terminals , the and gates 130 - 6 , and 130 - 7 further receive a shift c signal in their other input terminals , and the and gates 130 - 6 , and 130 - 7 further receive a shift d signal in their other input terminals . further , in the construction of fig1 , the and gate 134 - 14 receives a read shift a signal and a decoded data bit b0 &# 39 ;, and the and gate 134 - 6 receives a read shift b signal and a decoded data bit b0 &# 39 ;. the or gate 132 - 2 further receives the output of the and gate 135 - 2 , and the and gate 135 - 2 receives a parallel load signal b in its one input terminal , and the output bit no . 00 of the data buffers 114 in the other input terminal . in the construction of fig1 , the and gate 134 - 15 receives a read shift a signal and a decoded data bit b1 &# 39 ;, and the and gate 134 - 7 receives a read shift b signal and a decoded data bit b1 &# 39 ;. the or gate 132 - 3 further receives the output of the and gate 135 - 3 , and the and gate 135 - 3 receives a parallel load signal b in its one input terminal , and the output bit no . 01 of the data buffers 114 in the other input terminal . furthermore , a two - bit shift clock a is applied to the edge - triggered input terminals of the flip - flop circuits 133 - 8 to 133 - 15 , and a two - bit shift clock b is applied to the edge - triggered input terminals of the flip - flop circuits 133 - 0 to 133 - 7 . both the two - bit shift clocks a and b are the same as the aforementioned two - bit shift clock clk2 in the first and second embodiments in the data writing ( encoding ) operation . in the data reading ( decoding ) operation , the two - bit shift clock a becomes active only when the aforementioned shift a signal is active , and the two - bit shift clock b becomes active only when the aforementioned shift b signal is active . the outputs of the flip - flop circuits 133 - 0 and 133 - 2 in the shift register 117 are supplied to the input terminals b00 and b02 of the coding table 119 of fig1 , and the outputs of the flip - flop circuits 133 - 1 and 133 - 3 in the shift register 116 are supplied to the input terminals b01 and b03 of the coding table 119 of fig1 . in the data writing ( encoding ) operation , the above parallel load signal a is the same as the aforementioned parallel load signal 1 , and the above parallel load signal b is the same as the parallel load signal 2 in the first and second embodiment . namely , the parallel load signal a is a periodic signal having a frequency of 2 . 25 mhz , and is supplied to the constructions of fig1 and 18 for loading in parallel the outputs of the data buffers 113 and 114 in the flip - flop circuits 133 - 2i and 133 - 2i + 1 ( i = 0 to 7 ). the parallel load signal b is a periodic signal having a frequency of 2 . 25 mhz , and is supplied to the constructions of fig1 and 18 , at the timing one cycle before the parallel load signal a , so that the bits of nos . 00 and 01 in a data byte next to the data byte the last two bits of which are output from the shift registers 116 and 117 to the coding table 119 at the moment , are respectively applied to the flip - flop circuits 132 - 2 and 132 - 3 . the decoded data bits bo &# 39 ; and b1 &# 39 ; are the output of the decoding table 120 in fig1 . the decoding table 120 in fig1 is the same as the decoding table 85 in fig1 , receives through the shift register 121 at its input terminals s0 &# 39 ;, s1 &# 39 ;, and s2 &# 39 ;, a coded data bit sequence which has been read from a rotating disc medium , and converts the coded data bit sequence to decoded data bit sequence corresponding to the received coded data bit sequence to output the converted result as successive pair of bits synchronized with the system clock clk1 of 54 mhz . the read shift a signal and the read shift signal b are each a periodic signal having a frequency of 4 . 5 mhz , and alternatively become active as shown in fig2 when reading ( decoding coded ) data from the rotating disc medium . the other operations of the constructions of fig1 and 18 including the above shift signals a , b , c , and d are explained below with reference to fig1 and 20 . fig1 shows the timing of the encoding operation in the encoding and decoding circuit of fig1 and 17 as the fourth embodiment of the present invention . in the example shown in fig1 , the data which is first held in the data buffers 113 and 114 , is again &# 34 ; 9222 &# 34 ; in hexadecimal notation (&# 34 ; 1010100100000010 &# 34 ; in binary notation ). at the time t0 , the parallel load signal a becomes active . corresponding to the active parallel load signal a , the output bits nos . 00 to 15 of the data buffers 113 and 114 are entered in parallel in the corresponding flip - flop circuits in the shift registers 116 and 117 through the corresponding and gates 131 - j ( j = 0 to 15 ) and the or gates 133 - j ( j = 0 to 15 ) at the time t1 . during the parallel loading , the shift signals a , b , c , and d are maintained inactive as shown in fig1 . since , as shown in fig1 , the shift a , b , and c signals are active from the time t1 to t8 , and the shift d signal are active from the time t1 to t7 , the content of each flip - flop circuit is shifted by one bit in the direction from the no . 14 bit to the no . 00 bit in the shift register 117 , and the content of each flip - flop circuit is shifted by one bit in the direction from the no . 15 bit to the no . 01 bit in the shift register 116 every time the two - bit shift clocks a and b rise . thus , from the time t2 to t8 , the bit of no . 2i ( i = 0 to 6 ) held in the data buffers 113 or 114 , is applied to the input port b00 - of the coding table 119 , after being shifted through the flip - flop circuits 133 - 2i to 133 - 0 . at the same time , the next bit of no . 2 ( i + 1 ) is also applied to the input port b02 of the coding table 119 , after being shifted through the flip - flop circuits 133 - 2 ( i + 1 ) to 133 - 2 . the bit of no . 2i + 1 ( i = 0 to 6 ) held in the data buffers 113 and 114 , is applied to the input port b01 of the coding table 119 , after being shifted through the flip - flop circuits 133 - 2i + 1 to 133 - 1 . at the same time , the next bit of no . 2 ( i + 1 )+ 1 is also applied to the coding table 119 through the flip - flop circuits 133 - 2 ( i + 1 )+ 1 to 133 - 3 , and the input port b03 of the coding table 119 . from the time t8 to t9 , the bit of no . 14 held in the data buffers 113 and 114 , is applied to the input port b00 of the coding table 119 , after being shifted through the flip - flop circuits 133 - 14 to 133 - 0 , and the bit of no . 15 held in the data buffers 113 and 114 , is applied to the input port b01 of the coding table 119 , after being shifted through the flip - flop circuits 133 - 15 to 133 - 1 . on the other hand , the next two byte - data &# 34 ; 88cb &# 34 ; in hexadecimal notation is held in the data buffers 113 and 114 between the times t3 and t4 . as mentioned above , the parallel load signal b becomes active at the time t7 , which is one cycle before the parallel load signal a becomes active . corresponding to the above active parallel load signal b , the bit of no . 00 in the above next data byte is applied through the and gate 135 - 2 and the or gate 132 - 2 to the flip - flop circuit 133 - 2 , and the bit of no . 01 in the above next data byte is applied through the and gate 135 - 3 and the or gate 132 - 3 to the flip - flop circuit 133 - 3 . then , at the time ts , the above bits of nos . 00 and 01 are respectively loaded in the flip - flop circuits 133 - 2 and 133 - 3 . thus , at the same time as the above bits of nos . 14 and 15 from the flip - flop circuits 133 - 0 and 133 - 1 , the above bits of nos . 00 and 01 in the next data byte are respectively supplied to the coding table 119 from the flip - flop circuits 133 - 2 and 133 - 3 . fig2 shows the timing of the decoding operation in the encoding and decoding circuit of the fourth embodiment of the present invention . in the example shown in fig2 , from the time to t4 , the read shift a signal and the shift a are active . therefore , the decoded data bit b0 &# 39 ; from the decoding table 120 is applied to the flip - flop circuit 133 - 14 through the and gate 134 . 14 and the or gate 132 - 14 , and is latched in the flip - flop circuit 133 - 14 when the two - bit shift clock a rises . at the same time , the decoded data bit b1 &# 39 ; from the decoding table 120 is applied to the flip - flop circuit 133 - 15 through the and gate 134 - 15 and the or gate 132 - 15 , and is latched in the flip - flop circuit 133 - 15 when the two - bit shift clock a rises . the data bits latched in the flip - flop circuits 133 - 2 ( i + 1 ) ( i = 4 to 6 ) in fig1 are shifted to the flip - flop circuit 133 - 2i through the and gate 130 - 2i and the or gate 132 - 2i when the two - bit shift clock a rises next , and the data bits latched in the flip - flop circuits 133 - 2 ( i + 1 )+ 1 (= i = 4 to 6 ) in fig1 are shifted to the flip - flop circuit 133 - 2i + 1 through the and gate 130 - 2i + 1 and the or gate 132 - 2i + 1 when the two - bit shift clock a rises . thus , at the same time t4 , four successive decoded bits b0 &# 39 ; s are held in the flip - flop circuits 133 - 8 to 133 - 14 in fig1 , and four successive decoded bits b1 &# 39 ; s are held in the flip - flop circuits 133 - 9 to 133 - 15 in fig1 . namely , one byte of decoded data is loaded in the upper half bits of the shift registers 117 and 116 at the time t4 . since the above two - bit shift clock a is inactive after the time t4 , the above one byte of decoded data which is loaded in the upper half bits of the shift registers 117 and 116 is maintained until the time t8 . the maintained one byte data is latched in the data buffers 113 of fig1 after the time t5 as shown in fig2 . fig2 shows the connection between the output bits of the buffer registers 113 and 114 and the input bits of the shift registers 116 and 117 in the construction of fig1 . a shown in fig2 , the above one byte data held in the upper halves of the shift registers 117 and 116 is latched in the data buffer 113 . from the time t4 to t8 , the read shift b signal and the shift b are active , instead of the read shift a signal and the shift a . therefore , the decoded data bit b0 &# 39 ; from the decoding table 120 is applied to the flip - flop circuit 133 - 6 through the and gate 134 - 6 and the or gate 132 - 6 , and is latched in the flip - flop circuit 133 - 6 when the two - bit shift clock b rises . at the same time , the decoded data bit b1 &# 39 ; from the decoding table 120 is applied to the flip - flop circuit 133 - 7 through the and gate 134 - 7 and the or gate 132 - 7 , and is latched in the flip - flop circuit 133 - 7 when the two - bit shift clock b rises . the data bits latched in the flip - flop circuits 133 - 2 ( i + 1 ) ( i = 0 to 2 ) in fig1 are shifted to the flip - flop circuit 133 - 2i through the and gate 130 - 2i and the or gate 132 - 2i when the two - bit shift clock a rises next , and the data bits latched in the flip - flop circuits 133 - 2 ( i + 1 )+ 1 ( i = 0 to 2 ) in fig1 are shifted to the flip - flop circuit 133 - 2i + 1 through the and gate 130 - 2i + 1 and the or gate 132 - 2i + 1 when the two - bit shift clock a rises . thus , at the time t8 , four successive decoded bits b0 &# 39 ; s are held in the flip - flop circuits 133 - 0 to 133 - 6 in fig1 , and four successive decoded bits b1 &# 39 ; s are held in the flip - flop circuits 133 - 1 to 133 - 7 in fig1 . namely , one byte of decoded data is loaded in the lower half bits of the shift registers 117 and 116 at the time t8 . since the above two - bit shift clock b is inactive after the time t8 , the above one byte of decoded data which is loaded in the lower half bits of the shift registers 117 and 116 is maintained until the two - bit shift clock b becomes active again . the maintained one byte data is latched in the data buffer 114 of fig1 after the time t8 as shown in fig2 . the combination between the outputs bits of the buffer registers 114 and the input bits of the shift registers 116 and 117 is also shown in fig2 , where the above one byte data held in the lower halves of the shift registers 117 and 116 is latched in the data buffer 114 . in all the above embodiments , all the control signals used therein are periodical , and therefore , are generated from the system clock of 54 mhz by dividing its frequency by suitable frequency dividing ratios , respectively . | 6 |
the radiating device 100 shown in fig1 ( a ) contains numerous elements constructed around an led substrate 102 . the leds 104 are mounted to the substrate , preferably in strips . in the example shown , three strips are illustrated , corresponding to an embodiment where full colour printing is achieved via red , blue and green ( rbg ) leds 104 exciting different active elements of a print medium . the substrate 102 is described in more detail below with reference to fig3 . the radiating device 100 is adapted to form part of a larger print head unit which , in combination with appropriate additional mechanical and electrical components , together with a lens system in certain examples , selectively exposes a print medium ( such as photographic paper ) in order to produce a patterned article . in this document , the term led is used to refer to a light emitting diode adapted to radiate light of any wavelength unless otherwise stated , that is , including ultraviolet , visible and infrared ‘ light ’. the substrate 102 is mounted onto a thermal pad 106 which is situated further away from the print medium when in use ( as indicated by fig1 ( a )). this aids the dispersal of heat produced by the leds 104 themselves . without temperature controlling precautions , the leds 104 would heat up in use which would cause a number of unwanted side effects . in particular , the optical properties of the leds and of other elements in the system are temperature dependant , which affects performance . in extreme circumstances excessive heat can cause severe damage to the leds 104 . the thermal pad 106 is in thermal contact with the substrate at least adjacent to the area of the substrate to which the leds 104 are mounted , as this is where the majority of the heat is produced . active temperature control may also be provided as is described in more detail below . below the substrate 102 ( towards the print media ) is another thermal pad 110 . this is similar to the thermal pad 106 , but is shaped so that it does not obscure the light emitted from the leds 104 . the substrate is thus ‘ sandwiched ’ between the two thermal pads 106 , 110 . these heat pads are described in more detail below with reference to fig5 and 6 . above the first heat pad 106 ( further away from the print media ) is a back plate 108 . in the example shown in fig1 , this conforms to the shape of the heat pad 106 . this is made out of a material with a low thermal resistance ( high thermal conductance ) such as aluminium . this acts to guide the heat produced by the leds 104 away from the leds 104 , and to dissipate it into the surrounding environment , or into a further heat sink ( not shown ). below the lower thermal pad 110 ( towards the print media ) is a spacing element 112 ( preferably in the form of a ceramic plate ). this plate 112 is provided with three parallel apertures , and the plate 112 is positioned so that these apertures are located in register with each of the three led strips . this is discussed in more detail below with reference to fig4 . adjacent to the spacing element 112 , further towards the print media , is the radiation modification element 114 . this element 114 modifies the properties of the light passing through the system , which is discussed in more detail below with reference to fig2 . the component shown to be nearest the print media in fig1 is front plate 116 . this adds to the structural rigidity of the device as a whole , and , together with back plate 108 , enables all the components to be securely fastened together by screws 118 . the front plate 116 and back plate 108 are shown in more detail in fig7 and 8 respectively . fig1 ( b ) shows a side view of the assembled radiating device . screws 118 pass through apertures 700 ( shown in fig7 ) provided in the top plate 116 and screw into screw - threaded cavities 800 provided in the back plate 108 . by tightening these screws 118 , the components are secured in place . fig2 shows the radiation modification plate ( or correction plate ) 114 in more detail . in order to correct for inaccurately placed leds 104 , the radiation modification plate 114 is provided with a mask . this mask is an optically opaque material ( for the relevant wavelength ( s ) of light being used ) that is applied onto the plate 114 using physical vapour deposition ( pvd ). this process applies a very thin layer of the opaque material ( several atoms thick ) in a very precise pre - defined pattern . alternatively this could be achieved by chemical vapour deposition ( cvd ), hand coating and / or use of gelatine filters . in any such example , the pattern is to cover the plate 114 whilst leaving uncovered the desired locations of the leds 104 . any misplaced leds will have the light they emit blocked from transmitting further towards the print medium . the power that reaches the print medium from these misplaced leds would be less than accurately placed leds , but by a negligible amount if the misplacement is small . the defects in printing due to errors of this kind are far less serious than the defects created by misalignment and cross - talk between neighbouring leds . in one example , the mask is placed on the side nearest the leds ( furthest away from the print medium ). this reduces the possibility of diffraction and cross talk by minimising the amount of light entering the radiation modification plate 114 . in a further example , the mask might be placed on the other side of the plate 114 . further to this opaque coating , subsequent coatings are applied in a similar manner , either applied on the same side as the mask or on the opposing side . these coatings alter the properties of the light which could affect the quality of the final printed product , namely the emission spectrum of the leds . these filters may again be applied onto the plate using pvd , cvd , hand coating and / or use of gelatine filters . in the example shown , there are three strips of leds ; red , blue and green . it is important that each led is of the same colour as the others in the strip . this is because the print media has a wavelength dependent sensitivity . even if leds are produced in identical conditions , their peak wavelength may vary by up to 20 nm , which is enough to produce noticeable errors in the final printed product . furthermore , the leds may produce light with a spectrum which extends into other active areas of the print media . for example , in the rbg example given , the wavelength response of some media is such that part of the ‘ green ’ sensitive area can be activated by the tail of the spectrum from a blue led . there is therefore a need to constrain the wavelength of the leds within a tight window . band pass filters which block light of unwanted wavelengths are employed for this purpose . the filters are deposited onto the specified areas of the radiation modification plate 114 , for example , a filter for blue light is applied over the areas through which the blue light is radiated . alternatively , a single filter with ‘ windows ’ at each of the relevant wavelength bands could be applied , covering each of the three different colour led strips . this would mean fewer pvd iterations , and potentially less additional material through which the light needs to pass . in the rbg example , there may not be a need for a ‘ red ’ filter as there is negligible overlap between the red sensitive spectrum of the media with that of other colours . in this case , only green and blue filters would be necessary . the filters shown in fig2 ( d ) are illustrated schematically and in reality are ‘ bandpass ’ filters , which cut off wavelengths above or below a certain wavelength . they will also not have perfectly sharp edges , rather have a steep drop off and a small ‘ tail ’. this is described in more detail below with reference to fig2 ( d ). the radiation modification plate 114 , in one example , is a sheet of glass , approximately 0 . 5 mm - 1 mm thick , preferably around 0 . 69 mm thick . in one example , the glass used is optical grade glass so that there is less scattering or attenuation and that a broader spectrum of light can be transmitted through it . however it is also possible to use standard glass . in a preferred example , the radiation modification plate 114 is a sheet of ‘ glass fibres ’, or an ‘ optic fibre plate ’ as shown by fig2 ( c ). this is a collection of optical fibres collected or bundled and fused together . this would also be approximately 0 . 5 mm - 1 mm thick , preferably around 0 . 69 mm . fig2 ( c ) shows a magnified view of such a construction . the plate 114 is comprised of a large number of individual optical fibres 200 which have been bundled and fused together . in one example each optical fibre 200 is around 18 - 20 μm in diameter . typically the plate is formed by “ salami - slicing ” or shaving off a section of a length of fused optical fibres thereby forming the plate 200 . each optical fibre 200 consists of cladding 202 and a core 204 . this construction provides a number of advantages over a sheet of glass . in particular , there is less scope for cross - talk between neighbouring leds , and scattering in the radiation modification plate 114 is reduced . the fibres 200 have a low numerical aperture ( na ), meaning that there is less ‘ cross talk ’ between neighbouring leds . the light is also guided down much more accurately through the plate 200 . the fibres 200 guide the light directly down , whereas a glass plate would allow some spreading , which would eventually lead to errors on the final printed item . the use of a fibre plate is also preferable when using a ‘ fibre taper ’ as discussed below as the fibre - to - fibre interface results in less scattering and other losses than a glass - to - fibre interface . fig2 ( d ) shows the spectrum of leds , medium response sensitivity and filters , illustrating the function of the filters . in an ideal system , each led would emit a single wavelength of light which exactly corresponds with a single wavelength to which the media is sensitive . in real systems this is not the case as the leds emit light in a range of wavelengths , and the media is sensitive to a range of wavelengths . as shown in fig2 ( d ), the radiation from certain leds can excite the media in a range of varying colours . this is best seen with the ‘ blue led spectrum ’ overlapping with the ‘ media response sensitivity to green light ’ curves . the result of such overlap means that led light that is meant to activate ‘ blue ’ in the media , also activates ‘ green ’ ( and vice versa ). this leads to errors in the final colour of the printed item . to overcome this , filters are employed so that only light that activates the correct colour on the print media is transmitted to the print medium . these band - pass filters are shown schematically by dashed blocks in fig2 ( c ), indicating the wavelength range that is allowed to propagate . there is a trade off between letting more light through and avoiding overlap which is dependent on a number of factors such as the speed and quality of printing required . fig3 ( a ) shows a more detailed view of the front face ( light emitting side ) of the led substrate 102 . there are approximately 100 individual leds 104 in each strip , each 0 . 4 mm wide , which together span a width of approximately 40 mm . in another example , leds with a die size of between 0 . 3 mm and 1 mm are used . the leds are mounted to the substrate using surface mounting techniques . each set of 100 leds 104 - 1 , 104 - 2 , 104 - 3 are arranged in two rows of 50 so that the emission profiles of adjacent leds 104 in each row overlap to such a degree that components of an image , pattern or mark printed on a photo - sensitive medium and attributable to adjacent leds are not readily resolvable . in an alternative example , the leds might be arranged in a single row in a non - overlapping fashion . the different rows 104 - 1 , 104 - 2 , 104 - 3 are shown to be linearly offset from one another ; this is to avoid ‘ banding ’ where errors in the movement of the print head results in under or over exposure between print swathes . this linear offset means that the join between adjacent swathes of the final image resulting from exposure of the photographic medium by the red row 104 - 1 ( say ) occurs at a different location on the photosensitive medium to joins between adjacent swathes of that image which are attributable to the blue and green rows 104 - 2 , 104 - 3 . in an alternative example , the different rows 104 - 1 , 104 - 2 , 104 - 3 are arranged with their ends substantially aligned . further details relating to the led array are provided in wo2007138318 , published 6 dec . 2007 with the title ‘ improvements relating to optical printers ’ which is incorporated in its entirety herein by reference . in the example of an rbg array , the wavelengths of the different rows 104 - 1 , 104 - 2 and 104 - 3 would be 690 - 700 nm ( r ), 430 - 440 nm ( b ) and 540 - 550 nm ( g ). in addition to the passive temperature management elements described above , in certain examples , active cooling control is provided . the wavelength and power of light emitted from the leds varies depending on the ambient temperature , and in one example , temperature control of the leds within a range of 0 . 5 ° c . is necessary . in one example , the active cooling elements are in the form of a peltier element and / or an air - blower situated outside the radiating device 100 . in one example , in addition to the leds 104 , there are also thermistors 302 mounted on the substrate 102 . these are preferably spaced as close to the led strips 104 - 1 , 2 , 3 as possible , in one example , between the strips . the placement of thermistors 302 enables accurate temperature measurements of the leds 104 to be taken . these measurements can be fed to the active cooling elements to effect feedback temperature control of the substrate 102 . fig3 ( c ) shows a more detailed view of the rear face of the led substrate 102 . this shows a number of connectors 300 which enable the individual leds to be connected via wire - bonding to further circuitry to control individually the power and timing of each of the leds . in one example application specific integrated circuits ( asics ) or field programmable gate arrays ( fgpas ) are used for this purpose . in certain examples , two connectors 300 for each led , and two for each thermistor 302 are provided . in one example , a printed circuit board or motherboard is provided which is connectable to the connectors , and the location holes 304 are provided to guide this board into place . fig4 shows the spacing element 112 described above with reference to fig1 . in the example shown there are three parallel apertures 400 which are locatable in register with the three rows of leds 104 - 1 , 104 - 2 , 104 - 3 . this plate acts as a spacer so that the leds and wire bonds are protected from being damaged when pressed against the other components in the device . in other systems , leds and wire bonds are coated with epoxy in order to protect them . this epoxy can damage the connectors themselves upon application and in use , and also introduces another source of scattering for the light . the introduction of the spacing element 112 thus offers better protection for the leds and wire bonds and improves the optical properties of the system . in a preferred example , this plate 112 is less than 1 mm thick , and preferably 0 . 51 mm thick . the plate 112 is preferably ceramic , due to its advantageous thermal properties . ceramic materials have a low thermal conductance , which means that heat produced by the leds is not transferred to the radiation modification plate 114 which could adversely affect its optical properties of the plate 114 . fig5 and 6 show the thermal pads which were described above in relation to fig1 . the front thermal pad 110 is shaped to correspond with the shape of the substrate 102 . it has an aperture large enough to accommodate the ceramic plate 112 and the radiation modification plate 114 . the back thermal pad 106 is similarly sized , but has two apertures which correspond in size and position to the connectors 300 provided on the rear face of the substrate 102 . each pad has a high thermal conductivity so as to draw heat from the substrate 102 ( where the leds 104 are producing heat ) and conduct it to the front 116 and back 108 plates respectively , which dissipate the heat into the surroundings . the pads 110 , 106 are in thermal contact with both the substrate 102 and the front 116 or back 108 plate . in a preferred example , they are less than 1 mm thick , and preferably 0 . 67 mm thick . fig7 and 8 show the top plate 116 and back plate 108 of the radiating device . the faces of these plates have a size larger than the that of the other components , but correspond with one another . this is so that screws 118 can pass through holes 700 and fasten into corresponding screw - threaded cavities 800 in the back plate 108 without interfering with intermediate components . the act of tightening these screws 118 secures the components together , thereby ‘ sandwiching ’ them in place . to avoid damaging the components , a gasket may be introduced between the front and back plates , and / or between any other pair of layers within the ‘ sandwich ’. the front plate has an aperture 702 of a size corresponding to that of the radiation modification plate 114 and ceramic plate 112 . the aperture 702 is preferably shaped so that the top ( print medium facing ) edge protrudes slightly so as to hold the plates 114 , 112 in place when secured . this is shown in fig1 ( b ). alternatively or in addition the plates may be secured together in some other manner , for example , they may be glued together . the back plate 108 has two apertures 802 which are shaped so as to allow access to the electrical connectors 300 of the substrate plate 102 . fig8 ( b ) and ( c ) show that the back plate 108 has a depth far greater than any other component , preferably 10 mm thick . this is to aid in its role as a heat sink . the plate 108 is made from a material with a high thermal conductance , preferably aluminium . the extra depth provides greater heat capacity and thus serves as a more efficient heat sink . the above description mainly focuses on one example of a radiating device . there are of course numerous alternatives and modifications that can be made and still remain within the scope of the invention . for example , although the above description and corresponding figures describe an rbg macro - led array as being the light source , other arrangements are possible , and preferable in certain circumstances . an alternative arrangement would be to have an led array of infra red ( ir ) and / or ultra violet ( uv ) leds . this arrangement would enable the device to print onto optically sensitive media . the examples shown above all describe a distinct print head radiating device , but it is envisaged that a plurality of such radiating devices will be coupled together to form part of a much larger print head , that is , a bar - like structure . in an led printhead , the light produced at the bottom of the radiating device as described above is often not of a small enough spot size to generate high resolution images on the print media . in order to rectify this , the radiating device is attached to an apparatus which reduces the spot size . this could be in the form of a ‘ tapered fibre ’, details of which are described in wo0135633 published 17 may 2001 with the title ‘ digital photographic reproduction apparatus ’ which is hereby incorporated in its entirety by reference . alternatively , this reduction could be performed by a lens system as described below . in order to get the required resolution for the final printed article , the accurate control of exposure to the medium is required . the size of an area which is exposed by a single led is called the ‘ spot size ’ and is often the limiting factor of the resolution of the printed article . for this reason , reduction of the spot size is an essential function of a high resolution led printer . as discussed above , one solution is to use a ‘ fibre taper ’. this is a bundle of optical fibres which are heated and pulled to form an hourglass shaped bundle which is then cut in half . this generates a device which focuses light entering the bundle down onto a smaller spot size . an alternative solution is to use a telecentric lens system as described below . in the description that follows , the object aperture of the lens system is the aperture which is to be illuminated by the leds and the image aperture is the aperture of the lens system which projects the image onto the print medium . fig9 shows a schematic ray diagram of a bi - telecentric lens system . telecentric lenses are different from standard lens systems as they correct for perspective . for this reason they are used in the imaging of objects such as apertures or objects which are vibrating . the correction for perspective in these situations allows a user to accurately measure the size of an aperture or vibrating object , which would be difficult when using a standard lens due to magnification changes or distortion due to lack of focus . the property which allows these effects is that for a range of distances there is effectively a constant magnification . this means that the spot size produced by an led illuminating a telecentric lens will be substantially constant for a range of distances away from the image aperture . this range of distances is called the ‘ depth of field ’ of the system . conventional lens systems have a very limited depth of field , which results in large errors when a part of the print medium is at a different distance from the previous part . for example , the depth of field of the ‘ fibre taper ’ described above is in the micron range whereas for a typical telecentric lens system it is in the millimetre range . the image lens 950 can be adjusted in the system , moved longitudinally along the axis of the lens so as to ‘ fine tune ’ the magnification factor . this may be necessary as two telecentric lenses produced to the same specification may have slightly different magnification factors . in order to correct for this , a grid is imaged through a lens , and matched up to a calibration grid by altering the position of the image lens 950 via bevel adjuster 906 ( fig1 ). in one example , the lens 950 can be adjusted by up to 0 . 5 mm using the bevel adjuster 906 . the depth of field of a telecentric lens is determined by two factors — the tolerable error in magnification and the ‘ telecentric slope ’ of the lens by the following formula : δm = change in spot size radius ( in the same units as dof ) for example , if the medium can be placed with an accuracy of 1 mm ( required dof ) of the lens and the telecentricity of the lens is 0 . 15 °, the change in spot size radius is 2 . 6 μm over that 1 mm range . for the system as described herein , where the final spot size diameter is 80 μm , this is error of around 3 %. this error increases linearly with increasing telecentricity , so a lower limit on the quality of the telecentric lens can inferred from the maximum error tolerable . a more general formula for determining the error in spot size as a percentage of the final spot size is given by : for example , if the error tolerable in a system as shown in fig1 and table 1 below is 5 %, and the required dof is 1 mm , the highest telecentricity the lens could have would be 0 . 23 °. in a preferred embodiment , the lens has a telecentricity of below 0 . 2 °, even more preferably below 0 . 15 °. in one example , where uv leds 104 are used the lens is preferably constructed from uv transparent materials such as fused quartz or fused silica . a corollary of using such materials , and to a lesser extent , standard glass , is that the transmission properties are significantly improved . in one example , the intensity of light is increased by 95 % compared to a fibre taper . fig1 shows an example telecentric lens 900 adapted for use with the rbg led radiating device 100 described above . the print medium 904 and an illumination source 902 have been included in order to show relative distances . table 1 below describes preferred properties and characteristics of this example : in one example , shown schematically in fig1 , the telecentric lens 900 described above is used in combination with the led radiating device 100 , also described above , to produce a media exposure device . the telecentric lens 900 is optically coupled to the radiating device 100 by mechanically connecting the radiating device 100 to the lens 900 using a mechanical coupling 912 , in the form of a cage mount 912 . a base portion 911 of the cage mount 912 is attached to a flange 910 which is itself attached to the top of the telecentric lens 900 . this cage mount 912 houses the radiating device 100 and a plurality of controlling motherboards 908 . the radiating device 100 fits into a recess provided in the base portion 911 of the cage mount 912 . the radiating device 100 is shown expanded for clarity . the motherboards 908 contain the necessary electronics to power , control and cool the leds 104 . the motherboards 908 are connected to the connectors 300 on the substrate 102 via a further printed circuit board having push connectors , extended pins , or other suitable connecting means , which pass through the apertures in the back plate 108 and rear thermal pad 106 . in one example , the lens 900 is mounted 5 mm below ( closer to the print medium 904 ) the led substrate 102 for optimum operation . fig1 shows a diagram of two such lenses 900 and cage mounts 912 as described above . an advantage of having multiple devices on the same printhead is that each swathe of print is wider , resulting in faster printing . for this to be possible , accurate alignment of the swathes is necessary , which is discussed in below with reference to fig1 and 14 . fig1 shows a diagram of two lenses 900 which during an alignment process . the first lens 900 is attached to a mounting bar 913 using a ‘ key - slot mount ’ 914 - 1 . this aligns the lens vertically ( i . e . at the correct distance from print medium ) and ensures it is orthogonal to the print medium . the mounting bar 913 in one example is a print bar along which the print head moves when producing a swathe of print . the second lens is attached to the same print bar 913 by a second key - slot mount 914 - 2 . this is set back longitudinally along the bar 913 by a preset amount , and also laterally offset perpendicular to the bar 913 by a preset amount . this lateral distance sets the distance between the swathes , and must be very accurate otherwise ‘ banding ’ will occur as discussed above . the longitudinal distance it is set back along the bar 913 does not affect this so does not necessarily need to be finely controlled . the process of aligning the second swathe from the second lens 900 - 2 with respect to the first is described in detail below . a micrometer 916 is attached to the underside of the cage mount 912 and contacts the lens 900 - 2 . the bolts securing the lens 900 - 2 to the cage mount 912 are loosened or removed . this allows the cage mount 916 ( and hence the position of the leds 104 ) to be moved relative to the lens 900 - 2 . in one example , the bolt holes are slots so that the bolts can be loosened , then the adjustment to position can be made , then re - tightened . this movement is focused by the lens 900 - 2 , so a 0 . 1 mm movement of the micrometer results in a 20 μm movement of the swathe at the print medium ( for a lens with a magnification factor of 5 : 1 ). this allows for the accurate positioning of the second swathe . the second lens 900 - 2 is positioned as accurately as possible to begin with using the key - slot mount 914 - 2 , as only a limited amount of movement can be achieved using the micrometer 916 before the leds 104 move out of the lens &# 39 ; field of view . although fig1 and 13 show two lenses 900 - 1 , 900 - 2 , any number may be arranged onto a print bar using the method described . a physical limit on the number of lenses may occur however when the weight of additional lenses may make it quicker and more accurate to print using multiple passes of smaller swathes rather than in one large swathe . fig1 shows a flow diagram of the method used to align an additional swathe with the previous swathe . in step s 1 , the first lens 900 - 1 , together with its radiating device 100 ( not shown ) is mounted onto the print bar 913 using the key - slot mount 914 described above . the second lens 900 - 2 is then mounted in a similar fashion in step s 2 , offset laterally and longitudinally from the first lens 900 - 1 . a micrometer 916 is attached to the lower panel of the cage mount 911 adjacent to the second lens 900 - 2 and contacts the second lens 900 - 2 itself in step s 3 . the bolts securing the lens 900 to the cage 911 are loosened / removed in step s 4 so that adjustment of their relative positions can take place in step s 5 . this step involves moving the cage 911 ( and hence leds 104 ) relative to the lens 900 - 2 so that the swathes coincide . in the example of the rbg led strips 104 - 1 , 104 - 2 , 104 - 3 above , this is where the ‘ g ’ strip coincides with the ‘ r ’ strip from the neighbouring array . in one example , there may be some overlap as when the apparatus is in use it expands due to the raised temperature . such calibration can be worked out once and then used for all subsequent alignments . step s 6 indicates the feedback loop used to effect the alignment of the swathes . the swathes may be compared by exposing a photosensitive media , or by passing the heads over a camera . when the swathes are suitably aligned , the bolts are tightened in step s 7 and the micrometer 916 is removed in step s 8 . if the printhead is complete ( step s 9 ), the process terminates , if another lens 900 is to be added , the process returns to step s 2 . table 2 shows example properties of a telecentric lens adapted for use with uv leds . although the above lenses are described as bi - telecentric , it is envisaged that a lens with just image - space telecentricity may be used . this would suffice as the positioning of the leds relative to the object aperture of the lens ( distance c ) can be controlled to a great degree of accuracy and reproducibility , and does not change once mounted . conversely , the image side distance d is subject to variation as the print medium is moved for example . it is thus far more important to have image - space telecentricity than object - space telecentricity . it will be understood that the present invention has been described above purely by way of example , and modifications of detail can be made within the scope of the invention . reference numerals appearing in the claims are by way of illustration only and shall have no limiting effect on the scope of the claims | 7 |
in the following , embodiments of the present invention will be described with reference to the accompanying drawings . [ 0060 ] fig1 is a block diagram of an idlc system including a subscriber - system transmission apparatus according to an embodiment of the present invention . in fig1 the subscriber - system transmission apparatus 1 is connected to tr303 - type digital switches 2 a , 2 b , and 2 c corresponding to respective vendors a , b , and c . this connection is established via optical - fiber transmission lines based on ds 1 interface . further , the subscriber - system transmission apparatus 1 is connected to analog switches 4 a , 4 b , and 4 c corresponding to respective vendors a , b , and c via optical - fiber transmission lines and a center - station - system transmission apparatus 5 . the subscriber - system transmission apparatus 1 covers a plurality of isdn subscriber terminals 7 via nt 1 ( network - terminal - apparatus - 1 ) apparatuses 6 . each user of the subscriber terminals 7 belongs to his / her choice of a service - provider network where service - provider networks adopt switches manufactured by vendors of their own choice . when a user attempts to transmit or receive a call , he / she establishes connection with the service - provider network to which he / she belongs . a control console 10 connected to the subscriber - system transmission apparatus 1 is comprised of a personal computer or the like , which is used for making various settings to the subscriber - system transmission apparatus 1 in terms of switch options and the like . in this manner , the subscriber - system transmission apparatus 1 is provided with the ds 1 interface for the idts ( integrated digital terminals ), and includes an eoc interface unit and a cross - connect unit therein for switching between the 3ds 0 time - division - multiplexing scheme and the 4 : 1 time - division - multiplexing scheme . this makes it possible to assume an idlc configuration based on the 4 : 1 time - division - multiplexing scheme . further , this system can be regarded as the 3ds 0 - scheme system having an additional configuration based on the 4 : 1 time - division - multiplexing scheme . a mode - switch unit is provided to operate under control of the operation system to switch between the 3ds 0 time - division - multiplexing scheme and the 4 : 1 time - division - multiplexing scheme . because of such a configuration , this system can be connected to both the switches of 3ds 0 time - division - multiplexing scheme and the switches of the 4 : 1 time - division - multiplexing scheme . [ 0065 ] fig2 is a block diagram of a relevant portion of the subscriber - system transmission apparatus 1 according to this embodiment for the purpose of explaining an eoc path during the 4 : 1 time - division - multiplexing mode . as show in fig2 the subscriber - system transmission apparatus 1 includes a common shell 11 and narrow band shells 12 . the common shell 11 includes a multiplexing / demultiplexing card 13 , a cross - connect card 14 , a sw - interface unit 15 , and an eoc control card 16 . the multiplexing / demultiplexing card 13 is comprised of a hc 1 a / ho 10 unit , a ts 1 a unit , mc 1 o unit , etc . the cross - connect card 14 is comprised of a ts 1 c unit or the like , and the sw - interface unit 15 includes an ep 1 c unit or the like . the eoc control card 16 includes an emlc unit or the like . the narrow band shells 12 are provided as many as 10 units in parallel , and are connected to the cross - connect card 14 of the common shell 11 . each narrow band shell 12 includes a multiplexing / demultiplexing card 17 and 48 isdn channel cards 18 . the multiplexing / demultiplexing card 13 of the common shell 11 is connected to the optical - fiber transmission lines via various interfaces such as oc 3 / oc 12 , oc 3 / d 3 / sts 1 , or ds 1 . main signals 2 b + d demultiplexed by the multiplexing / demultiplexing card 13 are supplied to the cross - connect card 14 during a period when the 4 : 1 time - division - multiplexing scheme is selected . in an opposite direction , the main signal 2 b + d multiplexed by the cross - connect card 14 are supplied to the multiplexing / demultiplexing card 13 . an eoc signal demultiplexed by the multiplexing / demultiplexing card 13 is supplied to the cross - connect card 14 as an internal eoc after passing through the sw - interface unit 15 and the eoc control card 16 . in the opposite direction , the internal eoc multiplexed by the cross - connect card 14 is supplied to the multiplexing / demultiplexing card 13 via the eoc control card 16 and the sw - interface unit 15 . the narrow band shells 12 attend to eoc / eoc conversion processing and eoc / i - bit conversion processing , and supply or receive the 2 b + d and m channels at the u - point interface . in fig2 showing the eoc path during the 4 : 1 time - division - multiplexing mode , signals transmitted to or received from oc 3 / oc 12 are exchanged with the cross - connect card 14 via the multiplexing / demultiplexing card 13 . on the other hand , the eoc ( e . g ., eoc bit + i bit ) during the 4 : 1 time - division - multiplexing mode is exchanged between the multiplexing / demultiplexing card 13 and the narrow band shells 12 via the sw - interface unit 15 and the eoc control card 16 where sw - interface unit 15 provides necessary interface , and the eoc control card 16 attends to eoc control . as shown in fig1 the switch system employing the subscriber - system transmission apparatus 1 does not require the related - art center - station ( cot ) transmission device 5 when it is connected to the tr303 - type digital switches 2 a through 2 c . that is , the subscriber - system transmission apparatus 1 is connected to the tr303 - type digital switches 2 a through 2 c via interface such as ds 1 . since interface specifications ( e . g ., isdn alarm detection ) differ from vendor to vendor who manufacture the tr303 - type digital switches 2 a through 2 c , a method of notifying an isdn alarm is changed depending on the types of the tr303 - type digital switches 2 a through 2 c . to this end , the control console 10 connected to the subscriber - system transmission apparatus 1 is used for making settings to switch options swopt . these settings make it possible to perform isdn - alarm notification that complies to each of the switches . in the subscriber - system transmission apparatus 1 , the switch options swopt may define that the companies a and c correspond to swopt 1 and that the company b correspond to swopt 2 . the control console 10 serving as a switch - option setting unit is used for setting appropriate data to the sw - interface unit 15 , the eoc control card 16 , and the isdn channel cards 18 , thereby complying to the requirements of the switch to be connected . switch option swopt 3 is not in use because there is no vendor corresponding to this option . however , operation is guaranteed based on software specifications prior to correction of problems , so that backward compatibility is secured so as not to cause malfunction in apparatuses having only the emlc unit thereof updated . [ 0074 ] fig3 is a block diagram showing details of a portion relevant to settings of switch options in the subscriber - system transmission apparatus 1 . fig3 is used for explaining a method of controlling alarm when the subscriber - system transmission apparatus 1 is connected to all the switches . in fig3 the tr303 - type digital switch 2 a is made by the manufacturer a , and is connected to the subscriber - system transmission apparatus 1 via ds 1 . the switch setting is swopt 1 . the tr303 - type digital switch 2 b is made by the manufacturer b , and is connected to the subscriber - system transmission apparatus 1 via oc 3 . the switch setting is swopt 2 . the tr303 - type digital switch 2 c is a product of the manufacturer c , and is connected to the subscriber - system transmission apparatus 1 via oc 12 . the switch setting is swopt 1 . the sw - interface unit 15 of the subscriber - system transmission apparatus 1 includes three sw - interface units 151 through 153 corresponding to the respective tr303 - type digital switches . the sw - interface units 151 through 153 can be set to the switch option swopt 1 , swopt 2 , or swopt 3 by using the control console ( swopt setting unit ) 10 . in this example , the sw - interface units 151 and 153 respectively connected to the tr303 - type digital switches 2 a and 2 c are set to the switch setting ( switch option ) swopt 1 , and the sw - interface unit 152 connected to the tr303 - type digital switch 2 b is set to the switch option swopt 2 . the sw - interface units 151 through 153 attend to conversion resembling language conversion , as will be described later , which corresponds to specifications of each of the tr303 - type digital switches 2 a through 2 c . the eoc control card 16 includes three eoc - control units 161 through 163 , which correspond to the sw - interface units 151 through 153 of the sw - interface unit 15 , respectively . the eoc - control units 161 through 163 are set to the switch option swopt 1 , swopt 2 , or swopt 3 to conform to the switch - option settings of the sw - interface units 151 through 153 set by the control console 10 . in the example shown in fig3 the eoc - control unit 161 has the switch option thereof set to swopt 1 in conformity with the switch option setting of the sw - interface unit 151 , and controls the eoc supplied from the sw - interface unit 151 via an eoc - termination unit 164 . further , the eoc - control unit 161 exchanges the internal eoc with the isdn channel cards 18 via an internal - eoc - exchange unit 165 . the eoc - control units 161 through 163 convert alarm formats to conform to the specifications of the tr303 - type digital switches 2 a through 2 c , which will be described later . the cross - connect card 14 is provided between the eoc control card 16 and the isdn channel cards 18 , and attends to cross - connect processing . under the remote control of the control console 10 , the cross - connect card 14 can switch between the 4 : 1 time - division - multiplexing scheme and the 3ds 0 time - division - multiplexing scheme with respect to each subscriber , and can establish a cross - connect between a given subscriber and any given subscriber number of any given switch . further , the cross - connect card 14 has service statuses ( e . g ., used / unused statuses of the b 1 and b 2 channels ) and provisioning ( e . g ., settings of 4 : 1 tdm and 3ds 0 tdm ) thereof set through remote controlling . each of the isdn channel cards 18 has 2 channels , each of which is connected to a corresponding one of the subscriber terminals ( te ) 7 via the nt 1 apparatus 6 . each channel of each isdn channel card 18 includes three alarm - control units 181 through 183 , an internal - eoc - exchange unit 184 , and a u - point - termination unit 185 . the alarm - control units 181 through 183 are set to the switch option swopt 1 , swopt 2 , or swopt 3 . the internal - eoc - exchange unit 184 is equipped with the function of eoc / eoc conversion and the function of eoc / i - bit conversion . [ 0082 ] fig4 is a block diagram showing a configuration of the u - point - termination unit 185 . the u - point - termination unit 185 includes a u - point - synchronization - deviation - detection unit 1851 , a nt 1 - power - supply - disconnection - detection unit 1852 , a t - point - synchronization - deviation - detection unit 1853 , alarm - control - switching unit 1854 . the u - point - synchronization - deviation - detection unit 1851 detects loss of synchronization when synchronization is lost at the u point serving as connection interface with the nt 1 apparatus 6 . the nt 1 - power - supply - disconnection - detection unit 1852 detects disconnection of power supply to the nt 1 apparatus 6 . the t - point - synchronization - deviation - detection unit 1853 detects loss of synchronization when synchronization is lost at the t point . the alarm - control - switching unit 1854 selectively connects to one of the alarm - control units 181 through 183 . the alarm - control - switching unit 1854 is almost permanently connected to one of the alarm - control units 181 through 183 . this connected one of the alarm - control units 181 through 183 has the switch option swopt thereof set to conform to a tr303 - type digital switch that is employed by the network to which the user of the channel belongs . in the example of fig3 the channel ch 1 of the isdn channel card 18 is used by a user who belongs to a service - provider network that employs the tr303 - type digital switch 2 a manufactured by the manufacturer a . in order to connect the channel ch 1 to the tr303 - type digital switch 2 a , the control console 10 is used to make connection settings to the cross - connect card 14 . after this connection is established , the channel ch 1 is set by the eoc control card 16 such as to carry out alarm control of the switch option swopt 1 . [ 0086 ] fig5 through fig7 are tables showing isdn - alarm - notification commands and values thereof that are transmitted in response to the switch option settings corresponding to each switch vendor . fig5 shows a case in which the alarm condition indicates loss of synchronization at the u point . fig6 shows a case where the power supply to the nt 1 is disconnected . fig7 shows a case in which synchronization is lost at the t point . with respect to the switch venders a and c , a notification command that corresponds to the switch option swopt of 1 is used . with respect to the switch vendor b , a notification command that corresponds to the switch option swopt of 2 is used . since the switch option swopt of 3 does not correspond to any vendor , it is not currently used . however , operation is guaranteed based on software specifications prior to correction of problems , so that backward compatibility is secured so as not to cause malfunction in apparatuses having only the em 1 c unit thereof updated . what is shown in the figure is an eop report that the subscriber - system transmission apparatus 1 transmits to the switch 2 . ltoh represents m bits directed downstream at the u point , and ntoh represents m bits directed upstream at the u point . in the case of loss of synchronization at the point u as shown in fig5 the alarm status change report is transmitted if the switch setting is swopt 1 corresponding to the vendor a . in this case , if the switch setting is swopt 2 corresponding to the vendor b , the alarm status change report and the nt 1 overhead change report are transmitted . in this case , where “ x ” is the same value as one observed before loss of synchronization at the u point . if the switch setting is a default setting swopt 3 corresponding to no vendor , the alarm status change report is transmitted . in this case , in this manner , the u - point - synchronization - deviation - detection unit detects loss of synchronization at the u point , and notifies the switch of the alarm status . in so doing , only the alarm status change report should be sent to the switch if the switch is a product of the vendor a or c corresponding to the switch option swopt 1 . further , the act bit of ltoh should be set to 0 , and all bits of ntoh should be set to 0 . if the switch is a product of the vendor c corresponding to the switch option swopt 2 , both the alarm status change report and the nt 1 overhead change report should be sent . in this case , the act bit of ltoh should be set to 0 . further , the act bit , the ps 1 bit , the ps 2 bit , and the sai bit of ntoh should be set to 0 . in the case of disconnection of power supply to the nt 1 as shown in fig6 the alarm status change report is transmitted if the switch setting is swopt 1 corresponding to the vendor a . in this case , if the switch setting is swopt 2 corresponding to the vendor b , the alarm status change report and the nt 1 overhead change report are transmitted . in this case , where “ x ” is the same value as one observed before disconnection of power supply to the nt 1 . if the switch setting is a default setting swopt 3 corresponding to no vendor , the alarm status change report is transmitted . in this case , in this manner , the status of disconnection of power supply to the nt 1 is the same as the status of loss of synchronization at the u point , resulting in transmission of the same messages . in the case of loss of synchronization at the t point as shown in fig7 the nt 1 overhead change report is transmitted if the switch setting is swopt 1 corresponding to the vendor a . in this case , where “ x ” is the same value as one observed before loss of synchronization at the t point . if the switch setting is swopt 2 corresponding to the vendor b , the nt 1 overhead change report are transmitted . in this case , where “ x ” is the same value as one observed before loss of synchronization at the t point . if the switch setting is a default setting swopt 3 corresponding to no vendor , the nt 1 overhead change report is transmitted . in this case , in this manner , the t - point - synchronization - deviation - detection unit detects loss of synchronization at the t point , and notifies the switch of the alarm status . the switch corresponding to the switch setting swopt 1 detects loss of synchronization at the t point if the act bit of ltih is 1 and the act bit of ntoh is 0 . on the other hand , the switch corresponding to the switch setting swopt 2 detects loss of synchronization at the t point if the act bit of ltoh , the act bit of ntoh , and the sai bit are 1 , 0 , 0 , respectively . because of this , values as shown in fig7 are transmitted to let the switches properly detect loss of synchronization at the t point . [ 0118 ] fig8 through fig1 are tables showing isdn alarm notification commands and values thereof transmitted in response to switch settings of the eoc - control unit of the eoc control card 16 . fig8 shows a case in which no isdn channel card is in a card slot . fig9 shows a case in which synchronization is lost at the u point . fig1 demonstrates a case where the power supply to the nt 1 is disconnected . fig1 exhibits a case in which synchronization is lost at the t point . when no isdn channel card is in a card slot as shown in fig8 for example , only the m event report for isdn - line - termination purposes should be transmitted if the switch setting is swopt 1 . if the switch setting is swopt 2 , however , the m event report for isdn - framing - path - termination - change purposes in the overhead bit report should be transmitted in addition to the m event report for isdn - line - termination purposes . the m event report for isdn - framing - path - termination - change purposes in the overhead bit report should include data of ltoh ad ntoh as shown in fig8 . [ 0120 ] fig1 through fig1 are tables showing standards of isdn alarm messages that are transmitted in response to switch settings of the sw - interface unit of the sw - interface unit 15 . fig1 shows isdn alarm messages where the switch option is swopt 1 corresponding to the vendor a . fig1 illustrates isdn alarm messages where the switch option is swopt 2 corresponding to the vendor b . fig1 exhibits isdn alarm messages where the switch option is set to a default value swopt 3 corresponding to no existing vendor . the subscriber - system transmission apparatus 1 operates as follows based on the mechanism as described above . in the following , it is assumed that the subscriber terminal 7 covered by the channel ch 1 of the isdn channel cards 18 belongs to the service - provider network employing the tr303 - type digital switch 2 a of the vendor a , and that the subscriber terminal 7 covered by the channel ch 2 belongs to the service - provider network employing the tr303 - type digital switch 2 b of the vendor b . as a consequence , the alarm - control - switching unit 1854 of the u - point - termination unit 185 for the channel ch 1 is controlled so as to select the alarm - control unit 181 that corresponds to the switch setting swopt 1 of the vendor - a switch . further , the alarm - control - switching unit 1854 of the u - point - termination unit 185 for the channel ch 2 is controlled so as to select the alarm - control unit 182 that corresponds to the switch setting swopt 2 of the vendor - b switch . when the isdn channel card 18 is taken out of the slot , for example , the eoc - control units 161 and 162 of the eoc control card 16 transmits alarm messages to the tr303 - type digital switches 2 a and 2 b , respectively , thereby notifying the inoperative statuses of the channels ch 1 and ch 2 . when synchronization is lost at the u point of the channel ch 1 in the isdn channel card 18 , for example , the u - point - termination unit 185 of the channel ch 1 detects loss of synchronization at the u point . in response , the alarm - control unit 181 transmits an alarm - notification command that conforms to the switch option swopt 1 , and this command is supplied to the tr303 - type digital switch 2 a from the internal - eoc - exchange unit 184 via the cross - connect card 14 , the eoc control card 16 , and the sw - interface unit 15 . this tr303 - type digital switch 2 a corresponds to the switch option swopt 1 . when synchronization is lost at the u point of the channel ch 2 , for example , the u - point - termination unit 185 of the channel ch 2 detects loss of synchronization at the u point . in response , the alarm - control unit 182 transmits an alarm - notification command that conforms to the switch option swopt 2 , and this command is supplied to the tr303 - type digital switch 2 b from the internal - eoc - exchange unit 184 via the cross - connect card 14 , the eoc control card 16 , and the sw - interface unit 15 . this tr303 - type digital switch 2 b corresponds to the switch option swopt 2 . when synchronization is lost at the t point of the channel ch 1 in the isdn channel cards 18 , the nt 1 apparatus 6 connected to the channel ch 1 sends a m - bit message indicative of loss of t - point synchronization to the channel ch 1 of the isdn channel cards 18 by passing the message through the u point . the alarm - control unit 181 then uses an alarm - notification command to transmit the eoc where the alarm - notification command conforms to the requirements of the vendor a . in the following , operation of the u - point - termination unit 185 will be described in detail with reference to fig4 . as was previously described , the u - point - termination unit 185 includes the u - point - synchronization - deviation - detection unit 1851 , the nt 1 - power - supply - disconnection - detection unit 1852 , and the t - point - synchronization - deviation - detection unit 1853 . it should be noted here that the number of m bits used for reporting loss of synchronization at the t point varies depending on the types of nt 1 apparatuses . some notify by use of the act bit that is 0 , and others notify by use of the sai bit that is 0 . there are still some others that notify by use of the act bit and sai bit that are both zero . in order to detect loss of t - point synchronization with respect to any variation of these , the t - point - synchronization - deviation - detection unit 1853 of the u - point - termination unit 185 detects loss of t - point synchronization by checking if either one of the act bit and the sai bit is 0 . when the m - bit message is supplied to the switch without any processing thereof , the switch cannot properly detect the loss of t - point synchronization . because of this reason , the alarm - control unit 181 attends to conversion into ltoh and ntoh values that conform to the requirements of the vendor - a switch . this ensures that any type of a switch can be properly notified of loss of t - point synchronization regardless of the type of the nt 1 that is connected to the isdn channel card . in the description provided above , the switches connected to the subscriber - system transmission apparatus 1 have been referred to as the tr303 - type digital switches . if the switches of a network - service provider to which subscriber terminals belong are tr08 - type digital switches , then , connection is established by using the tr08 - type - switch mode . by the same token , if analog switches are used , connection is established by using the analog - switch mode . for connection during the tr08 - type - switch mode , none of the sw - interface unit 15 and the eoc control card 16 of the subscriber - system transmission apparatus 1 are used . signals from the tr08 - type digital switch are provided from the multiplexing / demultiplexing card 13 to the cross - connect card 14 , which has switched to the 3ds 0 time - division - multiplexing scheme . the alarm - control unit of the isdn channel card 18 in this case is comprised of only one type of alarm - control unit that conforms to the specifications of the tr08 - type digital switch . for connection during the analog - switch mode , the nt 1 apparatus 6 of the subscriber terminal 7 is connected via the u - point - termination unit 185 of the isdn channel card 18 directly to the cross - connect card 14 , which has switched to the 3ds 0 time - division - multiplexing scheme . this connection is established without having the alarm - control units 181 through 183 or the internal - eoc - exchange unit 184 as intervening units . further , the connection is extended from the cross - connect card 14 to the center - station - system transmission apparatus 5 via an analog - switch multiplexing / demultiplexing unit 19 and the optical - fiber transmission line . as described above , according to the present invention , no special work such as exchange of modules is necessary when there is a need to connect with switches operating based on the 4 : 1 time - division - multiplexing scheme . a relatively simple configuration includes the eoc - interface unit , the 4 : 1 tdm - cross - connect unit , the eoc / eoc -& amp ;- eoc / i - bit - conversion unit , etc ., which is all that is necessary to implement the isdn service providing connections with digital switches based on 4 : 1 time - division - multiplexing scheme in addition to rendering of the 3ds 0 time - division - multiplexing service . further , the same configuration as in the conventional art is used with regard to mux / dmux interface , u - point interface , line structures , etc ., thereby making it possible to cope with switches of the 4 : 1 time - division - multiplexing scheme without requiring major changes that may affect existing services . further , the present invention is not limited to these embodiments , but various variations and modifications may be made without departing from the scope of the present invention . the present application is based on japanese priority application no . 2000 - 076034 filed on mar . 17 , 2000 , with the japanese patent office , the entire contents of which are hereby incorporated by reference . | 7 |
the following detailed description is of the best presently contemplated modes of carrying out the invention . this description is not to be taken in a limiting sense , but is made merely for purposes of illustrating the general principles of the invention . referring to fig1 inventive carabiner 10 is shown linking climbing rope 12 to webbing 14 looped around rock 16 . fig1 exemplifies one of the many ways that a carabiner can be used to link climbing aids together . referring to fig2 carabiner 10 includes body 20 and gate 50 . the inventive locking mechanism is contained within gate 50 , only button 70 protrudes externally . body 20 and gate 50 are fabricated from a lightweight , high strength material , for example aluminum alloy type 7075 heat treated to condition t 6 . the simplest , and preferred , configuration of the inventive locking mechanism is illustrated by fig2 - 12 . referring to fig5 gate 50 is slotted at both ends by parallel slots 52 and 34 . leg ends 22 and 24 of body 20 nest loosely within the confines of slots 32 and 34 respectively . gate 30 is hinged to body 20 by pin 36 which transverses slot 32 through a slip - fitting hole in leg end 22 . referring to fig3 and 5 , the opening end of gate 30 includes pin 38 which transverses slot 34 . when gate 30 is closed , pin 38 rests against the top of notch 28 in body 20 , thereby limiting the closing movement of gate 30 . notch 28 also serves to capture pin 38 when high tensile loads deform bodily 20 , thereby enabling gate 30 to carry part of the load transmitted through body 20 . alternate means of limiting the travel of gate 30 are possible . for example , forming the end of gate 30 to abut directly against a mating recess of body 20 can eliminate pin 38 . as another alternative , the end of gate 30 and the associated leg of body 20 can be formed or machined to provide an interlocking relationship that transmits tensile loads . referring to fig5 gate 30 is held in the closed position by the combined action of compression spring 40 , spring pin 50 and link 60 . compression spring 40 and spring pin 50 are loosely contained within hole 42 . hole 42 opens into slot 32 and the axis of hole 42 is approximately parallel to the axis of gate 30 . as best seen in fig6 hole 42 has an oblong cross section . compression spring 40 is typically fabricated by coiling a corrosion resistant material , for example 17 - 7 ph stainless steel spring wire . machining or forcing a corrosion resistant material , for example brass , is a typical way to fabricate spring pin 50 . machining and swaying a corrosion resistant material , for example type 316 stainless steel wire , is a typical way to fabricate link 60 . compression spring 40 , in conjunction with spring pin 50 , applies a force in one direction against abutment 44 in hole 42 and in the other direction against joint 62 between spring pin 50 and link 60 . link 60 transmits the force to notch 26 on body 20 . notch 26 is adjacent but offset inward from the center of hinge pin 36 . the offset distance provides the leverage which forces gate 30 closed . when gate 30 opens , link 60 pushes spring pin 50 into hole 42 , compressing spring 40 . when gate 30 is open , the force of spring 40 against link 60 urges gate 30 to return to the closed position . referring again to fig3 and 5 , lock button 70 is located within slot 32 adjacent leg 22 of body 20 . lock button 70 transverses the width of gate 30 . referring to fig5 and 7 , link 60 passes loosely through hole 72 , which transverses lock button 70 , thereby retaining lock button 70 within slot 32 . the longitudinal axis of lock button 70 is approximately perpendicular to the longitudinal axis of gate 30 , and intersects the longitudinal axis of hole 42 . sufficient clearance is provided between slot 32 and lock button 70 so that lock button 70 can move without binding . referring to fig8 lock button 70 can be pushed either in or out as depicted by the outline arrows “ a ” and “ b ” respectively . moving lock button 70 in one direction or the other pushes against link 60 at the location where link 60 passes through hole 72 . one end of link 60 is restrained axially by notch 26 , however link 60 is free to pivot around notch 26 thereby moving joint 62 between link 60 and spring pin 50 . moving button 70 in the direction of arrow “ a ” causes link 60 , spring 40 and spring pin 50 to move to the unlocked position shown in fig8 . moving lock button 70 in the direction of arrow “ b ” causes link 60 , spring 40 and spring pin 50 to move to the locked position shown in fig4 and 5 . referring to the locked position shown in fig4 and 5 , shoulder 52 of spring pin 50 abuts shelf 46 in hole 42 . the engagement of shoulder 52 with shelf 46 blocks the opening movement of spring pin 50 and thereby immobilizes gate 30 . referring to the unlocked position shown in fig8 the movement of button 70 in direction “ a ” has moved shoulder 52 away from shelf 46 . without the engagement of shoulder 52 with shelf 46 , spring pin 50 is free to move axially within hole 42 ; therefore gate 30 can be opened as shown in fig1 . in fig1 , the outline arrow depicts the force opening gate 30 . referring to fig5 end 54 of spring pin 50 passes through hole 48 at the bottom of hole 42 . sufficient clearance is provided between spring pin 50 and hole 48 so that spring pin 50 can move axially without binding . the difference between the diameters of hole 42 and hole 48 provide abutment 44 for one end of spring 40 . hole 48 provides guidance for the axial movement of spring pin 40 . alternately , hole 48 can be eliminated , spring pin 50 shortened , and guidance of spring pin 50 provided by spring 40 itself . the location of abutment 44 with respect to notch 26 , and the dimensions of hole 42 are chosen to enable spring pin 50 and link 60 to have two stable positions , either locked or unlocked . as such , spring pin 50 and link 60 operate as an over - center switch that can be changed from one stable position to the other by moving button 70 . movement from the locked to the unlocked position , and the opposite , produces an audible “ snap ” that can be heard by the climber . in addition , the position of button 70 , either up or down , provides a visual and tactile indication of the state of the inventive locking mechanism . [ 0080 ] fig9 is a free - body diagram of spring 40 , spring pin 50 and link 60 showing the forces acting on the assembly when in the locked position . f 44 is the force against spring 40 from abutment 44 . f 26 is the force against link 60 from notch 26 . because the forces f 44 and f 26 are offset upward when in the locked position , joint 62 between spring pin 50 and link 60 will buckle upward , which is resisted by f 46 from shelf 46 . similarly , fig1 is a free - body diagram of spring 40 , spring pin 50 and link 60 showing the forces acting on the assembly when in the unlocked position . f 44 is the force against spring 40 from abutment 44 . f 26 is the force against link 60 from notch 26 . because the forces f 44 and f 26 are offset downward when in the unlocked position , joint 62 between spring pin 50 and link 60 will buckle downward , which is resisted by f 42 from the sidewali of hole 42 . climbers are often in precarious positions in which only one hand is available to insert a climbing aid or rope into a carabiner ( typically the other hand is occupied holding on to another climbing aid or the rock surface ). under such circumstances it may be imperative that the carabiner be easily unlocked and opened and subsequently relocked with only one hand . because the inventive locking carabiner of fig3 - 12 has two stable positions , either locked or unlocked , and lock button 70 can be easily moved with one finger , a climber can first unlock the carabiner , open and close gate 30 as many times as need , and when appropriate , relock the carabiner , all with the use of one hand . as described supra , when shoulder 52 engages shelf 46 , gate 30 cannot move . for the inventive carabiner to be assembled and function properly , manufacturing tolerances must be controlled so that shoulder 52 lines - up with shelf 46 when gate 30 is closed . referring to fig1 , the distance d 61 of link 60 plus the shouldered portion of pin 50 must equal the distance between notch 26 and shelf 46 when gate 30 is closed . if link 60 is fabricated so that d 61 is too short , some opening movement of gate 30 will occur even when shoulder 52 and shelf 46 are engaged . conversely , if d 61 is fabricated overlong , it will not be possible to engage shoulder 52 with shelf 46 . these problems are avoided by the alternate configuration of fig1 . [ 0084 ] fig1 shows the configuration of fig5 but spring pin 50 has been replaced by threaded rod 51 and nut 55 . nut 55 provides shoulder 52 that engages shelf 46 . threaded rod 51 and nut 55 are adjusted to compensate for dimensional variations of the various components . screwing rod 51 in or out with respect to nut 55 adjusts the location of joint 62 a , thereby lengthening or shortening distance d 61 to precisely match the distance between shelf 46 and notch 26 . screwdriver slot 55 facilitates adjustment of d 61 after the carabiner has been assembled . during assembly of the inventive carabiner , threaded rod 51 is overly threaded into nut 53 to provide ample clearance between the various components . after the inventive carabiner is assembled , threaded rod 51 is screwed outward until shoulder 52 just makes contact with shelf 46 . at the point when shoulder 52 makes contact with shelf 46 , gate 30 will be unable to open unless lock button 70 is moved to the unlocked position . furthermore , other means of adjustment can be conceived . for example , the location of notch 26 can be adjusted by utilizing a setscrew , or the like , threaded at an angle into body 20 adjacent the proper location of notch 26 ( see fig2 ). this adjustment configuration will be described in more detail following . fig1 - 23 shows alternate configurations of the instant invention . referring to fig1 , lock release 71 is located within hole 73 in the top of gate 30 . the center axis of hole 73 is approximately perpendicular to the longitudinal axis of gate 30 , and intersects the center axio of hole 42 . sufficient clearance is provided between hole 73 and lock release 71 so that lock release 71 can move axially within hole 75 without binding . lock release 71 is retained within hole 75 by spring 40 at one end ; and by indenting or peening outside corner 75 ( see fig1 ) to provide an interference fit that allows only a part of lock release 71 to protrude beyond the top surface of gate 30 . lock release 71 is preferably a rigid sphere fabricated of a corrosion resistant material , for example a type 316 stainless steel ball bearing . alternately , lock release 71 can be a short cylindrical shape , or the like , for example a stepped cylindrical lock release 77 as shown in fig2 . referring to fig1 and 14 , pin 45 is inserted through the top wall of gate 30 and extends approximately to the center of hole 42 . the center axis of pin 45 is approximately perpendicular to the longitudinal axis of gate 30 ; and intersects the center axis of hole 42 . pin 45 is firmly attached to gate 30 by press - fit , welding , bonding , or the like . pin 45 is preferably a hard , rigid , corrosion resistant material , for example a type 316 stainless steel rivet . referring again to fig1 and 14 , the length of pin 45 is adjusted so that pin end 47 just barely passes through hole 63 in link 61 . sufficient clearance is provided between hole 63 and pin 45 so that pin 45 can slip in and out of hole 63 without binding . when pin 45 is engaged with hole 63 , movement of gate 30 is impossible because movement of link 61 , and subsequent compression of spring 40 , is blocked . without the movement of link 61 , gate 30 cannot open . [ 0091 ] fig1 shows lock release 71 pushed inward ( the force pushing lock release 71 inward is depicted by the outline arrow ). inward movement of lock release 71 forces spring 40 , and link 61 with it , to the other side of the oblong cross section of hole 42 . consequently , end 47 of pin 45 is disengaged from hole 63 , freeing link 61 to move , and therefore gate 30 can be opened as shown in fig1 ( the outline arrow depicts the force opening gate 30 .) note that after gate 30 opens a small amount , hole 63 no longer lines up with pin 45 and consequently the force applied against lock release 71 is no longer needed . [ 0092 ] fig1 is a free - body diagram of spring 40 and link 61 showing the forces acting on the assembly . f 49 is the force against spring 60 from end 49 of hole 42 . f 26 is the force against link 61 from notch 26 on body 20 . because the forces f 49 and f 26 are offset , joint 65 between spring 40 and link 61 will buckle upward , which is resisted by force f 47 from end 47 of pin 45 . the force of spring 40 against link 61 urges gate 30 to return to the closed position . when gate 30 returns to the closed position , the buckling force will automatically move joint 65 upward as soon as hole 63 lines - up with pin 45 , reengaging pin 45 with hole 63 , which immediately blocks the opening movement of gate 30 . as described supra , when link 61 is at the locked position , gate 30 cannot move because . pin 45 engages hole 63 , which blocks movement of link 61 . for this configuration to be assembled and function properly , manufacturing tolerances must be controlled so that hole 63 lines - up with pin 45 when gate 30 is closed . referring to fig2 , the distance d 61 on link 61 between hole 63 and its end adjacent notch 26 must equal the distance between pin end 47 and notch 26 when gate 30 is closed . if link 61 is fabricated so that d 61 is too short , some opening movement of gate 30 will occur even when pin 45 and hole 65 are engaged . conversely , if d 61 is fabricated overlong , it may not be possible to properly assemble the carabiner . these problems are avoided by the alternate inventive carabiner configuration of fig2 . referring to fig2 , setscrew 90 provides the means to adjust for dimensional variations of the various components . setscrew 90 is threaded at an angle into body 20 adjacent the proper location of notch 26 . the angle of the central axis of the thread is chosen so that the intersection of the surface of body 20 with the tip of setscrew 90 forms a notch for link 61 . setscrew 90 has slot 92 , or the like , to facilitate adjustment . by adjusting setscrew 90 in or out , the location of notch 26 will move so that it is possible to precisely locate notch 26 with respect to dimension d 61 . the use of standard off - the - shelf components will lower manufacturing costs . costs are kept low when fabricating the alternate configuration shown in fig1 - 17 by using a standard ball bearing for lock release 71 , and a standard rivet for pin 45 , however , lock release 71 requires that hole 73 be machined in the side wall of gate 30 . fig1 - 22 shows another alternate configuration of the instant invention that eliminates the need for hole 73 . referring to fig1 - 22 , lock release 80 is an approximately l - shaped bracket having hole 82 in one leg . as best seen in fig1 and 20 , the holed leg of lock release 80 is positioned in hole 42 between link 61 and the wall of gate 30 . pin 45 loosely passes through hole 82 . the other leg of lock release 80 protrudes outward from slot 32 adjacent lee end 22 of body 20 . the engagement of hole 82 with pin 45 holds lock release 80 at its proper location . lock release 80 is typically fabricated by stamping and bending a corrosion resistant , rigid flat material , for example 316 stainless steel strip stock . [ 0098 ] fig2 and 22 show lock release 80 pushed inward ( the force pushing lock release 80 inward is depicted by the outline arrow in fig2 .) inward movement of lock release 80 forces link 61 to the other side of the oblong cross section of hole 42 , which disengages end 47 of pin 45 from hole 63 , with link 61 free to move , gate 30 can be opened as shown in fig2 ( the outline arrow depicts the force opening gate 30 .) note that after gate 30 moves a small amount , hole 63 no longer lines up with pin 45 and consequently the force applied against lock release 80 is no longer needed . the function and operation of the configuration of fig1 - 22 is the same as the function and operation of the configuration of fig1 - 18 . the only difference is lock release 71 and associated hole 73 have been replaced with lock release 80 , which does not require hole 73 because it is located in the gap between the hinge of gate 30 and body 20 . fig2 - 27 show yet another alternate configuration of the instant invention that eliminates the need for pin 45 . referring to fig2 and 25 , shelf 46 is cut into the opening of hole 42 . shelf 46 serves the same function as pin 45 . extension 69 of link 67 extends upward a sufficient distance to engage shelf 46 when gate 30 is closed . movement of link 67 is blocked when extension 69 engages shelf 46 , [ 0101 ] fig2 shows lock release 71 pushed inward ( the force pushing lock release 71 inward is depicted by the outline arrow ). inward movement of lock release 71 forces spring 40 , and link 67 with it , to the other side of the oblong cross section of hole 42 . consequently , extension 69 of link 67 is disengaged from shelf 46 , freeing link 67 to move , and therefore gate 30 can be opened as shown in fig2 ( the outline arrow depicts the force opening gate 30 .) note that after gate 30 opens a small amount , extension 69 no longer lines up with shelf 46 and consequently the force applied against lock release 71 is no longer needed . referring again to fig2 , another configuration of the instant invention replaces lock release 71 with lock release 88 . lock release 88 is a stubby l - shaped member located adjacent leg 22 of body 20 . lock release 88 is held adjacent leg 22 by shoulder 89 , which will abut against wall 41 should lock release 88 attempt to escape outward . lock release 88 functions similarly to lock release 80 . lock release 88 is fabricated from a lightweight , rigid material , for example aluminum alloy type 6061 . [ 0103 ] fig2 shows yet another configuration of the instant invention that eliminates the need for a separate lock release component . link 61 has l - shaped leg 96 extending downward from notch 26 under hinge pin 36 . when leg 96 is pushed sideways ( depicted by the outline arrow ) go shown in fig2 , link 61 pivots around notch 26 and hole 63 disengages from pin 45 . the arrangement of fig2 can be applied to the configurations of fig2 as well . in contrast to the configuration of fig4 which has two stable positions : locked or unlocked , the configurations illustrated by fig1 - 28 are always locked unless the release component is being pushed . furthermore , the configurations illustrated by fig1 - 28 automatically lock as soon as gate 30 closes . however , as illustrated by fig4 , a climber can simultaneously unlock and open gate 30 with one hand . in fig4 , gate 30 is shown being pinched between the thumb and index finger so that the lock release is depressed ( in fig4 , the force that moves the lock release is depicted by an outline arrow ) thereby unlocking and opening gate 30 . fig2 - 32 show yet another alternate configuration of the instant invention . referring to fig2 , compression spring 40 and pin 150 are loosely contained within gate 30 . compression spring 40 in conjunction with pin 150 and link 160 applies a force against body 20 adjacent but off - set inward from the center of hinge pin 36 , thereby holding gate 30 closed . as best seen in fig2 and 30 , gate 30 is transversed by hole 138 . the size of hole 138 is chosen so that the strength of gate 30 is not compromised . locking member 170 is carried by gate 30 in hole 138 . sufficient clearance is provided between hole 138 and member 170 so that member 170 can move axially within hole 138 without binding . referring to fig3 , at the intersection of pin 150 with locking member 170 , member 170 is transversed by elongated slot 178 . slot 178 allows end 158 of pin 150 to extend into member 170 . fin 150 in conjunction with slot 178 limits the axial movement of member 170 within hole 138 . end 158 of pin 150 abuts against surface 172 within slot 178 of member 170 when member 170 is in the locked position as shown by fig2 . member 170 is maintained in the upright or locked position by spring 176 pushing the face of piston 174 against end 158 of pin 150 . piston 174 and compression spring 176 are loosely contained within locking member 170 . during the course of opening gate 30 , link 160 pushes against and consequently moves pin 150 toward locking member 170 . the movement of pin 150 compresses spring 40 . the countering force of spring 40 against pin 150 , and subsequently link 160 , urges gate 30 to return to the closed position . [ 0110 ] fig2 pictures the inventive carabiner when it is locked . when the inventive carabiner is locked , gate 30 is prevented from pivoting around pin 26 because the abutment of pin end 158 against surface 172 of member 170 blocks movement of pin 150 . without the movement of pin 150 , gate 30 cannot open . referring to fig3 , when a force is applied to member 170 in the direction of the outline arrow , member 170 will move relative to gate 30 to the position depicted in fig3 . movement of member 170 compresses spring 176 against piston 174 , which bears against end 158 of pin 150 . preferably , pushing member 170 will first move it to the unlocked position and continued force will subsequently open gate 30 . this sequence is accomplished by sizing spring 176 so that its compressive force is overcome before the closing force of spring 40 is overcome . conversely , if an opening force is applied to gate 30 before member 170 moves to the unlocked position , end 158 of pin 150 will be jammed against surface 172 of member 170 . when end 158 of pin 150 is jammed against surface 172 of member 170 , member 170 will be unable to move to the unlocked position . movement of member 170 to the unlocked position shown in fig3 moves surface 172 away from end 158 of pin 150 , freeing pin 150 for axial movement . continued force against member 170 or gate 30 in the direction of the outline arrow of fig3 will cause pin 150 to slide further into slot 178 of member 170 , thereby opening gate 30 . fig3 is a close - up view of the relationship of the various components when the gate is opening . as described supra , when member 170 is at the locked position , gate 30 cannot move because member 170 blocks movement of pin 150 and consequently link 160 . for this configuration to be assembled and function properly , manufacturing tolerances must be tightly controlled . for example , if one or more of the components are too short and there is a gap between end 158 and surface 172 , excessive opening movement of gate 30 will occur even when locking member 170 is at the locked position . conversely , if any one of the components is fabricated oversize , it may not be possible to properly assemble the carabiner . these problems are avoided by the alternate inventive carabiner configuration of fig3 . the alternate inventive carabiner configuration of fig3 incorporates setscrew 190 and ball 192 . setscrew 190 is threaded to gate 30 adjacent slot 178 of member 170 . referring to fig3 , ball 192 is carried by member 170 within the widest part of keyhole shaped slot 178 . ball 192 is a rigid sphere , for example a stainless steel ball bearing . alternately , ball 192 can be replaced with a short cylindrical pin , or the like . ball 192 serves as a link between setscrew 190 and end 158 of pin 150 . end 158 of pin 150 abuts against ball 192 when member 170 is at the locked position . member 170 is maintained in the upright or locked position by spring 174 pushing the face of piston 174 against end 158 of pin 150 . ball 192 abuts against the end of setscrew 190 . ball 192 serves the same function as face 172 of the configuration depicted by fig2 . setscrew 190 can be adjusted to compensate for dimensional variations of the various carabiner components . during assembly of the inventive carabiner , setscrew 190 is backed out to provide clearance between the components . after the inventive carabiner is assembled , setscrew 190 is threaded inward , pushing ball 192 until it just makes contact with end 158 of pin 150 . at the point when ball 192 just makes contact with end 158 of pin 150 , gate 30 will be unable to open unless member 170 is moved to the unlocked position . referring to fig3 , locking member 170 is shown at the unlocked position ; therefore ball 192 is no longer located between setscrew 190 a end 158 of pin 150 . as a consequence of the opening movement of gate 30 , pin 150 has moved into the space formally occupied by ball 192 . [ 0120 ] fig3 shows another alternate configuration of the inventive carabiner . cantilever spring 180 , located on top of and external to gate 30 , replaces internal spring 176 and piston 174 . as best seen in fig3 and 37 , cantilever spring 180 is fabricated from rectangular spring stock , or alternately , can be formed or molded from plastic , for example nylon . cantilever spring 180 is firmly attached at end 184 to gate 30 . the other end of cantilever spring 180 is loosely attached to member 170 by rivet 182 . loose attachment of cantilever spring 180 to member 170 is preferable to prevent binding when member 170 moves . alternately , rivet 182 can be a screw , or - the - like , or can be a peened extension of member 170 . referring to fig3 , ball 192 is carried by member 170 within the widest part of keyhole shaped slot 178 . referring to fig3 , setscrew 190 provides the means to adjust for dimensional variations of the various components as described supra . the incorporation of cantilever spring 180 eliminates the need for a cavity in member 170 to house spring 176 and piston 174 . consequently , member 170 is less costly to fabricate and , also , can have a smaller cross - section . furthermore , unlocking and opening the inventive cgrabiner with a single finger or a rope is facilitated because member 170 can be pushed to the unlocked position by applying force , not only to the protruding end of member 170 but also by applying force anywhere along the exposed surface of cantilever spring 180 . [ 0124 ] fig4 is a partial cross section of a typical prior art , non - locking carabiner . a comparison of the preferred inventive configuration of fig4 with fig4 will reveal that only two ( 2 ) additional components are needed to convert the prior art . a conversion to the preferred inventive locking configuration requires the addition of lock release 70 and spring pin 50 , both of which are easy to fabricate . with respect to fabricating gate 30 to accommodate the added components , hole 42 must be elongated . because the gate return spring provides the force that , in addition to closing the gate , holds the inventive locking mechanism either in the locked or unlocked states , the new components and accompanying modifications can be incorporated with little addition to the manufacturing cost of a basic carabiner . consequently , a carabiner incorporating the preferred inventive locking mechanism can be sold for a relatively small price increase over the cost of a non - locking version . the figs . illustrate , a number of inventive locking configurations , all of which have several characteristics in common : all are contained within the carabiner gate , all function by blocking the opening movement of the gate return spring mechanism , and all are controlled by an unobtrusive button , or - the - like , which protrudes from the gate . other variations on the shape and / or relative locations of the carabiner body , gate , spring , linkage and lock release are contemplated . it is understood that those skilled in the art may conceive of modifications and / or changes to the invention described above . any such modifications or changes that fall within the purview of the description are intended to be included therein as well . this description is intended to be illustrative and is not intended to be limitative . the scope of the invention is limited only by the scope of the claims appended hereto . | 8 |
reference will now be made in detail to the subject matter disclosed , which is illustrated in the accompanying drawings . the scope of the invention is limited only by the claims ; numerous alternatives , modifications and equivalents are encompassed . for the purpose of clarity , technical material that is known in the technical fields related to the embodiments has not been described in detail to avoid unnecessarily obscuring the description . referring to fig1 , a block diagram of a computer apparatus according to one embodiment of the present invention is shown . in at least one embodiment , a bridge paving device includes a processor 100 , memory 102 connected to the processor 100 for storing computer executable program code and a data storage element 104 configured to store a bridge paving profile . the processor 100 may also be connected to an antenna 106 . the antenna 106 may be configured to receive location data from a surveying instrument such as a total station . alternatively , or in addition , the antenna 106 may receive a satellite based location signal such as a gps signal for determining the location of the bridge paving device . furthermore , a second antenna 106 may also be connected to the processor 100 ; the second antenna 106 may receive a second satellite based location signal such that the known difference in location between the first antenna 106 and the second antenna 106 may be used to determine an orientation of the bridge paving device . alternatively , or in addition , the processor 100 may receive orientation information through the antenna 106 from a separate surveying instrument . the processor 100 may correlate the location and orientation information to the bridge paving profile . the processor 100 thereby knows the location and orientation of the bridge paving device as it pertains to a desired location and orientation defined in the bridge paving profile . the processor 100 may actuate one or more hydraulic actuators 108 , 110 , 112 , 114 , for example through a hydraulic control system , to adjust the position and orientation of the bridge paving device to conform to parameters defined by the bridge paving profile . the processor 100 may receive updated location and orientation information through the antenna 106 , and periodically correlate the updated location and orientation information to the bridge paving profile . the processor 100 continuously adjusts the hydraulic actuators 108 , 110 , 112 , 114 to maintain the bridge paving device within the defined parameters as the bridge paving device moves linearly along the surface being paved . furthermore , the processor 100 may be connected to one or more powered transition adjusters 116 connected to portions of the bridge paving device . in at least one embodiment , the powered transition adjusters 116 are configured to adjust the shape of the main support structure of the bridge paving device to create or adjust a crown or inversion in the paved surface . alternatively , the height of a bridge paving carriage may vary along both the width of the paved surface and the length of the bridge span as defined by the bridge paving profile according to desired run - off parameters . referring to fig2 , a perspective environmental view of a bridge paving device according to one embodiment of the present invention is shown . in at least one embodiment , a bridge paving device 200 includes a power and control unit 204 configured to power and control hydraulic actuators 208 , 210 , 212 , 214 associate with the linear movement elements that move the bridge paving device linearly along a bridge structure to be paved . linear movement elements may include tracks , wheels , bogies or any other suitable device for producing linear movement in the bridge paving device . the power and control unit 204 also controls the motion of a paving carriage 202 which may comprise a cylinder finisher and in at least one embodiment , one or more powered transition adjusters 216 configured to adjust the shape of the main support structure . different shapes of the main support structure may alter the shape of a crown or inversion in the paved surface . furthermore , different shapes of the main support structure coupled with adjustments to the paving carriage 202 may allow the power and control unit 204 to apply continuous , variable slopes to the paved surface . the power and control unit 204 may also include an antenna configured to receive location data from a surveying instrument such as a total station 220 . alternatively , or in addition , the power and control unit 204 may receive a satellite 218 based location signal such as a gps signal for determining the location of the bridge paving device 200 . the bridge paving device 200 may be equipped with reference features such as surveying prisms , or gps receivers or both , sufficient to locate and orient the bridge paving device 200 with reference to a bridge paving profile . the power and control unit 204 may actuate one or more hydraulic actuators 208 , 210 , 212 , 214 associated with the linear movement elements that drive the bridge paving device 200 to adjust the position and orientation of the bridge paving device 200 to conform to parameters defined by the bridge paving profile . the power and control unit 204 may receive updated location and orientation information and periodically correlate the updated location and orientation information to the bridge paving profile . the power and control unit 204 continuously adjusts the hydraulic actuators 208 , 210 , 212 , 214 to maintain the bridge paving device 200 within the defined parameters as the bridge paving device 200 moves linearly along the surface being paved . in at least one embodiment , a bridge paving device 200 may be configured to distribute the load of the bridge paving device 200 on the bridge structure by directing the linear movement elements on one side of the bridge paving device 200 to maintain a relative position further along the bridge with reference to the linear movement elements on the other side . the bridge paving device 200 is thereby skewed in the direction of linear travel . where a bridge paving profile includes complex crown or inversion features , such complexity is significantly increased where the bridge paving device 200 is skewed . such complexity may require the power and control unit 204 to maintain intricate control and interrelation of the paving carriage 202 movement and powered transition adjuster 216 . referring to fig3 , a front environmental view of a bridge paving device according to the present invention is shown . in at least one embodiment , a bridge paving device 300 includes a power and control unit 304 configured to power and control hydraulic actuators 308 , 312 , associate with the linear movement elements that move the bridge paving device linearly along a bridge structure to be paved , the motion of a paving carriage 302 and in at least one embodiment , one or more powered transition adjusters 316 configured to apply a crown 318 to a surface being paved . the power and control unit 304 may include an antenna configured to receive location data from a surveying instrument or a satellite based location signal for determining the location of the bridge paving device 300 with reference to a bridge paving profile . the bridge paving profile may include a crown 318 or inversion that may vary along the length of the bridge span . the powered transition adjusters 316 may alter the shape in the main support structure of the bridge paving device 300 to create or adjust a crown 318 or inversion in the paved surface . alternatively , a paving carriage 302 may be raised and lowered according to the bridge paving profile . the height of the bridge paving carriage 302 , including a cylinder finisher , may vary along both the width of the paved surface and the length of the bridge span as defined by the bridge paving profile according to desired run - off parameters . referring to fig4 , a front environmental view of a bridge paving device according to another embodiment of the present invention is shown . in at least one embodiment , a bridge paving device 400 includes a power and control unit 404 configured to power and control hydraulic actuators 408 , 410 , 412 , 414 associate with the linear movement elements that move the bridge paving device linearly along a bridge structure to be paved . the power and control unit 404 also controls the motion of a paving carriage 402 which may comprise a cylinder finisher and in at least one embodiment , one or more powered transition adjusters 416 , 420 configured to change the shape of the main support structure of the bridge paving device 400 . different shapes of the main support structure may alter the shape of a crown or inversion in the paved surface . also , where a first powered transition adjuster 416 is configured to alter the shape of a first portion of the main support structure and a second powered transition adjuster 420 is configured to alter the shape of a second position of the main support structure , the power and control element 404 may induce a disparity of shapes in the main support structure to produce a desired frame shape and thereby a desired paved surface slope . furthermore , different shapes of the main support structure coupled with adjustments to the paving carriage 402 may allow the power and control unit 404 to apply continuous , variable slopes to the paved surface . while fig4 shows a bridge paving device 400 with two powered transition adjusters 416 , 420 , more than two powered transition adjusters 416 , 420 are contemplated . more than two powered transition adjusters 416 , 420 may be useful for producing a paved surface having a complex design profile . complex design profiles may include multiple crowns or inversions to achieve desired drainage characteristics , banked portions , or any other features that require shape alterations to the main support structure that are unachievable with two powered transition adjusters 416 , 420 . referring to fig5 , another environmental view of a bridge paving device according to the present invention is shown . in at least one embodiment , a bridge paving device 500 includes a power and control unit 504 configured to power and control hydraulic actuators 508 , 512 associate with the linear movement elements that move the bridge paving device linearly along a bridge structure to be paved 518 , the motion of a paving carriage 502 including a cylinder finisher and in at least one embodiment , one or more powered transition adjusters 516 configured to adjust the shape of the main support structure according to a desired paving profile to apply a crown or inversion to the surface being paved 518 . the power and control unit 504 may also include an antenna configured to receive location data from a surveying instrument such as a total station 520 . alternatively , or in addition , the power and control unit 504 may receive a satellite based location signal such as a gps signal for determining the location of the bridge paving device 500 . the bridge paving device 500 may be equipped with reference features such as surveying prisms , or gps receivers or both , sufficient to locate and orient the bridge paving device 500 with reference to a bridge paving profile . the linear movement elements that move the bridge paving device 500 linearly along the bridge structure to be paved 518 may run on guide elements 522 positioned according to the paving profile during construction of the bridge structure to be paved . in at least one embodiment , the tolerances for the location of the guide elements 522 are significantly less rigid as compared to the prior art . referring to fig6 , a flowchart of a method for controlling a bridge paving device according to one embodiment of the present invention is shown . in at least one embodiment , a bridge paving device receives 600 a bridge design profile that defines the necessary location of the bridge paving device , and in at least one embodiment , a variable crown or inversion to be applied to the paved surface . the bridge paving device also receives 602 location data corresponding to the position of the bridge paving device and orientation data 604 corresponding to the orientation of the bridge paving device . the bridge paving device correlates 606 the location and orientation data to the bridge design profile and adjusts 608 one or more hydraulic actuators to bring the location and orientation of the bridge paving device in line with the parameters of the bridge design profile . during paving , the bridge paving device continuously monitors 610 the location and orientation of the bridge paving device , either through continuously receiving updated data or adjusting the known location and orientation based on operations executed by the bridge paving device or both . based on the updated location and orientation data , and the parameters of the bridge design profile , the bridge paving device may periodically adjust 612 one or more hydraulic actuators or one or more powered transition adjusters or both simultaneously . a person skilled in the art may appreciate that while the exemplary embodiments disclosed herein describe hydraulic actuators , additional embodiments are envisioned . for example , linear mechanical actuators , screw jacks or other substantially equivalent mechanisms are contemplated . it is believed that the present invention and many of its attendant advantages will be understood by the foregoing description of embodiments of the present invention , and it will be apparent that various changes may be made in the form , construction , and arrangement of the components thereof without departing from the scope and spirit of the invention or without sacrificing all of its material advantages . the form herein before described being merely an explanatory embodiment thereof , it is the intention of the following claims to encompass and include such changes . | 4 |
it is a discovery of the present inventors that the channel inhibitory properties of the r domain of cftr protein can be separated from the channel activating properties . thus activating polypeptides can be used to treat cftr defective cells , without concern for inhibition at certain concentrations . activating polypeptides may also be used to enhance the activity of normal cftr , including that delivered by gene transfer . a polypeptide for use in treating cftr - defective cells contains a 22 amino acid sequence , glxisxxinxxxlkxxffxxxx , as shown in seq id no : 6 . the amino terminal residue is acetylated and the carboxy terminal residue is amidated . the residue x , at positions 3 , 6 , 7 , 10 , and 11 is either glutamic acid or glutamine ; at position 12 is aspartic acid or asparagine ; at position 15 is glutamic acid or glutamine ; at position 16 is cysteine or serine ; at positions 19 or 20 is aspartic acid or asparagine ; at position 21 is methionine or norleucine ; at position 22 is either glutamic acid or glutamine . the amino acid residue at position 16 is more preferably serine . the amino residue at position 21 is more preferable norleucine . the polypeptide of seq id no : 6 has a net negative charge . the net negative charge is preferably within the ranges of 1 - 8 , 2 - 8 , 3 - 8 , 4 - 8 , 5 - 8 , 6 - 8 , or 7 - 8 . the polypeptide more preferably has the sequence of seq id no : 1 , gleiseqinqqnlkqsffndle , wherein l at position 21 is norleucine . the amino terminal residue of the polypeptide is preferably acetylated and the carboxy terminal residue is preferably amidated . the polypeptide may also be present in a composition with a pharmaceutically acceptable carrier . pharmaceutically acceptable carriers are well known to those in the art . pharmaceutically acceptable carriers include , but are not limited to , large , slowly metabolized macromolecules , such as proteins , polysaccharides , polylactic acids , polyglycolic acids , polymeric amino acids , amino acid copolymers , and inactive virus particles . the composition can also contain liquids , such as water , saline , glycerol , and ethanol , as well as substances such as wetting agents , emulsifying agents , or ph buffering agents . buffering agents include hanks &# 39 ; solution , ringer &# 39 ; s solution , or physiologically buffered saline . it may be desirable that the polypeptide be fused to another polypeptide to provide additional functional properties . for example , fusion to another protein such as keyhole limpet hemocyanin can be used to increase immunogenicity . another desirable fusion partner is a membrane - penetrating peptide . such peptides include vp - 22 ( seq id no : 3 ), as well as the peptides shown in seq id no : 4 and seq id no : 5 . such peptides can be used to facilitate the uptake of the polypeptide by target cells . the polypeptides of the invention may also be fused to proteins that cause specific targeting to lung epithelial cells . for instance , the peptide thalwht directs dna to human airway epithelial cells . single chain antibody variable domains may be used to do the same . a cftr protein can be activated by the polypeptide . the cftr protein can be in a cell , preferably in the cell membrane and the cftr protein forms a camp - regulated chloride channel . an effective amount of a polypeptide that comprises the sequence of seq id no : 6 can be administered to the cell , and administration of the polypeptide activates the cftr protein . the polypeptide administered more preferably comprises the sequence of seq id no : 1 . the cells may be any cells that contain or express a cftr protein . the cells may naturally express the cftr protein , such as lung epithelial cells , or the cells may express the cftr protein after transient or stable transformation . the cells may be primary cells isolated from individuals that express a wild - type cftr protein , or may be primary cells isolated from individuals that express a mutant cftr protein . the cells may also be of a stable cell line . the cells may also exist in the body . the cftr protein is a wild type or a mutant cftr protein . the mutant cftr protein is a cftr protein that is expressed by the cells and that is transported to the cell surface . the mutant cftr protein also forms a camp - regulated chloride channel . the mutant cftr protein may contain alterations that are known and characterized , or may contain alterations that have not yet been discovered . a mutant cftr protein that fails to undergo full activation is a cftr protein that does not conduct ions to the same degree as wild - type cftr . the mutant cftr protein may not conduct ions at all . the mutant protein may also conduct ions to a similar extent as wild type cftr but be present in the membrane in substantially lower amounts than is true for normal individuals . activated is defined as any increase in conductance by the cftr protein . an increase in conductance may result when the opening of the cftr channel occurs with greater frequency than previously observed . an increase in cftr conductance may result when the duration of opening is increased each time the cftr channel opens . an increase in conductance may also result due to greater ability to conduct ions each time the cftr protein channel is open . the increase in open probability of the cftr protein is preferably at least 25 %, at least 50 %, at least 75 %, at least 100 %, at least 125 %, at least 150 %, at least 175 %, at least 200 %, or at least 300 %. an effective amount is any amount of polypeptide that is sufficient to activate the cftr protein , as activate is defined above . preferably , the polypeptide is administered to achieve a concentration of 0 . 5 to 14 μm . more preferably , the polypeptide is administered to achieve a concentration of 4 - 6 μm . the polypeptide may be administered by any means acceptable in the art . for instance , the polypeptide may be administered in vitro , or to cells in culture , by addition to the medium . the polypeptide may be administered in vivo , to a patient , by any route including intravenous , intrathecal , oral , intranasal , transdermal , subcutaneous , intraperitoneal , parenteral , topical , sublingual , or rectal . most preferably , the polypeptide is administered to a patient in an aerosol . the aerosolized polypeptide can be co - administered with an expression vector that encodes wild type cftr protein . an expression vector may be linear dna that encodes wild type cftr protein , or a plasmid or human artificial chromosome that expresses wild type cftr protein . the vector may be administered as naked dna or may be administered complexed to lipid molecules such as with liposomes , short polypeptides such as the thalwht polypeptide , or polycations such as polylysine , with or without stabilizing agents and / or receptor ligands . the dna may also be administered in a viral vector . viral vectors are known in the art . several nonlimiting examples include retroviruses , adenoviruses , adeno - associated viruses , lentiviruses , and herpes simplex virus . the gene encoding the wild type cftr protein may additionally comprise a promoter sequence to drive expression of the cftr gene . any promoter known in the art may be used . promoters include strong promoters such as the promoters of cytomegalovirus , sv40 , or rous sarcoma virus . the promoter may also be a tissue specific promoter . preferably the tissue specific promoter is a lung specific promoter . lung specific promoters include the promoters of surfactant protein a , keratin 18 , du clara cell secretory protein , and the promoter of cftr . a cftr protein can also be activated by applying an effective amount of a polypeptide to a cftr protein in a lipid bilayer . the polypeptide comprises the amino acid sequence of seq id no : 6 . the polypeptide more preferably comprises the amino acid sequence of seq id no : 1 . activating a cftr protein in a lipid bilayer is useful to the art for screening agents for the treatment of cystic fibrosis . a cftr protein in a lipid bilayer may be a cftr protein that is expressed in cells in culture . the cells may express the cftr protein without manipulation , or may be stably or transiently transfected to express the cftr protein . the lipid bilayer may also be such artificial preparations as , without limitation , a microsome preparation , a lipid - bilayer vesicle preparation , or liposomes . the polypeptide may be applied to the protein by its addition to cell culture media , or solution in which the lipid bilayers are maintained . a change in conductance may be measured by any means known in the art , such as patch clamping . a cftr activating polypeptide can be synthesized by sequentially linking units of one or more amino acid residues to form a polypeptide comprising the amino acid sequence of seq id no : 6 . preferably the polypeptide has the amino acid sequence of seq id no : 1 . synthesis of the cftr polypeptide can be performed using solid - phase synthesis , liquid - phase synthesis , semisynthesis , or enzymatic synthesis techniques . preferably the polypeptides are synthesized by solid - phase synthesis . more preferably the peptides are synthesized by f - moc synthesis . the polypeptide of the invention may alternatively comprise the sequence of seq id no : 2 , gleiseqinqqnlkqsffndme . the polypeptide of seq id no : 2 is not modified . it is similar to the sequence of seq id no : 1 , but for a methionine at position 21 , rather than a norleucine . like seq id no : 1 and seq id no : 6 , it may be fused to a membrane penetrating polypeptide . nucleic acid molecules comprise a nucleotide sequence that encodes the polynucleotide sequence of seq id no : 2 . one of skill in the art will recognize that many sequences will encode the polypeptide , as more than one codon can specify a given amino acid . the nucleic acid may further comprise regulatory sequences that enhance the expression of the polypeptide . promoters may be strong constitutive promoters , as discussed above , or may be tissue - specific promoters . preferably the tissue - specific promoter is a lung - specific promoter . the nucleic acid molecules may further comprise a vector . the vector can be any suitable vector for the delivery of the polynucleotide sequence into the lungs of a patient , resulting in expression of the polypeptide in the lungs of the patient . a cftr protein can be activated by expression of a polynucleotide . a nucleic acid comprising a sequence encoding a polypeptide according to seq id no : 2 is administered to a cell comprising the cftr protein . the polypeptide is expressed and the cftr protein is thereby activated . the polynucleotide may be administered by any acceptable means in the art . preferably the polynucleotide is administered as an aerosol . the administration of the polypeptides of the present invention are most useful in treatment of a class of mutations that encode cftr proteins that are properly delivered to the plasma membrane but that are residually or minimally active . minimally or residually active cftr proteins have the ability to mediate or modulate channel conductance . however , channel conductance is insufficient to sustain the healthy , not cystic fibrotic phenotype . residually or minimally active includes proteins for which the activity of the cftr can be recorded but may be at a level that is barely detectable . this invention will also be useful for cftr mutants that are , to a large extent , misprocessed and thus reach the plasma membrane in much lower quantities than normally processed cftr , and for cftr mutants that are , to a large extent , improperly spliced , but retain production of some properly spliced cftr . known mutants of cftr are listed in table 1 . in addition to its utility in the activation of mutant forms of cftr , this invention will be a useful adjunct to gene therapy for cystic fibrosis . by enhancing the per - cftr molecule chloride transport activity , this peptide will increase the chloride transport activity obtained at any level of expression of cftr , thereby increasing its effective efficacy . the above disclosure generally describes the present invention . a more complete understanding can be obtained by reference to the following specific examples which are provided herein for purposes of illustration only , and are not intended to limit the scope of the invention . development of a polypeptide that exerts only an activating effect on cftr the activating peptide of q4n2neg2 was created by substituting glutamine residues for glutamic acid residues at four sites and asparagines for aspartic acid residues at two sites of the authentic neg2 peptide sequence gleisfeineedlkecffddme ( seq id no : 7 ). in addition , a serine residue was substituted for cysteine , to prevent peptide dimerization , and norleucine was substituted for methionine , to prevent oxidation . these changes create a peptide with reduced chemical reactivity and high predicted helical structure , confirmed by circular dichroism , as well as reduced net negative charge ( from − 9 to − 3 ). attempts to eliminate negative charge completely resulted in an insoluble peptide . when this peptide was added to the cis ( intracellular ) side of cftr channels captured in the planar lipid bilayer , at concentration ranging 0 . 5 to 14 μm , marked dose - related stimulation of channel activity was observed . at concentrations of 4 - 6 μm po of cftr doubles . no inhibitory activity was seen in any experiment at any concentration of peptide . to test whether the q4n2neg2 polypeptide is responsible for increasing the open probability of the cftr channel , synthetic q4n2neg2 , a 22 amino acid peptide , was added to the cis - intracellular side of single cftr channels captured in the planar lipid bilayer ( fig1 ). the diary plot of open probability as a function of time shows the activity of a single wt - cftr channel during the course of the experiment ( fig1 a ). during stimulation , the open probability doubles and more transitions are observed between the open and closed states ( fig1 b ). the open probability observed in 5 experiments at 4 μm concentration q4n2neg2 is shown to be increased by about two - fold in the graph ( fig1 c ). the q4 n2 neg2 peptide sequence has been tested on one mutant form of cftr , g551d , which reaches the plasma membrane . in the planar lipid bilayer , q4n2neg2 increased the open probability of g551 by about threefold . thus , this peptide is useful to stimulate channel activity in mutant forms of cftr that reach the plasma membrane . the neg2 sequence can also be rendered inhibitory , with no stimulatory activity , by scrambling the sequence such that the resulting peptide is predicted to not have helical tendencies , as confirmed by circular dichroism measurements , but retains the full net negative charge of − 9 . this peptide , called scrambled neg2 , inhibits channel activity by about 90 % at 6 μm concentration , with no stimulation observed at any concentration . in addition , insertion of a proline residue into the middle of the neg2 sequence also results in a peptide which inhibits channel activity by about 60 %, but does not stimulate . proline residues are known to disrupt helical structures . the wt cftr cdna was subcloned into an epstein - barr virus - based episomal eukaryotic expression vector , pcep4 ( invitrogen , san diego , calif . ), between the nhe1 and xho1 restriction sites . a human embryonic kidney cell line ( 293 - ebna hek ; invitrogen ) was used for transfection and expression of the cftr proteins ( ma et al ., 1997 , ma et al ., 1996 , xie et al ., 1995 ). the hek - 293 cell line contains a pcmv - ebna vector , which constitutively expresses the epstein - barr virus nuclear antigen - 1 ( ebna - 1 ) gene product and increases the transfection efficiency of epstein - barr virus - based vectors . the cells were maintained in dulbecco &# 39 ; s modified eagle medium with 10 % fbs and 1 % l - glutamine . geneticin ( g418 , 250 ( g / ml ) was added to the cell culture medium to maintain selection of the cells containing the pcmv - ebna vector . lipofectamine reagent ( life technologies , inc ) in optimem media ( serum - free ) was used to transfect the hek - 293 cells with pcep4 ( wt ). after 5 hours , serum was added to the media ( 10 % final serum concentration ). twenty - four hours after transfection , the transfection media was replaced with fresh media . the cells were harvested two days after transfection and microsomal membrane vesicles were prepared for single channel measurements in the lipid bilayer reconstitution system . hek - 293 cells transfected with pcep4 ( cftr ) were harvested and homogenized using a combination of hypotonic lysis and dounce homogenization in the presence of protease inhibitors ( ma et al ., 1997 , ma et al ., 1996 , xie et al ., 1995 ). microsomes were collected by centrifugation of postnuclear supernatant ( 4500 × g , 15 min ) at 100 , 000 × g for 20 min and resuspended in a buffer containing 250 mm sucrose , 10 mm hepes , ph 7 . 2 . the membrane vesicles were stored at − 75 ° c . until use . lipid bilayer membranes were formed across an aperture of ˜ 200 ( m diameter with a mixture of phosphatidylethanolamine : phosphatidylserine : cholesterol in a ratio of 5 : 5 : 1 . the lipids were dissolved in decane at a concentration of 33 mg / ml . the recording solutions contained : cis ( intracellular ), 200 mm cscl , 1 mm mgcl 2 , 2 mm atp , and 10 mm hepes - tris ( ph 7 . 4 ); trans ( extracellular ), 50 mm cscl , 10 mm hepes - tris ( ph 7 . 4 ). vesicles ( 1 - 4 ( 1 ) containing wild - type cftr were added to the cis solution . the pka catalytic subunit was present at a concentration of 50 units / ml in the cis solution unless noted otherwise . single channel currents were recorded with an axopatch 200a patch clamp unit ( axon instruments ). the currents were sampled at 1 - 2 . 5 ms / point . single channel data analyses were performed with pclamp and tips softwares . anderson , m . p ., berger , h . a ., rich , d . p ., gregory , r . j ., smith , a . e ., and welsh , m . j . ( 1991 ). nucleoside triphosphates are required to open the cftr chloride channel . cell 67 , 775 - 784 . bear , c . e ., li , c ., kartner , n ., bridges , r . j ., jensen , t . j ., ramjeesingh , m ., and riordan , j . r . ( 1992 ). purification and functional reconstitution of the cystic fibrosis transmembrane conductance regulator ( cftr ). cell 68 , 809 - 818 . carson , m . r ., travis , s . m ., and welsh , m . j . ( 1995 ). the two nucleotide - binding domains of cystic fibrosis transmembrane conductance regulator ( cftr ) have distinct functions in controlling channel activity . j . biol . chem . 270 , 1711 - 1717 . cheng , s . h ., rich , d . p ., marshall , j ., gregory , r . j ., welsh , m . j ., and smith , a . e . ( 1991 ). phosphorylation of the r domain by camp - dependent protein kinase regulates the cftr chloride channel . cell 66 , 1027 - 1036 . cotten , j . f . and welsh , m . j . ( 1997 ). covalent modification of the regulatory domain irreversibly stimulates cystic fibrosis transmembrane conductance regulator . j . biol . chem . 272 , 25617 - 25622 . dulhanty , a . m . and riordan , j . r . ( 1994 ). phosphorylation by camp - dependent protein kinase causes a conformational change in the r domain of the cystic fibrosis transmembrane conductance regulator . biochemistry 22 , 4072 - 4079 . gadsby , d . c . and nairn , a . c . ( 1994 ). regulation of cftr channel gating . trends biochem . sci . 19 , 513 - 518 . geourjon , c . and deleage , g . ( 1995 ). sopma : significant improvements in protein secondary structure prediction by consensus prediction from multiple alignments . cabios 11 , 681 - 684 . gunderson , k . l . and kopito , r . r . ( 1995 ). conformational states of cftr associated with channel gating : the role of atp binding and hydrolysis . cell 82 , 231 - 239 . higgens , c . f . ( 1992 ). abc transporters : from microorganisms to man . annu . rev . cell biol . 8 , 67 - 113 . ma , j . and davis , p . b . ( 1998 ). what we know and what we do not know about cystic fibrosis transmembrane conductance regulator . clinics in chest medicine 19 , 459 - 471 . ma , j ., tasch , j . e ., tao , t ., zhao , j ., xie , j ., drumm , m . l ., and davis , p . b . ( 1996 ). phosphorylation - dependent block of cystic fibrosis transmembrane conductance regulator chloride channel by exogenous r domain protein . j . biol . chem . 271 , 7351 - 7356 . ma , j ., zhao , j ., drumm , m . l ., xie , j ., and davis , p . b . ( 1997 ). function of the r domain in the cystic fibrosis transmembrane conductance regulator chloride channel . j . biol . chem . 272 , 28133 - 28141 . picciotto , m . r ., cohn , j . a ., bertuzzi , g ., greengard , p ., and nairn , a . c . ( 1992 ). phosphorylation of the cystic fibrosis transmembrane conductance regulator . j . biol . chem . 267 , 12742 - 12752 . quinton , p . m . ( 1986 ). missing cl − conductance in cystic fibrosis . am . j . physiol . 251 , c649 - c652 . rich , d . p ., berger , h . a ., cheng , s . h ., travis , s . m ., saxena , m ., smith , a . e ., and welsh , m . j . ( 1993 ). regulation of the cystic fibrosis transmembrane conductance regulator cl − channel by negative charge in the r domain . j . biol . chem . 268 , 20259 - 20267 . rich , d . p ., gregory , r . j ., anderson , m . p ., manavalan , p ., smith , a . e ., and welsh , m . j . ( 1991 ). effect of deleting the r domain on cftr - generated chloride channels . science 253 , 205 - 207 . riordan , j ., rommens , j ., kerem , b .- s ., noa , a ., rozmahel , r ., grzelczak , z ., zielenski , j ., lok , s ., plavsic , n ., chou , j .- l ., drumm , m ., iannuzzi , m ., collins , f ., and tsui , l .- c . ( 1989 ). identification of the cystic fibrosis gene : cloning and characterization of complementary dna . science 245 , 1066 - 1073 . rost , b . and sander , c . ( 1993 ). prediction of protein structure at better than 70 % accuracy . j . mol . biol . 232 , 584 - 599 . rost , b . and sander , c . ( 1994 ). combining evolutionary information and neural networks to predict protein secondary structure . proteins 19 , 55 - 72 . tabcharani , j . a ., chang , x .- b ., riordan , j . r . and hanrahan , j . w . ( 1991 ). phosphorylation - regulated c − channel in cho cells stably expressing the cystic fibrosis gene . nature 352 , 628 - 631 . tao , t ., xie , j ., drumm , m . l ., zhao , j ., davis , p . b ., and ma , j . ( 1996 ). slow conversions among subconductance states of cystic fibrosis transmembrane conductance regulator chloride channel . biophys . j . 70 , 743 - 753 . vankeerberghen , a ., wei , l ., jaspers , m ., cassiman , j .- j ., nilius , b ., and cuppens , h . ( 1998 ). characterization of 19 disease - associated missense mutations in the regulatory domain of the cystic fibrosis transmembrane conductance regulator . hum . mol . genet . 7 , 1761 - 1769 . welsh , m . j . and smith , a . e . ( 1993 ). molecular mechanisms of cftr chloride channel dysfunction in cystic fibrosis . cell 73 , 1251 - 1254 . winter , m . c . and welsh , m . j . ( 1997 ). stimulation of cftr activity by its phosphorylated r domain . nature 389 , 294 - 296 . xie , j ., drumm , m . l ., ma , j ., and davis , p . b . ( 1995 ). intracellular loop between transmembrane segments iv and v of cystic fibrosis transmembrane conductance regulator is involved in regulation of chloride channel conductance state . j . biol . chem . 270 , 28084 - 28091 . zielenski , j . and tsui , l . c . ( 1995 ). cystic fibrosis : genotypic and phenotypic variations . annu . rev . genetics 29 , 777 - 807 . ile arg val thr val cys glu gly lys asn leu leu gln arg ala asn | 0 |
the following examples set forth techniques for the synthesis of polymers in accordance with the invention , and various uses thereof . it is to be understood that these examples are provided by way of illustration only and nothing therein should be taken as a limitation upon the overall scope of the invention . acetone ( 111 ml ), maleic anhydride ( 20 g ), vinyl acetate monomer ( 19 ml ), and the radical source initiator di - tertbutyl peroxide ( 2 . 4 ml ) were stirred together under inert gas ( such as nitrogen or argon ) in a reactor . the reactor provided included a suitably sized glass spherical flask equipped with a magnetic stirrer , an inert gas inlet , a contents temperature measurement device in contact with the contents of the flask , and a removable reflux condenser . this combination of materials was heated in a hot water bath with stirring at an internal temperature of about 70 ° c . for five hours . at that point , the contents of the flask were evaporated ( by removing the condenser with continued heating ) to a thick oil , and 100 ml of water was added . then , 18 g of granular sodium hydroxide ( naoh ) was added to the above dispersion . the resulting mixture was heated again to about 100 ° c . and allowed to reflux for about two hours . the mixture was then allowed to evaporate by removal of the condenser to a slightly viscous mass . this mass was precipitated by adding the evaporated mixture to about 0 . 5 liters of ethanol while stirring was continued . the solids were recovered and then dried . the resulting product was a white - colored powder . these reactions proceeded as follows : this reaction was carried out similarly to that of example 1 . however , in this case the following quantities of ingredients were used : acetone ( 50 ml ), maleic anhydride ( 44 g ), vinyl acetate monomer ( 42 ml ), and di - tertbutyl peroxide ( 8 . 3 ml ). this mixture was heated in a hot water bath with stirring at an internal temperature of about 70 ° c . for five hours . the contents of the reactor flask were then evaporated to a thick oil and 100 ml of water was added . next , 57 g granular naoh was added . this mixture was heated again to about 100 ° c . and allowed to reflux for about one hour . after refluxing , the mixture evaporated to a slightly viscous mass . this mass was precipitated by adding it , with stirring to 0 . 9 liters of ethanol . the solids were then recovered and dried . the resulting product was a tan - colored powder . this reaction was also carried out as in example 1 . however , the following quantities of ingredients were used : acetone ( 273 . 0 ml ), maleic anhydride ( 49 g ), vinyl acetate monomer ( 46 ml ), and di - tertbutyl peroxide ( 5 . 9 ml ). this mixture was heated in a hot water bath with stirring at an internal temperature of about 70 ° c . for five hours . the contents of the flask were then evaporated into a thick oil ( once again by removing the condenser ), and 250 ml of water was added . following the water addition , 63 g of granular naoh was added . the resulting mixture was heated to about 100 ° c . again , and allowed to reflux for about one hour . this mixture was then evaporated to a slightly viscous mass . the mass was precipitated with stirring into about 2 liters of ethanol . solids were recovered and dried and the product was a very bright white powder . in this example , copper was complexed with the polymer isolated in example 1 . five grams of the example 1 polymer was mixed with 50 g ( dry weight ) of ion exchange resin ( strong acid macro reticular , 4 . 9 meq / gram dry ) which had been soaked in water until the mixture was fluid . the acid form of the polymer was then washed out with several aliquots of water . the resultant water - polymer mixture was then mixed with 6 g of cuso 4 pentahydrate . the aqueous solution containing the copper complex was then evaporated to dryness and the material was collected . one gram of the polymer prepared and isolated in example 1 was dissolved into 20 ml of room temperature water . 1 . 3 g sodium bisulfate was added to this dispersion with stirring . while stirring was continued , 0 . 5 g of ferric sulfate ( fe 2 ( so 4 ) 3 ) tetrahydrate was added slowly with stirring . this product was isolated by evaporating the water from the solution to dryness . thereafter , the isolated dry material was collected . the resultant product was an iron complex of the polymer of example 1 . in this example , 1 g of the polymer prepared and isolated in example 1 was added to 20 ml of room temperature water . sulfuric acid ( 98 %) was added to the dispersion with stirring , until the ph dropped to about 2 . 1 . 5 g of manganese dichloride tetrahydrate was added slowly to the dispersion with vigorous stirring . the material ( a manganese complex of the example 1 polymer ) was then evaporated to dryness and the material was collected . five grams of the polymer prepared and isolated in example 1 was dissolved in 100 ml of water . sulfuric acid ( 98 %) was added until the ph dropped to about 2 . 7 g of zinc sulfate heptahydrate was added slowly with vigorous stirring to the dispersion . the resulting solution had the product ( a zinc complex of the example 1 polymer ) isolated by evaporating the water to dryness and was collected thereafter . water ( 30 g ), and maleic anhydride ( 20 g ) is put into the reactor with stirring under inert gas , such as nitrogen or argon . during this time , the anhydride is converted to the acid form . di - tertbutyl peroxide ( 2 . 4 ml ) is added to the flask . the resulting mixture is heated and refluxed until the reflux head temperature gradually rises to about 100 ° c . at this point , vinyl acetate monomer ( 19 ml ) is gradually added to the reaction at about the same rate that it is consumed . the reaction is carried out until substantially all monomer is consumed . the product of this synthesis is then hydrolyzed as in example 1 . this example demonstrates that the preferred polymerization may be carried out in an aqueous medium . the product of the reaction described in example 8 is refluxed overnight at about 100 ° c . and then subjected to a short - path distillation under inert atmosphere in order to remove the acetic acid hydrolysis product . due to the high temperature and high product concentration , lactone formation is minimized , and the fraction of dicarboxylic acid functional groups that are available is maximized . the desired product is isolated by spray - drying the aqueous solution to give a white amorphous powder . this example is similar to that described in example 8 ; however , water is replaced with a 1 : 1 ( w / w ) mixture of water and ethanol . 20 g of maleic anhydride is added to this mixture . next , di - tertbutyl peroxide ( 2 . 4 ml ) is added to the reactor and the resulting mixture is heated to reflux until the reflux head temperature rises to about 100 ° c . vinyl acetate monomer is then gradually added to the reaction at about the same rate it is consumed . once again , 19 ml of vinyl acetate monomer is used . the reaction is carried out until substantially all of the monomer is consumed . the resulting product is then refluxed overnight and subjected to a short - path distillation under inert atmosphere in order to remove the acetic acid hydrolysis product . once again , due to the high temperature and high product concentration , lactone formation is minimized and the fraction of dicarboxylic acid functional groups is maximized . the desired product is then isolated by spray - drying the aqueous solution to give a white amorphous powder . this example demonstrates that the polymerization may be carried out using uv free radical initiation instead of peroxide . water ( 30 g ) and maleic anhydride ( 20 g ) is mixed in the reactor under inert gas . a 10 watt lamp emitting uv radiation at the 190 - 210 nm wavelength range is immersed in the reaction vessel . the mixture is heated to reflux until the reflux head temperature gradually rises to about 100 ° c ., at which point 19 ml of vinyl acetate monomer is gradually added to the reaction at about the same rate as it is consumed . the reaction is carried out until substantially all of the monomer is consumed . once synthesis ( copolymerization ) is substantially complete , the resultant product is hydrolyzed as in example 1 . in this example , polymerization is carried out using uv free radical initiation in a mixture of organic solvent and water . the experiment is carried out as in example 11 , but water is replaced with a 1 : 1 ( w / w ) mixture of water and ethanol . the isolation and hydrolysis procedures are substantially the same as those used in examples 8 and 9 . in this example , the procedure of example 8 is carried out except that 1 ml of hydrogen peroxide ( 30 % w / w ) is used instead of di - tertbutyl peroxide . this example demonstrates acid hydrolysis in an aqueous medium . to the product of the reaction described in example 8 , 0 . 2 g 98 % of sulfuric acid is added and the mixture is refluxed overnight at about 100 ° c . next , the mixture is subjected to a short - path distillation under inert gas to remove the acetic acid hydrolysis product . due to the acidity , high temperature and high product concentration , lactone formation is minimized , and the fraction of dicarboxylic acid functional groups is maximized . the product is isolated by spray drying the aqueous solution to give a white amorphous powder . an aqueous solution composed of 40 g water , 11 . 6 g maleic acid and 8 . 1 g zinc oxide is formed . the oxide slowly reacts and dissolves to give zinc maleate derivative solution . this is used as a monomer source in a polymerization such as that described in example 8 where equimolar amounts of maleate and vinyl acetate were used . after that , a hydrolysis is performed using the procedures described in example 14 . the reaction proceeded as follows : an aqueous solution composed of 40 g water , 11 . 6 g maleic acid , and 11 . 5 g manganese carbonate is prepared . the carbonate slowly reacts and dissolves to give manganese maleate derivative solution . this manganese maleate solution is used as a monomer source in a polymerization such as that described in example 8 , wherein equimolar amounts of maleate and vinyl acetate were used . after that , a hydrolysis is performed using the procedures described in example 14 . the reaction proceeded as follows : an aqueous solution composed of 40 g water , 11 . g maleic acid , and 5 . 6 g very fine iron dust is formed . the metal slowly reacts and dissolves to give iron maleate derivative solution . this solution is used as a monomer source in a polymerization reaction such as that described in example 8 , wherein equimolar amounts of maleate and vinyl acetate were used . after that , a hydrolysis is performed using the procedures described in example 14 . this reaction proceeded as follows : a continuous reactor is provided including an in - line motionless tube mixer , pumps , thermostatted tubes , and associated valves , fittings , and controls . maleic anhydride ( 50 % w / w in acetone ), vinyl acetate and di - tertbutyl peroxide are pumped into the in - line tube mixer and then into the thermostatted tube . the mixture &# 39 ; s residence time in the tube is about 3 hours . the tube temperature is about 70 ° c . the flow rates are : maleic anhydride solution — 100 g / min ; vinyl acetate — 43 g / min ; and di - tertbutyl peroxide — 3 g / min . hydrolysis is performed using the procedures described in example 14 . aqueous dispersions containing 10 , 50 and 100 ppm of the copper , manganese and zinc copolymers formed in examples 4 , 6 and 7 were applied to the foliage of plum , maple and sweetgum trees , respectively , in order to obtain substantially uniform foliage coverage . prior to this application , the trees visually exhibited characteristic deficiency symptoms for each of the three micronutrients . this treatment alleviated the visual symptoms of the micronutrient deficiency in about 7 - 10 days . bluegrass was treated with aqueous dispersions of the iron copolymer from example 5 ( 20 , 50 and 100 ppm concentrations of iron copolymer ) and compared to an untreated control which received no iron copolymer . these foliar iron treatments were applied at three different times as pretreatments before bluegrass was harvested . photos of the plants were taken two weeks after the last treatment . the results ( table 1 ) clearly show that the bluegrass responded to the iron copolymer application . the total harvest weights for each of the three iron copolymer bluegrass test groups were at least twice that of the control bluegrass . as the amount of copolymer applied increased , harvest weight also increased . in this example , the effect of iron copolymer treatment on lisintus was determined . the iron copolymer of example 5 was used for this experiment . the first control group of plants received no iron copolymer treatment , the second group was foliarly treated with an aqueous dispersion containing 50 ppm of the iron copolymer on three different occasions before harvest , and the third group was similarly treated with an aqueous dispersion containing 100 ppm iron copolymer three times before harvest . the lisintus was harvested and analyzed ( by digestion followed by atomic absorption spectroscopy ) for iron concentration , and by spad meter to determine photosynthetically active chlorophyl levels . the results of this experiment are given in table 2 which shows that application of iron copolymer resulted in a higher iron concentration in the lisintus leaves . however , the amount of iron copolymer applied to the lisintus did not have an appreciable effect on ultimate iron concentration ( i . e . spad meter readings between lisintus treated with 50 ppm iron copolymer and 100 ppm iron copolymer did not differ significantly ). therefore , the most efficient treatment may occur at levels below 50 ppm . in this experiment , different amounts of the copolymer formed in example 1 were used in conjunction with phosphate fertilizer in soil , in order to test the effect of using the polymer with the fertilizer . in particular , the test was conducted on ryegrass grown in growth bags . the growth bags contained soil , water and a conventional , commercially available 8 - 14 - 9 n pk liquid fertilizer . one growth bag ( the control ) had no copolymer added . one bag labeled 0 . 5 × was treated with a fertilizer mixture containing 25 ppm of the copolymer ( the copolymer was added to the liquid fertilizer prior to addition thereof to the growth bags ). the bag labeled 1 × was treated with a liquid fertilizer mixture containing 50 ppm of copolymer . the fertilizer solution in the growth bags were replenished uniformly on an as - needed basis . after the grass was harvested , it was dried and weighed . results of this experiment are given in table 3 which shows no response to the 0 . 5 × copolymer application . the 1 × copolymer application resulted in a 25 % increase in dry weight . in this test , the copolymer from example 1 was tested with phosphate fertilizers in high phosphate - fixing soils in corn growth tests . the test was designed to determine the effect of the copolymer on the plant availability of phosphate based fertilizer in the soil . for this experiment , monoammonium phosphate ( map ) was tested although it is understood that similar results would occur with any phosphate based fertilizer . two soils were utilized in the study , an acid soil ( ph 4 . 5 - 4 . 7 ) from sedgewick county , ks and a calcareous soil ( ph 8 . 0 - 8 . 3 ) from the vicinity of tribune , ks . the acid soil is high in available p but owing to the high exchangeable al and fe content of the soil , p availability is limited . the calcareous soil was lower in available p . containers ( flats ) approximately 75 cm × 40 cm were used for the study . these flats held approximately 8 kg of soil filled to a depth of approximately of 7 . 5 cm , and allows planting in rows with band placement of the fertilizer material , beside the row or in seed contact if desired . multiple rows within each container were used as replications . the containers served as individual treatment for each crop and were rotated to eliminate any possible variables of light and / or temperature . corn was used as the test crop . the seeds were planted in rows , thinned to a constant population per row . only a single variety of corn was used for each crop . corn was taken to approximately the 6 - leaf stage before the whole plant was harvested for dry weight and plant composition analysis . in the corn test , four plants per row per replication were used , thinned back from ten plants . conventional cargill map fertilizer was used , with the fertilizer being coated with the copolymer product of example 1 at rates of 1 g copolymer / 100 g map ( p1 ×) and 2 g copolymer / 100 g map ( p2 ×). the map particles were sized prior to copolymer application to insure that the individual particles were of approximately the same size . in all instances , a single rate of application of 20 ppm phosphorus calculated as p 2 o 5 was employed . in addition , a no - phosphorus control was also included in the study for each crop on each soil . other nutrients were supplied at constant rates . the fertilizer - copolymer map product was applied in a banded fashion with a constant number of phosphate material particles utilized per row ( 63 particles per each 10 inch row section ). this procedure placed the experimental products close to the rows for maximum availability in the phosphate - fixing conditions , and allowed comparison of the effect of the copolymer with each phosphorus fertilizer . after harvesting , the plants were tested for dry weight , phosphorus concentration and phosphorus uptake . sas was utilized to analyze variance of the data . in this test , the effects of polymers on nitrogen volatilization was tested . a urea was sized by screening to a uniform size and was treated to form a 5 % by weight coating of a polymer in accordance with the present invention . the coating was prepared by solubilizing 5 grams of polymer in 3 ml of water . the mixture was then added uniformly to 95 g of urea . to the mixture , 7 g of clay was added which dried the mixture and provided a clay coating . the mixture was then applied to soil for comparison . there were two polymers tested , one which was 50 % calcium and 50 % hydrogen saturated and the other which was 100 % calcium saturated . each of these polymer mixtures were compared to an untreated urea . soil samples were taken and cumulative nitrogen losses were determined after 16 days . as shown in table 5 , coating the urea with clay or a polymer and clay combination greatly reduced nitrogen volatilization . untreated urea lost 37 . 4 % of its total nitrogen . the polymers , calcium / hydrogen mixtures and calcium alone , lost only 20 . 6 % and 19 . 5 % respectively . unexpectedly , the polymer combination significantly reduced nitrogen volatilization . this experiment determined the effects of polymers in accordance with the invention on phosphorus fertilizer availability . an acid soil ( ph 4 . 7 ) and a calcareous soil ( ph 7 . 8 ) treated as in example 23 were collected . these soils were chosen for their p fixing characteristics , preformed by fe and al in the acid soil and ca in the calcareous soil . all treatments involved four replication . soil samples were collected from the area of banded p beside the corn row after the plants had been harvested . the phoshporus material was map ( although it is understood that all fertilizers should have similar results ) with and without an experimental coating of 1 . 0 % on the exterior of the map particles . the coating was prepared using the procedures described above in example 24 . phosphorus rates were 5 , 10 and 20 ppm p205 banded beside the seed ( 1 inch to the side , 1 inch below ) of corn in flats containing 7 kilograms of soil . composited cores from each treatment were processed and analyzed using conventional testing procedures . a single weak acid extractant ( bray p - 1 ) was utilized for both the acid and calcareous soils . the p fertilizer had been in contact with the soil for approximately 5 weeks at the time of sampling . results of this experiment are given below in table 6 . coating map with the experimental product produced consistently higher soil test p values indicating that the extractability of the p was increased . therefore , normal soil p fixation had not progressed as rapidly in the presence of the polymer . the results from the acid soil displayed more differentiation that those of the calcareous soil , perhaps due to the tendency of the weak bray extractant to react with free calcium carbonate in the calcareous soil . plant growth data also demonstrated similar indications of greater p availability . thus , polymers in accordance with the present invention have significant effects on p availability from ammonium phosphate fertilizers . furthermore , these polymers may be of substantial value in improving p use efficiency from applied fertilizers on both acid and calcareous soils with p fixation capacities . in this example , a representative polymer in accordance with the invention was employed as a coating on granular fertilizer , in order to determine the effect of the polymer on increasing the abrasion resistance of the fertilizer . abrasion resistance is the resistance to the formation of dust and fines as a result of granule - to - granule and granule - to - granule equipment contact . increasing abrasion resistance reduces material losses from handling , storage and during application , and also decreases pollution and consequent need for pollution control equipment . in each case , conventional granular map fertilizer was used , and tests were run with no coating , a commercially available dust control coating ( arr - maz kga500 ) and a sodium - saturated polymer in accordance with example 1 ( 40 % solids ). the fertilizer samples were prepared by first screening the fertilizer over 3 . 35 and 1 . 00 mm sieves to obtain a 100 cm 3 portion . individual 20 g samples of the screened fertilizer were then coated by mixing the arr - max - kga500 and polymer of the invention at the levels set forth in table 7 below . after coating and drying , the samples were placed in respective 100 ml rectangular polyurethane bottles , along with 10 stainless steel 7 . 9 mm diameter balls . all sample bottles were taped together into one block and shaken for five minutes . at the end of the shaking , the balls were removed manually , and the bottle contents examined . fines were separated manually and weighed , and the percentage of dust after the shaking test was calculated . table 7 sets forth the results of this experiment . these results demonstrated that the polymers of the invention are highly useful as coatings for solid fertilizer products in order to enhance the abrasion resistance of the products . | 2 |
it is to be understood that the figures and descriptions of the present invention have been simplified to illustrate elements that are relevant for a clear understanding of the present invention , while eliminating , for the purposes of clarity , many other elements found in typical interactive and application programming interface ( api ) systems and methods . those of ordinary skill in the art will recognize that other elements are desirable and / or required in order to implement the present invention . however , because such elements are well known in the art , and because they do not facilitate a better understanding of the present invention , a discussion of such elements is not provided herein . fig1 is a block diagram illustrating a home having resident therein at least one television set having associated therewith at least one digital video recording unit ( hereinafter “ dvr ”). as defined herein , a dvr preferably includes at least one memory unit , such as a hard drive , ram , flash memory , or the like , at least one communication access point , the capability to read metadata received via one of the communication access points , and the capability to write metadata related to a user &# 39 ; s use of the dvr . such communication access points may include one or more of , for example , satellite communication , coaxial cable communication , wifi communication , wimax communication ( such as sprint / nextel , tier 1 , and clearwire , tier 3 ), other wireless lan ( local area network ) communication , telephonic or dsl communication , t - 111 or ethernet communication , or the like . further , the dvr preferably includes an operating environment that has associated therewith at least one application program interface ( api ). the at least one api allows for a programmer to write applications consistent with the operating environment . the api preferably includes a set of routines , protocols , and / or tools to allow for programmers to create software applications consistent with the operating environment , as will be apparent to those of ordinary skill in the art . programs consistent with the api may be pushed or pulled to or by the dvr over the one or more communication access points in response to or as a command to the operating environment . the dvr of the present invention may thus have accessible thereto a plurality of communication media types , including , but not limited to , cable television channels , satellite television channels , the worldwide web , email capabilities , data ( including video and audio ) libraries , and the like , each of which communication media types may form the basis for the creation of a “ program play ,” in which one or more programs ( audio or video ) are presented to a user . in prior embodiments , television programs that play through the dvr have associated therewith a limited amount of metadata that is indicative only of “ thematic ”, principally outerclip aspects of the television program , such as time of the program play , length of the program play , title of the program play , description of program play and significant actors or actresses associated with the program of the program play . the limited metadata associated with the program play received over one or more of the respective communication access points is then made available , in the prior art , for limited manipulation by the user with regard only to those aspects of the program play with which the thematic metadata is associated . because the api of prior art dvr technology is closed , programmers are not universally afforded the opportunity to make greater use of information in any respective program play . the present invention provides , via an open api dvr , an accessibility by the dvr to program plays or applications over any of a plurality of communication access point types mentioned hereinabove , as well as to play program plays of any communication media type as also mentioned hereinabove . as such , a myriad of applications may be written by programmers for operation on or in any of the variety of communication media , and for operation over nearly any communication access point type , and such applications may be pushed , pulled , or accessible over any of the aforementioned communication access points . further , such application may allow for pushing or pulling for numerous interactivity types , including server interactivity , peer interactivity ( including point - to - point sharing ), and program play feed interactivity , for example . such interactivity may be via an accessing of exposed application hooks to the aforementioned metadata . such applications written for the open api of the present invention may provide improved interactivity by , for example , exposing via the application metadata associated with each and every aspect of the program play on any given communication media . for example , metadata may be associated with each word spoken , sound made , and picture shown in any given program play , such as a television or radio program , and as such programmers may expose via the open api information not merely contained within or directly associated with the program play , but that is rather associated with the metadata associated with the program play . the metadata employed in the present invention is discussed further hereinbelow with respect to fig2 and 3 . the metadata may be made accessible to the user via , for example , application software in the form of a program play overlay , in which an overlay - user interface is placed at the forefront of the program play currently in view of the user , which program play is a television program in the example immediately hereinabove . such an overlay may take the form of , for example , an overlay that provides links , dropdown menus , windows , or other readily accessible user interfaces . further , it will be evident to those of ordinary skill in the art that applications may be written that provide multiple windows , menus , or the like simultaneously to a single user , wherein each window plays over a television interface and provides a different program play , and consequently a different overlay , to the user , thereby providing an enhanced version of the known “ picture in picture ” program plays . as mentioned hereinabove , the metadata associated with a particular program play of a particular communication media may allow for a “ hook ” to accessibility of any aspect of the program play , including , but not limited to , externally accessible media , such as other program plays starring the same actor , other program plays starring the same musician , advertising related to goods illustrated in the program play , purchasing points for goods illustrated in the program play , external information , such as world wide web ( www or web ) information regarding items illustrated in the program play , and the like . such external information may be accessible via a user activation of aspects of an overlay on the program play , or the accessing of certain aspects of an overlay or the program play itself may lead the user to menus , windows , or the like outside the program play , and the desired information may be accessible from such menus , windows , or the like . in an exemplary embodiment of the present invention , the open api dvr may allow for an application having an ebay ® overlay to be placed on a particular television show , such as “ the antiques roadshow ”, and the user may thereby access , via the overlay , similar items available on ebay ® to those items being illustrated in the show . alternatively , rather than the ebay ® overlay being placed upon the antiques roadshow ( the program play of the communication media television ), which is received by the dvr via the communication access point cable or satellite , ebay ®, an affiliate , or a third party programmer may create a unique channel for reception by the dvr over a different communication access point , which ebay channel shows still photographs , videos , audio , or the like , that relate to items of frequent interest to buyers of ebay ® goods , and the ebay ® overlay may be placed thereover to allow a user to access further information with regard to those goods or access points of purchase , such as by moving the user to the world wide web upon activation by the user of aspects of the overlay . as such , ebay ® may create its own unique communications media channel for display over television and may send this new channel for communication to the dvr via wimax or the like , and as such new “ television channels ” can be created for access via communication access points not generally used currently by televisions . in an additional exemplary embodiment , a user may be viewing a highly fashion - related program play , such as desperate housewives on abc , in which different fashions or accessories are highly prevalent . if all such information associated with that program play is metatagged , the user may access information on the fashions being worn , or the accessories being used , and such information may include accessibility to other external information , such as comments from fashion editors , available purchase points of the items of interest , and external payment sites to allow for the purchase of those items of interest . in an additional exemplary embodiment , a user may enter , to an application pulled to the dvr via the open api , a list of that user &# 39 ; s fantasy sports players . the present invention may make available to that user a menu listing those fantasy sports players , and the location at which those fantasy sports players may be watched , recorded , or auto - recorded , on any communication media via any communication access point , in real time . additionally , certain players may be highlighted , such as when that particular player &# 39 ; s team possesses the ball , so that the user may switch between communication media or communication access points to , in a targeted manner , allow that user to watch , record , or auto - record that user &# 39 ; s players . additionally and alternatively with regard to this exemplary embodiment , an application may allow the user to open multiple windows to watch multiple of that user &# 39 ; s players in real time , and may maintain in each window an overlay , or may display in a separate window the menu of fantasy players , or may allow the user to toggle between the menu and the video or audio of the games being played . thus , for example , a user may select what events certain actions by the dvr are to trigger on , such as autorecording certain events , such as each time a football running back entered into the fantasy football menu interface scores a touchdown . as such , a user can create his or her favorite , or most frequently accessed , metatags , and the metatags may be placed on all content , and on the user &# 39 ; s accessing of all content . in a broader sense , these exemplary embodiments illustrate that one or more applications pulled or pushed via the open api to the dvr may allow the user to assess , in real time , and / or watch , or auto - record , multiple programs , portions of programs , snippets , ads , or the like of interest , inside or outside of any program play ( such as via a selectable toolbar generated in accordance with a unique application ), use multiple windows of interest simultaneously , be presented with multiple overlays of interest , be presented with multiple menus of interest , all of which may allow the user to access multiple pieces of information or external information not currently available to the user via a television program play . further for example , as discussed hereinabove , the user may use any application , such as a software overlay , while watching a football game for example , to access any information related to all or any portion of that program play , such as information on the types of shoes worn by that user &# 39 ; s favorite player , where the user may buy the jersey worn by that user &# 39 ; s favorite player , may access an online purchase point for those shoes or that jersey , and / or may pay using an on - line point of payment account , such as paypal , all from the dvr of the present invention . as such , the present invention may also provide a highly targeted marketing tool for advertisers , in that each user will access information of interest to that particular user , thereby ensuring that an advertiser &# 39 ; s advertisement is played to a user that is most interested in the item being sold . thereby , advertisers will have less need to place ads in program plays in which 99 % of the viewers of the program play are not interested in the item being sold . further , the present invention will allow such commerce interaction by each user to be uniquely tracked . not only will the addition of metadata add more targeted marketing opportunities , such as to make television ads into drill downs rather than just thirty second videos , but additionally the addition of metadata will allow “ add - on programming ” associated with television shows , which is presently found on line on the web , to be brought back to the television media . for example , on line universes that are created for association with shows on television may , via metadata , menus , and / or overlays that access the metadata , allow for those on - line universes to be brought back on to television . further , the applications written for the dvr are of the present invention may , as do present dvr &# 39 ; s , collect metadata on use by the user of the dvr , as mentioned hereinabove . without violation of privacy laws , such information may , using the applications for the open api discussed herein , be passed to third parties and the metadata may be collected , thereby allowing third parties to generate yet more targeted advertising , more targeted programs plays , and more communication media ( such as communication channels ) of interest to the highest number of users . in light of that discussed hereinabove , the open api of the dvr of the present invention may provide hooks into all items of interest and into the operating environment of the dvr , and the exposure of those hooks via the open api will allow third parties to tie into those hooks . further , users can access applications associated with those hooks via the metadata tags associated with those hooks . such metadata tags may allow , for example , applications that make use of overlays , video overlays , water marking , auto pause , auto record , toolbars , menus , and the like . the applications so generated may be locally processed on the dvr ( such as for certified applications ), or can be streamed to the dvr , or can be associated with entirely new , externally generated communication channels . additionally , as discussed hereinabove , although the dvr may have associated therewith some local storage , vast quantities of remote storage may be made available , such as at external sites accessible via wimax or the like . as such , a user may be charged for any level of desired storage for programming , and will not be limited for storage by the hardware of the dvr resident within the user &# 39 ; s home . thus , the present invention may make available any of a variety of communication channels , and any of a variety of applications for accessing metatags associated with the communication media being played on any of those communication channels . for example , a real estate channel may be made available , and the real estate available on the real estate channel may be targeted to the preferences entered by the user of interest . alternatively , a completely interactive gaming channel may be made available wherein trivia games , casino games , or the like may be made available in accordance with user preferences , and actions undertaken by the user may be received by the dvr as metadata that may be made available to third parties . alternatively , complex interfaces may be made available via a metadata feed . for example , a user may watch a nature show on the discovery channel , and may hear or see mention of an animal of interest to that user . the user may then access , such as via an overlay , a link associated with that animal of interest . that link may provide the user with access to , for example , google earth , which may allow for illustration to the user of all animals of that type , anywhere in the world , that have been tagged and placed back into the wild and that are open to sponsorship by a user . the user may be then given the option to sponsor one of the animals in a location of interest to the user , and in the event the user selects an animal to sponsor , an on - line payment interface , such as paypal , may be accessible to the user for payment of the sponsorship fee . alternatively , either within the program play on the discovery channel , or after drilling down to the animal of interest , the user may be presented with a mention of a country of interest to the user , such as botswana . the user may pause , and either exit the program play via the overlay , or may exit the google earth interface displaying the animals of interest , and may redirect to find information , such as on wikipedia , on “ botswana .” after the user has redirected a sufficient number of times to receive the information of interest to the user with regard to botswana , the user may elect to be redirected back to the initial location of interest , which in this example is either the program play or the information on the animal of interest . the present invention may also include social networking . such social networking may include videoconferencing , video messaging , or placement of personal information or personal ads on line , or placement of video or audio generated by a user that the user would like to make accessible to third parties , from the communication access points accessible to the user via the open api dvr , thus making the user “ the star of ” his or her own show . the present invention may additionally include , for example , a mobile dvr , wherein dvr features accessed via mobile televisions , televisions not within the home residence , navigation screens within vehicles , or the like , accessible to any of the aforementioned communication access points , and such mobile dvr may communication with the home , open api dvr . more specifically with regard to the above - referenced metatagging , the metatagging of the present invention is typically to take place interclip , and may be thematically or non - thematically related . more specifically , the tagging may be done interclip and interframe , and / or frame - by - frame , and may relate to words , pictures , and the like that occur within the frame , whether or not related to the thematic nature of the programming . such tags may be associated with the interframe programming by , for example , the automatic nature of the application then running , may be inserted remotely at the programming for the programming displayed , or may inserted by the users as the programming is viewed . further , such tagging allows for actions to be taken on discrete portions of an overall program play , unlike the actions made available by the prior art . additionally , such metatags may be streamed in - content , or in a separate metastream tied to the program play , as discussed with particularity immediately hereinbelow . as will be apparent to those skilled in the art , a metatag as used herein is a computer - readable language , such as xml , html , or the like , syntax statement that may be sent along with a program play , such as by being sent as a secondary stream fed to a user along with a streamed program play , or that may be sent as part of a program play , such as in the “ header ” information that describes the computing characteristics of the program play . the metatag may convey information about that with which it is associated ( i . e . the program play in this example ), and such information may or may not actually be found within such a program play . for example , such metatags may be hooks , such as for user commands , or may make requests of the user , or may be used as keywords in searching of program plays or program play portions . each such metatag must be given a unique name , or tag , and have associated therewith unique content . such association of keywords and content may be done automatically , such as by an automated search of a document , such as a script of a program play , or such as by spider searching , or such as by index searching , or may be done manually . further , metatags included within frames may be linked and / or correlated to other metatags , within or outside of the program then within view . for example , correlation may be performed from metatag to metatag , in frame , or from metatag to metatag from a frame of one program play to a frame in a separate program play , or from metatag to content stream , for example . alternatively , correlation of metatag to metatag may occur from a frame within one program play to another frame within the same program play , or interframe between program plays . correlation may be employed using authoring standard techniques and / or languages , such as synchronized multimedia integration language ( smil ) or microsoft synchronized accessible media interchange ( sami ), among others , which may be separate from , and in a different syntax than , the program play stream ( s ). further or alternatively , correlation functions and correlation branching known to those skilled in the art of mathematics may be employed by the applications programmed into the open api of the present invention , with regard to each frame , or frame portion , of every program play accessible to the open api dvr . in certain exemplary embodiments , watermarking techniques typically employed for embedding correlated audiovisual interaction information may be used to correlate frames , inter - frames , or program plays in the present invention , with or without modification to the typical metatag data stream or headers ( see , e . g ., “ stream based interactive video language authoring using correlated audiovisual watermarking ,” xu , et al ., icita &# 39 ; 05 proceedings , ieee ). further , as such , upon placement into or into association with the program play , inframe metatags may have correlated therewith not only aspects of inframes of other program plays , but additionally any of the number of functions to be performed by the respective applications discussed herein throughout . the association of metatags to other metatags may , in fact , create “ clickable video .” clickable video provides true interactivity to a watcher of any program play that presents the video to the user . as such , for example , the user may pause the video and use display objects known to those skilled in the art , such as a mouse cursor , to interact with portions of the video , or may call up such an interactive cursor to interact with the video while the video is playing . further , metatagging may allow for variations in the mouse cursor that correspond to those aspects of the video currently playing when the mouse cursor is brought up on the screen . for example , if a portion of the video includes an actor in the video drinking a can of coke , the mouse cursor , if called during that portion of the video , might display as a miniature can of coke . thus , once the metastream is defined , clickable video frames can be created , correlation to the same or other metastreams may be performed , and passive processing may be performed with third party api &# 39 ; s . such third party processing may include , for example , remote commands such as dvr commands , that may , for example , allow for the taping of certain snippets of interest within larger program shows . the manner of metatagging used in the present invention may , for example , be any methodology of metatagging known to those skilled in the art . further , a program play may be metatagged before initial broadcast , before rebroadcast , or during the streaming of a broadcast stream . as such , rights in such metatagging may be available and divisible by pre - initial broadcast , in - broadcast , and rebroadcast , for example . the present invention may be hierarchically organized as shown in fig2 . fig2 illustrates , as the focal point of the present invention , a video which will be displayed to the user as a program play . the video is metatagged as shown , and the hierarchy outside , but associated with , the metatags may then communicate with and using the metatags via a message bus . surrounding the message bus may be a variety of filters , and surrounding the filters may be a variety of applications . the applications may access any of a number of the filters , and both the applications and the filters may have accessible thereto the message bus . the message bus may make available a variety of operation commands for interaction with the metatags , and the metatags may provide interoperability of the commands with the video . the filters may be mapped into a variety of commands made available in the message bus , and thus the filters may be of a variety of types . for example , filters may include key word filters , commerce - type filters , location filters , geolocation filters , correlation filters , insertion filters such as for secondary feeds , and social filters , programmatic publishing filters , automatic publishing filters , and the like . the mapping o f user commands performed by the filters , and performed by the applications that run the filters , may cause the application of one filter type to be a causation for application of a filter of another type . as such , applications can likewise feed one another , such as wherein an application of one type , such as a search application , accesses an application of another type , such as a wikipedia engine , whereby answers to a user inquiry into a search engine can be obtained . further , for example , one application and / or filter may allow the saving of certain aspects of a program based on the application of another application indicating that the user wishes to seek certain snippets associated with certain topics . further , once such snippets are saved , yet another application may allow the shipment of the frames or snippets of interest , based on the metadata illustrating that such frames are of interest , between users , such as via email programs , internet mail or wifi for example . additionally , as mentioned hereinabove , the open api aspects of the dvr of the present invention may allow for programmatic publishing , wherein an application actively publishes certain metadata or certain information received into the programming via , for example , automatic publishing ( wherein such publishing occurs passively ). in a more specific example illustrated in fig3 , certain applications and / or filters interact with the message bus . as illustrated , the applications and / or filters may have associated therewith core applications , and may be surrounded by metatags in a manner similar to the base video of interest . in an exemplary embodiment , the metatags of the application into which the user expresses interest in the location of certain animals of the world may come from a mapping application , wherein interaction b , as shown , interacts with the message bus based on the interaction b from the user . the metatag reached by interaction b may be a geographic location within a program then within view of the user , and may lead to interaction a reaching out to make other assessments of the user &# 39 ; s mapped location of interest . for example , a different application may then be accessed by the first application based on the correlation of interactions a and b , and this different application may assess a variety of different animals , available animal sponsorships , records of national disasters , phone books , flora , or the like , that are resident in that particular geographic location . such information may then be fed back to the user via the message bus interface , or the interest from the user may simply be written to the external application , and may be tracked by the application programmer . as such , multiple applications may collaborate as between the applications , may correlate as between the applications , and may filter as between the applications , and such actions may occur automatically , via programmatic publishing , and / or may be based on certain permissions . the filtering and applications of the present invention made available via the open api dvr interface may thus be dependent on the capability to create an instream metastream that is not necessarily thematically related to any of the programs shown to the user . such an instream metastream may include a metastream associated with any instream programming , which may include not only the programming of interest but also advertising associated with , or accessible from , the programming of interest . although the invention has been described and pictured in a preferred form with a certain degree of particularity , it is understood that the present disclosure of the preferred form has been made by way of example , and that numerous changes in the details of construction and combination and arrangement of parts and steps may be made without departing from the spirit and scope of the invention . | 7 |
in fig1 a curve labeled 111 schematically illustrates a transmission spectrum for o 2 having a transmission minimum ( absorption maximum ) at 1849 . 38 a , and a half - width of about 0 . 1 a . a second curve labelled 113 represents the atomic emission line of hg which is centered at 1849 . 50 a ( which will hereinafter be designated as &# 34 ; λ cg &# 34 ;, the center - of - gravity of the hg emission spectra ). this hg emission line is a superposition of emission ( or absorption ) lines generated by each of the hg isotopes which are present in the lamp . in a preferred embodiment , the isotope mixture is that occurring in a natural sample of hg . it is also possible to utilize a &# 34 ; synthetic &# 34 ; isotope mix which permits more precise control of spectral content . in fig2 the relative positions of the naturally occurring isotope lines are indicated by arrows labeling the isotopic state and hyperfine state where applicable . by passing the radiation emitted by an hg lamp through a cell containing an isotope which absorbs at a wavelength below λ cg a spectrum can be obtained whose center - of - gravity will be displaced to a wavelength longer than λ cg . this is illustrated in fig3 a for the particular case in which the filter cell contains the isotope 198 hg . in this case incident radiation 313 is passed through the filter cell having an absorption curve 317 to produce an emergent radiation spectrum 319 having a central wavelength λ ls ≈ 1849 . 51 a , which is &# 34 ; long - shifted &# 34 ; relative to λ cg . in fig3 b , on the other hand , a natural mercury emission spectrum 313 is passed through a filter containing 204 hg vapor having an absorption spectrum 321 to produce a resultant &# 34 ; short - shifted &# 34 ; emission spectrum 323 whose central wavelength is λ ss ≈ 1849 . 49 a . fig4 shows the higher wavelength edge of o 2 transmission curve 411 on a scale expanded from the scale of fig1 . also shown are the long - shifted and short - shifted hg emission curves 419 and 423 , respectively . because of the steepness of the o 2 transmission curve 411 , there will be an appreciable difference between the transmission of the long - shifted and short - shifted mercury emissions when these are passed through a sample containing o 2 . however , other uv absorbers such as h 2 o will display an absorption curve which is essentially flat over the small wavelength region encompassing λ ss and λ ls ( δl ≈ 0 . 02 a ). such a curve is schematically illustrated in fig4 by the line labelled 425 . thus , in a sample containing o 2 and other broadband uv absorbers , the other absorbers will absorb the long - shifted radiation 419 and short - shifted radiation 423 about equally , while the o 2 will absorb these differentially . a measurement of the difference in the percent absorption of these two lines will therefore give an indication of the amount of o 2 which is present in the sample . it should be noted that u . s . pat . no . 3 , 869 , 613 issued mar . 4 , 1975 to w . t . link , et al . discloses a device for detecting a specific gas using an infra - red beam which is alternately passed through different filter cells containing different isotopes of the specific gas to be detected . the beam emerging from each filter cell will have had removed the wavelength corresponding to the isotope in that cell . in the patent the isotopes are selected as those which occur in different proportions in the specific gas to be detected . thus , the two beams will be absorbed differently by the sample ( containing different proportions of the isotopes ), but will be absorbed about equally by other absorbers . for the detection of o 2 this technique would entail the use of a broadband uv source ( in place of an infrared source ) generating a beam to be passed through filter cells containing different isotopes of o 2 . such a procedure does not appear to be useful for the detection of o 2 , because any band of uv radiation sufficiently narrow to have essentially constant absorption of interfering gases over that band will be too narrow to allow wavelength shifting by oxygen isotopes . the present o 2 detection device differs from that disclosed in the above - referenced patent in various respects : no broadband uv source is used ; instead a narrow line source from an atomic transition of an element ( e . g . mercury ) is employed . further , no isotopes of the specific gas to be detected ( i . e . o 2 ) are used , rather ; the present invention employs isotopes of only the radiation source element . fig5 shows a simple system for implementing the oxygen detection scheme discussed above . a mercury vapor lamp 527 emits a spectrum characteristic of the atomic transistions of hg , including a radiation line centered about 1849 . 5 a . this particular transition line includes radiation from the various isotopes shown in fig2 . radiation from mercury lamp 527 is passed through a monochromator 529 which filters out all of the mercury emission except a small bandwidth centered on the 1849 . 5 a line . for example , an acton research corporation 185 - n filter ( acton , ma ) may be used which has a half - width of about 275 a . the mercury radiation which has passed through monochromator 529 is then passed through a filter wheel 531 which includes filter cells 533 and 535 each containing a single isotope of mercury whose absorption peak lies on one side or the other 1849 . 5 a emission line . the hg isotope in the cell preferably consists of a small amount of liquid hg in equilibrium with its vapor . for example , one cell may contain 198 hg and the other cell 204 hg . cells 533 and 535 should provide a pathlength greater than about two millimeters to provide adequate absorption . filter wheel 531 is rotated to present alternately one or the other of cells 533 and 535 in the path of the emission from lamp 527 . thus , in accordance with the discussion above , radiation having passed through one cell or the other will display a short - shifted or long - shifted emission spectrum . the radiation emergent from filter wheel 531 is incident upon a beamsplitter 537 such as a quartz plate with a thin aluminum coating so that a portion of the radiation is directed to a &# 34 ; reference &# 34 ; detector 539 while another portion of the radiation is directed through a sample cell 541 to a &# 34 ; sample &# 34 ; detector 543 . in order to prevent the occurrence of spurious signals arising from ambient o 2 which may be present in the vicinity of the filter wheel , sample cell etc ., the optical path length from beamsplitter 537 to reference detector 539 should be equal to the optical path length from beamsplitter 537 to sample detector 543 , less the length of sample cell 541 . alternately , the system can be hermetically sealed to prevent any spurious o 2 from entering the system . sample cell 541 contains a gas to be analyzed including an amount of oxygen to be determined by the measurement , so that sample detector 543 provides an indication of the intensity of the long - shifted and short - shifted radiation transmitted through the oxygen - containing sample . reference detector 539 on the other hand provides an indication of the intensity of the long - shifted and short - shifted emission spectra which has not been subject to absorption by the sample . use of a beamsplitter and reference detector therefore renders the detection scheme insensitive to sources of long - term drift , such as temperature variations , power variations etc . if these are insignificant in a given system , the reference detector can be omitted . in accordance with the discussion above , the difference in the amounts of the long - shifted and short - shifted emission spectra detected by detectors 539 and 543 therefore gives an indication of the amount of oxygen present in sample cell 541 . to make the detection scheme discussed above more precise consider the following definitions : i ls , r = signal amplitude at reference detector due to light which passed through the 198 hg cell . i ss , r = signal amplitude at reference detector due to light which passed through the 204 hg cell . in terms of these quantities the following amplitudes i 1 , r through i 4 , r can be measured at the reference detector 539 ; ## equ1 ## consider now the radiation passing through sample cell 541 containing a certain partial pressure of oxygen defined as &# 34 ; p0 2 &# 34 ;. this amount of o 2 will produce an attenuation of the short - shifted and long - shifted spectra by a factor of exp (- k ss po 2 ) and exp (- k ls po 2 ) respectively , where k ss and k ls are attenuation coefficients characteristic of the two spectra . additional attentuation due to absorption by water , scattering , deflections , etc . will also occur , and is accounted for by a factor of exp (- c ), where c is the same constant for both the short - shifted and long - shifted radiation ( see the discussion of fig4 ). thus , analagously to the reference amplitudes i 1 , r - i 4 , r , the following amplitudes can be measured at sample detector 543 : ## equ2 ## a ratio r can now be formed and manipulated , preferably by means of an associated digital electronics processor 545 , as follows : ## equ3 ## since beamsplitter 537 does not alter the ratio of long - shifted to short - shifted light incident upon the reference detector 539 and the sample cell 541 , ## equ4 ## thus , ## equ5 ## from which the partial pressure of oxygen is given by ## equ6 ## in an alternate embodiment the oxygen absorption curve may be differentially detected using two separate isotopic lines of the mercury ultraviolet emission line close to 1849 . 5 a . in this embodiment , shown in fig6 two separate sources are provided , each containing a pure mercury isotope . for example , fig6 shows a lamp 627 containing substantially pure 204 hg . thus , each of the lamps will display an emission spectrum near the 1849 . 5 a hg line which is characteristic of the pure isotope contained in that lamp . these spectra are switched into a beam combining element 631 similar to beamsplitter 537 in fig5 . the switching may be accomplished mechanically , for example by using a rotating wheel 630 as shown . alternatively , electrical beam switching could be accomplished by electrically modulating the intensities of lamps 627 and 628 . the combined beam is directed through a monochromator 629 such as the monochromator 529 in fig5 having a passband centered on 1849 . 5 a . the remaining elements of the system including a beamsplitter 637 , sample cell 641 , reference detector 639 , and sample detector 643 are the same as the equivalent elements in fig5 . operation of the device of fig6 is governed by the same equations as described above with respect to the device of fig5 . however , since the two slightly different hg spectra are here provided by the two different pure isotope lamps 627 and 628 , the amount of oxygen present in the sample cell will ultimately be determined by the equation ## equ7 ## where k 198 and k 204 represent the oxygen absorption coefficients for the 198 hg and 204 hg isotope emission lines , respectively . in an alternate embodiment each lamp can be a &# 34 ; natural &# 34 ; hg lamp having an associated isotope filter , in which case the above discussion yields an expression similar to equation 14 where k 198 and k 204 are replaced by k ss and k ls , as earlier defined . in fig7 there is shown an embodiment in which a sample detector 743 and a reference detector 745 are silicon photodetectors , such as a model uv100b manufactured by eg & amp ; g company in salem , massachusetts . the silicon surface of reference detector 745 is highly reflective to the uv radiation utilized in the present o 2 detection scheme . it is thus possible to use the surface of reference detector 745 to deflect a portion of the optical beam through sample cell 741 , while absorbing another portion of the beam as a reference signal . in this embodiment the requirement for a separate beamsplitter is eliminated . to facilitate implementation of the oxygen detector in a compact and inexpensive package some preferred embodiments of the invention may utilize techniques other than or in addition to a monochromator for eliminating the mercury atomic emission lines other than the 1849 a line . this may be accomplished pursuant to fig8 which shows the hg atomic emission lines in the ultraviolet . the line labeled 845 is the 1849 a line which overlaps the oxygen absorption spectra . a low intensity line labelled 847 occurs at a wavelength of 1942 a and a high intensity line labeled 849 occurs at a wavelength of 2537 a . fig8 also shows a transmission curve 851 for a nominal 3 mm thickness of h 2 o and another transmission curve 853 for a nominal 3 mm thickness of vycor ®, a 96 % pure quartz material which does not transmit short wavelength ultraviolet light . from fig8 it can be seen that if radiation from a mercury lamp is passed through a cell containing h 2 o , the 1849 a line will be filtered out of the emission spectra . similarly , if the mercury radiation is passed through a vycor ® element all emission lines having wavelengths shorter than 2500 a ( including the 1849 a line ) will be filtered out . the relationships among the mercury emission lines and the transmission characteristics of water or vycor ® illustrated in fig8 may be exploited in a device according to the present invention by observing that ## equ8 ## where i total is the total hg intensity of the hg atomic emission spectrum , i 1849 is the intensity of the atomic emission at 1849 a and i other is the combined intensities of all other hg emission lines at wavelengths longer than 1849 a . this relationship can also be expressed as ## equ9 ## thus , i 1849 may be inferred by measuring the total mercury emission and also measuring the mercury emission having the 1849 a line eliminated . the difference of these will be i 1849 . if the radiation is passed through the 198 hg and 204 hg filters as discussed above in connection with fig3 an emergent radiation is governed by the equivalent relationships for long - shifted and short - shifted emissions : ## equ10 ## fig9 shows a schematic representation of a filter system for the determination of i 1849 , ls and i 1849 , ss according to the equations above . a beam of radiation 955 is emitted from a mercury source ( not shown ). radiation beam 955 is incident upon four cells 957 , 959 , 961 and 963 , two of which contain 198 hg ( cells 957 and 959 ), and two of which contain 204 hg ( cells 961 and 963 ). the entry and exit windows 964 and 965 of cell 957 are of a material which transmits all of the wavelengths in the mercury ultraviolet emission spectrum ; e . g . suprasil ® quartz windows are suitable . thus , the radiation emergent from cell 957 will contain all mercury emission lines including specifically the 1849 a line . however , because of the presence of the 198 hg isotope in cell 957 the 1849 a line will be long - shifted , as was discussed above in connection with fig3 . the radiation emergent from cell 957 will therefore have an intensity of i 1849 , ls + i other . cell 959 includes at least one window , e . g . an exit window 967 , of a material such as vycor ® which effectively blocks transmission of the mercury 1849 a line . thus , the radiation emitted from cell 959 will have an intensity i other ( in an alternate embodiment , h 2 o could be incorporated into the cell in lieu of the vycor ® window , which would also yield a spectrum in which the 1849 a line would be absent ). in a similar manner radiation passing through cell 961 containing 204 hg and suprasil ® windows 869 will emerge having an intensity of i 1849 , ss + i &# 39 ; other , while radiation passing through cell 963 having a vycor ® window 971 will emerge with an intensity i &# 39 ; other . to make the oxygen measurement each of the beams emerging from the filter cells in fig9 is directed to the sample and reference detectors as described above in connection with fig5 . for example , the various cells of fig9 may be configured in a rotating filter wheel such as the one illustrated in fig5 . the intensities measured at the sample and reference detectors are electronically stored , e . g . in a digital calculating apparatus and are combined according to equations 17 and 18 . note that if extreme accuracy is required , it may be necessary to account for small differences in transmissivity between e . g . cells 957 and 959 , so that i other exactly cancels in equation 16 . this can be accomplished e . g . by calculating a normalizing coefficient based on a comparison of the intensities of radiation passing through the two cells when i 1849 is blocked . the normalized combined intensity values are then inserted into equation 13 to indicate the partial pressure of o 2 in the sample cell . | 6 |
fig1 shows a module 11 with the cover removed to show the various components including an evaporator coil 12 , a condenser coil 13 , a plurality of evaporator blowers 14 and associated drive motors 16 , and a condenser fan motor 17 for driving a condenser fan ( see fig3 ). outside the module 11 is a compressor 18 which is driven by a motor drive 19 to pump refrigerant from the compressor 18 through refrigerant line 21 to the condenser coil 13 and eventually to the evaporator coil 12 by way of an expansion valve 22 ( see fig3 ). the refrigerant vapor then passes back to the compressor 18 by way of refrigerant line 23 . the drive engine 19 is also operatively connected to an electrical generator 15 , ( or alternator , if desired ) for providing electrical power to the module by way of line 25 . also shown in fig1 is an electrical resistance heater 24 which is downstream of the evaporator coil 12 such that , for periods of heating , the air is drawn by the evaporator blower 14 through the evaporator coil 12 and the heater 24 such that the air being delivered to the passenger compartment of the bus is heated . the electrical power to the heater 24 , as well as to the evaporator blower motor 16 and the condenser fan motor 17 , is provided by way of the electrical line 25 receiving dc power from the generator 15 . the heater 24 can be powered by either dc or ac currents with the heat output being independent of the speed of the drive engine 19 . with the module as shown in fig1 , dc power is available to power all of the motor components and is therefore preferred for the heater 24 . referring now to fig2 , a modified module 26 is shown to include all of the components as described hereinabove . further , it includes a horizontal rotary compressor 27 which is operatively interconnected between the evaporator coil 12 and the condenser coil 13 so as to circulate refrigerant in a manner similar as described hereinabove . the difference over the earlier described system , however , is that the hermetic compressor 18 is driven by an internal electric motor 20 , with the power being provided by way of the generator 29 , driven by the main engine 19 , and an inverter / controller 28 as shown in fig3 . the inverter / controller 28 , which receives input from various control sensors 30 and which includes a rectifier and an inverter , receives ac power from a generator or alternator 29 and provides , by way of the inverter , controlled ac power to the evaporator blower motor 16 , the condenser blower motor 17 , the compressor drive motor 20 and the heater 24 . since the invertor / controller 28 is capable of providing controlled ac power , each of the motors are ac motors , thereby ensuring a more maintenance free system . with the inverter / controller providing controlled ac power , a preferred type of heat 24 is a positive temperature coefficient ( pic ) heater wherein electrical resistance increases relatively fast as the temperature increases . whereas this type of heater is relatively expensive in it initial installation , it acts as a self limiter and does not require a thermostat to maintain a safe temperature limit . referring now to fig4 , the module is shown with the various components as described hereinabove enclosed within a housing 29 and including a condenser fan 31 . also shown are the various openings in the housing 29 , including a return air opening 32 , a condenser outlet opening 33 and a condenser / fresh air intake opening 34 . a fresh / return / exhaust air flap 36 is provided between the condenser coil 13 and the evaporator coil 12 to control the mix of air passing to the evaporator coil 12 , depending on the particular demands of the system , as well as the existing ambient conditions . the air flow pattern , as indicated by the arrows , is thus controlled by the condenser fan 31 , the evaporator fan 14 and the position of the air flap 36 . as the return air enters the return air opening 32 , it is caused to flow out the condenser outlet air opening and / or through the evaporator coil 12 depending on the position of the air flap 36 . similarly , the fresh air coming in the intake opening 34 passes through the condenser coil 13 and then out the condenser outlet air opening 33 and / or , depending on the position of the air flap 36 , it is allowed to pass through the evaporator coil 12 . thus , with the use of the air flap 36 it is possible to have all of the return air pass through the condenser air outlet opening 33 , with all fresh air passing into the air intake opening 34 and then through the evaporator coil 12 , or when the flap 36 is placed in the other extreme position , all of the return air passes through the evaporator coil 12 and all of the fresh air entering the air intake opening 34 passes through the condenser coil 13 and out the condenser outlet air opening 33 . a more likely operating condition , however , is an intermediate position of the air flap 36 wherein a selective mix of return air and fresh air are passed through the evaporator coil 12 . as will be seen , a filter 37 is positioned in the air flow stream which enters the fresh air intake opening 34 and passes through the evaporator coil 12 . its purposes is to filter out any debris that may be in the air stream entering the air intake opening 34 . after passing through the evaporator coil 12 , the conditioned air is caused to flow by the evaporator blower 14 out a supply air opening 38 as shown . considering now the manner in which the module 11 is positioned on the rooftop in such a way as to interface with the existing air path openings on the rooftop , reference is made to fig5 a – 5 c . as will be seen , the position of the various openings on a bus can vary substantially from application to application . for example , in a wide bus application as shown in fig5 a , the supply air duct 39 is located near the outer side of the bus , whereas the return air duct 41 is disposed at a substantial distance from the longitudinal center line thereof . in a narrow bus application as shown in fig5 b , the supply air duct 42 is moved a small distance inwardly from the outer side of the bus , and the return air duct is located adjacent the longitudinal centerline as shown . in a curved - roof bus as shown in fig5 c , the supply air duct 44 is moved slightly more inwardly from the outer side of the bus , and the return air duct 46 is located in an intermediate position , somewhat outwardly of the longitudinal centerline , but not as far as for a wide bus application . of course , in all of the bus applications , a balanced arrangement is provided wherein each side of the bus is provided with both a supply air duct and a return air duct , in a substantially mirror image arrangement as shown . thus , the modules are placed in back - to - back relationship , with the space therebetween being varied to accommodate the individual application requirements . for example , for the wide bus application of fig5 a , there is a substantial space between the two modules wherein for the narrow bus application of fig5 b , they are substantially in an abutting relationship . for the curved roof bus application , they are somewhat angled from a true horizontal position , with the spacing therebetween being at an intermediate degree as shown . it should be understood that the three types of installations shown are presented as a sampling of the possible installation requirements , and there are also others that have heretofore required unique designs in order to meet the particular requirements . the present design , on the other hand , provides a single module which will meet the needs of all of the various applications of rooftop air conditioners . as will be seen , the supply air opening is relatively small , and in each of the three cases described above , the module 11 is placed in such a position that the supply air opening 38 is located substantially over the individual supply air ducts 39 , 42 and 44 . the return air opening 32 , on the other hand is relatively large and therefore can accommodate the various positions of the return air ducts 41 , 43 and 46 as shown . in order to describe the length ( i . e ., the extent that it spans a lateral dimension of the bus ), of the return air opening 32 , it is necessary to briefly review the design features , including the exhaust air flap 36 as shown in fig6 a – 6 c . in fig6 a , the fresh / return / exhaust air flap 36 is placed in such a position that all of the return air coming into the return air opening 32 passes through the evaporator coil 12 as shown , and with all of the fresh air entering the fresh air intake opening 34 passing through the condenser coil 13 and out the outlet air opening 33 . in fig6 b , the fresh / return / exhaust air flap 36 is placed in the other extreme position wherein none of the return air passing into the return air opening 32 is passed to the evaporator coil 12 and the only air entering the evaporator coil 12 is the fresh air , a portion of which passes through the evaporator coil 12 and a portion of which passes through the condenser coil 13 as shown . in fig6 c , the fresh / return / exhaust air flap 36 is placed in an intermediate position wherein a portion of the return air passes through the evaporator coil 12 , and a portion thereof is diverted to pass through the condenser coil 13 . in this case , fresh air is also diverted from the air intake opening 34 and mixed with the return air as it passes through the evaporator coil 12 . in all of the three positions of the fresh / return / exhaust air flap 36 as shown , and for any other position thereof , the return air opening 32 of the module is rather extensive in length , with the length thereof being represented by the designation l 1 . it is because of this substantial length l 1 , of the return air opening 32 that the module 11 can accommodate the various installation requirements as described hereinabove . the relative size of l 1 , can be established by a convenient comparison with the overall length l 2 of the module . that is the ratio of longitudinal length l 1 , of the opening to the longitudinal length l 2 of the module is it is therefore greater than 45 % and close to 50 %. another reference point is the width of the bus rooftop or more appropriately , the half width of a bus . a wide bus has a half width of approximately 51 inches and a narrow bus has a half width of approximately 48 inches . thus , for a wide bus ( fig5 a ), the ratio of the length l 1 to the bus half width l 3 ( i . e . the dimension between a longitudinal centerline thereof and the outer side of the bus ) is for a narrow bus ( fig5 b ) it is in fig7 – 10 , there is shown various pairings of modules as installed on various locations of the bus rooftop . in fig7 , a pair of modules are positioned in back - to - back relationship near the longitudinal center of the bus . in fig8 , there are two such pairings ( i . e ., four modules ) in back - to - back relationship near the longitudinal center of the bus , and in fig9 there are shown three such pairings . in fig1 , there is shown a pair of modules in back - to - back relationship , but with a substantial space therebetween , both near the longitudinal center of the bus and near the trailing end thereof with all being aligned along lines parallel to the longitudinal centerline of the bus . in addition to those shown , it should be understood that various other installations can be accommodated with the module as described herein . | 8 |
the synthesis of the peptides of general formula i , including derivatization , activation , and coupling of protected amino acid residues , and their purification , and the analytical methods for determining identity and purity are included in the general body of knowledge of peptide chemistry , as described in houben weyl &# 34 ; methoden der organische chemie &# 34 ; vol . 16 , parts i & amp ; ii ( 1974 ) for solution - phase synthesis , and in &# 34 ; solid phase peptide synthesis &# 34 ; by stewart and young ( 1984 ) for synthesis by the solid - phase method of merrifield . any chemist skilled in the art of peptide synthesis can synthesize the peptides of general formula i by standard solution methods or by manual or automated solid - phase methods . the symbols and abbreviations used for amino acids , their derivatives and protecting groups , and peptides and their salts are those customarily used in peptide chemistry ( biochem . j . 126 : 773 , 1972 , the journal reference is hereby incorporated by reference .). for convenience several abbreviations are defined in table iii reproduced below . all amino acid residues , except gly , described in the specification but not the claims are of the l - configuration unless otherwise specified . table iii______________________________________abbreviations for amino acid residues______________________________________aib alpha - aminoisobutyric acidazt azetidine - 2 - carboxylic acidcdf para - chloro - d - phenylalanineclf para - chloro - l - phenylalaninehphe homo - phenylalaninehyp 4 - hydroxy - prolineinip isonipecotic acidmdy o -- methyl - d - tyrosinenal beta -( 2 - naphthyl )- alanineδpro 2 , 3 - dehydroprolinepal beta -( 3 - pyridyl )- alaninephg alpha - phenylglycinesar sarcosinethi beta -( 2 - thienyl )- alaninethz thiazolidine - 2 - carboxylic acid______________________________________ ( all other abbreviations follow the iupac standards for amino acid residues ) the following examples are illustrative of compounds of this invention with general formula i and are not limitative . all percentages and ratios are by weight when solids are involved and by volume when only liquids are involved . a mixture of 6 . 4 gm of tertiary butyloxy carbonyl - ( g - paratoluene sulfonyl )- arg [ boc - arg ( tos )]( 15 mmole ) and 183 mg of n , n - dimethylaminopyridine ( 1 . 5 mmole ) was dissolved in a mixture of 20 ml of dimethylformamide ( dmf ) and 125 ml of dichloromethane ( dcm ). fifteen g of hydroxymethyl - polystyrene - divinyl benzene ( 1 % crosslinked , containing 0 . 74 mmole of free hydroxyl group per g of resin ) was added , followed by 60 ml of a 0 . 25 m solution of dicyclohexylcarbodiimide ( dcc ) in dcm at room temperature . the suspension was stirred at room temperature overnight , filtered , and the resin was washed three times with 60 ml of dcm , three times with 60 ml of methyl alcohol ( meoh ), and reswollen in 120 ml of dcm . the coupling of another portion of boc - arg ( tos ) was conducted on the resin as above . after filtering and washing the resin it was reswollen in 120 ml of dcm , and 2 . 1 ml of benzoyl chloride and 1 . 5 ml of triethylamine ( et 3 n ) were added . after stirring the suspension for 30 minutes at room temperature the resin was filtered , washed three times with 60 ml portions of dcm , meoh , washed three times with 60 ml portion of meoh and finally washed three times with 60 ml portions of dcm . the resin was air dried to constant weight to give 18 . 5 gm of boc - arg ( tos )- hydroxymethyl - resin , with an actual amino acid content of 0 . 272 millimoles of arg per g of resin as determined by quantitative amino acid analysis of a sample of the amino acid resin following hydrolysis ( 4 hr , 130 ° c .) in 6n hcl / propionic acid . the resin , 1 . 5 gm containing a total of 0 . 4 mmole of arg , was placed in the reaction vessel of an automatic solidphase synthesizer ( beckman model 990 ) and subjected to one cycle of addition for the coupling of boc - phe as follows ; the resin was washed three times with 20 ml portions of dcm . the resin was then equilibrated with 20 ml of a 1 : 3 ratio of trifluoroacetic acid ( tfa ) in dcm containing 0 . 1 % indole for 1 . 5 minutes . the equilibration was then repeated for 30 minutes . the resin was then washed six times with 20 ml portions of dcm followed by neutralization with a 10 % solution of ( et 3 n ) in dcm for one and one half minutes , then the neutralization step was repeated . the resin was washed six times with 20 ml of dcm and then equilibrated with a solution of 1 . 0 mmole of boc - phe in dcm for one and one half minutes . then four ml of 0 . 25n dcc in dcm was added and the mixture stirred for two hours . then the resin was washed three times with 20 ml portions of dcm . a second cycle of addition was performed according to program b : the procedure of program a through neutralization and following washes was repeated . then 1 . 0 mmole of dcc in 4 ml of dcm was added and the resin and solution were mixed for one and one - half minutes . then 1 . 0 mmole of boc - d - phe in 12 ml dcm was added and the resin and solution were mixed for two hours . the resin was then washed six times with 20 ml portions of dcm . the n - terminal protecting group was removed according to the following sequence : the procedure of program a up to the neutralization with triethylamine was repeated . the resin was then washed 6 times with 20 ml portions of ethyl alcohol and the peptide - resin was air dried giving 1 . 66 gm of dphe - phe - arg - resin as the trifluoroacetic acid salt . synthesis was continued with 410 mg of the dphe - phe - arg - resin tfa salt . the next residue was added according to program d . the peptide - resin salt was first washed three times with 20 ml portion of dcm , then neutralized with 10 % et 3 n dcm for 1 . 5 minutes . the neutralization step was then repeated and the peptide - resin - salt was washed six times with 20 ml portions of dcm . the peptide - resin was then equilibrated with a solution of 1 . 0 mmole of boc - ser ( 0 bzl ) in dmf for 1 . 5 minutes . four ml of 0 . 25n dcc in dcm was added and mixed with the resin for two hours . the product was washed three times with dcm . the following amino acid derivatives were added to the growing peptide chain according to the listed programs : boc - phe ( a ), boc - gly ( a ), boc - pro ( a ), boc - pro ( a ), followed by recouple of boc - pro ( d ), boc - arg ( tos )( dissolved in 2 ml dmf + 9 ml dcm ), ( a ), followed by program c . this gave 530 mg of protected nonapeptide - resin as the tfa salt . a 510 mg portion of the peptide - resin above was suspended in 10 ml of liquid anhydrous hf containing 1 ml of anisole at - 70 ° c . and stirred 45 min . at 0 ° c . hf and anisole were removed by vacuum ( 1 hr water pump , 1 hr vacuum pump ), the peptide plus resin was washed three times with 20 ml portions of ethyl ether ( et 2 o ) and the peptide extracted into glacial acetic acid using three 6 ml extractions . the acetic acid solution was lyophilized to give 185 mg of crude deprotected peptide . the peptide was purified by countercurrent distribution ( ccd ) ( 100 upper phase transfers in a post ccd apparatus ) in the solvent system nbuoh : 1 % tfa ( 1 : 1 ). the content of the tubes corresponding to the main peptide - containing peak , as determined by the quantitative sakaguchi reagent , was collected , the solvent evaporated under reduced pressure , the residue dissolved in glacial acetic acid ( acoh ) and lyophilized to give 140 mg of peptide with a partition coefficient ( k ) from the ccd of 5 . 7 . repeating the countercurrent distribution in the solvent system nbuoh : acoh : h2o ( 4 : 1 : 5 ) gave , upon detection and workup as described above , 73 mg of arg - pro - pro - gly - phe - ser - dphe - phe - arg as the tfa salt ( k = 0 . 2 ). thin layer chromatographs ( tlc ) on merck glass precoated silica gel plates in the solvent systems nbuoh : acoh : h2o ( 8 : 3 : 4 ) and etoac : pyridine : acoh : h2o ( 5 : 5 : 1 : 3 ) gave rf ( 834 ) of 0 . 17 and rf ( 5513 ) of 0 . 36 for the pure peptide , as visualized by the chlorine - tolidine peptide identification spray . quantitative amino acid analysis ( beckman 120 instrument ) after acid hydrolysis ( 17 hr in sealed glass vials under n 2 at 110 ° c . in 2 ml 6n hcl containing 2 drops 2 - mercaptoethanol and 40 microliters of phenol ) gave the following ratios of amino acids : arg ( 2 . 12 ); pro ( 1 . 93 ); gly ( 1 . 01 ); phe ( 2 . 98 ); ser ( 0 . 96 ). this peptide was prepared by the method in example 1 , except that boc - beta - 2 - thienyl - d - ala ( boc - dthi ) was used in place of boc - dphe : k ( 415 )= 0 . 24 ; arg ( 2 . 02 ), pro ( 2 . 18 ), gly ( 1 . 00 ), phe ( 1 . 99 ), ser ( 0 . 89 ), thi ( 0 . 99 ). this peptide was prepared by the method in example 1 , except that boc - 2 - pyridyl - dala ( boc - dpal ) was used in place of boc - dphe : k ( 1 : 1 )= 0 . 22 ; arg ( 2 . 03 ), pro ( 2 . 01 ), gly ( 1 . 02 ), phe ( 1 . 99 ), pal ( 1 . 02 ). this peptide was prepared by the method in example 1 , except that boc - dphe was used in place of boc - ser ( bzl ): k ( 415 )= 1 . 3 ; arg ( 2 . 12 ), pro ( 1 . 94 ), gly ( 1 . 00 ), phe ( 3 . 94 ). this peptide was prepared by the method in example 1 , except that boc - dphe was used in place of boc - ser ( bzl ) and boc - pcl - d - phe ( boc - cdf ) was used in place of boc - dphe : k ( 415 )= 0 . 82 ; arg ( 1 . 98 ), pro ( 1 . 93 ), gly ( 0 . 97 ), phe ( 3 . 10 ), cdf ( 1 . 02 ). this peptide was prepared by the method in example 1 , except that boc - beta - 2 - thienyl - ala ( boc - thi ) was used in the two addition cycles in which boc - phe was used in example 1 : k ( 415 )= 0 . 21 ; arg ( 1 . 98 ), pro ( 1 . 94 ), gly ( 1 . 04 ), phe ( 1 . 04 ), ser ( 0 . 96 ), thi ( 2 . 05 ). this peptide was prepared by the method in example 6 , except that boc - dthi was used in place of boc - dphe : k ( 415 )= 018 ; arg ( 2 . 07 ), pro ( 2 . 08 ), gly ( 1 . 00 ), ser ( 0 . 93 ), thi ( 2 . 88 ). this peptide was prepared by the method in example 6 , except that boc - dpal was used in place of boc - dphe : k ( 1 : 1 )= 0 . 15 ; arg ( 2 . 00 ), pro ( 2 . 20 ), gly ( 1 . 09 ), ser ( 0 . 89 ), thi ( 1 . 92 ), pal ( 0 . 89 ). preparation of arg - pro - pro - gly - thi - dphe - cdf - thi - arg ( thi 5 , 8 dphe 6 cdf 7 - bk ). this peptide was prepared by the method in example 5 , except that boc - thi was used in two cycles of addition in place of boc - phe : k ( 415 )= 0 . 75 ; arg ( 1 . 89 ), pro ( 2 . 08 ), gly ( 1 . 06 ), phe ( 1 . 02 ), thi ( 1 . 88 ), cdf ( 1 . 07 ). this peptide was prepared by the method in example 1 , except that one additional cycle using boc -( tos )- darg was performed with program a followed by terminal deprotection with program c : k ( 1 : 1 )= 3 . 55 ; arg ( 2 . 89 ), pro ( 2 . 07 ), gly ( 1 . 02 ), phe ( 3 . 05 ), ser ( 0 . 98 ). preparation of darg - arg - pro - dpro - gly - phe - ser - dphe - phe - arg ( darg 0 pro 3 dphe 7 - bk ). this peptide was prepared by the method in example 10 , except that boc - dpro was used in place of boc - pro in the first addition of boc - pro : k ( 415 )= 0 . 15 ; arg ( 3 . 12 ), pro ( 1 . 90 ), gly ( 1 . 05 ), phe ( 3 . 02 ), ser ( 0 . 92 ). preparation of arg - pro - dpro - gly - thi - dphe - cdf - thi - arg ( dpro 3 thi 5 , 8 dphe 6 cdf 7 - bk ). this peptide was prepared by the method in example 9 , except that boc - dpro was used in place of boc - pro in the first addition of boc - pro : k ( 415 )= 0 . 18 ; arg ( 2 . 00 ), pro ( 1 . 98 ), gly ( 1 . 04 ), phe ( 0 . 99 ), thi ( 1 . 89 ), pcf ( 1 . 11 ). this peptide was prepared by the method in example 1 except that two additional cycles of addition were performed with boc -( e - clz ) lys , the first with program d , the second with program a followed by program c : k ( 1 : 1 )= 0 . 52 ; arg ( 2 . 04 ), pro ( 1 . 99 ), gly ( 0 . 96 ), phe ( 3 . 00 ), ser ( 0 . 96 ), lys ( 2 . 01 ). this peptide was prepared by the method in example 13 , except that boc - thi was used in place of boc - phe in the two cycles of addition of boc - phe : k ( 1 : 1 )= 0 . 33 ; arg ( 1 . 98 ), pro ( 1 . 97 ), gly ( 1 . 01 ), phe ( 1 . 03 ), ser ( 0 . 97 ), thi ( 1 . 96 ), lys ( 2 . 08 ). preparation of darg - arg - pro - pro - gly - thi - ser - dphe - thi - arg ( darg 0 thi 5 , 8 dphe 7 - bk ). this peptide was produced by the method in example 6 , except that one additional cycle of addition with boc -( tos ) darg was performed with program d , followed by program c : k ( 1 : 1 )= 2 . 33 ; arg ( 3 . 00 ), pro ( 1 . 99 ), gly ( 0 . 96 ), phe ( 0 . 99 ), ser ( 0 . 95 ), preparation of darg - arg - pro - dpro - gly - thi - ser - dphe - thi - arg ( darg 0 dpro 5 , 8 dphe 7 - bk ). this peptide was produced by the method in example 15 , except that boc - dpro was used in place of boc - pro in the first addition of boc - pro : k ( 415 )= 0 . 22 ; arg ( 2 . 10 ), pro ( 1 . 96 ), gly ( 1 . 05 ), phe ( 0 . 98 ), ser ( 0 . 94 ), thi ( 1 . 96 ). this peptide was prepared by the method in example 13 , except that boc -( 4 - hydroxy )- pro ( boc - hyp ) was used in place of boc - pro in the first addition of boc - pro : k ( 1 : 1 )= 0 . 35 ; arg ( 2 . 00 ), pro ( 1 . 03 ), gly ( 1 . 00 ), phe ( 3 . 08 ), ser ( 0 . 94 ), lys ( 1 . 95 ), hyp ( 1 . 01 ). preparation of arg - hyp - pro - gly - thi - ser - dphe - thi - arg ( hyp 2 thi 5 , 8 dphe 7 - bk ). this peptide was produced by the method in example 6 , except that boc - hyp was used in place of boc - pro in the second addition of boc - pro , including the recoupling with program d : k ( 1 : 1 )= 2 . 45 ; arg ( 2 . 03 ), pro ( 0 . 98 ), gly ( 1 . 06 ), phe ( 1 . 05 ), ser ( 0 . 95 ), thi ( 1 . 97 ), hyp ( 0 . 95 ). preparation of lys - lys - arg - hyp - gly - thi - ser - dphe - thi - arg ( lys - lys - hyp 2 thi 5 , 8 dphe 7 - bk ). this peptide was produced by the method in example 18 , except that two additional cycles of addition with boc -( e - clz ) lys were performed , the first with program d , the second with program a followed by program c : k ( 1 : 1 )= 0 . 27 ; arg ( 2 . 07 ), pro ( 0 . 92 ), gly ( 0 . 99 ), phe ( 1 . 03 ), ser ( 0 . 93 ), thi ( 1 . 92 ), lys ( 2 . 06 ), hyp ( 1 . 10 ). preparation of arg - pro - hyp - gly - thi - ser - dphe - thi - arg ( hyp 3 thi 5 , 8 dphe 7 - bk ). this peptide was produced by the method in example 6 , except that boc - hyp was used in place of boc - pro in the first addition of boc - pro : k ( 1 : 1 )= 2 . 23 ; arg ( 2 . 08 ), pro ( 0 . 98 ), gly ( 1 . 04 ), phe ( 1 . 01 ), ser ( 0 . 99 ), thi ( 1 . 95 ), hyp ( 0 . 94 ). preparation of darg - arg - pro - hyp - gly - thi - ser - dphe - thi - arg ( darg 0 - hyp 3 thi 5 , 8 dphe 7 - bk ). this peptide was produced by the method in example 20 , except that one additional cycle of addition with boc -( tos ) darg was done with program d , followed by program c : k ( 1 : 1 )= 0 . 18 ; arg ( 3 . 01 ), pro ( 1 . 02 ), gly ( 0 . 98 ), phe ( 1 . 02 ), ser ( 0 . 92 ), thi ( 2 . 07 ), hyp ( 0 . 97 ). preparation of arg - hyp - hyp - gly - thi - ser - dphe - thi - arg ( hyp 2 , 3 thi 5 , 8 dphe 7 - bk ). this peptide was produced by the method in example 6 , except that boc - hyp was used in place of boc - pro in those cycles where boc - pro had been used : k ( 1 : 1 )= 1 . 56 ; arg ( 2 . 04 ), gly ( 1 . 06 ), phe ( 1 . 02 ), ser ( 1 . 01 ), thi ( 1 . 94 ), hyp ( 1 . 93 ). preparation of arg - hyp - hyp - gly - thi - dphe - cdf - thi - arg ( hyp 2 , 3 thi 5 , 8 dphe 6 cdf 7 - bk ). this peptide was produced by the method in example 9 , except that boc - hyp was used in place of boc - pro in those cycles where boc - pro had been used : k ( 415 )= 0 . 89 ; arg ( 2 . 06 ), gly ( 1 . 00 ), phe ( 1 . 03 ), pcf ( 1 . 05 ), thi ( 1 . 92 ), hyp ( 1 . 93 ). preparation of arg - pro - pro - gly - leu - gly - dphe - leu - arg ( gly 6 leu 5 , 8 dphe 7 - bk ). this peptide was produced by the method in example 1 , except that boc - leu was used in place of boc - phe in those cycles where boc - phe had been used , and boc - gly was used when boc -( obzl ) ser had been used : k ( 415 )= 0 . 30 ; arg ( 2 . 04 ), pro ( 2 . 05 ), gly ( 1 . 98 ), phe ( 0 . 98 ), leu ( 1 . 95 ). the following examples were prepared by methods identical to the methods described above for similarly substituted peptides , and are not limitative : 25 . arg - pro - pro - gly - phe - ser - dnal - phe - arg ( dnal 7 - bk ): k ( 415 )= 0 . 37 ; arg ( 2 . 09 ), pro ( 2 . 02 ), gly ( 0 . 98 ), phe ( 2 . 06 ), ser ( 0 . 96 ), nal ( 0 . 95 ). 26 . arg - pro - pro - gly - phe - ser - mdy - phe - arg ( mdy 7 - bk ): k ( 1 : 1 )= 4 . 88 ; arg ( 2 . 10 ), pro ( 1 . 91 ), gly ( 0 . 96 ), phe ( 2 . 08 ), ser ( 0 . 94 ), mdy ( 1 . 04 ). 27 . arg - pro - pro - gly - phe - ser - dphg - phe - arg ( dphg 7 - bk ): k ( 1 : 1 )= 3 . 55 ; arg ( 2 . 01 ), pro ( 1 . 90 ), gly ( 1 . 03 ), phe ( 2 . 07 ), ser ( 0 . 99 ), 28 . arg - pro - pro - gly - phe - ser - dhis - phe - arg ( dhis 7 - bk ): k ( 1 : 1 )= 0 . 30 ; arg ( 2 . 04 ), pro ( 2 . 09 ), gly ( 0 . 94 ), phe ( 2 . 00 ), ser ( 1 . 00 ), his ( 0 . 93 ). 29 . arg - pro - pro - gly - phe - ser - dtrp - phe - arg ( dtrp 7 - bk ): k ( 415 )= 0 . 30 ; arg ( 2 . 04 ), pro ( 1 . 95 ), gly ( 1 . 02 ), phe ( 2 . 05 ), ser ( 0 . 95 ), trp ( 0 . 98 ). 30 . arg - pro - pro - gly - phe - ser - dtyr - phe - arg ( dtyr 7 - bk ): k ( 1 : 1 )= 2 . 70 ; arg ( 1 . 94 ), pro ( 1 . 88 ), gly ( 1 . 04 ), phe ( 2 . 10 ), ser ( 0 . 97 ), tyr ( 1 . 08 ). 31 . arg - pro - pro - gly - phe - ser - dhphe - phe - arg ( dhphe 7 - bk ): k ( 415 )= 0 . 37 ; arg ( 1 . 99 ), pro ( 1 . 94 ), gly ( 0 . 97 ), phe ( 2 . 02 ), ser ( 0 . 88 ), hphe ( 1 . 20 ). 32 . arg - pro - pro - gly - phe - dphe - dthi - phe - arg ( dphe 6 dthi 7 - bk ): k ( 415 )= 0 . 59 ; arg ( 2 . 14 ), pro ( 1 . 87 ), gly ( 1 . 00 ), phe ( 3 . 01 ), thi ( 0 . 98 ). 33 . arg - pro - pro - gly - phe - dthi - dthi - phe - arg ( dthi 6 , 7 - bk ): k ( 415 )= 0 . 54 ; arg ( 2 . 04 ), pro ( 2 . 00 ), gly ( 1 . 01 ), phe ( 2 . 04 ), thi ( 1 . 91 ). 34 . arg - pro - pro - gly - phe - dphe - dnal - phe - arg ( dphe 6 dnal 7 - bk ): k ( 415 ) = 1 . 04 ; arg ( 2 . 02 ), pro ( 2 . 04 ), gly ( 1 . 01 ), phe ( 2 . 94 ), nal ( 0 . 99 ). 35 . arg - pro - pro - gly - phe - dphe - mdy - phe - arg ( dphe 6 mdy 7 - bk ): k ( 415 )= 0 . 59 ; arg ( 2 . 11 ), pro ( 1 . 90 ), gly ( 0 . 97 ), phe ( 3 . 02 ), mdy ( 1 . 01 ). 36 . arg - pro - pro - gly - phe - dphe - dpal - phe - arg ( dphe 6 dpal 7 - bk ): k ( 415 ) = 0 . 16 ; arg ( 1 . 86 ), pro ( 2 . 12 ), gly ( 1 . 07 ), phe ( 2 . 90 ), pal ( 1 . 05 ). 37 . arg - pro - pro - gly - phe - gly - dval - phe - arg ( gly 6 dval 7 - bk ): k ( 415 )= 0 . 20 ; arg ( 2 . 08 ), pro ( 2 . 00 ), gly ( 1 . 96 ), phe ( 1 . 98 ), val ( 0 . 98 ). 38 . arg - hyp - pro - gly - phe - ser - dphe - phe - arg ( hyp 2 dphe 7 - bk ): k ( 1 : 1 )= 3 . 76 ; arg ( 2 . 00 ), pro ( 0 . 93 ), gly ( 1 . 02 ), phe ( 3 . 16 ), ser ( 0 . 94 ), hyp ( 0 . 94 ). 39 . arg - pro - hyp - gly - phe - ser - dphe - phe - arg ( hyp 3 dphe 7 - bk ): k ( 1 : 1 )= 3 . 35 ; arg ( 1 . 96 ), pro ( 0 . 97 ), gly ( 1 . 01 ), phe ( 3 . 10 ), ser ( 0 . 94 ), hyp ( 1 . 02 ). hyp ( 40 arg - hyp - hyp - gly - phe - ser - dphe - phe - arg ( hyp 2 , 3 dphe 7 - bk ): k ( 1 : 1 )= 2 . 33 ; arg ( 2 . 03 ), gly ( 1 . 02 ), phe ( 3 . 10 ), ser ( 0 . 94 ), hyp ( 1 . 91 ). 42 . arg - pro - pro - gly - thi - dthi - dthi - thi - arg ( thi 5 , 8 dthi 6 , 7 - bk ): k ( 415 )= 0 . 37 ; arg ( 2 . 08 ), pro ( 2 . 08 ), gly ( 0 . 99 ), thi ( 3 . 86 ). 43 . arg - pro - pro - gly - thi - dthi - dpal - thi - arg ( thi 5 , 8 dthi 6 dpal 7 - bk ): k ( 1 : 1 )= 0 . 70 ; arg ( 1 . 93 ), pro ( 2 . 11 ), gly ( 1 . 08 ), thi ( 2 . 86 ), pal ( 1 . 02 ). 44 . arg - pro - pro - gly - thi - dthi - dnal - thi - arg ( thi 5 , 8 dthi 6 dnal 7 - bk ): k ( 415 )= 0 . 59 ; arg ( 2 . 19 ), pro ( 2 . 08 ), gly ( 1 . 00 ), nal ( 0 . 93 ), thi ( 2 . 88 ). 45 . arg - pro - pro - gly - thi - dthi - cdf - thi - arg ( thi 5 , 8 dthi 6 cdf 7 - bk ): k ( 415 )= 0 . 54 ; arg ( 2 . 16 ), pro ( 1 . 97 ), gly ( 1 . 00 ), pcf ( 1 . 06 ), thi ( 2 . 81 ). 46 . ar g - pro - pro - gly - thi - dphe - dala - thi - arg ( thi 5 , 8 dphe 6 dala 7 - bk ): k ( 415 )= 0 . 32 ; arg ( 2 . 06 ), pro ( 1 . 89 ), gly ( 0 . 97 ), phe ( 1 . 02 ), ala ( 0 . 96 ), thi ( 2 . 12 ). 47 . arg - pro - pro - gly - thi - cdf - dala - thi - arg ( thi 5 , 8 cdf 6 dala 7 - bk ): k ( 415 )= 0 . 39 ; arg ( 1 . 96 ), pro ( 1 . 93 ), gly ( 1 . 00 ), ala ( 0 . 99 ), thi ( 2 . 05 ), pcf ( 1 . 08 ). 48 . thi - arg - pro - pro - gly - thi - ser - dphe - thi - arg ( thi 0 - thi 5 , 8 - dphe 7 - bk ): k ( 415 )= 0 . 27 ; arg ( 2 . 16 ), pro ( 1 . 89 ), gly ( 1 . 03 ), phe ( 1 . 04 ), ser ( 0 . 93 ), thi ( 2 . 95 ). 49 . darg - arg - pro - pro - gly - phe - ser - dphg - phe - arg ( darg 0 - dphg 7 - bk ): k ( 1 : 1 )= 2 . 03 ; arg ( 3 . 05 ), pro ( 2 . 00 ), gly ( 0 . 97 ), phe ( 2 . 04 ), ser ( 0 . 94 ), phg ( 1 . 00 ). 50 . darg - arg - pro - pro - gly - phe - ser - dtrp - phe - arg ( darg 0 - dtrp 7 - bk ): k ( 1 : 1 )= 4 . 88 ; arg ( 3 . 07 ), pro ( 1 . 99 ), gly ( 1 . 00 ), phe ( 2 . 04 ), ser ( 0 . 89 ), trp ( 0 . 97 ). 51 . darg - arg - pro - pro - gly - phe - ser - dtyr - phe - arg ( darg 0 - dtyr 7 - bk ): k ( 1 : 1 )= 1 . 56 ; arg ( 2 . 96 ), pro ( 2 . 09 ), gly ( 1 . 03 ), phe ( 1 . 99 ), ser ( 0 . 90 ), tyr ( 1 . 04 ). 52 . darg - arg - pro - pro - gly - phe - ser - dhis - phe - arg ( darg 0 - dhis 7 - bk ): k ( 1 : 1 )= 0 . 18 ; arg ( 3 . 08 ), pro ( 1 . 99 ), gly ( 1 . 02 ), phe ( 2 . 07 ), ser ( 0 . 89 ), his ( 0 . 96 ). 53 . darg - arg - pro - pro - gly - phe - ser - dhphe - phe - arg ( darg 0 - dhphe 7 - bk ): k ( 415 )= 0 . 18 ; arg ( 3 . 06 ), pro ( 1 . 98 ), gly ( 0 . 95 ), phe ( 2 . 05 ), ser ( 0 . 86 ), dhphe ( 1 . 11 ). 54 . lys - lys - arg - pro - pro - gly - phe - ser - dphe - phe - arg ( lys - lys - dphe 7 - bk ): k ( 1 : 1 )= 0 . 52 ; arg ( 2 . 04 ), pro ( 2 . 01 ), gly ( 0 . 96 , phe ( 3 . 00 ), ser ( 0 . 96 ). 55 . lys - lys - arg - pro - pro - gly - phe - ser - dtrp - phe - arg ( lys - lys - dtrp 7 - bk ): k ( 1 : 1 )= 0 . 67 ; arg ( 2 . 01 ), pro ( 2 . 00 ), gly ( 1 . 01 ), phe ( 2 . 03 ), ser ( 0 . 91 ), trp ( 0 . 88 ), lys ( 2 . 03 ). 56 . lys - lys - arg - pro - pro - gly - phe - ser - dtyr - phe - arg ( lys - lys - dtyr 7 - bk ): k ( 1 : 1 )= 0 . 21 ; arg ( 2 . 01 ), pro ( 2 . 11 ), gly ( 0 . 99 ), phe ( 2 . 02 ), ser ( 0 . 97 ), tyr ( 1 . 02 ), lys ( 1 . 90 ). 57 . lys - lys - arg - pro - pro - gly - phe - ser - dhis - phe - arg ( lys - lys - dhis 7 - bk ): k ( 1 : 1 )= 0 . 08 ; arg ( 1 . 91 ), pro ( 2 . 06 ), gly ( 0 . 94 ), phe ( 2 . 08 ), ser ( 0 . 93 ), his ( 0 . 95 ), lys ( 2 . 12 ). 58 . lys - lys - arg - pro - pro - gly - phe - ser - dhphe - phe - arg ( lys - lys - dhphe 7 - bk ): k ( 1 : 1 )= 1 . 13 ; arg ( 1 . 99 ), pro ( 1 . 93 ), gly ( 0 . 98 ), phe ( 2 . 06 ), ser ( 0 . 92 ), dhphe ( 1 . 11 ), lys ( 2 . 01 ). 59 . arg - pro - dpro - gly - phe - ser - dphe - phe - arg ( dpro 3 dphe 7 - bk ): k ( 415 )= 0 . 27 ; arg ( 2 . 07 ), pro ( 1 . 97 ), gly ( 0 . 98 ), phe ( 3 . 02 ), ser ( 0 . 95 ). 60 . arg - pro - dpro - gly - phe - cdf - dala - phe - arg ( dpro 3 cdf 6 dala 7 - bk ): k ( 415 )= 0 . 59 ; arg ( 1 . 99 ), pro ( 2 . 03 ), gly ( 0 . 97 ), phe ( 2 . 02 ), ala ( 0 . 99 ), pcf ( 1 . 02 ). 61 . arg - pro - dpro - gly - thi - ser - dphe - thi - arg ( dpro 3 thi 5 , 8 dphe 7 - bk ): k ( 415 )= 0 . 22 ; arg ( 2 . 10 ), pro ( 1 . 96 ), gly ( 1 . 05 ), phe ( 0 . 98 ), ser ( 0 . 94 ), thi ( 1 . 96 ). 62 . darg - arg - pro - pro - gly - thi - dphe - dala - thi - arg ( darg 0 - thi 5 , 8 dphe 6 dala 7 - bk ): k ( 1 : 1 )= 4 . 00 ; arg ( 2 . 89 ), pro ( 1 . 95 ), gly ( 1 . 03 ), phe ( 0 . 98 ), ala ( 1 . 01 ), thi ( 2 . 14 ). 63 . darg - arg - pro - pro - gly - thi - cdf - dala - thi - arg ( darg 0 - thi 5 , 8 cdf 6 dala 7 - bk ): k ( 415 )= 0 . 19 ; arg ( 3 . 00 ), pro ( 1 . 99 ), gly ( 1 . 00 ), ala ( 0 . 96 ), thi ( 2 . 03 ), pcf ( 1 . 02 ). 64 . darg - arg - hyp - pro - gly - thi - ser - dphe - thi - arg ( darg 0 hyp 2 thi 5 , 8 dphe 7 - bk ): k ( 1 : 1 )= 1 . 50 ; arg ( 3 . 11 ), pro ( 0 . 97 ), gly ( 1 . 03 ), phe ( 1 . 04 ), ser ( 0 . 95 ), thi ( 1 . 88 ), hyp ( 1 . 02 ) 65 . darg - arg - hyp - hyp - gly - thi - ser - dphe - thi - arg ( darg 0 - hyp 2 , 3 thi 5 , 8 dphe 7 - bk ): k ( 1 : 1 )= 0 . 96 ; arg ( 3 . 19 ), gly ( 0 . 97 ), phe ( 0 . 98 ), ser ( 1 . 00 ), thi ( 1 . 95 ), hyp ( 1 . 90 ) 66 . thi - arg - hyp - pro - gly - thi - ser - dphe - thi - arg ( thi 0 - hyp 2 thi 5 , 8 dphe 7 - bk ) 67 . thi - arg - pro - hyp - gly - thi - ser - dphe - thi - arg ( thi 0 - hyp 3 thi 5 , 8 dphe 7 - bk ) 68 . thi - arg - hyp - hyp - gly - thi - ser - dphe - thi - arg ( thi 0 - hyp 2 , 3 thi 5 , 8 dphe 7 - bk ) 69 . arg - hyp - pro - gly - thi - dphe - cdf - thi - arg ( hyp 2 thi 5 , 8 dphe 6 cdf 7 - bk ): k ( 415 )= 1 . 04 ; arg ( 2 . 02 ), pro ( 1 . 01 ), gly ( 1 . 00 ), phe ( 1 . 01 ), pcf ( 1 . 09 ), thi ( 1 . 89 ), hyp ( 0 . 98 ) 70 . arg - pro - hyp - gly - thi - dphe - cfd - thi - arg ( hyp 3 thi 5 , 8 dphe 6 cdf 7 - bk ): k ( 1 : 1 )= 0 . 96 ; arg ( 2 . 01 ), pro ( 1 . 11 ), gly ( 0 . 97 ), phe ( 1 . 06 ), thi ( 1 . 86 ), pcf ( 1 . 06 ), hyp ( 0 . 95 ) 71 . arg - hyp - dpro - gly - thi - dphe - cdf - thi - arg ( hyp 2 pro 3 thi 5 , 8 dphe 6 cdf 7 - bk ) 72 . lys - lys - arg - hyp - pro - gly - phe - ser - dphe - phe - arg ( lys - lys - hyp 2 dphe 7 - bk ): k ( 1 : 1 )= 0 . 37 ; arg ( 1 . 99 ), pro ( 0 . 96 ), gly ( 0 . 99 ), phe ( 3 . 13 ), ser ( 0 . 94 ), hyp ( 0 . 98 ), lys ( 2 . 00 ) 73 . lys - lys - arg - hyp - hyp - gly - phe - ser - dphe - phe - arg ( lys - lys - hyp 2 , 3 dphe 7 - bk ): k ( 1 : 1 )= 0 . 28 ; arg ( 2 . 03 ), gly ( 0 . 95 ), ser ( 0 . 94 ), phe ( 3 . 08 ), lys ( 2 . 08 ), hyp ( 1 . 92 ) 74 . lys - lys - arg - pro - pro - gly - thi - ser - dthi - thi - arg ( lys - lys - thi 5 , 8 dthi 7 - bk ): k ( 1 : 1 )= 0 . 22 ; arg ( 2 . 07 ), pro ( 2 . 01 ), gly ( 1 . 04 ), ser ( 0 . 89 ), thi ( 3 . 02 ), lys ( 1 . 96 ) 75 . lys - lys - arg - pro - pro - gly - thi - ser - dpal - thi - arg ( lys - lys - thi 5 , 8 dpal 7 - bk ): k ( 1 : 1 )= 0 . 06 ; arg ( 2 . 12 ), pro ( 1 . 94 ), gly ( 1 . 01 ), ser ( 0 . 87 ), thi ( 1 . 81 ), pal ( 0 . 98 ), lys ( 2 . 22 ) 76 . lys - lys - arg - pro - pro - gly - thi - dphe - cdf - thi - arg ( lys - lys - thi 5 , 8 dphe 6 cdf 7 - bk ): k ( 415 )= 0 . 11 ; arg ( 2 . 02 ), pro ( 2 . 00 ), gly ( 1 . 02 ), phe ( 1 . 00 ), pcf ( 1 . 06 ), thi ( 1 . 85 ), lys ( 2 . 06 ) 77 . lys - lys - arg - pro - hyp - gly - thi - ser - dphe - thi - arg ( lys - lys - hyp 3 thi 5 , 8 dphe 7 - bk ): k ( 1 : 1 )= 0 . 22 ; arg ( 2 . 05 ), pro ( 0 . 96 ), gly ( 1 . 04 ), phe ( 1 . 03 ), ser ( 0 . 94 ), hyp ( 1 . 10 ), thi ( 1 . 84 ), lys ( 2 . 04 ) 78 . lys - lys - arg - hyp - hyp - gly - thi - ser - dphe - thi - arg ( lys - lys - hyp 2 , 3 thi 5 , 8 dphe 7 - bk ): k ( 1 : 1 )= 0 . 15 ; arg ( 2 . 00 ), pro ( 2 . 06 ), gly ( 1 . 01 ), phe ( 1 . 03 ), ser ( 0 . 94 ), thi ( 1 . 92 ), hyp ( 2 . 04 ) 79 . lys - lys - arg - hyp - pro - gly - thi - dphe - cdf - thi - arg ( lys - lys - hyp 2 thi 5 , 8 dphe 6 cdf 7 - bk ): k ( 1 : 1 )= 6 . 69 ; arg ( 1 . 96 ), pro ( 1 . 14 ), gly ( 0 . 96 ), phe ( 1 . 03 ), thi ( 1 . 77 ), pcf ( 1 . 06 ), lys ( 1 . 93 ), hyp ( 1 . 14 ) 80 . lys - lys - arg - pro - hyp - gly - thi - dphe - cdf - thi - arg ( lys - lys - hyp 3 thi 5 , 8 dphe 6 cdf 7 - bk ): k ( 1 : 1 )= 6 . 14 ; arg ( 2 . 04 ), pro ( 0 . 97 ), gly ( 1 . 01 ), phe ( 0 . 98 ), pcf ( 1 . 06 ), thi ( 1 . 89 ), hyp ( 1 . 01 ), lys ( 2 . 05 ) 81 . lys - lys - arg - hyp - hyp - gly - thi - dphe - cdf - thi - arg ( lys - lys - hyp 2 , 3 thi 5 , 8 dphe 6 cdf 7 - bk ): k ( 1 : 1 )= 4 . 88 ; arg ( 2 . 02 ), gly ( 0 . 99 ), phe ( 0 . 96 ), pcf ( 1 . 10 ), thi ( 1 . 84 ), hyp ( 2 . 01 ), lys ( 2 . 06 ) 82 . arg - thz - pro - gly - thi - ser - dphe - thi - arg ( thz 2 thi 5 , 8 dphe 7 - bk ): k ( 415 )= 0 . 24 ; arg ( 1 . 97 ), pro ( 1 . 04 ), gly ( 1 . 02 ), phe ( 1 . 06 ), thi ( 1 . 91 ) 83 . arg - pro - thz - gly - thi - ser - dphe - thi - arg ( thz 3 thi 5 , 8 dphe 7 - bk ): k ( 1 : 1 )= 5 . 25 84 arg - thz - thz - gly - thi - ser - dphe - thi - arg ( thz 2 , 3 thi 5 , 8 dphe 7 - bk ): k ( 1 : 1 )= 6 . 69 85 . arg - aib - pro - gly - thi - ser - dphe - thi - arg ( aib 2 thi 5 , 8 dphe 7 - bk ): k ( 415 )= 0 . 18 86 . arg - pro - aib - gly - thi - ser - dphe - thi - arg ( aib 3 thi 5 , 8 dphe 7 - bk ): k ( 415 )= 0 . 24 ; arg ( 2 . 09 ), pro ( 0 . 99 ), gly ( 1 . 05 ), ser ( 0 . 95 ), phe ( 1 . 07 ), thi ( 1 . 94 ), aib ( 0 . 91 ) 87 . arg - aib - aib - gly - thi - ser - dphe - thi - arg ( aib 2 , 3 thi 5 , 8 dphe 7 - bk ): k ( 415 )= 4 . 00 88 . arg - azt - pro - gly - thi - ser - dphe - thi - arg ( azt 2 thi 5 , 8 dphe 7 - bk ): k ( 415 )= 0 . 18 ; arg ( 2 . 07 ), pro ( 0 . 99 ), gly ( 1 . 02 ), phe ( 1 . 04 ), ser ( 0 . 95 ), thi ( 1 . 97 ), azt ( 0 . 99 ) 89 . arg - pro - azt - gly - thi - ser - dphe - thi - arg ( azt 3 thi 5 , 8 dphe 7 - bk ) 90 . arg - azt - azt - gly - thi - ser - dphe - thi - arg ( azt 2 , 3 thi 5 , 8 dphe 7 - bk ) 91 . arg - inip - pro - gly - thi - ser - dphe - thi - arg ( inip 2 thi 5 , 8 dphe 7 - bk ): k ( 415 )= 0 . 21 92 . arg - pro - inip - gly - thi - ser - dphe - thi - arg ( inip 3 thi 5 , 8 dphe 7 - bk ): k ( 415 )= 0 . 18 ; arg ( 2 . 10 ), pro ( 0 . 95 ), gly ( 1 . 04 ), phe ( 1 . 03 ), ser ( 0 . 93 ), thi ( 1 . 95 ) 93 . arg - inip - inip - gly - thi - ser - dphe - thi - arg ( inip 2 , 3 thi 5 , 8 dphe 7 - bk ): k ( 415 )= 0 . 18 the bradykinin antagonists were assayed on isolated rat uterus in natural or induced estrus and on guinea pig ileum , according to the commonly accepted assay methods for bradykinin and related kinins as described by trautschold ( handbook of expt . pharmacol . vol 25 , springer verlag , pp 53 - 55 , 1970 ) for inhibition of the myotropic activity of bradykinin . the inhibition potencies , as determined according to the commonly accepted manner described by schild for antagonists of biologically active compounds ( br . j . pharmacol . 2 : 189 , 1947 ), are determined on isolated rat uterus ( rut ) and isolated guinea pig ileum ( gpi ). in the assays , a dose - response curve is determined for the reference substance bradykinin . the dose of bradykinin which produced a half maximal contraction of tissue is the ed50 dose . an amount of bradykinin equivalent to twice the ed50 dose is administered to the tissue 30 seconds after the start of incubation of the tissue with a dose of antagonist . doses of antagonist are increased in this protocol until pre - incubation with a dose of antagonist reduces the contraction in response to the double ed50 dose of bradykinin to response of a single ed50 dose of bradykinin . the pa2 value represents the negative logarithm of the molar concentration of antagonist necessary to reduce the response of a double ed50 dose of bradykinin to that of an ed50 dose . one unit of pa2 value represents an order of magnitude change in potency . for comparison , the negative log of the dose of bk , the dose which causes half maximal contraction of the tissues , is commonly known as the pd2 value . the pd2 value for bradykinin is 7 . 9 on the rat uterus and 7 . 4 on the guinea pig ileum . ______________________________________potency of bradykinin antagonistsex - am - ple # structure pa2 / rut pa2 / gpi______________________________________ 1 dphe . sup . 7 -- bk 5 . 0 2 dthi . sup . 7 -- bk 4 . 6 3 dpal . sup . 7 -- bk 5 . 0 4 . 8 4 dphe . sup . 6 , 7 -- bk 5 . 2 5 dphe . sup . 6 cdf . sup . 7 -- bk 4 . 9 5 . 8 6 thi . sup . 5 , 8 dphe . sup . 7 -- bk 6 . 5 6 . 3 7 thi . sup . 5 , 8 dthi . sup . 7 -- bk 4 . 2 5 . 8 8 thi . sup . 5 , 8 dpal . sup . 7 -- bk 4 . 210 darg . sup . 0 -- dphe . sup . 7 -- bk 5 . 611 darg . sup . 0 -- dpro . sup . 3 dphe . sup . 7 -- bk 4 . 013 lys -- lys -- dphe . sup . 7 -- bk 5 . 114 lys -- lys -- thi . sup . 5 , 8 dphe . sup . 7 -- bk 6 . 0 5 . 315 darg . sup . 0 -- thi . sup . 5 , 8 dphe . sup . 7 -- bk 5 . 5 6 . 116 darg . sup . 0 -- dpro . sup . 3 thi . sup . 5 , 8 dphe . sup . 7 -- bk 5 . 218 hyp . sup . 2 thi . sup . 5 , 8 dphe . sup . 7 -- bk 5 . 619 lys -- lys -- hyp . sup . 2 thi . sup . 5 , 8 dphe . sup . 7 -- bk 5 . 820 hyp . sup . 3 thi . sup . 5 , 8 dphe . sup . 7 -- bk 7 . 0 4 . 721 darg . sup . 0 -- hyp . sup . 3 thi . sup . 5 , 8 dphe . sup . 7 -- bk 7 . 222 hyp . sup . 2 , 3 thi . sup . 5 , 8 dphe . sup . 7 -- bk 6 . 723 hyp . sup . 2 , 3 thi . sup . 5 , 8 dphe . sup . 6 cdf . sup . 7 -- bk 6 . 564 darg . sup . 0 -- hyp . sup . 2 thi . sup . 5 , 8 dphe . sup . 7 -- bk 5 . 765 darg . sup . 0 -- hyp . sup . 2 , 3 thi . sup . 5 , 8 dphe . sup . 7 -- bk 7 . 172 lys -- lys -- hyp . sup . 2 dphe . sup . 7 -- bk 5 . 677 lys -- lys -- hyp . sup . 3 thi . sup . 5 , 8 dphe . sup . 7 -- bk 6 . 7______________________________________ the specificity of bradykinin antagonists of this invention is demonstrated by their ability to inhibit the myotropic activity of bradykinin ( bk ) and two physiologically important bk - related kinins , kallidin ( kal , lys - bk ) and methionyl - lysyl - bk ( mk - bk ), but not the myotropic activity induced by non kinin - related peptides , such as angiotensin - ii ( ang ) or substance - p ( sp ). in each case , as shown , the bk - related antagonists inhibited contractions produced by bk - related agonists , but had no effect on the non - kinin myotropic peptide substances . the inhibition potencies are listed as pa2 values as described above . __________________________________________________________________________specificity of bradykininantagonists in guinea pig ileum assay guinea pig ileumexample # structure bk kal mk - bk ang sp__________________________________________________________________________ 1 dphe . sup . 7 -- bk 5 . 0 5 . 6 6 . 0 no no 6 thi . sup . 5 , 8 dphe -- bk 6 . 3 6 . 4 5 . 2 no no10 darg . sup . 0 -- dphe . sup . 7 -- bk 5 . 6 6 . 0 6 . 3 no no15 darg . sup . 0 -- thi . sup . 5 , 8 dphe . sup . 7 -- bk 6 . 1 6 . 7 6 . 4 no no__________________________________________________________________________ the in vivo effects of bradykinin antagonists on blood pressure in the anesthetized rat are determined according to the assay described by roblero , ryan and stewart ( res . commun . pathol . pharmacol . 6 : 207 , 1973 ). when compounds # 6 ( thi 5 , 8 dphe 7 -- bk ), # 10 ( darg 0 - dphe 7 - bk ) and # 15 ( darg 0 - thi 5 , 8 dphe 7 - bk ) are infused at a rate of 25 ug / min , the response to a 25 mm depressor dose ( ed25 mm ) of bradykinin is reduced from 25 mm to 10 mm . the depressor effect of bradykinin returns to a normal response within 5 minutes of terminating the infusion of antagonist . the antagonists also produce inhibition of the bradykinin response when injected as a bolus admixture of bradykinin plus antagonist by either the ia or iv route of administration . examples of conferring resistance to enzymatic degradation by extension at the n - terminal of bradykinin analog the ability of bradykinin analogs to withstand enzymatic degradation ( for example by kininases ) in vivo can be conveniently assessed , for example , by determining residual vasodepressor activity of a particular analog after a single pass in the pulmonary circulation in the anesthetized rat ( j . roblero , j . w . ryan , and j . m . stewart , res . commun . pathol . pharmacol . 6 : 207 , 1973 ) following intraaortic and intravenous administration . in this system , using n - terminal substituted bradykinin analogs ( agonists ), the following results are obtained : ______________________________________rat pulmonary destruction of bk analogsmodified at the n - terminalpeptide structure % destruction______________________________________bradykinin ( bk ) 98lys -- bk 95darg -- bk 92dlys -- bk 89lys -- lys -- bk 0thi . sup . 5 , 8 -- bk 95lys -- lys -- thi . sup . 5 , 8 -- bk 0______________________________________ the resistance of n - terminal - extended bk analogs to kininase degradation , especially those with lys - lys - extensions , suggests that long - acting antagonists of bk activity would be obtained by modifying the [ d - phe 7 ]- bk inhibitors with a lys - lys - extension . additionally , observations that a d - arg residue added to the n - terminal of bk agonists tends to increase uterine potency without effecting ileum activity prompted the synthesis of d - arg - extended d - phe 7 bk analogs as tissue - specific inhibitors . n - terminal extension of d - phe 7 bk with lys - lys - or with the d - arg residue reduced agonist potency in the uterus assay but has no effect on the antagonism seen in the ileum assay . similarly , the inhibitory effect of thi 5 , 8 dphe 7 bk was diminished on the uterus with the addition of either lys - lys - or d - arg to the n - terminal . in the ileum assay addition of d - arg to the very potent thi 5 , 8 dphe 7 bk antagonist had little effect on inhibitory potency . examples of conferring tissue selectivity by modification of bradykinin antagonists at position 2 and 3 bradykinin agonists produced by modification of the bradykinin nonapeptide sequence exhibit similar potencies in the classic rat uterus ( rut ) and guinea pig ileum ( gpi ) assays relative to bradykinin . recently , dissociation of smooth muscle activities towards significantly higher uterine activity vs ileum activity has been reported in bradykinin analogs containing aminoisobutyric acid ( aib ) in position 7 ( r . j . vavrek & amp ; j . m . stewart , peptides 1 : 231 , 1980 ), and in bradykinin analogs with multiple d - amino acid substitutions in position 6 and 7 ( r . j . vavrek & amp ; j . m . stewart , in kinins 1984 , l . m . greenbaum , ed , plenum press , ny , 1985 ). the addition of a d - amino acid residue to the n - terminus of the ileum - selective bradykinin antagonist dphe 7 - bk ( i . e ., darg ) does not change selectivity for inhibiting bradykinin activity on the ileum ( i . e ., darg 0 - dphe 7 - bk ). modification of dphe 7 - bk at position 3 by the substitution of a dpro residue ( i . e ., dpro 3 dphe 7 - bk ) eliminates antagonist activity in the ileum assay and destroys agonist activity in the uterus assay . replacement of the pro residue at position 3 of darg 0 - dphe 7 - bk reverses the spectrum of smooth muscle activity towards uterine - selective antagonism , with complete loss of antagonism of bradykinin in the ileum assay . likewise , substitution of the pro residue at position 3 of the nonspecific antagonist darg 0 thi 5 , 8 dphe 7 - bk with a dpro residue eliminates antagonism of bradykinin action on the ileum , but full antagonist activity in the uterine assay is retained . ______________________________________antagonist specificity in smooth muscleassays by modification of position 3ex - am - ple # structure rut gpi______________________________________ 1 dphe . sup . 7 -- bk ( 1 % ag ) pa . sub . 2 = 5 . 010 darg . sup . 0 -- dphe . sup . 7 -- bk ( 0 . 1 % ag ) pa . sub . 2 = 5 . 059 dpro . sup . 3 -- dphe . sup . 7 -- bk 0 011 darg . sup . 0 -- dpro . sup . 3 -- dphe . sup . 7 -- bk pa . sub . 2 = 4 . 6 015 darg . sup . 0 -- thi . sup . 5 , 8 dphe . sup . 7 -- bk pa . sub . 2 = 5 . 2 pa . sub . 2 = 6 . 116 darg . sup . 0 -- dpro . sup . 3 thi . sup . 5 , 8 dphe . sup . 7 -- bk pa . sub . 2 = 5 . 2 0______________________________________ ag = agonist potency relative to bk = 100 . pa . sub . 2 is the inhibition potency as defined by schild ( br . j . pharmacol . 2 : 189 , 1947 ). tissue selectivity of bradykinin analogs can also be altered by modification of the pro at position 2 . it has been found that substitutions of val , sar , pro , ala , hyp and aib ( alpha - aminoisobutyrate ) at position 2 confer differential tissue selectivity of selected bradykinin analogs in an assay of myotropic activity determined on guinea pig ileum versus rat uterus ( r . j . vavrek and j . m . stewart , peptides , 231 - 235 , 1980 ). the tissue selectivity conferred upon various bradykinin analogs by such substitutions at position 2 suggests that similar substitution in any bradykinin analog , including those with antagonist activity , will confer tissue selectivity . theraputic applications of the novel bradykinin antagonists include not only treatmemt for the production of bradykinin or related kinins by the animal but also the injection of bradykinin related peptides into an animal as a result of bites and stings . topical application alone or in combination with subcutaneous utilization of the bradykinin antagonists of the invention can be employed to treat the effects of bradykinin - related peptides causing pain , inflammation and swelling . the therapeutic use of bradykinin antagonists of this invention for other traumatic , inflammatory or pathological conditions which are known to be mediated by bradykinin or exacerbated by an overproduction of bradykinin can also be achieved . these conditions include local trauma such as wounds , burns and rashes , angina , arthritis , asthma , allergies , rhinitis , shock , inflammatory bowel disease , low blood pressure , systemic treatment of pain and inflammation , and low sperm motility which produces male infertility . the present bradykinin antagonists , as discussed may be advantageously administered in a variety of ways including sublingual absorption as with nitroglycerine or patch administration using agents for assisting absorption through the skin such as for the treatment of angina . based upon the pa 2 and ed 50 data disclosed in this invention and in the prior art related to agonist potency , it is possible for one skilled in the art to make a determination of the dosage of the novel bradykinin antagonists of the invention . it is therefore estimated that the dosage range for typical application in such conditions as the pain and inflammation of wound , burns and rashes would be 0 . 1 - 5 mg / ml ; for a nasal spray formulation suitable for treating rhinitis , allergies and asthma suitable dosage range would be 0 . 1 - 5 mg / ml ; for intravenous formulation suitable for the treatment of systemic inflammation , shock , arthritis , allergies , asthma and for increasing sperm motility , a suitable dosage range would be 0 . 1 - 10 mg / kg ; for an oral formulation for the treatment of inflammatory bowel disease or general pain and inflammation a suitable dosage range would be 10 - 100 mg / kg . bradykinin antagonists can also be administered intravaginally , intrarectally , intrabuccally or any other accepted internal application . as will be recognized by those skilled in the art the present invention has a wide range of applicability to providing competitive inhibitors to the biological activities of bradykinin produced by the body in illness , injury and shock . the advantages of the invention in substituting the l - pro position 7 with amino acids of the d - configuration to convert bradykinin agonists to antagonists provide a wide variety of specific and competitive antagonists for reducing the known effects of bradykinin . the additional advantages of the invention of modifying the l - pro position 7 in conjunction with modifications at the other positions of the novel bradykinin antagonists provides a variety of useful compounds . it will further be appreciated the present invention is susceptible to these and other modifications within the parameters of the invention without departing from the scope of the following claims . | 0 |
the present invention provides an n - phenyl - 3 - cyclopropylpyrazole - 4 - carbonitrile of formula i , above . unless otherwise specified , “ compounds of formula i ” includes all the embodiments thereof hereinafter described . surprisingly , it has now been found that compounds of formula i may be useful in the fields of veterinary medicine and livestock husbandry and in the maintenance of public health against ectoparasites and their infection or infestation . as used in this specification and the appended claims , the term halogen designates f , cl , br or i , and the term heteroaryl designates a c 5 - c 10 aromatic ring system containing 1 , 2 or 3 heteroatoms , which may be the same or different , selected from n , o or s . such heteroaryl ring systems include pyrrolyl , azolyl , oxazolyl , thiazolyl , imidazolyl , furyl , thienyl , quinolinyl , isoquinolinyl , indolyl , benzothienyl , benzofuranyl , benzisoxazolyl and the like . the term aryl designates a carbocyclic aromatic ring system such as phenyl , naphthyl , anthracenyl or the like . the term haloalkyl as used herein designates a c n h 2n + 1 group having from one to 2n + 1 halogen atoms which may be the same or different and the term haloalkoxy as used herein designates an oc n h 2n + 1 group having from one to 2n + 1 halogen atoms which may be the same or different . in the specification and claims , when the terms c 1 - c 6 alkyl , c 2 - c 6 alkenyl , c 2 - c 6 alkynyl , c 3 - c 7 cycloalkyl , aryl or heteroaryl are designated as being optionally substituted , the substituent groups which are optionally present may be one or more of those customarily employed in the development of veterinary or pharmaceutical compounds or the modification of such compounds to influence their structure / activity , persistence , absorption , stability or other beneficial property . specific examples of such substituents include halogen atoms , nitro , cyano , thiocyanato , cyanato , hydroxyl , alkyl , alkanediyl , haloalkyl , alkoxy , haloalkoxy , amino , alkylamino , dialkylamino , formyl , alkoxycarbonyl , carboxyl , alkanoyl , alkylthio , alkylsulphinyl , alkylsulphonyl , carbamoyl , alkylamido , phenyl , phenoxy , benzyl , benzyloxy , heterocyclyl or cycloalkyl groups , preferably halogen atoms or lower haloalkyl or lower haloalkoxy groups . typically , 0 - 3 substituents may be present , preferably 1 or 2 . when any of the foregoing substituents represents or contains an alkyl substituent group , this may be linear or branched and may contain up to 12 , preferably up to 6 , more preferably up to 4 carbon atoms . optionally substituted c 1 - c 6 alkyl includes methyl substituted by c 2 - c 6 alkanediyl , i . e . includes c 3 - c 7 cycloalkyl . compounds of the invention may exist as one or more stereoisomers . the various stereoisomers include enantiomers , diastereomers , atropisomers and geometric isomers . one skilled in the art will appreciate that one stereoisomer may be more active or may exhibit beneficial effects when enriched relative to the other stereoisomer ( s ) or when separated from the other stereoisomer ( s ). additionally , the skilled artisan knows how to separate , enrich or selectively prepare said stereoisomers . accordingly , the present invention comprises compounds of formula i , the stereoisomers thereof and the tautomers thereof . the compounds of the invention may be present as a mixture of stereoisomers , individual stereoisomers , or as an optically active or enantiomerically pure form . compounds of formula i may exist in one or more tautomeric forms that may give rise to geometric isomers around the tautomeric double bond . one skilled in the art will recognize that said tautomers often exist in equilibrium with one another . as these tautomers interconvert under environmental and physiological conditions , they provide the same useful biological effects . the present invention includes mixtures of such tautomers as well as the individual tautomers of compounds of formula i . preferred compounds of the invention include compounds of formula i wherein r is halogen or haloalkyl . another group of preferred compounds are those formula i compounds wherein r 1 is h , halogen or nr 9 r 10 . a further group of preferred compounds are those of formula i wherein r 5 and r 6 are h . more preferred compounds of the invention include formula i compounds wherein r is halogen or haloaklyl ; n is 3 ; and r 2 is h , halogen , methyl or optionally substituted phenyl . another group of more preferred compounds are those of formula i wherein r is cl or cf 3 ; n is 3 ; r 2 is cl or ch 3 ; and r 1 is h or cl . especially preferred compounds include those having the formula i set forth above , but with the further proviso that r 3 , r 4 , r 5 and r 6 are not all — h , unless r 1 is halogen . compounds of formula i may be prepared using conventional synthetic techniques and , if required , standard separation and isolation techniques . in one preferred embodiment of the method of this invention , compounds of formula i wherein r 1 is nh 2 ( ia ) may be prepared by reacting a phenyl hydrazine of formula ii with a cyclopropylcarboxylic acid of formula iii to give the intermediate of formula iv ; reacting the formula iv intermediate with a chlorinating agent such as thionyl chloride to give the chloroenamine of formula v ; and reacting the formula v enamine with malononitrile to give the desired product of formula ia . this method is shown in flow diagram i . the compounds of formula ia may be used as chemical intermediates to prepare the other compounds having formula i using standard derivatization procedures . for instance , the compounds having formula ia may be used to prepare the other compounds having formula i in which r 1 is nr 9 r 10 by standard methods of converting primary amines into secondary amines and tertiary amines , for example , by standard alkylation procedures . in the compounds having formula i in which r 1 is nr 9 r 10 , r 9 and r 10 are preferably independently selected from h and c 1 - c 6 alkyl . the compounds of formula i in which r 1 is nr 9 r 10 ( including the compounds having formula ia ) may be recovered in the form of their free bases or in the form of their pharmaceutically acceptable acid addition salts . the compounds of formula ia and those having formula i in which r 1 is nhr 10 , r 10 being an optionally substituted c 1 - c 4 alkyl group , may be used to prepare the compounds having formula i in which r 1 is nr 11 cor 12 by standard methods of converting primary amines into amdes and imides and secondary amines into amides . such methods may use reactive derivatives of the carboxylic acid r 12 co 2 h where r 12 is as defined above . r 12 is preferably c 1 - c 6 alkyl or c 3 - c 7 cycloalkyl . similarly to the aforesaid derivitization , using formula ia as substrate and employing the procedures described in u . s . pat . no . 5 , 814 , 652 or journal of heterocyclic chemistry , 2000 , 37 , 1617 , compounds of formula i wherein r 1 is nchor 13 or nchnr 9 r 10 , respectively , may be prepared . the compounds of formula ia may be used as chemical intermediates to prepare the compounds having formula i in which r 1 is halogen or nitro via diazonium salts as intermediates . for instance , the compounds having formula i in which r 1 is nitro may be prepared in known manner by treatment of diazonium salts with sodium nitrite in the presence of cuprous ions in neutral or alkaline solution . the compounds having formula i in which r 1 is fluorine may be prepared via diazonium salts by the balz - schiemann reaction . the other compounds of formula i wherein r 1 is halogen ( ib ) may be prepared by reacting the formula ia compound with , in the case wherein the halogen is cl , concentrated hcl , nano 2 and cucl 2 . this reaction is shown in flow diagram ii wherein hal represents cl , br or i . compounds of formula i wherein r 1 is h may be prepared using conventional deamination techniques such as reacting a compound of formula ia with amylnitrite or n - pentylnitrite , as described in ep 303118 . advantageously , it has now been found that an n - phenyl - 3 - cyclopropylpyrazole - 4 - carbonitrile compound of formula i may be used to effectively control , prevent or ameliorate infection and infestation of ectoparasites on homeothermic animals , such as cattle , sheep , horses , goats , pigs , camels , water buffalo , donkeys , rabbits , fallow deer , reindeer , minks , chinchillas , raccoons , chickens , geese , turkeys , ducks , dogs , cats and the like . ectoparasites against which a compound of formula i is useful include biting and sucking ectoparasitic insects such as diptera , muscidae , acarina or siphonáptera , in particular , diptera : muscidae such as musca autumnalis ( face flies ), haemtobia irritans ( horn flies ) stomoxys calcitrans ( stable flies ), heel flies , tsetse flies , blow flies and the like ; diptera : hippoboscidae ( louse flies ) such as melophagus ovinus ( sheep ked ); acarina , including ticks , e . g ., ixodes spp ., boophilus microplus , amblyomma spp ., hyalomma spp ., rhipicephalus spp ., e . g , rhipecephalus sanguineus , rhipicephalus appendiculatus , haemaphysalis spp ., dermacentor spp ., e . g . dermacentor variables , and the like ; the phthiraptera families , including trichodectidae such as bovicola bovis ( important cattle - biting louse ), b . ovis ( sheep - biting louse ), b . equi ( horsebiting louse ), haematopinidae such as haematopinus suis ( hog louse ), and h . asini ( horse sucking louse ), linognathidae such as linognathus stenopsis ( goat sucking louse ) and l . vituli ( long - nosed cattle louse ), and the like ; and the siphonáptera families , including pulicìdae such as archaeopsyllnìae ( cat and dog fleas ), spilopsyllìnae ( rabbit fleas ), and the like . accordingly , the present invention provides a method for the prevention , amelioration or control of ectoparasitic infection or infestation in a homeothermic animal which comprises providing to a homeothermic animal in need thereof a prophylactically , therapeutically or pharmaceutically effective amount of a compound of formula i as described hereinabove . the term “ providing ” as used herein with respect to providing a compound or substance embraced by the invention , designates either directly administering or applying such a compound or substance , or administering or applying a prodrug , derivative or analog which forms an equivalent amount of the compound or substance at the locus of administration or application or within the body of the target ectoparasite . protection of homeothermic animals from the infestation of ectoparasites , particularly of the orders diptera , acarina , phthiraptera or siphonáptera may be achieved by the application or administration of a prophylactically , therapeutically or pharmaceutically effective amount of a compound of formula i . in actual practice , the formula i compound may be applied to the animal as a dip , spray , pour - on , spot - on , ear tag , collar , medallion , backrubber , oiler , dustbag , powder , lotion , parenteral injection , or the like , preferably as a topical application such as a spray , pour - on or spot - on . the effective amount of the formula i n - phenyl - 3 - cyclopropylpyrazole - 4 - carbonitrile compound to be used in the method of invention will vary according to the specific compound used , the mode of application used , the identity of the ectoparasite to be controlled , the degree of infestation , the extent of the ectoparasitic insect population , the nature of the target host , the weather conditions or the like . effective dosages in the practice of this invention typically will range from 0 . 1 mg / kg to 100 mg / kg , preferably about 1 . 0 mg / kg to 50 mg / kg based on body weight . naturally , quantities greater than the effective amounts of the formula i compound may be administered , but are not required for the protection of the target animal from the ectoparasite . the present invention also provides a veterinary composition which comprises a pharmaceutically acceptable carrier and an ectoparasiticidally effective amount of a compound of formula i . the composition of the invention may be formulated as an aqueous dip for animals such as cattle , sheep , goats or the like or the inventive composition may be prepared as a wettable powder , emulsifiable concentrate , aqueous flowable or the like , which are dispersed in a suitable solvent and applied as sprays to the fur or hide of the animals . such sprays usually contain about 0 . 1 ppm to 5000 ppm and preferably about 0 . 5 ppm to 1000 ppm of the active formula i compound . also preferred is a range of about 0 . 2 ppm to 20 . 0 ppm . advantageously , the compounds of formula i may also be prepared as pour - on formulations and poured on the backs of the animals such as cattle , sheep or companion animals to protect them against infestation by arthropod ectoparasites . the pour - on compositions of the invention are generally prepared by dissolving , suspending or emulsifying the formula i compound in a suitable nontoxic pharmaceutically acceptable diluent for pour - on administration . the diluent must be compatible with the ectoparasiticidal compound and should not be a source of irritation or damage to the animal &# 39 ; s skin or hair . such diluents include mono and polyhydric alcohols , vegetable oils , spreading oils , aliphatic and aromatic hydrocarbons , lower alkyl ketones , esters and fatty acids ; such diluents are well - known in the art . those skilled in the art will readily be able to identify suitable diluents for use in this invention . in one embodiment of this invention , a pour - on formulation comprises about 0 . 5 % to 30 % by weight of the compound of formula i , about 0 . 5 to 30 % by weight of a spreading oil , 30 % to 60 % by weight of an aliphatic or aromatic hydrocarbon , mono or polyhydric alcohol , lower alkyl ketone or mixtures thereof and 0 % to 20 % by weight of a vegetable or mineral oil . a more preferred embodiment thereof comprises about 10 % to 25 % by weight of the compound of formula i , about 20 to 30 % by weight of a spreading oil , 40 % to 50 % by weight of an aliphatic or aromatic hydrocarbon , mono or polyhydric alcohol , lower alkyl ketone or mixtures thereof and 5 % to 15 % by weight of a vegetable or mineral oil . in another embodiment of this invention , a pour - on formulation comprises 45 % by weight of xylene , 25 % by weight of cyclohexanone , 15 % by weight of said antagonist compound , 10 % by weight of corn oil or mineral oil and 5 % by weight of other pharmaceutically acceptable diluents such as surfactants , spreading agent , antifoam agents or the like . among the spreading oils that can be utilized in pour - on formulations of this invention are fatty acids , fatty acid esters , triglycerides and fatty alcohols including : isopropyl myristate , capryl / caproic acid esters of saturated ( c 12 - c 18 ) fatty alcohols with waxy fatty acid esters , isopropyl palmitate and the like . useful alcohols , glycols and ketones in the practice of this invention include : ethyl alcohol , isopropyl alcohol , propylene glycol , dipropylene glycol , benzyl alcohol , dipropylene glycol monoethyl ether , cyclohexanone , methylethyl ketone , methylisobutyl ketone , n - butoxybutylethoxyethanol and the like . also , the vegetable oils that may be utilized in these formulations include : corn oil , olive oil , peanut oil , sunflower oil , cottonseed oil , soybean oil , and the like . hydrocarbons that can be used in the formulation of this invention include : xylene , toluene , and the like . surfactants may also be utilized in the formulations if desired . those skilled in the art will readily be able to determine which surfactants known in the art will be suitable in the practice of this invention , and will understand how to incorporate such surfactants into formulations of this invention . in order to present a more clear understanding of the invention , the following specific examples are set forth below . these examples are merely illustrative and are not to be understood as limiting the scope and underlying principles of the invention in any way . indeed , various modifications of the invention , in addition to those illustrated and described herein , will become apparent to persons skilled in the art from the following examples and the foregoing description . such modifications are also intended to fall within the scope of the appended claims . the terms hnmr and thf designate proton nuclear magnetic resonance and tetrahydrofuran , respectively . unless otherwise noted , all parts are parts by weight . a mixture of 2 , 6 - dichloro - 4 -( trifluoromethyl ) phenyl hydrazine ( 25 g , 102 mmol ) and 2 , 2 - dichloro - 1 - methylcyclopropylcarboxylic acid ( 17 g , 102 mmol ) in ch 2 cl 2 is treated portion - wise over a 15 min . period with 1 -[ 3 -( dimethylamino ) propyl ]- 3 - ethylcarbodiimide hydrochloride ( 20 g , 102 mmol ), stirred at room temperature for 18 h , diluted with water , stirred for 0 . 5 h and filtered . sthe filtercake is dried , washed with 1 : 1 mixture of ether : hexanes and dried in vacuo to afford the title product as a white solid , 33 g ( 82 % yield ), mp 174 - 175 ° c ., identified by hnmr and mass spectral analyses . a stirred mixture of 2 , 2 - dichloro - 1 - methylcyclopropyl carboxylic acid , n ′-[ 2 , 6 - dichloro - 4 -( trifluoromethyl ) phenyl ] hydrazide ( 9 . 4 g , 23 . 7 mmol ) in toluene is treated dropwise with thionyl chloride ( 7 . 0 ml , 95 mmol ), heated at reflux temperature for 3 h , cooled to room temperature and concentrated in vacuo . the resultant oil residue is purified through a short bed of silica gel using hexanes as eluent to afford the title product as a tan solid , 9 . 1 g ( 93 % yield ), identified by hnmr and mass spectral analyses . a solution of malonitrile ( 7 . 23 ml , 115 mmol ) in thf is treated with nah ( 2 . 30 g , 57 . 5 mmol ), cooled to 0 ° c ., treated with a solution of [ ex . 2 ] ( 9 . 10 g , 23 mmol ) in thf over a 0 . 5 h period , stirred at 0 ° c . for 1 h , warmed to 20 ° c ., stirred for 0 . 5 h and diluted with water and ether . the phases are separated . the organic phase is washed with brine , dried over na 2 so 4 and concentrated in vacuo . the resultant residue is purified by flash chromatography ( silica gel , 40 % ether in hexanes as eluent ) to afford the title product as a white solid , 6 . 15 g ( 60 % yield ), mp & gt ; 200 ° c ., identified by hnmr and mass spectral analyses . a mixture of 5 - amino - 3 -( 2 , 2 - dichloro - 1 - methylcyclopropyl )- 1 -[ 2 , 6 - dichloro - 4 -( trifluoromethyl ) phenyl ]- 1h - pyrazole - 4 - carbonitrile ( 5 . 00 g , 11 . 3 mmol ) in concentrated hcl ( 30 ml ) at 0 ° c . is treated portion - wise with nano 2 ( 7 . 80 g , 113 mmol ) over a 15 min . period , stirred for 1 h at 0 ° c ., treated with cucl 2 ( 2 . 24 g , 22 . 6 mmol ), heated slowly to 55 ° c ., stirred at 55 ° c . for 1 h , cooled to room temperature and decanted . the remaining solid is dispersed in a mixture of water and ether . the phases are separated . the organic phase is dried over na 2 so 4 and concentrated in vacuo . the resultant residue is purified by flash chromatography to afford the title product as a red resin , 3 . 40 g ( 65 % yield ), identified by hnmr and mass spectral analyses . using essentially the same procedures described in the foregoing examples 1 - 4 and employing the appropriate hydrazine and cyclopropylcarboxylic acid , the compounds shown in table i are obtained and identified by hnmr and mass spectral analyses . table i ex . mp no . ( r ) n r1 r2 r3 r4 ° c . 5 a 2 , 6 - di - cl - 4 - cf 3 h ch 3 cl cl 97 - 98 . 5 6 2 , 4 , 6 - tri - cl h ch 3 cl cl 119 - 121 7 a 2 , 6 - di - cl - 4 - cf 3 h ch 3 cl cl 123 - 125 8 2 , 6 - di - cl - 4 - cf 3 h ch 3 h h — 9 2 , 6 - di - cl - 4 - cf 3 h 4 - ch 2 o — c 6 h 4 h h — 10 2 , 6 - di - cl - 4 - cf 3 h 4 - cl - c 6 h 4 h h — 11 2 , 4 , 6 - tri - cl h ch 3 h h — 12 2 , 4 , 6 - tri - cl h 4 - cl — c 6 h 4 h h — 13 2 , 4 , 6 - tri - cl h 4 - ch 3 o — c 6 h 4 h h — 14 2 , 6 - di - cl - 4 - cf 3 h ch 3 br br — 15 2 , 4 , 6 - tri - cl h ch 3 br br — 16 2 , 6 - di - cl - 4 - cf 3 h 4 - ch 3 — c 6 h 4 h h — 17 2 , 6 - di - cl - 4 - cf 3 h 2 , 4 - di - cl — c 6 h 3 h h — 18 2 , 4 , 6 - tri - cl h 2 , 4 - di - cl — c 6 h 3 h h — 19 2 , 6 - di - cl - 4 - cf 3 nh 2 ch 3 cl cl & gt ; 200 20 2 , 6 - di - cl - 4 - cf 3 cl ch 3 br br 95 - 98 21 2 , 6 - di - cl - 4 - cf 3 nh 2 ch 3 br br 233 - 235 dec 22 2 , 6 - di - cl - 4 - cf 3 br ch 3 br br 110 - 114 23 2 , 6 - di - cl - 4 - cf 3 h h h h 102 - 106 24 2 , 6 - di - cl - 4 - cf 3 nh 2 h h h 158 - 159 25 2 , 4 , 6 - tri - cl nh 2 ch 3 cl cl 185 - 190 26 2 , 6 - di - cl - 4 - cf 3 cl h h h — 27 2 , 4 , 6 - tri - cl cl ch 3 cl cl 128 - 132 28 2 , 4 , 6 - tri - cl br ch 3 cl cl 133 - 134 29 2 , 6 - di - cl - 4 - cf 3 br ch 3 cl cl 123 - 124 30 2 , 6 - di - cl - 4 - cf 3 no 2 ch 3 cl cl resin 31 2 , 6 - di - cl - 4 - cf 3 i ch 3 cl cl 128 - 130 32 2 , 6 - di - cl - 4 - cf 3 n ( ch 3 ) 2 ch 3 cl cl 114 - 115 33 2 , 6 - di - cl - 4 - cf 3 n ( c 2 h 5 ) 2 ch 3 cl cl 122 - 123 34 2 , 6 - di - cl - 4 - cf 3 nhcot - bu ch 3 cl cl & gt ; 220 35 2 , 6 - di - cl - 4 - cf 3 n ( co - cyclopropyl ) 2 ch 3 cl cl 162 - 164 36 2 , 6 - di - cl - 4 - cf 3 nhco - cyclopropyl ch 3 cl cl — 37 2 , 6 - di - cl - 4 - cf 3 n ═ choch 3 ch 3 cl cl 89 - 91 38 2 , 6 - di - cl - 4 - cf 3 n ═ chn ( ch 3 ) 2 ch 3 cl cl 133 - 134 39 2 , 6 - di - cl - 4 - cf 3 n ═ chonc 3 h 7 ch 3 cl cl oil 40 2 , 6 - di - cl - 4 - cf 3 n ═ choc 2 h 5 ch 3 cl cl 82 - 84 the contact activity of a test compound against ctenocephatides felis , adult cat fleas , is evaluated in a coated , glass vial assay . in this evaluation , a solution of test compound in acetone is allowed to dry on the interior surface of a 20 ml vial . ten unfed adult cat fleas are added to the treated vial and mortality is assessed periodically for up to 48 h . all treatments are replicated 2 times . the data are averaged . the results are shown in table ii . table ii test compound conc . % mortality ( ex . no .) ( ug / cm2 ) 4 h 24 h 4 2 100 100 4 0 . 2 60 100 4 0 . 002 20 100 5 2 0 33 7 2 0 100 14 2 10 100 15 2 10 80 19 2 0 10 20 2 20 100 21 2 0 0 22 2 0 100 26 2 100 100 27 2 10 100 28 2 0 10 29 2 50 100 29 0 . 2 20 100 29 0 . 02 10 100 30 2 0 100 31 2 20 100 32 2 0 100 33 2 20 100 37 2 10 100 39 2 0 70 40 2 0 100 standard 1 2 30 100 standard 1 0 . 2 10 100 standard 1 0 . 02 0 100 control 2 0 0 0 the contact activity of a test compound against rhipacephalus sanguineus , adult ticks evaluated in a coated glass vial assay . in this evaluation , a solution of test compound in acetone is allowed to dry on the interior surface of a 20 ml vial . five unfed adult ticks are added to the treated vial and mortality is assessed periodically for up to 48 h . all treatments are replicated 2 times . the data are averaged . the results are shown in table iii . table iii test compound conc . % mortality ( ex . no .) ( ug / cm2 ) 4 h 24 h 4 7 . 80 60 100 4 0 . 78 60 100 7 7 . 80 10 80 7 0 . 78 0 10 14 7 . 80 50 80 14 0 . 78 40 40 19 7 . 80 40 70 19 0 . 78 0 20 20 7 . 80 20 50 20 0 . 78 0 20 21 7 . 80 0 40 21 0 . 78 10 10 22 7 . 80 0 60 22 0 . 78 20 30 29 7 . 80 20 60 29 0 . 78 0 40 31 7 . 80 50 50 31 0 . 78 10 20 32 7 . 80 0 30 32 0 . 78 0 60 standard 1 7 . 80 100 100 standard 1 0 . 78 90 100 control 2 0 0 3 the efficacy of a test compound against newly emerged larvae of lucilia sericata , blowfly , is evaluated using a treated paper / serum bioassay . in this evaluation , a solution of test compound in acetone is applied to a filter paper disc and the disc is allowed to dry . bovine serum and about 20 newly emerged blowfly larvae are added to the treated paper disc and the mortality is assessed at 24 h and 48 h . the data are averaged . the results are shown in table iv . table iv test compound conc . % mortality ( ex . no .) ( ppm ) 24 h 48 h 4 20 . 0 100 100 4 2 . 0 100 100 4 0 . 2 100 100 6 20 . 0 70 70 6 1 . 0 10 10 7 20 . 0 77 90 7 2 . 0 0 0 9 20 . 0 0 0 10 20 . 0 0 0 11 20 . 0 0 0 13 20 . 0 0 0 14 20 . 0 95 100 14 2 . 0 100 100 14 0 . 2 50 50 15 20 . 0 90 90 15 2 . 0 95 95 15 0 . 2 0 0 17 20 . 0 0 0 18 20 . 0 0 0 19 20 . 0 75 95 19 2 . 0 100 100 19 0 . 2 0 0 20 20 . 0 100 100 20 2 . 0 100 100 20 0 . 2 0 0 21 20 . 0 90 100 21 2 . 0 95 100 21 0 . 2 0 0 22 20 . 0 100 100 22 2 . 0 100 100 22 0 . 2 0 0 24 10 . 0 0 0 25 20 . 0 5 5 25 10 . 0 0 0 26 20 . 0 97 97 26 10 . 0 0 50 26 2 . 0 0 0 27 20 . 0 100 100 27 2 . 0 100 100 27 0 . 2 0 0 28 20 . 0 100 100 28 2 . 0 95 100 28 0 . 2 0 0 29 20 . 0 100 100 29 2 . 0 100 100 29 0 . 2 15 15 30 20 . 0 20 20 30 10 . 0 10 50 31 20 . 0 97 100 31 2 . 0 95 100 31 0 . 2 0 0 32 20 . 0 91 96 32 2 . 0 0 0 32 0 . 2 0 0 33 20 . 0 100 100 33 2 . 0 90 90 33 0 . 2 0 0 34 20 . 0 0 0 35 20 . 0 0 0 36 20 . 0 10 10 36 10 . 0 0 — 37 20 . 0 100 100 37 2 . 0 0 0 38 20 . 0 0 0 39 20 . 0 100 100 39 2 . 0 70 70 39 0 . 2 0 0 40 20 . 0 100 100 40 2 . 0 0 0 standard 1 20 . 0 100 100 standard 1 2 . 0 100 100 standard 1 0 . 2 0 100 control 2 0 0 0 tables ii , iii and iv show considerable efficacy for the compounds of the invention . those compounds displaying zero activity at all tested levels will need to be tested at higher doses to ascertain their effective concentrations . | 0 |
this invention relates to developing nanofiber - supported catalysts and applying them as additives to create a reinforced layer that in turn can be used in conjunction with non - reinforced layers that together make up multilayer fuel cell membranes . by applying thin ( for example , less than 1 - 2 μm ) coatings via multiple passes , the nanofiber additives in the reinforced layers may be substantially maintained in the in - plane direction to optimize the strengthening effect in the deposited plane . the nanofiber materials may be organic ( e . g ., polymer ( such as polyvinylidene fluoride ( pvdf ) or polyether sulfone ( pes )) or inorganic ( e . g ., carbon , metal , ceramic oxide and composites ( e . g ., ceo 2 , mno 2 , tio 2 , zro 2 , or cezro 4 )). the nanofiber materials can be electrically conductive ( e . g ., carbon , or metal ) or non - conductive ( e . g ., ceramic oxide and composites ). as shown below , an mea made with such a multilayer membrane having reinforced and non - reinforced layers demonstrates improved chemical and mechanical durability in fuel cell tests . referring first to fig1 and 2 , one example of the nanofiber - supported catalyst 1 includes a carbon nanofiber 1 a that provides support for a pt particle catalyst 1 b . the inventors prepared a nanofiber - supported catalyst 1 b with 10 % pt supported on carbon nanofiber 1 a . a 1 g quantity of carbon ( which was pre - treated in 5m hno 3 acid at 80 ° c . for 24 hours ) nanofibers and 0 . 3 g chloroplatinic acid hydrate ( h 2 ptcl 6 . 6h 2 o ) was mixed in 600 to 1200 ml ethylene glycol for the above 10 wt % target . the mixed solution was sonicated for 1 hour for full dispersion and dissolution , after which its ph value was adjusted from 9 to 11 using 1m sodium hydroxide ( naoh ) in ethylene glycol . the solution was stirred at room temperature under n 2 flow for 24 hours , and subsequently heated up to 130 ° c ., followed by holding at the final temperature for approximate 10 hours . the resulting pt - coated nanofiber was filtered , washed with deionized water , and dried in an oven at 80 ° c . for 24 hours . the resulting nanofiber - supported catalyst 1 was examined by scanning electron microscopy ( sem ), as shown . the size of carbon nanofiber 1 a was about 150 nm in diameter , and the pt particles 1 b distributed on the nanofibers 1 a had particle size of less than 10 nm . referring with particularity to fig2 , a procedure for constructing a notional three - layer 20 membrane configuration with alternating layers 10 , 15 of reinforced and non - reinforced material is shown . it will be apparent from the remainder of the disclosure that configurations with only two layers ( not shown , specifically , a single layer of reinforced material 10 and a single layer of non - reinforced material 15 ), as well as those with larger numbers ( not shown ) of both reinforced and non - reinforced layers 10 , 15 are also within the scope of the present invention . in the first part of the procedure , randomly - oriented nanofibers 1 a and a noble metal catalyst precursor p ( for example , chloroplatinic acid hydrate ( h 2 ptcl 6 . 6h 2 o ) or potassium hexachloroplatinate ( k 2 ptcl 6 )) are mixed in a solvent such as ethylene glycol or alcohol to make up ink precursor dispersion 2 . in one form , the mixing is achieved by stirring 3 or by any other suitable method . for example , the ink precursor dispersion 2 may be sonicated ( e . g ., for about 1 hour ) to achieve full dispersion and dissolution . the ph value of the ink precursor dispersion 2 can be adjusted to a desired value by adding acidic ( e . g ., hno 4 , h 2 so 4 ) or basic ( e . g ., naoh ) ingredients as needed . after sonication , the ink precursor dispersion 2 is stirred ( e . g ., for about 24 hours ) at temperature ( e . g ., room temperature ) and gas purge ( e . g ., n 2 ) conditions . the reaction under this second stirring may be performed at other desired conditions ( e . g ., at higher temperature ( e . g ., 70 - 180 ° c .)) as needed . the chemical reduction reaction results in the formation of a nanofiber - supported catalyst 1 that is filtered 4 , washed 5 with deionized water , and dried or heat treated 6 ( for example , at about 80 ° c ., in air , for about 24 hours ), although it will be appreciated by those skilled in the art that the drying / heat treating conditions are not critical , and that any suitable conditions may be used . in the second part of the procedure , two different coating solutions 8 include the coating solution 8 a containing the nanofiber - supported catalyst 1 from the previous part of the procedure , as well as the coating solution 8 b that is devoid of the reinforcement . both solutions 8 a and 8 b include an ionomer ( not separately shown ); in one form , the ionomer is nafion ®- based , although other equivalents may also be used . it will be appreciated by those skilled in the art that the precise makeup of the coating solutions 8 a , 8 b ( as well as the aforementioned ink precursor dispersion 2 ) may be tailored to specific requirements ; for example , types and amounts of solvents , as well as the use of organic or inorganic additives . the concentration of nanofiber - supported catalysts 1 and ionomer , as well as the weight ratio between them can be adjusted by adding different amounts of solvent or other liquid . in this example , the resulting ink solution 8 a has a ratio of nanofiber - supported catalyst 1 to ionomer in the range from about 1 : 20 to about 1 : 2 by weight , to get about 5 to about 35 wt % of nanofiber - supported catalyst 1 in the dry reinforced layers . diluted nafion ® solution 8 b without additive reinforcements were also prepared with 5 - 20 wt % concentration . in the third part of the procedure , membranes 20 can be made by coating alternating layers of the unreinforced ionomer solution 8 b and the nanofiber - supported catalyst - reinforced ionomer solution 8 a onto a backer film that in turn can be deposited layer - by - layer , or by a single step procedure with the coating height adjusted for each layer . in either scenario , the resulting membrane 20 takes on multilayer attributes , as the non - homogeneity of the alternating reinforced and non - reinforced layers tends to be preserved , even in situations where subsequent membrane processing ( involving one or more of heat and compression , for example ) would have a tendency to blend or otherwise at least partially homogenize the stacked layers 10 , 15 . in one exemplary form , the present inventors used a 50 μm polytetrafluoroethylene ( ptfe ) backer film from saint - gobain as the backer film . an erichsen coater with 10 inches by 15 inches of active membrane coating area was used . the thickness of each layer 10 , 15 of the membranes 20 can be controlled by one or both of the amount of respective solution 8 a , 8 b applied , as well as the concentration of the same . a bird applicator ( such as available from paul e . gardner co .) with selected slot thickness ( in the range of 25 - 150 μm ) was used to coat each specific membrane layer 10 , 15 . the thickness of each membrane layer 10 , 15 was controlled by the height of the bird applicator slot , which determined the amount of respective solution 8 a , 8 b applied , as well as the concentration of the coating solution 8 a , 8 b . for the layer - by - layer procedure , multiple coating passes ( also known as ramps ) were conducted for the reinforced layer 10 to ensure the in - plane direction of the nanofiber - supported catalyst 1 , and that the thickness of each pass was less than 2 μm after drying . so long as the orientation of the fibers was substantially within the plane of the deposited layer ( rather than oriented in a through - the - thickness direction ), neither coating layer deposition nor the distribution within the plane fiber orientation was taken into consideration for the built - up reinforcing layers . once each of the layers 10 , 15 are deposited , the membranes are then dried ( typically at about room temperature for at least a half an hour after each layer or pass of coating ); afterward , once all of the layers 10 , 15 or the whole membrane 20 are coated , they are heat treated ( typically between 250 ° f . to 300 ° f . for 1 to 24 hours ). in one particular form , the heat treatment was conducted at 140 ° c . for 12 hours . for comparative purposes , single layer membranes ( not shown ) were also prepared without nanofiber additives . the thickness of all of the membranes in this example were controlled to the same value ( about 20 μm ), although as shown in fig2 , at least one of the layers 15 may be made to have a different thickness , depending on the need . referring next to fig5 , a fuel cell 40 with anode bipolar plate 50 , cathode bipolar plate 60 , anode ccdm 70 and cathode ccdm 80 is shown . membrane 20 ( such as that prepared from the steps of fig2 described above ) is shown disposed between adjacent ccdms 70 , 80 in general , and between the catalytically - active electrode layers 75 ( anode electrode layer ), 85 ( cathode electrode layer ) that form part of the respective ccdms 70 , 80 in particular . although shown presently in a ccdm - based configuration ( where the creation of the work - producing external electric current extends between catalytic layers of the ccdms ), it will be appreciated by those skilled in the art that the present invention is equally applicable to a ccm - based configuration ( where the creation of the work - producing external electric current extends between catalytic layers formed on the outer opposing surfaces of the membrane ). the arrangement may optionally include a subgasket ( for example , an 8 μm layer of kapton , not shown ) positioned between it and the ccdms 70 , 80 on one or both sides . the subgasket has the shape of a frame , and the size of the window is smaller than the footprint of the membrane 20 and the ccdms 70 , 80 . pt / vulcan was used to form the electrocatalyst layer . as will be understood by those skilled in the art , pt / vulcan or pt / v is a type of catalyst used in fuel cells . when preparing electrode layers , pt / v may be mixed with ionomer in a solvent to form catalyst / ionomer inks , after which the inks may be coated on gdm with controlled loadings to form ccdms . in the present invention , the inventors used a pt loading ( weight of a normal metal ( for example , pt ) per unit area of mea ) of 0 . 4 mg / cm 2 at the cathode and 0 . 05 mg / cm 2 at the anode . in one form , the reinforced layer 10 of membrane 20 may be biased toward the cathode ccdm 80 ; such construction compensates for the faster travel of the crossover hydrogen by having them traverse a longer path than the crossover oxygen . chemical catalytic reaction of hydrogen and oxygen from crossover takes place at a pt active surface inside of the membrane thereby reducing reactant gas crossover . meas made up of membranes 20 with ccdms 70 , 80 were tested for mechanical and chemical durability . meas made from membranes without reinforcement were also prepared . in one form , the mechanical durability testing was based on rh cycling . in the rh cycling tests , the portion conducted without loads was used to evaluate the mechanical durability of meas containing membranes with and without reinforced layers . for each test , 50 cm 2 active area graphite plates with 2 mm width straight channels and lands were used for the cell build . the rh cycling test was conducted at 80 ° c ., and ambient outlet gas pressure , while 2 slpm constant flow rate of air was introduced in both the anode and cathode of the cell in a counter - flow format . the air supplies to the anode and cathode were periodically by - passed or passed through humidifiers controlled at 90 ° c ., to achieve 150 % rh and 0 % rh with a duration of 2 min at each condition . the mea failure criteria was arbitrarily defined as 10 sccm crossover gas leak between from anode to cathode or vice versa . the target of the rh cycling test for a mea is at least 20 , 000 rh cycles with less than 10 sccm crossover gas leak . the results of rh cycling tests are shown in fig3 , where the meas containing the membrane without the reinforced layer failed with significant leakage at fewer than 20 , 000 cycles , whereas the meas containing the multilayer membranes 20 with reinforced layer passed the test criteria . as such , the present inventors have inferred that the reinforced layers containing nanofiber - supported pt catalyst additives improved fuel cell durability by enhancing membrane mechanical stability . the meas were also subjected to chemical durability tests under open circuit voltage ( ocv ) conditions . some of the meas were configured as having multilayer membrane containing nanofiber - supported pt catalysts in the reinforced layer , while others were configured as comparison membrane samples without a reinforced layer ; each were individually assembled in fuel cell hardware and tested for chemical durability under various ocv conditions , including a standard test procedure at 95 ° c ., and 50 % rh for 100 hours duration , and then at 95 ° c ., 25 % rh for another 100 hours duration . under these conditions , the meas were subject to chemical degradation due to the production of oxidants including hydroxyl radical (• oh ) and h 2 o 2 . during this test , the fuel cell ocv , as well as the fluoride release rate ( frr ), were evaluated and recorded . as shown in fig4 , the mea containing nanofiber - supported pt catalysts in the reinforced layer of the membrane demonstrated better durability than the membrane without the reinforced layer : it has smaller ocv loss and lower averaged frr throughout the test duration . in the mea with the reinforced layer , the pt reduced crossover of reactant gases ( e . g ., h 2 , o 2 ) and by - product ( e . g ., h 2 o 2 ), therefore , provided protection to the membrane for improved membrane durability . it is noted that terms like “ generally ,” “ commonly ,” and “ typically ,” when utilized herein , are not utilized to limit the scope of the claimed embodiments or to imply that certain features are critical , essential , or even important to the structure or function of the claimed embodiments . rather , these terms are merely intended to identify particular aspects of an embodiment or to emphasize alternative or additional features that may or may not be utilized in a particular embodiment . further , it is noted that recitations herein of a component of an embodiment being “ configured ” in a particular way or to embody a particular property , or function in a particular manner , are structural recitations as opposed to recitations of intended use . more specifically , the references herein to the manner in which a component is “ configured ” denotes an existing physical condition of the component and , as such , is to be taken as a definite recitation of the structural factors of the component . for the purposes of describing and defining embodiments herein it is noted that the terms “ substantially ,” “ significantly ,” and “ approximately ” are utilized to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison , value , measurement , or other representation , and as such may represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue . having described embodiments of the present invention in detail , and by reference to specific embodiments thereof , it will be apparent that modifications and variations are possible without departing from the scope of the embodiments defined in the appended claims . more specifically , although some aspects of embodiments of the present invention are identified herein as preferred or particularly advantageous , it is contemplated that the embodiments of the present invention are not necessarily limited to these preferred aspects . | 7 |
the method according to the disclosure is described in an exemplary and non - limiting manner in fig1 to 6 . in this case , the same reference signs are used for corresponding structural parts or components in the figures . fig1 shows a carrier plate 10 that can be part of a fluidic , in particular a microfluidic , device . in accordance with the method according to the disclosure , in a first step said carrier plate 10 is shaped in an injection - molding machine in a mold for injection - compression molding . for this purpose , an injection unit can inject a plastic into a mold , or into a mold for injection - compression molding . in this case , the plastic used is preferably a transparent plastic , such as , for instance , a cycloolefin polymer ( cop ). the carrier plate 10 can be shaped by the action of a structured compression ram into the mold . a compression pressure of ≦ 200 bar is particularly preferred for this purpose . in this case , the carrier plate 10 can be shaped with little distortion , that is to say dimensionally stably . a film gate that forms can subsequently be cut off and removed from the injection - molding machine or from the mold for injection - compression molding . in this case , the mold and / or the ram of the injection - molding machine are / is preferably shaped in such a way that the carrier plate 10 produced is structured , that is to say has structures for the desired function of the fluidic device to be produced . said structures can comprise , for example , a receptacle 12 for an analysis component , such as a sensor , for instance , or a receptacle 14 for a component of a pump , as is shown with reference to fig2 . moreover , further receptacles are conceivable for further functional elements to be arranged in the fluidic device . furthermore the structures can comprise a channel system 16 , in which the fluid can be guided during the operation of the fluidic device . furthermore , an undercut 34 can be formed , in particular during the process of shaping or structuring the carrier plate 10 , which undercut can be engaged by a cover plate 30 in the later course of the method , as can be discerned with reference to fig6 . this is possible by virtue of the provision of at least one , preferably a plurality of webs 18 . the web 18 can be part of the mold for injection - compression molding and can therefore form a cutout in the carrier plate 10 . the at least one web 18 can be initially maintained in further method steps in order to provide for increased stability during the arrangement of further functional elements . in a next step , the surface of the shaped and advantageously structured carrier plate 10 can be treated using a plasma . for this purpose , a plasma gun can aim into the open mold and thus enable a plasma to act on the surface of the carrier plate 10 . the surface of the carrier plate 10 can be cleaned and activated in this way . in the completed fluidic connection , this step improves the adhesion of a cover plate 30 to the carrier plate 10 and thus the stability of the fluidic device as such . subsequently , for example by means of a handling system , various functional elements can be arranged on the carrier plate 10 and , if appropriated , fixed there . exemplary functional elements comprise an analysis component 20 , such as a sensor , for instance , or a pump element 22 , as can be discerned in fig2 . fixing of the functional elements can be realized by providing a suitable adhesive , for example . in a next step , as further functional element , a pump membrane 24 can be arranged on the carrier plate 10 , as is shown in fig3 . in this case , the pump membrane 24 serves for conveying a fluid to be treated in the fluidic device and is expediently expandable . in this case , the pump membrane 24 can be formed from a thermoplastic elastomer ( tpe ), a thermoplastic polyurethane ( tpu ), a thermoplastic vulcanizate ( tpv ) or else a thermosetting elastomer . expediently , as further functional element , an intermediate plate 26 , also designated as control plate , is subsequently arranged above the pump membrane 24 , in accordance with fig4 . in this case , the intermediate plate 26 is preferably structured at its underside , the structures 28 being indicated schematically in fig4 . in this case , the structures 28 are expendiently adapted to the structures of the channel system 16 in such a way that the pump membrane 24 can at least partly move into these structures 28 during a conveying process , for instance as a result of a vacuum being applied . a pump system that is well suited to a fluidic system is provided in this way . the intermediate plate 26 in turn can be produced in another injection - compression molding process carried out in the injection - molding machine in a mold for injection - compression molding . the intermediate plate is advantageously molded from a cost - effective plastic having little distortion . particularly preferred plastics from which the intermediate plate 26 can be molded comprise , for example , polyphenylene sulfide , in particular with a mineral filler , such as quartz sand or chalk , for instance . in the above mentioned steps of the method according to the disclosure , the at least one web 18 can advantageously be arranged in the mold in order to stabilize the applied functional elements . for the next method step , the at least one web 18 is removed from the mold . the mold for injection - compression molding in the injection - molding machine can then be closed and a further plastic can be injected into the mold in order to shape a cover plate 30 , as is shown in fig5 and 6 . for this purpose , the injected plastic preferably comprises a cycloolefin copolymer or else polyphenylene sulfide , in particular with one or more mineral fillers . in this case , the mineral fillers can comprise glass fibers , glass beads or mineral fillers such as quartz sand or chalk . once this plastic has been injected into the mold , a preferably planar ram is pressed into the mold , thereby compressing the second plastic onto the carrier plate 10 . a cover plate 30 is shaped in the process by virtue of the configuration of the mold and of the compression ram . the film gate produced can thereupon be removed . the plasma treatment of the surface of the carrier plate 10 carried out in an earlier step gives rise to a good support of the cover plate 30 on the carrier plate 10 , such that the fluidic device produced becomes very stable . if , as described with reference to fig1 , a web 18 or a plurality of webs 18 was / were used , said web ( s ), as already explained , was / were removed prior to the process of shaping the cover plate 30 . this cavity is subsequently filled by a holding region 32 of the cover plate 30 . this can be discerned in fig6 . as a result of a suitable structuring of carrier plate 10 and cover plate 30 , the carrier plate 10 has an undercut 34 , into which engages a lug 36 of the cover plate 30 for fixing the cover plate 30 to the carrier plate 10 in a positively locking manner . in this case , the size , shape and geometry of the undercut 34 and / or of the lug 36 are dependent on the corresponding mold and / or ram of the injection - compression molding machine in which the carrier plate 10 and the cover plate 30 are shaped . particularly preferably , the method according to the disclosure is carried out completely under clean room conditions . for this purpose , by way of example , the two - component injection - molding machine or the mold for injection - compression molding and the handling system can be completely integrated in a clean room . in this case , the method according to the disclosure is particularly well suited to producing microfluidic devices for high - precision analytical , preparative or medical applications . | 1 |
referring now to the figures of the drawing in detail and first , particularly , to fig1 thereof , there is shown a perspective view of a refrigerator equipped with door - opening sensors according to the present invention . the refrigerator has two doors 50 , 51 each closing , for example , a normal refrigerating compartment and a chiller compartment or a normal refrigerating compartment and a freezer compartment 52 , 53 . a door - opening sensor 54 is disposed on the front side of the housing of the refrigerator , beneath each of the compartments 52 , 53 , such that it is directed toward a bottom periphery of the respective door 50 , 51 . the door - opening sensors 54 are disposed approximately centrally on the front side of the housing of the refrigerator , with the result that they have the same level of sensitivity irrespective of the side of the housing on which the doors 50 , 51 are hinge - mounted . a magnet which is to be sensed in each case by the door - opening sensor 54 is incorporated in the door 50 , 51 in a position which is located opposite the door - opening sensor 54 . it would , of course , also be possible for the door - opening sensors 54 to be disposed at other locations on the front side of the housing of the refrigerator , in particular also in openings made in the inner container of the refrigerator . fig2 shows a section through a door - opening sensor 54 in a horizontal plane in relation to the configuration of the door - opening sensors 54 which are shown in fig1 . fig3 shows a section through the same door - opening sensor along a vertical plane . the section plane of fig3 is designated iii — iii in fig2 , and the section plane of fig2 is designated ii — ii in fig3 . the door - opening sensor 54 is essentially constructed from three parts : a reed switch 1 , a printed circuit board 2 , on which the reed switch 1 is soldered , and a housing 3 , which accommodates the printed circuit board 2 with the reed switch 1 . the housing 3 , which is produced in one piece from plastic , has a substantially cuboidal body 17 , which is open on the rear side and is enclosed on four side walls by an encircling collar 8 . narrow side walls 18 of the body 17 have on their inside , as is shown in fig3 , a groove 19 which tapers from the open rear side to the closed front side of the body 17 and serves for guiding and securing of the printed circuit board 2 . the printed circuit board 2 is retained by these grooves 19 in an essentially play - free manner in the region of the front side and with freedom of movement in the region of the rear side . on the open rear side , the body 17 is extended by two flexible arms 20 , which extend from the edges between one of the broad side walls 21 and the narrow side walls 18 and each bear a latching hook 24 at their free ends . the arms 20 can be displaced outward when the printed circuit board 2 is pushed into the groove 19 and are adapted to the length of the printed circuit board 2 such that the latching hooks 24 engage behind the rear edge 22 of the printed circuit board 2 when the front edge 23 of the latter reaches the narrow front end of the grooves 19 . it is thus possible to latch the printed circuit board 2 in the housing 3 . the shape of the latching hook 24 engaging behind the rear edge 22 of the printed circuit board 2 is selected , in adaptation to the freedom of movement of the printed circuit board in the rear region of the groove 19 , such that , in any position which the printed circuit board 2 can assume , the engagement between the latching hook 24 and the rear edge 22 is not lost without the arm 20 being bent at the same time . the printed circuit board 2 bears the reed switch 1 on a surface that is directed away from the arms 20 . conductor tracks 6 extend over the surface of the printed circuit board 2 from the connections of the reed switch 1 to conductor surfaces 7 on the rear edge 22 of the printed circuit board 2 , these conductor surfaces being wider than the conductor track 6 and serving as plug - in contacts for the electrical contact with the plug - in bushing illustrated in fig3 and 4 . the narrow side walls 18 bear , on their outer sides , two clasps or clips 14 which can be pressed together in the plane of fig2 . as will become clear in a later stage in the text , these serve for the releasable fastening of the housing 3 by latching in an opening . fig4 and 5 each show a section through a plug - in bushing 32 which is installed in an opening 30 of a wall 4 of the refrigerator and is provided in order to push the housing 3 into the same and to make contact with the reed switch 1 . the plug - in bushing 32 , which is formed from plastic , is constructed from two approximately cuboidal , hollow portions , referred to as plug - in portion 33 and wire - feed portion 34 . the plug - in portion 33 has an open front side that is directed toward the wall 4 and is enclosed by an encircling flange 35 . the flange 35 is adhesively bonded firmly to the inside of wall 4 . the cavity of the plug - in portion 33 is higher and wider than an opening 30 behind which it is disposed . broad side walls 36 of the plug - in portion 33 , of which one can be seen from the view in fig4 , bear a plurality of ribs 15 and 16 , which project into the interior of the cavity of the plug - in portion 33 . two of these ribs , the ribs 16 , extend over the entire depth of the plug - in portion 33 , and their height is dimensioned such that the broad side walls 21 of the housing 3 introduced into the plug - in portion 33 are retained in a play - free manner , or subjected to a slight clamping - in action , by them . the shorter ribs 15 are of such a length that they do not reach the rear side of the housing 3 , once introduced , and of such a height that they guide the rear edge of the printed circuit board 2 between them , and direct it into an accommodating slot 37 of a contact component 5 , when the printed circuit board is plugged in . as can be seen in fig5 in particular , the contact component 5 is retained in a sleeve 40 that is formed in a wall 39 that separates the portions 33 , 34 off from one another . in order to fix the contact component 5 in the plug - in direction of the housing 3 , on the one hand , use is made of two latching hooks 41 , which are connected to two of the short ribs 15 via flexible tongues 42 and can be displaced to the side when the contact component 5 is pushed into the sleeve 40 . on the other hand , a shoulder 43 formed in the sleeve 40 limits the movement capability of the contact component 5 in the direction of the opening 30 and thus prevents the contact component from being drawn out together with the printed circuit board 2 if the door - opening sensor has to be exchanged . two wires 44 for the contact - connection of the reed switch 1 extend from the contact component 5 , through the wire - feed portion 34 , to a non - illustrated lead - through , at which they pass out of the wire - feed portion 34 into an insulating - foam layer 13 , which encloses the outer sides of the plug - in bushing 32 . the lead - through is formed by one or two cutouts in a side wall of the wire - feed portion 34 which are adjacent to a rear wall 31 , which is separate from the rest of the wire - feed portion 34 . the door - opening sensor according to the invention is installed , in the first instance , by the flange 35 of the plug - in bushing 32 being adhesively bonded to the inside of the wall 4 , enclosing the opening 30 . at this point in time , it is possible for the contact component 5 already to be provided with connection wires and to be latched in the sleeve 40 and for the rear wall 31 to be fitted on the wire - feed portion 34 ; however , it is also possible for the contact component 5 and the rear wall 31 to be fitted only when the plug - in bushing 32 has been installed on the wall 4 . the rear wall 31 secures the wire - feed portion 34 against the penetration of the foam 13 when the door - opening sensor is encapsulated by the foam . once the plug - in bushing 32 has been installed on the wall 4 , the housing 3 can be introduced into the plug - in portion 33 through the opening 30 . fig6 and 7 show , once again in sections taken along two planes which are perpendicular to one another , and correspond to the planes ii — ii and iii — iii , the door - opening sensor installed on the wall 4 of the refrigerator . the clips 14 , which are pressed together when the housing 3 is pushed in to the opening 30 , have returned to their original configuration , with the result that the housing 3 is fixed on the wall 4 by clamping between the collar 8 and the clips 14 . fig6 shows a sealing ring 9 clamped in - between the collar 8 and the wall 4 . the sealing ring may be provided as required if there is a high risk of moisture penetrating into the plug - in portion 33 , e . g . because the region of the wall 4 in which the opening 30 is located may be subjected to wetting by defrosting water forming in the interior of the refrigerator . in order to exchange the door - opening sensor in the case of malfunctioning , it is sufficient for the front region of the housing 3 , this region projecting beyond the outer surface of the wall 4 , to be gripped , e . g . using pliers , and drawn out of the opening 30 . it is then possible , by virtue of the arms 20 being bent , for the printed circuit board 2 to be removed from the housing 3 and exchanged . all that is then required is for the housing 3 to be pushed into the opening 30 again . | 7 |
the controlling agent of the present invention comprises , as an active ingredient , a compound represented by the following formula ( 1 ) and having pyrazole bonded to the 4 - position of the piperidine ring via an oxygen or sulfur atom . wherein r 1 is a halogen atom , a c 1 - 4 haloalkyl group , a cyano group , a nitro group , or a c 1 - 4 alkoxycarbonyl group ; r 2 , r 3 , r 4 , r 5 , r 6 , r 7 , r 8 , and r 9 are each a hydrogen atom or a c 1 - 4 alkyl group ; each pair of r 2 and r 8 , and r 4 and r 6 , may join to form a c 1 - 4 alkylene group ; r 10 is a hydrogen atom ; a c 1 - 20 alkyl group ; a c 3 - 8 cycloalkyl group ; a c 2 - 6 alkenyl group ; a c 2 - 6 alkynyl group ; a c 1 - 6 haloalkyl group ; a c 2 - 6 haloalkenyl group ; a c 1 - 6 alkylcarbonyl group ; a c 1 - 6 alkoxycarbonyl group ; a benzoyl group optionally substituted on the phenyl ring with 1 to 5 halogen atoms ; a phenyl group optionally substituted on the phenyl ring with one or more substituents each independently selected from the group consisting of halogen , c 1 - 4 alkyl , and c 1 - 4 haloalkyl ; a heterocyclic group optionally substituted on the heterocyclic ring with one or more substituents each independently selected from the group consisting of halogen , c 1 - 4 alkyl , c 1 - 4 haloalkyl , and optionally substituted heterocyclic groups ; or a c 1 - 4 alkyl group optionally substituted with one or more substituents each independently selected from the group consisting of optionally halogen - substituted c 3 - 8 cycloalkyl , cyano , nitro , formyl , c 1 - 6 alkoxy , c 1 - 4 haloalkoxy , benzyloxy , phenoxy , — con ( r 12 )( r 13 ), phenyl optionally substituted on the phenyl ring with one or more halogen atoms , and heterocyclic groups optionally substituted on the heterocyclic ring with one or more c 1 - 4 alkyl groups ; wherein r 12 and r 13 are each a c 1 - 4 alkyl group , or r 12 and r 13 may join to form a c 2 - 7 alkylene group ; r 11 is a halogen atom ; a c 1 - 6 alkyl group ; a c 1 - 4 haloalkyl group ; a c 1 - 4 hydroxyalkyl group ; a c 1 - 4 alkoxycarbonyl group ; a c 1 - 4 alkylcarbonyl group ; a mono or di ( c 1 - 4 alkyl ) aminocarbonyl group ; a nitro group ; a cyano group ; a formyl group ; — c ( r 14 )═ no ( r 15 ); a phenyl group optionally substituted on the phenyl ring with one or more substituents each independently selected from the group consisting of halogen , c 1 - 6 alkyl , c 1 - 4 haloalkyl , c 1 - 6 alkoxy , c 1 - 4 haloalkoxy , c 1 - 4 alkylthio , cyano , and nitro ; or a heterocyclic group optionally substituted on the heterocyclic ring with one or more substituents each independently selected from the group consisting of halogen , c 1 - 4 alkyl , and c 1 - 4 haloalkyl ; wherein r 14 is a hydrogen atom or a c 1 - 4 alkyl group , and r 15 is a hydrogen atom , a c 1 - 4 alkyl group , or a benzyl group ; x is an oxygen atom , a sulfur atom , or — so 2 —; m is an integer of 1 to 4 , and when m is an integer of 2 or more , the r 1 &# 39 ; s , the number of which is represented by m , may be the same or different ; and n is an integer of 1 or 2 , and when n is 2 , the two r 11 &# 39 ; s may be the same or different . examples of the halogen atom include fluorine , chlorine , bromine , and iodine atoms . examples of the c 1 - 4 haloalkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms and substituted with 1 to 9 , preferably 1 to 5 , halogen atoms . specific examples thereof include fluoromethyl , chloromethyl , bromomethyl , iodomethyl , difluoromethyl , trifluoromethyl , chlorodifluoromethyl , bromodifluoromethyl , dichlorofluoromethyl , 1 - fluoroethyl , 2 - fluoroethyl , 2 - chloroethyl , 2 - bromoethyl , 2 - iodoethyl , 2 , 2 , 2 - trifluoroethyl , 2 , 2 , 2 - trichloroethyl , pentafluoroethyl , 1 - fluoroisopropyl , 3 - fluoropropyl , 3 - chloropropyl , 3 - bromopropyl , 4 - fluorobutyl , 4 - chlorobutyl , 4 , 4 , 4 - trifluorobutyl , and like groups . examples of the c 1 - 4 alkoxycarbonyl group include groups formed by the bonding of a linear or branched alkoxy group having 1 to 4 carbon atoms to a carbonyl group . specific examples thereof include methoxycarbonyl , ethoxycarbonyl , n - propoxycarbonyl , isopropoxycarbonyl , n - butoxycarbonyl , sec - butoxycarbonyl , tert - butoxycarbonyl , and like groups . examples of the c 1 - 4 alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms , such as methyl , ethyl , n - propyl , isopropyl , n - butyl , isobutyl , sec - butyl , and tert - butyl . examples of the c 1 - 4 alkylene group include linear or branched alkylene groups having 1 to 4 carbon atoms , such as methylene , ethylene , trimethylene , tetramethylene , propylene , and ethylethylene . examples of the c 1 - 6 alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms , such as n - pentyl , isopentyl , neopentyl , tert - pentyl , n - hexyl , isohexyl , and 2 - ethyl - n - butyl , in addition to those mentioned as examples of the c 1 - 4 alkyl group . examples of the c 1 - 20 alkyl group include linear or branched alkyl groups having 1 to 20 carbon atoms , such as n - heptyl , n - octyl , n - nonyl , n - decyl , n - undecyl , n - dodecyl , n - tridecyl , n - tetradecyl , n - pentadecyl , n - hexadecyl , n - heptadecyl , n - octadecyl , n - nonadecyl , and n - icosyl , in addition to those mentioned as examples of the c 1 - 4 alkyl group and c 1 - 6 alkyl group . examples of the c 3 - 8 cycloalkyl group include cyclic alkyl groups having 4 to 8 carbon atoms , such as cyclopropyl , cyclobutyl , cyclopentyl , cyclohexyl , cycloheptyl , and cyclooctyl . examples of the c 2 - 6 alkenyl group include linear or branched alkenyl groups containing 2 to 6 carbon atoms and having at least one double bond at any position . specific examples thereof include vinyl , 1 - propenyl , allyl , isopropenyl , 2 - butenyl , 3 - butenyl , 1 - methyl - 2 - propenyl , 1 , 3 - butadienyl , 1 - pentenyl , 2 - pentenyl , 3 - pentenyl , 4 - pentenyl , 1 , 1 - dimethyl - 2 - propenyl , 1 - ethyl - 2 - propenyl , 1 - methyl - 2 - butenyl , 1 - methyl - 3 - butenyl , 1 - hexenyl , 2 - hexenyl , 3 - hexenyl , 4 - hexenyl , 5 - hexenyl , 1 , 1 - dimethyl - 2 - butenyl , 1 , 1 - dimethyl - 3 - butenyl , and like groups . examples of the c 2 - 6 alkynyl group include linear or branched alkynyl groups containing 2 to 6 carbon atoms and having at least one triple bond at any position . specific examples thereof include ethynyl , 2 - propynyl , 1 - methyl - 2 - propynyl , 1 , 1 - dimethyl - 2 - propynyl , 1 - butynyl , 2 - butynyl , 3 - butynyl , 1 - pentynyl , 2 - pentynyl , 3 - pentynyl , 4 - pentynyl , 1 - methyl - 2 - butynyl , 1 - methyl - 3 - butynyl , 1 , 1 - dimethyl - 2 - butynyl , 1 , 1 - dimethyl - 3 - butynyl , 1 - methyl - 3 - pentynyl , 1 - methyl - 4 - pentynyl , and like groups . examples of the c 1 - 6 haloalkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms and substituted with 1 to 13 , preferably 1 to 7 , halogen atoms . specific examples thereof include 5 - chloropentyl , 5 - fluoropentyl , 6 - chlorohexyl , and 6 - fluorohexyl , in addition to those mentioned as examples of the c 1 - 4 haloalkyl group . examples of the c 2 - 6 haloalkenyl group include c 2 - 6 linear or branched alkenyl groups having at least one double bond at any position and substituted with 1 to 13 , preferably 1 to 7 , halogen atoms . specific examples thereof include 2 , 2 - dichlorovinyl , 2 , 2 - dibromovinyl , 3 - chloro - 2 - propenyl , 3 , 3 - difluoro - 2 - allyl , 3 , 3 - dichloro - 2 - allyl , 4 - chloro - 2 - butenyl , 4 , 4 , 4 - trifluoro - 2 - butenyl , 4 , 4 , 4 - trichloro - 3 - butenyl , 5 - chloro - 3 - pentenyl , 6 - fluoro - 2 - hexenyl , and like groups . examples of the heterocyclic group include thienyl , furyl , tetrahydrofuryl , dioxolanyl , dioxanyl , pyrrolyl , pyrrolinyl , pyrrolidinyl , oxazolyl , isoxazolyl , oxazolinyl , oxazolidinyl , isoxazolinyl , triazolyl , isothiazolyl , thiazolinyl , thiazolidinyl , isothiazolinyl , pyrazolyl , pyrazolidinyl , imidazolyl , imidazolinyl , imidazolidinyl , oxadiazolyl , oxadiazolinyl , thiadiazolinyl , triazolyl , triazolinyl , triazolidinyl , tetrazolyl , tetrazolinyl , pyridyl , dihydropyridyl , tetrahydropyridyl , piperidyl , oxazinyl , dihydroxazinyl , morpholino , thiazinyl , dihydrothiazinyl , thiamorpholino , pyridazinyl , dihydropyridazinyl , tetrahydropyridazinyl , hexahydropyridazinyl , oxadiazinyl , dihydrooxadiazinyl , tetrahydrooxadiazinyl , thiadiazolyl , thiadiazinyl , dihydrothiadiazinyl , tetrahydrothiadiazinyl , pyrimidinyl , dihydropyrimidinyl , tetrahydropyrimidinyl , hexahydropyrimidinyl , pyrazinyl , dihydropyrazinyl , tetrahydropyrazinyl , piperazinyl , triazinyl , dihydrotriazinyl , tetrahydrotriazinyl , hexahydrotriazinyl , tetrazinyl , dihydrotetrazinyl , indolyl , indolinyl , isoindolyl , indazolyl , quinazolinyl , dihydroquinazolyl , tetrahydroquinazolyl , carbazolyl , benzoxazolyl , benzoxazolinyl , benzisoxazolyl , benzisoxazolinyl , benzothiazolyl , benzisothiazolyl , benzisothiazolinyl , benzimidazolyl , indazolinyl , quinolinyl , dihydroquinolinyl , tetrahydroquinolinyl , isoquinolinyl , dihydroisoquinolinyl , tetrahydroisoquinolinyl , pyridoindolyl , dihydrobenzoxazinyl , cinnolinyl , dihydrocinnolinyl , tetrahydrocinnolinyl , phthalazinyl , dihydrophthalazinyl , tetrahydrophthalazinyl , quinoxalinyl , dihydroquinoxalinyl , tetrahydroquinoxalinyl , purinyl , dihydrobenzotriazinyl , dihydrobenzotetrazinyl , phenothiazinyl , furanyl , benzofuranyl , benzothienyl , and like groups . these heterocyclic groups include those substituted at any substitutable position with an oxo or thioketone group . these heterocyclic groups further include those optionally substituted at any substitutable position with 1 to 5 ( preferably 1 to 3 ) substituents , such as halogen atoms , c 1 - 4 alkyl groups , c 1 - 4 haloalkyl groups , or substituted heterocyclic groups ( e . g ., 3 - chloropyridin - 2 - yl , 4 - trifluoromethyl - 1 , 3 - thiazol - 2 - yl , and 5 - trifluoromethylpyridin - 2 - yl ). among these heterocyclic rings , thienyl , furyl , tetrahydrofuryl , dioxolanyl , dioxanyl , oxazolyl , isoxazolyl , thiazolyl , pyrazolyl , pyridyl , and piperidyl are preferable . thienyl , tetrahydrofuryl , dioxolanyl , dioxanyl , thiazolyl , and pyridyl are particularly preferable . examples of the optionally halogen - substituted c 3 - 8 cycloalkyl group include cyclic alkyl groups having 3 to 8 carbon atoms , such as the above - mentioned c 3 - 8 cycloalkyl groups that are optionally substituted at any position with one to the maximum substitutable number of ( preferably 1 to 5 , and more preferably 1 to 3 ) halogen atoms . examples of the c 1 - 6 alkoxy group include linear or branched alkoxy groups having 1 to 6 carbon atoms , such as methoxy , ethoxy , n - propoxy , isopropoxy , cyclopropyloxy , n - butoxy , sec - butoxy , tert - butoxy , n - pentyloxy , isopentyloxy , neopentyloxy , tert - pentyloxy , n - hexyloxy , and isohexyloxy . examples of the c 1 - 4 haloalkoxy group include linear or branched alkoxy groups having 1 to 4 carbon atoms and substituted with 1 to 9 , preferably 1 to 5 , halogen atoms . specific examples thereof include fluoromethoxy , chloromethoxy , bromomethoxy , iodomethoxy , dichloromethoxy , trichloromethoxy , difluoromethoxy , trifluoromethoxy , chlorodifluoromethoxy , bromodifluoromethoxy , dichlorofluoromethoxy , 1 - fluoroethoxy , 2 - fluoroethoxy , 2 - chloroethoxy , 2 - bromoethoxy , 2 - iodoethoxy , 2 , 2 , 2 - trifluoroethoxy , 2 , 2 , 2 - trichloroethoxy , pentafluoroethoxy , 1 - fluoroisopropoxy , 3 - fluoropropoxy , 3 - chloropropoxy , 3 - bromopropoxy , 4 - fluorobutoxy , 4 - chlorobutoxy , and like groups . examples of the c 1 - 4 alkylthio group include linear or branched alkylthio groups having 1 to 4 carbon atoms , such as methylthio , ethylthio , n - propylthio , isopropylthio , and tert - butylthio . examples of the c 2 - 7 alkylene group include ethylene , trimethylene , tetramethylene , pentamethylene , hexamethylene , heptamethylene , and the like . these alkylene groups may contain an optionally substituted nitrogen , oxygen , or sulfur atom , or a phenylene group . examples of such alkylene groups include — ch 2 nhch 2 —, — ch 2 nhch 2 ch 2 —, — ch 2 nhnhch 2 —, — ch 2 ch 2 nhch 2 ch 2 —, — ch 2 nhnhch 2 ch 2 —, — ch 2 nhch 2 nhch 2 —, — ch 2 ch 2 ch 2 nhch 2 ch 2 ch 2 —, — ch 2 och 2 ch 2 —, — ch 2 ch 2 och 2 ch 2 —, — ch 2 sch 2 ch 2 —, — ch 2 ch 2 sch 2 ch 2 —, and like groups . these alkylene groups may be substituted at any position or on the nitrogen atom . examples of such substituents include c 1 - 4 alkyl , c 1 - 6 alkoxycarbonyl , hydroxy , and like groups . examples of the c 1 - 4 alkylcarbonyl group include linear or branched alkylcarbonyl groups having 1 to 4 carbon atoms , such as methylcarbonyl ( acetyl ), ethylcarbonyl ( propionyl ), n - propylcarbonyl ( butyryl ), isopropylcarbonyl ( isobutyryl ), n - butylcarbonyl ( valeryl ), isobutylcarbonyl ( isovaleryl ), sec - butylcarbonyl , and tert - butylcarbonyl . examples of the mono - or di ( c 1 - 4 alkyl ) aminocarbonyl group include alkylaminocarbonyl groups in which nitrogen atoms of the aminocarbonyl groups are mono - or di - substituted with linear or branched alkyl groups having 1 to 4 carbon atoms , such as methylaminocarbonyl , dimethylaminocarbonyl , ethylaminocarbonyl , methylethylaminocarbonyl , diethylaminocarbonyl , n - propylaminocarbonyl , isopropylaminocarbonyl , n - butylaminocarbonyl , sec - butylaminocarbonyl , tert - butylaminocarbonyl , and dibutylaminocarbonyl . examples of the hydroxyalkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms and substituted with 1 or 2 hydroxy groups , such as hydroxymethyl , 2 - hydroxyethyl , 1 - hydroxy - 2 - propyl , 3 - hydroxypropyl , 4 - hydroxybutyl , and 3 , 4 - dihydroxybutyl . the n - pyridylpiperidine compound represented by formula ( 1 ) includes n - pyridylpiperidine compounds represented by the following formulas ( 1a ), ( 1b ), and ( 1c ): wherein r 1 , r 2 , r 3 , r 4 , r 5 , r 6 , r 7 , r 8 , r 9 , r 10 , r 11 , x , m , and n are as defined above . the n - pyridylpiperidine compound of formula ( 1 ), wherein r 2 and r 8 join to form a c 1 - 4 alkylene group may exist as , for example , cis - trans isomers represented by the following formulas ( 1d ) and ( 1e ). the n - pyridylpiperidine compound of the invention represented by formula ( 1 ) includes such isomers . wherein r 1 , r 3 , r 4 , r 5 , r 6 , r 7 , r 9 , r 10 , r 11 , x , m , and n are as defined above , and y is a c 1 - 4 alkylene group . the n - pyridylpiperidine compound of formula ( 1 ), wherein r 4 and r 6 join to form a c 1 - 4 alkylene group may exist as , for example , cis - trans isomers represented by the following formulas ( 1f ) and ( 1g ). the n - pyridylpiperidine compound of the invention represented by formula ( 1 ) includes such isomers . wherein r 1 , r 2 , r 3 , r 5 , r 7 , r 8 , r 9 , r 10 , r 11 , x , m , and n are as defined above . the n - pyridylpiperidine compound of formula ( 1 ), wherein at least one of r 2 , r 3 , r 4 , r 5 , r 6 , r 7 , r 8 , and r 9 is a c 1 - 4 alkyl group may exist as stereoisomers in relation to the 4 - position of the piperidine ring . the n - pyridylpiperidine compound of the invention represented by formula ( 1 ) includes such isomers . the n - pyridylpiperidine compound represented by formula ( 1 ) may exist as n - oxides formed by oxidation of the nitrogen atom of the pyridine ring or piperidine ring of the n - pyridylpiperidine compound . the n - pyridylpiperidine compound of the invention represented by formula ( 1 ) includes these n - oxides . in this specification , for convenience , n - oxide formed by oxidation of the nitrogen atom on the pyridine ring is called n - pyridyl oxide , whereas n - oxide formed by oxidation of the nitrogen atom on the piperidine ring is called n - piperidyl oxide . the n - pyridylpiperidine compound represented by formula ( 1 ) has basic properties , and therefore can form salts with , for example , inorganic acids , such as hydrochloric acid , sulfuric acid , and phosphoric acid ; organic acids , such as formic acid , acetic acid , fumaric acid , oxalic acid , and sulfonic acid ; and acid salts , such as sodium hydrogen sulfate and potassium hydrogen sulfate . the n - pyridylpiperidine compound of the invention represented by formula ( 1 ) includes these salts . among the n - pyridylpiperidine compounds represented by formula ( 1 ), those wherein r 1 is a c 1 - 4 haloalkyl group , a cyano group , or a nitro group are preferable , and those wherein r 1 is a c 1 - 4 haloalkyl group are more preferable . specifically , those wherein r 1 is a trifluoromethyl group are particularly preferable . preferable among the n - pyridylpiperidine compounds represented by formula ( 1 ) are those wherein r 10 is a c 1 - 20 alkyl group ; a c 2 - 6 alkenyl group ; a c 1 - 6 haloalkyl group ; a c 1 - 6 alkylcarbonyl group ; a phenyl group ( optionally substituted on the phenyl ring with one or more , and preferably one or two substituents each independently selected from the group consisting of halogen , c 1 - 4 alkyl , and c 1 - 4 haloalkyl ); a heterocyclic group ( optionally substituted on the heterocyclic ring with one or more , and preferably one or two substituents each independently selected from the group consisting of c 1 - 4 alkyl and c 1 - 4 haloalkyl ); or a c 1 - 4 alkyl group substituted with one or more , and preferably one or two substituents each independently selected from the group consisting of c 1 - 6 alkoxy , phenyl ( optionally substituted on the phenyl ring with one or more , and preferably one or two halogen atoms ), and heterocyclic groups . more preferable are those wherein r 10 is a c 1 - 6 alkyl group ; a c 2 - 6 alkenyl group ; a phenyl group ( optionally substituted on the phenyl ring with one or more , and preferably one or two halogen atoms or c 1 - 4 alkyl groups ); a pyridyl group ( optionally substituted on the pyridine ring with one or more , and preferably one or two c 1 - 4 alkyl groups ); or a c 1 - 4 alkyl group substituted with one or two substituents each independently selected from the group consisting of c 1 - 6 alkoxy , phenyl ( optionally substituted on the phenyl ring with one or more , and preferably one or two halogen atoms ), and 1 , 3 - dioxolan - 2 - yl . particularly preferable are the compounds wherein r 10 is a c 1 - 6 alkyl group , a pyridyl group , a 2 , 2 - dimethoxyethyl group , or a ( 1 , 3 - dioxolan - 2 - yl ) methyl group . preferable among the n - pyridylpiperidine compounds of the invention represented by formula ( 1 ) are those wherein r 11 is a c 1 - 6 alkyl group , a c 1 - 4 haloalkyl group , a phenyl group ( optionally substituted on the phenyl ring with one or more , and preferably one to three substituents each independently selected from the group consisting of halogen , c 1 - 4 alkyl , nitro , c 1 - 4 haloalkyl , and c 1 - 4 haloalkoxy ), or a heterocyclic group ( optionally substituted on the heterocyclic ring with one or more , and preferably one or two halogen atoms ). more preferable are those wherein r 11 is a trifluoromethyl group or a phenyl group ( optionally substituted on the phenyl ring with one to three halogen atoms ). preferable among the n - pyridylpiperidine compounds of the invention represented by formula ( 1 ) are those wherein x is an oxygen atom . more preferable are compounds of formula ( 1 ) wherein r 1 is a c 1 - 4 haloalkyl group , a cyano group , or a nitro group ; r 10 is a c 1 - 20 alkyl group ; a c 2 - 6 alkenyl group ; a c 1 - 6 haloalkyl group ; a c 1 - 6 alkylcarbonyl group ; a phenyl group ( optionally substituted on the phenyl ring with one or more , and preferably one or two substituents each independently selected from the group consisting of halogen , c 1 - 4 alkyl , and c 1 - 4 haloalkyl ); a heterocyclic group ( optionally substituted on the heterocyclic ring with one or more , and preferably one or two substituents each independently selected from the group consisting of c 1 - 4 alkyl and c 1 - 4 haloalkyl ); or a c 1 - 4 alkyl group substituted with one or more , and preferably one or two substituents each independently selected from the group consisting of c 1 - 6 alkoxy , phenyl ( optionally substituted on the phenyl ring with one or more , and preferably one or two halogen atoms ), and heterocyclic groups ; r 11 is a c 1 - 6 alkyl group , a c 1 - 4 haloalkyl group , a phenyl group ( optionally substituted on the phenyl ring with one or more , and preferably one to three substituents each independently selected from the group consisting of halogen , c 1 - 4 alkyl , nitro , c 1 - 4 haloalkyl , and c 1 - 4 haloalkoxy ), or a heterocyclic group ( optionally substituted on the heterocyclic ring with one or more , and preferably one or two halogen atoms ); and x is an oxygen atom . among these preferable compounds , particularly preferable are those wherein r 1 is a c 1 - 4 haloalkyl group ; r 10 is a c 1 - 6 alkyl group ; a c 2 - 6 alkenyl group ; a phenyl group ( optionally substituted on the phenyl ring with one or more , and preferably one or two halogen atoms or c 1 - 4 alkyl groups ); a pyridyl group ( optionally substituted on the pyridine ring with one or more c 1 - 4 alkyl groups ); or a c 1 - 4 alkyl group substituted with one or two substituents each independently selected from the group consisting of c 1 - 4 alkoxy , phenyl ( optionally substituted on the phenyl ring with one or more , and preferably one or two halogen atoms ), and 1 , 3 - dioxolan - 2 - yl ; r 11 is a trifluoromethyl group or a phenyl group ( optionally substituted on the phenyl ring with one to three halogen atoms ); and x is an oxygen atom . among the n - pyridylpiperidine compounds of the invention represented by formula ( 1 ), those represented by formulas ( 1a ), ( 1b ), and ( 1f ) are preferable , and those represented by formulas ( 1a ) and ( 1f ) are more preferable . wherein r 1 , r 2 , r 3 , r 5 , r 7 , r 8 , r 9 , r 10 , r 11 , x , m , and n are as defined above . among the n - pyridylpiperidine compounds of the invention represented by formulas ( 1a ) and ( 1f ), those wherein r 1 is a c 1 - 4 haloalkyl group or a cyano group are preferable , and those wherein r 1 is a c 1 - 4 haloalkyl group are more preferable . specifically , the compounds wherein r 1 is a trifluoromethyl group are particularly preferable . among the n - pyridylpiperidine compounds of the invention represented by formulas ( 1a ) and ( 1f ), preferable are those wherein r 10 is a c 1 - 20 alkyl group ; a c 2 - 6 alkenyl group ; a c 1 - 6 haloalkyl group ; a c 1 - 6 alkylcarbonyl group ; a phenyl group ( optionally substituted on the phenyl ring with one or more , and preferably one or two substituents each independently selected from the group consisting of halogen , c 1 - 4 alkyl , and c 1 - 4 haloalkyl ); a heterocyclic group ( optionally substituted on the heterocyclic ring with one or more , and preferably one or two substituents each independently selected from the group consisting of c 1 - 4 alkyl and c 1 - 4 haloalkyl ); or a c 1 - 4 alkyl group substituted with one or more , and preferably one or two substituents each independently selected from the group consisting of c 1 - 6 alkoxy , phenyl ( optionally substituted on the phenyl ring with one or more , and preferably one or two halogen atoms ), and heterocyclic groups . more preferable are those wherein r 10 is a c 1 - 6 alkyl group ; a c 2 - 6 alkenyl group ; a phenyl group ( optionally substituted on the phenyl ring with one or more , and preferably one or two halogen atoms or c 1 - 4 alkyl groups ); a pyridyl group ( optionally substituted on the pyridine ring with one or more , and preferably one or two c 1 - 4 alkyl groups ); or a c 1 - 4 alkyl group substituted with one or two substituents each independently selected from the group consisting of c 1 - 6 alkoxy , phenyl ( optionally substituted on the phenyl ring with one or more , and preferably one or two halogen atoms ), and 1 , 3 - dioxolan - 2 - yl . particularly preferable are compounds wherein r 10 is a c 1 - 6 alkyl group , a pyridyl group , a 2 , 2 - dimethoxyethyl group , or a ( 1 , 3 - dioxolan - 2 - yl ) methyl . among the n - pyridylpiperidine compounds of the invention represented by formulas ( 1a ) and ( 1f ), preferable are those wherein r 11 is a c 1 - 6 alkyl group , a c 1 - 4 haloalkyl group , a phenyl group ( optionally substituted on the phenyl ring with one or more , and preferably one to three substituents each independently selected from the group consisting of halogen , c 1 - 4 alkyl , nitro , c 1 - 4 haloalkyl , and c 1 - 4 haloalkoxy ), or a heterocyclic group ( optionally substituted on the heterocyclic ring with one or more , and preferably one or two halogen atoms ). more preferable are compounds wherein r 11 is a trifluoromethyl group or a phenyl group ( optionally substituted on the phenyl ring with one to three halogen atoms ). among the n - pyridylpiperidine compounds of the invention represented by formulas ( 1a ) and ( 1f ), those wherein x is an oxygen atom are preferable . more preferable are compounds of formulas ( 1a ) and ( 1f ) wherein r 1 is a c 1 - 4 haloalkyl group or a cyano group ; r 10 is a c 1 - 20 alkyl - group ; a c 2 - 6 alkenyl group ; a c 1 - 6 haloalkyl group ; a c 1 - 6 alkylcarbonyl group ; a phenyl group ( optionally substituted on the phenyl ring with one or more , and preferably one or two substituents each independently selected from the group consisting of halogen , c 1 - 4 alkyl , and c 1 - 4 haloalkyl ); a heterocyclic group ( optionally substituted on the heterocyclic ring with one or more , and preferably one or two substituents each independently selected from the group consisting of c 1 - 4 alkyl and c 1 - 4 haloalkyl ); or a c 1 - 4 alkyl group substituted with one or more , and preferably one or two substituents each independently selected from the group consisting of c 1 - 6 alkoxy , phenyl ( optionally substituted on the phenyl ring with one or more , and preferably one or two halogen atoms ), and heterocyclic groups ; r 11 is a c 1 - 6 alkyl group , a c 1 - 4 haloalkyl group , a phenyl group ( optionally substituted on the phenyl ring with one or more , and preferably 1 to 3 substituents each independently selected from the group consisting of halogen , c 1 - 4 alkyl , nitro , c 1 - 4 haloalkyl , and c 1 - 4 haloalkoxy ), or a heterocyclic group ( optionally substituted on the heterocyclic ring with one or more , and preferably one or two halogen atoms ); and x is an oxygen atom . among these preferable compounds , particularly preferable are those wherein r 1 is a c 1 - 4 haloalkyl group , r 10 is a c 1 - 6 alkyl group ; a c 2 - 6 alkenyl group ; a phenyl group ( optionally substituted on the phenyl ring with one or more , and preferably one or two halogen atoms or c 1 - 4 alkyl groups ); a pyridyl group ( optionally substituted on the pyridine ring with one or more , and preferably one or two c 1 - 4 alkyl groups ); or a c 1 - 4 alkyl group substituted with one or two substituents each independently selected from the group consisting of c 1 - 6 alkoxy , phenyl ( optionally substituted on the phenyl ring with one or more , and preferably one or two halogen atoms ), and 1 , 3 - dioxolan - 2 - yl ; r 11 is a trifluoromethyl group or a phenyl group ( optionally substituted on the phenyl ring with one to three halogen atoms ); and x is an oxygen atom . among the n - pyridylpiperidine compounds of the invention represented by formula ( 1a ), preferable are those wherein any one of r 4 , r 5 , r 6 , and r 7 is a c 1 - 4 alkyl group that is positioned trans to the x on the 4 - position of the piperidine ring . particularly preferable are compounds wherein the c 1 - 4 alkyl group is a methyl group . the n - pyridylpiperidine compound represented by formula ( 1 ) can be produced , for example , by the method described in wo 2008 / 026658 . the animal ectoparasite - controlling agent of the present invention characteristically comprises the n - pyridylpiperidine compound represented by formula ( 1 ) as an active ingredient . the controlling agent of the present invention is effective against fleas , mites , lice ( cattle lice , horse lice , sheep lice , linognathus vituli , head lice , etc . ), biting lice ( trichodectes canis , etc . ), and the like that live in the body surface of host animals . in particular , the controlling agent of the present invention has the beneficial effect of preventing mites . in addition , the controlling agent of the present invention is effective against blood - sucking dipteran insects , such as flies , biting midges , black flies , and stable flies . fleas refer to ectoparasitic wingless insects belonging to siphonaptera , specifically fleas belonging to pulicidae , ceratophyllus , or the like . examples of fleas belonging to pulicidae include ctenocephalides canis , ctenocephalides felis , pulex irritans , echidnophaga gallinacea , xenopsylla cheopis , monopsyllus anisus , nosopsyllus fasciatus , etc . mites are , for example , ticks . examples thereof include haemaphysalis longicornis , haemaphysalis japonica , dermacentor reticulatus , dermacentor taiwanesis , haemaphysalis flava , ixodes ovatus , ixodes persulcatus , boophilus microplus , etc . examples of host animals for which the controlling agent of the present invention is effective include pets , such as dogs , cats , mice , rats , hamsters , guinea pigs , squirrels , rabbits , ferrets , and birds ( e . g ., pigeons , parrots , myna birds , paddy birds , parakeets , lovebirds , and canaries ); livestock , such as cattle , horses , pigs , and sheep ; poultry , such as ducks and chicken ; and the like . ectoparasites are parasitic and live on the back , infra - axillary region , lower abdominal region , inner thigh region , etc ., of these host animals . the controlling agent of the present invention may be used as it is , without the addition of any other components . alternatively , the controlling agent can be mixed with various suitable carriers in the form of liquids , solids , or gases , optionally followed by addition of surfactants and other auxiliary materials for preparation of formulations , and then formulated into granules , fine granules , tablets , powders , capsules , premix formulations , solutions , emulsions , and other dosage forms . the amount of the compound of the present invention as an active ingredient in such formulations can be suitably selected from a wide range , depending on various conditions including the type of formulation , place of application , etc . such formulations usually contain the compound in an amount of about 0 . 01 to 95 wt . %, and preferably about 0 . 1 to 50 wt . %. the aforementioned suitable carriers may be those generally used in animal feed drugs . examples thereof are lactose , sucrose , glucose , starch , wheat flour , corn flour , soybean oil cake , defatted rice bran , calcium carbonate , and other commercially available feed raw materials . examples of the surfactant include anionic surfactants ( e . g ., alkali stearate , sodium abietate , alkyl sulfate , sodium dodecylbenzenesulfonate , sodium dioctylsulfosuccinate , and fatty acids ), cationic surfactants ( e . g ., water - soluble quaternary ammonium ), nonionic surfactants ( optionally selected from polyoxyethylenated sorbitan esters , polyoxyethylenated alkyl ethers , polyethylene glycol stearate , polyoxyethylenated derivatives of castor oil , polyglycerol esters , polyoxyethylenated fatty alcohols , polyoxyethylenated fatty acids , copolymers of ethylene oxide and propylene oxide , etc . ), amphoteric surfactants ( e . g ., lauryl - substituted betaine compounds ), and the like . examples of auxiliary materials for preparation of formulations include fixing agents , dispersing agents , thickeners , preservatives , anti - freezing agents , stabilizers , adjuvants , and the like . examples of fixing agents and dispersing agents include casein , gelatin , polysaccharides ( e . g ., starch , gum arabic , cellulose derivatives , and alginic acid ), lignin derivatives , bentonite , sugars , water - soluble synthetic polymers ( e . g ., polyvinyl alcohol , polyvinylpyrrolidone , and polyacrylic acids ), and the like . examples of thickeners include water - soluble polymer compounds , such as xanthan gum and carboxymethyl cellulose , high - purity bentonite , white carbon , and the like . examples of preservatives include sodium benzoate , p - hydroxybenzoic acid ester , and the like . examples of anti - freezing agents include ethylene glycol , diethylene glycol , and the like . examples of stabilizers include pap ( acidic isopropyl phosphate ), bht ( 2 , 6 - di - tert - butyl - 4 - methylphenol ), bha ( a mixture of 2 - tert - butyl - 4 - methoxyphenol and 3 - tert - butyl - 4 - methoxyphenol ), vegetable oils , mineral oils , surfactants , fatty acids and esters thereof , and the like . examples of adjuvants include soybean oil , corn oil , and like vegetable oils , machine oil , glycerin , polyethylene glycol , and the like . such formulations may be colored with an organic or inorganic dye . the thus - obtained formulations can be used as they are or after being diluted with water or the like . however , fine granules , granules , etc ., are generally used as they are , without being diluted . when emulsions , wettable powders , flowable formulations , etc ., are used after being diluted with water or the like , the active ingredient concentration is generally 0 . 0001 to 50 wt . %, and preferably about 0 . 001 to 10 wt . %. in addition , the controlling agent of the present invention may be previously mixed with other agents , such as insecticides , nematocides , acaricides , fungicides , antifungals , antibacterial agents , anti - inflammatory agents , antiprotozoan drugs , synergists ( e . g ., piperonyl butoxide ), or the like , and then formulated . alternatively , the formulations of the present invention and other such agents may be used in combination when used . when the controlling agent of the present invention is mixed with other animal drugs , the proportion of n - pyridylpiperidine compound and other animal drugs is not particularly limited , but is generally 100 : 0 to 1 : 99 ( weight ratio ). although the dose of the controlling agent of the present invention varies depending on the administration method , the purpose of administration , disease symptoms , etc ., the controlling agent of the present invention may generally be administered to a host animal in a dose of 0 . 01 mg or more and 100 g or less , and preferably 0 . 1 mg or more and 10 g or less , per kg of body weight of the host animal . the controlling agent of the present invention is orally or parenterally administered to a host . when orally administered , for example , the controlling agent of the present invention is mixed with feed of a host animal , and then administered together with the feed ; or tablets , solutions , capsules , wafers , biscuits , minced meat , etc ., containing the controlling agent of the present invention are administered . when parenterally administered , for example , the controlling agent of the present invention is formed into suitable formulations , and then incorporated into the body by intravenous infusion administration , intramuscular administration , intracutaneous administration , subcutaneous administration , spot - on treatment , pore - on treatment , or the like ; or resin pieces , etc ., containing the controlling agent of the present invention are implanted under the skin of a host animal . the present invention is described in more detail below with reference to test examples of the controlling agent of the present invention ; however , the present invention is not limited thereto . test example : mortality of ixodid ticks by filter paper clipping method among the compounds disclosed in wo 2008 / 026658 , compound nos . 1a - 16 , 1a - 17 , 1a - 62 , 1a - 75 , 1a - 76 , 1a - 174 , 1a - 201 , 1a - 208 , 1a - 234 , 1a - 251 , 1a - 262 , 1a - 267 , 1a - 268 , 1a - 274 , 1a - 302 , 1f - 38 , and 1f - 39 were used as test compounds 1 to 17 . acetone was added to each of test compounds 1 to 17 so that the concentration was 0 . 5 mg / ml , thereby preparing solutions . although test compound 15 , which was not dissolved in acetone , formed a heterogeneous suspension , the suspension was used as it was . each of the above prepared solutions was added dropwise in an amount of 1 ml to a square filter paper ( 5 × 10 cm ; area : 50 cm 2 ), and dried on aluminum foil at room temperature for 24 hours . then , each filter paper was folded double on the long side , and both sides were secured with bulldog clips into a bag shape . about 20 ixodid ticks were placed in the bag - like filter paper , and the opening was sealed with a bulldog clip . after 72 hours , the number of dead ticks was calculated . thereafter , the surviving ticks were killed in a freezer , and the total number of ticks was calculated . as a result , a mortality of 70 % or more was achieved by all of test compounds 1 to 17 . | 0 |
a solid - state relay 100 according to an embodiment of the present invention is illustrated in fig1 . the solid - state relay 100 includes : a light emitting diode 101 : a light receiving element ( phototriac ) 102 : a driving triac 103 ; a resistance 104 : and a normally - on driving element 105 coupled in series to the driving triac 103 . now , a case will be considered in which , an inductive load 106 which gives rise to a load current whose phase is shifted substantially by 90 ° with respect to a supply voltage is coupled to the solid - state relay 100 , the load being driven with an electric power which is half of that required in a full - phase on - driving mode , first , phase control which may be performed in a conventional solid - state relay 900 ( fig9 ) will be described . as illustrated in fig8 a , input currents are applied to a light emitting element 902 at respective times t 1 , t 2 , t 3 and t 4 approximately corresponding to 90 ° phase points of a current waveform , so as to activate the solid - state relay 900 . a load current li 1 approximately has its peak values at times t 1 , t 2 , t 3 and t 4 . accordingly , a substantial inrush current may occur at each of these times , thereby adversely affecting the device . moreover , a supply voltage dv 1 approximately has its peak values at the off - points , i . e ., at t 81 , t 82 , t 83 and t 84 , so that a commutation failure may be caused in the solid - state relay 900 due to its ( dv / dt ) c characteristics . next , referring to fig8 b , an operation of the solid - state relay 100 ( fig1 ) according to an embodiment of the present invention will be described , in which the load 106 is activated with a half amount of electric power in comparison to that of a full - phase on - driving mode . it is assumed that input current pulses i 5 , i 6 , i 7 and i 8 for turning on the driving triac 103 are applied to the light emitting diode 101 at times t 5 , t 6 , t 7 and t 8 , respectively , approximately corresponding to 0 ° phase points of the load current phase and that trigger pulses tg 9 , tg 10 tg 11 and tg 12 for turning off the normally - on driving element 105 are applied to the normally - on driving element 105 at times t 9 , t 10 , t 11 and t 12 , respectively , approximately corresponding to 90 ° phase points . under such conditions , an inrush current can be prevented since the phase of a load current l 12 in the on - states , i . e ., at times t 5 , t 6 , t 7 and t 8 . is approximately at 0 °. moreover , the phase of a supply voltage dv 2 is approximately at 0 ° in the off - states , i . e ., at times t 9 , t 10 , t 11 and t 12 . thus , no steep overvoltage is applied to the device , thereby preventing commutation failures . therefore , since the solid - state relay 100 is capable of turning itself off with a predetermined timing , it is possible to achieve a stable operation of the load 106 . fig2 illustrates a structure of a solid - state relay 200 according to an embodiment of the present invention in which a normally - on driving element 105 a includes a mosfet 205 . like reference numerals to those of the solid - state relay 100 according to the previous embodiment of the present invention discussed with reference to fig1 denote like elements in the present embodiment , and will not be further described below . the normally - on driving element 105 a , which is coupled in series to a driving triac 103 , includes a light emitting diode 101 a and the normally - on mosfet 205 . when the solid - state relay 200 is turned on , an input current is applied to a light emitting diode 101 associated with a light receiving element 102 / driving triac 103 so as to activate the driving triac 103 . when the solid - state relay 200 is turned off afterward at a predetermined time , an input current is applied to the light emitting diode 101 a associated with the mosfet 205 so as to turn off the normally - on mosfet 205 . therefore , it is possible to prescribe the timing for turning off , as well as turning on , the solid - state relay 200 . fig3 illustrates a structure of a solid - state relay 300 according to an embodiment of the present invention in which a normally - on driving element 105 b is a mechanical relay . like reference numerals to those of the solid - state relay 100 according to an embodiment of the present invention previously discussed with regard to fig1 denote like elements , and will not further be described below . the normally - on driving element 105 b coupled in series to a driving triac 103 includes a normally - on mechanical relay 305 . when the solid - state relay 300 is turned on , an input current is applied to a light emitting diode 101 so as to activate the driving triac 103 . when the solid - state relay 300 is turned off afterward at a predetermined time , a trigger pulse is applied to the normally - on mechanical relay 305 , that is , an input current is applied to a coil 306 so as to turn off the normally - on mechanical relay 305 . therefore , it is possible to prescribe the timing for turning off , as well as turning on , the solid - state relay 300 . fig4 illustrates a structure of a solid - state relay 400 according to an embodiment of the present invention in which a temperature detecting circuit 406 is provided associated with a light emitting diode 101 a which controls a normally - on mosfet 205 . like reference numerals to those of the solid - state relay 100 according to the previous embodiment of the present invention discussed with regard to fig1 denote like elements in the present embodiments , and will not be further described below . a normally - on driving element 105 a , which is coupled in series to a driving triac 103 , includes the light emitting diode 101 a and the normally - on mosfet 205 . the light emitting diode 101 a controls the mosfet 205 . the solid - state relay 400 further includes the temperature detecting circuit 406 coupled in series to the light emitting diode 101 a . by preconditioning the solid - state relay 400 so that an input current will flow into the light emitting diode 101 a ( which controls the normally - on , mosfet 205 ) when an abnormality occurs , e . g ., an ambient temperature rises to an extremely high level , the normally - on mosfet 205 is turned off , thereby compulsorily turning off the solid - state relay 400 . accordingly , it is possible to prevent an abnormal operation of the solid - state relay 400 at high temperatures , for example . fig5 illustrates a structure of a solid - state relay 500 according to an embodiment of the present invention , in which a resistance element 507 having a negative temperature coefficient is coupled in series to a light emitting diode 101 a . a normally - on driving element 105 a coupled in series to a driving triac 103 includes the light emitting diode 101 a and a normally - on mosfet 205 . the light emitting diode 101 a controls the normally - on mosfet 205 . the solid - state relay 500 further includes the resistance element 507 coupled in series to the light emitting diode 101 a . the resistance element 507 has a negative temperature coefficient . by preconditioning the solid - state relay 500 so that an input current sufficient to turn off the normally - on mosfet 205 will flow into the light emitting diode 101 a ( which controls the normally - on mosfet 205 ) by reducing a resistance value of the resistance element 507 having a negative temperature coefficient when an abnormality occurs , e . g ., an ambient temperature rises to an extremely high level , the normally - on mosfet 205 is turned off , thereby compulsorily turning off the solid - state relay 500 . accordingly , it is possible to prevent an abnormal operation of the solid - state relay 500 at high temperatures , for example . fig6 illustrates a structure of a solid - state relay 600 according to an embodiment of the present invention , in which a light emitting diode 101 associated with a driving triac 103 is coupled to a light emitting diode 101 a associated with a normally - on driving element 105 a via an ic 608 having a delay function . the normally - on driving element 105 a coupled in series to the driving triac 103 includes the light emitting diode 101 a and a normally - on mosfet 205 . the light emitting diode 101 a controls the normally - on mosfet 205 . the solid - state relay , 600 further includes the ic 608 coupled in series to the light emitting diode 101 and the light emitting diode 101 a . the ic 608 has a delay function . therefore , when a phase control is performed , the solid - state relay 600 can maintain a stable on - state during the time delay provided by the integrated circuit 608 . accordingly , it is possible to facilitate the design of the device by using the integrated circuit 608 . fig7 illustrates a structure of a solid - state relay 700 according to an embodiment of the present invention in which a plurality of normally - on driving elements 105 are coupled in series to a driving triac 103 . the solid - state relay 700 includes the plurality of normally - on driving elements 105 coupled in series to the driving triac 103 . for example , as shown in fig7 two normally - on driving elements 105 may be coupled in series to the driving triac 103 . in this case , one of the normally - on driving elements 105 may be dedicated to the “ off controlling ” of the device , and the other may be dedicated to the compulsory shutting off of the device operation , at high temperatures , for example . as a result , it is possible to realize a device which is capable of being controlled so as to be on / off with a predetermined timing and , moreover , it is possible to compulsorily turn off the solid - state relay 700 when the solid - state relay 700 is abnormally heated , for example . although the above embodiment illustrates an example in which two driving elements 105 are coupled together , the present invention is . not limited thereto . three or more driving elements 105 may be coupled to the driving triac 103 . although the above - described embodiments of the present invention illustrate examples directed to the solid - state relays , the present invention is not limited thereto . the present invention is applicable to any optocoupler which incorporates a thyristor or triac as a driving element , e . g ., a photothyristor , a phototriac coupler , etc . as described above , the present invention provides an optocoupler capable of preventing an increase in inrush current or commutation failure . the present invention further provides an optocoupler whose off - timing can be controlled . the present invention further provides an optocoupler capable of compulsorily turning itself off when an abnormality occurs , e . g ., an ambient temperature rises to an extremely high level . accordingly , there is provided an optocoupler such as a solid - state relay , etc ., which can be not only turned on , but also turned off , with a predetermined timing . thus , when the optocoupler is employed for driving a load while performing a phase control , an increase in inrush current or commutation failure can be prevented . moreover , it is possible to compulsorily turn off the device when an abnormality occurs , e . g ., an ambient temperature rises to an extremely high level . various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the scope and spirit of this invention . accordingly , it in not intended that the scope of the claims appended hereto be limited to the description as set forth herein , but rather that the claims be broadly construed . | 7 |
referring to fig1 , a wireline logging tool ( 106 ) is suspended from an armored cable ( 108 ), and may have optional centralizers ( not shown ). the cable ( 108 ) extends from the borehole ( 104 ) over a sheave wheel ( 110 ) on a derrick ( 112 ) to a winch forming part of surface equipment , which may include an analyzer unit ( 114 ). well known depth gauging equipment ( not shown ) may be provided to measure cable displacement over the sheave wheel ( 110 ). the tool ( 106 ) may include any of many well known devices to produce a signal indicating tool orientation . processing and interface circuitry within the tool ( 106 ) amplifies samples and digitizes the tool &# 39 ; s information signals for transmission and communicates them to the analyzer unit ( 114 ) via the cable ( 108 ). electrical power and control signals for coordinating operation of the tool ( 106 ) may be generated by the analyzer unit ( 114 ) or some other device , and communicated via the cable ( 108 ) to circuitry provided within the tool ( 106 ). the surface equipment includes a processor subsystem ( 116 ) ( which may include a microprocessor , memory , clock and timing , and input / output functions — not separately shown ), standard peripheral equipment ( not separately shown ), and a recorder ( 118 ). the logging tool ( 106 ) is representative of any logging device that may be used in accordance with principles described herein . it will be understood by those of skill in the art having the benefit of this disclosure that the gas separation and detection tool described in detail below can be implemented as a wireline , mwd , lwd , or other type of tool , including but not limited to tools mounted in the formation or mounted in a completion of the borehole to perform ongoing measurements over time . referring to fig2 , an embodiment of the gas separation and detection tool includes a separation module ( 200 ) and a detection module ( 202 ). a test chamber ( 204 ) may also be defined between the separation module and detection module . gas that is present in a borehole fluid in a flowline ( 206 ) enters the chamber via the separation module , i . e ., the gas is separated from the fluid in the flowline . differential pressure between the flow line and the chamber may facilitate gas separation . the detection module subjects the separated gas in the chamber to a testing regime which results in production of an indicator signal ( 208 ). the indicator signal is provided to interpretation circuitry ( 210 ) which characterizes the gas sample , e . g ., in terms of type and concentration . referring to fig2 and 3 , the separation module may include a membrane ( 300 ). the membrane has characteristics that inhibit traversal by all but one or more selected compounds . one embodiment of the membrane ( 300 ) is an inorganic , gas - selective , molecular separation membrane having alumina as its base structure , e . g ., a ddr type zeolite membrane . nanoporous zeolite material is grown on the top of the base material . examples of such membranes are described in us20050229779a1 , us6953493b2 and us20040173094a1 . the membrane has a pore size of about 0 . 3 - 0 . 7 nm , resulting in a strong affinity towards specific gas compounds such as co2 . further enhancement of separation and selectivity characteristics of the membrane can be accomplished by modifying the surface structure . for example , a water - impermeable layer such as a perfluoro - based polymer ( e . g . teflon af or its variations ), polydimethyl siloxane based polymer , polyimide - based polymer , polysulfone - based polymer or polyester - based polymer may be applied to inhibit water permeation through the membrane . other variations of the separation membrane operate as either molecular sieves or adsoption - phase separation . these variations can formed of inorganic compounds , inorganic sol - gel , inorganic - organic hybrid compounds , inorganic base material with organic base compound impregnated inside the matrix , and any organic materials that satisfy requirements . the chamber ( 204 ), if present , is defined by a rigid housing ( 302 ). the membrane ( 300 ) occupies an opening formed in the housing ( 302 ). the housing and membrane isolate the chamber from the fluid in the flowline , except with respect to compounds that can traverse the membrane . as already mentioned , when partial pressure of gas compounds is greater in the flowline than in the chamber , differential pressure drives gas from the flowline into the chamber . when the partial pressure is greater in the chamber than in the flowline , differential pressure drives gas from the chamber into the flowline . in this manner the chamber can be cleared in preparation for subsequent tests . operation of the detector module ( 202 ) may be based on techniques including but not limited to infrared ( ir ) absorption spectroscopy . an ir absorption detector module may include an infrared ( ir ) light source ( 304 ), a monitor photodetector ( pd ) ( 306 ), an ir detector ( 308 ), and an optical filter ( 310 ). the ir source ( 304 ) is disposed relative to the optical filter ( 310 ) and ir detector ( 308 ) such that light from the ir source that traverses the chamber ( 204 ), then traverses the filter ( unless filtered ), and then reaches the ir detector . the module may be tuned to the 4 . 3 micrometer wavelength region , or some other suitable wavelength . the monitor pd ( 306 ) detects the light source power directly , i . e ., without first traversing the chamber , for temperature calibration . if multi - wavelength spectroscopy is used , e . g ., for multi - gas detection or baseline measurement , several leds or lds can be provided as light sources and a modulation technique can be employed to discriminate between detector signals corresponding to the different wavelengths . further , spectroscopy with nir and mir wavelengths may alternatively be employed . in each of these variant embodiments the absorbed wavelength is used to identify the gas and the absorption coefficient is used to estimate gas concentration . fig4 illustrates embodiments of the invention both with and without a test chamber . these embodiments may operate on the principle of measuring electromotive force generated when the gas reacts with a detecting compound , i . e ., the gas sensor module ( 202 ) includes a compound that reacts with the target gas . because the electromotive force resulting from the reaction is proportional to the gas concentration , i . e ., gas partial pressure inside the system , gas concentration in the flowline can be estimated from the measured electromotive force . alternatively , these embodiments may operate on the principle of measuring resistivity change when the gas reacts with the detecting compound . because the resistivity change is proportional to the gas concentration , i . e ., gas partial pressure inside the system , gas concentration in the flowline can be estimated from the measured resistivity change . other features which enhance operation may also be utilized . for example , a water absorbent material ( 400 ) may be provided to absorb water vapor that might be produced from either permeation through the membrane or as a by product of the reaction of the gas with a detecting compound . examples of water absorbant material include , but are not limited to , hygroscopic materials ( silica gel , calcium sulfate , calcium chloride , montmorillonite clay , and molecular sieves ), sulfonated aromatic hydrocarbons and nafion composites . another such feature is a metal mesh ( 402 ) which functions as a flame trap to help mitigate damage that might be caused when gas concentration changes greatly over a short span of time . another such feature is an o - ring seal ( 404 ) disposed between the housing and the flowline to help protect detection and interpretation electronics ( 406 ). materials suitable for construction of components of the gas sensor module include sno2 , doped with copper or tungsten , gold epoxy , gold , conductive and non - conductive polymer , glass , carbon compounds and carbon nanotube compounds for the purpose of proper sealing , maintaining good electrical connection , increasing sensitivity and obtaining stable measurements . the housing may be made of high performance thermoplastics , peek , glass - peek , or metal alloys ( ni ). referring to fig5 and 6 , various features may be employed to help protect the membrane from damage , e . g ., due to the force caused by the pressure differential where the chamber contains only gas . one such feature is an integrated molecular separation membrane . the integrated membrane can include a water impermeable protective layer ( 500 ), a gas selective membrane ( 502 ), an inorganic base layer ( 504 ) and a metal support layer ( 506 ). the metal support layer increases the mechanical strength of the membrane at high - pressure differentials . gas permeates through the molecular separation layer and goes into the system via small holes in the metal support . in another embodiment the integrated molecular separation membrane includes a molecular separation membrane / layer bonded to a metal support layer and sealed with epoxy ( 508 ) or any other sealant . the epoxy can be a high temperature - resistant , non - conductive type of epoxy or other polymeric substances . the molecular separation layer can act as a water / oil separation membrane . gas permeates through the molecular separation layer and goes into the system via small holes in the metal support . in another embodiment the integrated separation membrane includes a molecular separation membrane / layer bonded to a metal support layer and sealed with epoxy ( 508 ). the metal support is designed to accommodate insertion of the molecular separation membrane . the epoxy or sealant can be a high temperature , non - conductive type of epoxy or other polymeric substances . gas permeates through the molecular separation layer and goes into the system via small holes in the metal support . referring to fig7 , in an alternative embodiment the integrated membrane includes a molecular separation membrane / layer ( 700 ) bonded between porous metal plates ( 702 , 704 ). in addition to integrating the gas separation and pressure balancing functions into one mechanical assembly , this alternative embodiment provides support for the membrane both at a pressure differential where flowline pressure is greater than chamber pressure and at a pressure differential where chamber pressure is greater than flowline pressure . referring to fig8 , an alternative embodiment utilizes an incompressible liquid buffer ( 800 ) to help prevent membrane damage due to pressure differential . the liquid buffer ( 800 ) may be implemented with a liquid material that does not absorb the target gas . because the liquid buffer is incompressible , buckling of the membrane due to the force caused by higher pressure in the flowline than in the chamber is inhibited when the chamber is filled with liquid buffer . a bellows ( 803 ) can be provided to compensate for small changes in compressibility within the chamber due to , for example , introduction or discharge of the target gas . the bellow is one example of a pressure compensator . fig8 illustrates a membrane ( 804 ) and a spectrometer module ( 806 ), to which the above embodiments of fig2 - 7 can be applied either alone or in combination . fig8 illustrates an optical window ( 801 ), an input optical path ( 802 ) and an output optical path ( 805 ). fig9 illustrates an alternative embodiment that is different from the above embodiments of fig2 - 7 in utilizing a solid state chamber ( 900 ). the solid state chamber is formed by filling the cavity defined by the housing with a nanoporous solid material ( 901 ). suitable materials include , but are not limited to , tio 2 , which is transparent in the nir and mir range . the target gas which traverses the membrane enters the nanospace of the solid material . since the chamber is solid state , buckling of the membrane due to higher pressure in the flowline than in the chamber is inhibited . however , because the chamber is porous , gas can be accommodated . fig9 illustrates a spectrometer module ( 902 ). fig9 illustrates an alternative embodiment that is different from the above embodiments of fig2 - 7 in utilizing a solid state chamber ( 900 ). the solid state chamber is formed by filling the cavity defined by the housing with a nanoporous solid material . suitable materials include , but are not limited to , tio 2 , which is transparent in the nir and mir range . the target gas which traverses the membrane enters the nanospace of the solid material . since the chamber is solid state , buckling of the membrane due to higher pressure in the flowline than in the chamber is inhibited . however , because the chamber is porous , gas can be accommodated . fig1 illustrates another alternative embodiment of the gas separation and detection tool . the tool includes a non h2s - scavenging body ( 1000 ) with a gas separation module ( 200 ) which may include a membrane unit ( 1002 ) as illustrated in fig2 - 9 . the separated gas enters a test chamber defined by the body and membrane unit due to differential pressure . a monochromator including optical fibre is used to facilitate gas detection . in particular , light from a lamp source ( 1004 ) is inputted to an optical fibre ( 1006 ), which is routed to one side of the chamber . a corresponding optical fibre ( 1008 ) is routed to the opposite side of the chamber , and transports received light to a receiver ( 1010 ). a microfluidic channel fibre alignment feature ( 1012 ) maintains alignment between the corresponding fibres ( 1006 , 1008 ). the arrangement may be utilized for any of various gas detection techniques based on spectroscopy , including but not limited to infrared ( ir ) absorption spectroscopy , nir and mir . in each of these variant embodiments the absorbed wavelength is used to identify the gas and the absorption coefficient is used to estimate gas concentration . while the invention is described through the above exemplary embodiments , it will be understood by those of ordinary skill in the art that modification to and variation of the illustrated embodiments may be made without departing from the inventive concepts herein disclosed . moreover , while the preferred embodiments are described in connection with various illustrative structures , one skilled in the art will recognize that the system may be embodied using a variety of specific structures . accordingly , the invention should not be viewed as limited except by the scope and spirit of the appended claims . | 6 |
referring now to the drawings , and particularly to fig1 and 6 , there is shown in top perspective and plan views an automatic doughnut making machine according to the present invention including a rectangular tank 10 having the conventional bottom wall 11 and front , back and side walls . suspended from the top edge of the back wall is a control box 12 containing conventional automatic thermostatic control means for an electrical heating element 13 along with an on - off switch , temperature selection dial , pilot light , etc ., all as are well known . also suspended from the back wall of the tank is an electric motor and gear box 14 with a readily disconnected coupling 15 to a pump 16 for circulating cooking medium within the tank as hereinafter more fully described . another electric motor and gear box 17 is suspended from the tank for driving the turn - over and discharge means , as hereinafter more fully described . a dough extruder is movably and detachably mounted above the tank 10 by means of a bracket 20 secured to one upper corner of the tank from which a support arm 21 is pivotally secured at one end 22 at the top of a vertical post or standard raising the extruder to the required height . the opposite end 23 of arm 21 pivotally supports a bracket 24 to which are fixedly secured the funnel - like hopper 25 of the dough extruder and electric motor and gear box 26 for driving the extruder . the hopper 25 serves as a repository for dough to be extruded into the cooking tank . in operative position , the extruder is positioned over the upstream end of the doughnut flow path , as seen in fig1 and 2 . the dough extruder has a diminshing conical or funnel portion at its lower end terminating in a circular opening 27 which functions as an extruding die . a vertically reciprocable rod or shaft 28 is disposed within the hopper sliding in a spider 29 disposed in the narrow throat of the hopper . the bottom end of shaft 28 carries a circular cutting disc or plate 30 which forms the dough into doughnut shape coacting with opening 27 . a dough advancing plate 31 is slidably mounted on shaft 28 . an adjusting screw 32 threadably engages the top end of shaft 28 . handle or knob 33 facilitates adjustment of the stroke of the extruder plate 30 . reciprocation of the dough extruder shaft is by virtue of an actuating arm 35 pivotally supported intermediate of its ends at 36 by bracket 24 . one end of actuating arm 35 has a pair of vertically spaced apart fingers 37 and 38 which engage a crank arm 39 driven by the electric motor within motor and gear box 26 . the opposite end of actuating arm 35 includes a pair of horizontally spaced apart arm extensions 40 and 41 detachably secured by virtue of wing nut and bolt 42 for ready disengagement for cleaning of the extruder . each arm extension 40 and 41 has a longitudinal slot 43 which engages the ends of a pin 44 carried by adjusting screw 32 . as best seen in fig3 rotation of crank arm 39 causes rocking movement of actuating arm 35 on its pivot 36 . the rocking movement is translated into reciprocatory movement of shaft 28 by virtue of engagement of pin 44 with the actuating arm extensions . a removable guide insert , indicated generally at 45 , is supported within tank 10 by virtue of flanges 46 - 48 which engage the top edges of the front and side walls , respectively , of the tank . the guide insert includes a bottom wall 50 spaced from the bottom wall 11 of the tank above the heating element to permit the bottom of the tank to function as a sump for recirculating of the cooking medium . the guide insert includes a plurality of elongated parallel spaced apart vertical plates 51 - 56 which define a plurality of flow channel segments 57 - 61 between each adjacent pair of wall members . alternate vertical walls are interconnected by vertical semi - circular walls 62 - 65 to define a continuous serpentine flow path . thus , vertical walls 51 and 53 are connected by semi - circular wall 62 to interconnect flow channel segments 57 and 58 ; the opposite ends of walls 52 and 54 are similarly connected by vertical wall 63 to interconnect channel segments 58 and 59 ; etc . to facilitate partial submersion of the channel insert into a tank of cooking medium , a plurality of holes 66 are provided in bottom wall 50 , as seen in fig6 . each hole 66 is covered by a pivotable flap 67 which functions as a check valve during operation of the machine . the discharge of pump 16 is provided with an outwardly flaring nozzle 70 covered with a screen 71 and of width corresponding generally to that of flow channel segment 57 and height corresponding generally to the intended depth of cooking medium within that channel . screen 77 is partially covered by a flap 72 which divides the flow from pump 16 into a surface flow through slot 73 and a submerged flow through the shielded screen opening . the cooking medium is circulated , being drawn from the sump below floor 50 and discharged through nozzle 70 . during operation , the dough extruder is positioned above the upstream end of channel segment 57 immediately downstream from the pump nozzle . the initial raw dough is carried along the surface of the cooking medium in that channel segment . it passes from channel segment 57 into channel segment 58 and thence downstream through the successive flow channel segments to the discharge . as it travels , that portion of the dough which is submerged in the cooking medium cooks and browns . at the aproximate midpoint of the flow channel , the partially cooked doughnut is turned over to complete the cooking on the other side . an open wire basket 77 is disposed within flow channel segment 59 fixed to a shaft 78 journaled in walls 53 and 54 . a toothed pinion 79 is fixed to shaft 78 and is engaged by a toothed rack 80 carried by rod 81 supported for sliding movement in guides 82 and 83 supported by the top edge of wall 54 . as rod 81 is reciprocated , as explained in greater detail hereinafter in connection with the doughnut discharge and ejector , shaft 78 is rotated through about 120 ° to lift a partially cooked doughnut received therein , turn it over and discharge in on the opposite side of the backet . to prevent interference by successively following partially cooked doughnuts with the return movement of the turn - over basket , hold - back means are provided in the form of a transverse plate 86 supported from a rectangular wire frame 87 which in turn is pivotally supported from shaft 78 by means of a pair of spaced apart arms 88 . one end of a coil spring 89 is connected to the frame 87 by means of clip 90 and the opposite end of the spring is anchored at 91 to the floor 50 of the guide channel insert . as best seen in fig8 when turn - over basket 77 is in its downward doughnut - receiving position , the bottom of the basket bears against the hold - back means stretching spring 89 and holding plate 86 out of the flow path of the doughnuts . when basket 77 is operative to turn over a doughnut , as the basket is lifted the tension of spring 89 causes frame 87 to rotate on arms 88 bring plate 87 into position to hold back the next succeeding doughnut until the basket returns to doughnut receiving position . similar basket means 95 are provided to remove the fully cooked doughnut from the cooking medium . basket 95 is fixed to shaft 96 journaled in vertical walls 55 and 56 defining the final downstream flow channel segment 61 . pinion 97 is fixed to shaft 96 and is engaged by rack 98 carried by reciprocating rod 99 guided in slides 100 and 101 mounted on the top edge of vertical wall 56 . shafts 78 and 96 are rotated in unison to operate baskets 77 and 95 in unison by virtue of a connecting bar 102 whose opposite ends are affixed to rods 81 and 99 . intermediate of its ends , bar 102 is connected to one end of an actuating arm 103 whose opposite end is connected to a crank arm 104 driven by motor and gear box 17 . another hold - back means 86a is provided which is similar in all material respects to that already described . the operation of the discharge basket and hold - back means are likewise similar to the operation of the turn - over basket and its hold - back means . as seen in fig1 and 13 , a discharge chute is provided at the extreme downstream end of the serpentine flow path defined by vertical walls 108 and 109 . a rectangular wire ejector slide 110 is fixed to a shaft 111 whose ends are journaled in chute walls 108 and 109 . a lifter plate 112 is secured to the under - side of slide 110 . a lifter arm 113 is journaled on shaft 96 to rotate with hold - back means 86a - 88a . the free end of arm 113 bears against plate 112 and supports slide 108 in an inclined position when basket 95 is in the down position . as discharge basket 95 rotates with its shaft 96 , arm 113 also rotates with the hold - back means . as hold - back means 86a raises , the free end of arm 113 is lowered . as support is withdrawn from slide 110 , it pivots downwardly on its shaft 111 to a horizontal position . thus , the doughnut is discharged from basket 95 onto the top surface of slide 110 . then , as basket 95 is returned to its original position , pushing down hold - back means 86a , the free end of arm 113 is lifted and in turn lifts slide 110 to its inclined position . the completely cooked doughnut then slides off into a waiting receptacle . a transverse weir plate 120 is provided at the downstream end of the last flow channel segment . a perforated crumb collector receptacle 121 is provided immediately adjacent to the weir 120 . any crumbs discharged from the cooking doughnuts and circulated downstream with the circulating cooking medium are collected in receptacle 21 and the cooking medium is recirculated by pump 16 . in the normal operation of the doughnut making machine , according to the present invention , the tank 10 is filled to the appropriate level with cooking fat or oil and the heating element is turned on . pump 16 may also be turned on to circulate the cooking medium to hasten bringing the oil to the proper uniform temperature . the extruder hopper is filled with dough and the variable speed extruder drive motor is set at the proper speed depending upon the desired volume of doughnuts to be produced . when the oil is at the proper temperature , the extruder motor and the turn - over and discharge motor are turned on . the time required to cook each doughnut completely remains substantially constant , independent of the volume of production . in order for the doughnuts to cook properly , it is necessary to hold back a certain number of doughnuts at the turning point between channel segments 58 and 59 until they cook to the desired degree , according to the following schedule : ______________________________________doughnuts held back dozen per hour______________________________________1 52 103 154 205 256 307 358 409 4510 5011 5512 60______________________________________ and so on , holding back one doughnut for each dozen per hour desired . each time an adjustment in speed is made to vary the volume of production , then it is necessary to adjust the number of doughnuts held back accordingly , following the table . as each doughnut is cooked on one side , it is turned over and cooked on the other side as it flows toward the discharge . it is discharged onto the ejector slide and ejected from the machine . all parts which come into contact with the dough or the cooking medium or the cooked doughnuts , including the dough extruder , the circulating pump , the guide insert , crumb collector , etc ., are detachable and removable for easy cleaning . it is apparent that many modifications and variations of this invention as hereinbefore set forth may be made without departing from the spirit and scope thereof . the specific embodiments described are given by way of example only and the invention is limited only by the terms of the apended claims . | 0 |
referring to the figures generally , and in particular to fig1 there is illustrated in perspective view the sandwich container or package 10 . sandwich container 10 is illustrated in a closed , latched position and is composed of a first or bottom compartment 12 , a second or top compartment 14 and an insert 16 , which in this case is an insulating platform . first or bottom compartment 12 is composed of a bottom portion or wall 18 and side portions 20 , which in this case are upwardly extending side walls that terminate with an outwardly extending lip surface 22 , as better illustrated in fig5 . side portions 20 , as illustrated in fig3 extend slightly outwardly as they extend upwardly . in the illustrated embodiment , bottom portion 18 includes a trough 24 extending around the periphery of the interior of bottom portion 18 . trough 24 serves to collect any fluids that may drain from the contents and raise bottom portion 18 to facilitate removal of the contents . bottom portion 18 could also be ribbed ( not shown ) in addition or in place of trough 24 for providing a space between the contents and bottom portion 18 as well as for providing for airflow and fluid collection . top compartment 14 includes a top surface 26 and side portions 28 which in this case are downwardly extending side walls that terminate at a lip surface 30 that is complementary to lip surface 22 of bottom compartment 12 . bottom and top compartments 12 and 14 are joined together by a hinge section 32 which can be integrally formed in the material of which bottom and top compartments 12 and 14 are formed . such a hinge is well known in the art , for example , see u . s . pat . no . 4 , 132 , 344 , the disclosure of which is hereby incorporated by reference thereto . hinge 32 is almost as wide as sandwich container 10 , which promotes stability of and facilitates closing of container 10 . front wall portions 34 and 34a of bottom and top compartments 12 and 14 , respectively , have structure that defines a latch mechanism 36 . latch mechanism 36 includes a locking aperture 38 in top compartment 14 and a locking latch 40 that extends from lip surface 22 of bottom compartment 12 . locking aperture 38 is dimensioned to receive locking latch 40 therein . such a latch mechanism is well known in the art and thus is not described in detail . for example , such a latch is illustrated in u . s . pat . no . 4 , 132 , 344 . hinge 32 allows top compartment 14 to be folded over and onto bottom compartment 12 to close sandwich container 10 as illustrated in fig1 . hinge 32 also permits the container to be opened by lifting and pivoting top compartment 14 about hinge 32 to an open position , as illustrated in fig5 for example . insert 16 , which in this case is an insulating platform forms part of sandwich container 10 and is more completely illustrated in fig2 . insert 16 generally corresponds to the open portion of bottom and top compartments 12 and 14 , respectively , as illustrated in fig6 . insert 16 also includes a support tab 42 and a gripping tab 44 , which extends the periphery of insert 16 beyond the otherwise generally corresponding shape described above . gripping tab 44 may be embossed or otherwise labelled with a suitable legend , such as &# 34 ; pull &# 34 ; as illustrated in fig1 and 2 . insert 16 can be of any desired shape . a slot or slots complementary to such support tab or tabs could also be provided in appropriate locations of the container side portions to allow insertion and removal of the support tab ( s ). support tab 42 is insertable into a complementary slot 46 that is located in side portion 28 of top compartment 14 , as illustrated in fig3 - 5 , which restrains movement of insert 16 relative to side portion 28 . when so inserted , support tab 42 rests on side portion 28 of top compartment 14 . complementary slot 46 can be about the same width and / or height as the width and / or thickness of support tab 42 to provide a snug fit of support tab 42 in complementary slot 46 . gripping tab 44 preferably extends beyond at least one of side portions 28 and 20 of container 10 to facilitate removal of insert 16 from container 10 when container 10 is in a closed position , as illustrated in fig1 and 3 . fig3 illustrates in sectional view along lines 3 -- 3 of fig1 sandwich container 10 which contains a hamburger sandwich h therein . hamburger sandwich h is composed of a bun crown bc , condiments c , which in this case include tomato slices t , lettuce pieces l and a slice of cheese ch . bun crown bc and condiments c are contained within top compartment 14 of sandwich container 10 . a hamburger patty hp and a bun heel bh are contained within bottom compartment 12 as illustrated in fig3 . in the illustrated embodiment , the contents of the bottom compartment are relatively hot and the contents of the top compartment are relatively cool . as illustrated in fig3 insert 16 serves to separate and insulate bottom compartment 12 and its contents from top compartment 14 and its contents . moreover , insert 16 carries the weight of the contents of top compartment 14 since the contents , in this case bun crown bc and condiments c rest on insert 16 . the weight of the contents of top compartment 14 and the weight of insert 16 is at least partially carried by side portions 20 and 28 of container 10 . the support formed by support tab 42 and gripping tab 44 which transmits at least a portion of the weight to the side portions of sandwich container 10 restrain insert 16 from being displaced into bottom compartment 12 . this has the effect of preventing or substantially preventing insert 16 from contacting and deforming the contents of bottom compartment 12 , which in this case are hamburger patty hp and bun heel bh . support tab 42 and gripping tab 44 provide other advantages as hereinafter described . when the consumer desires to assemble and consume hamburger sandwich h , insert 16 is removed from container 10 merely by grasping gripping tab 44 and pulling insert 16 in the direction of arrow r without handling by the consumer . fig4 illustrates sandwich container 10 with insert 16 removed . the effect of removal of insert 16 is to assemble the sandwich by causing the contents of top compartment 14 to contact the contents of bottom compartment 12 . in this case , bun crown bc and condiments c of hamburger sandwich h contact hamburger patty hp . upon opening sandwich container 10 by releasing latch mechanism 36 and lifting and pivoting top compartment 14 , hamburger sandwich h is presented in a configuration ready for removal and consumption ( not shown ). the loading and packaging of hamburger sandwich h into sandwich container 10 is illustrated in fig5 - 7 . in fig5 sandwich container 10 is in the open position and bun crown bc and condiments c have been placed with the condiments c face up in top compartment 14 . bun heel bh and hamburger patty hp are placed in bottom compartment 12 with hamburger patty hp facing upwardly . after bun crown bc and condiments c are placed in top compartment 14 , insert 16 can be placed over top compartment 14 , as illustrated in fig6 . insert 16 is placed in position by inserting support tab 42 into complementary slot 46 and otherwise placing insert 16 so that it covers or substantially covers the opening of top compartment 14 . placing insert 16 in position can occur either before or after the loading of bun heel bh and hamburger patty hp , as will be readily appreciated . after hamburger sandwich h has been loaded into container 10 , and insert 16 is in place , container 10 is ready for closing . closing of container 10 is illustrated in fig7 where a human operator ho grasps gripping tab 44 and lip surface 30 between thumb t and finger f . top compartment 14 is lifted and rotated about hinge 32 in the direction of arrow r &# 39 ; while gripping gripping tab 44 and lip surface 30 as aforesaid until top compartment 14 is over bottom compartment 12 and sandwich container 10 is closed . thereafter , latch mechanism 36 can be engaged by inserting locking wedge 40 into locking aperture 38 . sandwich container 10 with hamburger sandwich h contained therein is ready for storage or delivery to a customer . sandwich container 10 can be constructed of materials as desired . suitable materials include polystyrene , which may be foamed as well as other foamed material . foamed material is advantageous because of its insulating properties . other materials can be of course used as those skilled in the art will recognize . for example , other plastics , paper , cardboard and similar materials can be used . compartments 12 and 14 can be fabricated from a single piece of material as disclosed in u . s . pat . no . 4 , 132 , 344 . the specific embodiments shown and described are only illustrative of the present invention . changes in the structure and method of the present invention would be readily apparent to one skilled in the art . for example , a sandwich container in accordance with the invention can be formed of separate top and bottom compartments that are not connected by a hinge but could be connected by , for example , a pair of latch mechanisms which could be similar to latch mechanism 36 , one on either side of the container . the shape of the container in accordance with the invention can of course be as desired . in describing various embodiments herein , the compartments and portions of the container are sometimes referred to as top and bottom . it is to be understood that such relative positions can be reversed or could be otherwise described and the particular orientations utilized herein are for convenience and are not to be construed as a limitation upon the invention . while the invention has been described with respect to specific embodiments , it is to be understood that the invention is capable of numerous modifications , rearrangements and changes and such modifications , rearrangements and changes are intended to be covered by the scope of the appended claims . | 8 |
the workstation of the invention is comprised of a rectangular , parallelepiped sheet metal cabinet 8 which includes a front side or panel 10 , a first lateral side panel 12 , a second lateral side panel 14 , and a back panel 16 . the panels 10 , 12 , 14 , and 16 define a rectangular parallelepiped cabinet with an open front to which a hinged door 18 is preferably attached . a bottom panel 20 reinforces the connected side panels 10 , 12 , 14 , 16 . the first lateral side panel 12 includes first and second wheels 24 and 26 attached thereto . affixed to the bottom panel 20 on each of the bottom corners of the cabinet is an adjustable foot , for example foot 28 , which may be used to adjust the height of the cabinet . the top of the cabinet is open . attached to the open top of the cabinet is a tool support plate 30 . the support plate 30 is typically a wood or composite material rather then a metal material inasmuch as the plate 30 may be drilled with holes for attachment for a power tool such as the circular saw 32 in fig1 . preferably , the plate 30 has a generally rectangular shape as illustrated in fig1 and 3 , for example , and is preferably in the range of ½ to 1 inch thick . in the preferred embodiment , the plate 30 includes a rectangular or four - sided insert 34 on which a tool is mounted . the insert 34 rests on a flange 36 defined in and extending around the periphery of a congruent opening 38 in the plate 30 . the opening 38 typically is four sided or rectangular in shape and the flange 36 is likewise four sided or rectangular to thereby support the congruent insert 34 . manually actuated fasteners 40 and 42 are provided to retain the insert 34 in place in the opening 38 on the flange 36 . the insert 34 has a thickness , which renders the top of the insert 34 coplanar with the top of plate 30 when placed in the opening 38 . this is the preferred embodiment of the invention . the insert 34 , as well as the plate 30 , are typically fabricated from wood , or composite material which may be drilled or otherwise worked in order to facilitate attachment of a power tool and in order to provide openings therethrough for passage of dust to a bin 44 within the interior of the cabinet . the bin 44 is attached by means of a flexible hose 46 to a dust recovery system of the type typically found in wood shops and the like . the insert 34 may itself include a further auxiliary panel insert 50 for support of a tool such as a router thereon , or alternatively the plate 30 may include a special panel insert 52 with a centered opening 54 therethrough . a router ( not shown ) could then be mounted on the underside of the panel insert 52 with a router blade extending through the opening 54 for exposure to work a work piece passing over the surface of the plate 30 and panel insert 52 . as depicted in fig6 a number of separate power tools and other tools such as a vice , drill press , etc . may each be mounted on a separate insert 34 and stored on separate shelves of a cabinet 60 . the cabinet 60 is typically an open sided cabinet with multiple spaced horizontal shelves 61 . access to the tools stored in the cabinet is thus rendered easy and the tool desired for use in combination with a workstation may be easily removed for placement in the congruent opening 38 of plate 30 . sawdust or other material resulting from a power tool operation can then be collected in the bin 44 , for example , and directed through a tube 46 to the work shop exhaust system and dust collection system . preferably the plate 30 extends beyond the edges of the cabinet defined by the panels 10 , 12 , 14 , and 16 . this provides a handhold for tilting of the cabinet when movement of the cabinet is desired . additionally , this provides for protection of the worker that is using the tool and also provides improved access around the sides of the cabinet . further , since the corners 33 , 34 of the plate 30 are radiused or chamfered , a worker will not be exposed to a sharp corner when moving about the circumference of the workstation as the tool at the station is being used . the shape of the plate 30 may be varied in other respects to accommodate needs of the workstation operator and the tool room in which the work stations are situated . for example , as shown in fig5 a specially configured plate 35 is designed to permit placement of a workstation cabinet in a corner . thus the plate 35 includes five sides with the backsides 64 and 66 at right angles for placement in a corner . the front side 68 is parallel to the cabinet front panel and the lateral sides 70 and 72 of plate 35 define an angle so that an adjacent rectangular work station plate 30 will fit against the side . latch 42 typically comprises a rotatable stem 43 mounted in plate 30 with a projecting lug 45 for holding insert 34 in place upon rotation by griping handle 47 . further features of the modular cabinets include a plate 30 or insert 34 which includes a pattern of passages or openings 79 to facilitate collection of sawdust , grit and shavings in a dust collection bin on the inside of the cabinet from a sander , for example , or a drill . additionally , the openings 80 may receive dogs or stops that maintain a work piece . thus , an insert 34 may include a pattern of openings or recesses for mounting work piece dogs or stops 82 which are adjustable . the storage cabinet 60 may or may not include access doors . storage cabinet 60 may include adjustable shelves or opposed support flange members 85 in fig6 for support of inserts 34 with a tool mounted thereon . the storage cabinet and a plurality of cabinets 8 in combination with inserts 34 may be arrayed in a workroom in a desired and efficient array which is adjustable inasmuch as the cabinets 8 are mounted on wheels and the inserts 34 with assorted tools may all be moved easily . as depicted in fig4 a supplemental work support stand 90 may be attached to a cabinet 8 by bolting support arms 92 to the top bolt openings 94 of cabinet 8 . the stand 90 thus includes a vertical leg 96 , horizontal arms 92 and a top work platform 98 . various modifications of the construction may be implemented . that is , the height of the sheet metal cabinet may be varied . the arrangement and position of doors and shelves may be varied . the particular plate fastener such as fasteners 40 and 42 may be varied . thus the invention is to be limited only by the following claims and equivalents thereof . | 1 |
fig1 shows diagrammatically a teletext transmission system to explain the method according to the invention . the system comprises a transmission station 1 , a transmission medium 2 and a receiver 3 . the transmission station comprises a television signal generator 11 , a teletext signal generator 12 , a teletext inserter 13 and a modulator 14 . the television generator . 11 generates a picture signal tv , the teletext generator 12 generates a teletext signal tx . both signals are combined in teletext inserter 13 to a video signal which is applied to the modulator 14 and transmitted via transmission medium 2 . the receiver 3 comprises a tuner 31 for demodulating the video signal . the demodulated video signal cvbs is applied for further processing and display to a television monitor 32 . the video signal is also applied to a teletext decoder 33 . this decoder decodes the teletext signal accommodated therein and applies a teletext picture signal rgb to the television monitor 32 . the teletext signal comprises for each transmitted teletext page a plurality of data packets which are accommodated in further known manner in picture lines of the video signal during the field retrace period . fig2 shows some possible forms of these data packets in greater detail . as has been attempted to show in this figure , each data packet comprises 45 bytes of 8 bits each . the first 2 bytes having a fixed value 1010 .. 10 are referred to as &# 34 ; clock - run - in &# 34 ; and are denoted by cri in the figure . the third byte is referred to as the &# 34 ; framing code &# 34 ; f and also has a fixed value . the next 2 bytes comprise a 3 - bit magazine number m and a 5 - bit row number r . the significance of the other 40 bytes is dependent on the value of the row number r . if the row number r has one of the values 1 - 25 , as assumed in fig2 b , then the 40 bytes constitute a text row of 40 characters for display on a display screen in the level 1 display format . if the row number r has the value 0 , as is assumed in fig2 a , the data packet constitutes a header of a teletext page . the series of 40 bytes of such a header starts with two digits t ( tens ) and u ( units ) of the page number , a sub - code sc and a plurality of control bits c . the digits t and u each comprise four bits and may thus assume the values 0 - f ( in the hexadecimal numerical system ). the remaining part of the header comprises 24 character positions with a page header hdr and 8 character positions for display of the current time . the transmission of a teletext page starts with , and implies , the header of this page and subsequently comprises the relevant text rows . generally , a series of teletext pages is transmitted in a repetitive cycle . the 3 - digit page number is constituted by the magazine number m , tens t and units u . the basic pages which can be called by the user have a decimal page number in the range between 100 and 899 . for extension pages a hexadecimal page number is often used , of which at least one digit t or u has a value in the range between a and f . one of the transmitted teletext pages is a top page ( table of pages ). fig3 shows a possible example . as described hereinbefore , the page comprises 25 rows of 40 characters each . the character positions are numbered horizontally from 0 to 39 and vertically from 0 to 24 . two consecutive characters constitute a code cc , one of which is denoted in the figure by the reference numeral 30 . the code cc indicates , for example for a teletext page whether this page is actually transmitted or whether it is the first of a group of pages about a given subject , or whether it is a rotating page , and the like . the top page shown in fig3 comprises only the codes for the teletext pages of one magazine . it will be assumed that this is the magazine in which the top page itself is transmitted . in fig3 in which the top page has the number 1ff , all codes thus relate to the teletext page numbers 100 - 1ff . the top page shown in fig3 forms a table . there is an unambiguous relation between the coordinates of the elements of the table and a teletext page number . for the purpose of explanation , fig4 shows an example of the table indicating the corresponding teletext page numbers . the table comprises 14 rows ( r = 0 - 13 ) and 20 columns ( c = 0 - 19 ). the corresponding page numbers are indicated by means of two digits in the range between 00 and ff . the first digit ( i . e . the magazine number ) is identical for all pages , viz . 1 . the top page of other magazines is divided in a corresponding manner . as is shown in fig4 the table comprises a field 41 of 5 rows ( r = 0 .. 4 ) in which the codes are accommodated for the decimal pages 100 - 199 . a further field 42 of 3 rows ( r = 6 - 8 ) comprises the codes of a portion of the hexadecimal pages . more particularly , the first row of this field corresponds to the pages 1a0 - 1a9 and 1b0 - 1b9 , the second row corresponds to the pages 1c0 - 1c9 and 1d0 - 1d9 , and the third row corresponds to 1e0 - 1e9 and 1f0 - 1f9 . this division is , as it were , a continuation of the division of the first field . in the horizontal direction , the numerical sequence of 0 - 9 of the units of the page numbers is maintained and in the vertical direction the series of tens in the hexadecimal range a - f is continued . the codes for the remaining pages are accommodated in a third field 43 . as is known , empty text rows of teletext pages ( i . e . rows having 40 spaces ) need not be transmitted . in fact , non - transmitted text rows are automatically provided with spaces by a teletext decoder ( hexadecimal code 20 ) when the page is erased . the division of the table shown in fig4 benefits therefrom . in practice , only a limited number of hexadecimal teletext pages is transmitted . by arranging that a space code in the table has the significance of absence of the corresponding page in the transmission , the transmission of text rows for the fields 42 and 43 in fig4 may be dispensed with in many cases . this yields an efficient transmission of the top page ( s ). fig5 shows in greater detail the teletext decoder denoted by 33 in fig1 . the decoder comprises a data slicer 51 for regaining the data packets from the video signal cvbs , an acquisition circuit 52 for selecting the data packets of a desired page , a memory 53 for storing the selected data packets and a character generator 54 for displaying a page . the decoder further comprises a microprocessor 55 . said microprocessor may read and write the memory 53 via a communication bus 56 . particularly , the microprocessor may read the received top pages and use the codes accommodated therein for reserving memory space for extension pages . the operation of the teletext decoder shown in fig5 is determined by a control programme which is stored in the microprocessor . fig6 shows the flow chart of a control program for computing the teletext page number corresponding to a code cc at position ( r , c ) in the top page ( see fig3 ). in a step 60 of the control program the row number r ( 1 ≦ r ≦ 14 ) and the character position c ( 0 ≦ c ≦ 39 ) are converted into a row number r ( 0 ≦ r ≦ 13 ) and column number c ( 0 ≦ c ≦ 19 ), respectively , of the table ( see fig4 ). for computing the page number , a distinction is made in a step 61 between r ≦ 7 ( the fields 41 and 42 shown in fig4 ) on the one hand and r & gt ; 7 ( field 43 ) on the other hand . for r ≦ 7 the tens t and the units u of the page number are computed in a step 62 by means of the following operations . here , int ( c / 10 ) and mod ( c / 10 ) are the quotient and the remainder , respectively , of the division c / 10 . for r & gt ; 7 , the following operations are performed in a step 63 : in a step 64 the page number p is composed from the magazine number m of the top page ( in this case 1 ), the tens t and the units u . fig7 shows the flow chart of a further control program being a control program for reading , in the top page , of the code cc for a given page number . in a step 70 of the control program the magazine number m , the tens t and the units u are determined for the page number p . in a step 71 the control programme checks whether the units u constitute a decimal number ( u ≦ 9 ). in that case the following operations are performed in a step 72 : a position ( r , c ) in one of the fields 41 or 42 of the table ( see fig4 ) is obtained thereby . in the other case the operations are performed in a step 73 . a position ( r , c ) in field 43 of the table is obtained thereby . in a step 74 the table position ( r , c ) is converted into a character position ( r , c ) of the top page and the code is read at this and the subsequent character position . | 7 |
the following description is presented to enable any person skilled in the art to make and use the invention , and is provided in the context of a particular application and its requirements . various modifications to the disclosed embodiments will be readily apparent to those skilled in the art , and the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the present invention . thus , the present invention is not intended to be limited to the embodiments shown , but is to be accorded the widest scope consistent with the principles and features disclosed herein . additionally , as used herein , the term “ substantially ” is to be construed as a term of approximation . fig1 is a cross - sectional view of a subterranean production tool 10 embodying features of the present invention , and specially configured as a reservoir comingling tool . tool 10 may comprise several sections . in the embodiment illustrated , tool 10 comprises a top sub 100 , a computer section 200 , a valve assembly 300 , and a sensor assembly 400 . the names of the sections and assemblies are merely for convenience and not intended to completely describe , require , or limit the contents of any section of tool 10 , and as used here , do not . it is known that the beginnings and ends of the sections may be located to include or exclude certain equipment . it is also known that certain teachings of the present invention can be applied to other subterranean tools besides a comingler . top sub 100 may be connected to computer section 200 by means of a non - threaded , and non - rotated connection 500 . connection 500 may be described as a linear key - slot connection 500 . such connections 500 are not known to have been used previously in the connection of tubulars for subterranean production . computer section 200 is connected to valve assembly 300 by key - slot connection 500 . similarly , valve assembly 300 is connected to sensor assembly 400 by key - slot connection 500 . fig2 is a cross - sectional view of top sub 100 of tool 10 of fig1 . top sub 100 comprises a tubular having a threaded pin connection 102 for connection to a production string component 20 , such as a submersible pump . top sub 100 has a hollow center 104 . an electrical connector 230 is sealed in place inside hollow center 104 of top sub 100 by a bushing 232 . in this manner , electrical connections can be passed between the interior of computer section 200 and top sub 100 for connection to a power source , such as an electrical submersible pump , without passing environmental conditions and contaminants past bushing 232 . the lower end of top sub 100 has a male connector flange 110 having a circular exterior . a first groove 112 extends circumferentially over the circular exterior of male connector 110 . in an optional embodiment , first groove 112 does not extend over the full circumference of the exterior surface male connection 110 . computer section 200 has a female connector 210 having a circular interior locatable over male connector 110 of top sub 100 . a second groove 212 extends circumferentially over a portion of the female connector interior . in the preferred embodiment , second groove 212 does not extend over the full circumference of the interior surface of female connector 210 . in the embodiment illustrated , top sub 100 includes one or more dowel holes 120 for receiving a portion of a dowel 570 . computer section 200 includes one or more dowel holes 220 for receiving the opposite portion of dowel 570 . dowel 570 serves to align top sub 100 with computer section 200 so that first groove 112 and second groove 212 are in matching alignment . in matching alignment , first groove 112 and second groove 212 form a keyway 516 . fig3 is a cross - sectional view of a non - threaded , non - rotatable key - slot coupling system that is suitable for use with tool 10 . as best seen in this cross section , a male connector 510 has a circular exterior . a first groove 512 extends circumferentially over a portion or all of the circular exterior of male connector 510 . optionally , first groove 512 does not extend over the full circumference of the exterior surface male connection 510 , and an ungrooved portion 514 remains . a female connector 520 has a circular interior , and is locatable over male connector 510 . a second groove 522 extends circumferentially over a portion of the interior of female connector 520 . second groove 522 does not extend over the full circumference of the interior surface of female connector 520 . an ungrooved portion 524 is provided . an electrical passage 590 extends laterally through ungrooved portion 524 of female connector 520 . fig4 is an isometric view of key 540 , as used in coupling assembly 500 of the present invention , and as illustrated in fig8 . as seen in fig4 , key 540 may have a threaded hole 542 through it . key 540 has a curved outer surface 546 and a curved inner surface 544 . key 540 has a curved inner surface 544 for sliding relationship with external groove 512 of male flange 510 . key 540 has a curved outer surface 546 designed for sliding relationship with inner groove 522 of female flange 520 . outer surface 546 and inner surface 544 are parallel . key 540 has a pair of opposing end surfaces 548 and 550 . in the preferred embodiment , end surfaces 548 and 550 are not parallel . referring to fig5 , complementary dowel slots 568 are provided in male connector 510 and female connector 520 . when male connector 510 is located inside female connector 520 , dowels 570 are located in slots 568 to provide alignment such that first groove 512 and second groove 522 align to form a keyway 516 . referring back to fig3 , a first surface access relief 532 is provided on the surface of female connector 520 to provide passage to keyway 516 . a plurality of keys 540 is insertable through access relief 532 for sliding fit in keyway 516 . optionally , a second surface access relief 534 is provided . second access relief allows entry of a tool to push keys 540 out through first access relief 532 , and vice - versa , for disassembly of tool 10 . a fastener hole 528 is provided on female connector 520 for receiving a fastener 530 . one or more keys 540 has a threaded hole 542 for receiving fastener 530 in threaded engagement . connection of fastener 530 to key 540 locks key 540 in position inside keyway 516 . in this manner , male connector 510 of a first section of tool 10 , and female connector 520 of a second section of tool 10 are locked in engagement , without the use of a conventional threaded connection . dowels 570 resist relative rotation between male connector 510 of a first section of tool 10 , and female connector 520 of a second section of tool 10 . keys 540 prevent lateral separation of male connector 510 of a first section of tool 10 , and female connector 520 of a second section of tool 10 . a second fastener hole 530 can also be provided on the opposite side of ungrooved portion 524 . locating a second fastener hole 530 creates a stop for the remaining keys 540 to stack against . alternatively , ungrooved portion 514 and / or ungrooved portion 524 may be used as an end - stop when inserting keys 540 . fig5 is a cross - sectional side view of one embodiment of key - slot coupling system 500 illustrated in which a single male flange 510 is used to couple female flanges 520 a and 520 b of adjacent tubular sections of tool 10 . as illustrated , seals 562 are located in seal grooves 560 to create a sealed relationship between male flange 510 and female flanges 520 a and 520 b . also as shown , a dowel 570 can be located in matching dowel holes 568 between female flanges 520 a and 520 b as well as between male flange 510 and female flange 520 . receiving grooves 584 are shown on male flange 510 for receiving set screws 582 through threaded holes 580 ( see example in fig9 ) in female flanges 520 a and 520 b . fig6 and 7 are cross - sectional views of computer section 200 of tool 10 . as seen in fig3 , computer section 200 is connected to valve assembly 300 by key - slot connection system 500 . in the embodiment illustrated , computer section 200 and valve assembly 300 are joined together over a gear insert 280 . gear insert 280 provides the male connector for each key - slot connection 500 to which computer section 200 and valve assembly 300 are connected . as seen in fig6 , a threaded hole 580 is located through the female connector of computer section 200 . the male connector of gear insert 280 has a receiving groove 584 ( see fig5 ) for receiving the tip of a set screw 582 located in threaded hole 580 . another threaded hole 580 is located in the female connector of valve assembly 300 over the male connector of gear insert 280 for receiving a set screw 582 for engagement with a second receiving groove 584 on the male connector of gear insert 280 . optionally , a drill point may be used in place of receiving groove 584 . fig7 illustrates tool 10 rotated 90 degrees from the orientation illustrated in fig3 . computer section 200 has a chamber 240 for housing a circuit board 242 . as used herein , circuit board 242 includes a computer or processor or other electrical system device for controlling tool 10 . circuit board 242 is electrically connected to electrical connector 230 by electrical wiring ( not shown ). bushing 232 seals electrical connector 230 to maintain an atmospheric pressure inside chamber 240 for the protection of circuit board 242 . an electrical passage 244 intersects the lower end of chamber 240 . a longitudinal electrical passage 250 also intersects chamber 240 . electrical passage 250 is located near the outer diameter of tubular computer section 200 and runs substantially parallel to the centerline of computer section 200 . a motor 260 is located inside computer section 200 . motor 260 is electrically connected to circuit board 242 through electrical passage 244 . an electrical connector 246 may be located between circuit board 242 and motor 260 . electrical connector 246 may be sealed to computer section 200 to maintain the atmospheric ( or near atmospheric ) pressure condition inside chamber 240 . a gearbox 262 is connected to motor 260 . gearbox 262 converts the speed of motor 260 into torque . a harmonic drive 264 may be connected to gear box 262 to further convert the speed of motor 260 into torque . an electrical passage 350 is located near the outer diameter of tubular valve section 300 . electrical passage 350 is aligned with electrical passage 250 to form a continuous electrical passage for electrical connection of devices in valve section 300 with circuit board 242 . a spool seal 290 provides sealed connection of electrical passage 250 to electrical passage 350 . fig8 and 9 are cross - sectional side views of valve section 300 of tool 10 . fig9 illustrates tool 10 rotated 90 degrees from the orientation illustrated in fig8 . referring to fig8 , a shaft 362 is connected to harmonic drive 264 . the opposite end of shaft 362 is connected to a rotatable valve 370 . rotatable valve 370 has a vented opening 372 . valve 370 rotates over a stationary valve body 380 that has a body opening 382 . valve assembly 300 has an outlet port 306 connecting the exterior of tool 10 with the interior valve assembly 300 when valve 370 is open . valve 370 is opened by aligning vented opening 372 between outlet port 306 and valve body opening 382 . a resolver 360 is positioned over shaft 362 . resolver 360 is electrically connected to circuit board 242 through electrical passage 350 and electrical passage 250 . resolver 360 is a condition monitoring device , used to determine the position of shaft 362 and thus the position of valve 370 . resolver 360 communicates this information along data wires electrically connected to circuit board 242 . a computer or processor on circuit board 242 can be used to control the amount that valve 370 is opened as well as the opening and closing of valve 370 . advantageous to the present invention is the ability to open valve 370 in any partially rotated amount . this gives tool 10 the ability to fully control the amount of fluid flow from the lower reservoir that is comingling with the production of the upper reservoir . fig1 is a cross - sectional side view of sensor section 400 of tool 10 . sensor section 400 is connected to valve section 300 by key - slot connection system 500 . an electrical passage 450 is located near the outer diameter of tubular sensor section 400 . electrical passage 450 is aligned with electrical passage 350 to form a continuous electrical passage for electrical connection of devices in sensor section 400 with circuit board 242 . fig1 is a cross - sectional side view of the connection between valve section 300 and sensor section 400 , illustrating the continuous sealed coupling of electrical passages 350 and 450 . in this embodiment , a spool bore 352 is provided at the end of each electrical passage 350 and 450 . a spool seal 390 is inserted in spool bores 352 . spool seal 390 has a seal groove 394 on each end , and a spool o - ring 396 is located in each seal groove 394 . spool o - rings 396 seal spool seal 390 to each of electrical passages 350 and 450 to provide a sealed connection of electrical passage 350 to electrical passage 450 . as a result , the environmental conditions inside electrical passage 450 are controlled to be the same as for chamber 240 . fig1 is a side cross - sectional view of the analog to digital chamber of sensor section 400 of tool 10 . an analog to digital board 460 is located inside chamber 462 . chamber 462 has a cover 464 that provides an environmentally protective enclosure for chamber 462 . an electrical passage 466 ( see fig1 ) connects electrical passage 450 to sensor board chamber 462 located beneath cover 464 . fig1 is a side cross - sectional view of a casing sensor chamber 472 of sensor section 400 of tool 10 . a casing sensor 470 is located inside sensor chamber 472 , in communication with annulus between the production casing and tool 10 . in this position , casing sensor 470 can measure environmental conditions such as pressure of the production zone flow outside of tool 10 . chamber 472 has a cover 474 that provides an environmentally protective enclosure of chamber 472 . an electrical passage 476 connects chamber 470 with chamber 462 to provide a path for electrical connection of casing sensor 470 with analog to digital board 460 . fig1 is a side cross - sectional view of a tubing sensor chamber 442 of sensor section 400 of tool 10 . a tubing sensor 440 is located inside sensor chamber 442 , in communication with annulus between the production tubing and tool 10 . in this position , tubing sensor 440 can measure environmental conditions such as pressure of the production zone flow inside tool 10 . chamber 442 has a cover 444 that provides an environmentally protective enclosure of chamber 442 . an electrical passage 446 connects chamber 440 with chamber 462 to provide a path for electrical connection of tubing sensor 440 with analog to digital board 460 . as described herein above , the unique and novel features of tool 10 provide the beneficial ability to electronically connect electronic devices located in separate tool sections with a continuous electrical connector without the use of exposed plug connectors . further , the unique and novel features of tool 10 provide the beneficial ability of maintaining an atmospheric pressure condition within tool 10 across several tool section connections 500 , where external conditions down hole include extreme pressures . references to section names , such as “ upper ” and “ lower ” or “ computer ,” “ valve ,” or “ sensor ,” are merely for convenience and not intended to completely describe , require , or limit the contents of any section of tool 10 , and as used here , do not . it is known that the beginnings and ends of the sections may be variously located to include or exclude certain equipment . it is also known that certain teachings of the present invention can be applied to other subterranean tools besides a comingler . unique to the present inventions , among other aspects , is the non - threaded , and non - rotated coupling of contiguous sections 200 , 300 and 400 . connection system 500 may be described as a linear key - slot connection . such connections 500 are not known to have been used previously in the connection of tubulars for subterranean production . computer section 200 is connected to valve assembly 300 by key - slot connection 500 . similarly , valve assembly 300 is connected to sensor assembly 400 by key - slot connection 500 . as seen in fig2 , top sub 100 comprises a tubular having a threaded pin connection 102 for connection to a production string component 20 , such as a submersible pump . top sub 100 has a hollow center 104 . the submersible pump has electrical power supplied to it . power wiring from the submersible pump is connected to electrical connector 230 in top sub 100 to power tool 10 . electrical connector 230 is sealed in place inside hollow center 104 of top sub 100 by a bushing 232 . bushing 232 seals chamber 240 in computer section 200 from the environmental pressure on the other side of bushing 232 . key - slot connection 500 is fully detailed above , and only selected features are further detailed here . as described above , contiguous sections of tool 10 can be combined with a male flange 510 and a female flange 520 . they can also be combined as in fig5 , with abutting female flanges 520 a and 520 b over an internal male flange 510 . dowels 570 serve to align the internal grooves 512 and external grooves 522 to form keyways 516 . dowels 570 sections also serve to prevent relative rotation between the connecting sections of tool 10 . as seen in fig3 , keys 540 must slip into access relief 532 . excessively large or excessively small keys 540 are undesirable , as they become difficult and time consuming to assemble , and lack body strength to accept fastener 530 , or support the tensile loads between the sections of tool 10 . to strike a balance between access and function , the preferred number of keys is between about 8 and 11 , although a few more or less can be conveniently used . set screws 582 are located in threaded holes 580 and intersect receiving grooves 584 to axially bias the load between the connecting sections of tool 10 ( such as computer section 200 and gear insert 280 ) such that keys 540 support the primary tensile load between the connecting sections of tool 10 . as illustrated in fig5 , seals 562 can be located in seal grooves 560 to create a sealed relationship between male flange 510 and female flanges 520 a and 520 b . dowels 570 , set screws 582 intersecting receiving grooves 584 , and seals 562 can be combined with the system of keys 540 in keyways 516 to form a more durable , linear , non - rotated , key - slot connection system 500 . it will be understood by a person of ordinary skill in the art that individual components of this system can be modified or substituted without departing from the teaching , suggestion , spirit , and scope of the invention . for example , receiving grooves may be replaced with drill points , or simply not included . a fundamental advantage of the use of key - slot connection 500 is that it enables tool 10 to incorporate a system of environmentally controlled electronic passages ( 250 , 350 , 450 ) and chambers ( 240 , 442 , 462 , 472 ) connected by secondary passages ( 446 , 466 , 476 ). by use of key - slot connection 500 , the interconnected chamber and passage system ( collectively “ 600 ”) can be created as between multiple sections ( e . g ., 200 , 300 , 400 ). in particular , it is both unconventional and challenging to provide small diameter electronic passages such as 250 , 350 , and 450 in the cylinder wall portion of a tubular body section of a subterranean tool . referring fig3 , electrical passage 590 extends laterally through ungrooved portion 524 of female connector 520 of key - slot connection 500 . as seen in fig1 , a seal , such as spool seal 390 is inserted in spool bores 352 . spool seal 390 provides a sealed connection between the electrical passages ( e . g ., 250 and 350 ; 350 and 450 ) in contiguous sections 200 , 300 and 400 . as a result , the environmental conditions inside interconnected chamber and passage system 600 is protected . referring to fig7 , circuit board 242 receives electrical power through electrical connector 230 in top sub 100 ( fig2 ). the submersible pump is the source of the electrical power . circuit board 242 can send and receive data to the surface , through wiring connected to electrical connection 230 . electrical connection 230 may be four wire connections and may include a fifth wire for ground . additional connections may be provided . as stated above . circuit board 242 includes a computer or processor as necessary to operate tool 10 . circuit board 242 provides power through wiring in secondary passage 244 to connector 246 which is sealed to the body of computer section 200 to maintain the environmental integrity of chamber and passage system 600 . electrical connector 246 provides the connection for power to motor 260 for rotating valve 370 . gearbox 262 converts the speed of motor 260 into torque . a harmonic drive 264 may be connected to gearbox 262 to further convert the speed of motor 260 into torque , transmitted through shaft 362 to operate valve 370 . resolver 360 is electrically connected to circuit board 242 through electrical passage 350 and electrical passage 250 . resolver 360 determines the position of shaft 362 and thus the position of valve 370 , and communicates this information to circuit board 242 . the lower end of tool 10 is connected to a packer set between the upper and lower producing zones . tool 10 has an inlet orifice 402 near the lower end of tool 10 , for receiving a fluid from the lower producing zone into the inside 404 of sensor section 400 . tubular sensor 440 obtains pressure and temperature data from the lower zone fluid inside tool 10 , and transmits the data to analog to digital board 460 . casing sensor 470 obtains pressure and temperature data from the production fluid outside tool 10 , and transmits the data to analog to digital board 460 . analog to digital board 460 converts the analog readings from the sensors and transmits the data to circuit board 242 , which transmits the information to the surface . an outlet port 306 extends through the cylindrical wall of sensor section 400 , adjacent to valve 370 . valve 370 has a vented portal 372 . by instructions from the surface to circuit board 242 , valve 370 is controllably rotatable between an open position in which vented portal 372 is aligned with the outlet port 306 so that lower zone fluid inside tool 10 may flow through outlet port 306 . lower zone fluid flowing through outlet port 306 is thus comingled with the upper zone fluid and pumped together by the submersible pump . when valve 370 is rotated to a closed position , vented portal 372 is not aligned with outlet port 306 , and the flow of lower zone production fluid through outlet port 306 is blocked by valve 370 . in the preferred embodiment , valve 370 valve is positionable to select any desired degree of alignment between the vented portal 372 with outlet port 306 to selectively control the rate of flow of lower zone fluid to be comingled with the upper zone fluid . a computer or processor on circuit board 242 can be used to control the amount of opening and closing of valve 370 , based on instructions from the surface , or based on a preprogrammed algorithm that responds to data from sensors 440 , 470 , or other input . advantageous to the present invention is the ability to open valve 370 in any partially rotated amount . this provides tool 10 with the desirable ability to fully control the amount of fluid flow from the lower reservoir that is comingling with the production of the upper reservoir . as described herein above , the unique and novel features of tool 10 provide the beneficial ability to electronically connect electronic devices located in separate tool sections with a continuous electrical connector without the use of exposed plug connectors . further , the unique and novel features of tool 10 provide the beneficial ability of maintaining an atmospheric pressure condition within tool 10 across several tool section connections 500 , where external conditions downhole include extreme pressures . having thus described the exemplary embodiments , it is noted that the embodiments disclosed are illustrative rather than limiting in nature and that a wide range of variations , modifications , changes , and substitutions are contemplated in the foregoing disclosure and , in some instances , some features of the present invention may be employed without a corresponding use of the other features . many such variations and modifications may be considered desirable by those skilled in the art based upon a review of the foregoing description of preferred embodiments . accordingly , it is contemplated that the appended claims will cover any such modifications or embodiments that fall within the true scope of the invention . | 4 |
by taking as an example a splitting and sticking process of a stress film in a cmos structure , preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings . fig1 is a schematic cross - sectional view of an essential part of a mosfet formation step . a basic cmos structure having an n - mosfet 10 and a p - mosfet 20 as shown in fig1 is first formed according to a normal process . the cmos structure is , formed , for example , using a p - type si substrate 1 . the n - mosfet 10 and the p - mosfet 20 are subjected to element isolation by a shallow trench isolation ( sti ) 2 . the n - mosfet 10 is formed as follows . within the si substrate 1 for forming the n - mosfet 10 , a p - type well region 11 is formed , for example , using a p - type impurity such as boron ( b ). on such an si substrate 1 , a gate electrode 13 made of polysilicon is formed through a gate insulating film 12 made of silicon oxide ( sio 2 ). on side walls of the gate insulating film 12 and the gate electrode 13 , a sidewall 14 made of sio 2 is formed . within the si substrate 1 on both sides of the gate electrode 13 , a source drain extension region 15 and a source drain region 16 are formed using an n - type impurity such as phosphorus ( p ) or arsenic ( as ). on a surface layer of the gate electrode 13 as well as on a surface layer of the source drain region 16 , silicide layers 17 are formed . no well region 11 may be formed within the si substrate 1 of the n - mosfet 10 . the p - mosfet 20 is formed as follows . within the si substrate 1 for forming the p - mosfet 20 , an n - type well region 21 is formed , for example , using p or as . on such an si substrate 1 , a gate electrode 23 made of polysilicon is formed through a gate insulating film 22 made of silicon oxide ( sio 2 ). on side walls of the gate insulating film 22 and the gate electrode 23 , a sidewall 24 made of sio 2 is formed . within the si substrate 1 on both sides of the gate electrode 23 , a source drain extension region 25 and a source drain region 26 are formed using a p - type impurity such as b . on a surface layer of the gate electrode 23 as well as on a surface layer of the source drain region 26 , silicide layers 27 are formed . the cmos structure ( substrate ) including the n - mosfet 10 and p - mosfet 20 each having the above - described structure is formed according to a normal process . herein , a film thickness and impurity concentration of each portion in this cmos structure are arbitrarily set in response to demand characteristics of the cmos structure . by way of example , the gate electrodes 13 and 23 are each formed to a gate length of about 30 to 40 nm and a gate height of about 100 nm . the sidewalls 14 and 24 are each formed to a width of about 50 nm . fig2 is a schematic cross - sectional view of an essential part of a tensile stress film deposition step . after formation of the n - mosfet 10 and the p - mosfet 20 , a tensile stress film 3 made of sin and having a film thickness of about 70 nm is deposited over the whole surface of the substrate . the tensile stress film 3 is deposited , for example , using a chemical vapor deposition ( cvd ) method . in the method , silane gas ( sih 2 cl 2 , sih 4 , si 2 h 4 , si 2 h 6 ) is used as an si material and ammonia ( nh 3 ) gas is used as an n material . during the deposition , a flow rate of the silane gas is set in the range of 5 to 50 sccm and a flow rate of the nh 3 gas is set in the range of 500 to 10000 sccm . further , nitrogen gas ( n 2 ) or argon ( ar ) gas is used as a carrier gas and a flow rate thereof is set in the range of 500 to 10000 sccm . a chamber for introducing each gas is controlled to have an inner pressure of 0 . 1 to 400 torr and a temperature of 400 ° c . to 450 ° c . herein , the flow rate unit sccm is a reduced value of the flow rate ml / min at 0 ° c . and 101 . 3 kpa . 1 torr is about 133 . 322 pa . the tensile stress film 3 deposited under such conditions has a tensile stress of about 400 to 500 mpa . in the formed tensile stress film 3 , hydrogen ( h ) usually remains . herein , after the deposition of the tensile stress film 3 over the whole surface of the substrate , the process proceeds to the next step without performing the uv irradiation to the film 3 . fig3 is a schematic cross - sectional view of an essential part of an oxide film deposition step . after depositing the tensile stress film 3 over the whole surface of the substrate , a sio 2 film 4 is deposited on the film 3 . the sio 2 film 4 is deposited to a film thickness of about 25 nm , for example , using a plasma cvd method . on this occasion , for example , a mixed gas composed of sih 4 and oxygen ( o 2 ) is used and a substrate temperature is set to about 400 ° c . the sio 2 film 4 herein formed functions as an etching stopper in etching the after - mentioned compressive stress film 6 ( see fig8 ). fig4 is a schematic cross - sectional view of an essential part of an oxide film etching step . after the deposition of the sio 2 film 4 , a resist mask 5 is formed on the n - mosfet 10 side and the sio 2 film 4 deposited on the p - mosfet 20 side is removed by etching . the etching of the sio 2 film 4 is performed , for example , by a reactive ion etching ( rie ) method using a c 4 f 8 / ar / o 2 gas . fig5 is a schematic cross - sectional view of an essential part of a tensile stress film etching step . after the etching of the sio 2 film 4 , the tensile stress film 3 deposited on the p - mosfet 20 side is removed by etching using the same resist mask 5 . the etching of the film 3 is performed , for example , by the rie method using a chf 3 / ar / o 2 gas . after the etching of the tensile stress film 3 on the p - mosfet 20 side , the resist mask 5 is removed . through the etching of the sio 2 film 4 shown in fig4 as well as the etching of the tensile stress film 3 shown in fig5 , the tensile stress film 3 and the sio 2 film 4 are left only on the n - mosfet 10 . to a channel region of the n - mosfet 10 , a tensile stress is applied by this tensile stress film 3 . fig6 is a schematic cross - sectional view of an essential part of a uv irradiation step . after the removal of the resist mask 5 shown in fig5 , uv irradiation is performed to the tensile stress film 3 which remains on the n - mosfet 10 . using a uv irradiation apparatus capable of performing the uv irradiation while controlling a chamber inside to a predetermined environment , the uv irradiation is performed , for example , under conditions where the irradiation temperature is about 450 ° c . and the irradiation time is about 20 minutes . the irradiated uv transmits the thin sio 2 film 4 to reach the tensile stress film 3 under the film 4 . the tensile stress film 3 irradiated with uv is increased in the tensile stress as well as is cured as compared with that before the uv irradiation . this results from the fact that hydrogen which remains in the tensile stress film 3 is removed by the uv irradiation . by this uv irradiation , the tensile stress which is about from 400 to 500 mpa before the uv irradiation can be improved to about 2 gpa . in order to improve a tensile stress , the uv irradiation to the tensile stress film 3 may be performed over the whole surface of the film 3 after the deposition of the film 3 over the whole surface of the substrate shown in fig2 . in this case , however , the tensile stress film 3 is cured with the improvement of the tensile stress . therefore , when subsequently removing by etching the film 3 from the p - mosfet 20 surface ( see fig5 ), it becomes difficult to remove the film 3 with high accuracy as well as with no damage to a foundation layer of the film 3 . accordingly , by performing the uv irradiation after the etching of the film 3 as shown in fig6 , the removal by etching of the film 3 is made easy and at the same time , an improvement of the tensile stress can be attained . in the case of performing uv irradiation over the whole surface of the tensile stress film 3 after the deposition of the film 3 shown in fig2 , the uv irradiation is performed , for example , under conditions where the irradiation temperature is about 450 ° c . and the irradiation time is about 25 minutes . in other words , in order to obtain a constant improvement effect of the tensile stress , since the film 3 is formed over the whole surface of the substrate , uv irradiation for a longer time is required . on the contrary , when performing uv irradiation after the etching of the tensile stress film 3 as shown in fig6 , since the film 3 is formed only on the n - mosfet 10 , uv irradiation for a shorter time is enough . in the uv irradiation step shown in fig6 , uv is irradiated not only to the tensile stress film 3 which remains on the n - mosfet 10 but also to the p - mosfet 20 which is exposed by the removal of the film 3 in the step shown in fig5 . however , no characteristic deterioration of the p - mosfet 20 due to this uv irradiation is recognized . accordingly , by performing the uv irradiation , an improvement in the tensile stress of the film 3 which remains on the n - mosfet 10 can be attained without exerting any influence on the p - mosfet 20 . a sidewall of a mosfet is generally formed using sio 2 or sin . in the n - mosfet 10 and the p - mosfet 20 , the sidewalls 14 and 24 are preferably formed using sio 2 as described above . the reason is that in the uv irradiation step shown in fig6 , uv is irradiated not only to the tensile stress film 3 on the n - mosfet 10 but also to the sidewall 14 of the n - mosfet 10 or to the sidewall 24 of the p - mosfet 20 . in other words , when the sidewalls 14 and 24 are formed using sin , a tensile stress may occur on the sidewalls due to the uv irradiation , depending on the composition of the sidewalls . when the tensile stress occurs on the sidewall 14 of the n - mosfet 10 , the tensile stress is applied to a channel region of the n - mosfet 10 from the tensile stress film 3 as well as from the sidewall 14 . on the other hand , when the tensile stress occurs on the sidewall 24 of the p - mosfet 20 , the tensile stress is applied to a channel region of the p - mosfet 20 . therefore , even when the compressive stress film 6 is formed on the p - mosfet 20 as described later , an effect of the film 6 is reduced . it is also technically possible to form the sidewall 14 using sin and to form the sidewall 24 using sio 2 . however , considering that the tensile stress of the uv - irradiated tensile stress film 3 sufficiently increases , there is no need to form the sidewalls 14 and 24 using different materials . therefore , it is simple and effective to form both of the sidewalls 14 and 24 using sio 2 . fig7 is a schematic cross - sectional view of an essential part of a compressive stress film deposition step . after the uv irradiation to the tensile stress film 3 on the n - mosfet 10 , the compressive stress film 6 made of sin and having a film thickness of about 70 nm is deposited over the whole surface of the substrate where the film 3 and the sio 2 film 4 remain . the compressive stress film 6 is deposited , for example , using the cvd method . in the method , sih 4 gas is used as an si material and nh 3 gas is used as an n material . during the deposition , a flow rate of the sih 4 gas is set in the range of 100 to 1000 sccm and a flow rate of the nh 3 gas is set in the range of 500 to 10000 sccm . further , nitrogen ( n 2 ) gas or argon ( ar ) gas is used as a carrier gas and the flow rate thereof is set in the range of 500 to 10000 sccm . a chamber for introducing each gas is controlled to have an inner pressure of 0 . 1 to 400 torr and a temperature of 400 to 450 ° c . rf power is about 100 to 1000 w . the compressive stress film 6 deposited under such conditions has a compressive stress of about 3 gpa . fig8 is a schematic cross - sectional view of an essential part of a compressive stress film etching step . after depositing the compressive stress film 6 over the whole surface , a resist mask 7 is formed on the p - mosfet 20 side . using the sio 2 film 4 as an etching stopper , the compressive stress film 6 deposited on the n - mosfet 10 side is removed by etching . the etching of the compressive stress film 6 is performed , for example , by the rie method using a chf 3 / ar / o 2 gas . after the etching of the compressive stress film 6 on the n - mosfet 10 side , the resist mask 7 is removed . fig9 is a schematic cross - sectional view of an essential part of an interlayer insulating film deposition step . after removing the resist mask 7 , a teos oxide film 8 as an interlayer insulating film is deposited over the whole surface . using tetra - ethoxysilane ( teos , si ( oc 2 h 5 oh ) 4 ) as a raw material , the teos oxide film 8 is deposited using the plasma cvd method . the teos oxide film 8 is first deposited over the whole surface to a film thickness of about 600 nm . then , the film 8 is flattened using a chemical mechanical polishing ( cmp ) method and finally reduced to a film thickness of about 350 nm . through the steps so far , there is completed the cmos structure in which the tensile stress film 3 and the compressive stress film 6 are split and stuck on the n - mosfet 10 and the p - mosfet 20 , respectively . thereafter , a contact electrode and a wiring layer are formed according to a normal process . thus , a device having the cmos structure is completed . as described above , in the first embodiment , the tensile stress film 3 is formed over the whole surface . then , the film 3 is removed by etching from the p - mosfet 20 surface while being left on the n - mosfet 10 . further , uv irradiation is performed to the remaining film 3 . thereafter , the compressive stress film 6 is formed on the p - mosfet 20 . therefore , the etching of the tensile stress film 3 is performed with ease and with high accuracy as well as the tensile stress film 3 having a large tensile stress can be formed on the n - mosfet 10 . accordingly , there can be realized a high - performance and high - quality cmos device in which a large tensile stress is applied to the channel region of the n - mosfet 10 and a large compressive stress is applied to the channel region of the p - mosfet 20 . the uv irradiation to the tensile stress film 3 removes hydrogen which remains in the film as described above . accompanying with the removal , a tensile stress of the film 3 is improved and as a result , an improvement in an electron mobility in the n - mosfet 10 is attained . further , by the removal of hydrogen from the tensile stress film 3 , negative bias temperature instability ( nbti ) in the cmos device may be suppressed . in the second embodiment , the same elements as those shown in the first embodiment are indicated by the same reference numerals as in the first embodiment and the detailed description is omitted . the second embodiment differs from the first embodiment in the following point . in the second embodiment , the tensile stress film 3 and the compressive stress film 6 are formed on the n - mosfet 10 and the p - mosfet 20 , respectively . then , uv irradiation is collectively performed to both of the tensile stress film 3 and the compressive stress film 6 . more specifically , deposition of the tensile stress film 3 shown in fig2 , formation and etching of the sio 2 film 4 shown in fig3 and 4 , and etching of the tensile stress film 3 shown in fig5 are performed on the cmos structure shown in fig1 . then , without performing the uv irradiation , the process proceeds to the deposition step of the compressive stress film 6 shown in fig7 . further , the film 6 on the film 4 is removed by etching and then , a resist mask 7 is removed as shown in fig8 . in the second embodiment , when the patterning of the films 3 and 6 is thus completed , uv irradiation is performed to the films 3 and 6 . fig1 is a schematic cross - sectional view of an essential part of a uv irradiation step to a tensile stress film and a compressive stress film . when removing the resist mask 7 after the etching of the compressive stress film 6 shown in fig8 , a state as shown in fig1 is obtained . that is , the tensile stress film 3 before the uv irradiation is formed on the n - mosfet 10 and the compressive stress film 6 before the uv irradiation is formed on the p - mosfet 20 . then , uv irradiation is collectively performed to both of the tensile stress film 3 and the compressive stress film 6 . using a uv irradiation apparatus capable of performing uv irradiation while controlling a chamber inside to a predetermined environment , the uv irradiation is performed for example , under conditions where the irradiation temperature is about 450 ° c . and the irradiation time is about 20 minutes . by this uv irradiation , the tensile stress in the film 3 , which is about from 400 to 500 mpa before the uv irradiation , can be improved to about 2 gpa . during the uv irradiation , uv is irradiated to the tensile stress film 3 as well as to the compressive stress film 6 . the uv irradiation to the compressive stress film 6 leads to reduction in the compressive stress . however , when depositing the film 6 under the above - described conditions ( see the description of fig7 ), the amount of reduction in the compressive stress due to uv irradiation can be suppressed to 200 mpa or less ( the compressive stress in the film 6 before the uv irradiation is about 3 gpa ). after the uv irradiation shown in fig1 , the teos oxide film 8 having a predetermined film thickness is formed as shown in fig9 . thus , there is completed the cmos structure in which the tensile stress film 3 and the compressive stress film 6 are split and stuck on the n - mosfet 10 and the p - mosfet 20 , respectively . thereafter , a contact electrode and a wiring layer are formed according to a normal process . thus , a device having the cmos structure is completed . in this second embodiment , the tensile stress film 3 is first deposited over the whole surface . then , the film 3 deposited on the p - mosfet 20 side is removed by etching so as to be left on the n - mosfet 10 . thereafter , the compressive stress film 6 is deposited over the whole surface . then , the film 6 deposited on the n - mosfet 10 side is removed by etching so as to be left on the p - mosfet 20 . a deposition order of the tensile stress film 3 and the compressive stress film 6 may be reversed . more specifically , the compressive stress film 6 is first deposited over the whole surface . then , the film 6 deposited on the n - mosfet 10 side is removed by etching so as to be left on the p - mosfet 20 . thereafter , the tensile stress film 3 is deposited over the whole surface . then , the film 3 deposited on the p - mosfet 20 side is removed by etching so as to be left on the n - mosfet 10 . also in this case , after completion of the etching to remove from the p - mosfet 20 side the tensile stress film 3 deposited over the whole surface and to leave the film 3 on the n - mosfet 10 surface , uv irradiation under the predetermined conditions may be collectively performed to the tensile stress film 3 and the compressive stress film 6 . as described above , in the second embodiment , after completion of the etching of the tensile stress film 3 and compressive stress film 6 deposited under the predetermined conditions , the uv irradiation is collectively performed to the films 3 and 6 . therefore , the etching of the tensile stress film 3 is performed with ease and with high accuracy as well as the tensile stress film 3 having a large tensile stress can be formed on the n - mosfet 10 . further , the tensile stress of the compressive stress film 6 is kept large even after the uv irradiation . accordingly , there can be realized a high - performance and high - quality cmos device in which a large tensile stress is applied to the channel region of the n - mosfet 10 and a large compressive stress is applied to the channel region of the p - mosfet 20 . the collective uv irradiation to the tensile stress film 3 and the compressive stress film 6 removes hydrogen which remains in the films 3 and 6 , as described above . when hydrogen is removed from the films 3 and 6 , the nbti in the cmos device may be suppressed . in the above description , the splitting and sticking process of the tensile stress film and the compressive stress film in the cmos structure is described by way of example . the above - described method for performing the uv irradiation to the tensile stress film after completion of the etching can be similarly applied to a forming process of the cmos device as well as of various devices having an n - mosfet . more specifically , there may be employed a method for depositing over the whole surface of the substrate having formed thereon the n - mosfet the tensile stress film having the tensile stress , removing by etching the film while leaving it on the n - mosfet , and performing uv irradiation to the tensile stress film which remains on the n - mosfet . in the above description , the tensile stress film having a certain level of tensile stress is previously deposited on the n - mosfet . then , uv irradiation is performed to the tensile stress film to increase the tensile stress of the film . in addition , there may be employed , for example , a method for depositing the compressive stress film having a certain level of compressive stress and performing uv irradiation to the film to produce the compressive stress . also to a case of performing the uv irradiation to the compressive stress film for the purpose of modification and nbti suppression , the above - described method for performing the uv irradiation after the etching can be applied . in the present invention , the stress film is formed on the substrate having formed thereon a transistor , the stress film is removed while being left on the transistor and then , uv irradiation is performed to the remaining stress film . therefore , removal of the stress film can be performed with high accuracy . as a result , there can be realized the high - performance and high - quality semiconductor device having a transistor in which the carrier mobility is improved by the stress film . the foregoing is considered as illustrative only of the principles of the present invention . further , since numerous modifications and changes will readily occur to those skilled in the art , it is not desired to limit the invention to the exact construction and applications shown and described , and accordingly , all suitable modifications and equivalents may be regarded as falling within the scope of the invention in the appended claims and their equivalents . | 7 |
the pest repellent of the present invention may be the active ingredient of imiprothrin itself , but providing imiprothrin as a formulation is generally standard . more specifically , a formulation wherein imiprothrin is supported on an appropriate carrier is standard . sheet formulations , formulations wherein imiprothrin is kneaded into a resin , emulsifiable concentrates , oil formulations , wettable powders , flowable formulations , granules , dusts , enmicrocapsulated formulations , aerosols , heat volatile formulations , and so on are examples of possible formulations . the sheet materials are not especially restricted when the pest repellent is formulated as a sheet . papers , synthetic resins , cloths , and so on are set forth as examples of the said sheet materials . the formulated sheet may generally comprise about 0 . 01 to 10 g of imiprothrin for every 1 m 2 of the said sheet . furthermore , in the event the pest repellent takes the formulation of emulsifiable concentrates or oil formulation , the said formulations generally comprise about 0 . 01 to 10 % by weight of imiprothrin . in addition to imiprothrin , any other pest repelling ingredient may be incorporated to the pest repellent . examples of the other pest repelling ingredients that may be additionally incorporated are n , n - diethyl - m - toluamide , carane - 3 , 4 - diol , 1 - methylpropyl 2 -( 2 - hydroxyethyl )- 1 - piperizinecarboxylate , p - menthane - 3 , 8 - diol , pest repelling plant essential oils and so on . the pest repellent is generally utilized by disposing the pest repellent at the targeted area of pest repelling . the typical household , warehouse , dining areas , and so on areas wherein the pest may invade are examples of objective areas wherein the pest repellent generally may be disposed . it is especially effective to repel pests such as cockroaches by setting the sheet formulation of the pest repellent under intricate machinery such as a personal computer , copy machine , and telephone , or under vending machines , or so on . the pest repellent may also be utilized to repel pests such as mosquitoes ( culicidae ), black flies ( simuliidae ), stable flies ( stomoxyidae ) by disposing onto the body or clothes when the pest repellent is formulated as an ethanol solution , isopropanol solution , lotion or cream formulation , or so on . the pest repellent may further be utilized to repel or stop the invasion of pests such as ants , pill bugs , sow bugs , millipedes ( anamorpha ), millipedes ( epimorpha ), centipedes , and so on by dispersing around the perimeter of a typical household , warehouse , dining areas , and so on . when the pest repellent is formulated as emulsifiable concentrates , wettable powders , flowable formulations , enmicrocapsulated formulations , and so on , a water dilution is applied . when the pest repellent is formulated as granules , dusts , aerosols , oil formulations , or so on , the pest repellent is applied by itself . the amount of imiprothrin employed for the pest repellent does vary with the objective location , utilization method , variation of formulation , targeted pest , and so on , but usually is about 0 . 01 g to 10 g for 1 m 2 . the pest repellent of the present invention may be employed in various methods but , a method wherein the pest is exposed with the present invention either directly or by previously preparing the pest repellent in an area that is possible for the pest to be exposed to the pest repellent is preferable . more specifically , the pest repellent may be applied in a pest repelling method such as dispersal , spraying , spreading , placing , pasting , or so on . in addition , the pest repellent may also be employed in a pest repelling method wherein the pest repellent is supported on the ingredients of household items by means of incorporation such as spreading , soaking , kneading and mixing , dripping / dropping , and so on before the said ingredient is formed to an household item . the utilization of the household item that was formed from the said ingredients that preserve the pest repellent will repel pests and is also a method to repel pests . the pest repellent is not limited to repel just dictyoptera such as german cockroach ( blattella germanica ), smokybrown cockroach ( periplaneta fuliginosa ), american cockroach ( periplaneta americana ), brown cockroach ( periplaneta brunnea ), oriental cockroach ( blatta orientalis ), and so on ; lepidoptera such as casemaking clothes moth ( tinea pellionella ), webbing clothes moth ( tineola bisselliella ), indian mean moth ( plodia interpunctella ), and so on ; diptera such as culex spp ., anopheles spp ., aedes spp ., muscidae , small fruit flies or vinegar flies ( drosophilidae ), moth flies or sand flies ( psychodidae ), phoridae , and so on ; coleoptera such as the maize weevil ( sitophilus zeamais ), adzuki bean weevil ( callosobruchus chinensis ), black carpet beetle ( attagenus unicolorjaponicus ), varied carpet beetle ( authrenus verbasci ), anobiidae , powderpost beetle ( lyctus brunneus ), robe beetle ( paederus fuscipes ), and so on ; hymenoptera such as ants ( formicidae ), bethylidae , and so on ; siphonaptera such as human flea ( pulex irritans ), cat flea ( ctenocephalides felis ), and so on ; lice ( anoplura ) such as body louse ( pudiculus humanus ), crab louse ( pthrius pubis ), and so on , isoptera such as reticulitermes speratus , formosan subterranean termite ( coptotermes formosanus ), and so on ; and so on harmful insects , but is also efficacious in repelling mites and ticks ( acarina ) such as house dust mites ( for example , acaridae , dermanyssidae , pyroglyphidae , chetyletidae , and so on ), ticks ( for example , boophilus microplus ), ornithonyssus spp ., and so on ; spiders ; scorpions ( scorpionida ); oniscoidea such as pillbugs and sow bugs ; millipeds ( chilopoda ) such as anamorpha , epimorpha , centipede , and so on ; gastropoda such as slugs and snails ; leeches ; and so on . namely , the pests include arthropod , mollusca , annelida , and so on . a shelter was prepared by constructing an entrance / exit into a paper box ( length 7 cm × width 10 cm × height 2 cm ). a sheet formulation ( 7 . 6 cm × 2 . 6 cm ) was then prepared by spreading 0 . 4 ml of an acetone solution comprising of 0 . 25 % by weight of imiprothrin onto a glass slide and then drying the formulation . the said sheet formulation was then located in a position on the floor in the said shelter wherein the said formulation follows the entrance / exit . food , water , the obtained shelter containing the sheet formulation , and 10 male and female adult cockroaches were deposited into a plastic case ( length 30 cm × width 20 cm × height 8 cm ). the quantity of cockroaches in the said shelter was counted 24 hours later . in addition , a shelter containing the sheet formulation was preserved for 2 weeks at 25 ° c . and wherein the humidity was at 60 %. food , water , the preserved shelter , and 10 male and female adult cockroaches were re - deposited into the emptied plastic case . the quantity of cockroaches in the said shelter was counted 24 hours later . furthermore , empenthrin and n , n - diethyl - m - toluamide ( deet ) were similarly tested for the ability to repel german cockroaches from the shelter . a control was also performed by utilizing a shelter without repellent disposal . the results are given in table 1 . within the table , a &# 34 ;-&# 34 ; represents that the invasion rate of cockroaches into the shelter was less than 30 %, a &# 34 ;+&# 34 ; represents 30 % or more to less than 50 %, and a &# 34 ;++&# 34 ; represents 50 % or more . table 1______________________________________ results right after disposal results 2 weeks later______________________________________imiprothrin - - empenthrin + ++ deet - ++ no compositional ++ disposal______________________________________ the insect repellent of the present invention is effective in repelling insects such as cockroaches . imiprothrin was able to repel insects 2 weeks after disposal while other well known pest repellents such as empenthrin and n , n - diethyl - m - toluamine were ineffective after such an elapse of time . the ability of imiprothrin to sustain repelling activity after a long period of time negates the necessity to tediously continue pest repellent disposal to efficaciously repel pests . in addition , the ability of imiprothrin to repel a difficult pest such as the cockroach also deems imiprothrin as an excellent repellent against a variety of pest . | 8 |
in view of the above , the present invention through one or more of its various aspects and / or embodiments is presented to provide one or more advantages , such as those noted below . referring to fig1 , a system 100 in accordance with an embodiment of the present invention is illustrated . a router 128 , asynchronous transfer mode ( atm ) switch 132 , digital subscriber line access multiplexer ( dslam ) 104 , dsl modem 134 , and customer premises equipment ( cpe ) 136 provide connectivity between the user and the internet 110 . a digital subscriber line access multiplexers ( dslam ) is a mechanism at a phone company &# 39 ; s central location that links many customer dsl connections to a single high - speed atm line . when the phone company receives a dsl signal , an adsl modem with a plain old telephone service ( pots ) splitter detects voice calls and data . voice calls are sent to the public switched telephone system ( pstn ), and data are sent to the dslam , where the data passes through the atm to the internet , then back through the dslam and adsl modem before returning to the customer &# 39 ; s personal computer ( pc ). the dslam records atm cell counts for each line and stores them in memory . the dslam 104 is coupled to the internet 110 and couples to a plurality of dsl lines such as illustrated dsl lines 120 , 122 , and 124 . the dslam receives signals from the dsl lines and connects them to the internet using well known multiplexing techniques . the present invention comprises a digital subscriber line ( dsl ) control system processor 102 coupled to the internet 110 , a line profile database storage 108 , and a historical dsl performance database storage 106 . the line profile database comprises a variety of data objects storing performance parameters related for each dsl line , such as dsl lines 120 , 122 , and 124 . performance parameters can include , among others , bit rates , signal attenuation , signal to noise ratios , observed crosstalk , observed echo due to taps , and bit loading anomalies due to bonding or grounding impairments that have a high degree of uniformity at a neighborhood level . the historical dsl performance database 106 maintains the history of dsl performance parameters associated with a customer &# 39 ; s communication line . the dsl control system processor 102 includes a decision model 130 for correlating performance parameters . the dsl control system 102 can be used to correlate performance parameters for a plurality of selected dsl lines . the dsl lines may be related as physically existing in the same general area such as the same street or neighborhood . dsl lines having degraded performance parameters may alternatively be determined based on historical performance data 106 . the dsl control system 102 may be implemented as a computer system that includes software to execute the decision model 130 and the dsl control system . the dsl performance database 106 and the line profile database 108 may be implemented with standard computer database technology . the dsl control system 102 collects data from one or all of the modem , cpe , atm switch , and router . data can be collected non - intrusively that is , data can be collected while an application is running over the dsl line for which data is being collected . the decision model selects data from the collected data . as is well known , adsl service architecture generally relies on pre - existing lines of the telephone distribution network . preexisting lines generally comprise copper wire connections . equipment is generally designed to operate at several levels of the network , from equipment designed to handle large quantities of communication lines to equipment designed for an individual user . at higher levels , a distribution plant serves multiple customers ( generally from 20 , 000 to 40 , 000 phone lines ). at a local level , an adsl serving terminal generally serves about 25 phone lines . customer lines connected to the same serving terminal are expected by general adsl performance guidelines to have similar loop lengths ( usually about 1000 feet ) and to have performance parameters displaying similar performance . adsl service rate and performance characteristics are a function of loop length , levels of attenuation , noise , observed crosstalk , etc . fig2 shows a flowchart 200 of the present invention . specific adsl performance parameters are recorded as shown in box 201 . dsl performance parameters include but are not limited to upstream and downstream bit rates and error counts . parameters can be collected , for example , during an initiation sequence for establishing an internet connection between modem 134 and dslam 104 , also known as “ handshaking ”, and are compiled most often in a periodic fashion , such as once a day or once a week . these performance parameters are stored in data objects within a relational database such as the line profile database 108 . as discussed in box 203 , data objects are selected according to selection criteria chosen by an operator . a useful selection criteria is to select data objects representing lines that are physically “ close ” to the problematic line , i . e ., share the same zip code , street , city block , etc . physically close lines are “ related ” lines sharing a same general location . other types of relationships such as similar performance parameters can be used to associate a group of “ related ” communication lines . any standard method for selecting from a database , such as structured query language ( sql ), can be used to perform the selection . in one aspect of the present invention , selection can be made via a web based graphical user interface . as discussed in box 205 , performance parameters of the selected lines are correlated . in one instance , correlation can be a comparison of performance parameters among the selected data objects representing performance data for related communication lines . if another one of the selected lines exhibits similar behavior , the operator may wish to address both problems in one truck roll ( i . e ., one field maintenance operation ). on the other hand , the operator may be alerted that a problem is not that of the individual customer , but is a result of equipment failure serving many customers . the operator can then alter a field maintenance plan appropriately to service the larger equipment failure rather than the individual line . such correlation can lead to more proactive and efficient service . fig3 shows a screenshot of an input screen 300 in one aspect of the present invention . an operator inputs a relevant selection criteria 302 , i . e ., the phone number of a customer reporting a network - related problem . fig4 shows a display screen 400 showing one possible result of performing a selection using the selection criteria input in fig3 . the selection criteria 302 is a dsl customer line . the search will return phone numbers of related dsl lines 412 proximate to the dsl line input 302 . proximate includes but is not limited to lines on the same street , in the same neighborhood or served by the same equipment . the returned proximate lines are “ related ” lines . as shown in fig4 performance parameters including , but not limited to , downstream bit rate 402 , downstream maximum attainable bit rate 404 , estimated loop length 406 and downstream relative capacity 408 for each of the related adsl lines . in the example of fig4 , related lines are those lines used by customers along the same street 410 as the input phone number 302 . a correlation can then be made of adsl performance of these related adsl lines . grouping the adsl lines by physical street address and performance enables identifying and pinpointing the common causes of adsl line performance degradation . since performance parameters are expected to behave similarly for related lines , empirical evidence of line performance for a single line can be the leading indicator of performance for related lines . assuming that an adsl line &# 39 ; s performance is tightly coupled ( highly correlated ) to a group of proximate related lines , if a related line is observed to have degradation of performance , then related adsl lines may likewise experience the same degradation . if this related adsl degradation is observed , a proactive maintenance treatment can be performed on the related adsl lines . for example , when an adsl customer calls in to report a technical problem , a service technician can retrieve information on related lines . if many of these related lines show similar performance degradation , the technician can treat these related lines in one service call rather than many individual calls to each line separately . as a result , not only is greater customer satisfaction achieved by proactive treatment related lines exhibiting the same problem before their users call or even disconnect , but also it is possible to reduce the amount of trouble tickets and truck rolls . thus , the present invention enables a single maintenance operation to benefit multiple lines . this reduces operation cost and labor cost . in addition , it is possible to normalize higher level performance for related lines with a single integrated maintenance operation . if one or more adsl lines is observed to have much a higher performance level than related adsl lines , the present invention enables an operator to normalize related lines to higher performance levels . in another aspect of the present invention , historical performance data can be maintained that statistically validates performance association or coupling between related lines ( tightly coupled or loosely coupled ) over time . if the performance parameters of related lines are found to diverge over time , a correlation can be made to factors within an individual living unit which can drive the divergence ( e . g ., inside wire , splitter or levels of micro - filter at a home , cpe differences ). thus , a determination can be made as to whether a degradation of service is attributable to an event occurring on a single line ( i . e ., installation of a new modem or cpe ) or if the problem is related to a network component addressing many related network connections , such as a dslam or a router . fig5 - 7 illustrate screenshots of data collected and displayed from a real - time loop performance analyzer in one aspect of the present invention . a real time loop performance analyzer collects performance data for a customer &# 39 ; s communication line , such as an adsl line . some of the performance data categories collected shown as dsl line attributes are : downstream speed 502 , upstream speed 504 , noise levels 506 for upstream noise 508 and downstream 510 and cell counts for upstream 514 and downstream 512 . displaying raw data collected from a selected customer line , line analysis as shown in fig5 . fig6 shows an analysis of the condition of a line , and a historical tracking of upstream 704 and downstream 702 line code violations and upstream 708 and downstream 706 errors ( fig7 ), which displays raw data recorded over time . as an example of an analysis output from the decision model ( 130 in fig1 ), fig6 displays a message ( 610 ) alerting the technician to unusual attenuation on the line as well as possible reasons for the attenuation . this analysis enables a technician to resolve a problem with improved efficiency and effectiveness . in another aspect of the present invention , data can be used to affect product marketing and promotion processes . usually , in order to raise a line to a higher speed , its line capacity is measured and analyzed . this is usually done on line - by - line basis . using the present invention , marketing and sales representatives can retrieve performance data on related lines . if some of the lines have already been running at higher speed tiers and operating without technical problems , related lines can most likely also be raised to higher speed tiers as well . marketing can therefore be targeted in a more focused manner . although the invention has been described with reference to several exemplary embodiments , it is understood that the words that have been used are words of description and illustration , rather than words of limitation . changes may be made within the purview of the appended claims , as presently stated and as amended , without departing from the scope and spirit of the invention in its aspects . although the invention has been described with reference to particular means , materials and embodiments , the invention is not intended to be limited to the particulars disclosed ; rather , the invention extends to all functionally equivalent structures , methods , and uses such as are within the scope of the appended claims . in accordance with various embodiments of the present invention , the methods described herein are intended for operation as software programs running on a computer processor . dedicated hardware implementations including , but not limited to , application specific integrated circuits , programmable logic arrays and other hardware devices can likewise be constructed to implement the methods described herein . furthermore , alternative software implementations including , but not limited to , distributed processing or component / object distributed processing , parallel processing , or virtual machine processing can also be constructed to implement the methods described herein . it should also be noted that the software implementations of the present invention as described herein are optionally stored on a tangible storage medium , such as : a magnetic medium such as a disk or tape ; a magneto - optical or optical medium such as a disk ; or a solid state medium such as a memory card or other package that houses one or more read - only ( non - volatile ) memories , random access memories , or other re - writable ( volatile ) memories . a digital file attachment to e - mail or other self - contained information archive or set of archives is considered a distribution medium equivalent to a tangible storage medium . accordingly , the invention is considered to include a tangible storage medium or distribution medium , as listed herein and including art - recognized equivalents and successor media , in which the software implementations herein are stored . although the present specification describes components and functions implemented in the embodiments with reference to particular standards and protocols , the invention is not limited to such standards and protocols . each of the standards for internet and other packet switched network transmission ( e . g ., tcp / ip , udp / ip , html , http ) represent examples of the state of the art . such standards are periodically superseded by faster or more efficient equivalents having essentially the same functions . accordingly , replacement standards and protocols having the same functions are considered equivalents . | 7 |
in accordance with the foregoing summary , the following presents several examples of actuators of various geometries which are considered to be the best modes of the invention for the embodiments they represent . actuators that may be used in accordance with the present invention three example applications of the electromagnetic forming actuator have been built and tested for experimental purposes . fig2 shows a plan view of an actuator in accordance with one embodiment of the present invention . fig2 shows schematically the primary or simplest geometry for an actuator 20 of the present invention , consisting of three straight prismatic bar conductors of the same cross section , i . e ., 0 . 375 by 0 . 750 inch . fig2 shows central conduit 21 which is split to form return conduits 22 and 23 substantially parallel thereto . the conduits 21 , 22 and 23 are mounted co - planar on the 0 . 375 inch sides and parallel on the 0 . 750 inch sides with a 0 . 375 inch separation between conductors . the structural and electrical connection is made at one end of the assembly by a through bolt using separation spacers of the same bar stock ( not shown ). the other end of the assembly is connected by right angle conductor pieces , to the double buss bar of the capacitor bank ( not shown ). the longer center conduit 21 is connected to the positive buss and the two shorter return conduits 22 and 23 are connected to the negative buss . current direction is indicated by arrows 24 and the polarity indicated by the plus (+) and minus (-) signs . the total assembly length is approximately twenty ( 20 ) inches . the central twelve inches of the actuator is surrounded on three sides by a aluminum support channel ( not shown ) which reacts to the repulsive forces generated between the conducting bars of the actuator . the support channel is insulated from the actuator by 0 . 125 inch thick polycarbonate sheet . the top side of the actuator is flush with the top of the support channel assembly and covered by a 0 . 010 inch thick sheet of mylar to insulate the actuator assembly from the work piece sheet which is placed atop the assembly . in this embodiment , the form tool for the test is then positioned on the test sheet centrally over the actuator assembly and weighted down with several heavy , one inch thick rubber pads prior to discharging the capacitor bank . it is also possible to incorporate such an actuator into a mold body by using a central conduit and a single return conduit in the form of a conductive body that surrounds the central conduit on two or three adjacent sides , leaving a side to face the work force area . in such an embodiment , the current pulse is &# 34 ; split &# 34 ; by being diffused into the mass of the single return conduit in at least two divergent directions , ultimately returning to the negative bus . fig2 a shows a cross - sectional view of the actuator 20 taken along line 2a -- 2a of fig2 . fig2 a shows a cross section of central conduit 21 and return conduits 22 and 23 . fig2 a also shows a general indication of the magnetic force distribution as indicated by magnetic force lines 25 . fig2 a shows that the maximum displacement would not be effected in a work piece 26 as reflected by the magnetic force lines 25 when attempting to deform the work piece 26 as indicated by dotted lines 27 . fig2 also shows die 28 against which the work piece 26 may be formed ( as may be the case with any of the embodiments of the present invention shown in the drawings ). an alternative embodiment , a coil assembly similar in construction to that of fig2 is constructed , except that its working length is forty inches , has a face width of 1 . 5 inches and is curved in a plane perpendicular to the working face , to form a 120 degree included angle with a six inch radius at the angle apex . the coil is mounted in a plywood housing consisting of a sandwich of four thicknesses of 0 . 75 inch ( nominal ) finish grade interior plywood which is contoured to match the coils curvature . the coil is supported by the two center sheets of plywood which also react the primary pressure pulse generated by the coil . the two outer plywood sheets extend up along the sides of the outer coil conductors to react the separation forces between the three coil conductor and are contoured to be approximately flush with the working face of the coil assembly . the plywood sheets held together by several through bolts which also provide clamping pressure to secure the coil assembly in the channel formed by the shorter center sheets and longer outer sheets of plywood . the form tool is clamped in a similar way in a plywood laminate assembly which forms a conjugate to the coil holder . the coil holder and tool holder are held together during forming by four threaded tie rods , nuts and simple , straight angle iron tie brackets . the assembled coil half and tool half form a rectangular plywood block approximately 24 by 36 inches and 3 inches thick . this experimental electromagnetic forming tool accepts a 40 inch long aluminum strip up to 6 inches wide and forms it into a 120 degree angle bracket with an integral stiffening rib along the center . the center rib has a cross - sectional shape defined by the form tool mounted in the upper plywood housing . both stretch ribs ( outside of the bracket ) and compression ribs ( inside of the bracket ) can be formed by selecting the proper plywood halves to mount the coil and the form tool . fig3 shows actuator coil 30 which has central conduit 31 which splits into two return conduits 32 and 33 which form inward turning coils . these coils may be co - planar with the return conduit and preferably are co - planar with the exception that the straight portions extending from the interior of each coil toward the negative (-) pole are shown as extending below the plane of the coils of the return conduits 32 and 33 . the conduit 31 is connected to the positive bus and the return conduits 32 and 33 are connected to the negative bus . current direction is indicated by arrows 34 . fig3 a shows a cross section taken along 3a -- 3a of fig3 . this figure shows central conduit 31 and portions of return conduits 32 and 33 . the magnetic field produced in the work - force area is indicated by general magnetic field lines 35 . fig3 a shows that the maximum displacement would be effected in a work piece 36 when attempting to deform the work piece 36 as indicated by dotted lines 37 . as in fig1 a and 2a , fig3 a indicates the direction of current flow by a single dot to indicate current flow out of the plane of the paper as presented to the reader while an asterisk design (*) indicates current flow into the plane of the drawing as viewed by the reader . also , the work force area is that area generally perpendicular to the plane defined by the dotted lines and above ( or below , as the case may be ) the actuator indicated by the position of the work pieces in these figures . fig4 shows yet another alternative embodiment of a geometry of an actuator coil in accordance with the present invention . fig4 shows an actuator coil 40 comprising central conduit 41 which is split twice to form return conduit coils 42 , 43 , 42a and 43a . in this embodiment all four return coils are shown as being co - planar with the straight portions extending toward the negative bus from the interior of each coil extending below the plane of the four return coils . such an embodiment gives a greater work force area but maintains the maximum displacement through the center of the work force area similar to the field shown in fig3 a as described above . yet another coil follows the fundamental principle of the present invention , that of splitting the pulse current in order to generate a magnetic field having a central high flux area . such a coil is shown in plan view in fig5 . in this embodiment , the work piece is to be formed so as to have an asymmetric bulge , 1 . 5 inches high and having an approximately isosceles triangular plan with two 6 inch edges 54 and 55 and one 7 inch edge 56 . the coil for this shape was constrained to lie entirely within the plan view of the bulge . the coil 50 was cut in one piece from a 0 . 375 inch thick copper plate . the central conduit 51 of the coil is about 0 . 500 inch wide and bisected the angle between the 6 . 0 inch edges 52 and 53 starting at the 7 . 0 inch edge . just short of the apex the conductor branched forming separate legs running parallel to each 6 . 0 inch plan edge . at the 7 . 0 inch plan edge the return conduits 52 and 53 turn back toward the central conduit along a line parallel to the 7 . 0 inch edge . the legs approach the within 0 . 375 inch of the central conduit 51 and then turn parallel to it . each return conduit essentially forms a 270 degree coil within itself maintaining a 0 . 375 spacing from the outer loop . the input and output leads are brazed at the ends of the branch legs and start of the central leg and are perpendicular to the plane of the coil . the coil was imbedded into a 3 . 0 inch thick layered plywood base 58 such that the face of the coil was flush with the top plywood sheet surface and the brazed lead bars extended from the bottom . four straight legs supported the coil - base assembly at the proper height above the buss bars to allow unstrained connection of the lead bars to the busses with bolted angle bracket connectors . a female form tool ( not shown ) was positioned and secured by two tie rods running through the assembly outside of the test blank nesting area . the tie rods also provided the work piece clamping force required to restrain sheet draw - in and flange wrinkling . fig6 shows still another coil 60 following another fundamental principle of the present invention , that of reversing the direction of the pulse current in the plane of the actuator coil in order to generate a magnetic field having a central high flux area . the piece to be formed by this actuator coil was to have an asymmetric bulge , 1 . 5 inches high and having an approximately equilateral triangular plan with 6 inch edges 61 and 62 , with one side further bordering upon the longest side of a trapezoidal shape having a long side of about 6 inches , a shorter opposing side 63 of about 4 inches and lateral sides 64 and 65 of about 2 inches . the coil was constrained to lie entirely within the plan view of the bulge . the coil was cut in one piece from a 0 . 375 inch thick copper plate . as can be appreciated from fig6 this coil provides that the pulse ( indicated by the directional arrows ) running through those portions of the coil intersecting a line 66 between the input lead 67 and the output lead 68 are substantially parallel , causing there to be generated a magnetic field having a high flux in this central area ( i . e ., one that is substantially uninterrupted by zones having little or no flux ). the input and output leads are brazed at the ends of the branch legs and start of the central leg and are perpendicular to the plane of the coil . the coil was imbedded into a 3 . 0 inch thick layered plywood base 69 ( as may any actuator coil of the present invention ) such that the face of the coil was flush with the top plywood sheet surface and the brazed lead bars extended from the bottom . four straight legs supported the coil - base assembly at the proper height above the buss bars to allow unstrained connection of the lead bars to the busses with bolted angle bracket connectors . a female form tool ( not shown ) was positioned and secured by two tie rods running through the assemble outside of the test blank nesting area . the tie rods also provided the work piece clamping force required to restrain sheet draw - in and flange wrinkling . to illustrate the advantages of the present invention over the prior art , the stresses in electromagnetic forming and the velocity vs . time profiles have been accurately predicted for expanding ring experiments using solenoid coils . computer codes that can model more complex two dimensional problems are also available . cale , a &# 34 ; c &# 34 ; language based code , originally developed at lawrence livermore national laboratory as an astrophysics code , is now being used to model these forming processes and the subsequent material response . fig7 shows an example of a cale simulation of a sheet forming problem . a flat spiral coil is used to form a clamped metal sheet . the irregular lines indicate lines of magnetic flux around the current - carrying elements ( shown in cross section ) in the simulation . two views from the simulation are shown as they would be at 90 and 300 microseconds . it is observed that the deformation begins at the edges of the sheet and progresses towards the center . the predicted time - profile of the deformation agrees with the profile obtained with a high speed camera in a real experiment reported by others under similar conditions . cale accurately simulates the trajectory and profile of the deforming sheet metal work piece . fig8 shows a profile of the sheet through the deformation process simulated in fig7 . though there are no fundamental limitations to the size of the parts that can be made by electromagnetic forming in accordance with the present invention , larger parts require more energy which translates into larger capacitor banks and higher initial capital expenditure . as a result , hybrid forming processes are also being considered where electromagnetic and electrohydraulic forming may be used in such a hybrid process . accordingly , the present invention may also be used in a matched tool set with electromagnetic coils built into sharp corners and other difficult - to - form contours , to form such parts . the matched tools would form the parts of the work piece which can be easily formed at low velocities using mechanical energy from the press . this semi - formed work piece would then be subjected to high rate forming with the electromagnetic coils to complete the forming operation . a schematic of such a process is shown in fig9 . fig9 shows hybrid matched tool - electromagnetic forming apparatus 90 including capacitor bank 91 , inner ram 92 , outer ram 93 with blank holder and die 94 ( on press bolster 100 . stage 1 punch 95 partially forms work piece 96 leaving one or more portions partially formed . the actuator coils of the present invention , such as 97 , powered by coaxial power distribution lines 99 , may then be applied to fill out the remaining portions ( indicated by voids such as 98 ), to reach the final desired shape of the work piece . similarly , a quasi static , fluid pressure process with an electrical discharge in the fluid at the end of the pressure cycle to form the sharp corners and bends could represent another embodiment of the hybrid method of making difficult parts . actuators of the present invention may find application in many industries that involve the formation of shaped metal pieces , such as in the making of parts for the automobile industry and the boating industry . other applications may be found in the making of specially shaped parts in a wide variety of other industries as well . if it is accepted as a primary motivation that the automotive industry is committed to reducing the weight of passenger automobiles by the extensive use of aluminum , then the specific character of the problem can be defined and potential solutions investigated . for example any forming method proposed must be basically capable of the production rates common for current practice [ du bois 1996 , henry 1995 ]. this production rate requirement is a severe restriction for two of the three processes which can extend the forming limits of aluminum beyond matched tools forming . these two are fluid pressure forming , described previously and super - plastic forming , which has been omitted for reasons stated previously . conversely , the high velocity , pulsed electric power methods , described previously , operate on a much shorter time scale than matched tool stamping while providing extended forming limits . however , with the exception of axisymmetric clinching , the electric pulse energy methods are not used by auto makers since no one has yet provided a means to apply it efficiently to large , high production parts . on the other hand , fluid pressure forming is marginally employed by the auto industry . its use has been principally restricted to experimental and special low production of aluminum parts . in such applications , the tooling cost saving provided by the single surface tools is no longer minor in comparison to the production rate penalty . in addition , cycle time in fluid pressure forming is related to the peek pressure requirements and might be improved by combination with a pulse energy method . not to be neglected is the capital cost of new press machines which would be required by the adopting of a fluid pressure forming method to produce aluminum parts . a hybrid method based principally on conventional matched tools would likely not require extensive replacement of the present , installed , press machines . however , unless aluminum alloys are developed that have the plastic strain behaviors comparable to draw steels , conventional matched tool forming will need to be abandoned or integrated with another method to meet the forming performance goals required to efficiently mass produce aluminum auto bodies . the present invention provides a well - designed combination of high velocity forming integrated with a quasi - static conventional forming process to meet the requirements for a reliable , cost effective method for the mass production of aluminum auto body and other commercial parts . there is ample evidence in the literature , as reported previously , that support the claim of extended plasticity , for many alloys , at deformation velocities above 50 m / sec . support for reduced springback and wrinkling at high deformation velocities can also be found [ astme 1964 , maha 1996 ]. the literature also reports on the problems involved in producing large deep shells exclusively by a high velocity , electric pulse energy process . due to the existence of an upper deformation velocity limit ( see fig1 ) and practical limits strength of tooling materials and capacitor bank size , the power pulses cannot be made arbitrary large in order to affect deformation over larger part areas . for example , if a very large single pulse were used , the sheet deformation velocity nearest the pulse generator would likely exceed the upper limit causing the local sheet ductility to fall off sharply . the use of an array of pulse generators to provide lower peak power per individual event and more uniform distribution of deformation forces is an obvious variation of the straight high rate forming concept . however , the actual methods of implementation and effective control of such pulse generator arrays is not obvious . in any case , the probability is still high that the forming of the larger parts by high power pulses would involve multiple sequential discharges which will obviously tend to lengthen the total cycle time . in addition , the form tools used in a straight high power pulse forming process requires a greater shock resistance capacity which generally means more massive construction . this is especially true for the electro - hydraulic discharge process . using the high power pulses only for final forming and only at the local areas of the part which require it , reduces the overall shock resistance requirements of the tools and subsequently , the construction costs . in order to reduce the discharge energy requirements for large parts , either multiple discharges were used or simple pre - forms were made by conventional quasi - static methods and the complex features and final sizing accomplished by high velocity methods [ astme , 1964 ]. high velocity processes generally exhibit sheet stretching over draw - in during part generation . the result can be undesirable thickness variation in deep shell geometries . the inertial forces generated by the mass of the sheet in the blank holder area , outside the energy pulse zone , increase the resistance to draw - in . concurrently the sliding friction between the work piece sheet and the blank holder surface is reduced due to the increase in the draw - in velocity . for simple axisymmetric type part geometries , these conflicting effects can counter - act , resulting in very similar draw - in performance for both high and low velocity processes [ kaplan , and kulkarni 1972 ]. however , sheet draw - in is more consistent and predictable and thus can be more finely controlled in a low velocity process . the potential benefits from the combination of the complementary attributes of static and dynamic forming methods are clear , providing that the attributes are , in practice , additive . another possible hybrid process is the combination of conventional matched tool stretch - draw forming with localized electromagnetic pulse forming . in this hybrid forming process , the part would be preformed , to some optimum extent by the conventional draw - in and stretch action of the match tooling . final forming of tight corners , sharper details and sizing would be accomplished by electromagnetic repulsion forces generated at the required areas of the part by a set of electromagnetic coils embedded in the tool halves . this hybrid method will be referred to as matched tool - electro - magnetic and will be abbreviated as mt - em , in accordance with one embodiment of the present invention . a concept schematic of a mt - em process system is shown fig1 . a embodiment of the present invention is the combination of a quasi - static fluid pressure process with localized shock events generated by electro - magnetically driven shock wave tube devises instead of electric arc discharges . since there is some evidence that shock tubes are more efficient than arc discharges in diaphragm expansion , a hybrid method using electromagnetic shock tubes may be more commercially viable than one using arc discharges [ vafiadakis et al , 1964 ]. this hybrid forming method of the present invention concept could be technically considered a combination of the fluid pressure , electro - hydraulic and electromagnetic processes . however its sheet forming characteristics should be quite similar to fp - eh forming although its system and energy requirements will differ . it will therefore not be given a separate name here and will be lumped with fp - eh for the remainder of this discussion . there are no fundamental reasons to dismiss any of these hybrid sheet forming concepts . moreover , these three process concepts are by no means exhaustive , only the more obvious combinations . one of the common central principles of these embodiments of the present invention is the combination of a relatively low power process to generate the bulk of the sheet deformation with localized high power pulses which provide the final forming , where required . the gross effect can be viewed as combining a pre - form step and a final form step into a single operation with additional process design freedom provided by virtue of the different physical processes . at a more specific level , a hybrid forming process should be able to demonstrate increased forming capability of auto body size parts with localized hyperplastic effects while avoiding the problems attendant to large energy , high power pulse events . the hybrid process of the present invention which combines a quasi - static fluid pressure forming method with multiple , distributed , electro - hydraulic discharges ( fp - eh ) has , by several measures , the greatest general performance potential . in terms of broadness of application , a fp - eh process can be used on many different types of sheet materials . for example , it is not restricted to materials which are good electrical conductors as is required by the electromagnetic forming process . the nature of the event ( submerged arc discharge ) allows it to be located further from the sheet and with less precision then the coils of a electromagnetic process . fp - eh requires only one form tool ( usually the female die ). the electrode / bridge wire assemblies in a fp - eh system would be part of the press machine and not integrated into the tool as will be the coils of a matched tool - electromagnetic ( mt - em ) hybrid process . the fact that each mt - em application requires a unique set of coils further increases the general complexity and cost of the process tooling of mt - em over fp - eh . further , mt - em requires a pair of form tool surfaces compared to the one for the fp - eh process . finally , the precision with which the work piece conforms to the coil face effects the magnetic pulse pressure generated and hence the forming energy efficiency . the repulsive sheet driving force drops rapidly (˜ 1 / r 4 ) as the sheet is moved away from the coil surface since the pressure on the sheet is proportional to the square of the flux density , b , which in turn , diminishes as the inverse of the squared distance from the current element [ plonus , 1978 ]. in contrast , the pressure pulse forming effectiveness of an electro - hydraulic discharge diminishes only as the inverse of the distance squared from the discharge , (˜ 1 / r 2 ) [ caggiano et al 1963 ] thus , much less rapidly with sheet deflection . the slower attenuation of available forming pressure makes the use of sequential discharges more practical in fp - eh than mt - em processes . in fact , a series of smaller discharges in place of a single event of much higher energy was reported to be the preferred method for producing large parts [ cadwell , 1968 ]. although the fp - eh process concept has several advantages for broad application over mt - em , it also has several significantly greater practical application hurdles to overcome . the principle development hurdle for the fp - eh process is that it cannot be easily implemented in the types of press machines existing in the auto industry . providing the quasi - static , fluid pressure pre - form stage requires a significant amount of specialized hydraulic machine components . moreover , the structure of many conventional presses , currently in use , may prove too light . the structural loads , at even the lower forming pressure range , when applied over the plan area of auto body panels , can be tremendously high . a tooling system which attempted a self - contained conversion of large double acting conventional presses to fluid pressure forming was patented but demonstrated only very limited success due to pressure induced structural deflection . [ hydro - stretch 1990 , henry , 1991 ]. the requirement of a specialized press machine for the fp - eh process represents a significant economic road block to acceptance by industry in the near term , although it remains technically feasible . another technical hurdle to the development of a fp - eh process is the modeling of multiple interacting discharge events and their effect on deformation of the part sheet . this topic has not been investigated to any significant extent . rinehart and pearson [ 1963 ] briefly discusses the topic with respect to multiple synchronized charges for explosive forming . they suggest the use of superposition principles in the analysis of multiple charges in under water explosive forming were the shock pressures are less than 69 mpa ( 10000 psi .). a robust design method for fp - eh would require a more thorough knowledge of multiple interacting events . however , modeling even a single eh discharge event is not trivial . the electro - hydraulic discharge event begins with the complex physics involved with the generation of the high temperature ( 5000 - 10000 k ) plasma kernel of the arc path . within a few micro seconds the expanding plasma generates shock waves whose propagation , reflection , refraction and interferences cannot be neglected in order to accurately predict the process actions . thus fp - eh employs generally more complex and harder to model physical phenomena than mt - em with electromagnetic pulse events . moreover , the simple existence of the intervening liquid medium required to transfer the deformation energy in the electro - hydraulic event , adds to the potential variability and complexity of the fp - eh process . the mt - em process may not have the broader applicability of the fp - eh process but , for several reasons , is a better choice for an initial hybrid process development . first , the mt - em process can be implemented using conventional mechanical or hydraulic , single or double acting presses . in principle , only minor alterations to existing presses themselves should be required for retrofitting . the lack of a liquid medium to transfer the deformation energy to the part not only reduces the overall complexity of the system , it also eliminates the maintenance overhead of an additional hydraulic system . the reduced development advantage of mt - em over fp - eh is exemplified by the requirements for electrode assemblies of a fp - eh process . high energy arcs can quickly erode electrode tips which in turn change the pressure pulse characteristics of the discharge . electrode problems accounted for a good deal of the trouble encountered with the old eh machines . it was found that variations in the location arc at end of the coaxial &# 34 ; spark plug &# 34 ; electrode used in one of the early systems could cause unacceptable variations in the parts . moreover , the spark plugs required rebuilding after only 100 discharges . the systems which used bridge wires to initiate the arc had much better repeatability but the wires required manual installation before each discharge . [ daughtery 1995 , fronabarger 1995 , bennetts 1995 ]. another point is that , at least for axisymmetric geometries , electromagnetic forming has been more fully development in terms of application , tooling and coil design [ belyy , et al 1988 , gilbert and lawrence , 1969 .]. this more organized knowledge , some available in handbook form , provides additional motivation for developing the mt - em process . further , electromagnetic forming developed a non - aerospace , industrial niche in axisymmetric swaging . this small commercial market supported continued work on metal deformation behavior using electromagnetic pulse energy after the military aerospace efforts ceased . although still incomplete , this existing body of knowledge is also more current than electro - hydraulic discharge forming [ daehn et al , 1995 ]. thus the literature of em forming provides a slightly higher level to start the development a hybrid process . the hyperplasticity effect of high velocity deformation is fairly well documented and the fundamental mechanism model of inertial stabilization has not been seriously challenged [ wood , 1963 , bruno , 1968 , balanethiram and daehn , 1992 ]. this fundamental phenomena that hybrid sheet forming processes will be utilizing to realize extended plasticity will be described here in greater detail to support the description of the sheet coupon tests to follow . the inertial effect of the sheet &# 34 ; particle &# 34 ; mass which provides a force resisting the localization of strain as a necking plastic flow instability tries to form . hu and daehn [ 1 ] extended the understanding of the phenomena by means of a simple and rather elegant one dimensional ridged - plastic , dynamic finite element analysis of a uniaxial tension and ring expansion test specimens ( fig1 ). the essence of the analysis formulation was simply the inclusion of a elemental mass and acceleration term in the nodal force balance ( eq . 1 . 1 below ) which added to the internal nodal force terms obtained from the derivative of the plastic work of the element with respect to the nodal displacements ( eq . 1 . 2 below ). ## equ1 ## equation 1 . 3 is the power law of the rigid - plastic , holloman type constitutive relationship used in their analysis . although thermal effects due to rapid plastic stains were ignored a 1 % taper in the specimen geometry was included to provide a defect like inhomegeneity . in the above equations , m is the element mass , u is the displacement ( axial or circumferential ), ak is the initial cross - sectional area of the element , l is initial element length . the results of this simple one dimensional model illustrated the basic effect of mass inertia on the extended ductility at high deformation velocities . fig1 shows the graphical results presented by hu and daehn , most pertinent to the present invention . fig1 illustrates that the influence of inertia is less as n and m becomes large but contributes to extending ductility for any fixed &# 34 ; n &# 34 ; or &# 34 ; m &# 34 ; as seen by the increase of the dynamic to static strain ratio with increasing velocity . this simple model also predicts a strong coupling between total strain at failure an deformation velocity . the inertia effect macroscopically resembles the ductility enhancing effect of strain rate hardening which is one reason that high velocity forming is suited to the working of stain rate insensitive , aluminum alloys . to qualitatively describe the suppression of localized neck formation by inertial effects as predicted by the hu and daehn model , consider the following . initially the velocity distribution of material elements in uniaxial extension varies linearly from the crosshead input velocity to zero at the fixed end of the sample . as a neck starts to form , the velocity distribution approaches a step function as the material velocity between the neck and the fixed end goes to zero while the specimen material between the neck area and the crosshead assume the crosshead velocity . in order to accommodate the velocity discontinuity the material in the necking region must experience an increasingly large acceleration . the force required to accelerate the mass of a material element outward from the neck area must be transmitted though the material outside of the necking region , thus the necking tendency is diffused . this effect is , of course , always present but only significant at high deformation velocities . the results from the simple , one dimensional model cited above , included minor geometry variations which indicates that the inertial drag suppression of necking is not critically sensitive to sheet flaws or thinning . however , variations in sheet hardness was not addressed in that model or in any other articles reviewed . information on the effects of these parameters on the maximum attainable strains in hybrid forming is of interest . from the preceding , one may expect that inertial effects at high deformation velocities will only extend plastic behavior of sheet materials whose dominant failure mode is necking . metals which exhibit little or no necking before fracture at low velocities are not expected to show a significant increase in ductility at high velocities unless there is phenomena other than inertial drag forces at work . the direct effect of this prediction to the present work is that the fully hard aluminum alloys are not expected to perform as well as a solutionized or a lightly worked condition . in the case of hybrid forming , the inertial drag model of neck suppression will thus be confounded by the various levels and distributions of pre - strain introduced into the sheet material during the quasi static initial forming stage of the process . in most cases , the pre - strain will introduce work hardening into the material . the work hardening thus introduced will , in general be non - uniformly distributed across the initial - form part . in addition , variation in sheet thickness could be considerable . the extent of the variations in sheet hardness and thickness will , in practice , depend heavily on the geometry of the initial - form . a variety of experiments were conducted to elucidate the relationship between the level and distribution of pre - existing strain and subsequent material strength variations and the amount of additional useful plasticity that can be obtained under high velocity deformation conditions . in addition , the foregoing indicates that one should correlate inertial controlled plasticity effects with deformation velocity rather than strain rate especially for comparisons between different geometries . the simple reason is that deformation velocity varies with gage length which means that high strain rates can generated by low deformation velocities if the initial gage length is small enough . the tendency to equate high strain rates with high deformation velocities in the literature is due to the fact that nearly all researchers are conducting investigations with identical specimen geometry for which strain rate and deformation velocity are uniquely related . the plastic behavior of any metal is temperature sensitive at to some extent . if local work sheet temperatures become high enough during forming to cause thermal softening , then neck formation can be promoted due to the subsequent strength variation in the load path . the particular case of aluminum , the deleterious effect of thermal softening is , at least partially , offset by the fact that the strain rate hardening effect (&# 34 ; m &# 34 ; in the simple power law model ,) increases with increasing temperature . the mt - eh process can induce a considerable amount of electrical joule heating as well as adiabatic heating due to dynamic plastic deformation . sheet temperature , local to the discharge event in space and time is a process variable of interest and importance to the prediction of the mt - em performance . the transient time - temperature data local to the forming pulse is difficult to measure directly due the micro - second time scale of the event alone . however , changes in sheet hardness is a process variable more directly related to plastic flow which can be measured easily . care must be exercised however in the use of superficial sheet hardness due to the confounded effects of adiabatic and joule heating with the temperature induced increase in strain rate hardening of aluminum . a simple analytic model of adiabatic joule heating can be employed to obtain an upper bound of the sheet temperature in the eddy current path . the induced eddy - current in the sheet can be estimated from the measured work coil current - time history . obviously , the numerical simulation of the high velocity event , to be discussed later , will need to provide an accurate estimate of the sheet temperature distribution to accurately model the over all process . the data of principle importance to the assessment of the mt - em process are the failure strain levels , distributions , and deformation velocity for the aluminum alloy sheet material acceptable for auto body use . the present investigation will be restriction the two basic aluminum alloy types , precipitation hardening and non - precipitation hardening . the specific alloys chosen are 6111 - t4 and 5754 these alloys are both currently used in auto body applications . the fundamental metallurgical differences between these aluminum alloys will result in some performance variations in the mt - em process . the variations are expected to be in rough proportion to static measured ductility and should not confuse the resulting assessment of the mt - em process for all similar alloys . further , if the extended dynamic plasticity effect is largely an inertial effect , then it is reasonable to expect that static - dynamic strain relationships should be found to be applicable to whole alloy groups . the high velocity sheet forming performance cited in the literature is almost entirely for fully dynamic deformations starting from flat blanks or uniform tubes . the state of initial cold work for these cases were at least uniform and often close to zero . the material cold work condition in a hybrid process after the quasi static forming stage will definitely be non - uniform to some extent . depending on the part geometry and static process , the cold work condition could vary widely . the early high velocity forming literature provides considerable information on static strengths of certain alloys after dynamic , high rate , forming which has been nicely summarized by a . a . ezra in the last chapter of his &# 34 ; principles and practices of explosive metalworking &# 34 ;, [ 1973 ]. the chief concern of the aerospace researchers of that time was to determine if the high rate forming processes degraded the structural properties of their alloys . extended plasticity was recognized but less of a concern since multiple forming cycles with intermediate annealing operations are common practice in aerospace fabricating . therefore , the literature contains quasi static stress - strain data after dynamic pre - straining for certain aerospace alloys . nothing was found concerning the reverse sequence of deformations . by the path dependency of plastic deformations , it would not be expected that the combined effect of static and dynamic deformations of a sheet material is symmetric or independent of application sequence . from the data currently available it would be reasonable to expect that , assuming modest initial stage strains , that a static - dynamic sequence would produce greater elongation than a dynamic - static . interestingly , the data summarized by ezra , [ ezra1971 ], shows that a dynamic - static process , in comparison to a straight quasi - static process , will reduce the total elongation for mild steels and increases it for both 5052 - 0 and 5456 - 0 aluminum . the material test results reviewed by ezra warn against too broad a generalization of the forming performance from hybrid forming experiments with any particular metal type to another . based upon the examples given herein the experimental results will provide predictive understanding of the relation between initial cold work and allowable final strains for process design purposes . how the process designer divides up the total strain required to form a desired part feature between the static and dynamic regimes determines the part shape at the end of the quasi - static forming stage and the subsequent pulse energy required . a significant enhancement has been demonstrated , the basics of which are discussed herein . with this knowledge in hand , one of ordinary skill will be able to design specific apparatus and practice methods in accordance with the present inventions . conventional matched tool forming , is itself such a complex process that analytic models have been developed for only simple axisymmetric geometries and those that can be accurately represented in one or two spatial dimensions . the sheet is generally assumed to behave as a simple membrane with bending corrections possibly included . there are a number of texts covering these analytic methods such as references [ hosford and cadell , mielnik 1991 ]. luckily the past ten years have seen a good deal of effort spent in the development of computer codes and microprocessors which are demonstrating impressive capabilities in the modeling of the conventional low velocity deep shell sheet forming processes . the design of a mt - em in accordance with the present invention typically will employ such computer codes and microprocessors to assist in defining the best obtainable pre - form part geometry . ideally , such computer codes and microprocessors will allow one to measure , assess and control full dynamic , electromagnetic and thermodynamic characteristics , as well as material constitutive relations capable of accurately predicting local necking and fracture . a preferred numerical modeling tool should be capable of simulating the entire mt - em process for the designer . although the ideal unified mt - em simulation code is not presently commercially available , there are codes that can model separate aspects of the process . it should not be assumed that hybrid forming process and mt - em in particular can only be applied if powerful simulation tools are available . if this were the case then the commercial viability of the hybrid processes would be quite questionable despite any extended forming capacity . in fact it is quite unnecessary that a means of approximating the requirements of a mt - em system exist and be outlined . a system which requires a computer simulation before anything can be known about its gross size and energy requirements is typically untenable . such approximate design calculations are available and can suffice to produce a functioning system without substantial additional experimentation . the final consideration in the development of a mt - eh process concerns the physical system design . the requirements of the electromagnetic pulse coils must be combined with those of the forming tool with which it / they cooperate or in which it / they are imbedded . the fatigue strength of the tool material must be sufficient to withstand the reaction forces generated by the coil pulses over the production life of the tool . since , the electrical conductivity of the tool material effect the energy efficiency of the coil , standard iron and steel matched tool materials may not be optimum for mt - em tools . the coils themselves must structurally absorb internal magnetic pressure , often of similar magnitude to the forming pulse . a means of replacing damaged coils with minimum down time must be considered the same as for the high wear insert sections / components of conventional tools . the replacement of coils during the production life requires reliable electrical connectors capable of peak currents of one half million amps or more . any arcing in coil connections causes rapid deterioration at the connection interface leading to catastrophic failure in a few cycles . alterations to existing press machines will be minimal , which is one advantage of mt - em over the other hybrid methods , as stated above . as an issue much subordinate to the forming performance and tool design aspects , press machine alterations will be discussed in only broad terms . the press machine must accommodate the energy storage capacitor sub - system either entirely or at least the ingress of the pulse power cables . stamping plant floor space is generally at a premium which indicates that the capacitors , charging , control and pulse energy distribution will preferably be integrated into the press machine volume . typically , the power systems for such retrofits can be accommodated in a home freezer size box next to an existing press . safety of a new industrial process is an issue to be addressed at the fundamental level early , in the development cycle . the main components of the safety issue of the mt - em process concern the high containment of the high power electrical pulses , possible high velocity debris , eye damage from arcs at connection failures and noise levels . none of the major safety concerns represent conditions or phenomena new to manufacturing or the automobile industry in particular . these hazards all currently exist in many manufacturing environments and standard practices are in place to deal with each one . the design and safety issues involve in the development of mt - em forming will be described briefly herein . in order to elucidate the mt - em process of the present invention , two demonstration trials involving actual , full size automotive body panels were undertaken . attempting full scale applications allows one to test practical design methods and to provide preview and feed - back to process development on real application problems . the inherent simplification of a system when scaled to convenient laboratory size can inadvertently mask real application problems . a prime example is in the estimation of the process energy requirements . arbitrarily constructed laboratory test system can generally be designed small enough that the equipment capacity becomes a non - issue and serious weakness in the estimation method can be glossed over . similar arguments can be proffered for the design of the driver coils and electrical bus work . ideas which seem to work fine at a few kilo joules and kilo amperes can literally come apart at much higher energy and current levels . in particular , direct experience was desired concerning the design of full scale work coils operated at near limit energy levels and their integration into the match tooling . two major deviations from standard automotive stamping practice were accommodated for these full - scale trials . first , there was no attempt to install the mt - em process into a press machine . the pre - forms were stamped out and transferred to tools containing the work coils were the em phase was performed as a second operation . second , the tools used for the em phase were not made of a malleable grade of cast iron , standard for production tools . except for the imbedded coils , the trial tools were made from a special iron filled plastic material recently developed for prototype stamping tools . this material is referred to by the acronym stamp , and is commercially available from itt industries . the deviations from what might be considered standard stamping practice conditions are not deemed to affect the applicability of the trial experiences to the application of the apparatus and methods of the present invention to actual mt - em automotive parts forming . the full scale trial part problems were chosen by a group of engineers from the major american automobile manufacturers and consisted of a hood feature line and a door inner panel lock face . the two parts and the sections of those parts chosen for mt - em application were considered to span the geometries most troublesome to currently produce in aluminum by the conventional matched tool method . the hood feature line trial was the less ambitious of the two and was undertaken first . simple applications utilizing relatively inexpensive tooling may not require a high degree of process optimization at the design stage in any case . to arrive at a good initial design point and to predict at least a lower bound on the energy requirements of an application , a good pencil and paper design method is needed . ideally , the method is simple enough that an unprogrammed hand calculator is sufficient to conduct a few preliminary design iterations and accurate enough to render the results dependable , if only as upper or lower bounds . approximate design methods for the quasi - static , conventional matched tool forming portion of the mt - em process have been available for many years . these methods will not be discussed here but can be found in many texts books on metal forming such as those by w . f . hosford and e . m . mielnik [ hosford and caddell , 1981 ] [ mielnik , 1991 ]. only a brief experience with the design space of em portion of mt - em applications is required to recognize that there actually are no time invariant factors in the process except mass . even the simple inductively coupled rlc circuit used in the present invention becomes quite complicated when the inductance capacitance and resistance are all taken as time dependent variables . additionally , the deformation mechanics of the work piece during the em phase are complicated by the fact that temperature effects are present and the inertial terms of the force balance equations are significant , even dominant . however , assuming constant circuit parameters does allow coarse predictions of the system response using simplified geometries and energy balances . the simplifying assumption which underlies the method must be kept in mind . adding insupportable layers of sophistication in an attempt to improve the accuracy should be avoided . a computer simulation method should be employed when the detail and accuracy of the preliminary design methods are insufficient . two questions that must be addressed early in any new application design are : &# 34 ; is the general level of plastic deformation required to finish the feature from the pre - form shape available through em pulse forming ?&# 34 ; and &# 34 ; how much energy will be required from the capacitor bank ?&# 34 ; the first question is best answered by previous experience with the alloy of the part in question . as a very general rule of thumb , the total useful strain available to the mt - em process is about 50 % greater than the quasi - static limit strain for the alloys commonly used for stamped parts . the distribution of the strain will be dictated to an appreciable extent by the geometry of the coil and the eddy current density . the second question is , of course , related to the first in that the plastic work is part of the energy required from the bank . however it is usually the smallest fraction . both of the questions will lead back to a new pre - form design iteration if the answers lie beyond the capabilities of em forming . the assessment of the em energy required will quickly becomes the prime issue of the early stage of an mt - em process design . to address this question , the simple geometry and energy method outlined below was developed . the method was generally based on others applied to axisymmetric parts presented in the literature [ bruno , 1968 ] [ gilbert & amp ; lawrence , 1969 ][ baines et al , 1965 ][ al - hassani et al , 1974 ] [ belyy i . v ., et al , 1996 ]. however , nowhere in the literature was found a method directly applicable to the mt - em conditions or presented as a clear step by step procedure . to apply the following method of estimating em energy requirements , some preliminary information is require . it is required to have in hand : 4 ) the geometry and material properties of a preliminary coil design . 7 ) the effective resistance and inductance of the capacitor bank up to the coil lead connection bus . the basis of the method is the first law of thermodynamics edited for this problem . the energy audit , for the capacitor bank system during discharge , can be written as : for frequencies below 500 khz , the radiation energy can be ignored [ terman , 1947 ]. a simplifying assumption used for this analysis is that the majority of the work done and energy expended occurs within the first current cycle . this assumption is common in the literature and is also supported by the high speed array camera images of the coupon expansion tests using the methods of the present invention . accepting the truncation approximation , the energy terms can be expanded as follows for first current cycle of the discharge : ## equ2 ## where c b = effective bank capacitance once the system is assembled the effective system parameters can be calculated directly from measured current - time data . in order to estimate δe b before building the system , the parameters of 5 . 1 b can only be approximated . the accuracy and completeness of the parameter estimations , along with the time invariant assumption , limit the predicted bank energy such that , even with care , significant error can be expected . however , this level of accuracy can be sufficient in the initial process design stage . the real value of such a rough model lie more in assessing relative merits of competing designs than accurate predictions . the estimation of l e and r e proceeds by expanding the parameters into their major constituent parts for separate evaluation . the effective system parameters are constructed as : where the subscripts b , c and l stand for bank , coil and leads . the coil induction will include the effect of the coupling with the work piece and therefore indirectly also includes the work piece resistance effect . work piece resistance generates and additional energy loss term due to eddy currents which increases the effective resistance of the system as seen by the bank . this proximity resistance is represented by the p subscript term . it is important to keep the parameters for the bank - coil connecting leads separate from the coil since the leads are not affected by the presence of the work piece and can be a major source of hidden inefficiency if not properly designed . it will be assumed the parameters of the capacitor bank including the bus are known from shunted tests . what remains is to estimate the coil and lead parameters by methods consistent with the required accuracy of the bank energy prediction . the sequence of the following calculation steps are not critical as long as the prerequisite values are available . given the initial design geometry and material of the coil and leads , the formulas found in grover [ grover ,] or other older electrical engineering handbooks can be applied . curved coils ( not doubled back ) can be flattened and the inductance of more complicated branching geometries can be assembled as series or parallel combinations of simpler geometries . unless specified otherwise , the inductance calculated by these formula are for isolated coils and transmission lines . the effect of the work piece and any surrounding conductive , non magnetic , material will be to lower the inductance of the coil as seen by the bank . close proximity of ferromagnetic material will have a smaller effect , but tends to increase the inductance of the coil . in either case , the effect is fairly small after a few centimeters and is therefore any change in coil inductance is chiefly due to the presence of the worksheet . unless the leads are closely surrounded by a metal duct or conduit , their open inductance value can be used . texts and handbooks such as grover provide methods for calculating the mutual inductance of the surrounding metal bodies and net effect on the coil or bus inductance . however , these calculations can become quite tedious and much better results can be obtained from commercial electromagnetic analysis programs with similar levels of effort . two other options are available for finding component inductance values . first , the flat plan of the coil work face can be translated from the design to a thin sheet of metal with electrical properties similar to the proposed coil . the inductance of this flat coil mock - up can be measured while covered by a plastic or paper layer and metal sheet simulating the work piece . the inductance measurement instrument used must be able to measure in the micro henry range and supply an excitation signal of approximately the same frequency as expected from the completed system . if the coil is easily to prototype , more accurate results can be obtained if not constrained by the accuracy of the induction meter . a simpler method is to use existing data from several coil face geometries and sizes that are candidates for the general type of em which have been mocked - up and measured as described above . examination of data generated from an inductance test for a mock - up similar in plan to the door trial coil as a general class of the trial parts , show that the ratio of covered to open inductance , for intermediate frequencies around 10 k hz , is approximately 0 . 25 for open inductance of 2 . 0 micro henry or less . the ratio drops to about 0 . 12 for open inductance of about 8 . 0 micro henry . using the open coil inductance and the bank capacitance and the frequency relation ## equ3 ## the best ratio can be quickly found . using eq . 5 . 2 , the estimated system inductance , l e , can now be assembled and the system undamped frequency , required for the next step , can be calculated . with the system undamped frequency , ω 0 approximating the actual damped frequency , ω d , the coil and leads skin depth of the current can be estimated with eq . 5 . 5 which is the same as 3 . 17 but in terms of resistivity ρ . ## equ4 ## the resistance of the coil are calculated by the standard conductor resistance equation ## equ5 ## were l is the conductor length and a e is the effective conductor cross sectional area given by the product of cross section perimeter and the skin depth . note that eq . 5 . 6 gives good estimates for conductor cross section aspect ratios & lt ; 2 . at higher aspect ratios 5 . 6 will under estimate the conductor resistance since the current will not be evenly distributed around the conductor perimeter . in wide thin conductors , the current will concentrate at the farthest edges of the conductor so as to minimize the number of magnetic flux lines encircling the current [ terman , 1947 ]. just as for the inductance estimations , the resistance of the more complicated branched coils such as a 3 - bar or multi - element leads , the effective component resistance is formulated as series of parallel combinations of sub elements . the general form for combining resistive ( or inductive ) elements can be found in any elementary text on electric circuits and is provided here for completeness . ## equ6 ## proximity resistance is the increase in effective system resistance seen by the bank , due to the energy supplied to resistance heating of the work piece . the power loss per unit area of surface with conductance , σ , and incident magnetic field , h s , is given by stoll [ stoll , 1974 ] as ## equ7 ## which can be written in terms of flux density , b i , and eddy current area a e and related to part of the effective resistance by the coil current . ## equ8 ## where σ is the conductance of the work piece i c is the coil current generating the eddy current through b i in area a e . if the work piece is within a few millimeters of the coil face a e can be approximated by the area of the coil elements facing the work piece . except for branched coils like a 3 - bar , the coil current is the same as the bank current . this system resistance term will generally be small in comparison with the others and can therefore often be neglected , at least initially . if this term is included its assessment will be more direct when the required flux and current are determined . the estimation of i b is the key to this method since it is the common factor in the inductive and resistive energy groups . estimation of i b requires quantities calculated in four sub steps to be acquired first . given the initial pre - form geometry and the final desired part shape , the energy needed for plastic deformation can be estimated using : ## equ9 ## where proportional loading and uniform condition , such as plane strain is assumed . the full details of choosing a constitutive equation , determining the limits of integration etc . are available in any good text on metal forming . in many cases , a plane strain condition can be assumed and the final strain level can be approximated by using a simple change in line length , ignoring redundant work . a constitutive equation which is simple , fairly accurate , includes prestrain and whose constants , n and k , are available for many alloys of interest is given by : if the plane strain condition is assumed , the strain energy can be written as : ## equ10 ## equation 5 . 9 will produce acceptable results if the required strain is rather small , less than static failure strain . however , em forming will often be used to produce plastic deformations beyond the static failure strain where eq . 5 . 9 and 5 . 10 are not defined . applying eq . 5 . 9 in such cases will likely seriously over estimate the plastic work . one reason for the over estimation is that the energy levels required to obtain the high plastic strains will likely induce local current heating with a corresponding reduction in flow stress . a solution to this problem might be to use a constitutive equation , such as the johnson - cook relation , ## equ11 ## which accounts for thermal effects and larger strains [ johnson , 1983 ]. the attended complexity involved with using such relations would however violate the simplicity tenet set down for this pencil and paper analysis . the development of constitutive relations for plastic flow in the em regime may be further explored . for these reasons the purpose of this rough model may best be served by using an elementary , ideal plastic relation for assessing plastic work . assuming ideal plastic behavior eq . 5 . 7 becomes ## equ12 ## determining a proper value for constant flow stress is an obvious source of additional error . in the absence of material data , the average of the yield and ultimate strengths might be used to take rough account of the thermal softening . step 3b : determination of the kinetic energy desired for work piece . free form coupon test data indicated that for ductile aluminum alloy , a velocity of about 200 . m / sec . will be sufficient to ensure the benefits of inertial suppression of local necking . the kinetic energy is approximated by considering the deforming sheet area as a free body , ignoring the restraining forces of the tensile stress in the sheet along the boundaries of the deformation area . this approximation assumes the energy in the work piece at any time during deformation is the superposition of kinetic and strain energies . the boundary is defined as the contour line representing some arbitrarily small iso - strain . this contour line will usually be close to the perimeter of the coil . the kinetic energy term is then given using the coil face area , a c , the sheet density , d , and thickness t s , by the familiar relation : ## equ13 ## during deformation , after the acceleration period , the kinetic energy is transferred into plastic work . if the acceleration is large , the period is short and the strain produced during it will be small . the magnetic energy absorption of the work piece can then be considered as a serial transfer process of magnetic field energy to kinetic energy which is dissipated by plastic work and other non - conservative terms ( which are ignored ). this implies a constant mechanical energy term such that ; accepting this analysis provides a means to determine minimum work piece velocity . ## equ14 ## from experience it is seen that velocity should not be less than 100 m / sec to maintain a minimum level of neck stabilization . the total energy of the work piece at any time during deformation , e s + e k , must be supplied by the magnetic field generated by the coil . initially the magnetic field or flux is confined , by the opposing field of the eddy currents , to the stand - off volume between the work sheet and the coil . this compression of the magnetic flux generates a pressure , analogous to a fluid pressure but acting only on the sheet and the coil . the magnetic pressure is define as : ## equ15 ## where b i and b o is the flux density on the coil and opposite side of the sheet . b o can be determined if the penetration of the magnetic field into the sheet is known . the differential equation which describes the diffusion of a magnetic field into a conductor has the same form as heat diffusion ( the laplace equation ); the form of the solution is therefore also the same . the instantaneous value of magnetic field in the sheet at depth y as a function of the surface value , skin depth ( δ ), frequency is , from a derivation by stoll [ stoll , 1974 ] as ; h = h s e - | y |/ δ cos ( ωτ -| y |/ δ ). this equation indicates that the magnetic flux density , b , ( b = μh ) in the sheet has a logarithmic decay and lags the coil side surface by | y |/ δ radians . if the skin depth is equal a fourth of the sheet thickness the flux magnitude will be less than 2 % of the coil side . however , this condition will seldom be met when forming thin gage sheets with large coils . fortunately because the flux density appears as a square term in 5 . 11 a , fairly high flux leakage can be accepted . a 25 % flux leakage through the sheet will reduce p m by only about 6 %. if it is desired to take leakage into account a estimated leakage ratio , can be included such that b o = ηb i and η ≅ e - t / δ so that the magnetic pressure becomes : ## equ16 ## p m can also be defined in terms of the force require to accelerate the work piece to the chosen kinetic energy velocity , v , and a selected interval . for a heuristic argument , it is noted that experimental evidence in free forming indicates that the usual em event scenario is a rise to peak velocity deceleration period . during deceleration , the remaining kinetic energy is dissipated into plastic work , gas compression and heat . if the work piece strikes a die face , there will be additional losses due to impact . in this first approximation of required bank energy , gas compression , deformation heating and die impact are considered negligible . assuming uniform acceleration over the first 1 / n current cycle , ## equ17 ## fixes the required magnetic pressure in terms of velocity v , sheet thickness t s , sheet density , d and damped frequency at : ## equ18 ## the magnetic pressure acting on the sheet during the deformation represents the energy that the coil is feeding into the sheet which is required to be equal to the kinetic and strain energy terms . the form of this relation is analogous to that for an ideal gas : ## equ19 ## where δv is the volume swept out by the sheet while p m is acting . however , the coil must first fill the stand - off gap volume v g , with flux to generate p m initially . the energy density of a magnetic field is given by ## equ20 ## so that magnetic energy in the initial gap is : ## equ21 ## therefore , the portion of the coil flux energy e c t , used to generate the velocity and strain of the work piece is the sum of the initial gap energy plus the &# 34 ; flow work &# 34 ; of the sheet displacement ## equ22 ## by combining eq . 5 . 15 , 5 . 16 and 5 . 17 to eliminate the common terms gives a relationship between coil energy and system parameters . ## equ23 ## note that eq . 5 . 16 estimates only the fraction of the total coil energy that is generating the pressure on the sheet . the remainder is contained in the rest of the magnetic field surrounding the coil . total energy of an inductor can be found if the product of magnetic field and differential volume is integrated over the volume that the field occupies , ## equ24 ## the field volume integral can be broken into the sum of the work gap volume and the remainder . ## equ25 ## the coil field fraction k c , is the ratio of the field energy supplied to the work piece to the total energy of the coil during the first cycle which can be written as : ## equ26 ## 5 . 18 simply states that if the work piece completely surrounds the coil all the coil energy can be used . however , for most sheet forming not more than half the field can be applied in which case the coil field energy will be twice that given by eq . 5 . 16 so that the total required coil energy is estimated by ## equ27 ## step 4 : assembly of the estimate the energy required from capacitor bank . with e c and l c the effective discharge current , i b , can be calculated using the inductor energy relation . ## equ28 ## i b is the same for all elements in the circuit so that the estimated bank energy is given by : ## equ29 ## to assess the eddy current resistance losses a value for r p , is required . however , it will be more accurate to isolate the eddy current resistive energy term and to limit it to the acceleration period so that ; ## equ30 ## redefining it using equations 5 . 7 , 5 . 13b and 5 . 14 produces equations 5 . 23b and 5 . 24 . ## equ31 ## if careful assessments are made of the component values of 5 . 23 , the predicted energy required should be a lower bound due to the truncation of the current to a single cycle . this estimate should be dependable enough to help in initial design decisions , especially if used as a comparative measure for evaluating alternative coil and lead designs . users should keep clearly in mind the simplifying approximations of this analysis : the em forming energy prediction method presented above was applied to the automobile hood and door inner part feature trials . the details of the part feature geometry , process and tooling design and trial results will be presented in sections . for discussion of the estimation method only , selected results of the analysis with comparisons to data taken during the trials are presented here . table 5 . 2 summarizes the predicted and measured system response characteristics . both parts were fabricated from 1 . 0 mm thick 611 1 - t4 alloy . the capacitor bank parameters used , including the bus system , measured at 10 kj discharge are : table 5 . 2__________________________________________________________________________em forming parameters for bank energy estimatepart . sup . parl . sub . c , h l . sub . 1 , h r . sub . c , 1 / 2 r . sub . l , 1 / 2 k . sub . c η n ε a . sub . c , m . sup . 2 v . sub . g , m . sup . 3__________________________________________________________________________hood 1 . 00e - 7 5 . 9e - 8 6 . 20e - 4 1 . 57e - 4 0 . 5 0 . 36 4 0 . 05 1 . 12e - 2 1 . 12e - 5door a * 1 . 93e - 7 2 . 59e - 7 1 . 06e - 3 4 . 2e - 4 0 . 5 0 . 36 2 0 . 25 4 . 06e - 2 4 . 06e - 5door b11 . 04e - 7 2 . 28e - 7 4 . 43e - 4 4 . 2e - 4 0 . 5 0 . 36 4 0 . 21 1 . 74e - 2 1 . 74e - 5door b21 . 50e - 7 1 . 22e - 7 9 . 0e - 4 2 . 0e - 4 0 . 5 0 . 36 4 0 . 21 1 . 74e - 2 1 . 74e - 5__________________________________________________________________________ table 5 . 3______________________________________comparison of calculated and measured responses value ω . sub . d , r / 2l δe . sub . b i . sub . bpart type rad / sec rad / sec joules amps______________________________________hood calc . 58600 . 5150 . 16800 . 187000 actual 59800 . 5070 . 27000 . * 313700 % error - 2 . 0 1 . 6 - 37 . - 40door i calc . 41800 . 3150 . 68400 . 275000 . actual 43000 4190 . 43200 .+ 188700 . % error - 2 . 8 - 25 . 58 . 45 . 7door iia calc . 47060 . 3327 . 33000 . 225000 . actual na na 48000 .+ na % error na na 31 .+ nadoor iib calc . 50500 4090 . 22600 . 187000 . actual 46200 . 7896 . 24000 .+ 199000 . % error 9 . - 48 . - 6 - 6 . ______________________________________ + limited die strike ; * hard die strike to add some clarification to the data in table 5 . 3 , it should be noted that the hood shown indications of significant impact velocity in much of the forming area which would require energy not accounted for in the analysis . at a discharge level of 18 kj , the hood feature was substantially formed with much less impact indicated . the error between the prediction and the 18 kj test is - 7 % for energy and - 6 % for rms current . the door i preform geometry inner panel did not under go the 0 . 25 true plane strain that was calculated by line length change between the pre - form and desired geometries . the analysis assumes only stretching occurs during deformation . even minor amounts of draw - in from surrounding material will reduce the strain levels in the em forming area . draw - in was evident in the door inner trials which reduced the measured strain to an average of approximately 0 . 16 . the predicted bank energy required for this level of uniform plane strain is 41 kj which reduces the predicted error to - 5 % for energy and 12 % for rms current . door iia and iib used different coil designs with the same preform geometry . coil b1 was a 3 - bar while iib was a 2 turn with the same face area of iia . three bar coils have lower efficiency which is clear from the results listed in table 5 . 3 . moreover , the method is considerably farther off in predicting the required energy in this case than for the hood . one consideration is that in the case of the hood , the metal requiring the most strain was covered more completely by the high pressure area generated by the coil which is not true for the door 3 - bar coil . however , this condition is more nearly met by the iia coil design and might therefore account for the better prediction . the method may have produced better results if closer attention was given to assessing the value of the coil ratio k , which describes the fraction of the total coil field energy that is transferred to the work piece . in addition to providing an estimate of bank energy and its general distribution in the system , this method provides a means of assessing the internal impulse forces in coil and the coil reaction against its support structure once the system current is estimated . for example , if the coil bar cross section are round or some what square , the force generated between coil elements can be roughly estimated by using the relation for the force per unit length , l , generated between parallel current filaments i 1 and i 2 , d length units apart given by : ## equ32 ## of course , if the coil bars are rectangular and close together , 5 . 25 will give a very poor estimate of the force between them . more accurate relationships for various cross section geometries can be found in older texts and handbooks of electric power engineering such as grover [ grover , 1947 ]. the energy estimation method presented here is intended only as a tool to aid in the early stages of a mt - em process design . like any other tool it has limitations which can be accepted and possibly improved if clearly understood . in addition the results available with such a tool are dependent , to some extent on the skill of the user . the real value of such approximations lie in their use in comparing competing design ideas . additionally , estimation methods often aid in the generation of new ideas from which solutions follow . initial coupon tests indicated a synergistic effect increasing limit plastic strain levels was possible in combining quasi - static and high velocity forming methods for aluminum alloy stamping . experimentation with coil geometries and materials produced results that further supported the expectation of success at full auto body panel size parts . alloy 6111 - t4 hoods were in production at the time of the trial . the original design intention was that the valley creases would run from each side of the wind screen , down the hood and around the nose to each side of the grill insert . during the prototype phase of production tool development , the valley crease could not be run to the grill area without producing wrinkles in the hood nose . the problem was correctly identified as bucking caused by unsupported compression of the material as the tool attempts to shorten the line length at the bottom of the crease traversing the hood nose . the object of this trial was to design and build an em tool which could extend the crease valley feature line ( s ) around the nose of the hood as originally intended . the extended feature valley crease could not exhibit buckling or restrict marks where the extended feature blended with the first form area . the amount of plastic strain required to complete the hood crease was only a few percent . the fact that the sheet could not be supported by tool surfaces during compression was the problem to be solved with em pulse forming . various options for constraining the high pressure area of the magnetic field over the narrow path of the valley crease were considered . high magnetic pressure outboard of the crease area would likely leave a impact mark in the sheet similar to a restrike mark in matched tools . the solution arrived at was the 3 - bar coil concept . the 3 - bar coil concept was subsequently also used in coupon tests . the coils for the hood and coupon tests are similar electrically in that the center bar carries the total current and the each of the two outer bars return half the total current . the 3 - bar coil configuration is not as energy efficient as a single turn coil consisting of the outer bars of the coil only . however the 3 - bar design is well suited to forming very high aspect ratio features which are not very deep . a simple straight , flat , trial coil , 4 . 75 cm × 30 . 00 cm was built of rectangular yellow brass bar stock and tested to validate the fundamental concept . the coil was pulsed against a flat sheet 6111 - t4 , ( 8 . 0 cm × 35 . 0 cm × 0 . 08 cm ) at 12 . kj , backup by a 2 . 5 cm thick sheet of neoprene ( 60 durometer ) about twice as wide as the test sheet . the result was a bead the same width as the center bar ( 1 . 0 cm ), formed in the sheet the same length as the center bar , approximately 0 . 5 cm high and having a nearly parabolic cross section . the sheet outboard of the bead had a slight dihedral away from the bead but no wrinkles . a question remained as to how well a 3 - bar would form a feature similar to the hood crease around a radius like the nose curvature of the hood . since the 3 - bar design was inexpensive and easily made from bar stock , a second trial coil fixture was built and tested . the second three bar coil , 4 . 75 cm wide by 92 . 0 cm long was constructed with a 15 cm radius through a 120 degree bend at the mid - point . a first trial coil was prepared with a test bead sheet and the second , mounted in a two half , plywood fixture , also with a test sheet . the top half of the second coil fixture carried a plastic die insert to form the test sheets against . either stretch or compression beads could be produced by interchanging the coil and the die insert from the male half to the female . the results of the 3 - bar trial coil tests provided an empirical basis for the design of the hood crease feature coil along with an expectation of its efficiency . geometrically , the hood coil was quite similar to the curved trial coil with a few notable exceptions . first , the hood coil was not planely curved . second , it was not level across the bars in cross section . the coil face needed to carry the same contours as the hood valley crease area to be reformed within approximately 1 . 0 mm to maintain good magnetic field coupling . last , the hood coil needed to be structurally self sufficient capable of resisting the internal forces generated during operation with minimal reliance on containment by tool material in which it was embedded . this last condition was supported by the trial coil tests which indicated loss of efficiency when surrounded too closely by a contiguous , conducting , support form material such as steel or aluminum . conversely , epoxies and other polymers in heavy section had alone , neither adequate stiffness or toughness to contain the internal coil impulse forces attendant with the estimated pulse energy levels . fig1 a , 19b and 19c show an approximate schematic of the geometry of the hood coil . contact between the outer bars through the steel clamps was allowed since the outer bars are at very nearly the same potential . since the steel clamps were thin and parallel to the magnetic field they developed very little eddy current and therefore did not reduce the coil force on the hood . using the simple energy analysis presented above , the peak coil current were estimated and applied to determining peak internal forces of the coil . it is these forces which size the clamping plates or tie rods used to maintain structural integrity of the coil . as reported earlier , a principal structural design rule for mt - em coils is sufficient strength to handle discharge forces independent of the surrounding tool material . the peak current was predicted to be 264000 amperes by the method presented in the previous section . internal forces of the coil , tending to spread the coil bars apart , at peak current were estimated at 210 kn . steel clamps were designed so that the span strength of the coil bars matched the load capacity of the clamps . the arrangement and size of the clamps shown in fig1 a , 19b and 19c resulted from the analysis of coil current and forces with an additional safety margin provided by the tooling material . the finished em tools with the imbedded coil used for the em restrike of the hood feature are made from the new , iron filled castable product which is a room temperature cured , epoxy like material . this material is currently being used in place of low melt temperature zinc alloys such as kirksite for prototype and short run production . cost of producing mt - em tools for auto body parts using the new iron filled epoxy is significantly lower than alternative constructions including the soft zinc metals . additional advantages of the material are that eddy currents are arrested due to the small particle size of the iron filler while the mass , is about 70 % that of iron . mass is a desirable property in mt - em tools as it supplements the tool material stiffness in providing local resistance to deflection at high work piece impact velocities . greater detail of the construction process for these castable mt - em tools will be given in the section describing the door inner panel trial . the automobile hood trial demonstrates that the apparatus and methods of the present invention allows sheet metals to be compressed without wrinkling , permits a formed panel to be restruck from an original / precursor shape to a final shape . the automobile door trial demonstrates that the apparatus and method of the present invention allows one to extend the forming limits of such metals as aluminum by forming a softened corner ( i . e . approximately 4 &# 34 ;× 4 &# 34 ;), and that the em forming may be used to finish the shape with higher strains . these trials demonstrate that the apparatus and methods of the present invention may be made commercially viable in the formation of actual commercial metal parts . with respect to the example of the automobile hood mock - up it was found that the subject shape could be achieved with a 3 - bar coil which was both robust and simple to manufacture . a feature of about 40 &# 34 ; in length could be formed at about 12 kj . it was also shown that a bead could be made in compression . the 3 - bar copper , wrapped coil was fabricated to conform to the hood contour and had internal clamps to react to forces on the coil during operation ( see fig2 ) the coil was embedded in general motors stamp metal / polyester composite , as was the balance of the top and lower die . over 30 discharges on a single embedded coil could be done without damage . the portion ( s ) of the mold requiring the em coil preferably was cut out to form cassettes that allowed iterative try - out and proofing , as well as modification and maintenance . in some applications the same cassette space could be provided with cassettes having different coil numbers , variations and arrangements for restriking . vacuum ports were provided on the top tool ( the side that defines the sheet shape ). with vacuum grease a vacuum of about 20 torr could be obtained . with respect to the automobile door trial , a geometry such as that shown in fig2 could be produced by locking the panel fully and forming the angled hinge face . this precursor shape was then reformed electromagnetically . this geometry was formed using only about 35 kj . high velocity forming after traditional forming can provide significantly enhanced total strains ( about 30 % in plane strain ). also , high levels of quasi - static pre - strain maximize total available strain . thermal softening was found to be an unexpected source of reduction in strain . thermal notching could be mitigated by protecting the work piece from heat with a copper driver foil . a good coil design , preferably one avoiding notches normal to stretch direction , and uniform current density , also reduced thermal notching . the use of 5000 series aluminum may less subject to such problems . the use of intermittent em pulses during die forming or other mechanical forming is shown to be useful in distributing strain in the forming process . the geometry of fig2 was found to be simpler to form as compared to that in fig2 . a 3 - bar coil was used to form this geometry . due to the relatively high lead inductance and low coil efficiency , this panel could not be taken to failure at energies over 40 kj , but significant forming was obtained . the corner of a j - car door inner , whose hinge face was largely formed traditionally , is softened to avoid tearing , and em forming is used to finish the shape , as shown in the schematics in fig2 . fig2 shows where an embedded coil may be supplied as a cassette . fig2 shows an em forming coil as it resides behind a mold face which is adapted to form a metal sheet into a precursor shape followed by finishing with em forming . fig2 shows an operator holding a cassette , containing an em forming coil , that fits into the balance of a correspondingly shaped portion of a mold body . as it resides behind a mold face which is adapted to form a metal sheet into a precursor shape followed by finishing with em forming . fig2 shows a plan view of an electromagnetic actuator coil used in accordance with the present invention . fig2 shows coil body 26 fig2 is a sectioned elevational view of an electromagnetic actuator coil with inner and outer coil leads . fig2 is a sectioned view of the electromagnetic actuator coil along a -- a of fig2 . fig2 , 26 and 27 show coil body 71 bearing coil body insulating tape 72 . also shown are flat outer insulating spacer 73 and flat inner insulating spacer 74 ; and curved outer insulating spacer 89 and flat inner insulating spacer 88 . fig2 also shows outer coil lead 81 and inner coil lead 82 , and corresponding negative bus lead 84 and positive bus lead 84 . also shown is coil lead insulator plate 83 and bus lead insulator plate . there is also a short tie rod insulator sleeve 79 and washer 76 which , together with hex nut 78 , hold short tie rod 80 in short tie rod insulator sleeve 79 . fig2 also shows bus lead insulator plate 90 . fig2 shows washer 76 and hex nut 78 holding long tie rod 77 in long tie rod insulator sleeve 75 , with flat inner insulating spacers 74 between portions of the coil body 72 , and flat outer insulating spacers 73 between portions of the coil body 72 and the washer 76 and hex nut 78 . fig2 shows a side elevational view of the coil , lead and bus assembly shown in fig2 , showing coil body 72 , coil lead insulator plate 83 , 0 . 25 - 20 nc × 0 . 88 soc hd scr 86 and 0 . 25 hard washer 87 . in view of the foregoing disclosure , it will be within the ability of one of ordinary skill in the art to make modifications to the present invention , such as through equivalent alternative mechanical arrangements and / or the integration or separation of component parts , without departing from the spirit of the invention as reflected in the appended claims . | 8 |
referring to fig1 for a method for producing a carbon nanotube electrode according to a preferred embodiment of the present invention , the carbon nanotube electrode 2 so produced as shown in fig2 can be used for a field emitting display or a light emitting device , etc . in the meantime , referring to fig2 and 3 for the carbon nanotube electrode 2 , which comprises a ceramic substrate 21 , an electrode unit 24 formed on the ceramic substrate 21 and an emitter source 23 formed on the ceramic substrate 21 . the ceramic substrate 21 is an integrated ceramic substrate comprising at least two vias 211 for an electrical connection and an internal circuit 213 formed between two ceramic tapes 212 and a plurality of vias 211 . the internal circuit also can be substituted by adopting a conductive layer produced by an electrically conductive material . the electrode base 24 is produced by an electrically conductive material such as a silver paste and electrically connected to the internal circuit 213 and thus applying the voltage onto the emitter source 23 . a carbon nanotube paste ( which is made by a carbon nanomaterial and a silver paste containing silver nanopowder ) are used for the screen printing method to produce an emitter source 23 having a circular shape and a width ranging from 50 μm to 400 μm . when a voltage is applied onto the electrode base 24 , each carbon nanotube in the carbon nanomaterial can be sued as an electron emitter . a macroscopic view of the structure of the carbon nanotube field emitter will be described briefly as follows first , and the manufacturing method and related experiment results will be elaborated in details . referring to fig1 , the fabrication of the carbon nanotube electrode 2 including the preparation of a carbon nanotube paste containing a plurality of carbon nanotubes . in this embodiment , the chemical vapor deposition process is applied to synthesize the carbon nanotubes , in the process , a carbon - based precursor such as xylene , cyclohexene , methylbenzene , benzene or n - hexane is mixed with ferrocene as a catalyst and thiophene as a promoter to synthesize multi - wall carbon nanotubes with a diameter in the range of 20 ˜ 250 nm . a silver paste , containing silver powder with a particle diameter of 0 . 15 ˜ 5 μm , which is commercial available in the market ( this invention adopts the mep - ag - ptg - 5575 ) is mixed uniformly with a silver nanopowder having a particle diameter of 30 ˜ 150 μm to produce a mixture . the silver content in the silver paste is 30 ˜ 100 wt % ( percentage by weight ). finally , the carbon nanomaterial with the additive amount of 1 ˜ 15 wt % is mixed with the silver paste ( containing silver nanopowder ) ( with the additive amount of 99 ˜ 85 wt %). a surfactant ( triton x - 100 in this invention ) with the amount ranging from 0 . 8 to 1 . 8 ml / g is used to produce the nanotube paste . of course , it is not compulsory to produce the carbon nanomaterial on your own . any multi - wall nanotube having a diameter of 20 ˜ 150 nm or any carbon nanofiber having a diameter of 50 ˜ 500 nm may be used as the carbon nanomaterial for this invention . in addition , the reactive surfactant is not limited to triton x - 100 , but any solvent with equivalent functions can be used as a substitute . on the other hand , process 12 can be carried out for producing a highly integrated ceramic substrate 21 . in the low temperature cofire ceramic ( ltcc ) process , a mixture of glass and aluminum oxide powder or a mixed compound material of aluminum oxide fibers is adopted as the material to produce a ceramic paste , and then a plurality of thin ceramic tapes is formed by the tape casting method , and a plurality of tape vias 211 are produced by laser . after the vias are filled , an electrically conductive material such as a silver paste is screen printed to produce an internal circuit ( or an electrically conductive layer ) 213 . finally , these screen printed internal circuits ( or electrically conductive layers ) 213 go through the process of stacking the ceramic tapes 212 , and the hot pressing and annealing processes are then applied to fabricate the ceramic substrate 21 by a low - cost and precise manufacturing process , so that the ceramic substrate 21 not only has highly integrated internal circuits ( or electrically conductive layers ) for integrating various different components , but also offers a high temperature resisting to bear with the follow - up thermal processes . then , another process 13 is carried out to form a circular emitter source 23 on the ceramic substrate 21 by screen printing the carbon nanotube paste prepared in the process 11 , and the external diameter of the circular emitter source 23 is in the range of 1200 μm ˜ 2000 μm and the width in the range of 150 μm ˜ 1500 μm . a silver paste is used as the material to form an electrode base 24 . it is noteworthy that the shape of the emitter source is not limited to the circular shape , and any rectangular , triangular or polygonal shapes can be used to achieve the expected effect of the present invention . a circular shape with a radius in the range of 500 ˜ 5000 μm can also achieve the expected result . a heat treatment process 14 is performed in the atmospheric environment at the temperature of 110 ˜ 220 ° c . for 10 ˜ 60 minutes first , and then at a temperature of 200 ˜ 300 ° c . for 30 ˜ 120 minutes . finally , a sintering process 15 is performed under oxygen / argon atmosphere with the concentration ratio of 3 ˜ 30 vol % ( by volume ) under a temperature in the range of 500 ˜ 900 ° c . and a pressure in the range of 100 ˜ 700 torrs for 10 ˜ 60 minutes . the foregoing processes are thus carried out to produce the carbon nanotube electrode 2 . it is noteworthy that after the circular emitter source 23 is formed , a substance capable of guiding the movement of electrons or a substance having a high dielectric constant including platinum , palladium , iron , cobalt and nickel metals , or an alloy consisting these metal elements can be used to fill the space enclosed by the circular emitter source 23 for affecting the movement of electrons in order to enhance the field emission efficiency . the carbon tube paste without mixing silver nanopowder ( such as the commercialized silver paste ) and the carbon nanotube paste mixed with silver nanopowder according to the present invention are used . after the screen printing , a soft baking , sintering , and annealing processes as described in the processes 14 and 15 are applied . it is obvious that the dispersion of the carbon tube paste without being mixed with silver nanopowder , as shown in fig4 and 5 , indicates non - uniform distribution of carbon nanotubes in silver particles . the dispersion of the silver nanotube paste mixed with silver nanopowder according to the present invention as shown in fig6 and 7 , indicates an uniform distribution . the uniformity of carbon nanotube paste can improve the electrical conductivity of the electrode . referring to fig8 . the carbon nanotube paste with silver nanopowder according to the present invention definitely perform a better field emission efficiency . referring to fig9 and 10 , the fabricated carbon nanotube electrode 2 according to the present invention is used as cathode , and indium tin oxide ( ito ) glass coated with a fluorescent powder is used as an anode . fig9 and 10 show the light emission performance of the light emitting device measured at the operating voltages of 300v and 400v , respectively . it is obvious that a larger light emitting area is obtained by the circular field emitter 23 according to the present invention . based on the results shown in fig1 , the carbon nanotube electrode produced by a carbon nanotube paste containing 10 wt % of carbon nanotube with an external diameter of 3 . 1 mm and a width of 0 . 25 mm shown has an outstanding field emission efficiency . in summation of the description above , since the carbon nanotube has a high inertia , a high electrical conductivity , and very small radius of curvature , therefore it is very suitable to be used as a material for fabricating a field emitter . the present invention adopts ceramic plate as the substrate and prepares multi - wall carbon nanotubes paste . the screen printing process for producing electron emitter source on carbon nanotube electrode is performed . the present invention not only fabricates a carbon nanotube electrode with highly integrated internal circuits , but also produces a carbon nanotube electrode having lower threshold voltage and better field emission efficiency . the present invention also involves simple manufacturing processes , low production cost for the field emitter manufacturing process for fabricating carbon nanotube electrode with high field emission efficiency . while the invention has been described by way of example and in terms of a preferred embodiment , it is to be understood that the invention is not limited thereto . to the contrary , it is intended to cover various modifications and similar arrangements and procedures , and the scope of the appended claims therefore should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements . | 1 |
this invention relates generally to engines and more particularly to recirculating of blow - by gases and a portion of the exhaust gas into the combustion system of the engine for reducing the pollution emitted from the engine . generally the engine is a naturally aspirated version of an internal combustion engine . the burning of hydrocarbon fuels in engines causes the engines to emit oxides of nitrogen ( nox ) and soot as a by - product of the combustion cycle . these particles are emitted through the exhaust system . many systems have been developed for recycling a portion of the exhaust gas through the engine thereby reducing the emission of these components into the atmosphere . the same engine also produces blow - by gases which escape past the piston rings and into the crankcase . the blow - by gases include unburned carbon which becomes coated with oil from the crankcase . blow - by gases are recycled to the intake manifold where they are mixed with incoming air and ingested into the engine combustion system . the recirculation of a portion of exhaust gas and blow - by is used to reduce pollutions emitted to the atmosphere . the combination of the hot exhaust gas and the oily carbon particles of the blow - by if left together over a period of time causes a negative reaction which can result in the engine malfunctioning . the heat of the exhaust will cause the oily carbon to cake along the walls of the intake passages and near the intake valves . the caking near the valves will cause the valve seat to overheat and crack resulting in oil leakage past the seat and into the intake passage . such oil compounds the caking problem by combining with the caking mixture forming a build - up which becomes excessive to the point where the engine malfunctions . the present invention is directed to overcoming one or more of the problems as set forth above . in one aspect of the present invention an exhaust gas and blow - by recirculation system for an internal combustion engine is disclosed . the engine includes a crankcase and a cylinder head which has an intake passage . also included with the engine is an intake manifold connected to the passage , means for directing a portion of the engine exhaust into the intake manifold , and a crankcase ventilation valve in communication with the crankcase . the improvement of the recirculation system is comprised of means for communicating the blow - by gases from the crankcase to the passage in the cylinder head through the crankcase ventilation valve . the invention as decribed above overcomes the caking of the oily carbon particles along the walls of the intake passages and enables the exhaust gases to be recirculated reducing oxides of nitrogen and prevents the caking problem as discussed earlier . fig1 is a front elevational view of an internal combustion engine embodying the exhaust gas and blow - by recirculation system of this invention ; fig2 is a partial sectional view disclosing a portion of the exhaust gas and blow - by recirculation system ; fig3 is a sectional view through the cylinder head disclosing a portion of the exhaust gas and blow - by recirculation system ; and fig4 is a sectional view of the sealing means shown in a nonassembled condition . in reference to fig1 an exhaust gas and blow - by recirculation system 10 for an internal combustion engine 12 is shown . although the engine 10 , as shown , is a naturally aspirated internal combustion engine , the scope of the invention should not be limited to this configuration . the engine 10 has a crankcase 14 and a cylinder head 16 . the cylinder head 16 has an air intake passage 18 for transmitting combustible air into one of a plurality of combustion chambers , and a bore 20 entering the passage 18 . also shown is an intake manifold 22 connected to the passage 18 and a means 23 for directing a portion of the engine exhaust into the intake manifold . the means 23 includes an exhaust manifold 24 connected to the cylinder head 16 , an exhaust pipe 26 , a valve mechanism 28 of conventional construction is disposed between the exhaust manifold 24 and the exhaust pipe 26 . also included with the means 23 is a tube 30 connects the valve mechanism 28 with the intake manifold 22 . a crankcase ventilation valve 32 is in communication with the crankcase 14 as is well known in the art . as shown in fig3 a director tube 34 has a straight portion 36 and a curved portion 38 . the straight portion 36 is located partially outside the cylinder head 16 and extends through the bore 20 in the cylinder head 16 . the curved portion 38 is located within the passage 18 and is oriented to direct the flow of blow - by in the same direction and into the fluid stream within the cylinder head 16 . as shown in fig2 and 3 , a fastening means 40 is rigidly connected to the director tube 34 and orientates the tube in line with the intake air flow . the fastening means 40 includes a strap 42 rigidly connected to the director tube 34 . the strap 42 has an end 44 and a notch 48 located on the end 44 of the strap 42 . a securing means 50 includes a tubular spacer 52 located between the strap 42 and the cylinder head 16 , a bore 54 in the strap 42 and a bolt 56 extends through the bore 54 and spacer 52 . a means 60 for sealing is provided between the director tube 34 and the cylinder head 16 as shown in fig3 . the means 60 includes a seal 62 which has a bore 64 sealably fitted around the director tube 34 . a first sealing surface 66 contacts the cylinder head 16 and a second sealing surface 68 contacts the fastening means 40 . as shown in fig4 the first sealing surface 66 has a plurality of annular concentric protrusions 70 thereon . a concentric extension 72 is longer than the protrusions and extends between the bore 20 and the director tube 34 . the first sealing surface 66 is at an angle of substantially 3 ° to the second surface 68 . the top surface of the cylinder head 16 has a cast surface which has a taper of approximately 3 ° required by conventional casting techniques . the relationship of the 3 ° angles of the cylinder head 16 and the sealing surface 66 are orientated by a tab 76 protruding from the second surface 68 and fitting within the notch 48 in the strap 42 . a means 78 for connecting the director tube 34 to the crankcase ventilation valve 32 is shown in fig1 . the means 78 includes a tube 80 , positioned between the director tube 34 and the crankcase ventilation valve 32 , and a plurality of couplings 82 . the couplings 82 attach the end portions of the formed tube 80 with the valve 32 and the director tube 34 forming a sealed passage 84 between the valve 32 and the director tube 34 . also shown in fig1 is a means 86 for communicating the blow - by gases from the crankcase 14 to the passage 18 in the cylinder head 16 through the crankcase ventilation valve 32 . the means 86 for communicating includes the bore 20 , the director tube 34 , means 40 for fastening the director tube 34 to the cylinder head 16 , means 60 for sealing between the director tube 34 and the cylinder head 16 and means 78 for connecting the director tube 34 to the crankcase ventilation valve 32 . the exhaust gas and blow - by recirculation system 10 for the internal combustion engine 12 reduces the pollution emitted from the engine 12 . the exhaust gases emitted from the engine 12 pass through the exhaust manifold 24 to the valve mechanism 28 connected between the exhaust manifold 24 and the exhaust pipe 26 . the valve mechanism 28 directs a portion of the exhaust through the tube 30 and into the intake manifold 22 at a location away from the passage 18 . inside the intake manifold 22 the exhaust gases are combined with intake air and directed into the combustion chambers through the cylinder head . the blow - by is collected in the crankcase 14 of the engine 12 . from the crankcase 14 , the blow - by enters the crankcase ventilation valve 32 . the blow - by passes through the formed tube 78 and into the director tube 34 . the director tube 34 is positioned within the passage 18 of the cylinder head 16 in such a manner so that the stream of blow - by is in line with the fluid flow going into the engine combustion chamber . the air entering the combustion chamber from the intake manifold 22 passes by the director tube 34 and into the combustion chamber . the director tube 34 orientates the flow of the blow - by in the same direction as the flow of the intake air . the director tube 34 reduces the size of the passage and increases the velocity of the air flowing around the tube 34 in the passage . the velocity of the air within the passage 18 is therefore high and reduces the time for mixing of the blow - by with the intake and exhaust mixture . the mixture is drawn directly into the combustion chamber preventing the caking of the oily blow - by and hot exhaust along the walls of the passage 18 . with the invention as disclosed above , the exhaust gas and blow - by recirculation system 10 reduces the amount of pollution added to the atmosphere and prevents the build - up and caking of materials within the engine 12 . the caking within the intake passage is prevented by locating the blow - by inlet or director tube 34 within the passage 18 of the cylinder head 16 . since the passage 18 is located in close proximity to one of the plurality of combustion chambers , the caking near the valves is reduced because of the high velocity with which the incoming air within the passage 18 is traveling . this high velocity reduces the time that the mixture of hot exhaust and oily blow - by resides along the walls of the passages 18 thereby preventing caking . other aspects , objects and advantages will become apparent from a study of the specification , drawings and appended claims . | 5 |
fig2 is a simplified block diagram of the rom address arrangement of the present invention . address output terminals of processor 10 are connected to processor address bus 12 , which are coupled to one input of multiplexer 30 . the output of multiplexer 30 feeds rom address signals to rom 20 via rom address bus 16 . the bit width of the rom address input , rom bus address , and multiplexer output are the same and in excess of the bit width of the processor address bus 12 . the maximum number of rom addresses thus exceeds the address capacity of the processor address bus . merely by way of example , a 16 bit processor address bus would have an address capacity in excess of 64 kbytes of memory , while a 24 bit rom address bus would have an address capacity in excess of 16 mbytes of memory . data bus 14 is connected between the rom and the processor for conveying data accessed from the rom to the processor and for loading data from the processor to counter 70 . the bit width of the data bus is significantly smaller than the bit width of the rom access bus . each time that the rom is addressed in a read mode , data equal in number to the data bus bit width is accessed . processor address bus 12 is also connected to the input of decoder circuit 40 , the output of which is connected to logic circuit 50 . logic circuit 50 is connected to counter 70 for actuation and control of the counter . counter 70 has an input connected to data bus 14 and an output connected to another input of multiplexer 30 . the contents of the counter contain the same number of bits as the rom address bus . logic circuit 50 is also connected the multiplexer 30 for applying a control signal thereto . logic circuit 50 has inputs for receiving signals such as read enable and write enable signals from the processor 10 . these inputs are not shown for simplicity of illustration . in a rom read operation , the processor outputs an address to address bus 12 , which applies the address to both multiplexer 30 and decoder 40 . as to be more fully explained below , decoder 40 has been set to a specific address that is associated with a sequential access mode of read operation . if the address output by the processor is the specific decoder address , the decoder outputs an enable signal to the logic circuit 50 . in response , the logic circuit applies a read control signal to the multiplexer 30 that is indicative of the sequential access mode . the multiplexer thereupon applies the contents of counter 70 to the rom address bus . logic circuit 50 contains a pulse delay circuit for thereafter applying a clock signal to the counter to increment the counter contents . subsequent output of the same specific address by the processor will be acted upon by the decoder , logic circuit , counter and multiplexer in the same manner to output the incremented counter contents , i . e ., the next sequential rom address , to the rom . successive output of the sequential mode address enables high speed data access . output of a random mode address by the processor does not match the decoder and the sequential access mode is not initiated . as no enable signal is generated by the decoder , the multiplexer is set to the random access mode of operation . the processor address output is applied by the multiplexer from the processor address bus to the rom address bus . in order to accommodate the greater number of multiplexer output lines that match the bit width of the rom address bus , the number of multiplexer output bit lines in excess of the number of processor address bus lines are tied to either a binary high or low state , depending on design considerations . preferably , the excess lines can be at the high end or low end of the rom address , although other terminal groupings can be tied if beneficial to a particular application . in system operation , the processor is responsive to an input signal , received at a terminal 15 , for implementing one of the modes of rom access . in a vehicle diagnostics device , the signal may be developed manually or automatically in response to vehicle parameter conditions . for example , in a diagnostic procedure , the sequential rom storage may include textual explanation for each of a plurality of possible conditions to aid the operator in performing the diagnostic service . upon occurrence of a condition , a signal may be applied to input 15 for accessing the relevant sequential string of data , the information for which can then be displayed for the operator . alternatively , the operator may issue a command signal to access the sequential rom storage to display explanatory text and / or graphics for reference purposes . while input 15 is illustrated as a single input for purposes of simplifying explanation , it should be realized that diagnostic applications are varied and that any number of interfacing connections may be made with the processor as appropriate to the particular application . fig3 is a more detailed block diagram of the sequential read mode elements in accordance with the present invention . in the sequential mode , the contents of counter 70 are applied by the multiplexer 30 to the rom address bus . the total number of counter output bits thus is equal to the bit width of the rom address bus . data representing the first rom address of a sequence of rom addresses are written into the counter from the data bus 14 . the writing operation is initiated in response to a write enable signal { overscore ( w )} output by the processor . the counter 70 may comprise any well known specific counter arrangement . in the preferred embodiment shown , the counter comprises a plurality of interconnected stages 72 , 74 76 , each having a bit width equal to the bit width of the data bus . the term “ counter ” as used herein is intended to likewise include a plurality of counter stages . to accommodate a complete rom address , the number of counter stages is equal to the rom address bit width divided by the data bus bit width . three counter stages are illustrated to correspond to the above described example of a twenty four bit width rom and an eight bit width data bus . while the bit width of the data bus typically may be one byte , design considerations for particular applications may indicate a different size . decoder 46 comprises a plurality of decoder stages 42 , 44 and 46 , each corresponding to a respective counter stage . the term “ decoder ” as use herein is intended to likewise include a plurality of decoder stages . logic circuit 50 comprises a plurality of logic elements connected as follows . and gate 52 has a first input connected through an inverter to decoder stage 42 . and gate 54 has a first input connected through an inverter to decoder stage 44 . and gate 56 has a first input connected through an inverter to decoder stage 46 . a second input of each of the and gates is connected through an inverter to the write enable line of the processor . the output of and gate 52 is connected to counter stage 72 . the output of and gate 54 is connected to counter stage 74 . the output of and gate 56 is connected to counter stage 76 . and gate 58 has a first input connected through an inverter to the output of decoder stage 42 and a second input connected through an inverter to the read enable signal line . the output of and gate 58 is connected to the multiplexer . pulse delay circuit 60 is connected between the output of and gate 58 and the multiplexer . each counter stage is activated in response to a signal received through logic circuit 50 and decoder 40 . counter stage 72 is activated in response to a signal received from its connection to and gate 52 . counter stage 74 is activated in response to a signal received from its connection to and gate 54 . counter stage 76 is activated in response to a signal received from its connection to and gate 56 . each decoder stage is connected to the address bus and is set to a unique one of the sequential mode addresses . in the write operation , the first sequential rom address is loaded into each counter stage in a succession of write commands from the processor . the processor generates a write enable signal and applies a sequential mode address to the address bus . for an address that matches decoder stage 42 , the decoder outputs an enable signal . and gate 52 , having high level signals at the decoder input and the write enable input , outputs a signal to activate counter stage 72 . one byte of data , representing one third of the first sequential rom address is output by the processor to the data bus and loaded into the activated counter stage 72 . data are loaded in the same manner to counter stages 74 and 76 . the address for each decoder is output and the appropriate data loaded from the data bus . during the write operation the rom is inactive as there is neither a read enable signal nor output enable signal output by the processor . thus no stored rom data can be overwritten . the read operation is initiated by generation of a read enable pulse signal by the processor . for the sequential read mode , the processor outputs the address to which decoder 42 is set to produce an output signal from the decoder . and gate 58 , in response to the decoder output signal and read enable signal at its inputs outputs a read control signal to the multiplexer . the multiplexer switches the counter contents received from the counter input to the rom address bus . the first sequential rom address is thereby input to the rom . as the read enable signal is also applied to the rom , in a manner well known in the art , a byte of data identified by the applied rom address is output to the data bus . the read enable pulse , conveyed through and gate 58 , is delayed by pulse delay circuit 60 for a period sufficient for the data to be accessed and then applied to a clk input of counter stage 72 to increment the counter stage . this operation is repeated for each successive output by the processor of the same address . in a manner well known in the art , all counter stages may be tied together so that , when the maximum count is reached by counter stage 72 ( taken as the least significant byte ), after the next read a carry signal is applied to increment the next counter stage while counter stage 72 rolls to zero . it is to be understood , also , that the address for decoder stage 42 is exemplified as the sequential mode address for simplicity of illustration and description . any of the other decoder stage addresses may be so utilized for the read mode sequence . as a further alternative , each of the decoder stages may be connected through appropriate logic circuitry to activate the sequential read operation in response to output by the processor of its corresponding address . in random access mode , the number of output lines ( 16 ) exceeds the width of the processor address bus ( 12 ). the multiplexer ( 30 ) input lines for the random access mode in excess of the number of processor address lines ( 12 ) are tied to fixed logic levels presenting sufficient input lines for each mix stage . in the random access read mode , an address is output by the processor that does not match any of the decoder stage addresses . while a read enable signal is also generated , gate 58 does not receive an output from a decoder stage and thus does not switch states . the multiplexer , therefore , will not switch its output from the process address bus to the counters . as the read enable pulse signal is not conveyed to the pulse delay circuit , no incrementation of the counter occurs . the illustrated address decoder may comprise any decoder well known in the art . a preferred arrangement is illustrated in fig4 . for ease of illustration and explanation , a four bit input is represented . it is to be understood that , for the 16 bit address bus example of fig3 or any other bit width input , the decoder stage is appropriately expanded . decoder 48 comprises a nand gate having four input terminals connected to lines a 0 - a 3 , which may correspond to individual address bit lines . when all input terminals are at a high level the nand gate outputs a low level signal . all of the input terminals of the gate can be set , or programmed , to be at a high level for any one of the sixteen possible combinations of inputs at lines a 0 - a 3 , by connecting one or more inverters at appropriate input terminals . in the illustration , inverter 49 is connected in the least significant bit line , while the remaining input lines are directly connected to the nand gate inputs . an address of 1 - 1 - 1 - 0 , a hexidecimal value e , would result in all nand input gates attaining a high level and an output signal of a change state ( low ). for any of the other fifteen possible input addresses , at least one of the gate inputs would be at a low level and the output of the gate , thus , at a high level . the illustrated arrangement is thus a decoder for hexidecimal e . the nand gate has been illustrated for correspondence with the negative level logic described for the embodiment of fig3 . as would be appreciated by one of ordinary skill in the art , positive logic can be used without changing the spirit of the invention . with this alternative , the nand gate would be replaced with an appropriate and gate . while the foregoing has described what are considered to be preferred embodiments of the invention it is understood that various modifications may be made therein and that the invention may be implemented in various forms and embodiments , and that it may be applied in numerous applications , only some of which have been described herein . for example , the described embodiment of fig3 permits a string of rom data to be read in sequential manner in response to successive outputs of a single address by the processor . it should be understood that a plurality of rom data portions can be defined for such sequential operation . for any such sequential string of rom data the same combination of counters and decoders can be used . the decoder starting address , loaded into the counters , for each string can be set to a respective one of a plurality of rom addresses to activate the sequential reading mode as well as to load the respective counter . each counter is output to a respective multiplexer input . through the use of appropriate logic circuitry , in accordance with a decoder output the appropriate counter output can be applied by the multiplexer to the rom bus address . it is further within the contemplation of the present invention that the rom consist of eeprom storage wherein data may be written to the memory . the dual random address mode / sequential address mode operation disclosed herein may be utilized for writing to memory having a greater number of address locations than the processor address bus bit width limit . decoders and counters may be correlated in the same manner to identify the expanded number of addresses to the rom address bus . the described preferred embodiments employ a plurality of decoder stages and counter stages . the plurality of counter stages can be replaced by an appropriately connected single counter stage . likewise , a single decoder may be employed with appropriate logic interconnections to the counter to successively load data to the counter . it is intended by the following claims to claim all such modifications and variations which fall within the true scope of the invention . | 6 |
as is apparent from fig1 an idealized qrs complex consists of a relatively high - amplitude oscillation that initially guides the ecg signal , in the q spike , away from the zero line 1 in a negative direction . afterwards the ecg signal is guided , in the r spike , into the positive range with a steep rise and with a subsequent steep drop back into the negative range while forming the s spike . in reality the ecg signal is accompanied by a certain level of noisiness , as indicated in fig1 by the dashed signal curve . if this noisy signal is now sampled and converted into discrete signal values in chronological order , the sign of each signal value can be determined and a check can be performed as to whether a zero crossing of the ecg signal though the zero line 1 has taken place between these signal values . outside the qrs complex a high number of zero crossings occurs in a defined segment n 1 , whereas a much lower number of zero crossings is detected during sampling of a segment n 2 in the qrs complex . the count of the number of zero crossings may thus be used to detect a qrs complex . the ecg signal is sampled and converted into discrete signal values x ( n ) in chronological order . the sampling rate may be f = 360 hz , for example , i . e ., the ecg signal is converted into a sequence of 360 measuring values per second . the detailed sequence of the inventive evaluation method will now be explained in more detail based on fig2 . according to that structural diagram , the sampled ecg signal x ( n ) is subjected , on the input side , to a band - pass filtering that serves to remove all signal components that do not belong to the qrs complex . this includes the p and t waves , as well as high - frequency noise that may originate , for example , from the bioelectrical muscle activity . this furthermore suppresses the base line drift and moves the ecg to the zero line 1 . the applied filter bp is non - recursive , linear - phase and has a band - pass characteristic with the pass frequencies f g1 = 18 hz and f g2 = 27 hz , as well as the limiting cutoff frequencies f g1 = 2 hz and f g2 = 50 hz . the filter order is n = 200 . the group delay of the band - pass filter bp accordingly corresponds to 100 sampling values and must be taken into consideration when determining the time of the occurrence of the qrs complex . the blocking attenuation of the filter is approximately 80 db . the signal values x f ( n ) attained in this manner are subsequently squared in a squaring step qs according to the following relation while maintaining the signs of the given signal values : in an adding phase 2 , a high - frequency sequence b ( n ) with a low amplitude that may be described as follows is subsequently overlaid to the band - pass filtered and squared ecg signal : wherein k ( n )& gt ; 0 . adding is sequence b ( n ) changes the number of zero crossings per segment . the upper limit of the number of zero crossings is the number n of the sampling values of the segment . with this sequence b ( n ) the number of zero crossings is increased to this maximum number in the non - qrs segments , whereas the ( lower ) number of zero crossings is maintained in the qrs complex . to attain this goal , a suitable value for the coefficients k ( n ) is adaptively estimated from the signal values x fq ( n ). the band - pass filtered and squared signals are determined flowingly for this purpose over a defined averaging interval of p sampling values according to the following equation : 〈 | x j q | 〉 ( n ) = 1 / p · ∑ i · 0 p - 1 | x f q ( n - i ) | the averaging time essentially determines the adaptation speed of this estimate and both , averaging segments that are too short , as well as averaging segments that are too long may impact the effectiveness of the signal evaluation method . during the occurrence of qrs complexes the adaptation is paused since the sequence b ( n ) is intended to only influence the zero crossings during the non - qrs segments . in fig2 the process complex that pertains to the determination of the coefficients k ( n ) has been marked as as . the multiplication of the basic function — indicated in fig2 as a kind of “ flip flop function ” with “+ 1 , − 1 , + 1 , − 1 , . . . ”— with the amplitude k ( n ) has been indicated in the form of the multiplication step 3 . the above discussed signal values are now subjected to the actual zero crossing count ndz . counting the zero crossings is principally performed per segment according to the following relation : d ( n ) = ∑ i = 0 n - 1 d ( n - i ) if d ( n )= 1 , this means “ zero crossing detected ”, d ( n )= 0 means “ no zero crossing detected .” in this manner a high number of zero crossings per segment results for high frequencies and accordingly fewer for low frequencies . from a signal technology point of view , counting the zero crossings essentially corresponds to a low - pass filtering ; in practice counting the zero crossings may be implemented with a filter having a square - pulse response , i . e ., the filter pulse response a i = 1 with i = 0 . . . n − 1 produces the number of zero crossings d ( n ). the advantage of this filter results from the implementation with n − 1 shift operations , which is favorable from a computing point of view , and feedback without multiplication . the filter function is , in fact , defined as follows : h ( z ) = ∑ i - 0 n - 1 z - 1 = ( 1 - z - ( n - 1 ) ) / ( 1 - z - 1 ) a further advantage of this implementation lies in the fact that the number of zero crossings takes exclusively whole - number values , the range of which is determined by the segment length n . this feature can be advantageously utilized in the subsequent decision phase es . the filter order n furthermore significantly influences the robustness of the sign evaluation method with respect to noise . larger filter orders increase the robustness , however , filters that are too long , on the other hand , due to the prolonged averaging interval , may lead to false - negative detection errors (“ false negative ” means that even though a qrs complex is present in the ecg signal , it was not detected .) in the present embodiment , the filter order n = 10 is used . the threshold value of the number of zero crossings that is significant for the detection of a qrs complex is determined by comparison with an adaptive threshold . the latter is determined from the average of the 0 . 1 and 0 . 5 quantiles of the frequency distribution f ( m ) of d ( n ). the statistical size “ quantile ” is used because it has a greater robustness , compared to average and variance , with respect to statistic freak values . in the present case it is very easy to calculate , as the signal values can take only whole - number values between 0 ≦ d ( n )≦ n . the frequency distribution f ( m ) with 0 ≦ m ≦ n is determined adaptively in two steps , namely : wherein a memory factor 0 & lt ; λ & lt ; 1 is used . for the numerical example briefly shown at the end of this description , this memory factor was selected as λ = 0 . 01 . it is now easy to determine from the frequency distribution the quantiles and from them , in the manner described above , the adaptive threshold . if d ( n ) is below the threshold , a qrs complex has been detected , otherwise not . in fig2 the process segment of the threshold estimation has been marked with sws . in other respects , the band - pass filtered and squared signal x fq ( t ) is used to determine the exact time of the occurrence of the r spike of a qrs complex . for this purpose the maximum in this signal is searched in a search interval around the starting point of a qrs complex , the occurrence of which is set as the time of the occurrence of the r spike . simultaneous with the actual detection of qrs complexes and to determine the time of the occurrence of the r spike , two additional variables are estimated in the evaluation process for the purpose of evaluating the signal , namely the useful signal strength p qrs and the noise signal strength p noise . one of the two variables is updated with each detected result . when a qrs complex is detected , the estimated useful signal strength is updated , otherwise the estimated interfering signal strength is updated . for this purpose the value | x fq ( t )| max is used in a suitable interval around the instant at which the number of zero crossings d ( n ) falls below the threshold value , with one exponential windows used in each case in the present implementation . this means the following derivation applies for the estimated useful and interfering signal strengths : p qrs ( i + 1 )=( 1 − λ qrs )· p qrs ( i )+ λ qrs ·| x fq ( t )| max p noise ( i + 1 )=( 1 − λ noise )· p noise ( i )+ λ noise ·| x fq ( t )| max the memory factors λ in the above two equations were selected as follows : lastly , a detection strength is calculated from the estimated signal strengths according to the following relation , the value of which provides information as to whether an event that would normally be qualified as a qrs complex is indeed a useful signal that should be attributed to a qrs complex for the signal evaluation method . the detection strength is calculated as follows : ds = (| x fq ( t )| max − p noise )/( p qrs − p noise ) in the present example a detected peak is classified as an interfering signal if the detection strength is less than 0 . 01 . in that case the interfering signal strength is updated . otherwise it is a qrs complex , after which the useful signal strength is updated accordingly . lastly , a time window of 75 ms is used in the signal evaluation . if multiple qrs complexes are detected within this time window , only the first complex is evaluated and the other complexes are extracted . this relatively short refractory time was selected to ensure a swift resumption of the normal detection in case of false - positive detections of a qrs complex , and to thus reduce false - negative recognition errors . the inventive signal evaluation method as described in detail above was tested and validated with the aid of a database with the designation “ mit / bih arrhythmia data base ” that is sold commercially for test purposes . this database contains 48 two - channel ecg signals with a length of approximately 30 minutes each . these ecg signals are ranged into classes , so that the location of the qrs complexes is known . the signal evaluation method was performed on a personal computer , with a frequency f used as the sampling rate . to evaluate the efficiency of the present method , the so - called sensitivity se and specificity + p were determined according to the following condition : wherein the number of correctly detected qrs complexes is included as tp , the number of false - negative detections is included as fn , and that of the false - positive detections is included as fp . a qrs complex was assumed detected correctly if it was detected within a time window of +/− 75 ms around the actual location of the time of its occurrence . the results of this simulation example are listed in the appended table 1 . from this table it can be seen that the sensitivity se and specificity + p were significantly higher than 99 % for the large majority of data sets — the so - called “ tapes ”— and in some instances exactly 100 %. only in very few cases of very noisy signals , such as in tapes no . 105 and 108 were these values lower , however , still high enough for good results to be obtained there as well . the simulation example is also shown graphically in fig3 by way of example . the signal curve 4 , for example , reflects the actual ecg signal . it clearly shows the r spike 5 , the immediately adjacent q and s spikes 6 , 7 are only implied . also entered is the adaptive threshold 8 for distinguishing between qrs and non - qrs segments . based thereon , the curve 9 reflects the course of the number of zero crossings of the ecg signal values . it is apparent how , after the occurrence of a qrs complex , the number of zero crossings breaks in with a delay t g that corresponds to the group delay time in the sampling and filtering of the ecg signal . this is reflected in the downward pointing spikes in the curve 9 . synchronously , the threshold value 8 is adapted after the occurrence of a qrs complex , as is apparent from the saw - tooth shaped curve of the threshold value 8 in fig3 . | 8 |
referring now to the figures of the drawings in detail and first , particularly , to fig1 thereof , there is seen an exemplary embodiment of a sheet - fed printing press 1 which includes six printing units 2 , a varnishing unit 3 disposed downstream of the printing units 2 , two driers 4 disposed downstream of the varnishing unit 3 and a stamping / embossing unit 5 . in the context of the present application , the printing units 2 , the stamping / embossing unit 5 and the varnishing unit 3 are referred to as production units . in addition , the printing press 1 includes a delivery 6 where the finished printing material is deposited and a feeder 7 at the entrance of the printing press 1 for feeding new printing material to the printing units 2 . in the printing press 1 , all of the printing units 2 , the varnishing unit 3 and the stamping / embossing unit 5 are mechanically coupled by a gear train . the gear train is driven by a main drive motor of the printing press 1 . it is likewise possible to provide an individual drive for every printing unit 2 , stamping / embossing unit 5 or varnishing unit 3 . in order to implement the present invention , however , it is sufficient to provide an individual drive motor 10 for a cylinder 8 in the varnishing unit 3 and in the stamping / embossing unit 5 , as seen in fig5 . these units are substantially formed of the cylinder 8 for receiving varnishing formes or stamping / embossing formes and an associated impression cylinder 9 . the separate drive motor 10 ensures that the cylinder 8 in the stamping / embossing unit 5 and in the varnishing unit 3 may be driven while mechanically uncoupled from the printing units 2 and from the impression cylinders 9 in the varnishing unit 3 and in the stamping / embossing unit 5 . thus , the stamping / embossing cylinder 8 in the stamping / embossing unit 5 and the varnishing cylinder in the varnishing unit 3 can be rotated relative to the associated impression cylinders 9 through the use of the associated electric drive motor 10 . fig2 illustrates a point of contact between the stamping / embossing forme on the cylinder 8 and the printing material on the impression cylinder 9 in the stamping / embossing unit 5 . in the varnishing unit 3 , the situation is similar , with the only difference being that the cylinder 8 does not carry a stamping / embossing forme but instead a varnishing forme made of a soft material . in the stamping / embossing unit 5 , the pressure between the cylinder 8 and the impression cylinder 9 is high since it is required for stamping / embossing . for this reason , no slip may occur between the cylinder 8 and the impression cylinder 9 . when the cylinder 8 and the impression cylinder 9 have a different circumference , they cannot rotate at the same rotational speed . therefore , in order to be able to start correctly for every sheet at every revolution , the angular offset between the cylinder 8 and the impression cylinder 9 caused by the different diameters must be compensated for . this correction of the angle of rotation , also referred to as a differential angle , is shown in fig3 . as can be seen , at the beginning of a new revolution and at the beginning of a new image , the differential angle starts at zero and increases to 2 . 5 degrees up until a gap of the impression cylinder 9 . as soon as the gap of the impression cylinder 9 is reached , the differential angle is re - set to zero by a corresponding modification of the rotational speed of the stamping / embossing cylinder 8 . this modification is achieved by suitably actuating the drive motor 10 and the cylinder 8 . fig4 illustrates a closed - loop control operation in which an optimum lead angle of 1 . 5 degrees is set by the control unit 11 in the power electronics of the drive motor 10 of the cylinder 8 . the closed - loop control is shown to be based on the detection of the motor torque or motor current . the first step is to detect that an increased torque of + 10 nm occurs . the ideal lead angle of 1 . 5 degrees results when there is no slip , i . e . when the motor torque is 0 nm . for this purpose , a counteracting motor torque of − 10 nm is applied to the drive motor 10 of the cylinder 8 to attain the desired lead angle of 1 . 5 degrees in the third revolution at 0 nm . this automatic adjustment by a control 11 of the drive motor 10 of the cylinder 8 is based on the detection of the respective motor torque and angle of rotation . in a closed - loop control operation based on the motor torque , the drive motor 10 is actuated on the basis of the measurement of the motor torque , which is then either increased or reduced depending on whether a lead angle or a lag angle is desired or required . if the differential angle is ideal , the motor 10 runs at the lowest torque . consequently , the lead or lag angle does not have to be set by the operator . instead , it can be automatically set by the control or power electronics 11 of the drive motor 10 of the cylinder 8 . fig5 illustrates the basic structure of the control loop for actuating the drive motor 10 for the stamping / embossing cylinder 8 . in this context , it is sufficient if the varnishing unit 3 and the stamping / embossing unit 5 include a control loop 11 in which the drive motor 10 includes detecting means such as a sensor 13 for sensing the motor torque and in which this torque is controlled to be as low as possible . alternatively , it is possible to detect the differential angle using a motor encoder of the motor 10 and an angular transmitter 12 on the impression cylinder 9 , for instance when an additional lead or lag is desired such as in a varnishing operation to achieve printing length correction . in this case the operator may set an additional desired correcting angle for printing length correction in the control of the printing press 1 . this correcting angle is then transmitted to the power electronics 11 of the drive motor 10 and is set on the basis of the detected angle of the impression cylinder 9 and the cylinder 8 . | 1 |
the feedstocks that can be used in this invention include hydrocarbon fractions rich in c 4 - c 6 normal paraffins . the term &# 34 ; rich &# 34 ; is defined to mean a stream having more than 50 % of the mentioned component . preferred feedstocks are substantially pure normal paraffin streams having from 4 to 6 carbon atoms or a mixture of such substantially pure normal paraffins . other useful feedstocks include light natural gasoline , light straight run naphtha , gas oil condensate , light raffinates , light reformate , light hydrocarbons , field butanes , and straight run distillates having distillation end points of about 77 ° c . ( 170 ° f .) and containing substantial quantities of c 4 - c 6 paraffins . the feed stream may also contain low concentrations of unsaturated hydrocarbons and hydrocarbons having more than 6 carbon atoms . the concentration of these materials should be limited to 10 wt . % for unsaturated compounds and 20 wt . % for heavier hydrocarbons in order to restrict hydrogen consumption and cracking reactions . hydrogen is admixed with the feed in an amount that will provide a hydrogen to hydrocarbon ratio equal to or less than 0 . 05 in the effluent from the isomerization zone . the hydrogen to hydrocarbon ratio of 0 . 05 or less at the effluent has been found to provide sufficient excess hydrogen for operation of the process . although no net hydrogen is consumed in the isomerization reaction , the isomerization zone will have a net consumption of hydrogen often referred to as the stoichiometric hydrogen requirement which is associated with a number of side reactions that occur . these side reactions include cracking and disproportionation . other reactors that will also consume hydrogen include olefin and aromatics saturation . for feeds having a low level of unsaturates , satisfying the stoichiometric hydrogen requirements demand a hydrogen to hydrocarbon ratio for the inlet stream of between 0 . 03 to 0 . 1 . hydrogen in excess of the stoichiometric amounts for the side reactions is maintained in the reaction zone to provide good stability and conversion by compensating for variations in feed stream compositions that alter the stoichiometric hydrogen requirements and to prolong catalyst life by suppressing these side reactions . if left unchecked , the side reactions reduce conversion and lead to the formation of carbonaceous compounds , usually referred to as coke , that foul the catalyst . it has now been found that the amount of hydrogen needed for suppressing coke formation need not exceed dissolved hydrogen levels . the amount of hydrogen in solution at the normal conditions of the isomerization zone effluent will usually be in a ratio of from about 0 . 02 to less than 0 . 01 . the amount of excess hydrogen over the stoichiometric requirements that is required for good stability and conversion is in a ratio of hydrogen to hydrocarbons of from 0 . 01 to less than 0 . 05 as measured at the effluent of the isomerization zone . adding the dissolved and excess hydrogen proportions show that the 0 . 05 hydrogen to hydrocarbon ratio at the effluent will satisfy these requirements for most feeds . when the hydrogen to hydrocarbon ratio exceeds 0 . 05 , it is not economically desirable to operate the isomerization process without the recycle of hydrogen to the isomerization zone . as the quantity of hydrogen leaving the product recovery section increases , additional amounts of c 4 and other product hydrocarbons are taken by the fuel gas stream from the product recovery section . the value of the lost product or the additional expense associated with recovery facilities to prevent the loss of product do not justify operating the process without recycle at hydrogen to hydrocarbon ratios above 0 . 05 . hydrogen may be added to the feed mixture in any manner that provides the necessary control for the addition of small hydrogen quantities . metering and monitoring devices for this purpose are well known by those skilled in the art . as currently practiced , a control valve is used to meter the addition of hydrogen to the feed mixture . the hydrogen concentration in the outlet stream or one of the outlet stream fractions is monitored by a hydrogen monitor and the control valve setting position is adjusted to maintain the desired hydrogen concentration . the direct effluent from the reaction zone contains a relatively high concentration of chlorides that can attack metal components of the monitor . thus , the monitor preferably measures the concentration of hydrogen in a stream that has undergone caustic treatment for chloride removal such as a stabilizer off gas stream . the hydrogen concentration at the effluent is calculated on the basis of total effluent flow rates . the hydrogen and hydrocarbon feed mixture is contacted in the reaction zone with an isomerization catalyst . the isomerization catalyst consists of a high chloride catalyst on an aluminum base containing platinum . the aluminum is an anhydrous gamma - alumina with a high degree of purity . the catalyst may also contain other platinum group metals . the term platinum group metals refers to noble metals excluding silver and gold which are selected from the group consisting of platinum , palladium , germanium , ruthenium , rhodium , osmium , and iridium . these metals demonstrate differences in activity and selectivity such that platinum has now been found to be the most suitable for this process . the catalyst will contain from about 0 . 1 to 0 . 25 wt . % of the platinum . other platinum group metals may be present in a concentration of from 0 . 1 to 0 . 25 wt . %. the platinum component may exist within the final catalytic composite as an oxide or halide or as an elemental metal . the presence of the platinum component in its reduced state has been found most suitable for this process . the catalyst also contains a chloride component . the chloride component termed in the art &# 34 ; a combined chloride &# 34 ; is present in an amount from about 2 to about 10 wt . % based upon the dry support material . the use of chloride in amounts greater than 5 wt . % have been found to be the most beneficial for this process . there are a variety of ways for preparing the catalytic composite and incorporating the platinum metal and the chloride therein . the method that has shown the best results in this invention prepares the catalyst by impregnating the carrier material through contact with an aqueous solution of a water - soluble decomposable compound of the platinum group metal . for best results , the impregnation is carried out by dipping the carrier material in a solution of chloroplatinic acid . additional solutions that may be used include ammonium chloroplatinate , bromoplatinic acid or platinum dichloride . use of the platinum chloride compound serves the dual function of incorporating the platinum component and at least a minor quantity of the chloride into the catalyst . additional amounts of the chloride must be incorporated into the catalyst by the addition or formation of aluminum chloride to or on the platinum - aluminum catalyst base . an alternate method of increasing the halogen concentration in the final catalyst composite is to use an aluminum hydrosol to form the aluminum carrier material such that the carrier material also contains at least a portion of the halogen . halogen may also be added to the carrier material by contacting the calcined carrier material with an aqueous solution of the halogen acid such as hydrogen chloride , hydrogen fluoride , or hydrogen bromide . it is generally known that high chlorided platinum - alumina catalysts of this type are highly sensitive to sulfur and oxygen - containing compounds . therefore , the feedstock must be relatively free of such compounds . a sulfur concentration no greater than 0 . 5 ppm is generally required . the presence of sulfur in the feedstock serves to temporarily deactivate the catalyst by platinum poisoning . activity of the catalyst may be restored by hot hydrogen stripping of sulfur from the catalyst composite or by lowering the sulfur concentration in the incoming feed to below 0 . 5 ppm so that the hydrocarbon will desorb the sulfur that has been adsorbed on the catalyst . water can act to permanently deactivate the catalyst by removing high activity chloride from the catalyst and replacing it with inactive aluminum hydroxide . therefore , water , as well as oxygenates , in particular c 1 - c 5 oxygenates , that can decompose to form water , can only be tolerated in very low concentrations . in general , this requires a limitation of oxygenates in the feed to about 0 . 1 ppm or less . the feedstock may be treated by any method that will remove water and sulfur compounds . sulfur may be removed from the feed stream by hydrotreating . a variety of commercial dryers are available to remove water from the feed components . adsorption processes for the removal of sulfur and water from hydrocarbon streams are also well known to those skilled in the art . operating conditions within the isomerization zone are selected to maximize the production of isoalkane product from the feed components . temperatures within the reaction zone will usually range from about 40 °- 235 ° c . ( 100 °- 455 ° f .). lower reaction temperatures are generally preferred since they usually favor equilibrium mixtures of isoalkanes versus normal alkanes . lower temperatures are particularly useful in processing feeds composed of c 5 and c 6 alkanes where the lower temperatures favor equilibrium mixtures having the highest concentration of the most branched isoalkanes . when the feed mixture is primarily c 5 and c 6 alkanes temperatures in the range of from 60 ° to 160 ° c . are preferred . when it is desired to isomerize significant amounts of c 4 hydrocarbons , higher reaction temperatures are required to maintain catalyst activity . thus , when the feed mixture contains significant portions of c 4 - c 6 alkanes most suitable operating temperatures are in the range from 145 ° to 225 ° c . the reaction zone may be maintained over a wide range of pressures . pressure conditions in the isomerization of c 4 - c 6 paraffins range from 7 barsg to 70 barsg . preferred pressures for this process are in the range of from 20 barsg to 30 barsg . the feed rate to the reaction zone can also vary over a wide range . these conditions include liquid hourly space velocities ranging from 0 . 5 to 12 hr . - 1 , however , space velocities between 1 and 6 hr . - 1 are preferred . operation of the reaction zone also requires the presence of a small amount of an organic chloride promoter . the organic chloride promoter serves to maintain a high level of active chloride on the catalyst as low levels are continuously stripped off the catalyst by the hydrocarbon feed . the concentration of promoter in the reaction zone is maintained at from 30 to 300 ppm . the preferred promoter compound is carbon tetrachloride . other suitable promoter compounds include oxygen - free decomposable organic chlorides such as propyldichloride , butylchloride , and chloroform to name only a few of such compounds . the need to keep the reactants dry is reinforced by the presence of the organic chloride compound which may convert , in part , to hydrogen chloride . as long as the process streams are kept dry , there will be no adverse effect from the presence of small amounts of hydrogen chloride . fig1 shows a two - reactor system with a first stage reactor 28 and a second stage reactor 30 in the reaction zone . the catalyst used in the process is distributed equally between the two reactors . it is not necessary that the reaction be carried out in two reactors but the use of two reactors confer several benefits on the process . the use of two reactors and specialized valving ( not shown ) allows partial replacement of the catalyst system without taking the isomerization unit off stream . for the short periods of time during which replacement of catalyst may be necessary , the entire flow of reactants may be processed through only one reaction vessel while catalyst is replaced in the other . the use of two reaction zones also aids in maintaining lower catalyst temperatures . this is accomplished by having any exothermic reaction such as hydrogenation of unsaturates performed in the first vessel 28 with the rest of the reaction carried out in a final reactor stage at more favorable temperature conditions . fig1 demonstrates this type of operation where the relatively cold hydrogen and hydrocarbon feed mixtures taken by line 32 are passed through a cold feed exchanger 34 that heats the incoming feed against the effluent from the final reactor 30 . line 36 carries the feed from the cold feed exchanger to the hot feed exchanger 38 where the feed is heated against the effluent carried from the first reactor 28 by line 40 . line 42 carries the partially heated feed from hot feed exchanger 42 through an inlet exchanger 44 that supplies any additional heat requirements for the feed and then into a first reactor 28 . effluent from first reactor 28 is carried to the second reactor 30 by line 40 after passage through exchanger 38 as previously described . line 46 carries the isomerization zone effluent from second reactor 30 through cold feed exchanger 34 as previously described and into separation facilities . at minimum , the separation facilities divide the reaction zone effluent into a product stream comprising c 4 and heavier hydrocarbons and a gas stream which is made up of lighter hydrocarbons and hydrogen . suitable designs for rectification columns and separator vessels are well known to those skilled in the art . the separation section may also include facilities for recovery of normal isoalkanes . normal isoalkanes recovered from the separation facilities may be recycled to the isomerization reaction zone to increase the conversion of normal alkanes to isoalkanes . the figure shows separation facilities comprising a stabilizer section 18 . line 46 carries the effluent from second reactor 30 to a stabilizer column 48 . stabilizer column 48 is operated to deliver a bottoms fraction containing c 4 and heavier hydrocarbons and an overhead fraction c 3 hydrocarbons and lighter boiling compounds . the stabilizer column includes a reboiler loop 50 from which the c 4 + product stream is withdrawn by line 52 . products taken by line 52 pass through a product exchanger 54 that heats the reactor effluent before it enters column 48 . cooled product is recovered from exchanger 54 via product line 20 . c 3 and lighter hydrocarbons and any excess hydrocarbons from the reaction zone are taken overhead from stabilizer column 48 through line 56 , cooled in condenser 58 and separated into a gas stream and reflux by separator vessel 60 . line 62 returns reflux from vessel 60 to the top of column 48 and line 22 carries the net gas from separator drum 60 to scrubber section 24 . scrubber section 24 contacts gas from drum 60 with a suitable treatment solution for neutralizing and / or removing acidic components that may have originated with the chloride addition to the isomerization zone and may be present in the gas stream . typically , the treatment solution will be a caustic that is pumped around a contacting vessel 64 in a loop 66 . spent caustic is withdrawn and fresh caustic is added to the scrubber section by a line 68 . after treatment in the scrubber section 24 , the net gas is removed from the process via line 26 . gas recovered by line 26 will usually be put to use as a fuel . the process of this invention is characterized by high conversion , high selectivity , and good stability as can be seen from the following example . in this example , a hydrocarbon feed having an average composition given in the table was charged to a two reactor zone system of the type shown generally in fig1 . before entering the reaction zone , hydrogen was admixed with the hydrocarbon feed to provide indicated hydrogen to hydrocarbon ratios as given in fig2 and ranging from 0 . 7 to 0 . 1 at the outlet of the reaction zone . each reaction zone contained an alumina catalyst having 0 . 25 wt . % platinum and 5 . 5 wt . % chlorine . table______________________________________compositionin wt . % reactor charge______________________________________sp . gr . 0 . 65ic . sub . 4 0 . 3nc . sub . 4 4 . 5ic . sub . 5 25 . 7nc . sub . 5 25 . 5cp 1 . 422dmb 0 . 923dmb 1 . 52mp 9 . 63mp 6 . 5nc . sub . 6 15 . 7mcp 6 . 0bz 1 . 4ch 0 . 5c7 + 0 . 1______________________________________ the catalyst was prepared by vacuum impregnating an alumina base in a solution of chloroplatinic acid , 2 % hydrochloric acid , and 3 . 5 % nitric acid in a volume ratio of 9 parts solution to 10 parts base to obtain a peptized base material having a platinum to base ratio of approximately 0 . 9 . the resulting mixture was cold - rolled for approximately 1 hour and evaporated until dry . afterward , the catalyst was oxidized and the chloride content adjusted by contact with a 1m hydrochloric acid solution at 525 ° c . at a rate of 45 cc / hour for 2 hours . the catalyst was then reduced in electrolytic hydrogen at 565 ° c . for 1 hour and was found to contain approximately 0 . 25 wt . % pt and approximately 1 wt . % chloride . impregnation of active chloride to a level of approximately 5 . 5 wt . % was accomplished by sublimating aluminum chloride with hydrogen and contacting the catalyst with the sublimated aluminum chloride for approximately 45 minutes at 550 ° c . the hydrocarbon feed mixture entered the first reaction zone at a temperature of approximately 160 ° c . the feed mixture at a temperature of approximately 175 ° c . was taken from the first reaction zone and after heat exchange with the incoming feed entered the second reaction zone at a temperature of approximately 140 ° c . the exit temperature of the second reaction zone was maintained at approximatey 140 ° c . and the feed passed through the reaction zones at a liquid hourly space velocity of about 2 . 4 hr . - 1 . an average pressure of about 31 barsg was maintained in both reaction zones . the effluent from the second reaction zone was recovered at a temperature of about 140 ° c . at the beginning of the run , the h 2 / hc ratio at the outlet was kept at about 0 . 7 which corresponds to the typical range for a low h 2 / hc ratio as practiced in the prior art . over a period of several months , the h 2 / hc ratio was lowered to the ratio of this invention . average values for the isopentane to c 5 hydrocarbon ratio , 2 , 2 - dimethylbutane to c 6 hydrocarbon ratio and research octane in the effluent were plotted at selected h 2 / hc ratios over the course of this run . as the data shows , the process of this invention was able to maintain substantially consistent values for these parameters as the h 2 / hc ratio was decreased . at the time of writing this application , the reactor system had experienced over 1200 hours of operation at a h 2 / hc ratio of about 0 . 05 without any appreciable loss of normal paraffin conversion or octane number reduction in the recovered effluent . therefore , it has been shown that the process of this invention , using the catalyst as herein described , will provide a stable conversion of normal paraffins to isoparaffins at hydrogen addition levels that leave a ratio no more than 0 . 05 h 2 to hydrocarbon in the effluent . | 2 |
in the following detailed description , certain specific terminology will be employed for the sake of clarity and particular embodiments described , but it is to be understood that the same is not intended to be limiting and should not be so construed inasmuch as the invention is capable of taking many forms and variations within the scope of the appended claims . this invention describes an improved process and apparatus for forming lines of weakness in an automotive trim piece for an airbag door installation in a way that improves the accuracy of the process , the trim piece quality , the airbag deployment performance , and , also , reduces trim piece production costs . the process will be described with respect to an instrument panel airbag door installation , but it is also applicable to other automotive and non - automotive installations , with or without an airbag . typical airbag installations include driver side airbags , front passenger airbags , side impact airbags , headliner airbags , knee airbags , and rear passenger airbags . the process will also be described in terms of a laser beam , but is also applicable to other cutting beams as described below . [ 0022 ] fig1 shows a first embodiment of a trim piece scoring apparatus 10 according to the invention . this includes a cutting beam source 12 which generates a cutting beam such as a laser beam which is used to carry out controlled scoring of a surface 14 on one side 14 of an instrument panel trim piece 16 that would overlie an airbag installation when installed . the trim piece 16 is positioned on a fixture 18 . a first sensor 20 is provided to determine the depth of scoring produced by the laser cutting beam onto the surface 14 of the trim piece 16 to weaken the same . the first sensor 20 and the cutting beam generator 12 are connected to a beam combining device 22 . the beam combining device 22 is designed to combine separately generated sensing beam or beams emanating from the first sensor 20 and the laser cutting beam downstream beam into segments an aligned collinear relationship so as to direct the combined signal beam b and cutting beam a to impinge the same precise spot on the trim piece surface 14 . this beam combining device 22 will also redirect any reflected returned beam or beams required for sensor operation from the trim piece surface 14 back to the first sensor 20 in carrying out the process . the trim piece 16 is moved relative to the cutting beam source 12 , as well as the first sensor 20 and the beam combining device 22 via a motion actuator 24 to cause tracing of a particular scoring pattern and to achieve a precisely controlled rate of scoring . the motion actuator 24 can directly move the trim piece 16 itself or move an optional fixture 18 onto which the trim piece 16 is mounted . alternatively , the motion actuator 24 could be used to move the laser beam source 12 and the first sensor 20 relative to the trim piece 16 . a second sensor 26 may be located on the side of the trim piece 16 opposite the first sensor 20 , a second sensor beam emanating therefrom , directed at the outer surface 28 of the trim piece 16 and aligned opposite the same trim piece point as is the laser cutting beam and the first sensor beam or beams are directed in order to control the scoring cutting so as to produce a programmed thickness of material remaining after scoring . this is done by combining signals generated by both sensors 20 , 26 to create a feedback signal corresponding to the thickness of the remaining material . the apparatus 10 is operated via one or more industrial controllers 30 that control the scoring effected by the laser and / or the movement of the motion actuator based on a particular program and feedback signals provided by the sensor 20 , 26 . lasers are particularly desirable for carrying out this type of scoring processes and they can be of the carbon dioxide , excimer , solid state , argon gas , or diode type . however , based on the primary trim piece materials utilized ( polymers , fabrics , wood , leather ), the carbon dioxide laser is likely to be the most preferable in terms of operability , efficiency and cost . the laser can be operated either continuously or in a pulsed mode . different type of sensors can be utilized to measure the extent of material removed or remaining during scoring of the trim piece . for the first sensor 20 , connected to the beam combining device 22 , a preferred type is a closed loop device that sends and receives a specific beam of electromagnetic radiation in order to determine the depth of scoring effected by the laser . the conoprobe sensors offered by optimet and based on the technique of conoscopic holography , is one such sensor commercially available . in this type of sensor , an emitted laser beam and reflected return beams of visible light have segments also traveling in a collinear relationship with each other and the laser beam . another type of sensor that could be utilized is one that detects reflected light beams such as a high speed ccd camera . in this application , the reflected beam will be reflected from the trim piece surface being scored by the cutting beam . for the second sensor 26 aimed at the outside surface of the trim piece , which is generally smooth and accessible , there are more numerous options including , infrared , laser , ultrasonic , conoscopic , ccd camera , proximity and contact type sensors . the signal spot size of the sensor selected can vary significantly . generally the smaller the spot size the better . for the first sensor , the preferred size would be not to exceed the size of the scoring produced on the trim piece by the cutting laser beam . for the second sensor , if surface finish variations , so called grain , are significant , its spot size should preferably not exceed 300 microns . the are numerous ways for combining the separately originated laser beam and sensor beam to create collinear segments . fig2 shows the inner details of the beam combining device 22 which combines the separate the laser beam a and the first sensor beam b to create collinear segments which impinge the trim piece surface 14 . the beam combining device 22 includes a reflector 32 having coatings causing reflection of light having the wavelength of the sensor beam a from its inclined surface while allowing the laser beam b to be transmitted . such coated selective reflectors are commercially available . this of course requires that the laser and sensor beams be of different wavelengths . a side entrance tube 29 directed at the reflector 32 is connected to the first sensor 20 . the main tube 31 mounts the reflector 32 , main tube 31 having an end opening 33 directed at the trim piece 16 . the segment of sensor beam a reflected from the reflector 32 aligned and coextensive with the laser beam 13 after , with both collinear segments then impinging the surface 14 at the same precise point . [ 0035 ] fig2 a shows a second form of a beam combining device 22 a having an inclined reflector 32 b having coatings causing reflection of the wavelength of the laser beam b while allowing transmission of the wavelengths of the sensor beam a to be transmitted therethrough to reverse the relationship shown in fig2 . [ 0036 ] fig2 b is a simplified diagrammatic view of another form of the beam combining device 22 b combining the laser beam b and the first sensor beam a to produce collinear downstream segments . this embodiment includes a simple mirror reflector 36 having a through hole 34 . the hole 34 is small in diameter relative to the diameter of the laser beam b in order to minimize or eliminate the effect that the presence of the hole 34 may have on reflecting the laser beam from the mirror reflector 36 to redirect the laser beam a . such a mirror does not require coatings that are wavelength - selective such as those shown in fig2 and 2a in order to combine segments of the beams into a collinear relationship . in this particular arrangement , the first sensor 20 could be a ccd camera receiving beams reflected from the trim piece surface being scored by the laser beam . the trim piece can be any of many automotive parts including instrument panels and / or their components ( skins , substrates , foams , scrims , etc . ), driver side airbag covers , door panels , seat covers , headliners , bumpers and seat belts . the scoring can be applied on either side of the trim piece but is preferably applied from the inside so that is substantially invisible from the outside surface facing the passenger . as shown in fig3 the scoring does not penetrate the outer surface 28 of the trim piece 16 shown as an instrument panel and would be essentially invisible to the passenger . different materials could be utilized in a trim piece including metals , polymers ( tpus , tpos , pvc , tpes , etc . ), leather , fabrics , wood and wood composites . as shown in fig4 through 6 , the trim piece 16 , 16 a , 16 b may consist of one or more layers of similar or dissimilar materials . in multilayer constructions , the scorings 40 , 40 a , 40 b could be applied to any one layer or any combination thereof as shown . manufacturing of the trim piece can be done in several ways using different materials . many of these materials can be formed in a solid state or in a cellular state . polymeric trim pieces can be formed by processes such as extrusion , injection molding , low pressure insert molding , blow molding , casting , thermoforming , lamination and foaming . the scoring applied can be in any shape , including a u , h , i , t , x , w , s and y pattern , required to form an opening for the airbag to deploy . the opening could include one or more door panels . the scoring can be either continuous or discontinuous including grooves , blind holes and dashes . furthermore , the cut orientation can be straight or offset . for successful and consistent airbag deployments , the degree of precision of cutting is particularly important to ensure that the amount of material remaining along the predetermined pattern is as intended . the penetration or depth of scoring , for an invisible airbag door application , can be up to about 95 % of the trim piece thickness . in order to apply the complete scoring pattern , the trim piece is preferably moved relative to the laser beam and / or the sensors . the relative motion can be applied by a number of motion actuators including robots and x - y tables . during cutting , the sensor thickness data can also be used to control the movement of the motion device in order to apply the scoring along the predetermined pattern . the trim piece may be held directly by the motion device or be attached to a holding fixture held by the motion device . the holding fixture may be shaped to match the shape of the trim piece and / or be designed to register specific surface features of the trim piece . vacuum or clamps could also be applied to the holding fixture to hold the trim piece surface in better contact with the fixture 18 . the fixture 18 can be designed to allow the second sensor 26 to have physical and / or optical access to the surface 26 of the trim piece ( i . e ., transparent fixture wall , opening in fixture wall , etc .). the process controller 30 is designed to control the operation of the laser and / or motion actuator based on the feedback signals provided by the two sensors 20 , 26 which , from opposites sides or surfaces of the trim piece 16 , monitor the location being scored . the two sensors 20 , 26 working in tandem determine the remaining thickness of the trim piece 16 at any point they are directed to . during laser scoring at a given point , the two sensors 20 , 26 provide signals from which a measurement of the material thickness remaining after the scoring can be derived by the control device 30 . based on this real - time thickness determination , the control device 30 controls the operation of the cutting beam source 12 to effect only the desired extent of material removal intended for any given point on the trim piece 16 . the remaining thickness data can also be used to control the motion actuator 24 to move the trim piece to the next desired location along the predetermined scoring pattern . due to the collinearity of the impinging segments of the first sensor beam and the cutting beam , several advantages are realized that could not be attained by any of the existing processes . since the first sensor beam and the laser beam are always impinging on the same point of the trim piece , the process becomes insensitive to a large number of key variables , including the angle of cutting , the depth of the penetration , the trim piece thickness , the configuration of the weakening pattern and , to a large extent , the speed of cutting . also , the combination of the two sensors provides for a direct remaining thickness measurement , superior scoring precision and excellent part to part repeatability . in addition , the process enables the user to overcome variations in trim piece thickness , material properties such as density , color , voids and surface grain . these and other benefits are obtained while operating with rapid adaptive control in a single - pass mode . a second embodiment of the apparatus 44 according to the invention is shown in fig7 where the outer surface 42 of the trim piece 16 is in intimate contact with the inner fixture wall 46 . in this arrangement , the distance between the first sensor 48 and the fixture inner wall 46 , along the predetermined scoring pattern , can be measured prior to starting the scoring operation . if this distance can be maintained constant from pass to pass , then the second outside sensor would not be necessary while still running the process in a single - pass , adaptive control mode . [ 0044 ] fig8 shows another embodiment of the apparatus 50 where the first sensor 52 is mounted immediately alongside the cutting beam source 12 so that both beams a , b are substantially collinear with each other to approximate the effect of using the beam combining device 22 described . the laser cutting beam may also function as the sensor . this arrangement also maintains the collinear configuration as the sensing signals and the laser beam are generated by the same laser . under this approach , the laser beam characteristics and control would be manipulated to conduct sensing measurements during or between cutting intervals ( i . e ., sensing after a preset number of cutting pulses ). | 1 |
fig1 illustrates a conventional , modern upwind wind turbine 24 according to the so - called “ danish concept ” with a tower 36 , a nacelle 25 and a rotor with a substantially horizontal rotor shaft . the rotor includes a hub 23 and three wind turbine blades 2 extending radially from the hub 23 , each having a wind turbine blade root 1 nearest the hub 23 and a wind turbine blade tip 32 furthest from the hub 23 . as seen from fig2 , the wind turbine blade 2 comprises a root region 26 with a substantially circular profile closest to the hub , an airfoil region 27 with a lift generating profile furthest away from the hub , and a transition region 28 between the root region 26 and the airfoil region 27 , the profile of the transition region 28 changing gradually in the radial direction from the circular profile of the root region 26 to the lift generating profile of the airfoil region 27 . the lift generating profile is provided with a suction side and a pressure side as well as a leading edge 34 and a trailing edge 33 . the airfoil region 27 has an ideal or almost ideal blade shape , whereas the root region 26 has a substantially circular cross section . the airfoil region 27 has an airfoil profile with a chord plane extending between the leading edge 34 and the trailing edge 33 of the wind turbine blade 2 . it should be noted that the chord plane does not necessarily run straight over its entire extent since the wind turbine blade 2 may be twisted and / or curved , thus providing a chord plane with a correspondingly twisted and / or curved course . the width of the transition region 28 increases substantially linearly with the increasing distance from the hub 23 . the wind turbine blade 2 is manufactured by bonding two shell parts together along a bonding region substantially following the leading edge 34 and the trailing edge 33 of the wind turbine blade 2 , such that each of the shell parts represents substantially either the pressure side or the suction side . preferably , the bonding region extends throughout the root region 26 , the transition region 28 and the airfoil region 27 . fig3 , 3 a , 3 b , 3 c , 3 d and 3 e show cross - sectional views of embodiments according to the invention . the shown cross - sectional views are all located in the root region 26 as shown in fig2 as a , but the concept of the invention also applies to any other cross section of the root region 26 , transition region 28 and airfoil region 27 , but only cross - sectional views of the root region are shown for simplicity . furthermore , it should be noted that the cross - sectional views have been made for illustrative purpose and thus should not be taken as an exact representation of the embodiments . the cross - sectional views in fig3 a , 3 b , 3 c , 3 d and 3 e are all part of cross - sectional views corresponding to the encircled portion b shown in fig3 . the resistive heating means 50 could be one or more conductive wires , and examples of material for the resistive heating means 50 could be a metal , such as steel . preferably , the resistive heating means is arranged along the entire bonding region and is preferably arranged so that the one or more conductive wires are substantially parallel with the longitudinal extension of the bonding region . fig3 shows a first embodiment according to the invention , where a first shell part 10 and a second shell part 15 are bonded together in a bonding region between the first shell part 10 and the second shell part 15 by a curable bonding means 40 . preferably , the first shell part 10 and the second shell part 15 are formed in a fibre - reinforced polymer . in at least the proximity of the bonding means , the first shell part 10 and / or the second shell part 15 comprises conductive fibres in the fibre reinforcement that functions as resistive heating means . the conductive fibres are not shown in fig3 as they form an integral part of the fibre - reinforcement . fig3 a and 3b show a second and third embodiment according to the invention , where the resistive heating means 50 is arranged either in the first shell part 10 or in the second shell part 15 , but in the proximity of the bonding means 40 . the resistive heating means 50 is provided by resistive wires 50 . the energy released from the resistive heating means 50 must be sufficiently high to heat the side of the bonding means proximal to the shell part not being provided with a heating means and to reach the opposite side of the bonding means . fig3 c shows a fourth embodiment according to the invention , where the resistive heating means 50 is arranged inside the bonding means 40 , preferably substantially at the centre of the bonding means so that a symmetrical heating of the bonding region is obtained . fig3 d shows a fifth embodiment according to the invention , where the resistive heating means 50 is arranged both in the first shell part 10 and in the second shell part 15 and in the proximity of the bonding means 40 . the resistive heating means 50 is provided by resistive wires 50 . this embodiment also provides a substantially symmetrical heating of the bonding region . fig3 e shows a sixth embodiment according to the invention , which is a combination of the fourth and the fifth embodiment and thus also provides a substantially symmetrical heating of the bonding region . the examples have been described according to advantageous embodiments . however , the invention is not limited to these embodiments and thus , the number of resistive wires may be altered , and also the thickness of the wires and their internal alignment may be modified without deviating from the scope of the invention . fig4 , 5 , 6 and 7 show cross - sectional views of additional embodiments according to the invention . the shown cross - sectional views are all located in the root region 26 as shown in fig2 as a , but the concept of the invention also applies to any other cross section of the root region 26 , transition region 28 and airfoil region 27 , but only cross - sectional views of the root region are shown for simplicity . furthermore , it should be noted that the cross - sectional views have been made for illustrative purpose and thus should not be taken as an exact representation of the embodiments . in all embodiments , the filaments 60 are preferably small enough to be considered as fibres so that they can interact properly and effectively with the bonding means 40 . dependent on the material and design of the filaments 60 , the filaments 60 can be flexible or rigid enough to carry their own mass . preferably , the thickness of the filaments 60 , e . g . diameter , is larger than 5 micrometres . the filaments 60 may comprise steel wires having a cross - sectional dimension in a range between 0 . 05 millimetres and 1 . 0 millimetres , or in a range between 0 . 07 and 0 . 75 millimetres , or in a range between 0 . 1 and 0 . 5 millimetres . the filaments 60 may also be chamfered in the end extending into the bonding means 40 so that the filaments 60 can cut through the bonding means 40 even when the bonding means 40 are fibre - reinforced . fig4 shows a first embodiment according to the invention , where a first shell part 10 and a second shell part 15 are bonded together in a bonding region between the first shell part 10 and the second shell part 15 by a curable bonding means 40 . preferably , the first shell part 10 and the second shell part 15 are formed in a fibre - reinforced polymer . the first shell part 10 comprises an end surface 11 facing and bonded to the bonding means 40 . the first shell part 10 further comprises a number of filaments 60 extending from the end surface 11 of the first shell part 10 or into the bonding means 40 and being bonded to both the bonding means 40 and the first shell part 10 from which the filaments 60 extend . fig5 and 6 show a second and a third embodiment according to the invention , where a first shell part 10 and a second shell part 15 are bonded together in a bonding region between the first shell part 10 and the second shell part 15 by a curable bonding means 40 . preferably , the first shell part 10 and the second shell part 15 are formed in a fibre - reinforced polymer . the first shell part 10 comprises an end surface 11 facing an end surface 16 of the second shell part 15 . the end surfaces face the bonding means 40 and are bonded thereto . the first and the second shell part 10 , 15 further comprise a number of filaments 60 extending from the end surfaces 11 , 16 into the bonding means 40 and being fastened to both the bonding means 40 and the respective shell part 10 , 15 from which the filaments 60 extend . further , fig6 discloses a modified bonding means 41 being essentially t - shaped and seen in a cross - sectional view , whereby flange portions of the bonding means are bonded to the respective inner surfaces of the first and second shell part 10 , 15 . fig7 shows a fourth embodiment according to the invention , where a first shell part 10 and a second shell part 15 are bonded together in a bonding region between the first shell part 10 and the second shell part 15 by a curable bonding means 42 . the bonding means is essentially l - shaped as seen in a cross - sectional view , whereby a flange portion of the bonding means is bonded to an inner surface of the first shell part 10 . preferably , the first shell part 10 and the second shell part 15 are formed in a fibre - reinforced polymer . the first and the second shell part 10 , 15 comprise an end surface 11 , 16 facing and being bonded to the bonding means 42 . the first and the second shell part 10 , 15 further comprise a number of filaments 60 extending from the end surfaces 11 , 16 into the bonding means 42 and being fastened to both the bonding means 42 and the respective shell part 10 , 15 from which the filaments 60 extend . it is clear from the previous description that the first and the second shell parts 10 , 15 may form substantially the pressure side and the suction side of the blade , respectively ( or an upper and lower blade shell that are glued together ). | 1 |
fig1 generally illustrates an engine starter equipped with a starter motor which is constructed according to the present invention , and the upper half of the drawing illustrates the starter at its inoperative state while the lower half of the drawing illustrates the starter at its operative state . this starter 1 produces a torque which is necessary for cranking and starting an internal combustion engine , and comprises an electric motor 3 equipped with a planetary gear reduction gear unit 2 , an output shaft 4 connected to the electric motor 3 via the reduction gear unit 2 , a one - way roller clutch 5 and a pinion 6 which are slidably mounted on the output shaft 4 , a switch unit 7 for selectively opening and closing the electric power line leading to the electric motor 3 , and a solenoid device 9 for axially moving a moveable contact 8 of the switch unit 7 as well as the pinion 6 . the electric motor 3 consists of a known commutator type dc electric motor , and its rotor shaft 10 carrying a motor armature 52 is pivotally supported in a central recess of a bottom plate 11 at its right end , and pivotally supported in a central recess provided in a right end surface of the output shaft 4 , which is coaxially disposed with respect to the rotor shaft 10 , at its left end . the bottom plate 11 closes a right end of a cylindrical motor casing 44 . the reduction gear unit 2 is provided in a recess defined on the inner surface of the top plate 12 of the electric motor 3 which closes the left end of the motor casing 44 . the top plate 12 may consist of synthetic resin material . the reduction gear unit 2 comprises a sun gear 13 which is formed in a part of the rotor shaft 10 adjacent to the output shaft 4 , a plurality of planetary gears 14 meshing with the sun gear 13 , and an internal teeth ring gear 15 formed along the outer periphery of the recess defined on the inner surface of the top plate 12 to mesh with the planetary gears 14 . a support plate 16 supporting the planetary gears 14 is attached , by press fitting , to the right end of the output shaft 4 which is pivotally supported in a central opening of the top plate 12 . to the top plate 12 is attached a pinion housing 17 which also serves as a securing bracket for mounting the starter to the engine . the left end of the output shaft 4 is pivotally supported in a central recess defined on the inner surface of the left wall of the pinion housing 17 . the outer circumferential surface of a middle part of the output shaft 4 engages the inner circumferential surface of a clutch outer member 18 of the oneway roller clutch 5 via a helical spline 19 . the clutch outer member 18 is normally urged to the right by a return spring 21 interposed between an annular shoulder defined in a cylindrical sleeve 18a extending from the clutch outer member 18 toward the electric motor 3 and a stopper plate 20 secured to a left end portion of the output shaft 4 . the right extreme end of the cylindrical sleeve 18a engages the helical spline 19 formed in the output shaft 4 . the clutch outer member 18 engages a clutch inner member 22 of the one - way roller clutch 5 in an axially fast but rotationally free relationship ( which depends on the direction of relative rotation ). the outer circumferential surface of the left end of the clutch inner member 22 is integrally formed with the aforementioned pinion 6 which meshes with the ring gear 23 of the engine to drive the same . the clutch inner member 22 integrally formed with the pinion 6 is fitted on the left end of the output shaft 4 in a both rotationally and axially free relationship . in an intermediate part of the pinion housing 17 is secured an energization coil 24 which surrounds the output shaft 4 made of non - magnetic material such as stainless steel . the energization coil 24 is surrounded by a yoke defined by a cup - shaped holder 25 having an internal flange 25a surrounding the output shaft 4 and an annular disk 26 . in a gap defined between the inner circumferential surface of the energization coil 24 and the outer circumferential surface of the output shaft 4 is disposed an armature outer member 27 and an armature inner member 28 , both made of ferromagnetic material , in a mutually coaxially nested and axially slidable relationship . the left ends of the armature members 27 and 28 oppose the axially inner surface of a central part of the internal flange 25a of the holder 25 , and the central part of the internal flange 25a serves as a magnetic pole for the armature members 27 and 28 . the first part of the armature or the armature outer member 27 is connected at its right end to a connecting plate 29 , and , via a connecting rod 30 passing through the top plate 12 of the electric motor 3 , to the moveable contact 8 of the switch unit 7 placed adjacent the commutator 31 of the electric motor 3 . the moveable contact 8 is mounted to the connecting rod 30 in an axially moveable manner , and is supported by a coil spring 32 in a floating relationship so as to be selectively engaged to and disengaged from a fixed contact 34 of the switch unit 7 which is fixedly secured to a brush stay 33 provided around the commutator 31 . in other words , the moveable contact 8 is linked to the armature outer member 27 via a lost motion mechanism . the armature outer member 27 is always urged to the right by a return spring 35 interposed between the armature outer member 27 and the internal flange 25a provided in the holder 25 of the energization coil 24 , but is normally at its neutral or rest position separating the moveable and fixed contacts 8 and 34 from each other . the second part of the armature or the armature inner member 28 is always urged to the left with respect to the top plate 12 by a coil spring 36 which is weaker that the return spring 21 of the clutch outer member 18 . the armature inner member 28 is connected to a shifter member 37 made of non - magnetic material , such as synthetic resin material , having a left end engaging the right end of the clutch inner member 22 . the energization coil 24 is electrically connected to an ignition switch not shown in the drawing via a connector 38 ( see fig2 ) provided in the switch unit 7 . the fixed contact 34 of the switch unit 7 is electrically connected to the positive terminal of a battery not shown in the drawings , and a pair of pigtails 40 connected to a pair of positive pole brushes 39 are attached to the fixed contact 34 by spot welding also as illustrated in fig2 . a pair of negative pole brushes 41 are provided in a line - symmetrically opposing positions with respect to the positive pole brushes 39 . the pigtails 42 for these negative pole brushes 41 are connected to a center plate 43 which is described hereinafter , and is connected to the negative terminal of the battery via the pinion housing 17 and the vehicle body which is not shown in the drawings . the switch unit 7 is provided in a space flanked by the positive pole brushes 39 . the brushes 39 and 41 are supported in a known manner by a brush stay 33 which is made of electrically insulating material . an annular metallic center plate 43 is interposed between the brush stay 33 and the top plate 12 to separate the reduction gear unit 2 from the electric motor 3 . a central part of the center plate 43 is provided with a cylindrical portion 43a which projects toward the commutator 31 with its inner circumferential surface receiving the outer circumferential surface of the rotor shaft 10 defining a small gap therebetween . the free end of the cylindrical portion 43a is received in a recess 31a formed in an axial end surface of the commutator 31 to prevent grease from leaking out of the reduction gear unit 2 to the commutator 31 . the switch unit 7 is located at a top part of the starter 1 , and the contacts , or the fixed contact 34 secured to the brush stay 33 and the moveable contact 8 , are covered by the brush stay 33 and a switch cover 45 to prevent any particulate foreign matters that may be produced from the brushes from getting into the switch unit 7 . at least a pair of permanent magnets 46 are arranged circumferentially along the inner circumferential surface of the motor casing 44 of the electric motor 3 , and the inner circumferential surface of the permanent magnets 46 is covered by a magnet cover 47 . the magnet cover 47 comprises a cylindrical main portion 47a which engages the inner circumferential surface of the permanent magnets 46 , a flange portion 47b extending in the shape of letter l radially from one of the cylindrical main portion 47a into abutting engagement with the inner circumferential surface of the motor casing 44 , and a large diameter portion 47c which is formed as a slightly enlarged section at the other axial end of the cylindrical main portion 47a so as to extend closely along a tapered sections of the permanent magnets 46 . the flange portion 47b is provided with a pair of holes 49 for passing set bolts 48 which extend in the axial direction to integrally join the pinion housing 17 , the top plate 12 , the motor casing 44 and the bottom plate 11 . each of the set bolts 48 is passed through a hole formed in the top plate 12 , and the interior of the motor casing 44 , and the free end of each set bolt 48 is provided with a threaded section which is received in a corresponding threaded hole formed in the pinion housing 17 . the set bolts 48 are circumferentially arranged at diagonally opposite positions , and are received in recesses defined between adjacent side edges of the permanent magnets 46 . the magnet cover 47 is made of malleable metallic material such as aluminum or an aluminum alloy , and the large diameter portion 47c is initially provided with a diameter which is even smaller than that of the main portion 47a thereof as illustrated in fig3 . the outer diameter of the main portion 47a of the magnet cover 47 is slightly larger than the inner diameter of the permanent magnets 46 arranged on the inner circumferential surface of the motor casing 44 . the magnet cover 47 is press fitted , with the large diameter portion 47c first , into the inner space defined by the permanent magnets 46 from the open end of the bottom plate 11 . the bolt passing holes 49 of the magnet cover 47 are each provided with a cylindrical guide collar 50 by a burring process or a stretch flanging process , and the length of each of the guide collars 50 is longer than the pitch of the thread of the set bolt 48 . therefore , when each of the set bolts 48 is passed into the bolt passing hole 47 from the open end of the bottom plate 11 as a step of assembling the motor 3 , the set bolt 48 is favorably guided by the guide collar 50 . now the operation of the above described embodiment is described in the following . in the inoperative condition , because no electric current is supplied to the energization coil 24 , the armature outer member 27 is at its rightmost position under the spring force of the return spring 35 , and the moveable contact 8 which is connected to the armature outer member 27 is spaced from the fixed contact 34 . at the same time , the clutch outer member 18 which is urged by the return spring 21 is at its rightmost position along with the clutch inner member 22 which is integral with the pinion 6 , the shifter member 37 and the armature inner member 28 with the result that the pinion 6 is disengaged from the ring gear 23 . when the ignition switch is turned to the engine start position , electric current is supplied to the energization coil 24 to magnetize the same . as a result , a magnetic path for conducting a magnetic flux is established in the armature inner and outer members 27 and 28 thereby moving the armature inner and outer members 27 and 28 to the left . the armature outer member 27 , as it is closer to the central part ( pole ) of the internal flange 25a of the holder 25 than the armature inner member 28 , moves before the armature inner member 28 does . as a result , the moveable contact 8 is moved to the left by the armature outer member 27 via the connecting plate 29 and the connecting rod 30 , and comes into contact with the fixed contact 34 . this in turn causes the electric power of the battery to be supplied to the electric motor 3 , and the rotor shaft 10 to be turned . because the moveable contact 8 comes into contact with the fixed contact 34 before the armature outer member 27 moves its full stroke , and the moveable contact 8 is mounted on the connecting rod 30 in an axially floating relationship , the pressure of the coil spring 32 is applied between the two contacts 8 and 34 . at this point , the armature outer member 27 comes to a stop with a certain gap defined between the left end surface of the armature outer member 27 and the central part of the internal flange 25a because of the presence of an external flange 27a integrally formed at the right end of the armature outer member 27 , serving as a stopper , comes into contact with the annular disk 26 . as the rotor shaft 10 turns , this rotation is reduced in speed by the reduction gear unit 2 , and is transmitted to the output shaft 4 . because of the inertia of the clutch outer member 18 which engages with the output shaft 4 via the helical spline 19 , the axial force owing to the helical spline 19 is applied to the clutch outer member 18 , causing it to move to the left . at the same time , the armature inner member 28 , which is subjected to the leftward attractive force by the energization coil 24 and the pressure from the coil spring 36 , starts moving to the left . in particular , because of the preceding movement of the armature outer member 27 , the magnetic gap is reduced , and this increases the magnetic attractive force acting on the armature inner member 28 . this force is applied to the clutch outer member 18 as an axial force via the shifter member 37 . according to the present embodiment , this axial force pushes the clutch outer member 18 leftward against the biasing force of the return spring 21 , and the pinion 6 , which is integral with the clutch inner member 22 and is therefore integrally engaged with the clutch outer member 18 , is also pushed leftward . once the clutch outer member 18 engages with the stopper plate 20 , and the pinion 6 comes into full mesh with the ring gear 23 , the rotation of the output shaft 4 is transmitted to the ring gear 23 , and starts the engine . at this point , the left end surface of the armature inner member 28 engages the central part of the internal flange 25a of the holder 25 , and a small gap is defined between the left end surface of the shifter member 37 which has integrally moved with the armature inner member 28 and the clutch outer member 18 . because the armature inner member 28 receives a maximum attractive force of the energization coil 24 as it engages the central part of the internal flange 25a of the holder 25 , even when the pinion 6 is subjected to a force which tends to disengage it from the ring gear 23 , the rightward movement of the clutch outer member 18 is prevented by the shifter member 37 , and the pinion 6 is prevented from dislodging from the ring gear 23 . the electric current that is required to keep the armature inner and outer members 27 and 28 stationary after they have moved the full stroke is substantially smaller than that required for starting the movement of the armature inner and outer members 27 and 28 . in other words , by making use of the axial force owing to the helical spline 19 for starting the movement of the one - way roller clutch 5 including the pinion 6 , the output requirement of the energization coil 24 can be reduced , and the size of the energization coil 24 can be accordingly reduced . once the engine has started and the rotational speed of the engine exceeds that of the pinion 6 , the pinion 6 will start turning freely by virtue of the one - way roller clutch 5 in the same manner as in the conventional engine starter . when the supply of electric current to the energization coil 24 ceases , owing to the biasing force of the return spring 21 acting upon the clutch outer member 18 and the biasing force of the return spring 34 acting upon the armature outer member 27 , the pinion 6 is disengaged from the ring gear 23 and the moveable contact 8 is separated from the fixed contact 32 , thereby stopping the electric motor 3 . in the above described embodiment , the cylindrical guide collars 50 were formed around the bolt passing holes 49 by a burring process , but other processes may be used for forming such guide collars . for instance , as illustrated in fig5 and 6 , it is also possible to make diagonal cuts at each position for forming the bolt passing hole 49 , and lifting the triangular pieces 51 formed by cuts away from the surface of the flange 47 , in the direction of passing the bolts 48 , so that the bolt passing holes 49 and the cylindrical guide collars 51 may be formed at the same time . thus , according to the present invention , the set bolts can be readily and accurately passed into the motor casing so as to allow the free ends of the set bolts to be threaded into the associated threaded openings . in particular , the cylindrical guide collars favorably assist the proper alignment of the set bolts . thereby , the assembly work is simplified for the assembling personnel , and is better adapted to automatic assembly processes . although the present invention has been described in terms of specific embodiments thereof , it is possible to modify and alter details thereof without departing from the spirit of the present invention . | 7 |
the best mode for carrying out the invention is presented in terms of its erred embodiment , herein depicted within the figures . referring now to fig1 a constant volume air conditioning / heat pump efficiency improvement apparatus 20 is shown , according to the present invention , for installation in a home or office building having a heat pump / air conditioning system . it is envisioned that a constant volume air conditioning / heat pump efficiency improvement apparatus 20 would be marketed and packaged as a kit for aftermarket installation by qualified professionals or could be made an integral part of a heat pump / air conditioning system at the factory . for purposes of disclosure , the aftermarket version is discussed . also , it is envisioned that a constant volume air conditioning / heat pump efficiency improvement apparatus 20 could be adapted for use in any environment that uses a heat pump / air conditioning type cooling system such as automobiles , airplanes , buses and trucks . it is stressed that this teaching implies no limitation on the possible application on the possible uses of the present invention . referring to fig2 a front view of a constant volume air conditioning / heat pump efficiency improvement apparatus 20 is shown connected to an otherwise conventional heat pump / air conditioning system 10 via piping 201 and 20m . piping 201 is connected to system piping 8 on the low pressure side of compressor 1 while piping 20m is connected to system piping 9 on the high pressure side of compressor 1 . fig2 shows the direction of flow of freon (™) in system 10 when it is in the cooling mode . as is well know , a heat pump / air conditioning system has two modes . in the cooling mode , heat is removed from within a structure and transferred to the atmosphere . the other mode reverses this cycle by removing heat from the atmosphere and transferring it to the structure to heat it . the constant volume air conditioning / heat pump efficiency improvement apparatus 20 works with both modes increasing the thermal efficiency therein . the distinctions on how the constant volume air conditioning / heat pump efficiency improvement apparatus 20 works in both modes will be explained further herein . the basic theory behind how the constant volume air conditioning / heat pump efficiency improvement apparatus 20 works and why it increases the thermal efficiency of the heat pump / air conditioning cycle requires an explanation on how the refrigeration / cooling cycle works . basically , it is a sealed system composed of copper tubing , some electronics , and three basic components : a compressor , a condenser , and an evaporator . the compressor 1 compresses a refrigerant , typically freon (™), into high pressure vapor . the refrigerant vapor enters the outside coil 2 ( condenser ) where a fan blows air across it . this condenses the refrigerant into a liquid by cooling it and removing the latent heat of vaporization . the refrigerant which is now liquid is pushed along the refrigerant line to the inside coil ( evaporator ) 7 where it encounters a metering device . the metering device 6 limits the amount of refrigerant entering the inside coil ( evaporator ) and creates a pressure drop across it . this allows the refrigerant to expand from a small diameter tube to a larger one . at this coil , a fan 3 blows air across it and the refrigerant absorbs the heat in the air regaining the previously lost latent heat of vaporization . this effectively cools the air exiting the coil 7 and the heat evaporates the refrigerant back to vapor . from here the refrigerant vapor returns to the compressor 1 to start the cycle over again . what is inherent in the foregoing is that as the refrigerant moves from one point in the cycle to another its temperature and pressure vary as does the volume of that point in the system . it is generally known that temperature , pressure , and volume are inversely proportional . when the system is initially charged with refrigerant it is pressurized to a pressure that is deemed optimal . but this only takes into consideration the pressure at the time of pressurization since the pressure will fluctuate with temperature . for example , the initial internal pressure in the system when pressurized on a 85 ° c . day will not be the same as the initial internal pressure if pressurized on a 60 ° c . day . so as the ambient temperature fluctuates the internal pressure of the system fluctuates somewhat as well so that the system does not operate at the optimum pressures throughout if the ambient temperature is not the same as at the time it was pressurized . the theory behind the present invention is to maintain the optimum operating pressure in the heat pump / air conditioning cooling cycle by monitoring the internal pressure of the refrigerant and either adding or removing refrigerant to maintain a constant volume and hence pressure throughout the system . as previously discussed , refrigerant is either added or removed from the cooling cycle via piping 20l and 20m tapped onto the low and high pressure lines respectively , on the both sides of compressor 1 . piping 20l and 20m are routed into a housing 20a and are connected on one side of and terminate at first solenoid valve 20k and second solenoid valve 20i , respectively , which control the flow of refrigerant into or out of the system . housing 20a contains the majority of the components of the apparatus 20 . housing 20a is designed to be mounted on a wall in a utility room where other household appliances such as the furnace or water heater are typically located and is sealed closed by housing cover 20b . the other side of first solenoid valve 20k and second solenoid valve 20i are connected to a common manifold 20p which is connected to manifold piping 20c connected to refrigerant reservoir 25 . refrigerant reservoir 25 is filled with the same refrigerant as the heat pump / air conditioning system and is for dispensing and receiving refrigerant . refrigerant reservoir 25 is connected to manifold 20p via piping 20c . a quick disconnect coupling allows easy removal and attachment refrigerant reservoir 25 to manifold piping 20c . a pressure switch 20h is in constant fluid communication with piping 201 connected to the low pressure line 8 of the air conditioning and heat pump system 10 . in this manner , when pressure in system 10 is higher than optimal , a signal from pressure switch 20h will open first solenoid valve 20i , normally closed , and refrigerant from the high pressure side of system 10 will flow into refrigerant reservoir 25 until the optimal pressure is achieved . conversely , when pressure in the system is lower than optimal , a signal from pressure switch 20h will open second solenoid valve 20k , normally closed , and refrigerant from the low pressure side of the system 10 will flow into refrigerant reservoir 25 until optimal pressure is achieved . a heating coil wrapped around refrigerant reservoir 25 warms the refrigerant therein when it is necessary to raise the total internal pressure of the refrigerant to meet the demands of system 10 when the total internal pressure of system 10 drops significantly . in order to prevent first solenoid valve 20i and second solenoid valve 20k from overcycling , in other words , operating for every small fluctuation of system 10 pressure , a timer 20d is used to control the amount of time either first solenoid valve 20i or second solenoid valve 20k is open . when the system 10 pressure drops requiring additional refrigerant to be added to the system 10 , timer 20d will keep first solenoid valve 20i open slightly longer to ensure that more than adequate refrigerant is added to prevent small perturbations in the system 10 pressure from triggering first solenoid valve 20i . similarly , timer 20d will keep second solenoid valve 20k open slightly longer to ensure that more than adequate refrigerant is added to prevent small perturbations in the system 10 pressure from triggering second solenoid valve 20k . of course , the extra time that timer 20d will keep first solenoid valve 20i and second solenoid valve 2k open is variable and will require adjustment when the constant volume air conditioning / heat pump efficiency improvement apparatus 20 is initially installed . pressure switch 20h also can be variably set to trigger first solenoid valve 20i when the system pressure falls below a pre - selected pressure or trigger second solenoid valve 20k when the pressure rises above a certain pre - selected pressure . also located in housing 20a is a transformer 20e for converting conventional 120 vac current to 24v dc current for powering first solenoid valve 20i and second solenoid valve 20k , timer 20d , and pressure switch 20h . a bus 20g and junction box 20f is also located therein for distributing power to the various aforementioned components . referring to fig3 shown is a front view of a constant volume air conditioning / heat pump efficiency improvement apparatus 20 identical to that shown in fig2 in almost all respects except that it is configured for use as a heat pump . the aim of the heat pump cycle , like that of the refrigeration cycle , is to move heat from one location to another . the only difference is that in the case of the heat pump cycle , the objective is to move the heat from a cool location ( outside ) to a warmer location ( inside ). the components are identical in the heat pump cycle , but their location is reversed . that is , the condenser which gives off heat is placed within the space to be heated , and the evaporator is placed outside so that it may pick up heat from the cooler surroundings . the heat pump cycle is far more efficient and cost effective than electric resistance heating common in baseboard and other heating units . in order for heat pumps to work effectively , the outside temperature must be higher than the temperature of the outside heat exchanger . heat pumps usually do not provide effective heating when the outside temperature is below 45 ° f . ( 72 ° c . ). in order for heat pump units to provide year - round functionality , electric resistance heating is often added , for use when the heat pump cycle itself does not provide satisfactory heating . the difference between fig2 and 3 is that fig3 shows the heat pump in heat mode . the difference in the two diagrams is the reversing valve 2 directs the compressed refrigerant to the inside coil 4 first . this makes the inside coil the condenser 4 and releases the heat energy . this heated air is ducted to the home or office . the outside coil 7 is used to collect the heat energy . this now becomes the evaporator . a metering valve 6 must also now be located on the inlet to coil 7 on the liquid refrigerant line 5 side to limit the amount of refrigerant flowing into coil 7 and effect the pressure drop as in the cooling cycle . referring to fig4 shown is an enlarged front view of a constant volume air conditioning / heat pump efficiency improvement apparatus 20 showing in greater detail the major components previously described . a pressure gauge 20n in fluid communication with the low pressure side piping 20l is also located therein to give visual indicia of the internal pressure of the heat pump / air conditioning system 10 to allow adjustment of timer 20d and pressure switch 20h . referring to fig5 shown are the electrical schematics interconnecting the various electronic components of a constant volume air conditioning / heat pump efficiency improvement apparatus 20 , according to a preferred embodiment of the present invention . the foregoing description is included to illustrate the operation of the preferred embodiment and is not meant to limit the scope of the invention . the scope of the invention is to be limited only by the following claims . | 1 |
according to the invention , it has been found that short - contact tazarotene therapy yields surprisingly improved and beneficial results in the treatment of acne . it has further been found that the short - contact tazarotene therapy actually reduces and even reverses the effects of sun - induced aging ( photoaging ). &# 34 ; short - contact tazarotene therapy &# 34 ;, as used herein , is intended to distinguish over conventional , or extended - contact , treatment ( s ) with tazarotene , wherein tazorac ™ gel is applied to a patient &# 39 ; s skin ( typically once a day ) and left on the skin indefinitely or until routine washing or showering occurs after a prolonged period of time ( typically overnight ). in accordance with the invention , short - contact tazarotene therapy thus comprises the steps of applying a tazarotene composition to an affected area of the skin for a brief time period followed by rinsing of the skin / affected area . in the case of acne , the usual contact time is of from about 30 seconds to about 15 minutes , preferably for a period of from about 2 to about 5 minutes . in the case of photoaging , the usual contact time is from about 30 seconds to about 10 minutes , preferably for about 1 to about 3 minutes . immediately following the prescribed period of time , the skin is rinsed thoroughly , typically with lukewarm water . in accordance with the invention and as used herein , a &# 34 ; tazarotene composition &# 34 ; comprises acetylenic retinoid compounds , or pharmaceutically - acceptable salts thereof , in admixture with a pharmaceutically acceptable carrier . the acetylenic retinoids of the invention are the compounds of formula i as represented by ## str2 ## wherein x is s , o , or nr &# 39 ; where r &# 39 ; is hydrogen or lower alkyl ; r is hydrogen or lower alkyl ; a is pyridinyl , thienyl , furyl , pyridazinyl , pyrimidinyl or pyrazinyl ; n is 0 - 2 ; and b is h , -- cooh or a pharmaceutically acceptable salt , ester or amide thereof , -- h 2 oh or an ether or ester derivative , or -- cho or an acetal derivative , or -- cor 1 or a ketal derivative where r 1 is --( ch 2 ) m ch 3 where m is 0 - 4 . hence the tazarotene compositions of the invention are not limited only to tazarotene but rather may contain any acetylenic retinoid , and preferably contains those represented by formula i . the term &# 34 ; ester &# 34 ; as used here refers to and covers any compound falling within the definition of that term as classically used in organic chemistry . where a is -- cooh , this term covers the products derived from treatment of this function with alcohols . where the ester is derived from compounds where a is -- ch 2 oh , this term covers compounds of the formula -- ch 2 oocr where r is any substituted or unsubstituted aliphatic , aromatic or aliphatic - aromatic group . preferred esters are derived from the saturated aliphatic alcohols or acids of ten or fewer carbon atoms or the cyclic or saturated aliphatic cyclic alcohols and acids of 5 to 10 carbon atoms . particularly preferred aliphatic esters are those derived from lower alkyl acids and alcohols . here , and where ever else used , lower alkyl means having 1 - 6 carbon atoms . also preferred are the phenyl or lower alkylphenyl esters . the term &# 34 ; amide &# 34 ; has the meaning generally accorded that term in organic chemistry . in this instance it includes the unsubstituted amides and all aliphatic and aromatic mono - and di - substituted amides . preferred amides are the mono - and di - substituted amides derived from the saturated aliphatic radicals of ten or fewer carbon atoms or the cyclic or saturated aliphatic - cyclic radicals of 5 to 10 carbon atoms . particularly preferred amides are those derived from lower alkyl amines . also preferred are mono - and di - substituted amides derived from the phenyl or lower alkylphenyl amines . unsubstituted amides are also preferred . acetals and ketals includes the radicals of the formula -- ck where k is (-- or ) 2 . here , r is lower alkyl . also , k may be -- or 1 o -- where r 1 is lower alkyl of 2 - 5 carbon atoms , straight chain or branched . a pharmaceutically acceptable salt may be prepared for any compound of this invention having a functionality capable of forming such salt , for example an acid or amine functionality . a pharmaceutically acceptable salt may be any salt which retains the activity of the parent compound and does not impart any deleterious or untoward effect on the subject to which it is administered and in the context in which it is administered . the preferred acetylenic retinoid compounds of this invention are those where the ethynyl group and the b group are attached to the 2 and 5 positions respectively of a pyridine ring ( the 6 and 3 positions in the nicotinic acid nomenclature being equivalent to the 2 / 5 designation in the pyridine nomenclature ) or the 5 and 2 positions respectively of a thiophene group respectively ; n is 0 ; and b is -- cooh , an alkali metal salt or organic amine salt , or a lower alkyl ester , or -- ch 2 oh and the lower alkyl esters and ethers thereof , or -- cho and acetal derivatives thereof . the most preferred compound is ethyl 6 -( 2 -( 4 , 4 - dimethylthiochroman - 6 - yl ) ethynyl )- nicotinate , also known as tazarotene . the compounds of the invention can be made by methods known in the art . one means to make such compounds is provided in u . s . pat . no . 5 , 089 , 509 which is incorporated herein by reference . the &# 34 ; tazarotene composition &# 34 ; contains an acetylenic retinoid compound in an amount suitable for topical use on humans . such compositions may be in the form of a gel , cream , lotion , ointment , cleanser or solution and include a variety of preservatives , carriers and other inactive or active ingredients . as demonstrated by the following examples , surprisingly good results are obtainable using short - contact tazarotene therapy . not only does it appear that there is no loss of effectiveness of the active tazarotene ingredient ( as compared with conventional extended - contact therapy ), but also that the effectiveness may be enhanced in some instances . even more important , the adverse reactions are substantially reduced to tolerable or even negligible levels , thereby resulting in the ability and willingness of the user to adhere to the novel regimen . this combination of effects , i . e ., equal or enhanced effectiveness , reduction in adverse reactions , and regimen adherence , yields surprisingly improved therapeutic efficacy . twenty ( 20 ) acne patients were treated with tazorac ™ ( 0 . 05 % or 0 . 1 %). they applied the gel to the facial skin once or twice daily for two to five minutes . immediately following treatment , the treated skin was thoroughly washed with lukewarm water ( the use of washcloth was not recommended , both because of its abrasiveness and tendency to retain the gel ). the results following four weeks of therapy were as follows ; 1 . signs of retinization ( slight reddening , peeling , and irritation ) occurred in 11 of 20 patients during the first 2 weeks of short - contact tazarotene therapy . 10 of these 11 reported only minor discomfort , but one reported marked redness and irritation . 2 . subjective improvement of acne occurred in 18 of 20 patients , usually by 2 to 3 weeks of therapy . one patient with recalcitrant acne of ten years duration had an 80 % reduction in lesion counts within 3 weeks . 8 of 20 patients had greater than 75 % reduction in lesion counts , 6 of 20 had greater than 50 % reduction in lesion counts , and 4 of 20 had greater than 25 % reduction in lesion counts after 4 weeks or more of short - contact tazarotene therapy . 3 . one patient with adult acne and photoaging noted subjective improvement in skin texture and pigmentation after 4 weeks of therapy . 4 . 19 of 20 patients viewed the short - contact tazarotene therapy as pleasant and convenient . as noted in example 1 , at least one of the patients noticed the improvement of skin damaged by the effects of photoaging . similar effects are observed in other patients following the short - contact tazarotene therapy . the contact period is from 30 - seconds to ten minutes , preferably one to three minutes , followed immediately by rinsing . once or , preferably , twice per day treatment is recommended . in addition to the patient noted in example 1 , two other patients have been treated with short - contact tazarotene therapy for photoaging , for a period of six weeks or longer . all three patients were examined and photographed at several intervals , and were found to have noticeable improvement in skin texture and pigmentation , a reduction in fine wrinkling and apparent diminution of solar keratoses , which are believed to be precancerous lesions . | 8 |
now in keeping with the objects of this invention , the method for forming the stacked capacitor with increased capacitance is covered in detail . the sequence of fabrication steps of this embodiment are shown in fig1 to 8 . this storage capacitor can be fabricated on a n - channel mosfet structures which are currently used in the manufacture of drams . therefore , only a brief description of the mosfet structure is given , sufficient for understanding the current invention . it should also be well understood by one skilled in the art that by including additional process steps , in addition to those described in this embodiment , other types of devices can also be included on the dram chip , for example , p channel mosfets can be formed by providing n - wells in the p substrate and complementary metal - oxide - semiconductor ( cmos ) circuits can also be formed therefrom . referring now to fig1 a cross - sectional view of the substrate 10 having a partially completed dram cell formed on and in the substrate surface , is schematically shown . the preferred substrate is composed of a p - type single crystalline silicon having a & lt ; 100 & gt ; crystallographic orientation . a relatively thick field oxide ( fox ) 12 is formed around the active device regions to isolate these individual device regions . this field oxide , only partially shown in fig1 is formed by depositing a thin silicon oxide ( pad oxide ) and a thicker silicon nitride layer as an oxidation barrier layer . conventional photolithographic techniques and etching are then used to remove the barrier layer in areas where a field oxide is desired while retaining the silicon nitride in areas where active devices are to be fabricated . the silicon substrate is then oxidized to form the field oxide . the preferred thickness is between about 4500 to 5500 angstroms . the semiconductor device is then formed in the active device regions after removing the silicon nitride barrier layer and pad oxide in a wet etch . the most commonly used device for dynamic random access memory is the metal - oxide - semiconductor field - effect transistor ( mosfet ). this device is formed by first thermally oxidizing the active device region to form a thin gate oxide 18 . the preferred thickness being from about 90 to 200 angstroms . an appropriately doped polysilicon layer 20 and an insulating layer 22 are deposited and conventional photolithographic techniques and etching are used to pattern the insulating layer 22 and polysilicon layer 20 . this forms the gate electrode 20 for the mosfet in the active device regions and conducting patterns elsewhere on the substrate with the insulating layer 22 thereon . these conducting patterns form the word lines that electrically connect the mosfet gate electrode to the appropriate peripheral circuits on the dram chip . the lightly doped source / drain 16 are formed next , usually by implanting a n - type dopant species such as arsenic or phosphorus . for example , a typical implant might consist of phosphorus p 31 at a dose of between 1 e 13 to 10 e 13 atoms / cm 2 and an energy of between about 30 to 80 kev . after forming the lightly doped source / drain , sidewall spacers 24 are formed on the gate electrode 20 sidewalls . these sidewall spacers are formed by depositing a low temperature silicon oxide and anisotropically etching back to the silicon surface . for example , the silicon oxide could be a chemical vapor deposition using tetraethoxysilane ( teos ) at a temperature in the range of about 650 ° to 900 ° c . and the etch back performed in a low pressure reactive ion etcher . the n + source / drain implantation is used to complete the source / drain regions 17 . for example , arsenic ( as 75 ) can be implanted at a dose of between 2 e 15 to 1 e 16 atoms / cm 2 and energy of between about 20 to 70 kev . alternatively , the source / drain contacts can be completed at a later process step whereby the dopant is out diffused from a doped polysilicon layer . the remainder of this embodiment relates more specifically to the objects of this invention , which addresses now in detail the method of forming a fin - shaped bottom electrode for increasing the electrode area . the invention utilizes a patterned multilayer of alternating dissimilar insulating layers and an isotropic etching to form a series of recesses in the sidewall of the multilayer for forming the fin - type bottom electrode . referring now to fig2 a first polysilicon layer 30 is deposited over the mosfet formed in the active device area and over the word lines elsewhere on the substrate and making electrical contact to the source / drain area of the mosfet . the insulating layer 22 and the sidewall spacers 24 providing electrical isolation of the gate electrode 20 and word lines from polysilicon layer 30 . the preferred thickness of the first polysilicon layer 30 is between about 200 to 1000 angstroms and the deposition process of choice is a low pressure chemical vapor deposition ( lpcvd ). the polysilicon layer 30 is then doped n - type by implantation using arsenic ions ( as 57 ). the preferred implantation dose is from between about 1 e 14 to 1 e 16 atoms / cm 2 and at implantation energy between about 40 to 100 kev . more specifically , the thickness of layer 30 is 500 angstroms and the implantation dose is 5 e 15 atoms / cm2 having an implantation energy of 50 kev . this first polysilicon layer 30 forms a portion of the bottom electrode of the stacked capacitor that makes the capacitor node contact to the source / drain area 17 of the mosfet . referring now to fig3 a multilayered structure 36 is deposited over the first polysilicon layer 30 and consisting of alternate layers of dissimilar insulator types , as labeled a and b in fig3 . the two insulator types having substantially different etch rates in a given solution or vapor phase etchant . the preferred materials are silicon oxide for layers labeled a and silicon nitride for layers labeled b . alternatively , other dissimilar insulator types having large etch rate differences can also be used . for example , phosphosilicate glass ( psg ) can be used as an alternative for silicon oxide and silicon oxynitride as an alternative for silicon nitride . the preferred method for depositing the silicon oxide and silicon nitride is an in situ multi - step deposition process where the alternate layers are deposited sequentially by changing the deposition gas mixture in the process chamber . for example , an applied materials corp . model p5000 deposition system utilizing a plasma enhanced chemical vapor deposition ( pecvd ) process can be used with a gas mixture of silane ( sih 4 ) and nitrous oxide ( n 2 o ) for depositing the silicon oxide and a gas mixture of silane ( sih 4 ) and ammonia ( nh 3 ) for depositing the silicon nitride . the preferred thickness of the silicon oxide layer labeled a is in the range of about 1000 to 2000 angstroms and more specifically having a thickness of 1500 angstroms and the preferred thickness of the silicon nitride layer labeled b is between about 300 to 1000 angstroms and more specifically having a value of 500 angstroms . for demonstration purposes only four layers are shown in fig3 but it should be well understood by one skilled in the art that additional layers can be used without departing from the spirit and scope of the invention . referring still to fig3 a conventional photolithography is used to form a patterned photoresist mask 38 over the multilayered structure 36 and aligned to the source / drain area 17 and having the top surface of the multilayer 36 exposed elsewhere on the substrate . the multi - layer 36 is then anisotropically etched to the surface of the first polysilicon layer 30 and the photoresist is removed by conventional means . as shown in fig4 . the anisotropic etch is preferably performed in a low pressure plasma etcher . one suitable etcher is an ame - 8310 etcher manufactured by applied materials corp . this etch results in an array of structures composed of multilayer 36 over the capacitor node contacts and dram cell areas having vertical sidewalls . only one of an array of cell areas is depicted in fig4 for practical reasons . referring now to fig5 an isotropic etch is used to etch and thereby recess the alternate silicon oxide layers a making up the multi - layer 30 while leaving unetched the silicon nitride layer b . this forms a fin shaped profile in the sidewall of the multi - layer 36 . the preferred etchant is a buffered hydrofluoric acid solution ( bhf ) which etches silicon oxide while leaving essentially unetched the silicon nitride . alternatively , a plasma etch ( dry etch ) can also be used . for example , the isotropic etch can be performed in a plasma mode etcher using a gas mixture of carbon tetrafluoride ( cf 4 ) and hydrogen ( h 2 ) and having an etch rate selectivity of about 20 . this fin shaped surface is now used to form the bottom electrode of the stacked capacitor . now , as shown in fig6 a second polysilicon layer 40 is deposited over the multi - layer 36 , forming a conformal polysilicon layer on and within the recesses of multilayer 36 and on the first polysilicon layer 30 that makes electrical contacting to the source / drain area 17 . the preferred polysilicon layer is deposited using a low pressure chemical vapor deposition ( lpcvd ) process and the polysilicon layer is also in - situ doped using a n - type impurity such a phosphorus . for example , the doping can be achieved by adding the phosphorous halide pocl 3 or phosphine ( ph 3 ) to the lpcvd reactant gas . the preferred thickness of layer 40 is between about 200to 400 angstroms and more specifically having a thickness of 300 angstroms and the preferred dopant concentration being between about 1 e 19 to 1 e21 atoms / cm 3 . conventional photolithographic techniques and reactive plasma etching are then used to patterned the first polysilicon layer 30 and the second polysilicon layer 40 leaving portion over the multilayer 36 and thereby forming the bottom electrode capacitor structure having a fin - like shape , as is also shown in fig6 . the complete removal of polysilicon layers 30 and 40 , by the etching , elsewhere on the substrate also electrically isolates each bottom electrode from the adjacent electrodes of the array of electrodes that are form simultaneously on the substrate . only one bottom electrode structure is shown in fig6 . referring next to fig7 the capacitor interelectrode dielectric layer 44 is formed on the remaining polysilicon layer 40 that forms the capacitor bottom electrode . preferably , the dielectric layer 44 is composed of layers of silicon nitride and silicon oxide ( si3n 4 / sio 2 ) or layers of silicon oxide , silicon nitride and silicon oxide ( ono ). for example , the dielectric layer 44 composed of silicon nitride and silicon oxide can be formed by depositing a silicon nitride layer using lpcvd and a reactive gas mixture of ammonia ( nh 3 ) and dichlorosilane ( sih 2 cl 2 ) followed by oxidation of the silicon nitride layer in wet oxygen at a temperature of about 850 ° c . for about 10 minutes . the preferred total thickness of the interelectrode dielectric is between about 30 to 150 angstroms . now as shown in fig8 a third polysilicon layer 48 is deposited on the interelectrode dielectric layer 44 , forming the top electrode of the storage capacitor and completing the fin shaped storage capacitors . the preferred thickness of polysilicon 48 is from between about 500 to 2000 angstroms and is doped with a n - type impurity , for example , by using a phosphorus species . the preferred concentration being in the range of between about i e 19 to 5 e 20 atoms / cm 3 . for example , low pressure chemical vapor deposition ( lpcvd ) and in - situ doping is used to deposit the conformal polysilicon layer 48 . it should be well understood by one skilled in the art that by including additional process steps the bit line contact and the bit line metallurgy can be formed either prior to or after the stacked storage capacitor is fabricated as is commonly reported in the literature and practice in the industry . in the particular embodiment , of this invention , the formation of the bit line contact and the bit line over the fin - shaped storage capacitor is described . the additional details shown in fig9 and described here are in sufficient detail to complete the fabrication of a dynamic random access memory ( dram ) cell for use in a dram circuit . as shown in fig9 a contact opening is formed to the second of the two source / drain contacts area 19 by photoresist masking and etching the third polysilicon layer 48 and the dielectric layer 44 . a first insulating layer 50 composed of a low flow temperature glass is then deposited and annealed to planarize the surface . the material of choice is a phosphoborosilicate glass ( pbsg ) and the preferred thickness is between about 3000 to 8000 angstroms . a bit line contact mask and an appropriate photolithographic technique are used to open the bit line contact in pbsg layer 50 over and to the second source / drain contact area 19 . a fourth polysilicon layer 54 is deposited and doped n - type , for example , by implanting with arsenic or phosphorus ions . the substrate is then annealed to drive - in the impurity from layer 50 to form the appropriate ohmic contact at the bit line contact area over the source / drain 19 . next , a metal silicide layer , not explicitly shown in fig9 is formed on the bit line polysilicon layer 54 to increase its conductivity . the preferred method is the deposition of a metal layer followed by a low temperature anneal . the preferred silicide being tungsten silicide ( wsi ). then the wsi bit line wiring is patterned using photolithographic techniques and reactive plasma etching and then a second insulating layer 58 is , for example composed of bpsg , is deposited and annealed at elevated temperatures to planarize the surface and complete the dynamic random access memory ( dram ) cell . while the invention has been particularly shown and described with reference to the preferred embodiments thereof , it will be understood by those skilled in the art that various changes in form and details may be made without departing from the spirit and scope of the invention . | 7 |
the foregoing and other features and advantages of various aspects of the invention ( s ) will be apparent from the following , more - particular description of various concepts and specific embodiments within the broader bounds of the invention ( s ). various aspects of the subject matter introduced above and discussed in greater detail below may be implemented in any of numerous ways , as the subject matter is not limited to any particular manner of implementation . examples of specific implementations and applications are provided primarily for illustrative purposes . unless otherwise defined , used or characterized herein , terms that are used herein ( including technical and scientific terms ) are to be interpreted as having a meaning that is consistent with their accepted meaning in the context of the relevant art and are not to be interpreted in an idealized or overly formal sense unless expressly so defined herein . for example , if a particular composition is referenced , the composition may be substantially , though not perfectly pure , as practical and imperfect realities may apply ; e . g ., the potential presence of at least trace impurities ( e . g ., at less than 1 or 2 %, wherein percentages or concentrations expressed herein can be either by weight or by volume ) can be understood as being within the scope of the description ; likewise , if a particular shape is referenced , the shape is intended to include imperfect variations from ideal shapes , e . g ., due to manufacturing tolerances . although the terms , first , second , third , etc ., may be used herein to describe various elements , these elements are not to be limited by these terms . these terms are simply used to distinguish one element from another . thus , a first element , discussed below , could be termed a second element without departing from the teachings of the exemplary embodiments . spatially relative terms , such as “ above ,” “ below ,” “ left ,” “ right ,” “ in front ,” “ behind ,” and the like , may be used herein for ease of description to describe the relationship of one element to another element , as illustrated in the figures . it will be understood that the spatially relative terms , as well as the illustrated configurations , are intended to encompass different orientations of the apparatus in use or operation in addition to the orientations described herein and depicted in the figures . for example , if the apparatus in the figures is turned over , elements described as “ below ” or “ beneath ” other elements or features would then be oriented “ above ” the other elements or features . thus , the exemplary term , “ above ,” may encompass both an orientation of above and below . the apparatus may be otherwise oriented ( e . g ., rotated 90 degrees or at other orientations ) and the spatially relative descriptors used herein interpreted accordingly . further still , in this disclosure , when an element is referred to as being “ on ,” “ connected to ” or “ coupled to ” another element , it may be directly on , connected or coupled to the other element or intervening elements may be present unless otherwise specified . the terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting of exemplary embodiments . as used herein , singular forms , such as “ a ” and “ an ,” are intended to include the plural forms as well , unless the context indicates otherwise . additionally , the terms , “ includes ,” “ including ,” “ comprises ” and “ comprising ,” specify the presence of the stated elements or steps but do not preclude the presence or addition of one or more other elements or steps . as shown in the embodiment illustrated in fig1 , a multi - stage membrane - distillation cycle can be carried out in a plurality of vacuum membrane - distillation modules 22 , 24 , each associated with a respective vapor condenser 12 / 16 and a liquid - liquid heat exchanger or “ permeate cooler ” 14 / 18 , all of which are in fluid communication . in the embodiment of fig1 , the vapor condenser 12 / 16 is external to the vacuum membrane - distillation module 22 / 24 . the condenser 12 / 16 can include corrugated metal tubing ( e . g ., from felton machine , niagara falls , n . y .) through which the liquid feed can flow and on which the permeate vapor can condense . a flow of feed liquid ( e . g ., sea water at 27 ° c .) is fed from the source 10 and split into respective portions that pass through the second condenser 12 and the second liquid - liquid heat exchanger 14 . the two portions are then recombined and then again split into respective portions that pass through the first condenser 16 and the first liquid - liquid heat exchanger 18 . these portions are then recombined and heated by a heat input ( q in ) at the heater 20 , which can be , e . g ., a solar heater , before being injected into a first feed - liquid containment chamber 19 in the first vacuum membrane distillation module 22 . in the first vacuum membrane distillation module 22 , water vapor from the feed liquid can permeate from the first feed - liquid containment chamber 19 through the membrane and into a first vapor - permeate containment chamber 21 in the first vacuum membrane distillation module 22 and then passed through the first condenser 16 where the vapor permeate can be condensed to form purified water . the condensed water from the first condenser 16 is then passed through the first liquid - liquid heat exchanger 18 , where heat from the condensed water is transferred to the feed liquid passing through the first liquid - liquid heat exchanger 18 . after passing through the first liquid - liquid heat exchanger 18 , the cooled water is passed through the second liquid - liquid heat exchanger 14 , where additional heat is extracted from the condensed water and transferred to the feed liquid passing through the second liquid - liquid heat exchanger 18 . a concentrated remainder 42 ′ of the feed liquid is extracted from the first feed - liquid containment chamber 19 after the water vapor is extracted and passed to a second feed - liquid containment chamber 23 in the second vacuum membrane distillation module 24 , where water vapor from the concentrated remainder 42 ′ of the feed liquid can permeate from the second feed - liquid containment chamber 23 through the membrane and into a second vapor - permeate containment chamber 25 in the second vacuum membrane distillation module 24 and then passed through the second condenser 12 where the vapor permeate can be condensed to form purified water . the condensed water from the second condenser 12 is then combined with condensed water from first condenser 16 and passed through the second liquid - liquid heat exchanger 14 , where heat from the condensed water is transferred to the feed liquid passing through the second liquid - liquid heat exchanger 14 before being ejected to a permeate outlet 34 ( e . g ., a reservoir of purified water ). a reduced vapor pressure is maintained in the first condenser 16 and a first vapor - permeate containment chamber 21 via a first regulator 28 in a conduit in fluid communication with the vacuum source 26 . likewise , a reduced vapor pressure is maintained in the second condenser 12 and a second vapor - permeate containment chamber 25 via a second regulator 30 in a conduit in fluid communication with the vacuum source 26 . as shown in fig4 and 5 , thermal energy from the brine output 37 of the second vacuum membrane distillation module 24 can be transferred to the initial feed liquid 42 from source 10 before the feed liquid 42 is passed through the condensers 12 and 16 and liquid - liquid heat exchangers 14 and 18 . in the embodiment of fig4 , the feed liquid 42 and brine 37 are both passed through an additional heat exchanger 33 , in which heat from the brine 37 is transferred to the cooler feed liquid 42 . in the embodiment of fig5 , the brine 37 is injected into the conduit carrying the feed liquid 42 at a juncture 35 such that the brine 37 and feed liquid 42 physically mix ( in which case , the brine 37 here as well provides initial heating to the feed liquid 42 ). although two modules 22 and 24 are shown here , many more modules ( with associated condensers and liquid - liquid heat exchangers ) can be incorporated in series with the apparatus shown here to continue to extract additional purified water from the concentrated remainder of the feed liquid at each stage . after the final module , the remaining brine is ejected to a brine outlet 32 . the respective pressure in the vapor - permeate containment chamber in each of up to 20 stages ( i . e ., 20 modules in series ) is shown in fig6 , where the pressure can be seen to range from up to about 75 kpa in the first module down to about 5 kpa in the twentieth module . additionally , in fig7 , the respective temperature of the feed liquid stream in each of the 20 stages is plotted as the feed liquid stream enters the module 52 , as it exits the liquid - liquid heat exchanger 54 , as it exits the condenser 56 , and as it enters the condenser 58 . further still , fig8 plots the temperature of the purified ( permeate ) water streams at each stage of the 20 - stage system as the permeate stream exits the module ( as vapor ) 62 , as it exits the condenser ( as liquid ) 64 , as it enters the liquid - liquid heat exchanger ( after mixing ) 66 , and as it exits the liquid - liquid heat exchanger 68 . the membrane distillation module 22 / 24 is typically made from some polymer material ( e . g ., polypropylene or acetyl ). as shown in fig2 , attached to the housing 36 of the module 22 / 24 is a membrane 38 that is very hydrophobic [ e . g ., formed of polytetrafluoroethylene ( ptfe ), aka teflon , or polyvinylidene fluoride ( pvdf )]. the membrane 38 may or may not have a support layer manufactured onto the active layer of the membrane 38 . the support is typically made from polypropylene , and provides additional mechanical strength to the membrane 38 and adds tearing resistance to tearing . membranes 38 typically have a pore size of 0 . 2 - 0 . 5 micrometers and a thickness of 50 - 200 micrometers . the pore channels can be selected to balance the heat - transfer coefficient ( to minimize temperature polarization ) and pressure drop . on one side of the membrane 38 , a heated saline / contaminated water stream flows , coming from a heating step , as in the case with the first stage , or the reject from a previous membrane - distillation module 22 / 24 , as with subsequent stages . a meniscus forms on the small pores and prevents liquid breakthrough . the water - vapor pressure of the water on the feed side of the membrane 38 increases with increasing temperature of the feed 42 ( the feed 42 provides the latent heat of evaporation ) and with higher molar fractions of water in the feed 42 at the membrane 38 . driven by the pressure differential across the feed and condensate sides of the membrane , a vapor stream 44 from the heated liquid - feed stream evaporates from the surface of the meniscus , through the pores of the membrane 38 , and enters a channel ( to the right of the membrane 28 , as shown ) kept at reduced pressure by a mechanical pump or vapor compressor 26 . pressure is regulated at each stage ( i . e ., with a differential height water column , or other mechanical regulator ). the reduced - pressure channel may also contain a woven screen / mesh 40 acting as a mechanical support against the pressure difference between the contaminated water stream 42 and the reduced - pressure vapor channel leading to the fresh water condensate flow 46 . as shown in fig3 , the membranes 38 can be laid out in parallel ( e . g ., 300 membrane sheets in parallel ) with alternating feed 42 and vapor 46 channels , separated by spacers . the length in the flow direction is typically shorter than other membrane - distillation systems , and a typical aspect ratio may be 5 : 1 . the membranes 38 can be sealed to the polymer housing 36 by adhesive , heat sealing or something similar . the housing 36 can also contain channels guiding liquid and vapor from piping connections to the channels . the vapor then passes to a condenser 12 / 16 , the interior of which is at the same reduced pressure of the attached membrane module 22 / 24 . this is typically a standard steam condenser 12 / 16 , made primarily of copper . the vacuum source 26 , which is powered by an energy input 27 , is connected through the condenser 12 / 16 to eliminate non - condensable vapors , such as air or carbon dioxide , and to maintain reduced pressure . the vacuum source 26 can establish a vacuum pressure sufficient to maintain the terminal temperature difference in the condenser at 3 ° c . the coolant comes from the inlet saline / contaminated stream flowing from the feed source 10 , allowing the latent heat of condensation to pre - heat the stream . pure water from the condensers 12 , 16 is sent to the liquid - liquid heat exchangers 14 , 18 . in stage 2 onward , the permeate joins the cooled permeate from the previous stage , which has been cooled to a temperature close to that of the permeate exiting the current stage . an amount of inlet water is bled off from the condenser 12 / 16 at that stage to act as cooling water for the liquid - liquid heat exchanger 14 / 18 . this amount is determined by balancing the heat capacity rates ( mass flow times specific heat capacity ). in the last stage the permeate exits at the temperature close to the inlet fluid . pressure from each stage is determined by the difference of saturation temperature of water vapor in each stage . the set point pressure is the saturation pressure corresponding to that temperature . the difference in saturation temperature from stage to stage may be in the range of 1 . 5 - 3 degrees celsius . the following figures show the temperature and pressure at each stage . in another embodiment , illustrated in fig9 , the vapor condenser 12 / 16 is integrated with the membrane - distillation module 22 / 24 . this embodiment is similar to the apparatus of fig1 in layout , except the external condenser 12 / 16 of fig1 is eliminated in favor of condensing the vapor that permeates ( as shown with arrows 44 ) through the membrane 38 to form , e . g ., liquid water 76 on a condensation surface 84 directly in the vapor - permeate containment chamber 21 / 25 , wherein the purified water flows 46 out of the base of the chamber 21 / 25 , as shown in fig1 . this can be considered a hybrid of a vacuum membrane distillation module 22 / 24 and an air - gap membrane - distillation module 70 / 72 , as the vapor stream 44 diffuses across and is condensed inside an air gap 74 ( e . g ., having a thickness on the order of 1 mm ), which provides thermal insulation between the hot liquid water stream 46 and the cold condensate 46 . the membrane 38 and module materials are similar to the system with an external condenser 12 / 16 , except a copper or other highly thermally conductive material plate 84 is used to collect condensate 46 . the surface of plate 84 may be enhanced to aid the removal of condensate droplets 76 . the condensate film 76 thickness can be , e . g ., one - tenth the width of the air gap 74 . the membrane 38 and condenser surface 84 are separated with a spacer , and pressure is reduced in this space in the same way it would be for an external condenser system . the copper condenser plate 84 separates the initial contaminated / saline feed liquid stream 78 as it collects the energy of condensation from the condensed water 76 , such that the initial feed liquid 78 acts as a coolant . the coolant 78 gains temperature and is passed to the next stage to again be used as a coolant 78 . it continues being used as a coolant until it reaches the first stage , where it is then passed through a heater 20 and sent to the first feed - liquid containment chamber 19 , where it is treated . an embodiment of a vapor - membrane - distillation / air - gap hybrid module 70 / 72 with a plurality of membranes 38 mounted in parallel is shown in fig1 . in this embodiment , alternating and cross - flowing channels of vaporizing feed liquid 42 and coolant 78 are separated by the parallel membrane 38 and condenser assemblies . in describing embodiments of the invention , specific terminology is used for the sake of clarity . for the purpose of description , specific terms are intended to at least include technical and functional equivalents that operate in a similar manner to accomplish a similar result . additionally , in some instances where a particular embodiment of the invention includes a plurality of system elements or method steps , those elements or steps may be replaced with a single element or step ; likewise , a single element or step may be replaced with a plurality of elements or steps that serve the same purpose . further , where parameters for various properties or other values are specified herein for embodiments of the invention , those parameters or values can be adjusted up or down by 1 / 100 th , 1 / 50 th , 1 / 20 th , 1 / 10 th , ⅕ th , ⅓ rd , ½ , ⅔ rd , ¾ th , ⅘ th , 9 / 10 th , 19 / 20 th , 49 / 50 th , 99 / 100 th , etc . ( or up by a factor of 1 , 2 , 3 , 4 , 5 , 6 , 8 , 10 , 20 , 50 , 100 , etc . ), or by rounded - off approximations thereof , unless otherwise specified . moreover , while this invention has been shown and described with references to particular embodiments thereof , those skilled in the art will understand that various substitutions and alterations in form and details may be made therein without departing from the scope of the invention . further still , other aspects , functions and advantages are also within the scope of the invention ; and all embodiments of the invention need not necessarily achieve all of the advantages or possess all of the characteristics described above . additionally , steps , elements and features discussed herein in connection with one embodiment can likewise be used in conjunction with other embodiments . the contents of references , including reference texts , journal articles , patents , patent applications , etc ., cited throughout the text are hereby incorporated by reference in their entirety ; and appropriate components , steps , and characterizations from these references may or may not be included in embodiments of this invention . still further , the components and steps identified in the background section are integral to this disclosure and can be used in conjunction with or substituted for components and steps described elsewhere in the disclosure within the scope of the invention . in method claims , where stages are recited in a particular order — with or without sequenced prefacing characters added for ease of reference — the stages are not to be interpreted as being temporally limited to the order in which they are recited unless otherwise specified or implied by the terms and phrasing . | 8 |
identically numbered elements in the accompanying drawings represent the same element . the term “ switch ” is used in this specification to describe equipment used to direct information over a network based on address information . those skilled in the art will understand that such equipment includes , for example , switches and routers . for example , a switch may direct an information packet based on address information contained within the packet . however , embodiments of the present invention are not limited to use in a switch , but may be used at any point in a network . thus , the term “ network ” as used herein is to be broadly construed to mean any communication system in which carried information has a characteristic subject to monitoring . embodiments are described using positive addends and activity values , but negative numbers may also be used . one embodiment of the present invention is an application specific integrated circuit ( asic ) used in a network switch , such as switch 10 in fig1 . fig2 is a block diagram showing components of switch 10 . as shown , switch 10 contains a plurality of port devices 50 a , 50 b , and 50 c . each individual port device 50 a , 50 b , and 50 c has a plurality of input / output ports represented by arrows 51 a , 51 b , and 51 c respectively . each port in each port device is connected to a particular source , destination , or combined source and destination ( fig1 ). switch 10 contains a data bus ( dbus ) 52 to which port devices 50 a - c are connected . a signal containing a packet may be directed to switch 10 via a particular port 51 d , for example . a signal received by a particular port device can be transferred to dbus 52 and signals on dbus 52 can be accessed by one or more components of switch 10 . for example , switch 10 contains conventional forwarding engine 54 connected to dbus 52 . forwarding engine 54 receives a data signal representing an information packet from dbus 52 and determines the packet &# 39 ; s proper address identification . after determining the packet &# 39 ; s address identification , forwarding engine 54 places a response signal on response bus ( rbus ) 56 , connected to port devices 50 a - c . the response signal directs one of port devices 50 a - c to direct the packet out a port 51 e , for example , towards a destination specified in the packet &# 39 ; s address . the packet information signal may be directed out any port or ports in any port device or devices in switch 10 . in accordance with the present invention , traffic monitor integrated circuit ( ic ) 58 is also connected to dbus 52 and rbus 56 . in the embodiment shown , ic 58 is application specific and contains random access memory ( ram ) 62 and monitor circuits 64 . ic 58 is configured to act as a sampler , a comparator , and a controller to implement a process that provides information regarding traffic flow rates on dbus 52 as described in detail below . the information is stored as a traffic activity table in ram 62 . the activity table contains packet address identification and relative activity values for each address identification in the table . the term “ identification ” as used in describing this embodiment means a source address , destination address , or source / destination address pair for a particular packet . for embodiments described below , conventional media access control ( mac ) addresses are monitored . other addressing protocols or other information signal characteristics may be monitored using embodiments of the present invention . in one embodiment , the table has a depth of 256 records . other table depths may be used , and the significance of table depth is described below . table 1 illustrates an activity table having 256 records . each record contains a field for a packet identification and a separate field for an activity value associated with the packet identification . manipulation of unique packet identifications and their associated activity values within the activity table is described in detail below . fig2 also shows central processing unit ( cpu ) 66 and clock 68 connected to ic 58 . as described below , cpu 66 provides information and instructions to ic 58 , and clock 68 provides clock pulses used during ic 58 operation . in one embodiment the clock is set at 62 . 5 mhz . fig3 a and 3b combined are a flow diagram representing tasks performed by a traffic monitor in accordance with the invention . these tasks correspond to code shown in the accompanying microfiche appendix . referring to fig3 a , a search pointer is initialized in step 102 . next , ram 62 ( fig2 ) is initialized in step 104 . both steps 102 and 104 are performed only once during a particular monitoring session . the remaining steps are performed as the monitor loops through the task flow as described below . all activity value fields are set to zero when ram is initialized . a zero activity value signifies that the record number is considered empty and may receive a new packet identification and associated activity value . as described below , an active packet identification is placed into an empty activity table record and has an activity value assigned during traffic monitor operation . as described below , if a particular packet identification activity ceases , the corresponding activity value eventually decreases to zero , the particular identification is “ timed out ” from the activity table , and a new , more active packet identification is put in its place . details of these procedures are discussed below . in one embodiment the search pointer ( initialized in step 102 ) points to the last activity table record . the exact record at which the pointer begins is not important , as long as the pointer eventually points to each activity table record . the monitor uses the search pointer to sequentially access each record in the activity table as it compares packet identification in the table to packet identifications being received by switch 10 . rather than track activity for every packet switch 10 receives , the monitor periodically samples identifications of received packets . the monitor may sample source , destination , or source / destination pair address identifications . as described in detail below , the monitor compares the sampled identification with the identification stored in each activity table record . thus , the monitor requires one sampled address each time it “ walks through ” all activity table records . the monitor may sample identifications in various ways . in one embodiment the monitor samples a received packet address identification using one of two modes . the monitor selects a sampling mode by referring to a binary bit state in ram 62 as written by cpu 66 in switch 10 ( fig2 ). in the “ fixed ” sampling mode , the monitor samples dbus 52 for a packet address after completing an activity table walk through . if a packet identification exists on dbus 52 at sampling time , the monitor stores the sampled identification in ram 62 , and sets an identification valid flag to true . if no packet signal exists on dbus 52 at the sampling time , the monitor waits for a specified time . if a valid packet arrives on dbus 52 during the specified time , the monitor takes the received identification as a sample , stores the identification in ram , and sets the identification valid flag to true . if no packet has arrived after the specified time expires , however , the monitor sets the identification valid flag to false . after sampling a valid address identification , or having waited the specified time , the monitor once again walks through the table and continues the procedure as described below . in a second , preferred “ random ” sampling mode , the monitor samples dbus 52 for a packet identification at a random time while performing the table walk - through . if a valid address identification is sampled , the identification valid flag is set to true . if no valid address identification is sampled , the monitor sets the identification valid flag to false . as soon as the monitor completes one table walk - through process , the monitor once again walks through the activity table regardless of whether a valid sampled identification exists for comparison . the advantage of the random sampling mode is that it avoids the possibility of sampling a particular packet address coincident with the packet &# 39 ; s periodic arrival time , yet ensures that sampling occurs at a fixed average rate . referring again to fig3 a , in step 106 the monitor samples the packet identification and sets the identification valid flag as appropriate , as just described . when no valid packet address is sampled , the previously sampled address remains in ram ( or the initialization value remains if no identification is sampled immediately after startup ). a false identification valid flag alerts the monitor to ignore the sampled identification during activity table identification comparisons . the traffic monitor sequentially compares the sampled packet identification against each identification stored in the activity table records . the monitor &# 39 ; s search pointer points to each activity table record in turn . the monitor uses a record number counter to indicate that an activity table record has been examined . when the record number counter value reaches the number of table records ( the table depth ), the monitor has examined each table record and then samples a new packet identification . in step 108 the table record counter is set to zero . in addition , in step 108 an “ identification found ” flag and “ empty record ” flag are each set to false . as the monitor walks through the activity table records , the activity table record actively being examined is referred to as the current record . in step 110 the monitor reads the current record and determines the current record &# 39 ; s current identification and current activity value . in step 112 , the monitor checks the current activity value to see if it equals zero . if the activity value does not equal zero , the current record contains information regarding an active traffic identification , and the monitor continues to step 113 . referring now to fig3 a , in step 113 the monitor checks if the sampled identification is valid by checking the identification valid flag status . if the identification is not valid , the monitor proceeds to step 130 which is described below . if valid , the monitor continues to step 114 and compares the sampled identification to the current identification in the current activity table record . if the sampled identification matches the current identification , this signifies that the sampled identification continues to be one of the more active identifications . therefore , an addend is determined in step 116 , and the addend is added to the current activity value in step 118 . in one embodiment , the appropriate addend is selected from a lookup table as shown in table 2 below . the lookup table is stored in ram 62 so that cpu 66 may alter the stored values ( fig2 ). in other embodiments the lookup table values may be stored in nonvolatile memory or in other computer readable storage media . or , the addend may be determined through direct calculation . as shown in table 2 the values in the “ activity value upper limit ” column represent ranges in which the current activity table record &# 39 ; s current activity value may fall . the corresponding value in the “ addend ” column represents the corresponding addend the monitor will use when a current activity value falls within one of the specified ranges . for example , if the current activity value associated with a particular identification in the activity table is greater than 1540 but less than 2048 , the monitor selects 43 as an addend . in the embodiment shown in table 2 , there is no corresponding sampled percent less than 0 . 78 . based on simulations , there is little significant traffic flow rate distinction between activity values less than 256 and those between 256 and 512 . for example , simulations show an identification that is sampled at slightly above 0 . 39 percent nevertheless will often have an activity value of less than 256 . therefore , a 0 . 39 corresponding sampled percent was omitted from this embodiment . other embodiments may include a corresponding sampled percent entry of 0 . 39 or similar number . the addend values to be selected in step 116 are varied to be inversely proportional to the current activity value . in this way , increasingly active packet identifications will have associated activity values that rise in progressively smaller increments . thus , for a constant rate of decrease for the activity value as described below , and for a given rate at which the monitor samples a particular identification , the identification &# 39 ; s associated activity value will stay below a selected upper value . fig4 illustrates monitor operation using values shown in table 2 . fig4 is a graph in which the abscissa represents time ( or sampling intervals ) and the ordinate represents a current record &# 39 ; s current activity value . as shown in interval a , the monitor initially samples a new identification twice so that the corresponding activity value is 511 at point a 1 ( 255 initial value + 256 addend ). the activity value then decreases over time because the monitor does not sample the corresponding identification , as described below , until reaching point a 2 at which time the monitor again samples the matching identification . the current activity value is less than 512 and the monitor once again selects 256 as an addend from the lookup table . the monitor adds the addend to the current activity value so that the new current activity value is in the range 512 to 1024 . this range signifies that the particular identification is being sampled at less than 0 . 78 percent of all packet identifications the monitor samples . still referring to fig4 as the particular packet identification activity increases , the monitor begins to sample the identification more frequently in interval b . the identification &# 39 ; s activity value continues its rising trend as the monitor now selects 128 as the appropriate addend . once the activity value reaches point c 1 , the activity value has crossed the 1024 threshold which now indicates that the particular identification is being sampled at between 0 . 78 and 1 . 6 percent of all identifications being monitored . if the monitor continues to sample this particular identification between 0 . 78 and 1 . 6 percent of the time , the activity value will remain in the range between 1024 and 1540 . if the monitor samples the particular identification more or less frequently , the associated activity value will move into a higher or lower range . both the individual addends and the activity value upper limit values may be varied . as shown for the embodiment in table 2 , the activity values and addends are based on the number of records in the traffic activity table . and as shown , the addends are selected so that the first sampled traffic flow indication occurs at just below one percent . in other embodiments , however , other activity value upper limit and addend values may be chosen to monitor other selected traffic rates . the number of rows in table 2 is selected to provide the number of distinct indications of traffic activity . the number of records therefore represents a granularity of the sampled identifications . in the embodiment shown , the number of intervals is selected as providing an acceptable number of indicated flow rates . in other embodiments , more or fewer ranges may be specified . referring again to fig3 b , the “ identification found ” flag is set to true in step 120 if the sampled identification matches the current identification in the table record . then , in step 122 the current record &# 39 ; s activity value is replaced with either the new increased activity value calculated in step 118 , or the new decreased activity value calculated in step 130 as described below . in the embodiment shown , the current identification is refreshed in step 122 when the associated activity value is written . referring again to step 112 shown in fig3 b , if the current activity value equals zero , the current activity table record is considered empty . the monitor checks the “ empty record ” flag in step 124 . if an empty record has already been found during a previous comparison between the sampled identification and an earlier table record , the monitor moves to step 122 as shown on fig3 b . if an empty record has not been previously found , step 126 sets an offset value equal to the current pointer . the monitor uses the offset value to show the record number of the empty record . then , the monitor sets the empty record flag to true in step 128 , and moves to step 122 . referring again to step 114 shown in fig3 b , if the sampled identification does not match the current identification , the monitor decreases the current activity value by a fixed value , as shown by step 130 . in the embodiments shown in the microfiche appendix , the activity value is decreased by one ( 1 ), but other values may be specified . thus , as the monitor walks through the activity table and examines each table record once per every sample , each activity table record containing a non - matching identification will have its corresponding activity value decreased . referring now to fig3 b , the monitor now performs step 132 and determines if all activity table records have been checked . if not , the monitor increments the table record counter in step 134 , increments the pointer in step 136 , and returns to step 110 to compare the sampled packet identification with the next activity table record using the procedure described above . if the monitor determines in step 132 that all activity table records have been checked , it next determines if the sampled packet identification should be added to the activity table . as shown in step 138 , if the sampled identification was found in an activity table record , the monitor returns to step 106 ( fig3 a ) and gets a new sampled packet identification . if the sampled identification was not found , however , the monitor performs step 140 and checks if the activity table contains an empty record . if the activity table contains an empty record , the monitor refers to the offset determined in step 126 ( fig3 a ) and puts the sampled identification and an initial activity value ( table 2 ) in the empty record . the monitor then returns to step 106 ( fig3 a ), samples another packet identification , and repeats the process as described above . in this way a table of active packet identifications and corresponding activity values is maintained in ram 62 ( fig2 ). the present invention is not limited to the embodiment described above . for example , referring to fig5 one embodiment may be a computer 80 configured to implement the process described above using instructions compiled from , for example , source code in the c language . as shown , computer 80 is connected to switch 10 by any conventional means . computer 80 may thus receive information regarding the packet identifications being received by switch 10 or another network device , from source / destination address pairs 18 a and 18 b for example . computer 80 may then implement computer readable instructions to monitor network traffic as described . such computer readable instructions may be contained in memory 81 which may be ram or nonvolatile storage . such computer readable instructions may also be stored on any conventional removable computer storage medium 82 . referring to the microfiche appendices , microfiche appendix a is a code representing a circuit design expressed in conventional verilog language which may , for example , be embodied in ic 58 . the source code is compiled using a synopsys v . 8 . 3 compiler using conventional methods . in one embodiment the code was compiled to be manufactured by international business machines , inc . using standard industry procedures . physical circuits in accordance with embodiments of the invention are conventional . as described above , one embodiment was constructed as an application specific integrated circuit . persons skilled in the art , having reviewed this description , may also construct embodiments of the invention using other conventional techniques and components . persons skilled in the art will therefore realize that the spirit and scope of the present invention exceeds the embodiments described above and that the invention is defined by the claims that follow . | 7 |
throughout all the figures , same or corresponding elements may generally be indicated by same reference numerals . these depicted embodiments are to be understood as illustrative of the invention and not as limiting in any way . it should also be understood that the figures are not necessarily to scale and that the embodiments are sometimes illustrated by graphic symbols , phantom lines , diagrammatic representations and fragmentary views . in certain instances , details which are not necessary for an understanding of the present invention or which render other details difficult to perceive may have been omitted . turning now to the drawing , and in particular to fig1 , there is shown a simplified schematic illustration of a power electronics system according to the present invention , generally designated by reference numeral 1 and explanatory for fig2 to 4 . the power electronics system 1 has a housing 2 comprised of three cuboid housing elements which define an upper cover element 20 , a central element 22 , and a lower cover element 24 . each of these housing elements 20 , 22 , 24 is formed by a cup - shaped housing member 206 , 226 , 246 and an assigned cover member 200 , 220 , 240 . this is shown particularly clearly for the two cover elements 20 , 24 . the upper cover element 20 is arranged with its connection surface 202 on the upper connection surface 222 of the central element 22 and likewise the lower cover element 24 with its connection surface 242 is arranged on the lower connection surface 224 of the central element 22 . the assigned connection surfaces only partially touch one another and are arranged at distances in sections , by providing at least one of the connection surfaces with a surface contour . as a result of this contouring of the surfaces , upper and lower cooling chambers and first connecting channels are formed . the central element 22 furthermore includes an inlet port 50 , an outlet port 52 and at least one second connecting channel 54 , 56 between the upper and lower chamber areas , which includes the respective cooling chambers and first connecting channels there . these elements form the liquid cooling system 5 of the power electronics system 1 . although not shown in detail , seals are , of course , provided and arranged as customary , for sealing the liquid cooling system 5 , in particular on the connection surfaces 202 , 222 , 224 , 242 . the lower cover element 24 accommodates three lower power electronics switching devices 34 . one of these switching devices comprises , in this embodiment , without restricting the generality , a control switching device 64 functionally connected thereto . similarly without restriction , the upper cover element 20 includes a power electronics circuit 30 and two control switching devices 60 non - functionally connected hereto . the central element 22 accommodates a condenser device 4 , which is formed here from three condensers 40 , which are functionally connected to the three lower power electronics switching devices 34 , without this connection being explicitly shown . a plurality of different cooling chamber configurations can essentially be embodied based on this embodiment of the power electronics system 1 . in a first variant of a cooling chamber 500 , 540 , here without restricting the generality , shown with an upper cooling chamber 500 , this is in exclusive thermal contact by means of an assigned cooling surface 522 with a condenser device 4 , in particular with its condensers 40 themselves or alternatively or in addition with its condenser connection elements 410 , 420 . in some embodiments of the power electronics system , the cooling of the condenser connection elements gains considerable significance . as is further shown in fig4 , the housing member 226 is provided with a terminal 600 for providing electrical connections . with a second variant of a cooling chamber 502 , here likewise shown as an upper cooling chamber , this is in thermal contact with the condenser device 4 and a control switching device 6 by means of two cooling surfaces 506 , 524 . with a third variant of a cooling chamber , here shown with an upper 504 and a lower 544 cooling chamber , this is thermal contact with the condenser device 4 by means of a cooling surface 526 , 528 respectively and with a respective power electronics switching device 30 , 34 by means of a further respective cooling surface , here in each case a main cooling surface 508 , 546 , 548 . the respective main cooling surface 508 , 546 , 548 has cooling fingers , as a result of which the cooling output of this main cooling surface is essentially better by at least a factor of two compared with a cooling surface with the same base surface . an increased pressure loss of the cooling liquid generally accompanies this improved cooling output . with a fourth variant of a cooling chamber 542 , here a lower cooling chamber , the single cooling surface 546 is in thermal contact with a power electronics circuit 34 . in order to be able to fulfill the cooling requirements of power electronics circuits , it is advantageous in each instance to embody the cooling surfaces assigned thereto , as shown , as main cooling surfaces . the liquid cooling system of a power electronics system , which , for the sake of clarity , is taken into consideration without control switching devices 60 , 64 , is particularly preferably , see hereto also fig5 , embodied such that the cooling liquid flows through the liquid cooling system 5 in the following order : inlet port 50 ; a lower cooling chamber 540 of the first variant ; connecting channel 54 from below to the upper chamber area ; one or a number of upper cooling chambers 500 of a first variant ; connecting channel 56 from the upper to the lower chamber area a plurality of lower cooling chambers 542 of a fourth variant ; outlet port 52 . it is herewith understandable that if necessary the upper or the lower connecting channels are likewise flowed through . fig2 to 4 show a power electronics system 1 according to this cited embodiment . fig5 shows the cooling liquid and its pressure loss in a power electronics system 1 of this type , wherein the liquid is provided here in corresponding areas of the power electronics system with a stroke following the reference character . the parts of the housing forming the liquid cooling system are thus not shown explicitly , but instead the cooling liquid contained in the liquid cooling system . fig2 shows the inventive power electronics system in a two - dimensional sectional representation along a section a - a according to fig3 , whereas fig3 and 4 show the power electronics system in an exploded view from two different viewing directions . the three - part housing 2 of the power electronics system is shown , consisting of the upper cover element 20 which ( not shown ) has an activation switching device . the upper cover element 20 is embodied like the remaining housing parts as a cup - type housing member 206 with an assigned cover member 200 . a condenser device 4 with condensers 40 and second condenser connection elements 420 for connection with a external dc source , and also with a plurality of first condenser connection elements 410 for connection with power electronics switching devices 34 of the power electronics system , is arranged in the central element 22 . similarly , the inlet port 50 and also the outlet port 52 are likewise arranged in this central element 22 for the cooling liquid to flow through the liquid cooling system 5 . the height extension of the central element 22 , in other words the distance between the upper and lower cover element , is dependent in this embodiment on the capacity of the condenser device 4 and can thus be embodied variably as a function hereof . three power electronics switching devices 34 , embodied in each instance as semibridge circuits , are arranged in the lower cover element 24 . the liquid cooling system 5 of the power electronics system consists , in addition to the inlet 50 and outlet port 52 , of an upper and a lower chamber area , which in each instance comprises cooling chambers and first connecting channels and second connecting channels 54 , 56 connecting the chamber areas . a cooling chamber herewith by definition , in contrast to a first connecting channel , comprises a cooling surface for thermal connection with a component to be cooled , such as a condenser device , a control switching device or a power electronics switching device . basically the cooling chamber and first connecting channel can pass into one another without a change in cross - section . the first chamber area , and / or the cooling chambers and first connecting channels there are embodied by a contouring of the connection surface 202 of the upper cover device 20 and the upper connection surface 222 of the central element 22 . similarly , the second chamber area is embodied by a contouring of the connection surface 242 of the lower cover device 24 and the lower connection surface 224 of the central element 22 . fig5 shows the cooling liquid , as it spreads in the liquid cooling system 5 and the pressure losses developing on account of the various embodiments of the cooling chambers . it can be seen that downstream of the inlet 50 , the cooling liquid flows through a first lower cooling chamber of a first variant , thereby only involving a minimal temperature rise and above all only a low pressure loss . the upper cooling chambers virtually degenerated to form a cooling chamber on account of the corresponding embodiment of the connecting channel are likewise embodied according to the first variant and comprise a comparably low pressure loss like the first lower cooling chamber . the heat input is likewise low here since the condenser device 4 requires a low heat discharge compared with the power electronics switching devices 30 , 34 . nevertheless , the thermal capacity , in particular the desired operating temperature of the condenser device 4 , is significantly lower than that of the power electronics switching devices . for instance , the operating temperature of the condenser device is not to exceed 90 ° c ., whereas the power semiconductor elements of the power electronics switching devices are configured for operating temperatures of up to 150 ° c ., frequently even up to 175 ° c . those cooling chambers , which are in thermal contact with the power electronics switching devices 30 , 34 , have the largest heat input into the cooling liquid , as a result of which the cooling surfaces are embodied as main cooling surfaces with cooling elements , such as cooling fins or cooling fingers . the significantly higher heat input is thus also accompanied by a higher pressure loss . in summary , the cooling chamber which is in exclusive thermal contact with the condenser device has the lowest pressure loss of all the cooling chambers . if such cooling chambers are not provided , the cooling chamber which is in exclusive thermal contact with the condenser device and a control switching device has the lowest pressure loss of all the cooling chambers . by contrast , the cooling chamber which is in exclusive thermal contact with a power electronics switching device has the highest pressure loss of all cooling chambers . this thus means that the last cooling chamber flowed through has a pressure loss which is higher by at least a factor of 1 . 6 , in particular by a factor of 3 , than the first cooling chamber flowed through . while the invention has been illustrated and described in connection with currently preferred embodiments shown and described in detail , it is not intended to be limited to the details shown since various modifications and structural changes may be made without departing in any way from the spirit and scope of the present invention . the embodiments were chosen and described in order to explain the principles of the invention and practical application to thereby enable a person skilled in the art to best utilize the invention and various embodiments with various modifications as are suited to the particular use contemplated . what is claimed as new and desired to be protected by letters patent is set forth in the appended claims and includes equivalents of the elements recited therein : | 7 |
the construction of a substrate treating apparatus according to the invention will be described hereinafter . this substrate treating apparatus is designed for removing a reaction product , which is an organic substance , from a substrate . in this embodiment , the apparatus removes a polymer as the reaction product from the surface of a substrate , e . g . a silicon semiconductor wafer , with a film formed thereon . the above polymer results from dry etching of the film under a resist film used as a mask . the resist herein is a photosensitive material , and more particularly a photosensitive material containing an organic substance . the film noted above is , for example , a film of metal such as copper , aluminum , titanium or tungsten , or a film of a mixture of metals such as copper , aluminum , titanium and tungsten , or an insulating film such as a silicon oxide film , a silicon nitride film , an organic insulating film , a low dielectric layer insulating film or a high dielectric layer insulating film . fig1 through 3 are schematic side views of the substrate treating apparatus , respectively . this substrate treating apparatus includes a spin chuck 58 driven by a motor 57 to rotate with a wafer w having a primary surface thereof in horizontal posture , a first nozzle 41 for supplying the removal liquid to the wafer w held by the spin chuck 58 , a second nozzle 42 for supplying deionized water to the wafer w held by the spin chuck 58 , and an annular , vertically movable cup 51 and an annular fixed cup 52 acting as a scatter preventive cup for capturing the removal liquid and deionized water scattering from the wafer w in time of wafer treatment . the first nozzle 41 is connected at a proximal end thereof to a support shaft 43 rotatably supported by a motor 45 . the motor 45 is connected to an air cylinder 48 through a bracket 47 . thus , the first nozzle 41 is driven by the air cylinder 48 to move vertically between a removal liquid supplying position shown in solid lines in fig1 through 3 , and a raised position shown in two - dot chain lines in fig1 through 3 . further , the first nozzle 41 is driven by the motor 45 to swing a distal end thereof between a position opposed to the center of wafer w held by the spin chuck 58 , a position opposed to the vicinity of an edge of wafer w held by the spin chuck 58 , and a position outside the movable cup 51 and fixed cup 52 . the first nozzle 41 is connected to a removal liquid reservoir 62 through a removal liquid circulating and heating mechanism for circulating and heating the removal liquid . the removal liquid circulating and heating mechanism includes a common supply line 63 extending between the removal liquid reservoir 62 and first nozzle 41 , a first circulating line 66 branching from a first branch point 1 on the common supply line and extending to the removal liquid reservoir 62 , and a second circulating line 65 branching from a second branch point 2 on the common supply line between the first branch point 1 and first nozzle 41 and extending to the removal liquid reservoir 62 . the common supply line 63 has , arranged between the removal liquid reservoir 62 and first branch point 1 , a circulating pump 64 in the form of a bellows pump , for example , and a removal liquid heating unit 69 with a heater for heating the removal liquid . the first circulating line 66 has a flow control valve 68 such as a flowmeter with a needle . the common supply line 63 has a filter 70 disposed between the first branch point 1 and second branch point 2 for filtering the removal liquid flowing between the two branch points 1 and 2 . the second circulating line 65 has a flow control valve 67 similar to the flow control valve 68 . an electromagnetic switch valve 71 is disposed between the second branch point 2 and first nozzle 41 . the electromagnetic switch valve 71 is normally closed . in this state , the removal liquid in the removal liquid reservoir 62 , by the action of circulating pump 64 , circulates through the common circulation line 63 and through both the first circulating line 66 and second circulating line 65 . that is , the removal liquid that circulates through the common circulation line 63 and first circulating line 66 , by the action of circulating pump 64 , passes through the removal liquid heating unit 69 to be heated , and flows through the flow control valve 68 to be collected in the removal liquid reservoir 62 . the removal liquid that circulates through the common circulation line 63 and second circulating line 65 , by the action of circulation pump 64 , passes through the removal liquid heating unit 69 to be heated , and after being filtered by the filter 70 , flows through the flow control valve 67 to be collected in the removal liquid reservoir 62 . the electromagnetic switch valve 71 is opened when supplying the removal liquid . in this state , the removal liquid that circulates through the second circulating line 65 is transmitted to the first nozzle 41 through the electromagnetic switch valve 71 to be supplied to the surface of wafer w held and rotated by the spin chuck 58 . the removal liquid feed rate per unit time is adjusted by the flow control valves 67 and 68 . that is , the quantity of the removal liquid circulating through the first circulating line 66 and the quantity of the removal liquid circulating through the second circulating line 65 are adjusted by the flow control valves 67 and 68 . at this time , the quantity of the removal liquid circulating through the first circulating line 66 is set to an appropriate flow rate for maintaining the removal liquid at a proper temperature . the quantity of the removal liquid circulating through the second circulating line 65 is set to such a flow rate that the removal liquid is supplied at a desired rate per unit time from the first nozzle 41 to the surface of wafer w . the removal liquid supplied from the first nozzle 41 to the wafer w may be an organic amine - based removal liquid containing an organic amine such as dimethyl sulfoxide or dimethylformamide , a removal liquid containing ammonium fluoride , or an inorganic removal liquid . specifically , the organic amine - based removal liquid may be a mixed solution of monoethanolamine , water and aromatic triol , a mixed solution of 2 -( 2 - aminoethoxy ) ethanol , hydroxyamine and catechol , a mixed solution of alkanolamine , water , dialkylsulfoxide , hydroxyamine and an amine - based anticorrosive , a mixed solution of alkanolamine , glycol ether and water , a mixed solution of dimethylsulfoxide , hydroxyamine , triethylene - tetramine , pyrocatechol and water , a mixed solution of water , hydroxyamine and pyrogallol , a mixed solution of 2 - amino - ethanol , ether and sugar alcohol , or a mixed solution of 2 -( 2 - aminoethoxy ) ethanol , n , n - dimethylacetamide , water and triethanolamine . the solution containing an ammonium fluoride substance ( called an ammonium fluoride removal liquid ) may be a mixed solution of an organic alkali , sugar alcohol and water , a mixed solution of a fluorine compound , an organic carboxylic acid and an acid / amide - based solvent , a mixed solution of alkylamide , water and ammonium fluoride , a mixed solution of dimethylsulfoxide , 2 - aminoethanol , an aqueous solution of an organic alkali and aromatic hydrocarbon , a mixed solution of dimethylsulfoxide , ammonium fluoride and water , a mixed solution of ammonium fluoride , triethanolamine , pentamethyldiethylene triamine , iminodiacetate and water , a mixed solution of glycol , alkyl sulfate , organic salt , organic acid and inorganic salt , or a mixed solution of amide , organic salt , organic acid and inorganic salt . an inorganic solution ( or inorganic removal liquid ) may be a mixed solution of water and a phosphoric acid derivative . the second nozzle 42 is connected at a proximal end thereof to a support shaft 44 rotatably supported by a motor 46 . the motor 46 is connected to an air cylinder 49 through the bracket 47 . thus , the second nozzle 42 is driven by the air cylinder 49 to move vertically between a deionized water supplying position shown in solid lines in fig1 through 3 , and a raised shown in two - dot chain lines in fig1 through 3 . further , the second nozzle 42 is driven by the motor 46 to swing a distal end thereof between a position opposed to the center of wafer w held by the spin chuck 58 , a position opposed to the vicinity of an edge of wafer w held by the spin chuck 58 , and a position outside the movable cup 51 and fixed cup 52 . the second nozzle 42 is connected by piping to a deionized water source not shown . deionized water fed from the deionized water source is supplied from the second nozzle 42 to the surface of wafer w held by the spin chuck 58 . the vertically movable cup 51 is connected to an air cylinder 54 through a support 53 . thus , the movable cup 51 is driven by the air cylinder 54 to move vertically between a position shown in fig1 for allowing loading and unloading of the wafer w , a deionized water collecting position shown in fig2 , and a removal liquid collecting position shown in fig3 . when the movable cup 51 is in the position shown in fig1 , a transport mechanism not shown may transport the wafer w into or out of the substrate treating apparatus . in the deionized water collecting position shown in fig2 , the movable cup 51 captures the deionized water scattering from the wafer w when the deionized water is supplied to the wafer w for treatment of the wafer w . in the removal liquid collecting position shown in fig3 , the movable cup 51 captures the removal liquid scattering from the wafer w when the removal liquid is supplied to the wafer w for treatment of the wafer w . the fixed cup 52 has a first recess 55 formed circumferentially , and a second recess 56 formed circumferentially and inwardly of the first recess 55 . the first recess 55 is used for collecting the removal liquid captured by the movable cup 51 in the removal liquid collecting position shown in fig3 . the second recess 56 is used for collecting the deionized water captured by the movable cup 51 in the deionized water collecting position shown in fig2 . the first recess 55 is connected to the removal liquid reservoir 62 through piping 61 . the removal liquid collected in the first recess 55 is once stored in the removal liquid reservoir 62 , and thereafter transmitted by the action of circulating pump 64 to the first nozzle 41 again to be supplied to the surface of wafer w held by the spin chuck 58 . the second recess 56 is connected to a deionized water collector 11 . the deionized water collected in the collector 11 is discarded . next , an operation of this substrate treating apparatus for treating a wafer w will be described . fig4 is a flow chart showing the treating operation of the substrate treating apparatus . first , a wafer w to be treated is loaded into the substrate treating apparatus ( step s 1 ). for loading the wafer w into the apparatus , the movable cup 51 is lowered to the position shown in fig1 for allowing loading and unloading of the wafer w . the distal ends of the first nozzle 41 and second nozzle 42 are kept outside the movable cup 51 and fixed cup 52 . after the transport mechanism places the wafer w on the spin chuck 58 , the removal liquid is supplied to the wafer w in the following manner ( step s 2 ). in time of supplying the removal liquid , the movable cup 51 is raised to the removal liquid collecting position as shown in fig3 . thereafter , the air cylinder 48 is operated to raise the first nozzle 41 once to the upper position shown in two - dot chain lines in fig3 , and then the motor 45 is operated to rotate the support shaft 43 , thereby moving the distal end of first nozzle 41 from the position outside the movable cup 51 and fixed cup 52 to the position opposed to the center of the wafer w held by the spin chuck 58 . next , the air cylinder 48 is operated to lower the first nozzle 41 to the removal liquid supplying position shown in solid lines in fig3 . in this state , the motor 57 is operated to spin the spin chuck 58 , and the electromagnetic switch valve 71 is opened to supply the removal liquid to the surface of the spinning wafer w held by the spin chuck 58 . in this way , a process is carried out for removing the reaction product . in time of this removing process , the supply per unit time of the removal liquid from the first nozzle 41 to the surface of wafer w and the rotational frequency of spin chuck 58 are controlled to be predetermined values . that is , in this removing step , the reaction product may be removed with high efficiency by supplying the removal liquid at a rate of 50 ml or more per minute . as noted hereinbefore , even when the removal liquid is heated to a proper temperature to realize a maximum rate of removing the reaction product , the removal liquid actually supplied to the wafer w loses some of its heat to the wafer w . this results in a phenomenon of lowering the efficiency of removing the reaction product . when the removal liquid is continuously supplied to the wafer w at 50 ml or more , the wafer w is heated by the removal liquid to restrain the removal liquid cooling down from the proper temperature . this effectively avoids the phenomenon of lowering the efficiency of removing the reaction product and impairing the quality of treatment of the wafer w . where the wafer w is the 8 - inch type , it is desirable to supply the removal liquid at a rate of 150 ml to 500 ml per minute to the wafer w . where the wafer w is the 12 - inch type , it is desirable to supply the removal liquid at a rate of 200 ml to 1 , 000 ml per minute to the wafer w . by setting the removal liquid supplying rate per unit time of the removal liquid to such values , the reaction product may be removed from the wafer w with increased efficiency . the wafer w described in this specification is a substantially circular semiconductor wafer . the wafer w of the 8 - inch type is a 200 mm wafer specified by semi international standards . the wafer w of the 12 - inch type is a 300 mm wafer specified by semi international standards . according to the dimensions provided by semi international standards , the wafer w of the 8 - inch type is 200 mm ± 0 . 2 mm , and the wafer w of the 12 - inch type 300 mm ± 0 . 5 mm . in the removing step , the reaction product may be removed with high efficiency by setting the rotational frequency of spin chuck 58 to a first speed of at least 100 rpm . when the rotational frequency of spin chuck 58 is lower than the above value , the removal liquid supplied to the wafer w does not spread quickly over the entire surface of wafer w . consequently , the wafer w spinning with the spin chuck 58 is lower in temperature adjacent the edge than adjacent the center of rotation . this causes a phenomenon of the temperature of the removal liquid lowering below the proper temperature adjacent the edge of the wafer w , to lower the efficiency of removing the reaction product decreases . this inconvenience may be avoided by setting the rotational frequency of spin chuck 58 to 100 rpm or higher it is desirable that the rotational frequency of spin chuck 58 at this time does not exceed 3 , 000 rpm . when the rotational frequency of spin chuck 58 exceeds the above value , the removal liquid scattering from the edge of the spinning wafer w could rebound from the movable cup 51 back to the surface of wafer w . since the removal liquid scattering from the edge of wafer w has a reduced temperature , this removal liquid could lower the temperature of the removal liquid supplied from the first nozzle 41 to the surface of wafer w , to lower the efficiency of removing the reaction product . further , contaminants could mix into the removal liquid scattering from the edge of wafer w and rebounding from the movable cup 51 , to affect the results of treatment of the wafer w . such an inconvenience may be avoided by setting the rotational frequency of spin chuck 58 to 3 , 000 rpm or less . the rotational frequency of spin chuck 58 noted above is controlled by controlling the rotational frequency of motor 58 acting as the driving device for spinning the spin chuck 58 . after completing the removal liquid supplying step under the above conditions , a removal liquid scattering step is executed next ( step s 3 ). in this scattering step , the spin chuck 58 is spun at a second speed faster than the above first speed to scatter the removal liquid from the wafer w . the removal liquid scattering from the edge of the wafer w is captured by the lower end of vertically movable cup 51 as indicated by arrows in fig3 , and collected in the removal liquid reservoir 62 through the first recess 55 in the fixed cup 52 . in this way , reuse may be made of the expensive removal liquid . upon completion of the process of removing the reaction product by using the removal liquid , the distal end of first nozzle 41 is moved outside the movable cup 51 and fixed cup 52 . in the removal liquid scattering step also , the rotational frequency of spin chuck 58 , preferably , is 3 , 000 rpm or less . next , a deionized water supplying step is executed ( step s 4 ). for executing the deionized water supplying step , the movable cup 51 is lowered to the deionized water collecting position shown in fig2 . the air cylinder 49 is operated to raise the second nozzle 42 once to the upper position shown in two - dot chain lines in fig2 , and then the motor 46 is operated to rotate the support shaft 44 , thereby moving the distal end of second nozzle 42 from the position outside the movable cup 51 and fixed cup 52 to the position opposed to the center of the wafer w held by the spin chuck 58 . next , the air cylinder 49 is operated to lower the second nozzle 42 to the deionized water supplying position shown in solid lines in fig2 . in this state , the wafer w is spun with the spin chuck 58 , and the deionized water is supplied from the second nozzle 42 to the surface of wafer w to clean the wafer w . at this time , the deionized water scattering from the edge of the wafer w is captured by the side wall of movable cup 51 as indicated by arrows in fig2 , and collected in the deionized water collector 11 through the second recess 56 in the fixed cup 52 . after the cleaning process using the deionized water , a spin - drying step is executed ( step s 5 ). in the spin - drying step , the spin chuck 58 is spun at high speed to spin - dry the wafer w . finally , a wafer unloading step is executed ( step s 6 ). for executing the wafer unloading step , the distal end of the second nozzle 42 is moved outside the movable cup 51 and fixed cup 52 . the movable cup 51 is lowered to the position for allowing loading and unloading of the wafer w . then , the transport mechanism , not shown , unloads the wafer w from the spin chuck 58 . the above embodiment discloses a process for removing a polymer , which is a reaction product generated during dry etching , from the wafer having undergone the dry etching . however , the invention is not limited to the removal from the wafer of a reaction product generated during dry etching . for example , the invention is applicable also to removal from the wafer of a reaction product generated during plasma ashing . when an impurity diffusion process is carried out with a resist film acting as a mask , the whole or part of the resist film changes into a reaction product . the invention includes the case of removing such reaction product also . thus , the invention is applicable also to removal from substrates of reaction products resulting from resists during various processes not limited to dry etching . further , the invention is not limited to removal of the resist - originated reaction product from the substrate , but includes also a case of removing the resist itself from the substrate . for example , a resist may be applied to a substrate to form a resist film thereon , a pattern ( e . g . a wiring pattern ) is exposed on the resist film , and the exposed resist film is developed . the pattern defined by the developed resist film may be used as a mask to perform a lower film process on a film ( which is called a lower film ) present under the resist . the invention is applicable also to removal of the resist film no longer necessary after the lower film process . more particularly , for example , the lower film may be etched after development of the resist film . whether the etching process is wet etching or dry etching such as rie , the resist film becomes unnecessary and should be removed after the etching process . the invention includes also such resist removal following the etching process . further , in a different case of removing a resist itself from a substrate , an impurity diffusion process may be conducted as a lower film process after the resist film is developed . the resist film becomes unnecessary and should be removed after the diffusion process . the invention includes also such resist removal . in these cases , any reaction product resulting from a change in property of the resist film may be removed together with the unwanted resist film . this is advantageous in improving throughput and reducing cost . when , for example , the lower film is dry - etched in the above etching process , a resist - originated reaction product is also generated . as a result , the resist film itself serving as a mask for the lower film during the dry etching and the reaction product resulting from a change in property of the resist film may be removed at the same time . a resist - originated reaction product is generated also when the impurity diffusion process ( e . g . ion implantation ) is conducted on the lower film . consequently , the resist film itself serving as a mask for the lower film during the impurity diffusion process and the reaction product resulting from a change in property of the resist film may be removed at the same time . furthermore , according to the invention , it is possible to remove not only the resist - originated reaction product and the resist itself , but also organic matter not originating from the resist , such as minute contaminants emanating from the human body . the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof and , accordingly , reference should be made to the appended claims , rather than to the foregoing specification , as indicating the scope of the invention . | 8 |
referring to the drawings in greater detail , and first to fig1 , the invention is embodied in a fanout connector , generally designated 20 and which is fabricated of three major components . as best seen in fig4 those components include a base housing , generally designated 22 , and a cover , generally designated 24 , which is slidably mounted onto the base housing in the direction of arrow “ a ”. the base housing and cover form a housing means for receiving a third major component , namely a fanout insert , generally designated 26 . a fiber optic cable 28 includes a plurality of individual optical fibers 30 which extend through the fanout insert and through a plurality of tubes 32 projecting forwardly of the insert . more particularly , base housing 22 of fanout connector 20 includes a through passage , generally designated 34 , for receiving cable 28 and fibers 30 along an axis 36 . the base housing is a one - piece structure unitarily molded of plastic material and includes a bottom wall 38 and a pair of upstanding side walls 40 which define a receptacle 42 which communicates with or is a part of through passage 34 . the receptacle generally is at a front end 44 of the housing , and a bottom lip 46 projects forwardly of front end 44 . an entrance section 48 of through passage 34 opens at a rear end 50 of the housing and through which cable 28 extends . the entrance section is enlarged relative to the dimensions of the cable so that the cable is freely positioned within the enlarged entrance section as best seen in fig3 . an intermediate section is defined by a pair of side walls 52 which gradually slope outwardly or diverge from entrance section 48 to receptacle 42 . a plurality of guide rails 54 are located along the upper edges of side walls 40 of the base housing , with the guide rails opening inwardly toward axis 34 . other features of base housing 22 include an upstanding octagonal mounting post 56 , a rearwardly projecting strain relief tongue 58 , a pair of upwardly opening latch recesses 60 ( fig4 ), a pair of bottom opening mounting holes 62 ( fig2 ) and a pair of cylindrical mounting members 64 , all for purposes described hereinafter . mounting members 64 are joined to one side wall 40 of the base housing by a pair of frangible webs 66 . cover 24 of connector 20 is a generally flat , elongated or rectangular member having guide ribs 68 along opposite edges thereof . the cover is a one - piece structure unitarily molded of plastic material . guide ribs 68 slide beneath guide rails 54 of base housing 22 when the cover is slidably mounted to the housing in the direction of arrow “ a ” ( fig4 ) as described hereinafter . the cover has an upstanding octagonal mounting post 70 similar to upstanding mounting post 56 of the base housing . the cover has a forwardly projecting top lip 72 similar to bottom lip 46 of the base housing . the cover has a rearwardly projecting strain relief shroud 74 which cooperates with strain relief tongue 58 of the base housing to provide a strain relief means for cable 28 , as will be seen hereinafter . referring to fig5 the bottom of cover 24 has a pair of integrally molded latch bosses 76 which latch within recesses 60 ( fig4 ) of the base housing . a stop 78 also projects from the bottom of the cover . finally , the cover includes a transparent window 80 which affords visual inspection of the cable within the connector . the entire cover may be molded of substantially transparent plastic material which is texturized in areas 82 so that substantially the entire cover is opaque except for transparent window 80 . referring to fig4 fanout insert 26 is molded of plastic material and includes a plurality of through holes 84 which receive fibers 30 of cable 28 and which spread the individual fibers apart from each other transversely of axis 36 . the number of through holes does not have to match the number of fibers of the cable . for instance , in the illustrated embodiment , there are sixteen through holes 84 and only fourteen fibers 30 of cable 28 . as stated above , the fibers extend through a plurality of tubes 32 projecting from a front end 86 of the fanout insert . the rear ends of the tubes preferably are fixed , as by epoxy , within the front ends of through holes 84 . the fiber ends project beyond the front ends of the tubes as seen in the drawings . the tubes provide both protection for the projecting fibers as well as means for readily manipulating the fibers . as seen in fig1 - 3 , the tubes , themselves , are protected by forwardly projecting top lip 72 of the cover and bottom lip 46 of the base housing . fig6 shows how a plurality of connectors 20 can be mounted on top of each other in a stacked array . when one connector is mounted on top of another connector , mounting post 56 which projects upwardly from base housing 22 and mounting post 70 which projects upwardly from cover 24 of a bottom connector are inserted into mounting holes 62 ( fig2 ) in the bottom of the base housing of a top connector . therefore , the cover of the bottom connector cannot move relative to the base housing thereof . the mounting posts may be sized for positioning into the mounting holes by a press - fit . although fig6 shows two connectors in a stacked array , of course more than two connectors can be stacked as described . furthermore , the mounting posts 56 and 70 may be press fit into mounting holes in a printed circuit board ( not shown ). fig7 - 10 show how cylindrical mounting members 64 can be brokenaway from base housing 22 for using the connector in applications wherein the connector is not mounted to a supporting structure . in other words , cylindrical mounting members 64 have through holes 88 ( fig7 and 8 ) for receiving therethrough appropriate fasteners , such as rivets , screws or bolts , for fastening the connector to an appropriate support structure . when an application dictates that the connector be used as a stand - alone unit , mounting members 64 are broken - away from base housing 22 . this is accomplished by using frangible webs 66 which join the mounting members to the base housing and which are much smaller than the mounting members . fig7 and 7a show that notches 90 are formed at the tops of the webs immediately adjacent the housing . fig8 and 8a show that notches 92 are formed at the bottoms of the webs immediately adjacent the housing . these notches weaken the junctures between the webs and the housing so that the webs readily break away from the housing leaving fairly clean breaking points as seen in fig9 and 10 . referring to fig1 and 12 in conjunction with fig4 fanout insert 26 includes a plurality of polarizing projections 94 on opposite sides thereof , and base housing 22 includes a plurality of polarizing projections 96 on the opposite sides of receptacle 42 defined by side walls 40 . these complementary interengaging polarizing projections 94 and 96 define a tongue and groove arrangement at the sides of fanout insert 26 and the sides of receptacle 42 to ensure that the fanout insert is positioned in the receptacle only in a given orientation so that the fibers of cable 28 are oriented according to an expected scheme in which they have been threaded through the insert and through tubes 32 . at this point , it can be seen in fig4 and 12 that a small tube or band 98 is positioned about cable 28 at a point where the outer cladding of the cable has been removed to expose individual fibers 30 . this band may be fabricated of heat shrinkable material and heat shrunk about the cable at this point . the band prevents the fibers from fraying the outer cladding of the cable after they have been exposed for spreading by fanout insert 26 . as seen in fig3 the band is free to move within enlarged entrance section 48 . this allows the cable and fibers to move axially of the entire connector within the limits of the band captured in the enlarged entrance section thereby improving temperature cycling performance . stop 78 on the underside of cover 24 defines the forward limit of such movement . after fanout insert 26 , cable 28 , fibers 30 and tubes 32 have been prepared as shown in fig4 and after this subassembly has been inserted and polarized within base housing 22 as shown in fig1 and 12 , cover 24 is assembled to the base housing as shown in fig1 and 14 . specifically , the cover is slidably mounted to the base housing in the direction of arrows “ a ”. during mounting , guide ribs 68 at opposite edges of the flat cover slide beneath guide rails 54 along the top edges of side walls 40 of the base housing . the cover is slidably mounted to the housing until a pair of stops 100 at opposite sides of the cover abut against a pair of stops 102 at opposite sides of the base housing as seen in fig1 . once cover 24 is fully slidably mounted onto base housing 22 with stops 100 and 102 in abutment , two functions occur as best seen in fig1 . first , latch bosses 76 ( fig5 ) on the underside of cover 24 snap into latching interengagement with latch recesses 60 ( fig4 ) in the top of the base housing . second , strain relief tongue 58 at the rear of the base housing enters strain relief shroud 74 at the rear of the cover . this sandwiches cable 28 between the tongue and the cover . as best seen in fig4 and 5 , shroud 74 is flattened and is generally c - shaped to define a pair of bottom , inwardly directed flanges 74 a . tongue 58 also is flat , whereby ribbon cable 28 is sandwiched between the flat tongue and the flat top of the shroud , with flanges 74 a of the shroud interengaging with the bottom of the tongue . the shroud is joined to the cover by a thin web 74 b . with the cover and the base housing being fabricated of plastic material , web 74 b of shroud 74 and tongue 58 are flexible whereby the interengaged strain relief means provide strain relief for the cable . the size and location of latch bosses 76 and latch recesses 60 in relation to tongue 58 and shroud 74 preferably should be such that the tongue enters the shroud before the latch bosses of the cover engage the base housing which , otherwise , might move the tongue and shroud out of alignment . this can be seen in fig1 where tongue 58 has entered shroud 54 before latch bosses 76 engage the housing for movement into the latch recesses . finally , fig1 shows a connector 20 a which does not include mounting post 56 ( fig4 ) on base housing 22 nor mounting post 70 ( fig4 ) on cover 24 . this simply shows that the connector can be made for non - stackable applications . it will be understood that the invention may be embodied in other specific forms without departing from the spirit or central characteristics thereof . the present examples and embodiments , therefore , are to be considered in all respects as illustrative and not restrictive , and the invention is not to be limited to the details given herein . | 6 |
referring now to the drawings , and in particular fig1 a reflective surgical drape generally indicated at 10 is used for covering a surgical patient and reducing heat loss from the patient &# 39 ; s body during a surgical procedure . as shown in fig1 the reflective surgical drape 10 may be fashioned as a blanket which may be wrapped closely about a portion or the entire body of a patient undergoing a surgical procedure . as shown in fig1 and 3 the reflective surgical drape may be fashioned as a cap 12 which serves as a head covering for a surgical patient . those skilled in the art will recognize that the cap may be provided with a peripheral elastic band or other means to ensure the cap remains on the patient &# 39 ; s head . also as shown in fig3 the reflective surgical drape may be fashioned as leggings 14 which comprise an open end for receiving a patient &# 39 ; s leg and an opposite closed end . additionally , as shown in fig3 the reflective surgical drape may be fashioned as a covering 16 for the torso of a patient undergoing a surgical procedure . those skilled in the art will recognize that the reflective surgical drape may be fashioned in any desired conformation to cover any selected portion of the body of a patient undergoing a surgical procedure . as shown in fig2 one embodiment of the drape 10 of the present invention is a four layer drape wherein a core layer 18 comprises non - conductive aluminum and a first and second adjacent layer 20 , 20 &# 39 ; comprise a thermoplastic material . a non - woven layer of absorbent material 22 is attached to the second adjacent layer 20 &# 39 ;. those skilled in the art will recognize that the non - woven layer of absorbent material 22 may be attached to either the first or second adjacent layer 20 , 20 &# 39 ;. preferably , the core layer 18 of non - conductive aluminum is vacuum deposited on the first adjacent layer 20 of thermoplastic material . the core layer 18 of non - conductive aluminum is a vacuum deposit of aluminum preferably having a thickness of from 270 å to 330 å and most preferably a thickness of approximately 300 å . the core layer 18 of non - conductive aluminum is preferably substantially enclosed or sandwiched between the first and second adjacent layers 20 , 20 &# 39 ; of thermoplastic material . the second adjacent layer 20 &# 39 ; of thermoplastic material is preferably laminated to the vacuum deposited core layer 18 of non - conductive aluminum using an adhesive . the adhesive is preferably moisture - proof and is most preferably an acrylic moisture - proof adhesive . alternatively , the second adjacent layer 20 &# 39 ; of thermoplastic material is preferably heat extruded to the vacuum deposited core layer 18 of non - conductive aluminum . the thermoplastic material of the first and second adjacent layers 20 , 20 &# 39 ; must be flexible but need not be transparent . the thermoplastic material of the first and second adjacent layers 20 , 20 &# 39 ; may , preferably , be low - density polyethylene , medium - density polyethylene , polypropylene , polyester or polybutylene . the thermoplastic material of the first and second adjacent layers 20 , 20 &# 39 ;, most preferably , is low - density polyethylene . those skilled in the art will recognize , however , that other flexible thermoplastic materials may be used as the thermoplastic material of the first and second adjacent layer 20 , 20 &# 39 ;. the first and second adjacent layers 20 , 20 &# 39 ; preferably have a thickness of from 0 . 00120 to 0 . 00130 mils and most preferably have a thickness of 0 . 00125 mils . the thermoplastic material of the first and second adjacent layers 20 , 20 &# 39 ; aids in the retention and reflection of body heat and provides puncture resistance to the drape . the non - woven layer of absorbent material 22 may be attached to the first or second adjacent layer 20 , 20 &# 39 ;. the non - woven layer of absorbent material 22 must be able to absorb modest amounts of perspiration so as to not reduce the infrared reflecting properties of the drape . the non - woven layer of absorbent material 22 may accordingly be one or a blend of cotton , polyester , rayon , polypropylene or cellulose . the non - woven layer of absorbent material 22 preferably has a thickness of from 0 . 0015 to 0 . 040 mils and most preferably has a thickness of 0 . 014 to 0 . 016 mils . the non - woven layer 22 is preferably attached to the first or second adjacent layer 20 , 20 &# 39 ; using an adhesive . the adhesive is preferably moisture - proof and is most preferably an acrylic moisture - proof adhesive . the non - woven layer of absorbent material 22 absorbs perspiration to prevent maceration of the skin of the patient and provides general comfort to the patient . in a preferred embodiment of the present invention , the second adjacent layer 20 &# 39 ; is omitted and the non - woven layer of absorbent material 22 is attached to the core layer 18 of non - conductive aluminum . the non - woven layer of absorbent material 22 is preferably attached to the core layer 18 of non - conductive aluminum using an adhesive . the adhesive is preferably moistureproof and is most preferably an acrylic moisture - proof adhesive . in another preferred embodiment of the present invention , the non - woven layer of absorbent material 22 is omitted . in this embodiment , the surgical drape of the present invention comprises the core layer 18 of non - conductive aluminum and the first and second adjacent layers 20 , 20 &# 39 ;. the reflective surgical drape of the present invention was tested for conductivity . the tests conducted utilized both 60 cycle per second current ( line power ) and radio frequency current ( electrosurgical power ). contact to the material was made with standard monitoring electrodes as well as by mechanically abrading the surface of the material . at 120 volts 60 cycle per second the resistance was determined to be in excess of 1 megaohm and well within the range of safety . at frequencies common to electrosurgery units it was determined that the material passed less than 1 / 10 the current ( or 1 / 100 the power ) that would pass through a patient at a maximum power of over 100 watts r . f . from an electrosurgical generator . this test simulated a worst case scenario of applying a cutting electrode directly to the reflective surgical drape . the inability of the reflective surgical drape of the present invention to conduct current is attributable to the layer of aluminum that is vacuum deposited on the thermoplastic layer . the aluminum layer would need to be many times thicker to perform as a conductor in a significant manner . these tests indicate that the reflective surgical drape of the present invention poses no problem when used in the presence of line voltage or electrosurgical generators . the reflective surgical drape of the present invention provides many safety features , the most important of which are its nonconductivity and its resistance to puncture . the drape is also inert to alcohol and betadine which insures that the drape maintains its integrity throughout a surgical procedure . the non - woven layer of absorbent material also absorbs perspiration to prevent maceration of the skin of the patient and to maintain the infrared reflecting properties of the drape . patients admitted for elective neurological , maxillofacial , gynecological and urological surgery were randomly assigned to treatment or control groups . control group patients were draped in a conventional manner for the surgical procedure . treatment group patients were draped in the same manner with the addition of the reflective surgical drape of the present invention placed closest to the patient prior to standard draping . all other treatment of the two groups was similar . the body temperature of each patient was systematically recorded with an oropharyngeal thermistor probe placed immediately after induction of general anesthesia . neurological and maxillofacial patients designated group a were draped with a full length section ( shoulder to foot ) of the reflective surgical drape of the present invention while urologic and gynecologic patients designated group b were draped with a half sheet section ( upper chest / abdomen ) and leggings made of the reflective surgical drape of the present invention . the induction temperature for both treatment and control groups was similar ( approximately 36 . 5 ° c ., p & gt ; 0 . 5 ). the average duration of surgery for group a patients was 1 . 75 hours , while the average duration of surgery for group b patients was 7 . 5 hours . the recorded temperature at the end of the procedure for group a patients was 37 . 2 ± 0 . 6 for treatment patients and 35 . 0 ± 0 . 5 for control patients ( p & lt ; 0 . 01 ). the recorded temperature at the end of the procedure for group b patients was 35 . 9 °± 0 . 3 ° c . for treatment patients and 34 . 7 °± 0 . 5 ° c . for control patients ( p & lt ; 0 . 01 ). group a and b control group patients experienced temperature decreases of an average of 1 . 6 ° to 1 . 8 ° c . which was statistically significant . group a and b treatment group patients experienced temperature decreases averaging 0 . 4 ° c ., which was not statistically significant . the results for group a and b patients are found in table i below and are shown graphically in fig4 and 5 , respectively . table 1______________________________________ temp starting ending______________________________________group a ( neurological , maxillofacial ) with drape 36 . 6 ± 0 . 3 37 . 2 ± 0 . 6 ( n = 20 ) without drape 36 . 6 ± 0 . 4 35 . 0 ± 0 . 5 * ( n = 20 ) group b ( gynecological , urological ) with drape 36 . 4 ± 0 . 4 35 . 9 ± 0 . 3 ( n = 20 ) without drape 36 . 5 ± 0 . 3 34 . 7 ± 0 . 5 * ( n = 20 ) ______________________________________ * statistically significant difference from starting temperature ( p & lt ; 0 . 01 ). one can conclude from these results that patients who were draped with the reflective surgical material of the present invention developed significantly less reduction in oropharyngeal temperature compared to control patients . in fact , in the majority of neurosurgical procedures in which the patient was draped with the reflective surgical drape of the present invention all other warming devices ( i . e . humidifier , heating pads , warmed intravenous fluids ) standardly used were discontinued due to maintenance of normal body temperature with the reflective surgical drape alone . no adverse effects were noted in any case in which the reflective drape material was used . while the present invention has been described in detail and with reference to specific examples thereof , it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof . | 1 |
referring to fig1 and 2 in one type of plastic blow molding machine shown in u . s . pat . no . 4 , 549 , 865 , there is disclosed the blow molding apparatus for embodying the invention that comprises a frame 20 in which a shaft 21 is mounted for rotation about horizontal axis by spaced bearings in cantilever fashion . a wheel plate 22 is mounted on the shaft 21 for rotation with the shaft 21 and supports a plurality of circumferentially spaced slide assemblies 23 . a hub 25 is also mounted on the shaft and has a plurality of circumferentially spaced mold supporting surfaces 26 corresponding in number to the number of slide assemblies 23 . each slide assembly 23 comprises mold section mounting means for supporting a section or part 27 of mold and the corresponding surface 26 of the hub 25 supports the second section 28 of a mold . each slide assembly 23 is adapted to move the mold section 27 toward and away from the other mold section 28 to close about a plasticized parison emanating from an extruder head 29 so that the parison can be blown to the shape of the mold cavity defined by the mold sections 27 , 28 as the wheel rotates . the parison is provided from the head 29 of an extruder in the two o &# 39 ; clock position as shown in fig1 . wheel plate 22 is rotated by a gear 30 driven by a motor 31 and meshing with a gear 32 on the periphery of the wheel plate 22 . each slide assembly 23 includes a cam follower 33 which engages a fixed arcuate cam 34 on the frame 20 to move mold section 27 toward and away from mold section 28 . a second cam follower 35 on each slide assembly 23 engages a second fixed cam 36 on frame 20 to hold the mold sections 27 , 28 in closed and clamped position . second cam 36 extends generally from the three o &# 39 ; clock position to just beyond the nine o &# 39 ; clock position as viewed in fig1 . the specific structure of each slide assembly 23 is disclosed and claimed in u . s . pat . no . 4 , 648 , 831 , which is incorporated herein by reference . an air valve assembly 42 is provided on each slide assembly 23 and is actuated by an actuator 43 along the path of the molds that functions to turn the blow air on for blowing the article and another actuator 44 is provided along the path to function to turn the air valve assembly 42 off , thereby cutting off the flow of blow air to the blowing apparatus . each valve assembly 42 includes an on - off valve 45 that functions to control the flow of blow air to a valve block 46 and , in turn , through lines 47 to a blow pin ( not shown ) which functions to provide blow air for blowing the hollow article when the molds are closed , in a manner well known in the art . the valve assemblies 42 and actuator assemblies 43 , 44 are disclosed and claimed in u . s . pat . no . 4 , 523 , 904 , which is incorporated herein by reference . in operation , the plastic material is continuously extruded in tubular form from the head 29 of the extruder and flows downwardly between the mold sections 27 , 28 . as the wheel plate continues to rotate , the mold sections 27 , 28 are brought together for pinching the plastic material , and then air is supplied to the interior of the tubular parison to blow the article in a manner well know in the art . as the article reaches the position when the blow mold is open ( 12 o &# 39 ; clock position as viewed in fig1 ), a fixed actuator 49 contacts an ejector on each mold section 28 to eject the articles onto a conveyor . in accordance with the invention , a vacuum cup conveyor system 60 is positioned to extend between the molds , when the molds are open , and receive the falling containers which have been molded , and grab the containers and move them in an oriented fashion to a delivery conveyor 62 ( fig4 ) to the trimming apparatus which may be of the type shown in u . s . pat . no . 4 , 614 , 018 , incorporated herein by reference . conveyor 62 is also of the endless belt type ( fig3 and 4 ) and , as best seen by the conveyor framework illustrated in fig7 delivery conveyor 62 is adjustable angularly with respect to vacuum conveyor 60 . each container c includes a body portion b and a moil portion m ( fig4 ). referring to fig2 and also to fig3 - 7 , the vacuum cup conveyor 60 comprises an endless belt 64 which supports a plurality of hollow stem vacuum cups 66 ( fig5 ) each of which has a diameter which is substantially less than the diameter of the body portion b of the container c . as shown in fig5 the belt 64 is trained over pulleys 68 , 70 and is supported between the pulleys by a plenum 72 that has an upper wall with openings 74 communicating with associated plenum troughs that in turn communicate with openings in the belt provided by the hollow stems of cups 66 , the troughs extending below the travel path of each vacuum cup 66 . as further shown in fig5 the plenum 72 is positioned so that the lower reach of the belt 64 is below the plenum 72 . vacuum is supplied to the plenum 72 such that the portion of the belt passing over the plenum is supplied with vacuum . preferably , an endless belt 76 ( fig2 and 3 ) is provided for supporting the generally planar moil m of each container as the container accelerates and is moved toward the trimming apparatus . the vacuum cup conveyor 64 is driven in timed relationship with an endless belt delivery conveyor 80 through a timing belt 82 and associated pulleys 84 , 86 , ( fig3 and 4 ) driven by motors d . in ( fig7 ) similar fashion the moil belt 76 is driven in timed relationship . the size and spacing of the vacuum cups is selected such that at least one and preferably two or more vacuum cups contact the body of the container diametrically and at least two and preferably three or more vacuum cups contact the container axially . in addition , the vacuum cups are in substantial tangential relationship . in order to maximize contact , the vacuum cups are provided in rows extending transversely of the conveyor belt and which rows are inclined at an angle to the direction of movement of the vacuum conveyor as best seen in fig4 . as each pair of containers c fall from the open mold when the vacuum is released holding the container in the upper mold , the pair of containers is immediately grabbed by the vacuum cups so that the axes of the containers remain parallel to that of the mold so that any rotation about the axis of the container is prevented . as a result , the moil m remains horizontal as it was in the mold . each pair is thus oriented and spaced for direct delivery on the trimming apparatus such as shown in the u . s . pat . no . 4 , 616 , 018 . | 8 |
referring to fig2 , and 6 , a lifting mechanism and treadmill arrangement 100 is composed of a base frame 10 , a treadbase 20 , two links 30 , a treadbase motor 40 , and a lifting mechanism 50 . the base frame 10 includes two parallel side bars 11 , a transverse bar 12 connected between rear ends of the side bars 11 , a supplementary bar 13 connected between front sections of the side bars 11 , a guide member embodied as guide frame 14 connected between the transverse bar 12 and the supplementary bar 13 and arranged in parallel to the side bars 11 , and a buffer block 15 provided in the guide frame 14 . the guide frame 14 includes two vertical side plates 141 and a bottom plate 142 . the side plates 141 each have a longitudinal sliding slot 143 defining a first dead point 144 and a second dead point 145 . the buffer block 15 is fixedly mounted in the guide frame 14 adjacent to the first dead point 144 . the treadbase 20 includes a treadbase frame 21 and an endless belt 22 . a receiving space 23 is defined between the treadbase frame 21 and a front side of the endless belt 22 . the two links 30 are bilaterally mounted near a front side of the treadbase frame 21 , each having a first coupling end portion 31 and a second coupling end portion 32 . the coupling end portion 31 is connected pivotally with a front end of the side bar 11 of the base frame 10 , defining a respective pivot a . the second coupling end portion 32 is connected pivotally with the front side of the treadmill base 21 , defining a respective pivot b . accordingly , the treadbase 20 can be turned about the pivot a between an operative position p 1 ( see fig2 ) and a non - operative position p 2 ( see fig6 ). the treadbase motor 40 is fixedly mounted in the receiving space 23 of the treadbase 20 and is controlled to rotate the endless belt 22 through a belt transmission mechanism 41 . the lifting mechanism 50 includes an inclining motor 51 , an internally threaded barrel 52 , a push member 53 , and stop means embodied as a stop pin 54 . the inclining motor 51 is mounted pivotally on the treadbase frame 21 . the barrel 52 has an end fixedly mounted to the inclining motor 51 . the push member 53 is a screw rod threaded into the barrel 52 . the stop pin 54 runs through a transverse through hole ( not shown ) at a front end of the push member 53 outside the barrel 52 , having two distal ends respectively inserted through the sliding slots 143 of the vertical side plates 141 of the guide frame 14 ( see fig6 ). when the inclining motor 51 is operated , the push member 53 is rotated in or out of the barrel 52 , thereby causing the stop pin 54 to move along with the push member 53 between the first dead point 144 and the second dead point 145 . the control of the angle of inclination of the treadbase 20 is described hereinafter . as illustrated in fig3 when the treadbase 20 is positioned horizontally , the push member 53 is received in the barrel 52 , the stop pin 54 is stopped at the first dead point 144 and the front end of the push member 53 is stopped against the buffer block 15 . when the treadbase 20 is controlled to lift , as shown in fig4 the inclining motor 51 is driven to rotate the push member 53 out of the barrel 52 . because the front end of the push member 53 is stopped against the buffer block 15 and the links 30 are coupled between the treadbase 20 and the base frame 10 , the push member 53 is rotated out of the barrel 52 and the front side of the treadbase 20 is lifted to change its angle of inclination , as shown in fig5 . when the treadbase 20 is turned to the non - operative position p 2 , the front side of the treadbase 20 is lowered to the position shown in fig3 ( where the push member 53 received in the barrel 52 ), and then a rear side of the treadbase 20 is lifted with hands . when turning the treadbase 20 about the pivots a to lift the rear side of the treadbase 20 , the stop pin 54 is moved along the sliding slots 143 toward the second dead point 145 , and at the same time the inclining motor 51 is rotated for enabling the treadbase 20 to be smoothly turned about the pivots a to the position shown in fig6 where the stop pin 54 is stopped at the second dead point 145 . lock means may be used to lock the treadbase 20 in the non - operative position . because the lock means can easily be obtained from known techniques and is not within the scope of the claims of the present invention , nor further detailed description in this regard is necessary . according to the aforesaid description , the present invention has advantages as follows : 1 . when the treadbase 20 is set horizontally , as shown in fig2 the treadbase motor 40 and the inclining motor 51 are received in the receiving space 23 without interfering each other , i . e . the treadmill does not occupy much vertical storage space when set horizontally . 2 . when the treadbase 20 is set in the operative position p 1 , the lifting mechanism 50 is held horizontally without hindering the front end of the treadbase 20 . 3 . the front side of the treadbase 20 is controlled to stably lift by means of the support of the lifting mechanism 50 , the guide frame 14 of the base frame 10 , and the links 30 . | 0 |
referring now to fig1 there is shown a video / audio simultaneous transmission system embodying the invention . in the figure , an audio signal is supplied from an input terminal 1 to an audio signal encoder 3 , while a video signal is supplied from an input terminal 2 to a sync signal separator 5 and also to a video signal encoder 4 . a clock generator 6 provides an audio sampling clock signal ( a second clock ), which is supplied to the audio signal encoder 3 and also to a time adjusting circuit 71 in a multiplexer circuit 7 . the clock generator 6 also provides a video sampling clock signal ( a first clock ), which is supplied to the video signal encoder 4 and also to a control circuit 72 in the multiplexer circuit 7 . the audio signal encoder 3 samples the audio signal under the control of the audio sampling clock signal and encodes the sampled audio signal . the encoded audio signal data thus obtained is supplied as a signal f to the time adjusting circuit 71 of the multiplexer circuit 7 . the video signal encoder 4 samples the video signal under the control of the video sampling clock signal and encodes the sampled video signal . the encoded video signal data thus obtained is supplied as a signal h to a switching circuit 73 in the multiplexer circuit 7 . the sync signal separator 5 separates the horizontal sync signal contained in the video signal and supplies it as a sync signal a to a sync signal switching circuit 8 , which in turn connected to the control circuit 72 in the multiplexer 7 to supply the same with a signal u . the multiplexer 7 , which receives the individual signals noted above , successively supplies a special code word for word synchronization and encoded audio and video data to a parallel - to - serial converter 10 as will be described later in detail . assuming now that the sync signal switching circuit 8 is omitted and the separator 5 is directly coupled to control circuit 72 as in the prior art mentioned above , when a signal representing the commencement of the horizontal sync signal appears in the signal a ( hereinafter referred to a sync signal ), the control circuit 72 in the multiplexer 7 now receiving the sync signal a instead of the signal u ( modified sync signal ) supplies a signal d indicative of suspension of the encoding of the video signal to the time adjusting circuit 71 and video signal encoder 4 and also supplies a signal b which contains a signal indicative of the sending of special code word and a special code word , to the switching circuit 73 . when the time adjusting circuit 71 receives the signal d indicative of the suspension of the encoding of the video signal , it supplies an encoded audio data having been received within a time interval between the occurrence of the preceding video encoding suspension signal and the occurrence of the instant signal d as a signal g to the switching circuit 73 . when the video encoder 4 receives the video encoding suspension signal d , it stops the encoding of the video signal or stops the sending of the signal h . the switching circuit 73 includes a switch group for switching the signal g , signal h and special code word . when the switching circuit 73 receives the signal e , it supplies the special code word and thereafter the encoded audio data during the period of presence of the signal indicative of the suspension of the encoding of the video signal . when the video signal encoding suspension signal vanishes , the switching circuit 73 then supplies the encoded video data . the multiplexer circuit 7 thus supplies the special code word and encoded audio and video data successively as a signal k . the parallel - to - serial converter 10 receives the signal k , which is a parallel signal , and converts it into a serial signal under the control of a transmission channel clock signal ( a third clock ) fed from the clock generator 6 . the serial signal thus obtained is sent out from an output terminal 11 . fig2 a shows an example of signals appearing at various points in the system of fig1 . at an instant a ( or f ), at which a horizontal sync signal corresponding to an encircled portion in the video signal as shown in fig2 b appears , a pulse of the sync signal a rises , indicating the commencement of the horizontal sync signal . without the sync signal switching circuit 8 , when the control circuit 72 in fig1 receives the sync signal a , it supplies a pulse signal b , which falls at the instant a and rises again at an instant b after the lapse of a predetermined period . the control circuit 72 also supplies a pulse signal d , which falls at the instant a and rises again at an instant e after the lapse of a predetermined period . further , the control circuit 72 supplies a signal c containing a special code word s during a period from the instant a till the instant b . as mentioned earlier , the signal d is supplied to the video encoder 4 and also to the time adjusting circuit 71 in fig1 and the signal e which contains the parallel signals b , c and d is supplied to the switching circuit 73 in fig1 . the special code word s has a code pattern , the use of which is inhibited in the encoded audio and video data , and it is used for establishing word synchronization . when the time adjusting circuit in fig1 receives the signal d , it supplies a signal f , which consists of an encoded audio data vi that has been supplied from the audio encoder 3 between the instant a at which the pulse d falls and an instant at which a preceding pulses d rises , as a multiplexed signal g during a period from the instant a till an instant f . in case when the encoded audio data within the same audio sampling clock period occurs both in the encoded audio data vi from the instant a till the instant f and in an ensuing encoded audio data vj from the instant f , a predetermined dummy code is provided in lieu of the latter encoded audio data . when the video encoder 4 receives the signal d , it supplies encoded video data d as a signal h for a period from the rising till the falling of the pulse of the signal d . in the switching circuit 73 , the switch group is switched according to the signals b and c contained in the signal e . the switching circuit 73 supplies as the signal k the special code word s for a period from the instant a till the instant b , the encoded audio data vi for a period from the instant b till the instant e and the encoded video data d for a period from the instant e till the instant f . the signal k is supplied as a parallel signal having a predetermined number of bits to the parallel - to - serial converter 10 in fig1 for conversion into a serial signal , which is sent out of the output terminal 11 . in the system of fig1 the audio signal encoder 3 may be constituted by an ordinary a / d converter , and the video signal encoder 4 by a dpcm ( difference pcm ) encoder . the control circuit 72 may be constructed as shown in fig3 . more particularly , the sync signal a indicaive of the commencement of the horizontal sync signal is read into a shift register 300 under the control of the first clock . through two nand gates 301 and 302 , the signal b indicative of the generation of the special code is sent onto a line 303 and the suspension signal d is sent onto a line 305 . if the number of bits sent out during one sampling period is 8 , the special code in the form of 8 - bit parallel code will be produced from a pattern generator 306 which is controlled by tap outputs from the first to sixth stages of the shift register 300 . the time adjusting circuit 71 may have a construction as shown in fig4 which operates in accordance with signals shown in fig5 . the encoded audio data f ( in the form of 8 bits , for example ) as shown at 501 in fig5 is written into an input register 400 under the control of the second clock as shown at 500 in fig5 . an output signal as shown at 502 in fig5 is fed to an output register 401 in response to the suspension signal d as shown at 503 in fig5 thereby being brought into synchronization with the timing for the special code . in this synchronization , a phase jump will occur as shown by a hatched pulse in the suspension signal 503 , which phase jump may be corrected by transmission of a specified dummy code . the phase jump can be detected at a phase jump detector 402 by sampling the second clock 500 on the basis of the suspension signal 503 . when the phase jump is detected , a dummy code insertion designating pulse 505 is produced from the detector 402 to control a signal switching circuit 403 . in this switching circuit , a movable contact 403 - 1 is normally transferred to a stationary contact 403 - 2 to pass the encoded audio signal from the output register 401 which is synchronized with the timing for the special code , and at an instant at which the dummy code insertion designating pulse occurs , the movable contact 403 - 1 is transferred to a stationary contact 403 - 3 to ensure that a specified dummy code ( phase jump information ) can be inserted . the switching circuit 73 may be constructed as shown in fig6 . respective output lines 601 to 608 are connected to 1 out of 3 selectors which select one input out of three inputs . normally , contacts 612 - 1 to 612 - 8 are selected so that 8 bits of the encoded video signal h are successively sent to the output lines 601 to 608 . when signal b is in its low level , contacts 610 - 1 to 610 - 8 are sequentially selected to send out &# 34 ; 1111 &# 34 ;, &# 34 ; 0000 &# 34 ;, &# 34 ; 0000 &# 34 ;, &# 34 ; 0000 &# 34 ;, &# 34 ; 0000 &# 34 ; and &# 34 ; 1111 &# 34 ;. after signal b resumes its high level and while signal d is in its low level , contacts 611 - 1 to 611 - 8 are selected so that 8 bits of voice signal g are successively sent to the output lines 601 to 608 . after 8 bits of the encoded audio signal have been sent out , the switching circuit 73 returns to the normal operation in which the contacts 612 - 1 to 612 - 8 are selected . in the foregoing description , the system of fig1 has been described on the assumption that the sync signal switching circuit 8 is omitted . when the sync signal switching circuit 8 is added , it receives the sync signal a from the sync signal separator 5 and also receives the video sampling clock signal from the clock generator 6 to thereby produce a local sync signal and a time window signal . thus , the sync signal switching circuit 8 decides whether the signal that appears first in a predetermined period of time is the sync signal a or the local sync signal , and supplies the signal that appears first as the modified sync signal u to the control circuit 72 in the multiplexer 7 . fig7 is a block diagram showing the sync signal switching circuit 8 . the sync signal a supplied from the sync signal separator 5 passes through a leading edge differntiating circuit 91 in a switching control section 9 and is supplied as a signal l to and gates 95 and 96 . the signal a is also supplied through a &# 34 ; not &# 34 ; gate 93 to an and gate 97 . in a signal generating section 13 , a counter 20 counts clock pulses of the video sampling clock signal supplied from the clock generator 6 , and its count is supplied to a signal generating circuit 21 . the signal generating circuit 21 includes a read only memory ( rom ) and a register . in response to the count data supplied from the counter 20 , data stored in a location of the rom corresponding to the count is read out into the register , whereby signals m and n are provided . the signals m and n are respectively a time window signal and a local sync signal . the signal m is fed to the and gate 95 in the switching section 9 and is also fed through a &# 34 ; not &# 34 ; gate 94 to the and gate 96 . the signal n is passed through a leading edge differentiating circuit 92 in the switching control section 9 to be supplied as a signal p to the and gate 97 . a signal q provided from the and gate 95 is fed as a set input to a flip - flop 99 . signals provided from the and gates 96 and 97 are passed through an or gate 98 to be fed as a reset signal r to the flip - flop 99 . a signal t is supplied from the flip - flop 99 to a signal switching section 12 . the signal switching section 12 receives the signals a and n , and in response to the signal t it supplies either signal a or n as a modified sync signal u to the control circuit 72 in the multiplexer 7 shown in fig1 . the modified sync signal u is also supplied as a reset signal to the couner 20 . fig8 is a waveform chart for explaining an example of the operation of the circuit of fig7 . the sync signal a supplied from the sync signal separator 5 in fig1 is subjected to leading edge differentiation to obtain a signal l . when a pulse of the signal l appears , a pulse appears as the signal q to set the flip - flop 99 in fig7 if the signal m , i . e ., time window signal , is at a high level ( hereinafter referred to as h level ) at this time . as a result , the output signal t of the flip - flop 99 goes to an h level , causing the signal switching section 12 in fig7 to pass the sync signal a as the modified sync signal u . the pulse that appears as the modified sync signal u is fed to the counter 20 in fig7 to reset the same . as a result , the signal m goes to a low level ( hereinafter referred to as l level ). the signal m remains at the l level for a predetermined period t1 ( which ends at an instant t1 ) from the appearance of the pulse as the modified sync signal u . after the lapse of the period t1 , the signal m goes to the h level . thus , the signal m serves as the time window signal . the signal n remains at the l level for a predetermined period t2 of time from the appearance of the pulse of the signal u , and after the lapse of the period t2 ( which ends at an instant t2 ) it goes to the h level . thus , the signal n serves as the local sync signal . when a pulse of the sync signal a appears after the appearance of the pulse of the signal u and before the pulse of the signal n while the signal m is at the l level , a pulse appears as the signal r to reset the flip - flop 99 in fig7 . as a result , the signal t from the flip - flop 99 goes to the l level , causing the signal switching section 12 in fig7 to pass the signal n as the modified sync signal u . that is , the insertion of the pulse of the sync signal a in the modified sync signal u is inhibited , so that the pulse of the modified sync signal u does not appear . if no pulse appears as the sync signal a during the period from the appearance of the pulse of the modified sync signal u till the appearance of the pulse of the signal n , a pulse appears as the signal p , so that a pulse appears as the signal r to reset the flip - flop 99 in fig7 . thus , the signal t from the flip - flop 99 goes to the l level , causing the signal switching section 12 in fig7 to pass the pulse of the signal n as the modified sync signal u . the pulse appearing as the modified sync signal u is also fed to the counter 20 in fig7 to reset the same . as has been described , if the interval ta of pulses appearing as the sync signal a , meets a condition t1 ≦ ta & lt ; t2 , the circuit shown in fig7 passes the sync signal a as the modified sync signal u . if the above condition is not met , the circuit inhibits the pulse of the sync signal a and , instead , supplies the signal n , i . e ., the local sync signal . subsequently , if the time interval tb between the pulse appearing as the modified sync signal u and the following pulse appearing as the sync signal a meets a condition t1 ≦ tb & lt ; t2 , the circuit of fig7 inserts the sync signal a in the modified sync signal u ; while the condition is not met , it inserts the signal n in the modified sync signal u . thus , the time interval tu of pulses of the modified sync signal u supplied to the control circuit 72 in the multiplexer 7 in fig1 always satisfies a condition t1 ≦ tu & lt ; t2 . the periods t1 and t2 are set as follows . if the periods t1 and t2 are so selected as to meet conditions t1 & gt ;( n &# 39 ;- 1 ) tv and t2 & lt ; n &# 39 ; tv , where th is the reference value of the horizontal sync signal period , tv is the audio sampling clock signal period and n &# 39 ; ( being an integer greater than 1 ) is the number of encoded audio data transmitted in one horizontal sync signal period , n &# 39 ; or n &# 39 ;- 1 audio sampling signals can be obtained between individual pulses appearing in the modified sync signal u . a drop - out or a large phase jump in the horizontal sync signal in the video signal usually occurs in the neighborhood of the vertical retrace period . therefore , even if the video encoding suspension period is slightly deviated with the switching over to the local sync signal at the time of the occurrence of a drop - out or large phase jump in the horizontal sync signal , this has no substantial adverse effect on the video reproduction . further , in normal situation without occurrence of any drop - out or large phase jump , the fluctuations of the horizontal sync signal period are very slight and about 0 . 1 % at the most . it will be seen that the period from the instant of switching over to the local sync signal due to a drop - out or large phase jump in the horizontal signal till the instant of switching over to the normal horizontal sync signal again , correspons to tv /( t2 - th ) lines at the most , and the retrace period mentioned above can be reduced by setting the period t1 , i . e ., the local sync signal period , to be equal to the maximum value in the range t2 n &# 39 ; tv . the system of fig1 added with the circuit 8 operates in the same way as the prior art except that the signal provided from the sync signal switching circuit 8 is supplied to the control circuit 72 in the multiplexer 7 . thus , by setting the periods t1 and t2 such as described above , video / audio simultaneous transmission can be obtained without having substantial adverse effect on the video and without possibility of occurrence of a drop - out of the encoded audio data . fig9 is a modification of the sync signal switching circuit 8 . in fig9 the sync signal a supplied from the sync signal separator 5 is fed to one input terminal of an or gate 31 . counters 33 and 34 count pulses of the clock signal supplied from the clock generator 6 and produce the time window signal and local sync signal respectively . more particularly , the counter 33 produces the time window signal , which is at the h level while the count is less than a predetermined small value m and goes to the l level when the count exceeds the value m . the counter 34 produces a local sync signal pulse , which goes to the h level when the count reaches a value n greater than the value m . the local sync signal is supplied to the other input terminal of the or gate 31 , and the output signal of the or gate 31 is fed to one input terminal of an and gate 32 . the time window signal is passed through a &# 34 ; not &# 34 ; gate 35 to be fed to the other input terminal of the and gate 32 . the output signal from the and gate 32 is supplied to the control circuit 72 in the multiplexer 7 in fig1 and also it is fed to the counters 33 and 34 to reset these counters . during the period t1 from the instant when the counter 33 is reset by the pulse supplied to the control circuit 72 till the instant when the count of the counter 33 reaches m , the signal supplied from the &# 34 ; not &# 34 ; gate 35 to the and gate 32 is at the l level . therefore , during this period any sync signal pulse is not passed through the and gate 32 , that is , the transmission of the sync signal is inhibited . during the period ( t2 - t1 ) from the instant after the lapse of the period t1 of resetting of the counters 33 and 34 till the instant when the count of the counter 34 reaches n , the signal supplied from the &# 34 ; not &# 34 ; gate 35 to the and gate 32 is at the h level . thus , a sync signal pulse appearing during this period is passed through the and gate 32 to be fed to the control circuit 72 , while also resetting the counters 33 and 34 . further , if no sync signal pulse appears during the period t2 from the instant of resetting of the counter 34 till the instant when the count reaches n , the local sync signal pulse output of the counter 34 is passed through the and gates 31 and 32 to the control circuit 72 , while also the counters 33 and 34 are rest . with the circuit of fig9 used as the sync signal switching circuit 8 in the system of fig1 the same operation as in the fig7 arrangement thus can be obtained . as has been described in the foregoing , with the video / audio simultaneous transmission system accoding to the invention , it is possible to effect simultaneous transmission of audio signals stably and accurately without need of greatly increasing the scale and complexity of hardware even in a case of a video signal subject to a drop - out or a large phase jump in the horizontal sync signal by allowing a local sync signal to be used when the instant of appearance of the horizontal sync signal deviates from a predetermined time range . further , the &# 34 ; off &# 34 ; state of the video signal can be detected by counting local sync signal pulses for a predetermined period of time , so that it is possible to dispense with the conventional video &# 34 ; off &# 34 ; detection circuit and reduce the scale of the hardware . | 7 |
this invention provides novel compounds , and pharmaceutically acceptable derivatives thereof , that are useful as jnk inhibitors . these compounds have the general formula i : r 1 is h , conh 2 , t ( n ) — r , or t ( n ) — ar 2 ; r is an aliphatic or substituted aliphatic group ; n is zero or one ; t is c (═ o ), co 2 , conh , s ( o ) 2 , s ( o ) 2 nh , coch 2 or ch 2 ; each r 2 is independently selected from hydrogen , — r , — ch 2 or , — ch 2 oh , — ch ═ o , — ch 2 sr , — ch 2 s ( o ) 2 r , — ch 2 ( c ═ o ) r , — ch 2 co 2 r , — ch 2 co 2 h , — ch 2 cn , — ch 2 nhr , — ch 2 n ( r ) 2 , — ch ═ n — or , — ch ═ nnhr , — ch ═ nn ( r ) 2 , — ch ═ nnhcor , — ch ═ nnhco 2 r , — ch ═ nnhso 2 r , - aryl , - substituted aryl , — ch 2 ( aryl ), — ch 2 ( substituted aryl ), — ch 2 nh 2 , — ch 2 nhcor , — ch 2 nhconhr , — ch 2 nhcon ( r ) 2 , — ch 2 nrcor , — ch 2 nhco 2 r , — ch 2 conhr , — ch 2 con ( r ) 2 , — ch 2 so 2 nh 2 , — ch 2 ( heterocyclyl ), — ch 2 ( substituted heterocyclyl ), -( heterocyclyl ), or -( substituted heterocyclyl ); each r 3 is independently selected from hydrogen , r , cor , co 2 r or s ( o ) 2 r ; g is r or ar 1 ; ar 1 is aryl , substituted aryl , aralkyl , substituted aralkyl , heterocyclyl , or substituted heterocyclyl , wherein ar 1 is optionally fused to a partially unsaturated or fully unsaturated five to seven membered ring containing zero to three heteroatoms ; q — nh is wherein the h of q — nh is optionally replaced by r 3 ; a is n or cr 3 ; u is cr 3 , o , s , or nr 3 ; ar 2 is aryl , substituted aryl , heterocyclyl or substituted heterocyclyl , wherein ar 2 is optionally fused to a partially unsaturated or fully unsaturated five to seven membered ring containing zero to three heteroatoms ; and wherein each substitutable carbon atom in ar 2 , including the fused ring when present , is optionally and independently substituted by halo , r , or , sr , oh , no 2 , cn , nh 2 , nhr , n ( r ) 2 , nhcor , nhconhr , nhcon ( r ) 2 , nrcor , nhco 2 r , co 2 r , co 2 h , cor , conhr , con ( r ) 2 , s ( o ) 2 r , sonh 2 , s ( o ) r , so 2 nhr , or nhs ( o ) 2 r , and wherein each saturated carbon in the fused ring is further optionally and independently substituted by ═ o , ═ s , ═ nnhr , ═ nnr 2 , ═ n — or , ═ nnhcor , ═ nnhco 2 r , ═ nnhso 2 r , or ═ nr ; wherein each substitutable nitrogen atom in ar 2 is optionally substituted by r , cor , s ( o ) 2 r , or co 2 r . as used herein , the following definitions shall apply unless otherwise indicated . the term “ aliphatic ” as used herein means straight chained , branched or cyclic c 1 - c 12 hydrocarbons , preferably one to six carbons , which are completely saturated or which contain one or moreunits of unsaturation . for example , suitable aliphatic groups include substituted or unsubstituted linear , branched or cyclic alkyl , alkenyl , alkynyl groups and hybrids thereof such as ( cycloalkyl ) alkyl , ( cycloalkenyl ) alkyl or ( cycloalkyl ) alkenyl . the term “ alkyl ” and “ alkoxy ” used alone or as part of a larger moiety refers to both straight and branched chains containing one to twelve carbon atoms . the terms “ alkenyl ” and “ alkynyl ” used alone or as part of a larger moiety shall include both straight and branched chains containing two to twelve carbon atoms . the terms “ haloalkyl ”, “ haloalkenyl ” and “ haloalkoxy ” means alkyl , alkenyl or alkoxy , as the case may be , substituted with one or more halogen atoms . the term “ halogen ” means f , cl , br , or i . the term “ heteroatom ” means n , o or s and shall include any oxidized form of nitrogen and sulfur , and the quaternized form of any basic nitrogen . the term “ aryl ”, used alone or as part of a larger moiety as in “ aralkyl ”, refers to aromatic ring groups having five to fourteen members , such as phenyl , benzyl , 1 - naphthyl , 2 - naphthyl , 1 - anthracyl and 2 - anthracyl , and heterocyclic aromatic groups or heteroaryl groups such as 2 - furanyl , 3 - furanyl , n - imidazolyl , 2 - imidazolyl , 4 - imidazolyl , 5 - imidazolyl , 3 - isoxazolyl , 4 - isoxazolyl , 5 - isoxazolyl , 2 - oxadiazolyl , 5 - oxadiazolyl , 2 - oxazolyl , 4 - oxazolyl , 5 - oxazolyl , 2 - pyrrolyl , 3 - pyrrolyl , 2 - pyridyl , 3 - pyridyl , 4 - pyridyl , 2 - pyrimidyl , 4 - pyrimidyl , 5 - pyrimidyl , 3 - pyridazinyl , 3 - pyridazinyl , 2 - thiazolyl , 4 - thiazolyl , 5 - thiazolyl , 5 - tetrazolyl , 2 - triazolyl , 5 - triazolyl , 2 - thienyl , or 3 - thienyl . aryl groups also include fused polycyclic aromatic ring systems in which a carbocyclic aromatic ring or heteroaryl ring is fused to one or more other rings . examples include tetrahydronaphthyl , benzimidazolyl , benzothienyl , benzofuranyl , indolyl , quinolinyl , benzodiazepinyl , benzothiazolyl , benzooxazolyl , benzimidazolyl , isoquinolinyl , isoindolyl , acridinyl , benzoisoxazolyl , and the like . also included within the scope of the term “ aryl ”, as it is used herein , is a group in which one or more carbocyclic aromatic rings and / or heteroaryl rings are fused to a cycloalkyl or non - aromatic heterocyclyl , for example , indanyl or tetrahydrobenzopyranyl . the term ,“ heterocyclic ring ” or “ heterocyclyl ” refers to a non - aromatic ring which includes one or more heteroatoms such as nitrogen , oxygen or sulfur in the ring . the ring can be five , six , seven or eight - membered and / or fused to another ring , such as a cycloalkyl or aromatic ring . examples include 3 - 1h - benzimidazol - 2 - one , 3 - 1 - alkyl - benzimidazol - 2 - one , 2 - tetrahydrofuranyl , 3 - tetrahydrofuranyl , 2 - tetrahydropyranyl , 3 - tetrahydropyranyl , 4 - tetrahydropyranyl , 2 - tetrahydrothiophenyl , 3 - tetrahydrothiophenyl , 2 - morpholino , 3 - morpholino , 4 - morpholino , 2 - thiomorpholino , 3 - thiomorpholino , 4 - thiomorpholino , 1 - pyrrolidinyl , 2 - pyrrolidinyl , 3 - pyrrolidinyl , 1 - piperazinyl , 2 - piperazinyl , 1 - piperidinyl , 2 - piperidinyl , 3 - piperidinyl , 4 - piperidinyl , 4 - thiazolidinyl , diazolonyl , n - substituted diazolonyl , 1 - phthalimidinyl , benzoxane , benzotriazol - 1 - yl , benzopyrrolidine , benzopiperidine , benzoxolane , benzothiolane , and benzothiane . a compound of this invention may contain a ring that is fused to a partially saturated or fully unsaturated five to seven membered ring containing zero to three heteroatoms . such a fused ring may be an aromatic or non - aromatic monocyclic ring , examples of which include the aryl and heterocyclic rings described above . an aryl group ( carbocyclic and heterocyclic ) or an aralkyl group , such as benzyl or phenethyl , may contain one or more substituents . examples of suitable substituents on the unsaturated carbon atom of an aryl group include a halogen , — r , — or , — oh , — sh , — sr , protected oh ( such as acyloxy ), phenyl ( ph ), substituted ph , — oph , substituted — oph , — no 2 , — cn , — nh 2 , — nhr , — n ( r ) 2 , — nhcor , — nhconhr , — nhcon ( r ) 2 , — nrcor , — nhco 2 r , — co 2 r , — co 2 h , — cor , — conhr , — con ( r ) 2 , — s ( o ) 2 r , — sonh 2 , — s ( o ) r , — so 2 nhr , or — nhs ( o ) 2 r , where r is an aliphatic group or a substituted aliphatic group . an aliphatic group or a non - aromatic heterocyclic ring may contain one or more substituents . examples of suitable substituents on the saturated carbon of an aliphatic group or of a non - aromatic heterocyclic ring include those listed above for the unsaturated carbon , such as in an aromatic ring , as well as the following : ═ o , ═ s , ═ nnhr , ═ nnr 2 , ═ n — or , ═ nnhcor , ═ nnhco 2 r , ═ nnhso 2 r , or ═ nr . a substitutable nitrogen on an aromatic or non - aromatic heterocyclic ring may be optionally substituted . suitable substituents on the nitrogen include r , cor , s ( o ) 2 r , and co 2 r , where r is an aliphatic group or a substituted aliphatic group . compounds derived by making isosteric or bioisosteric replacements of carboxylic acid or ester moieties of compounds described herein are within the scope of this invention . isosteres , which result from the exchange of an atom or group of atoms to create a new compound with similar biological properties to the parent carboxylic acid or ester , are known in the art . the bioisosteric replacement may be physicochemically or topologically based . an example of an isosteric replacement for a carboxylic acid is conhso 2 ( alkyl ) such as conhso 2 me . it will be apparent to one skilled in the art that certain compounds of this invention may exist in tautomeric forms or hydrated forms , all such forms of the compounds being within the scope of the invention . unless otherwise stated , structures depicted herein are also meant to include all stereochemical forms of the structure ; i . e ., the r and s configurations for each asymmetric center . therefore , single stereochemical isomers as well as enantiomeric and diastereomeric mixtures of the present compounds are within the scope of the invention . unless otherwise stated , structures depicted herein are also meant to include compounds which differ only in the presence of one or more isotopically enriched atoms . for example , compounds having the present structures except for the replacement of a hydrogen by a deuterium or tritium , or the replacement of a carbon by a 13 c - or 14 c - enriched carbon are within the scope of this invention . such compounds are useful , for example , as analytical tools or probes in biological assays . one embodiment of this invention relates to compounds of formula i where the xyz - containing ring is an isoxazole , as shown by the general formula ia below : where r 2 is preferably alkyl , such as methyl , or ch 2 ( heterocyclyl ), such as ch 2 ( n - morpholinyl ); g is preferably ar 1 ; and r 1 is preferably t ( n ) — ar 2 or t ( n ) — r , wherein n is most preferably zero . most preferred are those compounds where g , r 1 , and r 2 are as just described , and q — nh is an aminopyridine or aminopyrimidine where the nh is at the 2 position of the ring : table 1 below shows representative examples of ia compounds where q is a pyrimidine , pyridine or pyrazole and r 1 is ar 2 , represented by formula iia . for compounds of formula iia where r 1 is phenyl , preferred phenyl substituents are selected from hydrogen and one or more halo , aliphatic , substituted aliphatic ( preferably haloalkyl ), alkoxy , cn , co 2 h , co 2 ( alkyl ), s ( alkyl ), conh 2 , co ( alkyl ), so 2 ( alkyl ), co ( phenyl ), or no 2 . preferred g groups are phenyl rings optionally substituted with one or more groups independently selected from alkyl , alkoxy or halogen . examples of compounds of formula iia where r 1 is other than phenyl are shown below in table 2 . preferred iia compounds are those where ar 1 is an unsubstituted phenyl or a phenyl substituted with one or more halo , alkyl or alkoxy . more preferred iia compounds are those where ar 1 is as just described , and ar 2 is a naphthyl or phenyl optionally substituted with one or more halo , alkyl , alkoxy , haloalkyl , carboxyl , alkoxycarbonyl , cyano , or conh 2 , or an indanone ( as in compound iiaa - 11 ). also preferred are iia compounds where r 1 is an optionally substituted alkyl or optionally substituted cycloalkyl , more preferably alkoxyalkyl , alkoxycarbonylalkyl , hydroxyalkyl , pyridinylalkyl , alkoxycycloalkyl , alkoxycarbonylcycloalkyl , or hydroxycycloalkyl . examples of these preferred compounds include iiaa - 24 , iiaa - 33 through iiaa - 36 , iiaa - 38 and iiaa - 40 . one embodiment of this invention relates to compounds of formula ia where q is a pyrimidine ring and r 1 is t — ar 2 where t is selected from co , co 2 , conh , s ( o ) 2 , s ( o ) 2 nh , coch 2 and ch 2 . when r 1 is t — ar 2 , preferred compounds are those where t is c (═ o ), represented by formula iiia . table 3 below shows representative examples of iiia compounds . preferred iiia compounds are those compounds where ar 1 is an unsubstituted phenyl or a phenyl substituted with one or more substituents independently selected from halogen . more preferred iiia compounds are those where ar 1 is just described , and ar 2 is a thienyl , an unsubstituted phenyl or a phenyl substituted with one or more substituents independently selected from halogen , alkyl , alkoxy , co 2 h or co 2 r . examples of other compounds where r 1 is t — ar 1 are shown below where a is n or ch , and t is one of the following : ch 2 ( exemplified by iva - 1 ), s ( o ) 2 ( va - 1 ), conh ( via - 1 ), coch 2 ( viia - 1 ), co , ( viiia - 1 ), and s ( o ) 2 nh ( ixa - 1 ). in other examples of these embodiments the phenyl rings may be optionally substituted as described above . another embodiment of this invention relates to compounds of formula ia where r 1 is t — r , r is a c 3 - c 6 cycloalkyl ring or a c 1 - c 6 straight chain or branched alkyl or alkenyl group optionally substituted by halogen and t is as described above . when r 1 is t — r , preferred compounds are those where t is c (═ o ) as represented by formula xa . table 4 below shows representative examples of xa compounds . preferred r 2 groups of formula i include — ch 2 or , — ch 2 oh , — ch 2 ( heterocyclyl ), — ch 2 ( substituted heterocyclyl ), — ch 2 n ( r ) 2 , and an r group such as methyl . representative examples of compounds wherein r 2 is other than methyl ( formula ixa ) are shown in table 5 below . the xyz - containing ring of formula i may be an isoxazole ring as shown above or it may an isomeric isoxazole or “ reverse ” isoxazole ( ib ). in this embodiment q is preferably a pyrimidine or pyridine ring where a is n or ch , or q is a pyrazole ring , and r 2 is aliphatic or substituted aliphatic . other embodiments of this invention relate to compounds where the xyz - containing ring is a furan ( id ) or a triazole ( ie ). these embodiments are exemplified below where r 1 is phenyl , r 2 ′ is hydrogen , and a is n or ch . for compounds of formula ib - ie , the phenyl rings of ar 1 and ar 2 may be optionally substituted as shown above for the isoxazoles of formula ia . the compounds of this invention may be prepared in general by methods known to those skilled in the art for analogous compounds , as illustrated by the general schemes below and by the preparative examples that follow . scheme i above shows a route for making isoxazoles where q is a pyrimidine ring . the starting benzaldehyde oxime 1 may be converted to the α - chlorobenzaldehyde oxime 2 using n - chlorosuccinimide and a catalytic amount of pyridine . condensation of 2 with 2 , 4 - pentanedione provides the isoxazole 3 which may be treated with dimethylformamide dimethylacetal to obtain the enamine 4 . after an aqueous work - up and without purification , 4 may be cyclized with guanidine hydrochloride to the aminopyrimidine 5 . compounds of formula iia may be obtained from 5 according to step ( e ) using the appropriate arylbromide in the presence of tris ( dibenylideneacetone ) dipalladium . alternatively , 5 may be treated with the appropriate acid chloride in a pyridine / benzene solvent according to step ( f ) to give compounds of formula iva . if the acid chloride is a ar 2 cocl , compounds of formula iiia may be obtained in a similar manner . scheme ii above shows a route for making isoxazoles of this invention where q is a pyrimidine ring and r 2 is modified by various groups . scheme iii above shows a synthetic route for making isoxazoles of this invention where q is a pyridine and r 2 is modified by various groups . in scheme ii and scheme iii , the isoxazole ring is first constructed and then the 2 - position of the pyrimidine or pyridine ring is elaborated with the appropriate nhr 1 substitution . it will be apparent to one skilled in the art that position 2 of the pyrimidine or pyridine ring can be elaborated with the appropriate nhr 1 substitution before the isoxazole ring is constructed . accordingly , isoxazoles of this invention may be obtained by performing step ( b ) using an appropriate intermediate having the formula xii : where a is n or ch ; r 1 and r 2 are as described above ; and pg is hydrogen or a nitrogen protecting group . nitrogen protecting groups are well - known and include groups such as benzyl or co 2 r , where r is preferably alkyl , allyl or benzyl . scheme iv above shows a synthetic route king reverse isoxazoles of this invention q is a pyrimidine ring . scheme v above shows a synthetic route for making reverse isoxazoles of this invention where q is a pyridine ring . scheme vi above shows a general route for preparing compounds of this invention wherein q is a pyrazole ring . scheme vii above shows a general route for preparing compounds of this invention wherein the xyz ring is a pyrazole ring . certain of the intermediates that are useful for making the kinase inhibitors of this invention are believed to be novel . accordingly , one embodiment of this invention relates to compounds xii above and compounds represented by formula xiii : x — y is n — o or o — n providing an isoxazole or reverse isoxazole ring ; a is n or ch ; g is r , aryl or substituted aryl ; r is aliphatic or substituted aliphatic r 2 is selected from hydrogen , — r , — ch 2 or , — ch 2 oh , — ch ═ o , — ch 2 sr , — ch 2 s ( o ) 2 r , — ch 2 ( c ═ o ) r , — ch 2 co 2 r , — ch 2 co 2 h , — ch 2 cn , — ch 2 nhr , — ch 2 n ( r ) 2 , — ch ═ n — or , — ch ═ nnhr , — ch ═ nn ( r ) 2 , — ch ═ nnhcor , — ch ═ nnhco 2 r , — ch ═ nnhso 2 r , - aryl , - substituted aryl , — ch 2 ( aryl ), — ch 2 ( substituted aryl ), — ch 2 nh 2 , — ch 2 nhcor , — ch 2 nhconhr , — ch 2 nhcon ( r ) 2 , — ch 2 nrcor , — ch 2 nhco 2 r , — ch 2 conhr , — ch 2 con ( r ) 2 , — ch 2 so 2 nh 2 , — ch 2 ( heterocyclyl ), — ch 2 ( substituted heterocyclyl ), -( heterocyclyl ), or -( substituted heterocyclyl ); and r 1 is selected from halogen , nh 2 , sr , or so 2 r . the activity of the jnk inhibitors of this invention may be assayed in vitro , in vivo or in a cell line . in vitro assays include assays that determine inhibition of either the kinase activity or atpase activity of activated jnk . for example , see the testing examples described below . alternate in vitro assays quantitate the ability of the inhibitor to bind to jnk and may be measured either by radiolabelling the inhibitor prior to binding , isolating the inhibitor / jnk complex and determining the amount of radiolabel bound , or by running a competition experiment where new inhibitors are incubated with jnk bound to known radioligands . one may use any type or isoform of jnk , depending upon which jnk type or isoform is to be inhibited . the jnk inhibitors or pharmaceutical salts thereof may be formulated into pharmaceutical compositions for administration to animals or humans . these pharmaceutical compositions , which comprise an amount of jnk inhibitor effective to treat or prevent a jnk - mediated condition and a pharmaceutically acceptable carrier , are another embodiment of the present invention . the term “ jnk - mediated condition ”, as used herein means any disease or other deleterious condition in which jnk is known to play a role . such conditions include , without limitation , inflammatory diseases , autoimmune diseases , destructive bone disorders , proliferative disorders , cancer , infectious diseases , neurodegenerative diseases , allergies , reperfusion / ischemia in stroke , heart attacks , angiogenic disorders , organ hypoxia , vascular hyperplasia , cardiac hypertrophy , thrombin - induced platelet aggregation , and conditions associated with prostaglandin endoperoxidase synthase - 2 . inflammatory diseases which may be treated or prevented by the compounds of this invention include , but are not limited to , acute pancreatitis , chronic pancreatitis , asthma , allergies , and adult respiratory distress syndrome . autoimmune diseases which may be treated or prevented by the compounds of this invention include , but are not limited to , glomerulonephritis , rheumatoid arthritis , systemic lupus erythematosus , scleroderma , chronic thyroiditis , graves &# 39 ; disease , autoimmune gastritis , diabetes , autoimmune hemolytic anemia , autoimmune neutropenia , thrombocytopenia , atopic dermatitis , chronic active hepatitis , myasthenia gravis , multiple sclerosis , inflammatory bowel disease , ulcerative colitis , crohn &# 39 ; s disease , psoriasis , or graft vs . host disease . destructive bone disorders which may be treated or prevented by the compounds of this invention include , but are not limited to , osteoporosis , osteoarthritis and multiple myeloma - related bone disorder . proliferative diseases which may be treated or prevented by the compounds of this invention include , but are not limited to , acute myelogenous leukemia , chronic myelogenous leukemia , metastatic melanoma , kaposi &# 39 ; s sarcoma , multiple myeloma and htlv - 1 mediated tumorigenesis . angiogenic disorders which may be treated or prevented by the compounds of this invention include solid tumors , ocular neovasculization , infantile haemangiomas . infectious diseases which may be treated or prevented by the compounds of this invention include , but are not limited to , sepsis , septic shock , and shigellosis . viral diseases which may be treated or prevented by the compounds of this invention include , but are not limited to , acute hepatitis infection ( including hepatitis a , hepatitis b and hepatitis c ), hiv infection and cmv retinitis . neurodegenerative diseases which may be treated or prevented by the compounds of this invention include , but are not limited to , alzheimer &# 39 ; s disease , parkinson &# 39 ; s disease , amyotrophic lateral sclerosis ( als ), epilepsy , seizures , huntington &# 39 ; s disease , traumatic brain injury , ischemic and hemorrhaging stroke , cerebral ischemias or neurodegenerative disease , including apoptosis - driven neurodegenerative disease , caused by traumatic injury , acute hypoxia , ischemia or glutamate neurotoxicity . “ jnk - mediated conditions ” also include ischemia / reperfusion in stroke , heart attacks , myocardial ischemia , organ hypoxia , vascular hyperplasia , cardiac hypertrophy , hepatic ischemia , liver disease , congestive heart failure , pathologic immune responses such as that caused by t cell activation and thrombin - induced platelet aggregation . in addition , jnk inhibitors of the instant invention may be capable of inhibiting the expression of inducible pro - inflammatory proteins . therefore , other “ jnk - mediated conditions ” which may be treated by the compounds of this invention include edema , analgesia , fever and pain , such as neuromuscular pain , headache , cancer pain , dental pain and arthritis pain . the compounds of this invention are also useful as inhibitors of src - family kinases , especially src and lck . for a general review of these kinases see thomas and brugge , annu . rev . cell dev . biol . ( 1997 ) 13 , 513 ; lawrence and niu , pharmacol . ther . ( 1998 ) 77 , 81 ; tatosyan and mizenina , biochemistry ( moscow ) ( 2000 ) 65 , 49 . accordingly , these compounds are useful for treating diseases or conditions that are known to be affected by the activity of one or more src - family kinases . such diseases or conditions include hypercalcemia , restenosis , hypercalcemia , osteoporosis , osteoarthritis , symptomatic treatment of bone metastasis , rheumatoid arthritis , inflammatory bowel disease , multiple sclerosis , psoriasis , lupus , graft vs . host disease , t - cell mediated hypersensitivity disease , hashimoto &# 39 ; s thyroiditis , guillain - barre syndrome , chronic obtructive pulmonary disorder , contact dermatitis , cancer , paget &# 39 ; s disease , asthma , ischemic or reperfusion injury , allergic disease , atopic dermatitis , and allergic rhinitis . diseases that are affected by src activity , in particular , include hypercalcemia , osteoporosis , osteoarthritis , cancer , symptomatic treatment of bone metastasis , and paget &# 39 ; s disease . diseases that are affected by lck activity , in particular , include autoimmune diseases , allergies , rheumatoid arthritis , and leukemia . compounds of formula ii - a and i - b wherein . ar 2 is aryl are especially useful for treating diseases associated with the src - family kinases , particularly src or lck . in addition to the compounds of this invention , pharmaceutically acceptable derivatives or prodrugs of the compounds of this invention may also be employed in compositions to treat or prevent the above - identified disorders . a “ pharmaceutically acceptable derivative or prodrug ” means any pharmaceutically acceptable salt , ester , salt of an ester or other derivative of a compound of this invention which , upon administration to a recipient , is capable of providing , either directly or indirectly , a compound of this invention or an inhibitorily active metabolite or residue thereof . particularly favored derivatives or prodrugs are those that increase the bioavailability of the compounds of this invention when such compounds are administered to a mammal ( e . g ., by allowing an orally administered compound to be more readily absorbed into the blood ) or which enhance delivery of the parent compound to a biological compartment ( e . g ., the brain or lymphatic system ) relative to the parent species . pharmaceutically acceptable prodrugs of the compounds of this invention include , without limitation , esters , amino acid esters , phosphate esters , metal salts and sulfonate esters . pharmaceutically acceptable salts of the compounds of this invention include those derived from pharmaceutically acceptable inorganic and organic acids and bases . examples of suitable acid salts include acetate , adipate , alginate , aspartate , benzoate , benzenesulfonate , bisulfate , butyrate , citrate , camphorate , camphorsulfonate , cyclopentanepropionate , digluconate , dodecylsulfate , ethanesulfonate , formate , fumarate , glucoheptanoate , glycerophosphate , glycolate , hemisulfate , heptanoate , hexanoate , hydrochloride , hydrobromide , hydroiodide , 2 - hydroxyethanesulfonate , lactate , maleate , malonate , methanesulfonate , 2 - naphthalenesulfonate , nicotinate , nitrate , oxalate , palmoate , pectinate , persulfate , 3 - phenylpropionate , phosphate , picrate , pivalate , propionate , salicylate , succinate , sulfate , tartrate , thiocyanate , tosylate and undecanoate . other acids , such as oxalic , while not in themselves pharmaceutically acceptable , may be employed in the preparation of salts useful as intermediates in obtaining the compounds of the invention and their pharmaceutically acceptable acid addition salts . salts derived from appropriate bases include alkali metal ( e . g ., sodium and potassium ), alkaline earth metal ( e . g ., magnesium ), ammonium and n + ( c 1 - 4 alkyl ) 4 salts . this invention also envisions the quaternization of any basic nitrogen - containing groups of the compounds disclosed herein . water or oil - soluble or dispersible products may be obtained by such quaternization . pharmaceutically acceptable carriers that may be used in these pharmaceutical compositions include , but are not limited to , ion exchangers , alumina , aluminum stearate , lecithin , serum proteins , such as human serum albumin , buffer substances such as phosphates , glycine , sorbic acid , potassium sorbate , partial glyceride mixtures of saturated vegetable fatty acids , water , salts or electrolytes , such as protamine sulfate , disodium hydrogen phosphate , potassium hydrogen phosphate , sodium chloride , zinc salts , colloidal silica , magnesium trisilicate , polyvinyl pyrrolidone , cellulose - based substances , polyethylene glycol , sodium carboxymethylcellulose , polyacrylates , waxes , polyethylene - polyoxypropylene - block polymers , polyethylene glycol and wool fat . the compositions of the present invention may be administered orally , parenterally , by inhalation spray , topically , rectally , nasally , buccally , vaginally or via an implanted reservoir . the term “ parenteral ” as used herein includes subcutaneous , intravenous , intramuscular , intra - articular , intra - synovial , intrasternal , intrathecal , intrahepatic , intralesional and intracranial injection or infusion techniques . preferably , the compositions are administered orally , intraperitoneally or intravenously . sterile injectable forms of the compositions of this invention may be aqueous or oleaginous suspension . these suspensions may be formulated according to techniques known in the art using suitable dispersing or wetting agents and suspending agents . 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 conventionally employed as a solvent or suspending medium . for this purpose , any bland fixed oil may be employed including synthetic mono - or di - glycerides . fatty acids , such as oleic acid and its glyceride derivatives are useful in the preparation of injectables , as are natural pharmaceutically - acceptable oils , such as olive oil or castor oil , especially in their polyoxyethylated versions . these oil solutions or suspensions may also contain a long - chain alcohol diluent or dispersant , such as carboxymethyl cellulose or similar dispersing agents which are commonly used in the formulation of pharmaceutically acceptable dosage forms including emulsions and suspensions . other commonly used surfactants , such as tweens , spans and other emulsifying agents or bioavailability enhancers which are commonly used in the manufacture of pharmaceutically acceptable solid , liquid , or other dosage forms may also be used for the purposes of formulation . the pharmaceutical compositions of this invention maybe orally administered in any orally acceptable dosage form including , but not limited to , capsules , tablets , aqueous suspensions or solutions . in the case of tablets for oral use , carriers commonly used include lactose and corn starch . lubricating agents , such as magnesium . stearate , are also typically added . for oral administration in a capsule form , useful diluents include lactose and dried cornstarch . when aqueous suspensions are required for oral use , the active ingredient is combined with emulsifying and suspending agents . if desired , certain sweetening , flavoring or coloring agents may also be added . alternatively , the pharmaceutical compositions of this invention may be administered in the form of suppositories for rectal administration . these can be prepared by mixing the agent with a suitable non - irritating excipient which is solid at room temperature but liquid at rectal temperature and therefore will melt in the rectum to release the drug . such materials include cocoa butter , beeswax and polyethylene glycols . the pharmaceutical compositions of this invention may also be administered topically , especially when the target of treatment includes areas or organs readily accessible by topical application , including diseases of the eye , the skin , or the lower intestinal tract . suitable topical formulations are readily prepared for each of these areas or organs . topical application for the lower intestinal tract can be effected in a rectal suppository formulation ( see above ) or in a suitable enema formulation . topically - transdermal patches may also be used . for topical applications , the pharmaceutical compositions may be formulated in a suitable ointment containing the active component suspended or dissolved in one or more carriers . carriers for topical administration of the compounds of this invention include , but are not limited to , mineral oil , liquid petrolatum , white petrolatum , propylene glycol , polyoxyethylene , polyoxypropylene compound , emulsifying wax and water . alternatively , the pharmaceutical compositions can be formulated in a suitable lotion or cream containing the active components suspended or dissolved in one or more pharmaceutically acceptable carriers . suitable carriers include , but are not limited to , mineral oil , sorbitan monostearate , polysorbate 60 , cetyl esters wax , cetearyl alcohol , 2 - octyldodecanol , benzyl alcohol and water . for ophthalmic use , the pharmaceutical compositions may be formulated as micronized suspensions in isotonic , ph adjusted sterile saline , or , preferably , as solutions in isotonic , ph adjusted sterile saline , either with or without a preservative such as benzylalkonium chloride . alternatively , for ophthalmic uses , the pharmaceutical compositions may be formulated in an ointment such as petrolatum . the pharmaceutical compositions of this invention may also be administered by nasal aerosol or inhalation . such compositions are prepared according to techniques well - known in the art of pharmaceutical formulation and may be prepared as solutions in saline , employing benzyl alcohol or other suitable preservatives , absorption promoters to enhance bioavailability , fluorocarbons , and / or other conventional solubilizing or dispersing agents . the amount of jnk inhibitor that may be combined with the carrier materials to produce a single dosage form will vary depending upon the host treated , the particular mode of administration . preferably , the compositions should be formulated so that a dosage of between 0 . 01 - 100 mg / kg body weight / day of the inhibitor can be administered to a patient receiving these compositions . it should also be understood that a specific dosage and treatment regimen for any particular patient will depend upon a variety of factors , including the activity of the specific compound employed , the age , body weight , general health , sex , diet , time of administration , rate of excretion , drug combination , and the judgment of the treating physician and the severity of the particular disease being treated . the amount of inhibitor will also depend upon the particular compound in the composition . according to another embodiment , the invention provides methods for treating or preventing a jnk - mediated condition comprising the step of administering to a patient one of the above - described pharmaceutical compositions . the term “ patient ”, as used herein , means an animal , preferably a human . preferably , that method is used to treat or prevent a condition selected from inflammatory diseases , autoimmune diseases , destructive bone disorders , proliferative disorders , infectious diseases , degenerative diseases , neurodegenerative diseases , allergies , reperfusion / ischemia in stroke , heart attacks , angiogenic disorders , organ hypoxia , vascular hyperplasia , cardiac hypertrophy , and thrombin - induced platelet aggregation , or any specific disease or disorder described above . depending upon the particular jnk - mediated condition to be treated or prevented , additional drugs , which are normally administered to treat or prevent that condition , may be administered together with the inhibitors of this invention . for example , chemotherapeutic agents or other anti - proliferative agents may be combined with the jnk inhibitors of this invention to treat proliferative diseases . those additional agents may be administered separately , as part of a multiple dosage regimen , from the jnk inhibitor - containing composition . alternatively , those agents may be part of a single dosage form , mixed together with the jnk inhibitor in a single composition . in order that the invention described herein may be more fully understood , the following examples are set forth . it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting this invention in any manner . benzaldehyde oxime . to benzaldhyde ( 10 . 0 g , 94 mmol ) in ethanol ( 50 ml ) was added hydroxylamine hydrochloride ( 6 . 5 g , 94 mmol in h 2 o ( 50 ml ) followed by na 2 co 3 in h 2 o ( 50 ml ). reaction solution was stirred for 2 hr . poured into brine and extracted twice with diethyl ether . combined extracts were dried over mgso 4 . evaporation afforded benzaldehyde oxime ( 11 . 0 g , 96 . 5 % yield ) as a colorless oil . 1 h nmr ( cdcl 3 ) δ 7 . 40 - 7 . 50 ( m , 3h ), 7 . 60 - 7 . 70 ( m , 2h ), 8 . 22 ( s , 1h ), 9 . 1 ( bs , 1h ). α - chlorobenzaldehyde oxime ( benzoyl chloride oxime ). to benzaldehyde oxime ( 12 . 2 g , 0 . 1 mol ) in chloroform was added catalytic amount of pyridine , followed by n - chlorosuccinimide ( 13 . 35 g , 0 . 1 mol ) at room temperature . the reaction mixture was stirred for 1 . 5 h , then saturated aqueous nacl was added . the organic phase was washed with saturated aqueous nacl ( twice ) and dried with mgso 4 . the solvent was removed under reduced pressure . 13 . 85 g α - chlorobenzaldehyde oxime was obtained . the yield was 87 %. 1 -( 5 - methyl - 3 - phenyl - isoxazol - 4 - yl )- ethanone ( compound 3 ). to a solution of pentane - 2 , 4 - dione ( 13 . 23 g , 0 . 132 mol ) and triethylamine ( 13 . 35 g , 0 . 132 mol ) in ethanol was added α - chlorobenzaldehyde oxime ( 13 . 70 g , 0 . 088 mol ) at room temperature . the reaction mixture was stirred overnight at room temperature . to the reaction was added ethyl acetate and saturated aqueous nacl . the organic phase was washed with saturated aqueous nacl ( twice ) and dried with mgso 4 , and the organic solvent was removed under reduced pressure to provide 17 . 7 g of the title compound . the yield was 100 %. 4 -( 5 - methyl - 3 - phenyl - isoxazol - 4 - yl )- pyrimidin - 2 - ylamine ( compound 5 ). the above compound 3 ( 17 . 7 g , 0 . 088 mol ) and dimethylformamide dimethyl acetal ( dmf . dma ) ( 160 g , 0 . 132 mol ) were refluxed overnight . to the reaction mixture was added ethyl acetate and saturated aqueous nacl . the organic phase was washed with saturated aqueous nacl ( twice ) and dried ( mgso 4 ). the organic solvent was removed under reduced pressure , and the crude product material was dissolved in 200 ml methanol . to the solution was added guanidine hydrochloride ( 10 . 5 g , 0 . 110 mol ) in 100 ml methanol , followed by sodium methoxide ( 6 . 17 g , 0 . 114 mol ) in 100 ml methanol . the reaction mixture was refluxed overnight and then was cooled to room temperature . the reaction solvent was concentrated to approximately 100 ml total volume , and the precipitated product was filtered . the filtration cake afforded the title compound ( 9 . 3 g ). the overall yield for two steps was 46 %. [ 4 -( 5 - methyl - 3 - phenyl - isoxazol - 4 - yl )- pyrimidin - 2 - yl ]- phenyl - amine ( compound iia ). to a solution of 50 mg ( 0 . 2 mmol ) of 4 -( 5 - methyl - 3 - phenyl - isoxazole - 4 - yl )- pyrimidin - 2 - ylamine in 1 ml of toluene was added successively 63 μl ( 0 . 6 mmol ) of bromobenzene , 10 mg of tris ( dibenzylideneacetone ) dipalladium , 10 mg of binap and 39 mg ( 0 . 4 mmol ) of sodium tert - butoxide . the mixture was heated at reflux for 16 h , diluted with ethyl acetate , filtered , washed successively with saturated aqueous sodium bicarbonate and brine , dried ( mgso 4 ) and concentrated in vacuo . the residue was purified by column chromatography over silica gel eluted with ethyl acetate - hexanes 1 : 3 , to afford 24 mg ( 36 %) of the title compound as a yellow oil . 5 - methyl - 3 - phenyl - isoxazole - 4 - carboxylic acid methyl ester . an ethanol solution of freshly prepared benzoyl chloride oxime ( 14 . 0 g , 90 mmol ) ( 100 ml ) was added dropwise , at 5 ° c . to methyl acetoacetate ( 11 . 18 g , 96 mmol ) and triethyl amine ( 13 ml , 103 mmol ) in ethanol ( 50 ml ) after stirring for 12 hr at ambient temperature , the solution was diluted with ch 2 cl 2 , washed with 1n hcl . saturated nahco 3 , brine , dried over mgso 4 and evaporated togive amber oil . flash chromatography ( silica ) with 10 % ethyl acetate in hexanes afforded the title compound ( 7 . 56 g , 39 % yield ) as a white solid : ms m / z mh + 218 ( 100 ); 1 h nmr ( cdcl 3 ) δ 2 . 78 ( s , 3h ), 3 . 81 ( s , 3h ), 7 . 45 - 7 . 55 ( m , 3h ), 7 . 65 - 7 . 69 ( m , 2h ). 5 - methyl - 3 - phenyl - isoxazole - 4 - carboxylic acid . to 5 - methyl - 3 - phenyl - isoxazole - 4 - carboxylic acid methyl ester ( 0 . 853 g , 3 . 69 mmol ) in methanol ( 12 ml ) was added 2n naoh ( 8 ml ) the reaction solution was stirred at ambient temperature for 60 hr . the solution was dilute with waterand extracted twice with ethyl acetate . the combined extract was washed with brine and dried over mgso 4 and concentrated . recrystallization ( hexanes / ethyl acetate ) afforded a white solid ( 0 . 540 g , 72 % yield ). 5 - methyl - 3 - phenyl - isoxazole - 4 - carbonyl chloride . 5 - methyl - 3 - phenyl - isoxazole - 4 - carboxylic acid ( 0 . 54 g , 2 . 56 mmol ) was treated with socl 2 ( 2 ml ) at 70 ° c . for 1 hr . concentration in vacuum gave a yellow oil which was used without purification . 3 -( 5 - methyl - 3 - phenyl - isoxazol - 4 - yl )- 3 - oxo - propionitrile . to cyanoacetic acid ( 0 . 43 g , 5 . 12 mmol ) in thf at − 78 ° c ., containing one crystal of 1 , 1 ′- bipyridyl was added n - butyl lithium ( 6 . 4 ml , 10 . 24 mmol ). the temperature was allowed to warm to 0 ° c . resulting in a pink colored solution . after cooling to − 78 ° c ., 5 - methyl - 3 - phenyl - isoxazole - 4 - carbonyl chloride ( 0 . 567 g , 2 . 56 mmol ) in thf ( 5 ml ) was added dropwise . the mixture was stirred at − 78 ° c . for 1 hr . and at ambient temperature for an addition 1 hr . the reaction was quenched with 1n hcl ( 13 ml0 and extracted twice with ch 2 cl 2 . combined extracts were washed with saturated nahco 3 , brine , dried over mgso 4 to give the title compound ( 0 . 391 g , 67 % yield ). n -[ 5 -( 5 - methyl - 3 - phenyl - isoxazol - 4 - yl )- 2h - pyrazol - 3 - yl ]- benzamide . 3 -( 5 - methyl - 3 - phenyl - isoxazol - 4 - yl )- 3 - oxo - propionitrile ( 0 . 391 . g , 1 . 73 mmol ) in ethanol ( 3 ml ) was treated with hydrazine ( 0 . 168 ml , 3 . 46 mmol ) and heated to reflux . evaporation in vacuum gave 5 -( 5 - methyl - 3 - phenyl - isoxazol - 4 - yl )- 2h - pyrazol - 3 - ylamine used without purification . to the resulting amine ( 0 . 039 . g , 0 . 16 mmol ) in dioxane was added triethyl amine followed by benzyl chloride ( 0 . 019 ml , 0 . 16 mmol ). the reaction was stirred at 10 ° c . for 1 hr and 2 hr at ambient temperature . the solution was diluted with water extracted with ethyl acetate , washed with saturated nahco 3 , brine , dried over mgso 4 and concentrated in vacuum . hplc purification afforded 1 . 4 mg of title compound . 1 - benzyloxy - 3 -( 2 - methylsulfanylpyrimidin - 4 - yl )- propan - 2 - one ( compound 7 ). to a stirred solution of 4 - methyl - 2 - methylsulfanylpyrimidine ( 9 . 60 g , 68 . 5 mmol ) in thf ( 150 ml ) at − 78 ° c . was added lda ( 2 . 0 m thf / hex , 41 . 1 ml , 82 . 2 mmol ) dropwise over 10 min . the solution was stirred at − 78 ° c . for 15 minutes , warmed to 0 ° c . for 10 minutes and recooled to − 78 ° c . for 15 minutes . then , a solution of 3 - benzyloxy - n - methyl - n - methoxyacetamide ( 17 . 2 g , 82 . 2 mmol ) in thf ( 30 ml ) was added dropwise over 45 minutes . after 15 min . at − 78 ° c ., the solution was warmed to 0 ° c . and stirred for 30 min . the reaction was quenched with hcl ( 1m , 85 ml ) and stirred for 1 h . the solution was poured into saturated nahco 3 ( 300 ml ), extracted with et 2 o ( 3 × 200 ml ), dried ( mgso 4 ), filtered and concentrated . flash chromatography ( sio 2 , 20 % etoac - hexanes ) provided the title compound ( 13 . 75 g , 47 . 7 mmol , 69 % yield ). 4 -[ 5 - benzyloxymethyl - 3 -( 4 - fluoro - phenyl )- isoxazol - 4 - yl ]- 2 - methylsulfanyl - pyrimidine ( compound 8 ). to a stirred solution of the above compound 7 ( 13 . 75 g , 47 . 7 mmol ) and et 3 n ( 14 . 6 ml , 105 mmol ) in etoh ( 200 ml ), was added a solution of 4 - fluoro - benzoylchloride oxime ( 56 mmol ) in etoh ( 50 ml ) over 30 min . the solution was stirred at 25 ° c . for 15 min . then , the solution was heated to reflux for 90 min . the solution was cooled to 25 ° c . additional et 3 n ( 7 . 3 ml , 52 mmol ) was added followed by dropwise addition of a solution of 4 - fluoro - benzoylchloride oxime ( 38 . 5 mmol ) in etoh ( 50 ml ) over 1 h . to drive the reaction to completion . the solution was refluxed for 1 h . until tlc indicated that all of the starting isoxazole was consumed . the solution was cooled to 25 ° c . and concentrated . the crude material was picked up in ch 2 cl 2 ( 50 ml ) and poured into saturated aqueous nahco 3 ( 150 ml ), extracted with ch 2 cl 2 ( 3 × 150 ml ), dried ( mgso 4 ), filtered and concentrated . flash chromatography ( sio 2 , 20 % etoac - hexanes ) provided the title compound ( 14 . 2 g , 34 . 8 mmol , 60 %) in sufficient purity (& gt ; 85 %) for use in the next reaction . 4 -[ 5 - benzyloxymethyl - 3 -( 4 - fluoro - phenyl )- isoxazol - 4 - yl ]- 2 - methanesulfonyl - pyrimidine ( compound 9 ). to a stirred solution of the above compound 8 ( 2 . 00 g , 4 . 91 mmol ) in meoh ( 50 ml ) at 25 ° c . was added dropwise a solution of oxone ( 7 . 07 g , 11 . 5 mmol ) in h 2 o ( 50 ml ) over 10 min . after 20 h ., the solution was poured into h 2 o ( 75 ml ), extracted with ch 2 cl 2 , ( 3 × 75 ml ), dried ( mgso 4 ), filtered and concentrated . flash chromatography ( sio 2 , 45 % etoac - hexanes ) provided the title compound ( 1 . 60 g , 3 . 64 mmol , 74 %). [ 3 -( 4 - fluoro - phenyl )- 4 -( 2 - methanesulfonyl - pyrimidin - 4 - yl )- isoxazol - 5 - yl ]- methanol ( compound 10 ). to a stirred solution of the above compound 9 ( 750 mg , 1 . 70 mmol ) in chcl 3 ( 8 . 5 ml ) at 0 ° c . was added trimethylsilyl iodide ( 0 . 73 ml , 5 . 1 mmol ). the reaction was stirred at 0 ° c . for 30 min . then , additional trimethylsilyl iodide ( 0 . 48 ml , 3 . 4 mmol ) was added . after 40 min . the solution was warmed to 25 ° c . and stirring was continued for 22 h . the solution was quenched with h 2 o - meoh ( 2 ml ) and stirred for 1 h . the solution was poured into saturated aqueous nahco 3 ( 30 ml ), extracted with etoac ( 3 × 30 ml ), and concentrated . flash chromatography ( sio 2 , 80 % etoac - hexanes ) provided the title compound ( 530 mg , 1 . 52 mmol , 89 %). 4 -[ 5 -( bromomethyl )- 3 -( 4 - fluoro - phenyl )- isoxazol - 4 - yl ]- 2 - methanesulfonyl - pyrimidine ( compound 11 ). to a stirred solution of the above compound 10 ( 250 mg , 0 . 716 mmol ) and cbr 4 ( 473 mg , 1 . 43 mmol ) in ch 2 cl 2 ( 14 ml ) at 25 ° c . was added pph 3 ( 244 mg , 0 . 93 mmol ). after 10 min ., additional pph 3 ( 50 mg , 0 . 19 mmol ) was added to drive the reaction to completion . after 15 min ., the solution was concentrated . flash chromatography ( sio 2 , 50 % etoac - hexanes ) provided the title compound . ( 265 mg , 0 . 643 mmol , 90 %). 4 -[ 3 -( 4 - fluoro - phenyl )- 4 -( 2 - methanesulfonyl - pyrimidin - 4 - yl )- isoxazol - 5 - ylmethyl ]- morpholine ( compound 12 ). to a stirred solution of the above compound 11 ( 41 mg , 0 . 099 mmol ) and et 3 n ( 20 82 l , 0 . 15 mmol ) in ch 3 cn ( 0 . 5 ml ) at 25 ° c . was added morpholine ( 9 . 6 μl , 0 . 11 mmol ). after15 min . the solution was concentrated . preparative thin layer chromatography ( sio 2 , etoac ) provided the title compound ( 29 mg , 0 . 069 mmol , 70 %). 4 -{ 4 -[ 3 -( 4 - fluoro - phenyl )- 5 -( morpholin 4 - ylmethyl )- isoxazol - 4 - yl ] pyrimidin - 2 - ylamino } cyclohexanol ( compound xia - 42 ). a stirred solution of compound 13 ( 29 mg , 0 . 069 mmol ) and trans - 4 - aminocyclohexanol ( 24 mg , 0 . 21 mmol ) in dmso ( 0 . 21 ml ) was heated to 80 ° c . for 4 h . the solution was poured into half - saturated aqueous nahco 3 ( 5 ml ), extracted with etoac ( 5 × 5 ml ), dried ( mgso 4 ), filtered and concentrated . flash chromatography ( sio 2 , 10 % meoh — ch 2 cl 2 ) provided material which was further purified by ion exchange chromatography ( scx resin , eluent : 0 . 25m nh 3 in 50 % meoh — ch 2 cl 2 ) to give the title compound ( 27 mg , 0 . 057 mmol , 83 %). 4 -[ 5 - ethoxmethyl - 3 -( 4 - fluoro - phenyl )- isoxazol - 4 - yl ]- 2 - methylsulfanyl - pyrimidine ( compound 13 ). to a stirred solution of the above compound 8 ( 103 mg , 0 . 27 mmol ) in etoh ( 2 . 0 ml ) at 25 ° c . was added naoet ( 21 % w / v etoh , 0 . 40 ml , 1 . 23 mmol ). after 2 h . the reaction was quenched with saturated aqueous nh 4 cl ( 3 ml ), ch 2 cl 2 ( 3 × 5 ml ); dried ( mgso 4 ), filtered and concentrated . flash chromatography ( sio 2 , 25 % etoac - hexanes ) provided the title compound ( 58 mg , 0 . 17 mmol , 62 %). 4 -[ 5 - ethoxymethyl - 3 -( 4 - fluoro - phenyl )- isoxazol - 4 - yl ]- 2 - methanesulfonyl - pyrimidine ( compound 14 ). this compound was prepared in a manner similar to that described above in example 13 , except starting from the above compound 13 ( 58 mg , 0 . 17 mmol ) to provide the title compound ( 64 mg , 0 . 17 mmol , 100 %) which was used directly in the next reaction without purification or characterization . cyclohexyl -{ 4 -[ 5 - ethoxymethyl - 3 -( 4 - fluoro - phenyl )- isoxazol - 4 - yl ]- pyrimidin - 2 - yl } amine ( compound xia - 43 ) this compound was prepared in a manner similar to that described above in example 17 , starting from the above compound 14 ( 64 mg , 0 . 17 mmol ) and cyclohexylamine ( 58 μl , 0 . 51 mmol ) to provide the title compound as crude product . after hplc purification ( c - 18 , gradient elution , 10 - 90 % h 2 o — ch 3 cn ) and extraction into etoac , the crude product was converted to the hcl salt with hcl - et 2 o ( 1m , 1 ml ). the solvents were removed in vacuo the give the title compound as the hcl salt ( 55 mg , 0 . 13 mmol , 76 % over two steps from compound 13 ). cyclohexyl -{ 4 -[ 5 - benzyloxymethyl - 3 -( 4 - fluoro - phenyl )- isoxazol - 4 - yl ]- pyrimidin - 2 - yl } amine ( compound xia - 44 ) this compound was prepared in a manner similar to that described above in example 17 starting from the above compound 9 ( 500 mg , 1 . 14 mmol ) and cyclohexylamine ( 340 μl , 3 . 42 mmol ). flash chromatography ( sio 2 , 30 % etoac - hexanes ) provided the title compound ( 488 mg , 1 . 06 mmol , 93 %). [ 4 -( 2 - cyclohexylamino - pyrimidin - 4 - yl )- 3 -( 4 - fluoro - phenyl )- isoxazol - 5 - yl ] methanol ( compound xia - 45 ) a stirred solution of the above compound xia - 44 ( 461 mg , 1 . 01 mmol ) in tfa - h 2 o ( 3 : 1 , 8 ml ) was heated to 80 ° c . for 20 h . the solution was concentrated , and the crude mixture was taken up in ch 2 cl 2 ( 25 ml ), poured into saturated aqueous nahco 3 ( 30 ml ), extracted with ch 2 cl 2 ( 3 × 25 ml ), dried ( mgso 4 ), filtered and concentrated . tlc ( 50 % etoac - hexanes ) indicated about 50 % consumption of starting compound xia - 44 . the crude material was dissolved in tfa - h 2 o ( 3 : 1 , 8 ml ) and the resulting solution was heated to 100 ° c . for 22 h . the solution was concentrated , and the crude mixture was taken up in ch 2 cl 2 ( 25 ml ), poured into saturated aqueous nahco 3 ( 30 ml ), extracted with ch 2 cl 2 ( 3 × 25 ml ), dried ( mgso 4 ), filtered and concentrated . flash chromatography ( sio 2 , 40 % etoac - hexanes ) provided the title compound ( 313 mg , 0 . 85 mmol , 84 %). 1 -( 2 - bromo - pyridin - 4 - yl )- propan - 2 - one ( compound 16 ). to a stirred solution of 2 - bromo - 4 - methylpyridine ( compound 15 ) ( 20 . 20 g , 117 . 4 mmol ) in thf ( 250 ml ) at − 78 ° c . was added lda ( 2 . 0 m thf / hex , 70 . 5 ml , 141 mmol ) dropwise over 10 min . the solution was stirred at − 78 ° c . for 35 min . then a solution of n - methoxy - n - methyl acetamide ( 14 . 5 g , 141 mmol ) in thf ( 30 ml ) was added dropwise over 10 min . after 15 min . at − 78 ° c ., the solution was warmed to 0 ° c . and stirred for 1 h . the solution was poured into h 2 o ( 250 ml ), extracted with et 2 o ( 3 × 250 ml ), dried ( mgso 4 ), filtered and concentrated . flash chromatography ( sio 2 , 20 % etoac - hexanes ) provided the title compound ( 16 . 75 g , 78 . 2 mmol , 67 %). 2 - bromo - 4 -( 5 - methyl - 3 - phenyl - isoxazol - 4 - yl )- pyridine ( compound 17a ). to a stirred solution of compound 16 ( 1 . 71 g , 8 . 0 mmol ) and et 3 n ( 2 . 23 ml , 16 mmol ) in etoh ( 16 ml ) was added a solution of benzoylchloride oxime ( 1 . 62 g , 10 . 4 mmol ) in etoh ( 16 ml ) over 90 min . the solution was stirred at 25 ° c . for 90 min . then , the solution was heated to reflux for 24 h . the solution was cooled to 25 ° c . and concentrated . the crude material was taken up in ch 2 cl 2 ( 50 ml ) and poured into saturated aqueous nahco 3 ( 50 ml ), extracted with ch 2 cl 2 ( 3 × 50 ml ), dried ( na 2 so 4 ), and filtered . flash chromatography ( sio 2 , 20 % etoac - hexanes ) provided the title compound ( 1 . 32 g , 4 . 19 mmol , 52 %). 2 - bromo - 4 -( 5 - bromomethyl - 3 - phenyl - isoxazol - 4 - yl )- pyridine ( compound 18a ). a stirred solution of the above compound 17a ( 404 mg , 1 . 28 mmol ), n - bromosuccinimide ( 239 mg , 1 . 35 mmol ) and aibn ( 11 mg , 0 . 064 mmol ) in ccl 4 ( 3 ml ) was heated to reflux and placed under a 300 w lamp for 18 h . the solution was diluted with ch 2 cl 2 ( 15 ml ), extracted with h 2 o ( 3 × 10 ml ), brine ( 40 ml ), dried ( mgso 4 ), filtered and concentrated . flash chromatography ( sio 2 , 15 - 20 % etoac - hexanes ) provided the title compound ( 287 mg , 0 . 728 mmol , 57 %). 2 - bromo - 4 -( 5 - methoxymethyl - 3 -( 4 - fluoro - phenyl )- isoxazol - 4 - yl )- pyridine ( compound 19b ). to the above compound 18b ( 200 mg , 0 . 485 mmol ) was added naome ( 0 . 5 m in meoh , 2 . 0 ml , 1 . 0 mmol ). the solution was stirred at 25 ° c . for 90 min . then , the solution was poured into brine , extracted with etoac ( 4 × 15 ml ), dried ( mgso 4 ), filtered through a silica plug . evaporation of the solvent provided the title compound ( 175 mg , 0 . 482 mmol , 99 %). 4 -( 4 -( 2 - bromo - pyridin - 4 - yl )- 3 - phenyl - isoxazol - 5 - ylmethyl )- morpholine ( compound 20a ). a stirred solution of the above compound 18a ( 484 mg , 1 . 22 mmol ), morpholine ( 0 . 45 ml , 5 . 1 mmol ) and k 2 co 3 ( 340 mg , 2 . 45 mmol ) in anhydrous dmf ( 2 ml ) was warmed to 40 ° c . for 18 h . the solution was poured into brine ( 10 ml ), extracted with ch 2 cl 2 ( 3 × 15 ml ), dried ( mgso 4 ), and filtered . flash chromatography ( sio 2 , 50 % etoac - hexanes ) provided the title compound ( 461 mg , 1 . 15 mmol , 94 %). [ 4 -( 5 - methyl - 3 - phenyl - isoxazol - 4 - yl )- pyridin - 2 - yl ] phenyl - amine ( compound iia - 52 ). to a stirred solution of the above compound 17a ( 20 mg , 0 . 063 mmol ), aniline ( 7 . 0 μl , 0 . 076 mmol ) and binap ( 5 . 6 mg , 0 . 009 mmol ) in toluene ( 0 . 6 ml ) at 25 ° c . was added pd 2 ( dba ) 3 ( 2 . 7 mg , 0 . 003 mmol ) followed by naotbu ( 9 . 1 mg , 0 . 095 mmol ). the solution was heated to 80 ° c . for 2 h . the solution was cooled , filtered and concentrated . preparative thin layer chromatography ( sio 2 , 5 % etoac / ch 2 cl 2 ) provided the title compound ( 12 . 6 mg , 0 . 0385 mmol , 61 %). cyclohexyl -[ 4 -( 5 - methoxymethyl - 3 -( 4 - fluoro - phenyl )- isoxazol - 4 - yl )- pyridin - 2 - yl ]- amine ( compound xia - 29 ). to a stirred solution of the above compound 19b ( 20 mg , 0 . 050 mmol ), cyclohexylamine ( 11 μl , 0 . 13 mmol ), and binap ( 4 . 7 mg , 0 . 0075 mmol ) in toluene ( 0 . 4 ml ) at 25 ° c . was added pd 2 ( dba ) 3 ( 2 . 3 mg , 0 . 0025 mmol ) followed by naotbu ( 12 mg , 0 . 13 mmol ). the solution was heated to 80 ° c . for 15 h . the solution was cooled , poured into h 2 o ( 5 ml ), extracted with etoac ( 4 × 5 ml ), dried ( mgso 4 ), filtered and concentrated . hplc ( gradient elution , 90 - 10 % h 2 o — ch 3 cn ) provided the title compound ( 9 . 1 mg , 0 . 022 mmol , 44 %). 3 - methyl - 5 - phenyl - isoxazole - 4 - carbonitrile ( compound 24 ). to an ethyl alcohol solution of benzoylacetonitrile was added 1 . 5 eq of triethyl amine , followed by 1 . 5 eq of acetylchloride oxime , the reaction mixture was stirred at r . t . for 4 hours . to the reaction mixture was added ethyl acetate and brine . the organic phase was dried with magnesium sulfate and the solvent was removed under reduced pressure . after chromatographic purification the title compound was obtained in 72 % yield . 3 - methyl - 5 - phenyl - isoxazole - 4 - carbaldehyde ( compound 25 ). to a toluene solution of the above compound 24 was added 1 . 2 eq of dibal - h / hax at 0 ° c . the reaction was stirred at 0 ° c . for 3 hours , allowed to warm to room temperature and was stirred at r . t . overnight . the reaction mixture was transfered to 1n hcl slowly and then extracted with ethyl acetate . the organic phase was dried over magnesium sulfate and concentrated under reduced pressure . the crude product was purified by chromatograph providing the title compound in 57 % yield . 1 -( 3 - methyl - 5 - phenyl - isoxazol - 4 - yl )- ethanol ( compound 26 ). to the thf solution of the above compound 25 was slowly added 1 . 4 eq of methylmagnesium bromide at room temperature . the reaction mixture was stirred at r . t . for 1 h . to the reaction mixture was added ethyl acetate and 1n hcl . the organic phase was washed with brine and dried over magnesium sulfate . the solvent was removed under reduced pressure , and the crude product , obtained in 96 % yield , was used directly for the next step without purification . 1 -( 3 - methyl - 5 - phenyl - isoxazol - 4 - yl )- ethanone ( compound 27 ). to a dichlordmethane solution of oxalyl chloride was added dmso at − 78 ° c ., the mixture was stirred at − 78 ° c . for 15 min and followed by addition of a dichloromethane solution of compound the above compound 26 . the reaction mixture was stirred for 30 min at − 78 ° c ., then triethylamine was added , after which the reaction mixture was allowed to warm to room temperature gradually . to the reaction mixture was added ethyl acetate and brine . the organic phase was dried over magnesium sulfate , and the solvent was removed under reduced pressure . the crude product , obtained in 94 % yield , was used directly for the next step without purification . 3 - dimethylamino - 1 -( 3 - methyl - 5 - phenyl - isoxazol - 4 - yl )- propenone ( compound 28 ). a toluene solution of the above compound 27 and excess dmf - dma was refluxed for 20 hours . to the reaction mixture was added ethyl acetate and brine , the organic phase was dried over magnesium sulfate , and the solvent was then removed under reduced pressure . the crude product was used for the next step without purification . 4 -( 3 - methyl - 5 - phenyl - isoxazol - 4 - yl )- 2 - methylsulfanyl - pyrimidine ( compound 29 ). a methanol suspension of the above compound 28 , 2 equivalents : of thiourea and 1 . 5 equivalents of sodium methoxide was refluxed for 2 days . to the reaction mixture was added ethyl acetate and 1n hcl , the organic phase was washed with brine and dried over magnesium sulfate , and the solvent was then removed under reduced pressure . the crude product was dissolved in chloroform , to it was added 1 . 5 eq of iodomethane and 1 . 5 eq of pyridine . the reaction mixture was stirred at r . t . for 2 hours . to the reaction mixture was added dichloromethane and 1n hcl , the organic phase was washed with brine and dried with magnesium sulfate . the solvent was removed under reduced pressure , and the crude product was purified by chromatography to provide the title compound . the yield was 32 %. 4 -( 3 - methyl - 5 - phenyl - isoxazol - 4 - yl )- 2 - methanesulfonyl - pyrimidine ( compound 30 ). to a dichloromethane solution of the above compound 29 was added 2 eq of m - cpba , and the reaction was stirred at r . t . for overnight . the reaction mixture was washed with 1n naoh twice and brine twice and dried with magnesium sulfate . the solvent was removed under reduced pressure and the crude product was purified by chromatograph to provide the title compound in 79 % yield . compounds ib . a dmso solution of the above compound 30 and 3 equivalents of desired amine was heated at 80 ° c . for 4 hours . after analytical hplc indicated the reaction was completed , the crude product was purified by reversed hplc to provide the desired compound ib . the yield is generally greater than 80 %. the following examples demonstrate how the compounds of this invention may be tested as protein kinase inhibitors , especially inhibitors of c - jun - n - terminal kinases . a blast search of the est database using the published jnk3α1 cdna as a query identified an est clone , (# 632588 ) that contained the entire coding sequence for human jnk3α1 . polymerase chain reactions ( pcr ) using pfu polymerase ( strategene ) were used to introduce restriction sites into the cdna for cloning into the pet - 15b expression vector at the ncoi and bamhi sites . the protein was expressed in e . coli . due to the poor solubility of the expressed full - length protein ( met 1 - gln 422 ), an n - terminally truncated protein starting at ser residue at position 40 ( ser 40 ) was produced . this truncation corresponds to ser 2 of jnk1 and jnk2 proteins , and is preceded by a methionine ( initiation ) and a glycine residue . the glycine residue was added in order to introduce an ncoi site for cloning into the expression vector . in addition , systematic c - terminal truncations were performed by pcr to identify a construct that give rise to diffraction - quality crystals . one such construct encodes amino acid residues ser40 - glu402 of jnk3α1 and is preceded by met and gly residues . the construct was prepared by pcr using deoxyoligonucleotides : 5 ′ gctctagagctcc atg ggcagcaaaagcaaagttgacaa 3 ′ ( forward primer with initiation codon underlined ) ( seq id no : 1 ) and 5 ′ tagcggatcc tca ttctgaattcattacttccttgta 3 ′ ( reverse primer with stop codon underlined ) ( seq id no : 2 ) as primers and was confirmed by dna sequencing . control experiments indicated that the truncated jnk3 protein had an equivalent kinase activity towards myelin basic protein when activated with an upstream kinase mkk7 in vitro . e . coli strain bl21 ( de3 ) ( novagen ) was transformed with the jnk3 expression construct and grown at 30 ° c . in lb supplemented with 100 μg / ml carbenicillin in shaker flasks until the cells were in log phase ( od 600 ˜ 0 . 8 ). isopropylthio - β - d - galactosidase ( iptg ) was added to a final concentration of 0 . 8 mm and the cells were harvested 2 hours later by centrifugation . e . coli cell paste containing jnk3 was resuspended in 10 volumes / g lysis buffer ( 50 mm hepes , ph 7 . 2 , containing 10 % glycerol ( v / v ), 100 mm nacl , 2 mm dtt , 0 . 1 mm pmsf , 2 μg / ml pepstatin , 1 μg / ml each of e - 64 and leupeptin ). cells were lysed on ice using a microfluidizer and centrifuged at 100 , 000 × g for 30 min at 4 ° c . the 100 , 000 × g supernatant was diluted 1 : 5 with buffer a ( 20 mm hepes , ph 7 . 0 , 10 % glycerol ( v / v ), 2 mm dtt ) and purified by sp - sepharose ( pharmacia ) cation - exchange chromatography ( column dimensions : 2 . 6 × 20 cm ) at 4 ° c . the resin was washed with 5 column volumes of buffer a , followed by 5 column volumes of buffer a containing 50 mm nacl . bound jnk3 was eluted with a 7 . 5 column volume linear gradient of 50 - 300 mm nacl . jnk3 eluted between 150 - 200 mm nacl . 5 mg of jnk3 was diluted to 0 . 5 mg / ml in 50 mm hepes buffer , ph 7 . 5 , containing 100 mm nacl , 5 mm dtt , 20 mm mgcl 2 and 1 mm atp . gst - mkk7 ( dd ) was added at a molar ratio of 1 : 2 . 5 gst - mkk7 : jnk3 . after incubation for 30 minutes at 25 ° c ., the reaction mixture was concentrated 5 - fold by ultrafiltration in a centriprep - 30 ( amicon , beverly , mass . ), diluted to 10 ml and an additional 1 mm atp added . this procedure was repeated three times to remove adp and replenish atp . the final addition of atp was 5 mm and the mixture incubated overnight at 40 ° c . the activated jnk3 / gst - mkk7 ( dd ) reaction mixture was exchanged into 50 mm hepes buffer , ph 7 . 5 , containing 5 mm dtt and 5 % glycerol ( w / v ) by dialysis or ultrafiltration . the reaction mixture was adjusted to 1 . 1 m potassium phosphate , ph 7 . 5 , and purified by hydrophobic interaction chromatography ( at 25 ° c .) using a rainin hydropore column . gst - mkk7 and . unactivated jnk3 do not bind under these conditions such that when a 1 . 1 to 0 . 05 m potassium phosphate gradient is developed over 60 minutes at a flow rate of 1 ml / minute , doubly phosphorylated jnk3 is separated from singly phosphorylated jnk . activated jnk3 ( i . e . doubly . phosphorylated jnk3 ) was stored at − 70 ° c . at 0 . 25 - 1 mg / ml . compounds were assayed for the inhibition of jnk3 by a spectrophotometric coupled - enzyme . assay . in this assay , a fixed concentration of activated jnk3 ( 10 nm ) was incubated with various concentrations of a potential inhibitor dissolved in dmso for 10 minutes at 30 ° c . in a buffer containing 0 . 1 m hepes buffer , ph 7 . 5 , containing 10 mm mgcl 2 , 2 . 5 mm phosphoenolpyruvate , 200 μm nadh , 150 μg / ml pyruvate kinase , 50 μg / ml lactate dehydrogenase , and 200 μm egf receptor peptide . the egf receptor peptide has the sequence krelvepltpsgeapnqallr , and is a phosphoryl acceptor in the jnk3 - catalyzed kinase reaction . the reaction was initiated by the addition of 10 μm atp and the assay plate is inserted into the spectrophotometer &# 39 ; s assay plate compartment that was maintained at 30 ° c . the decrease of absorbance at 340 nm was monitored as a function of time . the rate data as a function of inhibitor concentration was fitted to competitive inhibition kinetic model to determine the k i . for selected compounds of this invention , activity in the jnk inhibition assay is shown in table 8 . compounds having a k i less than 0 . 1 micromolar ( μm ) are rated “ a ”, compounds having a k i between 0 . 1 and 1 μm are rated “ b ” and compounds having a k i greater than 1 μm are rated “ c ”. the compounds were assayed as inhibitors of full length recombinant human src kinase ( from upstate biotechnology , cat . no . 14 - 117 ) expressed and purified from baculo viral cells . src kinase activity was monitored by following the incorporation of 33 p from atp into the tyrosine of a random poly glu - tyr polymer substrate of composition , glu : tyr = 4 : 1 ( sigma , cat . no . p - 0275 ). the following were the final concentrations of the assay components : 0 . 05 m hepes , ph 7 . 6 , 10 mm mgcl 2 , 2 mm dtt , 0 . 25 mg / ml bsa , 10 μm atp ( 1 - 2 μci 33 p - atp per reaction ), 5 mg / ml poly glu - tyr , and 1 - 2 units of recombinant human src kinase . in a typical assay , all the reaction components with the exception of atp were pre - mixed and aliquoted into assay plate wells . inhibitors dissolved in dmso were added to the wells to give a final dmso concentration of 2 . 5 %. the assay plate was incubated at 30 ° c . for 10 min before initiating the reaction with 33 p - atp . after 20 min of reaction , the reactions were quenched with 150 μl of 10 % trichloroacetic acid ( tca ) containing 20 mm na 3 po 4 . the quenched samples were then transferred to a 96 - well filter plate ( whatman , uni - filter gf / f glass fiber filter , cat no . 7700 - 3310 ) installed on a filter plate vacuum manifold . filter plates were washed fourtimes with 10 % tca containing 20 mm na 3 po 4 and then 4 times with methanol . 200 μl of scintillation fluid was then added to each well . the plates were sealed and the amount of radioactivity associated with the filters was quantified on a topcount scintillation counter . the most active compounds in the src assay were found to be those compounds of formula i where g is an optionally substituted aryl and r 1 is ar 2 . the compounds were assayed as inhibitors of lck kinase purified from bovine thymus ( from upstate biotechnology , cat . no . 14 - 106 ). lck kinase activity was monitored by following the incorporation of 33 p from atp into the tyrosine of a random poly glu - tyr polymer substrate of composition , glu : tyr = 4 : 1 ( sigma , cat . no . p - 0275 ). the following were the final concentrations of the assay components : 0 . 05 m hepes , ph 7 . 6 , 10 mm mgcl 2 , 2 mm dtt , 0 . 25 mg / ml bsa , 10 μm atp ( 1 - 2 μci 33 p - atp per reaction ), 5 mg / ml poly glu - tyr , and 1 - 2 units of lck kinase . in a typical assay , all the reaction components with the exception of atp were pre - mixed and aliquoted into assay plate wells . inhibitors dissolved in dmso were added to the wells to give a final dmso concentration of 2 . 5 %. the assay plate was incubated at 30 ° c . for 10 min before initiating the reaction with 33 p - atp . after 20 min of reaction , the reactions were quenched with 150 μl of 10 % trichloroacetic acid ( tca ) containing 20 mm na 3 po4 . the quenched samples were then transferred to a 96 - well filter plate ( whatman , uni - filter gf / f glass fiber filter , cat no . 7700 - 3310 ) installed on a filter plate vacuum manifold . filter plates were washed four times with 10 % tca containing 20 mm na 3 po 4 and then 4 times with methanol . 200 μl of scintillation fluid was then added to each well . the plates were sealed and the amount of radioactivity associated with the filters was quantified on a topcount scintillation counter . the most active compounds in the lck assay were found to be those compounds of formula i where g is an optionally substituted aryl and r 1 is ar 2 . while we have described a number of embodiments of this invention , it is apparent that our basic examples may be altered to provide other embodiments which utilize the compounds and methods of this invention . therefore , it will be appreciated that the scope of this invention is to be defined by the appended claims rather than by the specific embodiments which have been represented by way of example . | 2 |
referring now to the drawings , fig1 illustrates a vehicle generally designated 10 including an exposed spare wheel 12 mounted thereon by a bracket or the like discussed later herein . the vehicle 10 , as it is well known , has a self - contained electrical system which includes taillights 14 . the taillights 14 include running light portions 16 which may be selectively turned on and off in response to the vehicle operator actuating a switch . such running lights aid in causing the vehicle to be more visible , especially during hours of darkness . the taillights 14 also include brake light portions 18 which are automatically turned on in response to the vehicle brakes being actuated . the spare wheel 12 has a wheel cover 20 mounted thereon . wheel cover 20 includes an insert member 22 having indicia thereon displaying , for example , a personalized message such as &# 34 ; john and mary ,&# 34 ; generally designated 24 . in fig2 the spare wheel 12 and wheel cover 20 including insert 22 are shown in exploded view . the wheel 12 , as it is well known , includes a tire portion 26 mounted on a wheel rim 28 connected to a bracket 30 by lugs 32 extending through lug holes 34 . the lugs are secured to the rim 28 by lug nuts 36 in the well known manner . also , a light source generally designated 38 is adapted to be mounted on the wheel 12 as will be discussed later in greater detail . in the preferred embodiment of this invention , as illustrated in fig1 and 6 , insert 22 is preferably a rigid disc - like member formed of light - penetrable or translucent material . the insert 22 generally has an annular periphery 40 although this may be varied to other geometric shapes if desired . insert 22 also includes opposite sides 42 , 44 as best shown in fig6 . a synthetic plastic - like material which is capable of being molded and / or cut to desired sizes is preferred , for example , the synthetic resin material sold under the trademark plexiglas . the insert material may also be color tinted or may be of no discernable color if desired . the preferred thickness of the insert 22 is from about 0 . 080 &# 34 ; to about 0 . 125 &# 34 ;. the insert 22 carries indicia 24 thereon . the indicia may display a personalized message as illustrated in fig1 and 2 or may display a pictorial scene or design . of course , a wide range of types and styles of indicia 24 may be applied to insert 22 if desired . as for applying the indicia 24 onto insert 22 , this may be accomplished by a wide variety of well known methods . indicia may be hand - painted , screen - printed or molded into insert 22 in a multi - colored application . also , a well known vinyl pressure - sensitive applied indicia or design may be applied onto insert 22 . the main prerequisite for the indicia is that it be substantially non - light - penetrable or less light - penetrable relative to the insert 22 . it is to be understood however that , alternatively , insert 22 can be substantially non - light - penetrable or less light - penetrable than the indicia 24 . in either case , one or the other of the insert 22 or indicia 24 provides a defined portion through which light may be penetrated to enhance the visibility of indicia 24 . means are provided for attaching insert 22 to spare wheel 12 . such means preferably comprises a flexible wheel cover portion 46 having a pocket 48 formed therein for receiving and retaining insert 22 , see fig2 and 6 . pocket 48 includes flexible means such as flaps 50 , 52 for releasably engaging opposite sides 42 , 44 , respectively , of insert 22 . flexible wheel cover portion 46 is generally provided for the purpose of protecting tire 26 from the elements . the preferred materials for the cover portion 46 are substantially non - porous , flexible , synthetic materials of from about 14 to about 24 gauge , for example , the synthetic vinyl - like material sold under the trademark naugahyd . any suitable rubberized , plasticized , canvas or vinyl - like materials may be used . as shown in fig2 and 6 , cover portion 46 is provided to fit over tire 26 . thus , since many tire sizes are available , cover portion 46 may be provided in various sizes . possibly , however , a single stretch - type cover portion 46 could be provided for a one - size - fits - all situation . cover portion 46 generally comprises a flexible circumferential portion 54 and two opposed sidewall portions 56 , 58 . annular opening 60 of sidewall 58 is peripherally bound by an elastic bead 62 retained thereby . bead 62 may be stretched or expanded to permit removal of cover portion 46 from tire 26 . however , bead 62 will tend to contract as far as permitted by sidewall 58 thus causing cover portion 46 to be retained on tire 26 , see fig6 . sidewall 56 terminates at two opposed flaps 50 , 52 attached to sidewall 56 and defining annular opening 64 peripherally bound by elastic bead 66 retained by flap 50 and elastic bead 68 retained by flap 52 . beads 66 , 68 are similar to bead 62 described above and may be stretched or expanded to permit removal of insert 22 from pocket 48 . however , beads 66 , 68 will tend to contract as far as permitted by flaps 50 , 52 thus releasably engaging opposite sides 42 , 44 , respectively , of insert 22 . in this manner , insert 22 is readily accessible to removal or mounting in cover portion 46 . means are provided for passing or penetrating light through light - penetrable insert 22 for enhancing the visibility of inidicia 24 . such means preferably comprises a light source such as that shown at 38 , fig2 or in a modified form at 38a in fig3 . light source 38 is adapted to be carried by spare wheel 12 and is electrically connected to the electrical system of the associated vehicle 10 . in this manner , light source 38 is adjacent insert 22 when the cover 20 is mounted on wheel 12 . light source 38 may comprise mounting plates 70 , 82 preferably formed of an electrically conductive material and adapted to be mounted on and grounded to wheel rim 28 . to accomplish this , slots 72 are provided in plate 70 and are circumferentially spaced for mating engagement with lugs 32 . thus , plate 70 can be secured to lugs 32 by lug nuts 36 . a commonly available receptacle 74 can be secured to plate 70 by any suitable conventional securing means . a light bulb 76 , preferably having from about 15 to about 32 candlepower illuminating strength , is received in receptacle 74 . such light bulbs are well known for automotive use . also , modified light source 38a , fig3 includes a housing 78 , light bulb receptacle 80 , bulb 88 , mounting plate 82 having a slot 84 for multi - positionable mounting and a reflective cover 86 of a well known plastic or other synthetic material . cover 86 is especially desirable to protect bulb 88 and receptacle 80 from the elements . returning now to fig2 a wire 90 , such as that commonly used in automotive electrical systems , is connected to receptacle 74 . a commonly known male - female quick connect - disconnect device 92 is preferably used to permit the electrical connection of wire 90 to wire 94 . wire 94 , or a similar or the same type as wire 90 , is connected to the automotive electrical system as illustrated in fig1 . preferably wire 94 connects to running light portions 16 so that insert 22 will be illuminated when the automotive lights are switched on . however , it is possible though not preferable to connect wire 94 to brake light portion 18 so that insert 22 will be illuminated only when the vehicle brakes are applied . connection of wire 94 to the automotive electrical system may be accomplished in any well known manner such as splicing , or using alligator - type clips or the like . of course , the desirable objective of this electrical connection is that it can be of temporary or quick connect - disconnect type such as is commonly used in making electrical connection between an automotive vehicle and , for example , a small trailer . thus , it an be seen that there are several well known alternatives available for making such connection . alternatively , it is possible , but not preferable , to mount insert 22 directly on wheel rim 28 by the use of spring stell clips 96 , see fig4 . mounting in this way is similar to mounting a commonly known hub cap to a wheel . light source 38 is mounted on wheel rim 28 adjacent insert 22 . also , as shown in fig5 insert 22 can alternatively be formed as a unit with a substantially rigid wheel cover 100 having an annular circumferential portion 102 for covering tire 26 . such a unit can be mounted by spring steel clips 96 as previously discussed . similarly , light source 38 is mounted on wheel rim 28 adjacent insert 22 . as a further alternative , it is possible to have insert 22 formed as a flexible member rather than a rigid member , see fig7 . in this case , the entire wheel cover 20 could be formed as a flexible unit having cover portion 46 retained on tire 26 by an elastic bead 62 similar to the preferred embodiment of fig6 . however , a flexible insert 22 would not be as readily removable or replaceable relative to cover portion 46 . also , it is believed that a flexible insert 22 would undesirably distort the indicia thereon . in operation , it can be seen that a flexible wheel cover portion 46 can be mounted on spare wheel 12 . a light source such as that shown at 38 or 38a can be mounted on wheel rim 28 adjacent insert 22 and electrically connected to the electrical system of the associated vehicle 10 . flexible pocket 48 having flaps 50 , 52 and elastic beads 66 , 68 releasably engage and retain opposite sides 42 , 44 , respectively , of insert 22 as is best illustrated in fig6 . flexible pocket 48 permits insert 22 to be quickly and easily removed or inserted . a variety of differently designed inserts could be interchangeably used with the same cover portion 46 . also , various colored light bulbs 76 can be interchangeably used to provide varying lighting effects as may be desired . the foregoing has described a vehicle wheel cover for exposed spare wheels . the cover includes a light - penetrable portion having indicia thereon . the light - penetrable portion can be illuminated to enhance the indicia . as a result , the wheel cover usefully provides protective , aesthetic and safety related value . ______________________________________list of elementsilluminated wheel coverfile no . 77 - 103______________________________________10 vehicle 60 opening12 spare wheel 62 elastic bead14 taillights 64 opening16 running light portion 66 elastic bead on 5018 brake light portion 68 elastic bead on 5220 wheel cover 70 mounting plate22 insert member 72 slots24 indicia 74 receptacle26 tire portion 76 light bulb28 wheel rim 78 housing30 bracket 80 receptacle32 lugs 82 mounting plate34 lug holes 84 slot36 lug nuts 86 cover38 light source 88 bulb38a modified light source 90 wire40 periphery of insert 22 92 disconnect device42 side of insert 22 94 wire44 another side of insert 22 96 spring clips46 wheel cover portion 100 rigid wheel cover48 pocket 102 circumferential portion50 flap52 flap54 circumference56 sidewall58 sidewall______________________________________ | 1 |
a feed forward ( ff ) rf amplifier implementing the principles of the invention that significantly cancels distortion while amplifying the dmt ( i . e ., multi - tone ) input signal . as shown in the functional diagram of fig1 a feed forward amplifier embodying the principles of the invention includes three distinct closed loops . an input high frequency multi - tone signal is applied to input coupler 101 and is coupled to a first amplification path 105 via a coupler 103 . input multi - tones are relayed by coupler 101 to a second amplification path 107 via a delay circuit 109 and coupler 123 . a first adjust path 111 couples to the input via coupler 103 and adjusts the phase of the input signal , in phase adjuster 111 by 180 ° degrees and delays the signal in delay circuit 113 to match corresponding delays in the first amplification path 105 . an output of the first amplification path is coupled to coupler 115 , and so is the adjusted and delayed signal output of delay circuit 113 . the coupler combines and applies these two signals to the imd inversion and phase adjustment circuit 117 . circuit 117 applies these signals , just prior to amplification processes , into the second amplification path 107 . phase adjustment and inversion adjusts the delayed input which when combined with the output of the first amplification path has a multi - tone component in phase with the delayed two tone input applied to the second amplification path . imd distortion components are inverted with respect to the imd output of the first amplification path . the outputs of the two amplification paths are combined in output coupler 121 . the output of the first amplification path is delayed in delay circuit 119 to correspond to delays introduced into the signal by the second amplification path 107 and is applied to output coupler 121 . the two processing loops including amplitude and phase adjustment circuits of 111 and 117 accomplish signal adjustments so that the multi - tone signal is increased in amplitude and the imd is canceled at the output coupler 121 . the amplification system of fig1 is shown in schematic form in the fig2 in which the controlling loops of the system are shown as well as the circuit components . the system is configured so that the main terms in the first and second amplification paths are of equal phase and are additive to increase and maximize rf power output . the imd terms are of opposite phase so that they completely cancel . a high frequency multi - tone rf signal is applied to the input 201 of the coupler 211 and is divided into two signal amplification paths . each amplification path includes an identical rf multi - tone amplifier 221 and 231 respectively . amplifier 221 receives the multi - tone rf and amplifies it and in the process generates signal distortions ( i . e ., imd ). this signal is applied , via delay circuit 202 , to an output coupler 223 where it is combined with a processed rf signal from the second amplification path that enhances the multi - tone rf signal and cancels the imd . amplifier 231 receives an input from the coupler 211 , which has been delayed by delay circuit 212 . a distortion correcting input is also applied to the input of amplifier 231 . a distortion cancellation circuit ( described below ) supplies this correcting input . input to distortion control circuitry is derived from multiple control points of the circuitry . a sensing coupler 242 , connected at the input to amplifier 221 , applies a signal representative of the multi - tone input to a first loop imd adjuster device 252 that controls a magnitude and phase of the sensed signal . this adjusted signal is applied to a delay circuit 254 to compensate for delays occurring in the amplifier 221 . this path may be disconnected by opening a normally closed switch 247 if adding the rf input to the signal processing of the loop is not desired . this adjusted signal is combined with a signal sensed by sensing coupler 244 at the output of amplifier 221 . the multi - tone signal plus imd terms from coupler 244 are combined with the multi - tone signal from delay element 254 in coupling device 256 such that the multi - tone signals cancel , leaving only imd at the output of coupler 256 . the amplitude and phase adjustment circuit from device 262 operates to invert the distortion terms sensed from the output of amplifier 221 . this modified signal is applied to the input of the amplifier 231 via coupler 246 . at this point , the input signal to amplifier 231 comprises a multi - tone rf signal accompanied by an inverted multi - one distortion signal . the inverted imd of the input signal counteracts the imd introduced by amplifier 231 ( i . e ., amplifiers 221 and 231 are identical ). the output of amplifier 231 is an amplified multi - tone rf signal with an accompanying inverted multi - tone distortion signal . when this signal is combined with the output of amplifier 221 as delayed by delay circuit 202 the distortion terms cancel and the multi - tone signals are additive . hence , the overall result is a distortion less multi - tone rf signal output at very high efficiency due to the additive effects from both amplifiers , 221 and 231 . it is readily apparent that the various delays must be selected so that the multi - tone rf signals and multi - tone distortion terms are in exact phase alignment whereby the various summing and inversions may properly cancel the distortion terms and enhance the amplitude of the dial tone rf signal . variable attenuators subject to control signals and variable phase shifting circuits subject to control signals may accomplish amplitude and phase adjustment . a signal sensing point is provided at the node 253 to monitor the signal level applied the second rf amplifier . adjustment of the signal component to a minimum at this point assures that the distortion circuitry is operating properly . as shown in the fig2 schematic , the ff rf amplifier includes inputs for injecting spreading signals into the amplification process . a spreading tone injection point 207 accepts a spreading tone just prior to the feedback coupler 244 . this injected spreading tone provides a mechanism to ensure that the adjustment of circuitry 262 provides proper imd cancellation . a spreading tone is also injected into the output of the amplifier 231 at injection point 245 . despreading of the spread tones is performed at the output at detection point 247 by a despreading circuit 249 . by nulling the spread tone signals at the output of despreading circuit 249 , the nulling of the distortion products is assisted . spreading tones are provided by an oscillation system so that spreading tones provided at points 207 and 237 are synchronized with each other as well as the despreading circuit 249 . while a specific embodiment of the invention has been disclosed , it is understood that those skilled in the art thereof may devise variations without departing from the spirit and scope of the invention . | 7 |
compositions , methods to prepare them , and methods to use them are provided in accordance with the invention . to clarify terminology used herein , compound designation mst - 204 represents 4 - methylumbellifer - 7 - yl - α - d - mannopyranoside . mst - 205 represents 4 - methylumbellifer - 7 - yl - - l - rhamnopyranoside . “ glycosylated coumarins ” as used herein describes many of the group of compounds provided by the invention , namely a coumarin linked by an oxygen or sulfur to a monosaccharide such as allose , altrose , glucose , mannose , idose , galactose , talose , gulose , fructose , tagatose , sorvose , psicose , ribulose , xylulose , ribose , arabinose , xylose , lyxose , or deoxyribose . as used herein the singular forms “ a ”, “ and ”, and “ the ” include plural referents unless the context clearly dictates otherwise . for example , “ a compound ” refers to one or more of such compounds , while “ the enzyme ” includes a particular enzyme as well as other family members and equivalents thereof as known to those skilled in the art . “ alkyl ” is a monovalent , saturated or unsaturated , straight , branched or cyclic , aliphatic ( i . e ., not aromatic ) hydrocarbon group . in various embodiments , the alkyl group has 1 - 20 carbon atoms , i . e ., is a c1 - c20 ( or c 1 - c 20 ) group , or is a c1 - c18 group , a c1 - c12 group , a c1 - c6 group , or a c1 - c4 group . independently , in various embodiments , the alkyl group has : zero branches ( i . e ., is a straight chain ), one branch , two branches , or more than two branches ; is saturated ; is unsaturated ( where an unsaturated alkyl group may have one double bond , two double bonds , more than two double bonds , and / or one triple bond , two triple bonds , or more than three triple bonds ); is , or includes , a cyclic structure ; or is acyclic . exemplary alkyl groups include c 1 alkyl ( i . e ., — ch 3 ( methyl )), c 2 alkyl ( i . e ., — ch 2 ch 3 ( ethyl )) and c 3 alkyl ( i . e ., — ch 2 ch 2 ch 3 ( n - propyl ), — ch ( ch 3 ) 2 ( i - propyl ) and — ch ( ch 2 ) 2 ( cyclopropyl )). “ alkenyl ” is a specie of alkyl group , where an alkenyl group has at least one carbon - carbon double bond . exemplary alkyl groups include c 2 alkenyl ( i . e ., — ch ═ ch 2 ( ethenyl )) and c 3 alkenyl ( i . e ., — ch ═ ch — ch 3 ( 1 - propenyl ), — ch 2 — ch ═ ch 2 ( 2 - propenyl ), and — c ( ch 3 )═ ch 2 ( 1 - methylethenyl )). “ alkynyl ” is a specie of alkyl group , where an alkynyl group has a least one carbon - carbon triple bond . exemplary alkyl groups include — c ≡ ch ( ethynyl )) and — c ≡ c — ch 3 ( 1 - propynyl ), and — ch 2 — c ≡ ch ( 2 - propynyl )). “ cycloalkyl ” indicates a carbocyclic aryl group selected from phenyl , substituted phenyl , naphthyl , and substituted naphthyl . suitable substituents on a phenyl or naphthyl ring include c 1 - c 6 alkyl , c 1 - c 6 alkoxy , carboxyl , carbonyl ( c 1 - c 6 ) alkoxy , halogen , hydroxyl , nitro , — so 3 h , and amino . cycloalkyl can include “ arylenes ” which are polyvalent , aromatic hydrocarbons , ring system . the ring system may be monocyclic or fused polycyclic ( e . g ., bicyclic , tricyclic , etc .). in various embodiments , the monocyclic arylene group is c5 - c10 , or c5 - c7 , or c5 - c6 , where these carbon numbers refer to the number of carbon atoms that form the ring system . the arylene group may be divalent , i . e ., it has two open sites that each bond to another group “ aryl ” is a monovalent , aromatic , hydrocarbon , ring system . the ring system may be monocyclic or fused polycyclic ( e . g ., bicyclic , tricyclic , etc .). in various embodiments , the monocyclic aryl ring is c5 - c10 , or c5 - c7 , or c5 - c6 , where these carbon numbers refer to the number of carbon atoms that form the ring system . a c6 ring system , i . e ., a phenyl ring , is a preferred aryl group . in various embodiments , the polycyclic ring is a bicyclic aryl group , where preferred bicyclic aryl groups are c8 - c12 , or c9 - c10 . a naphthyl ring , which has 10 carbon atoms , is a preferred polycyclic aryl group . “ heteroalkyl ” is an alkyl group ( as defined herein ) wherein at least one of the carbon atoms is replaced with a heteroatom . preferred heteroatoms are nitrogen , oxygen , sulfur , and halogen . a heteroatom may , but typically does not , have the same number of valence sites as carbon . accordingly , when a carbon is replaced with a heteroatom , the number of hydrogens bonded to the heteroatom may need to be increased or decreased to match the number of valence sites of the heteroatom . for instance , if carbon ( valence of four ) is replaced with nitrogen ( valence of three ), then one of the hydrogens formerly attached to the replaced carbon must be deleted . likewise , if carbon is replaced with halogen ( valence of one ), then three ( i . e ., all ) of the hydrogens formerly bonded to the replaced carbon must be deleted . as another example , trifluoromethyl is a heteroalkyl group wherein the three methyl groups of a t - butyl group are replaced by fluorine . “ heteroatom ” is a halogen , nitrogen , oxygen , silicon or sulfur atom . groups containing more than one heteroatom may contain different heteroatoms . a sugar may be a monosaccharide or a disaccharide . monosaccharides are the simplest carbohydrates in that they cannot be hydrolyzed to smaller carbohydrates . they are aldehydes or ketones with two or more hydroxyl groups . the general chemical formula of a monosaccharide is ( c . h2o ) n , with n ≧ 3 . examples of monosaccharides include glucose ( an aldohexose ), fructose ( ketohexose ), and ribose ( an aldopentose ). each carbon atom bearing a hydroxyl group (— oh ), with the exception of the first and last carbons , are asymmetric , making them stereocenters with two possible configurations each ( r or s ). because of this asymmetry , a number of isomers may exist for any given monosaccharide formula . the assignment of d or l is made according to the orientation of the asymmetric carbon furthest from the carbonyl group : in a standard fischer projection if the hydroxyl group is on the right the molecule is a d sugar , otherwise it is an l sugar . glucose can exist in both a straight - chain and ring form . the aldehyde or ketone group of a straight - chain monosaccharide will react reversibly with a hydroxyl group on a different carbon atom to form a heterocyclic ring with an oxygen bridge between two carbon atoms . rings with five and six atoms are called furanose and pyranose forms , respectively , and exist in equilibrium with the straight - chain form . “ azido sugars ” are sugars are sugars wherein an hydroxy grouup has been replaced by an azido , or n 3 group . allose , altrose , glucose , mannose , idose , galactose , talose , gulose , fructose , tagatose , sorbose , psicose , ribulose , xylulose , ribose , arabinose , xylose , lyxose , and deoxyribose . as used herein , and unless otherwise specified , the term heterocyclic encompasses both substituted and unsubstituted carbocyclic and heterocyclic groups . in one embodiment , the substitution present on a carbocyclic or heterocyclic group is selected from alkyl , heteroalkyl , aryl , and heteroaryl , preferably alkyl and heteroalkyl . “ pharmaceutically acceptable salt ” and “ salts thereof ” in the compounds of the present invention refers to acid addition salts and base addition salts . acid addition salts refer to those salts formed from compounds of the present invention and inorganic acids such as hydrochloric acid , hydrobromic acid , sulfuric acid , nitric acid , phosphoric acid and the like , and / or organic acids such as acetic acid , propionic acid , glycolic acid , pyruvic acid , oxalic acid , maleic acid , malonic acid , succinic acid , fumaric acid , tartaric acid , citric acid , benzoic acid , cinnamic acid , mandelic acid , methanesulfonic acid , ethanesulfonic acid , p - toluenesulfonic acid , salicylic acid and the like . base addition salts refer to those salts formed from compounds of the present invention and inorganic bases such as sodium , potassium , lithium , ammonium , calcium , magnesium , iron , zinc , copper , manganese , aluminum salts and the like . suitable salts include the ammonium , potassium , sodium , calcium and magnesium salts derived from pharmaceutically acceptable organic non - toxic bases include salts of primary , secondary , and tertiary amines , substituted amines including naturally occurring substituted amines , cyclic amines and basic ion exchange resins , such as isopropylamine , trimethylamine , diethylamine , triethylamine , tripropylamine , ethanolamine , 2 - dimethylaminoethanol , 2 - diethylaminoethanol , trimethamine , dicyclohexylamine , lysine , arginine , histidine , caffeine , procaines , hydrabamine , choline , betaine , ethylenediamine , glucosamine , methylglucamine , theobromine , purines , piperazine , piperidine , n - ethylpiperidine , and the like . briefly , the compounds of the invention derive from a new 1 class of inhibitors of the metalloenzyme carbonic anhydrase ( ca , ec 4 . 2 . 1 . 1 ) 2 , the coumarins . 3 in this patent we describe classes of coumarins that are newly found to be highly efficient , potent , isoform - selective ca ix / xii inhibitors , which also demonstrate efficacy in vivo in reducing the growth of primary tumors and metastases . the compounds of the invention are useful for the preparation of medicaments as well as in a method for the treatment of a hypoxic tumor that has caix or caxii highly overexpressed . the medicament has inhibiting action toward caix , and particularly it is effective for reversing acidification of a hypoxic tumor and its surrounding environment . the compounds of the invention may be compounded with known pharmaceutical excipients such as salts , water , lipids , and / or simple sugars to arrive at a formulation suitable for injection , topical application , or ingestion . pharmaceutically acceptable excipients make a chemical compound stable , tolerable and acceptable for human use . half - life in circulation can be increased , or better biodistribution achieved , by use of pharmaceutical excipients . formulations of the compounds including pharmaceutical excipients are devised , refined , and tested during the preclinical stage of drug development to ensure that the drug is compatible with any solubilizing , stabilizing , lyophilizing , or hydrating agents . the design of any formulation involves the characterization of a drug &# 39 ; s physical , chemical , and mechanical properties in order to choose what other ingredients should be used in the preparation . particle size , polymorphism , ph , and solubility , as all of these can influence bioavailability and hence the activity of a drug . the drug must be combined with inactive additives by a method which ensures that the quantity of drug present is consistent in each dosage unit e . g . each tablet . by the time phase iii clinical trials are reached , the formulation of the drug should have been developed to be close to the preparation that will ultimately be used in the market . stability studies are carried out to test whether temperature , humidity , oxidation , or photolysis ( ultraviolet light or visible light ) have any effect , and the preparation is analysed to see if any degradation products have been formed . in one embodiment , the compounds of the invention are formulated in polyethyleneglycol with ethanol and saline . in one particular embodiment , the formulation consists of 37 . 5 % peg400 , 12 . 5 % ethanol and 50 % saline . as used in this document , tumor may be taken to mean any primary or metastatic cancer , hypoxic tumor tissue , or malignant growth . any tumor susceptible to hypoxia and / or metastases , particularly breast , lung , renal cancers , cervical , pancreatic , colorectal , glioblastoma , prostate and ovarian cancer may be treated according to embodiments of the invention . tumors susceptible to treatment will have elevated levels of caix or caxii with respect to normal tissue . as demonstrated in the data , caix and caxii are associated with hypoxia and metastases . thus a hypoxic and metastatic tumor would not need to be tested to prove elevated levels of caix and caxii to indicate treatment using the compounds of the invention because of the data already supporting the supposition . tumor growth and / or spread may be said to be suppressed by compounds of the invention , or by their use . suppression in this application may mean induction of regression , inhibition of growth , and inhibition of spread , especially as these terms relate to tumors and cancers suffered by mammals , particularly humans . typical chemotherapeutic agents including , but not limited to docetaxel , vinca alkaloids , mitoxanthrone , cisplatin , paclitaxel , 5 - fu , herceptin , avastin , gleevec may be used concommitally or in combination with the compounds of the invention . compounds of the invention may be used preoperatively , perioperatively , or post - operatively . dosage is typically determined by dosing schemes which use patient size and weight to calculate the patient &# 39 ; s body surface area , which correlates with blood volume , to determine initial dosing . starting dosages are generally worked out during clinical testing of therapeutic compounds . the background and current approaches for the clinical approach to tumor treatment may be found in takimoto c h , calvo e . “ principles of oncologic pharmacotherapy ” in pazdur r , wagman l d , camphausen k a , hoskins w j ( eds ) cancer management : a multidisciplinary approach . 11 ed . 2008 , which is available at www . cancernetwork . com / cancer - management - 11 / chapter03 / article / 10165 / 1402628 . the following examples are used to illustrate aspects of the invention , but the invention is not limited to these illustrations . synthesis was done following and adapting procedures described by penverne , c . and ferrières , v . in synthesis of 4 - methylumbellifer - 7 - yl - alpha - d mannopyranoside : an introduction to modern glycosylation reactions j . chem . educ ., 2002 , 79 ( 11 ), p 1353 . although this example is given in the case of the mannose , similar procedures may be used for the synthesis of other sugar derivatives such as those shown below ( glucose , galactose , rhamnose , xylose , sucrose , and ribose ). numbering ( 1 , 2 , 3 , etc .) in the examples below is based on the numbering in the general synthetic scheme preceding this paragraph . as illustrated schematically above , d - mannose pentaacetate ( 1 ) ( 10 . 25 × 10 − 3 mol ) was dissolved in dry ch 2 cl 2 ( 40 ml ). morpholine ( 41 × 10 − 3 mol ) was then added , and the mixture was stirred under n 2 atmosphere at room temperature over night . the mixture was then washed twice with 40 ml of hcl 1n and 3 × 20 ml of water , dried ( mgso 4 ) and concentrated under vacuum to give the 2 , 3 , 4 , 6 - tetra - o - acetyl - d - mannopyranose ( 2 ). compound 2 , 3 , 4 , 6 - tetra - o - acetyl - d - mannopyranose ( 2 ) ( 4 . 31 × 10 − 3 mol ) was dissolved in dry ch 2 cl 2 ( 38 ml ). trichloacetonitrile ( 43 . 1 × 10 − 3 mol ) was added , and the mixture was stirred under n 2 atmosphere at 0 ° c . for 1 h . then diazabicyclo [ 5 . 4 . 0 ] undec - 7 - ene ( dbu ) ( 0 . 86 × 10 − 3 mol ) was added and the mixture was stirred under n 2 atmosphere at 0 ° c . for 30 min and concentrated under vacuum . the crude 2 , 3 , 4 , 6 - tetra - o - acetyl - d - mannopyranosyl trichloroacetimidate ( 3 ) was used without further purification in the next step . the crude 2 , 3 , 4 , 6 - tetra - o - acetyl - d - mannopyranosyl trichloroacetimidate ( 3 ) ( 4 . 31 × 10 − 3 mol ) was dissolved in dry ch 2 cl 2 ( 38 ml ). 7 - hydroxy - 4 - methyl coumarin ( 4 ) ( 4 . 31 × 10 − 3 mol ) and boron trifluoride metherate ( bf 3 . me 2 o ) ( 0 . 86 × 10 − 3 mol ) were then added and the mixture was stirred under n 2 atmosphere at room temperature over night . 20 ml of ch 2 cl 2 were further added and the solution was washed with water , dried over anhydrous mgso 4 and concentrated under vacuum . the crude product ( 5 ) was then purified by crystallization from meoh or by silica gel column chromatography ( ep / acoet v / v 5 / 5 ). the 2 , 3 , 4 , 6 - tetra - o - acetyl - α - d - mannopyranosyl coumarin ( 5 ) ( 0 . 59 × 10 − 3 mol ) was added to a solution of meona ( 0 . 88 × 10 − 3 mol ) in dry meoh ( 5 ml ). the mixture was stirred at room temperature for 30 min . the product ( 6 ) was then purified by crystallization or by silica gel column chromatography ( ep / acoet v / v 5 / 5 ) to provide : overall yield : 51 %; rf : 0 . 24 ( ch 2 cl 2 / meoh 9 / 1 ). mp : 132 - 134 ° c . 1 h - nmr ( 400 . 13 mhz , dmso - d6 ) δ ppm : 2 . 4 ( d , 3h , j = 0 . 8 hz ), 3 . 33 ( m , 1h ), 3 . 47 ( m , 1h ), 3 . 51 ( t , 1h , j = 9 . 4 hz ), 3 . 57 ( m , 1h ), 3 . 69 ( dd , 1h , j = 9 . 2 hz ), 3 . 86 ( d , 1h , j = 1 . 2 hz ), 5 . 53 ( d , 1h , j = 1 . 6 hz ), 6 . 24 ( d , 1h , j = 1 . 2 hz ), 7 . 09 ( d , 1h , j = 2 . 4 hz ), 7 . 11 ( dd , 1h , j = 8 . 8 hz , j = 2 . 4 hz ); 7 . 70 ( d , 1h , j = 8 . 8 hz ). 13 c - nmr ( 100 mhz , dmso - d6 ) δ ppm 18 . 82 , 61 , 66 . 95 , 70 . 43 , 71 , 76 . 06 , 99 . 48 , 104 . 31 , 112 . 38 , 114 . 38 , 114 . 79 , 127 . 14 , 160 . 80 , 159 . 83 , 155 . 02 , 154 . 05 . ms ( esi + ) m / z : 339 . 24 [ m + h ] + ; 361 . 29 [ m + na ] + ; 699 . 37 [ 2m + na ] + . anal . calcd . for c 16 h 18 o 8 : c , 56 . 80 ; h , 5 . 36 . found : c , 56 . 84 ; h , 5 . 33 . overall yield : 58 %; rf : 0 . 4 ( ch 2 cl 2 / meoh 9 / 1 ). mp : 207 - 209 ° c . 1 h - nmr ( 400 . 13 mhz , cdcl 3 ): δ ppm 1 . 14 ( d , 3h , j = 6 . 4 hz ), 2 . 35 ( d , 1h , j = 1 . 2 hz ), 3 . 86 ( q , 1h , j = 5 . 3 hz ), 5 . 10 ( t , 1h , j = 10 hz ), 5 . 42 ( d , 1h , j = 3 . 6 hz ), 5 . 44 ( t , 1h , j = 2 . 3 hz , h 2 ), 5 . 45 ( t , 1h , j = 2 . 2 hz ), 6 . 13 ( d , 1h , j = 0 . 8 hz ), 7 . 02 ( d , 1h , j = 2 . 4 hz ), 7 . 06 ( dd , 1h , j = 8 . 8 hz , j = 2 . 4 hz ), 7 . 47 ( d , 1h , j = 8 . 8 hz ). 13 c - nmr ( 100 mhz , cdcl 3 ): δ ppm 21 . 05 , 21 . 11 , 69 , 69 . 27 , 69 . 51 , 70 . 1 , 95 , 104 . 26 , 113 . 23 , 113 . 61 , 125 , 152 . 52 , 155 . 10 , 158 . 61 , 170 . 15 , 170 . 31 . ms ( esi + ) m / z : 345 . 31 [ m + na ] + ; 667 . 39 [ 2m + na ] + . anal . calcd . for c 16 h 18 o 7 : c , 59 . 62 ; h , 5 . 63 . found : c , 59 . 58 ; h , 5 . 65 . overall yield : 60 %; rf : 0 . 45 ( acoet / meoh 8 / 2 ). 1 h - nmr ( 400 . 13 mhz , dmso - d6 ): δ ppm 2 . 38 ( d , 3h , j = 1 . 2 hz ); 3 . 91 ( m , 1h ), 4 . 03 ( m , 1h ), 4 . 70 ( t , 1h , j = 5 . 4 hz ); 5 . 07 ( d , 1h , j = 6 hz ), 5 . 61 ( d , 1h , j = 2 hz ), 6 . 23 ( s , 1h ), 6 . 77 ( d , 1h , j = 2 hz ), 6 . 96 ( dd , 1h , j = 8 . 4 hz , j = 2 hz ), 7 . 68 ( d , 1h , j = 8 . 4 hz ). 13 c - nmr ( 100 mhz , dmso - d6 ): δ ppm 18 . 09 , 62 . 518 , 70 . 40 , 74 . 46 , 84 . 81 , 103 . 27 , 105 . 05 , 111 . 55 , 113 . 36 , 113 . 84 , 126 . 46 , 153 . 32 , 155 . 3 , 159 . 32 , 160 . 05 . ms ( esi + ) m / z : 331 . 26 [ m + na ] + , 639 . 25 [ 2m + na ] + . anal . calcd . for c 15 h 16 o 7 : c , 58 . 44 ; h , 5 . 23 . found : c , 58 . 40 ; h , 5 . 25 . overall yield : 55 %; rf : 0 . 39 ( ch 2 cl 2 / meoh 8 / 2 ). mp : 210 - 212 ° c . 1 h - nmr ( 400 . 13 mhz , dmso - d6 ): δ ppm 2 . 41 ( s , 3h ), 3 . 17 ( dd , 1h , j = 14 . 2 hz , j = 8 . 8 hz ); 3 . 29 ( dd , 2h , j = 11 . 9 hz , j = 7 . 4 hz ), 3 . 40 - 3 . 53 ( m , 2h ), 5 . 08 ( d , 1h , j = 5 . 3 hz ), 6 . 25 ( s , 1h ), 7 . 03 ( d , 1h , j = 2 . 4 hz ), 7 . 05 ( dd , 1h , j = 9 . 2 hz , j = 2 . 4 hz ), 7 . 71 ( d , 1h , j = 9 . 2 hz ). 13 c - nmr ( 100 mhz , dmso - d6 ): δ ppm 18 . 35 , 60 . 86 , 69 . 85 , 73 . 35 , 76 . 70 , 77 . 36 , 100 . 21 , 103 . 42 , 111 . 92 , 113 . 60 , 114 . 29 , 126 . 63 , 153 . 56 , 154 . 61 , 160 . 33 , 160 . 37 . ms ( esi + ) m / z : 361 . 38 [ m + na ] + . anal . calcd . for c 16 h 18 o 8 : c , 56 . 80 ; h , 5 . 36 . found : c , 56 . 85 ; h , 5 . 41 . overall yield : 64 %; rf : 0 . 35 ( ch 2 cl 2 / meoh 8 / 2 ). mp : 248 ° c . 1 h - nmr ( 400 . 13 mhz , dmso - d6 ): δ ppm 2 . 41 ( s , 3h ), 3 . 44 ( ddd , 1h , j = 9 . 2 hz , j = 5 . 5 hz , j = 3 . 3 hz ), 3 . 48 - 3 . 65 ( m , 3h ), 3 . 68 ( t , 1h , j = 6 . 3 hz ), 3 . 72 ( t , 1h , j = 3 . 8 hz ), 4 . 99 ( d , 1h , j = 7 . 7 hz ), 6 . 25 ( s , 1h ), 7 . 02 ( d , 1h , j = 2 . 4 hz ), 7 . 05 ( dd , 1h , j = 9 . 1 hz , j = 2 . 4 hz ); 7 . 70 ( d , 1h , j = 9 . 1 hz ). 13 c - nmr ( 100 mhz , dmso - d6 ): δ ppm 18 . 15 , 60 . 39 , 68 . 13 , 69 . 87 , 73 . 22 , 75 . 71 , 100 . 60 , 103 . 15 , 112 . 24 , 112 . 85 , 114 . 79 , 126 . 17 , 153 . 89 , 154 . 75 , 160 . 19 , 160 . 19 . ms ( esi + ) m / z : 361 . 35 [ m + na ] + . anal . calcd . for c 16 h 18 o 8 : c , 56 . 80 ; h , 5 . 36 . found : c , 56 . 75 ; h , 5 . 31 . overall yield : 45 %; rf : 0 . 58 ( ch 2 cl 2 / meoh 8 / 2 ). mp : 223 ° c . 1 h - nmr ( 400 . 13 mhz , dmso - d6 ): δ ppm 2 . 40 ( s , 3h ); 3 . 27 ( d , 2h , j = 2 . 3 hz ), 3 . 40 ( m , 2h ), 3 . 76 ( m , 1h ), 5 . 12 ( d , 1h , j = 3 . 9 hz ), 6 . 25 ( s , 1h ), 7 . 01 ( d , j = 2 . 4 hz , 1h ), 7 . 03 ( dd , 1h , j = 9 . 2 hz , j = 2 . 4 hz ), 7 . 70 ( d , j = 9 . 2 hz , 1h ). 13 c - nmr ( 100 mhz , dmso - d6 ): δ ppm 18 . 13 , 62 . 73 , 69 . 27 , 72 . 95 , 76 . 32 , 100 . 32 , 102 . 74 , 112 . 74 , 113 . 36 , 114 . 13 , 126 . 47 , 153 . 32 , 155 . 3 , 159 . 32 , 160 . 05 . ms ( esi + ) m / z : 331 . 32 [ m + na ] + . anal . calcd . for c 15 h 16 o 7 : c , 58 . 44 ; h , 5 . 23 . found : c , 58 . 49 ; h , 5 . 20 . overall yield : 47 %; rf : 0 . 1 ( acoet / meoh 8 / 2 ). mp : 103 - 105 ° c . 1 h - nmr ( 400 . 13 mhz , dmso - d6 ): δ ppm 2 . 41 ( s , 3h ), 3 . 18 ( dd , 1h , j = 25 . 6 hz , j = 13 . 2 hz ), 3 . 32 ( m , 3h ), 3 . 40 ( dd , 2h , j = 10 . 7 hz , j = 6 . 3 hz ), 3 . 55 ( m , 6h ), 4 . 65 ( d , 1h , j = 3 . 4 hz ), 5 . 00 ( d , 1h , j = 7 . 3 hz ), 6 . 26 ( s , 1h ), 7 . 04 ( d , 1h , j = 2 . 4 hz ), 7 . 10 ( dd , 1h , j = 8 . 8 hz , j = 2 . 4 hz ); 7 . 71 ( d , 1h , j = 8 . 8 hz ). 13 c - nmr ( 100 mhz , dmso - d6 ): δ ppm 20 . 66 , 59 . 99 , 60 . 08 , 68 . 25 , 68 . 35 , 69 . 88 , 70 . 09 , 71 . 14 , 74 . 32 , 75 . 05 , 77 . 26 , 98 . 89 , 100 . 02 , 104 . 67 , 111 . 38 , 112 . 53 , 114 . 23 , 126 . 55 , 154 . 17 , 160 . 28 , 166 . 57 , 173 . 79 . ms ( esi + ) m / z : 523 . 16 [ m + na ] + . anal . calcd . for c 22 h 28 o 13 : c , 52 . 80 ; h , 5 . 64 . found : c , 52 . 75 ; h , 5 . 61 . the huisgen reaction is a very versatile chemical transformation consistent in the coupling of an alkyne or alkene , as diapolarophile , and a 1 , 3 - dipolar compound such as an azide , nitriloxide and diazoalkane . the coupling of an acetylenic coumarin / thiocoumarin scaffold with phenylazide ( scheme 1 below ) and an azido coumarin with acetilenic compounds ( scheme 2 below ) via a copper catalyzed reaction is shown . the syntheses were carried out adapting the procedures reported in brant c . boren , sridhar narayan , lars k . rasmussen , et al ., j . am . chem . soc ., 2008 , 130 , 8923 - 8930 ; li zhang , xinguo chen , peng xue , et al ., j . am . chem . soc ., 2005 , 127 , 15998 - 15999 ; herna &# 39 ; n a . orgueira ,* demosthenes fokas , yuko ( some , et al ., tet . lett ., 2005 , 46 , 2911 - 2914 ; giancarlo cravotto , gianni balliano , silvia tagliapietra , et al ., eur . j . of med . chem ., 2004 , 39 , 917 - 924 ; jacob kofoed , tamis darbre and jean - louis reymond , org . biomol . chem ., 2006 , 4 , 3268 - 3281 ; and andrew fryer in pct publication wo 2008 / 147764 a1 . 7 - hydroxy coumarin 1 ( 1 . 0 g , 1 . 0 eq ), propargyl alcohol ( 1 . 0 eq ) and triphenylphoshine ( 1 . 0 eq ) were dissolved in dry thf ( 90 ml ). then the temperature was lowered to 0 ° c . and diisopropylazadicarboxylate ( 1 . 1 eq ) was added drop - wise under sonication . the orange solution was sonicated at r . t . under a nitrogen atmosphere until starting material was consumed ( tlc monitoring ). solvents were removed under vacuo to give a white solid that was recrystallized from meoh to give 2 as white solid . 7 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one 2 : m . p . 118 ° c . ( lit 120 ° c . ); page : 31 rodighiero , p . ; manzini , p . ; pastorini , g . ; bordin , f . ; guiotto , a ., journal of heterocyclic chemistry , 24 , 2 , 485 - 8 . silica gel tlc r f 0 . 53 ( ethyl acetate / n - hexane 50 % v / v ); v max ( kbr ) cm − 1 , 3310 ( c ≡ c — h ), c2160 ( c ≡ ch ), 1765 ( c ═ o ), 1604 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 3 . 69 ( 1h , t , j 2 . 4 , 3 ′- h ), 4 . 97 ( 2h , d , j 2 . 4 , 1 ′- h 2 ), 6 . 36 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 03 ( 1h , dd , j 8 . 5 , 2 . 3 , 6 - h ), 7 . 09 ( 1h , d , j 2 . 3 , 8 - h ), 7 . 69 ( 1h , d , j 8 . 5 , 5 - h ), 8 . 03 ( 1h , d , j 9 . 6 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ) 161 . 1 ( c - 2 ), 161 . 0 ( c - 7 ), 156 . 0 ( c - 8a ), 145 . 1 ( c - 4 ), 130 . 4 ( c - 5 ), 113 . 9 ( c - 3 ), 113 . 8 ( c - 4 - a ), 113 . 7 ( c - 6 ), 102 . 7 ( c - 8 ), 79 . 8 ( c - 2 ′), 79 . 4 ( c - 3 ′) and 57 . 0 ( c - 1 ′). 7 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one 2 ( 0 . 2 g , 1 . 0 eq ) and lawesson &# 39 ; s reagent ( 1 . 5 eq ) were dissolved in dry toluene ( 10 ml ) and the yellow solution was refluxed until starting material was consumed ( tlc monitoring ). then the solvent was removed under vacuo and the orange residue was partitioned between h 2 o and ethyl acetate . the organic phase was washed with h 2 o ( 2 × 20 ml ), brine ( 3 × 20 ml ), dried over na 2 so 4 , filtered off and concentrated under vacuo to give a red sticky oil that was purified by silica gel column chromatography eluting with 10 % ethyl acetate in n - hexane to give 3 as a yellow solid . 7 -( prop - 2 - ynyloxy )- 2h - chromene - 2 - thione 3 : m . p . 97 - 101 ° c . ; silica gel tlc r f 0 . 27 ( ethyl acetate / n - hexane 10 % v / v ); v max ( kbr ) cm − 1 , 3300 ( c ≡ c — h ), 2165 ( c ≡ ch ), 1601 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 3 . 72 ( 1h , t , j 2 . 4 , 3 ′- h ), 5 . 02 ( 2h , d , j 2 . 4 , 1 ′- h 2 ), 7 . 13 ( 1h , dd , j 9 . 2 , 2 . 4 , 6 - h ), 7 . 18 ( 1h , d , j 9 . 2 , 3 - h ), 7 . 31 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 80 ( 1h , d , j 9 . 2 , 5 - h ), 7 . 90 ( 1h , d , j 9 . 2 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ) 198 . 1 ( c - 2 ), 161 . 8 ( c - 7 ), 158 . 6 ( c - 8a ), 137 . 4 ( c - 4 ), 130 . 6 ( c - 5 ), 127 . 4 ( c - 3 ), 115 . 7 ( c - 4 - a ), 115 . 6 ( c - 6 ), 102 . 3 ( c - 8 ), 80 . 0 ( c - 2 ′), 79 . 2 ( c - 3 ′) and 57 . 3 ( c - 1 ′). anal . calc %. c , 66 . 65 ; h , 3 . 73 ; s , 14 . 83 ; anal . found . c , 65 . 36 ; h , 3 . 71 ; s , 9 . 37 . 7 -( prop - 2 - ynyloxy )- 2h - chromene - 2 - thione 3 ( 0 . 1 g , 1 . 0 eq ) and phenylazide ( 1 . 1 eq ) were dissolved in tert - butoh / h 2 o ( 1 / 1 , 2 . 0 ml ). then tetramethylamonium chloride ( 1 . 0 eq ) and copper nanosize ( 10 % mol ) were added . the mixture was vigorously stirred at r . t . until starting material was consumed ( tlc monitoring ). solvents were removed under vacuo ( temperature has not to exceed 40 ° c .) and the brown residue was purified by silica gel column chromatography eluting with 50 % ethyl acetate in n - hexane to give 4 as a yellow solid . characterization : 7 -[( 1 - phenyl - 1h - 1 , 2 , 3 - triazol - 4 - yl ) methoxy ]- 2h - chromene - 2 - thione 4 : silica gel tlc r f 0 . 50 ( ethyl acetate / n - hexane 10 % v / v ); v max ( kbr ) cm − 1 , 1604 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 5 . 50 ( 2h , s , 1 ′- h 2 ), 7 . 12 ( 1h , dd , j 9 . 6 , 2 . 4 , 6 - h ), 7 . 26 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 35 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 58 ( 1h , tt , j 7 . 6 , 1 . 2 , ar — h ), 7 . 70 ( 2h , d , j 7 . 6 , 2 × ar — h ), 7 . 72 ( 1h , d , j 9 . 6 , 5 - h ), 7 . 95 ( 2h , d , j 7 . 6 , 2 × ar — h ), 8 . 02 ( 1h , d , j 9 . 6 , 4 - h ), 9 . 01 ( 1h , s , 3 ′- h ); δ c ( 100 mhz , dmso - d 6 ) 198 . 0 ( c - 2 ), 162 . 0 ( c - 7 ), 157 . 0 ( c - 8a ), 146 . 3 ( c - 2 ′), 144 . 0 ( c - 4 ), 136 . 0 , 132 . 0 , 131 . 0 , 1230 , 124 . 6 , 121 . 0 , 115 . 0 , 114 . 0 , 113 . 7 , 103 . 0 ( 0 - 8 ) and 63 . 0 ( c - 1 ′). 7 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one 2 ( 0 . 08 g , 1 . 0 eq ) and phenylazide ( 1 . 1 eq ) were dissolved in tert - butoh / h 2 o ( 1 / 1 , 2 . 0 ml ) and then tetramethylamonium chloride ( 1 . 0 eq ) and copper nanosize ( 5 % mol ) were added . the mixture was vigorously stirred at r . t . until starting material was consumed ( tlc monitoring ). solvents were removed under vacuo ( temperature has not to exceed 40 ° c .) and the brown residue was purified by silica gel column chromatography eluting with 25 % ethyl acetate in n - hexane to give 5 as a white solid . characterization : 7 -[( 1 - phenyl - 1h - 1 , 2 , 3 - triazol - 4 - yl ) methoxy ]- 2h - chromen - 2 - one 5 : m . p . 170 - 174 ° c . silica gel tlc r f 0 . 11 ( ethyl acetate / n - hexane 25 % v / v ); v max ( kbr ) cm − 1 1750 ( c ═ o ), 1602 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 5 . 40 ( 2h , s , 1 ′- h 2 ), 6 . 35 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 10 ( 1h , dd , j 9 . 6 , 2 . 4 , 6 - h ), 7 . 24 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 55 ( 1h , tt , j 7 . 6 , 1 . 2 , ar — h ), 7 . 65 ( 2h , d , j 7 . 6 , 2 × ar — h ), 7 . 7 ( 1h , d , j 9 . 6 , 5 - h ), 7 . 95 ( 2h , d , j 7 . 6 , 2 × ar — h ), 8 . 04 ( 1h , d , j 9 . 6 , 4 - h ), 9 . 04 ( 1h , s , 3 ′- h ); δ c ( 100 mhz , dmso - d 6 ) 162 . 0 ( c - 2 ), 161 . 2 ( c - 7 ), 156 . 2 ( c - 8a ), 145 . 2 ( c - 2 ′), 144 . 1 ( 0 - 4 ), 138 . 0 , 130 . 9 , 130 . 5 , 129 . 8 , 124 . 1 , 121 . 2 , 113 . 8 , 113 . 7 , 113 . 6 , 102 . 6 ( 0 - 8 ) and 63 . 0 ( c - 1 ′). 7 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one 2 ( 0 . 1 g , 1 . 0 eq ) was dissolved in thf ( 10 ml ) and then cobalt carbonyl ( 1 . 05 eq ) was added . the black solution was stirred at r . t . for 40 min . then sio 2 ( 0 . 3 g ) was added and solvent removed under vacuo to give a black solid that was purified by silica gel column chromatography eluting with 20 % ethyl acetate in n - hexane to give 6 as a red solid . characterization : 7 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one hexacarbonyldicobalt 6 : silica gel tlc r f 0 . 22 ( ethyl acetate / n - hexane 20 % v / v ); v max ( kbr ) cm − 1 1752 ( c ═ o ), 1600 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 5 . 50 ( 2h , s , 1 ′- h 2 ), 6 . 35 ( 1h , d , j 9 . 4 , 3 - h ), 6 . 89 ( 1h , s , 3 ′- h ), 7 . 00 ( 1h , dd , j 8 . 8 , 2 . 4 , 6 - h ), 7 . 11 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 70 ( 1h , d , j 8 . 8 , 5 - h ), 8 . 04 ( 1h , d , j 9 . 4 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ) 200 . 9 ( c ═ o ), 161 . 7 ( c - 2 ), 161 . 0 ( c - 7 ), 156 . 2 ( c - 8a ), 145 . 1 ( c - 4 ), 130 . 5 ( c - 5 ), 113 . 7 , 113 . 6 , 113 . 4 , 102 . 4 ( c - 8 ), 90 . 8 ( c - 3 ′), 73 . 9 and 69 . 4 . 7 -( prop - 2 - ynyloxy )- 2h - chromene - 2 - thione 3 ( 0 . 02 g , 1 . 0 eq ) was treated with cobalt carbonyl ( 1 . 05 eq ) as for the procedure for 6 . the solvent removed under vacuo to gave a black solid that was purified by silica gel column chromatography eluting with 10 % ethyl acetate in n - hexane affording 7 as a red solid . characterization : 7 -( prop - 2 - ynyloxy )- 2h - chromene - 2 - thione hexacarbonyldicobalt 7 : silica gel tlc r f 0 . 13 ( ethyl acetate / n - hexane 10 % v / v ); v max ( kbr ) cm − 1 1750 ( c ═ o ), 1603 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 5 . 55 ( 2h , s , 1 ′- h 2 ), 6 . 90 ( 1h , s , 3 ′- h ), 7 . 09 ( 1h , dd , j 8 . 8 , 6 - h ), 7 . 20 ( 1h , d , j 9 . 2 , 3 - h ), 7 . 36 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 82 ( 1h , d , j 8 . 8 , 5 - h ), 7 . 90 ( 1h , d , j 9 . 2 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ) 200 . 7 ( c ═ o ), 198 . 3 ( c ═ s ), 166 . 5 , 162 . 4 , 158 . 9 , 137 . 2 , 131 . 0 , 127 . 9 , 115 . 4 , 101 . 9 , 73 . 9 , 69 . 7 and 57 . 4 ; anal . calc %. c , 44 . 12 ; h , 2 . 14 ; s , 6 . 20 . anal . found . 42 . 75 ; h , 1 . 22 ; s , 3 . 94 . propargylamine 8 ( 1 . 0 g , 1 . 0 eq ) and triethylamine ( 1 . 1 eq ) were dissolved in dcm ( 80 ml ). the solution was cooled to 0 ° c . and tert - butyloxycarbonylcarbonate ( 1 . 1 eq ) dissolved in 20 ml of dcm was added drop - wise . the solution was stirred at r . t . for 5 h then was quenched with aqueous hcl 1 . 0m ( 100 ml ) and the organic layer was washed with h2o ( 3 × 50 ml ), brine ( 3 × 20 ml ) and dried over na 2 so 4 , filtered off and concentrated under vacuo to give a brown oil that was purified by silica gel column chromatography eluting with 10 % ethyl acetate in n - hexane to give 9 as a colorless oil . characterization : tert - butyl prop - 2 - ynylcarbamate 9 : silica gel tlc r f 0 . 20 ( ethyl acetate / n - hexane 10 % v / v ); v max ( kbr ) cm − 1 3350 ( c ≡ c — h ), 2170 ( c ≡ ch ), 1760 ( c ═ o ); δ h ( 400 mhz , dmso - d 6 ) 1 . 42 ( 9h , s , 3 × ch 3 ), 3 . 08 ( 1h , t , j 4 . 0 , 4 - h ), 3 . 73 ( 2h , m , 2 - h 2 ), 7 . 29 ( 1h , brs , 1 - h ); δ c ( 100 mhz , dmso - d 6 ) 156 . 6 ( c ═ o ), 82 . 6 , 79 . 1 , 73 . 6 , 30 . 3 ( c - 2 ) and 29 . 9 ( 3 × ch3 ). 7 - amino - 4 - methyl - 2h - chromen - 2 - one 10 ( 0 . 1 g , 1 . 0 eq ) was dissolved in a freshly prepared 40 % solution of concentrated hydrochloric acid in deionised water ( 3 . 0 ml ) and then cooled down to − 5 ° c . then a 2 . 3 m aqueous solution of nano 2 ( 2 . 0 eq ) was added dropwise and the mixture was kept stirring at the same temperature until a persistent pale yellow solution was formed ( 5 - 10 min ). finally a 5 . 0 m aqueous solution of nano 2 ( 2 . 0 eq ) was added drop - wise the mixture was stirred at r . t . for 10 min ., extracted with dcm ( 3 × 25 ml ) and the combined organic layers were dried over na 2 so 4 , filtered off and concentrated under vacuo ( temperature has not to exceed 30 ° c .) to give a 11 as a yellow solid that was used without further purification . characterization : 7 - azido - 4 - methyl - 2h - chromen - 2 - one 11 : silica gel tlc r f 0 . 27 ( ethyl acetate / n - hexane 20 % v / v ); v max ( kbr ) cm − 1 2150 ( n 3 ), 1730 ( c ═ o ); δ h ( 400 mhz , dmso - d 6 ) 2 . 45 ( 9h , s , 3 × ch 3 ), 6 . 37 ( 1h , d , j 1 . 2 , 8 - h ), 7 . 16 ( 1h , dd , j 1 . 2 , 6 - h ), 7 . 19 ( 1h , d , j 1 . 2 , 3 - h ), 7 . 81 ( 1h , j 8 . 4 , 5 - h ); δ c ( 100 mhz , dmso - d 6 ) 160 . 4 ( c ═ o ), 155 . 0 , 153 . 8 , 144 . 2 , 127 . 9 , 117 . 7 , 116 . 5 , 114 . 1 , 107 . 7 and 19 . 0 ( ch 3 ). 7 - azido - 4 - methyl - 2h - chromen - 2 - one 11 ( 0 . 09 g , 1 . 0 eq ) and tert - butyl prop - 2 - ynylcarbamate 9 ( 1 . 0 eq ) were dissolved in tert - butoh / h 2 o ( 1 / 1 , 3 . 0 ml ) and then tetramethylamonium chloride ( 1 . 0 eq ) and copper nanosize ( 5 % mol ) were added . the mixture was vigorously stirred at r . t . until starting material was consumed ( tlc monitoring ). solvents were removed under vacuo ( temperature has not to exceed 40 ° c .) and the brown residue was purified by silica gel column chromatography eluting with 50 % ethyl acetate in n - hexane to give 12 as a yellow solid . characterization : tert - butyl [ 1 -( 4 - methyl - 2 - oxo - 2h - chromen - 7 - yl )- 1h - 1 , 2 , 3 - triazol - 4 - yl ] methylcarbamate 12 : silica gel tlc r f 0 . 13 ( ethyl acetate / n - hexane 50 % v / v ); v max ( kbr ) cm − 1 1735 ( c ═ o ), 1650 ( c ═ o ); δ h ( 400 mhz , dmso - d 6 ) 1 . 44 ( 9h , s , 3 × ch 3 ), 2 . 51 ( 3h , s , ch 3 ), 4 . 32 ( 2h , d , j 4 , 3 ′- h 2 ), 6 . 50 ( 1h , d , j 1 . 2 , 3 - h ), 7 . 43 ( 1h , t , j 4 , n — h ), 8 . 02 ( 3h , m , 5 , 6 , 8 - h ), 8 . 81 ( 1h , s , 1 ′- h ); δ c ( 100 mhz , dmso - d 6 ) 160 . 4 , 156 . 5 , 154 . 6 , 153 . 6 , 148 . 0 , 139 . 5 , 128 . 1 , 122 . 0 , 120 . 3 , 116 . 3 , 115 . 5 , 108 . 2 , 79 . 0 , 36 . 5 , 29 . 2 and 19 . 0 7 - azido - 4 - methyl - 2h - chromen - 2 - one 11 ( 0 . 05 g , 1 . 0 eq ) and 7 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one 2 ( 1 . 0 eq ) were dissolved in tert - butoh / h 2 o ( 1 / 1 , 1 . 0 ml ) and then tetramethylamonium chloride ( 1 . 0 eq ) and copper nanosize ( 5 % mol ) were added . the mixture was vigorously stirred at r . t . until starting material was consumed ( tlc monitoring ). solvents were removed under vacuo ( temperature has not to exceed 40 ° c .) and the brown residue was purified by silica gel column chromatography eluting with ethyl acetate in n - hexane from 20 % to 50 % to give 13 as a yellow solid . characterization : 4 - methyl - 7 -( 4 -(( 2 - oxo - 2h - chromen - 7 - yloxy ) methyl )- 1h - 1 , 2 , 3 - triazol - 1 - yl )- 2h - chromen - 2 - one 13 : silica gel tlc r f 0 . 32 ( ethyl acetate / n - hexane 50 % v / v ); v max ( kbr ) cm − 1 1735 ( c ═ o ), 1730 ( c ═ o ); δ h ( 400 mhz , dmso - d 6 ) 2 . 11 ( 3h , s , ch 3 ), 5 . 44 ( 2h , s , 3 ′- h 2 ), 6 . 35 ( 1h , d , j 9 . 6 , 3 ″- h ), 6 . 53 ( 1h , d , j 1 . 2 , 3 - h ), 7 . 11 ( 1h , dd , j 8 . 4 , 2 . 4 , 6 ″- h ), 7 . 25 ( 1h , d , j 2 . 4 , 8 ″- h ), 7 . 71 ( 1h , d , j 8 . 4 , 5 ″- h ), 8 . 06 ( 4h , m , 5 , 6 , 8 , 4 ″- h ), 9 . 22 ( 1h , s , 1 ′- h ); δ c ( 100 mhz , dmso - d 6 ) 161 . 9 , 161 . 0 , 160 . 3 , 156 . 2 , 154 . 3 , 153 . 7 , 145 . 2 , 144 . 5 , 139 . 3 , 130 . 5 , 128 . 2 , 124 . 4 , 120 . 6 , 116 . 6 , 115 . 8 , 113 . 9 , 113 . 7 , 108 . 6 , 108 . 0 , 102 . 6 , 62 . 5 and 32 . 2 . cinnamic acid ( 1 . 0 g , 1 . 0 eq ) was dissolved in dry dcm ( 20 ml ) and thionyl chloride ( 10 . 0 eq ) was added drop - wise at 0 ° c . the solution was refluxed until starting material was consumed ( tlc monitoring ), solvents removed under vacuo to afford a sticky oily residue that was dissolved in dry pyridine ( 10 ml ) at 0 ° c . and thiophenol ( 0 . 74 g , 1 . 0 eq ) was added drop - wise . the yellow solution was stirred at r . t . for 2 hrs , quenched with h2o ( 30 ml ), extracted with ethyl acetate ( 3 × 15 ml ) and the combined organic layers were dried over na 2 so 4 , filtered and concentrated in vacuo to give a residue that was purified by silica gel column chromatography eluting with 5 % ethyl acetate / n - hexane to afford 1 a pale yellow solid . ( e )- s - phenyl 3 - phenylprop - 2 - enethioate 1 ( 0 . 2 g , 1 . 0 eq ) was dissolved in toluene dry ( 5 . 0 ml ) and alcl 3 ( 0 . 56 g , 5 . 0 eq ) was added . the orange solution was stirred at 70 ° c . for 5 hrs ( tlc monitoring ), cooled down to r . t ., quenched with slush and entracte with etyla acetate ( 3 × 20 ml ). the combined organic layers were washed with h2o ( 2 × 20 ml ), dried over na2so4 , filtered off and concentrated in vacuo to give an orange residue that was purified by silica gel column chromatography eluting with 5 % ethyl acetate / n - hexane to afford 2 as a pale yellow solid . ( e )- s - phenyl 3 - phenylprop - 2 - enethioate 1 62 % yield ; 94 - 96 ° c . ( lit 91 - 92 ° c . ); silica gel tlc r f 0 . 17 ( ethyl acetate / n - hexane 5 % v / v ); v max ( kbr ) cm − 1 , 1670 ( c ═ o ), 1515 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 7 . 16 ( 1h , d , j 16 . 0 , 2 - h ), 7 . 49 ( 3h , m , 2 × 6 - h , 7 - h ), 7 . 54 ( 5h , s , s — ar — h ), 7 . 70 ( 1h , d , j 16 . 0 , 3 - h ), 7 . 84 ( 2h , m , 2 × 5 - h ); be ( 100 mhz , dmso - d 6 ), 188 . 0 ( c ═ o ), 142 . 5 , 135 . 4 , 134 . 6 , 132 . 0 , 130 . 5 , 130 . 3 , 130 . 0 , 129 . 9 , 128 . 2 , 125 . 2 . 2h - thiochromen - 2 - one 2 55 % yield ; 95 - 98 ° c . ( lit 91 - 92 ° c . ); silica gel tlc r f 0 . 11 ( ethyl acetate / n - hexane 5 % v / v ); v max ( kbr ) cm − 1 , 1660 ( c ═ o ), 1515 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 6 . 65 ( 1h , d , j 10 . 8 , 3 - h ), 7 . 64 ( 3h , m , 5 - h , 6 - h , 7 - h ), 7 . 92 ( 1h , d , j 8 . 0 , 8 - h ), 8 . 12 ( 1h , d , j 10 . 8 , 4 - h ); be ( 100 mhz , dmso - d 6 ), 185 . 1 ( c ═ o ), 145 . 8 , 137 . 2 , 133 . 0 , 131 . 4 , 127 . 8 , 126 . 8 , 126 . 7 , 124 . 4 ; anal . calc . c , 66 . 64 ; h , 3 . 73 ; s , 19 . 77 . anal . found . c , 62 . 96 ; h , 3 . 63 ; s , 12 . 08 . the proper lactone or thiolactone ( 1 . 0 eq ) was dissolved in dry toluene and treated with lawesson &# 39 ; s reagent ( 2 . 0 eq ). the reaction mixture was refluxed until consumption of the starting material ( tlc monitoring ). then solvent was removed in vacuo and the residue obtained was purified by silica gel column chromatography eluting with ethyl acetate in n - hexane to afford the corresponding thione . 2h - thiochromen - 2 - one 2 ( 0 . 03 g , 1 . 0 eq ) was treated according to the general procedure reported above at 70 ° c . for 12 h . purification of the crude residue by silica gel column chromatography eluting with 10 % ethyl acetate / n - hexane to afford the desired product 3 as a red solid . 2h - thiochromene - 2 - thione 3 : 33 % yield ; silica gel tlc r f 0 . 20 ( ethyl acetate / n - hexane 10 % v / v ); v max ( kbr ) cm − 1 , 1770 , 1520 , 1230 ; δ h ( 400 mhz , dmso - d 6 ) 7 . 43 ( 1h , d , j 10 . 0 , 3 - h ), 7 . 61 ( 1h , dt , j 8 . 0 , 1 . 6 , 5 - h ), 7 . 28 ( 2h , m , 6 - h , 7 - h ), 7 . 90 ( 1h , d , j 10 . 0 , 4 - h ), 8 . 00 ( 1h , d , j 8 . 0 , 8 - h ); be ( 100 mhz , dmso - d 6 ), 209 . 7 ( c ═ s ), 140 . 2 , 136 . 9 , 136 . 3 , 133 . 0 , 131 . 9 , 129 . 2 , 128 . 5 , 124 . 6 ; anal . calc . c , 60 . 63 ; h , 3 . 39 ; s , 35 . 97 . anal . found . c , 59 . 48 ; h , 3 . 05 ; s , 21 . 27 . 2h - chromen - 2 - one ( 0 . 5 g , 1 . 0 eq ) was treated according to the general procedure reported above at for 12 h . purification of the crude residue by silica gel column chromatography eluting with 20 % ethyl acetate / n - hexane to afforded the desired product as a yellow solid . 2h - chromene - 2 - thione 4 : 60 % yield ; silica gel tlc r f 0 . 27 ( ethyl acetate / n - hexane 20 % v / v ); v max ( kbr ) cm − 1 1765 , 1518 , 1220 ; δ h ( 400 mhz , dmso - d 6 ) 7 . 31 ( 1h , d , j 10 . 0 , 3 - h ), 7 . 61 ( 1h , dt , j 7 . 6 , 1 . 2 , 6 - h ), 7 . 64 ( 1h , d , j 8 . 4 , 5 - h ), 7 . 74 ( 1h , dt , j 7 . 6 , 1 . 2 , 7 - h ), 7 . 85 ( 1h , d , j 8 . 4 , 8 - h ), 7 . 96 ( 1h , d , j 10 . 0 , 4 - h ); be ( 100 mhz , dmso - d 6 ), 198 . 5 ( c ═ s ), 157 . 0 , 137 . 0 , 133 . 6 , 130 . 0 , 129 . 6 , 126 . 8 , 121 . 2 , 117 . 1 ; anal . calc . c , 66 . 64 ; h , 3 . 73 ; s , 19 . 77 . anal . found . c , 66 . 15 ; h , 3 . 43 ; s , 12 . 38 . 7 -( allyloxy )- 2h - chromen - 2 - one ( 0 . 5 g , 1 . 0 eq ) was treated according to the general procedure reported above at for 12 h . purification of the crude residue by silica gel column chromatography eluting with 20 % ethyl acetate / n - hexane to afforded the desired product as a yellow solid . 7 -( allyloxy )- 2h - chromene - 2 - thione 5 : 87 % yield ; silica gel tlc r f 0 . 32 ( ethyl acetate / n - hexane 20 % v / v ); v max ( kbr ) cm − 1 1760 , 1519 , 1215 ; δ h ( 400 mhz , dmso - d 6 ) 4 . 77 ( 2h , dt , j 5 . 6 , 1 . 6 , 1 ′- h 2 ), 5 . 35 ( 1h , dq , j 12 . 0 , 1 . 6 , 3 ′- hh ), 5 . 47 ( 1h , dq , j 17 . 2 , 1 . 6 , 3 ′- hh ), 6 . 11 ( 1h , m , 2 ′- h ), 7 . 11 ( 1h , dd , j 8 . 8 , 2 . 4 , 6 - h ), 7 . 12 ( 1h , d , j 9 . 2 , 3 - h ), 7 . 27 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 77 ( 1h , d , j 8 . 8 , 5 - h ), 7 . 88 ( 1h , d , j 9 . 2 , 4 - h ); be ( 100 mhz , dmso - d 6 ), 198 . 2 ( c ═ s ), 162 . 9 , 158 . 9 , 137 . 5 , 133 . 7 , 130 . 6 , 127 . 1 , 119 . 2 , 115 . 8 , 115 . 2 , 102 . 0 , 70 . 0 ; anal . calc . c , 66 . 03 ; h , 4 . 62 ; s , 14 . 69 . anal . found . c , 66 . 56 ; h , 4 . 32 ; s , 9 . 68 . 7 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one ( 0 . 1 g , 1 . 0 eq ) was treated according to the general procedure reported above at for 12 h . purification of the crude residue by silica gel column chromatography eluting with 10 % ethyl acetate / n - hexane to afforded the desired product as a yellow solid . 7 -( prop - 2 - ynyloxy )- 2h - chromene - 2 - thione 6 : 56 % yield ; silica gel tlc r f 0 . 27 ( ethyl acetate / n - hexane 10 % v / v ); v max ( kbr ) cm − 1 , 1762 , 1523 , 1210 ; δ h ( 400 mhz , dmso - d 6 ) 3 . 72 ( 1h , t , j 2 . 4 , 3 ′- h ), 5 . 02 ( 2h , d , j 2 . 4 , 1 ′- h 2 ), 7 . 12 ( 1h , dd , j 8 . 8 , 2 . 4 , 6 - h ), 7 . 15 ( 1h , d , j 9 . 2 , 3 - h ), 7 . 32 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 79 ( 1h , d , j 8 . 8 , 5 - h ), 7 . 90 ( 1h , d , j 9 . 2 , 4 - h ); be ( 100 mhz , dmso - d 6 ), 198 . 1 ( c ═ s ), 161 . 8 ( c - 7 ), 158 . 6 ( c - 8a ), 137 . 4 ( c - 4 ), 130 . 6 ( c - 5 ), 127 . 4 ( c - 3 ), 115 . 7 ( c - 4 - a ), 115 . 6 ( c - 6 ), 102 . 3 ( c - 8 ), 80 . 0 ( c - 2 ′), 79 . 2 ( c - 3 ′), 57 . 3 ( c - 1 ′); anal . calc . c , 66 . 65 ; h , 3 . 73 ; s , 14 . 83 . anal . found . c , 66 . 36 ; h , 3 . 71 ; s , 9 . 37 . ethanolamine ( 10 . 0 g , 1 . 0 eq ) was dissolved in a 1 . 0 m naoh aqueous solution ( 16 . 0 ml ). then a dcm solution ( 60 ml ) of ( boc ) 2 o ( 3 . 93 g , 1 . 1 eq ) was added drop wise at 0 ° c . under vigorous stirring . the mixture was stirred at r . t . for 1 h , quenched with 0 . 1m aqueous hydrochloride acid ( 3 × 20 ml ), 5 % nahco 3 aqueous solution ( 3 × 20 ml ), and then washed with brine ( 2 × 20 ml ), dried over na 2 so 4 , filtered off and solvent removed in vacuo to give an oily residue that was purified by silica gel column chromatography eluting with an increasing amount of meoh in dcm from 2 . 5 to 5 % to afford 7 a light colorless oil tert - butyl 2 - hydroxyethylcarbamate 7 : 90 % yield ; silica gel tlc r f 0 . 30 ( meoh / dcm 2 . 5 % v / v ); v max ( kbr ) cm − 1 , 3112 ( o — h ), 1770 ( c ═ o ); δ h ( 400 mhz , meod - d 4 ) 7 . 47 ( 9h , s , 3 × ch 3 ), 3 . 18 ( 2h , t , j 6 . 0 , 2 - h 2 ), 3 . 58 ( 2h , t , j 6 . 0 , 1 - h 2 ); be ( 100 mhz , dmso - d 6 ) 26 . 0 , 44 . 2 . 61 . 9 , 80 . 3 , 157 . 1 . 7 - hydroxy coumarin ( 0 . 44 g , 1 . 0 eq ), tert - butyl 2 - hydroxyethylcarbamate 7 ( 0 . 44 g , 1 . 0 eq ) and triphenylphoshine ( 0 . 72 g , 1 . 0 eq ) were dissolved in dry thf ( 60 ml ). then the temperature was lowered to 0 ° c . and diisopropylazadicarboxylate ( 0 . 55 g , 1 . 0 eq ) was added drop - wise under sonication . the orange solution was sonicated at room temperature under a nitrogen atmosphere until starting material was consumed ( tlc monitoring ). solvents were removed under vacuo to give a white solid that was recrystallized from h 2 o / meoh to give 8 as white solid . tert - butyl 2 -( 2 - oxo - 2h - chromen - 7 - yloxy ) ethylcarbamate 8 : 45 % yield ; silica gel tlc r f 0 . 47 ( ethyl acetate / n - hexane 50 % v / v ); v max ( kbr ) cm − 1 , 3120 , 1770 ( c ═ o ), 1520 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 1 . 41 ( 9h , s , 3 × ch 3 ), 3 . 32 ( 2h , appq , j 5 . 6 × 2 ′- h 2 ), 4 . 11 ( 2h , t , j 5 . 6 , 1 ′- h 2 ), 6 . 32 ( 1h , d , j 9 . 6 , 3 - h ), 6 . 97 ( 1h , dd , j 8 . 6 2 . 8 , 6 - h ), 7 . 02 ( 1h , d , j 2 . 8 , 8 - h ), 7 . 07 ( 1h , t , j 5 . 6 , exchange with d 2 o , nh ), 7 . 66 ( 1h , d , j 8 . 6 , 5 - h ), 8 . 03 ( 1h , d , j 9 . 2 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ), 162 . 6 ( c ═ o ), 161 . 2 ( c ═ o ), 156 . 6 , 156 . 3 , 145 . 3 , 130 . 5 , 113 . 7 , 113 . 4 , 103 . 1 , 102 . 2 , 78 . 8 , 68 . 1 , 29 . 1 ( ch 3 ), 22 . 8 ; anal . calc . c , 62 . 94 ; h , 6 . 27 ; n , 4 . 59 . anal . found . c , 61 . 90 ; h , 6 . 26 ; n , 4 . 58 . tert - butyl 2 -( 2 - oxo - 2h - chromen - 7 - yloxy ) ethylcarbamate 8 ( 0 . 1 g , 1 . 0 eq ) was suspended in dcm ( 20 ml ) and treated with tfa ( 5 . 0 eq ). the yellow solution was stirred o . n . at r . t . then solvents were removed in vacuo and the white solid residue was dissolved in chcl 3 ( 20 ml ) and treated with dipea ( 3 . 0 eq ). the pale yellow solution was stirred at r . t . for 1 h , diluted with h 2 o ( 50 ml ) and the organic layer was washed with brine ( 5 × 15 ml ), dried over na 2 so 4 , filtered off and solvent evaporated in vacuo to give a sticky yellow oil that was dissolved in dry dcm ( 15 ml ) and treated with 2 , 4 , 6 - pyrilium tetrafluoroborate ( 1 . 5 eq ) at reflux for 1 h . then solvent was removed in vacuo and the tannic residue treated with a 1 . 0 m aqueous solution of naclo 4 ( 3 . 0 eq ) to give a dark precipitate that was collected by filtration and crystallized from h 2 o / meoh to afford the desired product 9 as a white solid . 2 ″, 4 ″, 6 ″- trimethyl - 1 -( 2 -( 2 - oxo - 2h - chromen - 7 - yloxy ) ethyl ) pyridinium perchlorate salt 9 : 20 % overal yield ; v max ( kbr ) cm − 1 , 3112 ( o — h ), 1770 ( c ═ o ), 1522 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 2 . 53 ( 3h , s , 4 ″- ch 3 ), 2 . 93 ( 6h , s , 2 × 2 ″- ch 3 ), 4 . 63 ( 2h , t , j 4 . 8 , 1 ′- h 2 ), 5 . 01 ( 2h , t , j 4 . 8 , 2 ′- h 2 ), 6 . 35 ( 1h , d , j 9 . 2 , 3 - h ), 6 . 97 ( 1h , dd , j 8 . 6 2 . 8 , 6 - h ), 7 . 07 ( 1h , d , j 2 . 8 , 8 - h ), 7 . 67 ( 1h , d , j 8 . 6 , 5 - h ), 7 . 81 ( 2h , s , 2 × 3 ″- h ), 8 . 02 ( 1h , d , j 9 . 2 , 4 - h ); be ( 100 mhz , dmso - d 6 ), 160 . 2 , 158 . 2 , 157 . 0 , 152 . 4 , 147 . 9 , 144 . 2 , 128 . 8 , 128 . 5 , 114 . 2 . 113 . 9 , 110 . 5 , 109 . 6 , 70 . 0 , 45 . 2 , 26 . 3 , 22 . 4 ; anal . calc . c , 55 . 68 ; h , 4 . 92 ; n , 3 . 42 . anal . found . c , 42 . 4 ; h , 4 . 93 ; n , 2 . 56 . 7 - amino - 4 - methylcoumarin ( 0 . 1 g , 1 . 0 eq ) was dissolved in dry pyridine ( 5 . 0 ml ) and the solution cooled down to 0 ° c . then tosylchloride ( 0 . 14 g , 1 . 3 eq ) was added and the reaction mixture was stirred at r . t . until starting material was consumed ( tlc monitoring ). the reaction was quenched with slush , and the white precipitate formed was collected by filtration and purified by silica gel column chromatography eluting with 50 % ethyl acetate / n - hexane to afford the desired product 10 as a white solid . 4 - methyl - n -( 4 - methyl - 2 - oxo - 2h - chromen - 7 - yl ) benzenesulfonamide 10 : 54 % yield ; silica gel tlc r f 0 . 35 ( ethyl acetate / n - hexane 50 % v / v ); v max ( kbr ) cm − 1 , 3110 , 1770 ( c ═ o ), 1530 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 2 . 37 ( 6h , s , 4 - ch 3 , 4 ′- ch 3 ), 6 . 27 ( 1h , s , 3 - h ), 7 . 06 ( 1h , d , j 2 . 0 , 8 - h ), 7 . 12 ( 1h , dd , j 8 . 6 , 2 . 0 , 6 - h ), 7 . 41 ( 2h , d , j 8 . 4 , 2 × 3 ′- h ), 7 . 67 ( 1h , d , j 8 . 6 , 5 - h ), 7 . 77 ( 2h , d , j 8 . 4 , 2 × 2 ′- h ), 10 . 90 ( 1h , brs , exchange with d 2 o , nh ); be ( 100 mhz , dmso - d 6 ), 160 . 7 ( c ═ o ), 154 . 7 , 154 . 1 , 144 . 9 , 142 . 4 , 137 . 3 , 131 . 0 , 127 . 8 , 127 . 6 , 116 . 3 , 115 . 7 , 113 . 6 , 106 . 1 , 22 . 0 , 18 . 9 . alkine ( 1 . 0 eq ) was dissolved in thf dry and then dicobaltooctacarbonyl ( 1 . 05 eq ) was added . the black solution was stirred at r . t . under a nitrogen atmosphere until evolution of carbon monoxide ceased ( 1 - 2 h ). then silica gel was added and the solvent evaporated under vacuo to give a purple residue that was purified by silica gel column chromatography eluting with ethyl acetate / n - hexane to afford the corresponding acetylenehexacarbonyldicobalt complexes as reddish solids . 7 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one ( 0 . 1 g , 1 . 0 eq ) was dissolved in thf ( 10 ml ) and then cobalt carbonyl ( 1 . 05 eq ) was added . the black solution was treated as described above in the general procedure and the black residue obtained was purified by silica gel column chromatography eluting with 20 % ethyl acetate in n - hexane to give 11 as a red solid . 7 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one hexacarbonyldicobalt 11 : 82 % yield ; silica gel tlc r f 0 . 22 ( ethyl acetate / n - hexane 20 % v / v ); v max ( kbr ) cm − 1 1752 ( c ═ o ), 1600 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 5 . 50 ( 2h , s , 1 ′- h 2 ), 6 . 35 ( 1h , d , j 9 . 4 , 3 - h ), 6 . 89 ( 1h , s , 3 ′- h ), 7 . 00 ( 1h , dd , j 8 . 8 , 2 . 4 , 6 - h ), 7 . 11 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 70 ( 1h , d , j 8 . 8 , 5 - h ), 8 . 04 ( 1h , d , j 9 . 4 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ) 200 . 9 ( c ═ o ), 161 . 7 ( c - 2 ), 161 . 0 ( c - 7 ), 156 . 2 ( c - 8a ), 145 . 1 ( c - 4 ), 130 . 5 ( c - 5 ), 113 . 7 , 113 . 6 , 113 . 4 , 102 . 4 ( c - 8 ), 90 . 8 ( c - 3 ′), 73 . 9 and 69 . 4 . 7 -( prop - 2 - ynyloxy )- 2h - chromene - 2 - thione 6 ( 0 . 1 g , 1 . 0 eq ) was dissolved in thf ( 10 ml ) and then cobalt carbonyl ( 1 . 05 eq ) was added . the black solution was treated as described above in the general procedure and the black residue obtained was purified by silica gel column chromatography eluting with 10 % ethyl acetate in n - hexane to give 12 as a red solid . 7 -( prop - 2 - ynyloxy )- 2h - chromene - 2 - thione hexacarbonyldicobalt 12 : 79 % yield ; silica gel tlc r f 0 . 18 ( ethyl acetate / n - hexane 10 % v / v ); v max ( kbr ) cm − 1 1775 ( c ═ o ), 1530 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 5 . 55 ( 2h , s , 1 ′- h 2 ), 6 . 90 ( 1h , s , 3 ′- h ), 7 . 09 ( 1h , dd , j 8 . 8 , 2 . 4 , 6 - h ), 7 . 18 ( 1h , d , j 9 . 2 , 3 - h ), 7 . 36 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 80 ( 1h , d , j 8 . 8 , 5 - h ), 7 . 90 ( 1h , d , j 9 . 2 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ), 200 . 7 ( c ≡ o ), 198 . 3 ( c ═ s ), 166 . 5 , 162 . 4 , 158 . 9 , 137 . 2 , 130 . 0 , 127 . 1 , 115 . 4 , 101 . 9 , 73 . 9 , 69 . 7 , 57 . 4 ; anal . calc . c , 44 . 12 ; h , 2 . 14 ; s , 6 . 20 . anal . found . c , 44 . 75 ; h , 2 . 08 ; s , 3 . 94 . 7 -( pent - 4 - ynyloxy )- 2h - chromen - 2 - one ( 0 . 05 g , 1 . 0 eq ) was dissolved in thf ( 10 ml ) and then cobalt carbonyl ( 1 . 05 eq ) was added . the black solution was treated as described above in the general procedure and the black residue obtained was purified by silica gel column chromatography eluting with 20 % ethyl acetate in n - hexane to give 13 as a red solid . 7 -( pent - 4 - ynyloxy )- 2h - chromen - 2 - one hexacarbonyldicobalt 13 : 92 % yield ; silica gel tlc r f 0 . 20 ( ethyl acetate / n - hexane 20 % v / v ); v max ( kbr ) cm − 1 1762 ( c ═ o ), 1530 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 2 . 10 ( 2h , quaint , j 6 . 8 , 2 ′- h 2 ), 3 . 09 ( 2h , t , j 6 . 8 , 3 ′- h 2 ), 4 . 28 ( 2h , t , j 6 . 8 , 1 ′- h 2 ), 6 . 33 ( 1h , d , j 9 . 6 , 3 - h ), 6 . 84 ( 1h , s , 5 ′- h ), 7 . 01 ( 1h , dd , j 8 . 8 , 2 . 0 , 6 - h ), 7 . 06 ( 1h , d , j 2 . 0 , 8 - h ), 7 . 66 ( 1h , d , j 8 . 8 , 5 - h ), 8 . 03 ( 1h , d , j 9 . 6 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ), 200 . 9 ( c ≡ o ), 162 . 7 ( c ═ o ), 161 . 3 , 156 . 5 , 145 . 4 , 130 . 6 , 113 . 8 , 113 . 5 , 102 . 3 , 98 . 5 , 75 . 5 , 72 . 5 , 68 . 4 , 31 . 8 , 31 . 0 ;; anal . calc . c , 47 . 66 ; h , 2 . 86 . anal . found . c , 46 . 74 ; h , 2 . 27 . 7 - amino - 4 - methylcoumarin ( 0 . 1 g , 1 . 0 eq ) was dissolved in dry meoh ( 2 . 0 ml ) and 2 , 4 , 6 - trimethylpyrilium tetrafluoroborate was added . the mixture was refluxed for 5 h ( tlc monitoring ) the volume was reduced of 1 / 3 and the black residue was treated at r . t . with 1 . 0 m aqueous solution of naocl 4 ( 3 . 0 eq ). the precipitate formed was collected by filtration and crystallized from h 2 o to afford the desired product 14 as a white solid . 7 -( 2 ′, 4 ′, 6 ′- trimethylpyridinium )- 4 - methyl - 2h - chromen - 2 - one perchlorate salt 14 : 25 % yield ; v max ( kbr ) cm − 1 1760 ( c ═ o ), 1540 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 2 . 39 ( 6h , s , 2 × 2 ′- ch 3 ), 2 . 56 ( 3h , s , 4 - ch 3 ), 2 . 66 ( 3h , s , 4 ′- ch 3 ), 6 . 66 ( 1h , s , 3 - h ), 7 . 66 ( 1h , dd , j 8 . 4 , 2 . 0 , 5 - h ), 7 . 85 ( 1h , d , j 2 . 0 , 8 - h ), 8 . 00 ( 2h , s , 2 × 3 ′- h ), 8 . 18 ( 1h , d , j 8 . 4 , 6 - h ); be ( 100 mhz , dmso - d 6 ) 160 . 4 , 159 . 9 , 155 . 6 , 154 . 5 , 153 . 4 , 140 . 9 , 122 . 8 , 128 . 0 , 122 . 7 , 122 . 5 , 117 . 1 , 115 . 9 , 22 . 3 , 22 . 2 , 19 . 0 . halogenoaniline ( 0 . 3 g , 1 . 0 eq ) was dissolved in a solution h 2 o / acoh ( 1 / 2 , 10 ml ) at 0 ° c . nano 2 ( 1 . 4 eq ) was slowly added and the resulting solution was stirred at the same temperature for 1 h . then nan 3 ( 1 . 5 eq ) was added portion - wise and the mixture was stirred ar r . t . until starting material was consumed ( tlc monitoring ). the reaction was quenched with slush , extracted with ethyl acetate ( 2 × 20 ml ) and the combined organic layers were washed with 5 % nahco 3 ( 2 × 20 ml ), dried over na 2 so 4 , filtered off and solvent evaporated in vacuo to afford the corresponding phenylazide which was used without further purification . azide ( 1 . 0 eq ) and alkine ( 1 . 0 eq ) were dissolved in tert - butoh / h 2 o 1 / 1 and then tetramethylamonium chloride ( 1 . 0 eq ) and copper nanosize ( 5 % mol ) were added . the mixture was vigorously stirred at r . t . until starting material was consumed ( tlc monitoring ). solvents were removed under vacuo ( temperature has not to exceed 40 ° c .) and the brown residue was purified by silica gel column chromatography eluting with ethyl acetate in n - hexane . trimethylsylilazide ( 0 . 058 g , 1 . 0 eq ) and 7 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one ( 0 . 1 g , 1 . 0 eq ) were dissolved in tert - butoh / h 2 o 1 / 1 ( 2 . 0 ml ) and then tetramethylamonium chloride ( 0 . 048 g , 1 . 0 eq ) and copper nanosize ( 5 % mol ) were added . the mixture was treated as described and the residue was purified by silica gel column chromatography eluting with 50 % ethyl acetate in n - hexane to afford 15 as a white solid . 7 -[( 1 ′ h - 1 ′, 2 ′, 3 ′- triazol - 4 ′- yl ) methoxy ]- 2h - chromen - 2 - one 15 : 20 % yield ; silica gel tlc r f 0 . 10 ( ethyl acetate / n - hexane 50 % v / v ); v max ( kbr ) cm − 1 , 1760 ( c ═ o ), 1560 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 5 . 34 ( 2h , s , 1 ″- h 2 ), 7 . 66 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 06 ( 1h , dd , j 8 . 8 , 2 . 4 , 6 - h ), 7 . 19 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 68 ( 1h , d , j 8 . 8 , 5 - h ), 8 . 03 ( 1h , d , j 9 . 6 , 4 - h ), 8 . 10 ( 1h , s , 5 ′- h ); be ( 100 mhz , dmso - d 6 ) 162 . 2 , 160 . 3 , 152 . 4 , 144 . 0 , 143 . 5 , 130 . 0 , 129 . 2 , 115 . 1 , 114 . 2 , 112 . 0 , 108 . 2 , 76 . 2 . 1 - azido - 2 - bromobenzene ( 0 . 44 g , 1 . 1 eq ) and 7 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one ( 0 . 4 g , 1 . 0 eq ) were dissolved in tert - butoh / h 2 o 1 / 1 ( 2 . 0 ml ) and then tetramethylamonium chloride ( 0 . 4 g , 1 . 0 eq ) and copper nanosize ( 5 % mol ) were added . the mixture was treated as described and the residue was purified by silica gel column chromatography eluting with 33 % ethyl acetate in n - hexane to afford 16 as a white solid . 7 -[( 1 ′-( 2 - bromophenyl )- 1h - 1 ′, 2 ′, 3 ′- triazol - 4 ′- yl ] methoxy )- 2h - chromen - 2 - one 16 : 50 % yield ; m . p . 133 - 134 ° c . ; silica gel tlc r f 0 . 16 ( ethyl acetate / n - hexane 33 % v / v ); v max ( kbr ) cm − 1 , 1770 ( c ═ o ), 1560 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 5 . 41 ( 2h , s , 1 ″- h 2 ), 6 . 35 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 11 ( 1h , dd , j 8 . 8 , 2 . 4 , 6 - h ), 7 . 26 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 67 ( 4h , m , ar — h ), 7 . 96 ( 1h , dd , j 8 . 8 , 2 . 4 , 5 - h ), 8 . 04 ( 1h , d , j 9 . 6 , 4 - h ), 8 . 78 ( 1h , s , 5 ′- h ); be ( 100 mhz , dmso - d 6 ) 162 . 0 , 161 . 2 , 156 . 2 , 145 . 2 , 142 . 9 , 137 . 0 , 134 . 5 , 133 . 0 , 130 . 5 , 129 . 9 , 129 . 7 , 128 . 1 , 119 . 8 , 113 . 9 , 113 . 7 , 113 . 6 , 102 . 6 , 62 . 4 . 1 - azido - 2 - fluorobenzene ( 0 . 44 g , 1 . 1 eq ) and 7 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one ( 0 . 4 g , 1 . 0 eq ) were dissolved in tert - butoh / h 2 o 1 / 1 ( 2 . 0 ml ) and then tetramethylamonium chloride ( 0 . 4 g , 1 . 0 eq ) and copper nanosize ( 5 % mol ) were added . the mixture was treated as described and the residue was purified by silica gel column chromatography eluting with 25 % ethyl acetate in n - hexane to afford 17 as a pale yellow solid . 7 -[( 1 -( 2 - fluorophenyl )- 1h - 1 , 2 , 3 - triazol - 4 - yl ] methoxy )- 2h - chromen - 2 - one 17 : 30 % yield ; 161 - 163 ° c . ; silica gel tlc r f 0 . 09 ( ethyl acetate / n - hexane 25 % v / v ); v max ( kbr ) cm − 1 1765 ( c ═ o ), 1530 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 5 . 42 ( 2h , s , 1 ″- h 2 ), 6 . 35 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 10 ( 1h , dd , j 8 . 8 , 2 . 4 , 6 - h ), 7 . 25 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 50 ( 1h , m , ar — h ), 7 . 65 ( 2h , m , ar — h ), 7 . 70 ( 1h , d , j 8 . 8 , 5 - h ), 7 . 90 ( 1h , m , ar — h ), 8 . 04 ( 1h , d , j 9 . 6 , 4 - h ), 8 . 84 ( 1h , s , 5 ′- h ); be ( 100 mhz , dmso - d 6 ) 162 . 0 , 161 . 2 , 156 . 2 , 156 . 0 , 153 . 6 , 145 . 2 , 143 . 6 , 132 . 4 , 132 . 3 , 130 . 5 , 127 . 5 , 126 . 9 , 126 . 5 , 118 . 0 , 113 . 8 , 113 . 7 , 102 . 6 , 62 . 3 . 1 - azido - 2 - chlorobenzene ( 0 . 44 g , 1 . 1 eq ) and 6 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one ( 0 . 4 g , 1 . 0 eq ) were dissolved in tert - butoh / h 2 o 1 / 1 ( 2 . 0 ml ) and then tetramethylamonium chloride ( 0 . 4 g , 1 . 0 eq ) and copper nanosize ( 5 % mol ) were added . the mixture was treated as described and the residue was purified by silica gel column chromatography eluting with 33 % ethyl acetate in n - hexane to afford 18 as a light brown solid . 6 -(( 1 -( 2 - chlorophenyl )- 1h - 1 , 2 , 3 - triazol - 4 - yl ) methoxy )- 2h - chromen - 2 - one 18 : 45 % yield ; m . p . 164 - 166 ° c . ; silica gel tlc r f 0 . 10 ( ethyl acetate / n - hexane 33 % v / v ); v max ( kbr ) cm − 1 17562 ( c ═ o ), 1520 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 5 . 35 ( 2h , s , 1 ″- h 2 ), 6 . 55 ( 1h , d , j 9 . 4 , 3 - h ), 7 . 39 ( 2h , m , ar — h , 8 - h ), 7 . 51 ( 1h , d , j 2 . 4 , 5 - h ), 7 . 69 ( 3h , m , ar — h ), 7 . 82 ( 1h , dd , j 8 . 8 , 2 . 4 , 7 - h ), 8 . 06 ( 1h , d , j 9 . 4 , 4 - h ), 8 . 78 ( 1h , s , 5 ′- h ); be ( 100 mhz , dmso - d 6 ) 161 . 0 , 155 . 2 , 149 . 0 , 145 . 0 , 144 . 9 , 143 . 4 , 135 . 3 , 132 . 7 , 131 . 5 , 129 . 5 , 129 . 4 , 127 . 9 , 121 . 0 , 120 . 1 , 118 . 4 , 117 . 6 , 113 . 0 , 62 . 4 . 1 - azido - 2 - iodobenzene ( 0 . 44 g , 1 . 1 eq ) and 6 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one ( 0 . 4 g , 1 . 0 eq ) were dissolved in tert - butoh / h 2 o 1 / 1 ( 2 . 0 ml ) and then tetramethylamonium chloride ( 0 . 4 g , 1 . 0 eq ) and copper nanosize ( 5 % mol ) were added . the mixture was treated as described and the residue was purified by silica gel column chromatography eluting with 33 % ethyl acetate in n - hexane to afford 19 as a brown solid . 6 -(( 1 -( 2 - iodophenyl )- 1h - 1 , 2 , 3 - triazol - 4 - yl ) methoxy )- 2h - chromen - 2 - one 19 : 30 % yield ; 162 - 164 ° c . ; silica gel tlc r f 0 . 16 ( ethyl acetate / n - hexane 33 % v / v ); v max ( kbr ) cm − 1 1765 ( c ═ o ), 1518 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) δ h ( 400 mhz , dmso - d 6 ) 5 . 35 ( 2h , s , 1 ″- h 2 ), 6 . 54 ( 1h , d , j 9 . 4 , 3 - h ), 7 . 41 ( 3h , m , ar — h , 8 - h ), 7 . 51 ( 1h , d , j 2 . 4 , 5 - h ), 7 . 64 ( 2h , m , ar — h ), 8 . 06 ( 1h , d , j 9 . 4 , 4 - h ), 8 . 14 ( 1h , dd , j 8 . 4 , 2 . 4 , 7 - h ), 8 . 69 ( 1h , s , 5 ′- h ); be ( 100 mhz , dmso - d 6 ) 161 . 0 , 155 . 2 , 149 . 0 , 145 . 0 , 143 . 4 , 140 . 7 , 140 . 6 , 132 . 9 , 130 . 3 , 129 . 0 , 127 . 6 , 121 . 1 , 120 . 2 , 118 . 4 , 117 . 6 , 113 . 1 , 96 . 7 , 62 . 6 . 3 ′- azido - 3 ′- deoxythymidine ( 0 . 07 g , 1 . 0 eq ) and 6 -( prop - 2 - ynyloxy )- 2h - chromen - 2 - one ( 0 . 05 g , 1 . 0 eq ) were dissolved in tert - butoh / h 2 o 1 / 1 ( 2 . 0 ml ) and then tetramethylamonium chloride ( 0 . 024 g , 1 . 0 eq ) and copper nanosize ( 5 % mol ) were added . the mixture was treated as described and the residue was purified by silica gel column chromatography eluting with an increasing amount of ethyl acetate in n - hexane from 50 to 100 % to afford 20 as a pale yellow solid . 1 ′″-( 3 ″-( 4 ′-( 2 - oxo - 2h - chromen - 6 - yloxy ) methyl )- 1 ′ h - 1 ′, 2 ′, 3 ′- triazol - 1 ′- yl )- tetrahydro - 5 -( hydroxymethyl ) furan - 2 - yl )- 5 ′″- methylpyrimidine - 2 ′″, 4 ′″( 1 ′″ h , 3 ′″ h )- dione 30 % yield ; silica gel tlc r f 0 . 21 ( ethyl acetate 100 %); v max ( kbr ) cm − 1 , 3150 ( o — h ), 1760 ( c ═ o ), 1525 ( aromatic ); δ h ( 400 mhz , dmso - d 6 ) 1 . 85 ( 3h , s , 5 ″- ch 3 ), 2 . 72 ( 2h , m , 4 ″- h 2 ), 3 . 70 ( 2h , m , ch 2 oh ), 4 . 26 ( 1h , m , 2 ′- h ), 5 . 26 ( 2h , s , 1 ″- h 2 ), 5 . 32 ( 1h , t , j 5 . 6 , exchange with d 2 o , ch 2 oh ), 5 . 43 ( 1h , m , 3 ″- h ), 6 . 47 ( 1h , t , j 6 . 4 , 5 ″- h ), 6 . 54 ( 1h , d , j 9 . 2 , 3 - h ), 7 . 32 ( 1h , dd , j 8 . 8 , 2 . 4 , 7 - h ), 7 . 35 ( 1h , d , j 8 . 8 , 8 - h ), 7 . 47 ( 1h , d , j 2 . 4 , 5 - h ), 7 . 86 ( 1h , s , 6 ′″- h ), 8 . 05 ( 1h , d , j 9 . 2 , 4 - h ), 8 . 49 ( 1h , s , 5 ′- h ); be ( 100 mhz , dmso - d 6 ) 164 . 6 , 161 . 0 , 155 . 2 , 151 . 3 , 149 . 0 , 144 . 9 , 137 . 1 , 125 . 3 , 120 . 9 , 120 . 1 , 118 . 3 , 117 . 6 , 112 . 8 , 110 . 5 , 85 . 3 , 84 . 1 , 62 . 6 , 61 . 7 , 60 . 3 , 38 . 1 , 30 . 5 , 13 . 1 . a solution of 6 - hydroxy - 2h - chromen - 2 - one or 7 - hydroxy - 2h - chromen - 2 - one ( 0 . 5 g , 1 . 0 eq ) was treated at r . t . with tert - butyldimethylsilyl chloride ( 1 . 1 eq ) and et 3 n ( 1 . 0 eq ) in thf . the reaction was stirred at r . t . until starting material was consumed ( tlc monitoring ) then quenched with h 2 o ( 40 ml ) and extracted with ethyl acetate ( 3 × 15 ml ). the combined organic layers were washed with h 2 o ( 2 × 20 ml ), dried over na 2 so 4 , filtered - off and concentrated under vacuo to give a residue that was purified by silica gel column cromathography eluting with 20 % ethyl acetate / n - hexane v / v . 6 -( tert - butyldimethylsilyloxy )- 2h - chromen - 2 - one ( mst - 230 ): yield 64 % yield ; δ h ( 400 mhz , dmso - d 6 ) 0 . 25 ( 6h , s , — si —( ch 3 ) 2 ), 1 . 00 ( 9h , s , — si — c ( ch 3 ) 3 ), 6 . 51 ( 1h , d j 9 . 6 , 3 - h ), 7 . 13 ( 1h , dd , j 9 . 4 , 2 . 4 , 7 - h ), 7 . 25 ( 1h , d , j 2 . 4 , 5 - h ), 7 . 33 ( 1h , d , j 9 . 4 , 8 - h ), 8 . 00 ( 1h , d , j 9 . 6 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ) 161 . 0 ( c ═ o ), 152 . 2 , 149 . 2 , 144 . 8 , 124 . 9 , 120 . 3 , 118 . 6 , 118 . 3 , 117 . 4 , 26 . 4 , 18 . 8 , − 3 . 8 . 7 -( tert - butyldimethylsilyloxy )- 2h - chromen - 2 - one ( mst - 231 ): yield 58 % yield ; δ h ( 400 mhz , dmso - d 6 ) 0 . 29 ( 6h , s , — si —( ch 3 ) 2 ), 1 . 00 ( 9h , s , — si — c ( ch 3 ) 3 ), 6 . 34 ( 1h , d j 9 . 6 , 3 - h ), 6 . 88 ( 1h , dd , j 9 . 4 , 2 . 4 , 6 - h ), 6 . 92 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 65 ( 1h , d , j 9 . 4 , 5 - h ), 8 . 04 ( 1h , d , j 9 . 6 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ) 162 . 2 ( c ═ o ), 156 . 4 , 145 . 4 , 130 . 6 , 118 . 1 , 114 . 2 , 112 . 3 , 107 . 9 , 103 . 1 , 26 . 7 , 18 . 7 , − 2 . 3 . 6 -( tert - butyldimethylsilyloxy )- 2h - chromen - 2 - one ( mst230 ) or 7 -( tert - butyldimethylsilyloxy )- 2h - chromen - 2 - one ( mst - 231 ) ( 0 . 5 g , 1 . 0 eq ) was dissolved in dry toluene ( 20 ml ) and treated with lawesson &# 39 ; s reagents ( 1 . 5 eq ) at reflux for 3 h . the mixture was cooled down to r . t ., solvent was removed under vacuo and the residue was partitioned between h 2 o and ethyl acetate . the organic layer was washed with h 2 o ( 3 × 15 ml ), dried over na 2 so 4 , filtered and concentrated in vacuo o give a residue that was purified by silica gel column chromatography eluting with 20 % ethyl acetate / n - hexane v / v . 6 -( tert - butyldimethylsilyloxy )- 2h - chromene - 2 - thione ( mst - 232 ): yield 60 % yield ; silica gel tlc r f 0 . 40 ( ethyl acetate / n - hexane 20 % v / v ); δ h ( 400 mhz , dmso - d 6 ) 0 . 27 ( 6h , s , — si —( ch 3 ) 2 ), 1 . 01 ( 9h , s , — si — c ( ch 3 ) 3 ), 7 . 25 ( 1h , dd j 9 . 2 , 2 . 8 , 7 - h ), 7 . 29 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 32 ( 1h , d , j 2 . 8 , 5 - h ), 7 . 55 ( 1h , d , j 9 . 2 , 8 - h ), 7 . 90 ( 1h , d , j 9 . 6 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ) 198 . 0 ( c ═ s ), 153 . 3 , 152 . 2 , 136 . 8 , 130 . 1 , 126 . 0 , 122 . 2 , 118 . 4 , 118 . 3 , 26 . 4 , 18 . 8 , − 3 . 8 . 7 -( tert - butyldimethylsilyloxy )- 2h - chromene - 2 - thione ( mst - 234 ): yield 61 % yield ; silica gel tlc r f 0 . 38 ( ethyl acetate / n - hexane 20 % v / v ); δ h ( 400 mhz , dmso - d 6 ) 0 . 31 ( 6h , s , — si —( ch 3 ) 2 ), 1 . 00 ( 9h , s , — si — c ( ch 3 ) 3 ), 7 . 01 ( 1h , dd j 9 . 2 , 2 . 8 , 6 - h ), 7 . 03 ( 1h , d , j 2 . 8 , 8 - h ), 7 . 17 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 76 ( 1h , d , j 9 . 2 , 5 - h ), 7 . 90 ( 1h , d , j 9 . 6 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ) 198 . 2 ( c ═ s ), 159 . 0 , 158 . 2 , 137 . 2 , 130 . 9 , 127 . 5 , 126 . 1 , 119 . 8 , 115 . 9 , 26 . 3 , 18 . 9 , − 3 . 8 . 6 -( tert - butyldimethylsilyloxy )- 2h - chromene - 2 - thione ( mst - 232 ) or 7 -( tert - butyldimethylsilyloxy )- 2h - chromene - 2 - thione ( mst - 234 ) ( 0 . 3 g , 1 . 0 eq ) was dissolved in thf ( 2 . 0 ml ) and treated at r . t with tbaf 1 . 0 m in thf ( 1 . 1 eq ). the reaction was stirred at r . t . until starting material was consumed ( tlc monitoring ) and then was quenched with 3 . 0 m aqueous hydrochloric acid , extracted with ethyl acetate ( 3 × 15 ml ). the combined organic layers were washed with h 2 o ( 3 × 20 ml ), brine ( 3 × 20 ml ) dried over na 2 so 4 , filtered , concentrated under vacuo to give a residue that was purified by silica gel column chromatography eluting with 50 % ethyl acetate / n - hexane v / v . 6 - hydroxy - 2h - chromene - 2 - thione ( mst - 233 ): yield 96 % yield ; silica gel tlc r f 0 . 35 ( ethyl acetate / n - hexane 50 % v / v ); δ h ( 400 mhz , dmso - d 6 ) 7 . 12 ( 1h , d j 2 . 8 , 5 - h ), 7 . 18 ( 1h , dd , j 9 . 2 , 2 . 8 , 7 - h ), 7 . 25 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 50 ( 1h , d , j 9 . 2 , 8 - h ), 7 . 87 ( 1h , d , j 9 . 6 , 4 - h ), 10 . 05 ( 1h , brs , exchange with d 2 o , oh ); δ c ( 100 mhz , dmso - d 6 ) 197 . 8 ( c ═ s ), 155 . 8 , 151 . 1 , 137 . 0 , 129 . 9 , 122 . 1 , 121 . 9 , 118 . 2 , 112 . 9 . 6 - hydroxy - 2h - chromene - 2 - thione ( mst - 235 ): yield 55 % yield ; silica gel tlc r f 0 . 40 ( ethyl acetate / n - hexane 50 % v / v ); δ h ( 400 mhz , dmso - d 6 ) 6 . 93 ( 2h , m , 6 - h , 8 - h ), 7 . 09 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 68 ( 1h , d , j 9 . 2 , 5 - h ), 7 . 85 ( 1h , d , j 9 . 6 , 4 - h ), 10 . 96 ( 1h , brs , exchange with d 2 o , oh ); δ c ( 100 mhz , dmso - d 6 ) 198 . 1 ( c ═ s ), 163 . 3 , 159 . 0 , 137 . 8 , 130 . 9 , 126 . 0 , 115 . 9 , 114 . 1 , 102 . 8 . hydroxycoumarin ( 1 . 0 g , 1 . 0 eq ), cs 2 co 3 ( 3 . 0 eq ) and allylbromide ( 3 . 0 eq ) were dissolved in dry dmf ( 30 ml ) and the mixture was stirred at 60 ° c . o . n . the reaction was quenched with slush and extracted with dcm ( 3 × 20 ml ). the combined organic layers were washed with brine ( 3 × 20 ml ), h 2 o ( 5 × 20 ml ), dried over na 2 so 4 , filtered and concentrated under vacuo to give a residue that was crystallized from meoh / h 2 o . 4 -( allyloxy )- 2h - chromen - 2 - one yield ( mst - 236 ): 70 % yield ; δ h ( 400 mhz , dmso - d 6 ) 4 . 87 ( 2h , d j 8 . 0 , 1 ′- h 2 ), 5 . 40 ( 1h , dd , j 13 . 2 , 4 . 8 , 3 ′- hh ), 5 . 59 ( 1h , dd , j 15 . 6 , 4 . 8 , 3 ′- hh ), 5 . 96 ( 1h , s , 3 - h ), 6 . 15 ( 1h , m , 2 ′- h ), 7 . 41 ( 1h , m , 7 - h , 8 - h ), 7 . 22 ( 1h , dd , j 8 . 8 , 8 . 4 , 6 - h ), 7 . 89 ( 1h , d , j 8 . 8 , 5 - h ); be ( 100 mhz , dmso - d 6 ) 165 . 4 ( c ═ o ), 162 . 5 , 153 . 7 , 133 . 7 , 132 . 6 , 125 . 2 , 123 . 8 , 119 . 7 , 117 . 4 , 116 . 1 , 92 . 0 , 70 . 7 . 6 -( allyloxy )- 2h - chromen - 2 - one yield ( mst - 237 ): 62 % yield ; δ h ( 400 mhz , dmso - d 6 ) 4 . 64 ( 2h , d j 8 . 0 , 1 ′- h 2 ), 5 . 32 ( 1h , dd , j 13 . 2 , 4 . 8 , 3 ′- hh ), 5 . 48 ( 1h , dd , j 15 . 6 , 4 . 8 , 3 ′- hh ), 6 . 10 ( 1h , m , 2 ′- h ), 6 . 16 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 25 ( 1h , dd , j 9 . 2 , 2 . 4 , 7 - h ), 7 . 41 ( 1h , d , j 2 . 4 , 5 - h ), 7 . 36 ( 1h , d , j 9 . 2 , 8 - h ), 8 . 03 ( 1h , d , j 9 . 6 , 4 - h ); be ( 100 mhz , dmso - d 6 ) 161 . 0 ( c ═ o ), 155 . 4 , 148 . 8 , 144 . 9 , 134 . 3 , 120 . 8 , 120 . 1 , 118 . 7 , 118 . 3 , 117 . 5 , 112 . 7 , 69 . 7 . 7 -( allyloxy )- 2h - chromen - 2 - one yield ( mst - 238 ): 85 % yield ; δ h ( 400 mhz , dmso - d 6 ) 4 . 73 ( 2h , d j 8 . 0 , 1 ′- h 2 ), 5 . 32 ( 1h , dd , j 13 . 2 , 4 . 8 , 3 ′- hh ), 5 . 45 ( 1h , dd , j 15 . 6 , 4 . 8 , 3 ′- hh ), 6 . 09 ( 1h , m , 2 ′- h ), 6 . 33 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 00 ( 1h , dd , j 9 . 2 , 2 . 4 , 6 - h ), 7 . 05 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 67 ( 1h , d , j 9 . 2 , 5 - h ), 8 . 03 ( 1h , d , j 9 . 6 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ) 162 . 0 ( c ═ o ), 155 . 0 , 148 . 3 , 144 . 2 , 135 . 1 , 119 . 2 , 118 . 7 , 118 . 5 , 118 . 0 , 117 . 2 , 112 . 6 , 69 . 5 . 4 -( allyloxy )- 2h - chromene - 2 - thione ( mst - 239 ): 61 % yield ; δ h ( 400 mhz , dmso - d 6 ) 4 . 95 ( 2h , d j 6 . 0 , 1 ′- h 2 ), 5 . 42 ( 1h , dd , j 13 . 2 , 4 . 8 , 3 ′- hh ), 5 . 59 ( 1h , dd , j 15 . 6 , 4 . 8 , 3 ′- hh ), 6 . 15 ( 1h , m , 2 ′- h ), 6 . 97 ( 1h , s , 3 - h ), 7 . 51 ( 1h , t , j 8 . 8 , 7 - h ), 7 . 63 ( 1h , d , j 8 . 8 , 8 - h ), 7 . 80 ( 1h , t , j 8 . 8 , 6 - h ), 7 . 96 ( 1h , d , j 8 . 8 , 5 - h ); be ( 100 mhz , dmso - d 6 ) 198 . 5 ( c = 5 ), 160 . 9 , 157 . 2 , 134 . 4 , 132 . 5 , 126 . 6 , 123 . 8 , 119 . 9 , 117 . 5 , 117 . 2 , 107 . 6 , 71 . 2 . 6 -( allyloxy )- 2h - chromene - 2 - thione ( mst - 240 ): 62 % yield ; δ h ( 400 mhz , dmso - d 6 ) 4 . 68 ( 2h , d j 8 . 0 , 1 ′- h 2 ), 5 . 32 ( 1h , dd , j 13 . 2 , 4 . 8 , 3 ′- hh ), 5 . 49 ( 1h , dd , j 15 . 6 , 4 . 8 , 3 ′- hh ), 6 . 09 ( 1h , m , 2 ′- h ), 7 . 30 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 36 ( 1h , dd , j 9 . 2 , 2 . 4 , 7 - h ), 7 . 38 ( 1h , d , j 2 . 4 , 5 - h ), 7 . 59 ( 1h , d , j 9 . 2 , 8 - h ), 7 . 89 ( 1h , d , j 9 . 6 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ) 197 . 9 ( c ═ s ), 156 . 3 , 151 . 9 , 145 . 7 , 136 . 8 , 134 . 0 , 130 . 2 , 121 . 9 , 118 . 8 , 118 . 4 , 112 . 1 , 69 . 8 . a mixture of 7 - hydroxy - 2h - chromen - 2 - one ( 0 . 5 g , 1 . 0 eq ), k 2 co 3 ( 5 . 0 eq ), ki ( 1 . 0 eq ) and chloroethanol ( 1 . 0 eq ) in dmf dry ( 10 ml ) was stirred at 60 ° c . for 5 h . the reaction mixture was cooled down to 0 ° c ., quenched with 6m aqueous hydrochloric acid ( 50 ml ) and extracted with ethyl acetate ( 3 × 20 ml ). the combined organic layers were washed several timed with h 2 o , dried over na 2 so 4 , filtered - off and concentrated under vacuo to afford a residue that was purified by silica gel column chromatography eluting with 50 % ethyl acetate / n - hexane v / v . 7 -( 2 ′- hydroxyethoxy )- 2h - chromen - 2 - one ( mst - 241 ): 72 % yield ; silica gel tlc r f 0 . 10 ( ethyl acetate / n - hexane 50 % v / v ); δ h ( 400 mhz , dmso - d 6 ) 3 . 78 ( 2h , m , 2 ′- h 2 ), 4 . 13 ( 2h , m , 1 ′- h 2 ), 4 . 97 ( 1h , t , j 5 . 6 , exchange with d 2 o , o — h ), 6 . 30 ( 1h , d , j 9 . 6 , 3 - h ), 6 . 97 ( 1h , dd , j 9 . 2 , 2 . 4 , 6 - h ), 7 . 02 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 65 ( 1h , d , j 9 . 2 , 5 - h ), 8 . 01 ( 1h , d , j 9 . 6 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ) 162 . 8 , 161 . 3 , 156 . 3 , 145 . 3 , 130 . 4 , 113 . 7 , 113 . 4 , 102 . 1 , 71 . 3 , 65 . 9 , 60 . 3 . 7 -( 2 ′- hydroxyethoxy )- 2h - chromen - 2 - one ( mst - 241 ) ( 0 . 2 g , 1 . 0 eq ) was dissolved in dry pyridine ( 5 ml ) and treated at 0 ° c . with tscl ( 1 . 1 eq ). the yellow solution was stirred at r . t . until starting material was consumed ( tlc monitoring ) and then quenched with a 1 . 0m aqueous hydrochloric acid at 0 ° c . the mixture was extracted with ethyl acetate ( 3 × 15 ml ) and the combined organic layers were washed with brine ( 3 × 20 ml ), h 2 o ( 3 × 20 ml ) dried over na 2 so 4 , filtered - off and concentrated under vacuo to afford a residue that was purified by silica gel column chromatography eluting with 50 % ethyl acetate / n - hexane v / v . 2 ′-( 2 - oxo - 2h - chromen - 7 - yloxy ) ethyl 4 ″- methylbenzenesulfonate ( mst - 242 ): 35 % yield ; silica gel tlc r f 0 . 36 ( ethyl acetate / n - hexane 50 % v / v ); δ h ( 400 mhz , dmso - d 6 ) 2 . 44 ( 3h , s , ch 3 ). 4 . 32 ( 2h , m , 1 ′- h 2 ), 4 . 41 ( 2h , m , 2 ′- h 2 ), 6 . 34 ( 1h , d , j 9 . 6 , 3 - h ), 6 . 87 ( 1h , dd , j 9 . 2 , 2 . 4 , 6 - h ), 6 . 92 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 49 ( 2h , d j 8 . 4 , 2 × 2 ″- h / 3 ″- h ), 7 . 64 ( 1h , d , j 9 . 2 , 5 - h ), 7 . 83 ( 2h , d j 8 . 4 , 2 × 2 ″- h / 3 ″- h ), 8 . 02 ( 1h , d , j 9 . 6 , 4 - h ); δ c ( 100 mhz , dmso - d 6 ) 161 . 7 , 161 . 1 , 156 . 1 , 145 . 9 , 145 . 1 , 133 . 1 , 131 . 0 , 130 . 4 , 128 . 6 , 113 . 7 , 113 . 6 , 113 . 5 , 102 . 3 , 69 . 7 , 66 . 9 , 21 . 9 . 2 ′-( 2 - oxo - 2h - chromen - 7 - yloxy ) ethyl 4 ″- methylbenzenesulfonate ( mst - 242 ) ( 0 . 1 g , 1 . 0 eq ) was dissolved in thf ( 1 . 0 ml ) and treated with tbaf 1 . 0m in thf ( 1 . 05 eq ). the yellow solution was stirred at r . t . for 15 min . then solvents were removed in vacuo and the residue was purified by silica gel column chromatography eluting with 50 % ethyl acetate / n - hexane v / v . 7 -( 2 ′- fluoroethoxy )- 2h - chromen - 2 - one ( mst - 243 ): 40 % yield ; silica gel tlc r f 0 . 40 ( ethyl acetate / n - hexane 50 % v / v ); δ h ( 400 mhz , dmso - d 6 ) 4 . 36 ( 1h , m , 1 ′- hh ), 4 . 44 ( 1h , m , 1 ′- hh ), 4 . 74 ( 1h , m , 1 ′- hh ), 4 . 87 ( 1h , m , 1 ′- hh ), 6 . 34 ( 1h , d , j 9 . 6 , 3 - h ), 7 . 02 ( 1h , dd , j 9 . 2 , 2 . 4 , 6 - h ), 7 . 09 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 68 ( 1h , d , j 9 . 2 , 5 - h ), 8 . 03 ( 1h , d , j 9 . 6 , 4 - h ); be ( 100 mhz , dmso - d 6 ) 162 . 2 , 161 . 1 , 145 . 2 , 130 . 5 , 113 . 63 , 113 . 60 , 113 . 5 , 102 . 3 , 82 . 0 ( d , 1 j c - f 166 , c - 2 ′), 68 . 6 ( d , 2 j c - f 18 , c - 1 ′), δ f ( 376 mhz , dmso - d 6 ) − 222 . 23 ( 1f , s ). a suspension of 7 - amino - 4 - methyl - 2h - chromen - 2 - one ( 0 . 1 g , 1 . 0 eq ) in dcm dry ( 5 . 0 ml ) was treated with acetyl chloride ( 1 . 0 eq ) and et 3 n ( 1 . 0 eq ) under reflux for 7 h . solvents were removed under vacuo and the residue was purified by silica gel column chromatography eluting with 50 % ethyl acetate / n - hexane v / v . n -( 4 - methyl - 2 - oxo - 2h - chromen - 7 - yl ) acetamide ( mst - 244 ): 73 % yield ; silica gel tlc r f 0 . 11 ( ethyl acetate / n - hexane 50 % v / v ); δ h ( 400 mhz , dmso - d 6 ) 2 . 14 ( 3h , s , 1 ′- ch 3 ), 2 . 43 ( 3h , s , 4 - ch 3 ), 6 . 29 ( 1h , s , 3 - h ), 7 . 50 ( 1h , dd , j 9 . 2 , 2 . 4 , 6 - h ), 7 . 74 ( 1h , d , j 9 . 2 , 5 - h ), 7 . 79 ( 1h , d , j 2 . 4 , 8 - h ), 10 . 40 ( 1h , brs , exchange with d 2 o , n — h ); δ e ( 100 mhz , dmso - d 6 ) 170 . 0 , 161 . 0 , 154 . 6 , 154 . 0 , 143 . 5 , 126 . 8 , 115 . 9 , 115 . 7 , 113 . 0 , 106 . 3 , 25 . 1 , 18 . 9 . 7 - amino - 4 - methyl - 2h - chromen - 2 - one ( 0 . 1 g , 1 . 0 eq ) in acetone ( 10 ml ) was treated at reflux with 3 , 5 - dimethyyl isocyanate ( 1 . 0 eq ) and et 3 n ( 1 . 1 eq ) for 24 h . then the solvents were removed in vacuo and the residue was purified by silica gel column chromatography eluting with 50 % ethyl acetate / n - hexane v / v . 1 -( 3 ′, 5 ′- dimethylphenyl )- 3 -( 4 - methyl - 2 - oxo - 2h - chromen - 7 - yl ) urea ( mst - 245 ): 23 % yield ; silica gel tlc r f 0 . 22 ( ethyl acetate / n - hexane 50 % v / v ); δ h ( 400 mhz , dmso - d 6 ) 2 . 28 ( 6h , s , 2 × 3 ′- ch 3 ), 2 . 43 ( 3h , s , 4 - ch 3 ), 6 . 25 ( 1h , s , 3 - h ), 6 . 69 ( 1h , s , 4 ′- h ), 7 . 13 ( 2h , s , 2 × 2 ′- h ), 7 . 39 ( 1h , dd , j 9 . 2 , 2 . 4 , 6 - h ), 7 . 65 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 71 ( 1h , d , j 9 . 2 , 5 - h ), 8 . 72 ( 1h , s , exchange with d 2 o , n — h ), 9 . 20 ( 1h , s , exchange with d 2 o , n — h ); δ c ( 100 mhz , dmso - d 6 ) 161 . 1 , 254 . 2 , 153 . 4 , 144 . 5 , 140 . 6 , 140 . 0 , 138 . 9 , 138 . 6 , 126 . 9 , 124 . 9 , 124 . 3 , 117 . 3 , 116 . 8 , 115 . 3 , 22 . 1 , 19 . 0 . a suspension of 7 - amino - 4 - methyl - 2h - chromen - 2 - one ( 0 . 1 g , 1 . 0 eq ) in thf dry ( 2 . 0 ml ) was treated at reflux with di - tert - butyl dicarbonate ( 1 . 0 eq ) and et 3 n ( 1 . 1 eq ) for 24 h . then the solvents were removed in vacuo and the residue was purified by silica gel column chromatography eluting with 50 % ethyl acetate / n - hexane v / v . tert - butyl 4 - methyl - 2 - oxo - 2h - chromen - 7 - ylcarbamate ( mst - 246 ): 28 % yield ; silica gel tlc r f 0 . 42 ( ethyl acetate / n - hexane 50 % v / v ); δ h ( 400 mhz , dmso - d 6 ) 1 . 54 ( 9h , s , 3 × 2 ′- ch 3 ), 2 . 42 ( 3h , s , 4 - ch 3 ), 6 . 26 ( 1h , s , 3 - h ), 7 . 44 ( 1h , dd , j 9 . 2 , 2 . 4 , 6 - h ), 7 . 57 ( 1h , d , j 2 . 4 , 8 - h ), 7 . 70 ( 1h , d , j 9 . 2 , 5 - h ), 9 . 92 ( 1h , s , exchange with d 2 o , n — h ); δ c ( 100 mhz , dmso - d 6 ) 161 . 0 , 154 . 8 , 154 . 2 , 153 . 4 , 144 . 1 , 126 . 8 , 115 . 1 . 113 . 0 , 105 . 2 . 80 . 9 , 28 . 9 , 27 . 8 , 18 . 9 . metronidazole ( 1 equiv . ), 6 - or 7 - hydroxy - 4 - methyl coumarine ( 1 equiv . ), and triphenylphospine ( 1 . 2 equiv .) are mixed in thf and then diisopropyl azidocarboxylate ( diad ), ( 1 . 2 equiv .) is added dropwise . the reaction is stirred 2 days at room temperature . the precipitate is then filtered , washed two times with cold thf and dried under vacuum . yield 48 %; rf : 0 . 11 ( acoet 8 / et 2 o 2 ); mp : 238 - 240 ° c . ; 1 h nmr ( 400 mhz , dmso ): δ ppm 1 . 55 ( s , 3h ), 1 . 69 ( s , 3h ), 3 . 63 ( t , 2h , j = 5 . 00 hz ), 3 . 91 ( t , 2h , j = 5 . 00 hz ), 5 . 38 ( d , 1h , j = 1 . 05 hz ), 6 . 07 ( dd , 1h , j = 2 . 49 hz , j = 8 . 81 hz ), 6 . 15 ( d , 1h , j = 2 . 49 hz ), 6 . 84 ( d , 1h , j = 8 . 81 hz ), 7 . 20 ( s , 1h ); 13 c nmr ( 101 mhz , dmso ): δ ppm 14 . 10 , 18 . 08 , 45 . 00 , 67 . 02 , 101 . 28 , 111 . 38 , 112 . 27 , 113 . 45 , 126 . 54 , 132 . 87 , 151 . 71 , 153 . 25 , 154 . 56 , 160 . 00 , 160 . 66 . ms esi + / esi − : m / z 330 . 34 ( m + h ) + , 328 . 38 ( m − h ) − . yield 42 %; rf : 0 . 16 ( acoet 8 / et 2 o 2 ); mp : 190 - 191 ° c . ; 1 h nmr ( 400 mhz , dmso ): δ ppm 1 . 56 ( s , 3h ), 1 . 70 ( s , 3h ), 3 . 57 ( t , 2h , j = 5 . 00 hz ), 3 . 89 ( t , 2h , j = 5 . 00 hz ), 5 . 53 ( s , 1h ); 6 . 32 ( m , 2h ), 6 . 46 ( d , 1h , j = 9 . 70 hz ), 7 . 19 ( s , 1h ); 13 c nmr ( 101 mhz , dmso ): δ ppm 14 . 15 , 18 . 13 , 45 . 19 , 66 . 97 , 108 . 61 , 114 . 72 , 117 . 58 , 120 . 07 , 132 . 93 , 138 . 31 , 147 . 47 , 151 . 83 , 152 . 94 , 154 . 06 , 159 . 76 ; ms esi + / esi − : m / z 330 . 34 ( m + h ) + , 328 . 38 ( m − h ) − . the methods for achieving this data are shown , for example , in maresca , a . et al , j . med . chem . 2010 , 53 , 335 - 344 . for in vivo studies , the inhibitors were administered by intraperitoneal injection . the compounds were solubilized in 37 . 5 % peg400 / 12 . 5 % ethanol / 50 % saline prior to injection . inhibitor concentrations ranged from 4 . 5 mm to 12 mm . the exact concentrations used were dependent on the upper limit of solubility of a particular inhibitor in the peg400 / ethanol / saline vehicle . inhibitor concentrations were converted to mg / kg for in vivo administration and are reported as such in the examples . conversion to mg / kg was based on a 200 μl injection volume for a 20 g mouse . vehicle components were held constant as inhibitor concentrations were varied . inhibitors were administered daily for 5 - 6 days and images were acquired 24 hours following the final dose . all animal procedures were done in accordance with protocols approved by the institution animal care committee at the bc cancer research centre and the university of british columbia ( vancouver , bc , canada ). progression of metastases was monitored and quantified using non - invasive in vivo bioluminescent imaging ( ivis ) as previously described ( lou , y ., preobrazhenska , o ., auf dem keller , u ., et al . ( 2008 ) dev dyn 237 : 2755 - 2768 ). mice were monitored daily and moribund animals were sacrificed in accordance with ethical guidelines . for studies involving experimental lung metastasis , mice were injected intravenously through the tail vein with 2 × 10 5 cells per animal . mice were imaged once per week to follow the establishment and growth of lung metastases . mice were euthanized by 20 days post - injection . tumor burden in the lung was quantified using bioluminescence data acquired by imaging with ivis . results were subjected to statistical analysis using the data analysis toolpack ™ in excel software . two - tailed p values were calculated using student &# 39 ; s t - test . data were considered significant for p & lt ; 0 . 05 . 4t1 cells injected intravenously form robust lung metastases and subject mice have to be euthanized within 3 weeks post injection due to metastatic progression . novel caix inhibitor mst - 204 reduced the formation of metastases by 4t1 mammary tumor cells . in fig1 , the chemical structure of caix inhibitor mst - 204 is shown . representative bioluminescent images of metastases established following intravenous injection of 2 × 10 5 4t1 cells per mouse and treatment with mst - 204 are shown in fig1 b . animals were treated 24 hours post inoculation of cells . the inhibitor was administered daily by i . p . injection for 6 days and the mice were imaged 24 hours following the final dose of inhibitor . mst - 204 was delivered in a vehicle comprised of 37 . 5 % peg400 , 12 . 5 % ethanol and 50 % saline . mice dosed with vehicle alone served as controls . as for quantification of tumor - derived bioluminescence , as shown in fig1 c regions of interest were positioned around metastatic foci and total flux ( photons / sec ) at the mouse surface was calculated . data are reported as the mean ± s . e . m . n = 7 - 8 per group . * p & lt ; 0 . 01 . ** p & lt ; 0 . 005 . mst - 205 inhibits the formation of metastases by 4t1 mammary tumor cells . animals were treated 24 hours post inoculation of cells . the inhibitor was administered daily by i . p . injection for 6 days and the mice were imaged 24 hours following the final dose of inhibitor . mst - 205 was delivered in a vehicle comprised of 37 . 5 % peg400 , 12 . 5 % ethanol and 50 % saline . mice dosed with vehicle alone served as controls . representative bioluminescent images of metastases established following intravenous injection of 2 × 10 5 4t1 cells and treatment with mst - 205 ( fig2 b ). in images of tumor - derived bioluminescence , regions of interest were positioned around metastatic foci and total flux ( photons / sec ) at the mouse surface was calculated . data are reported as the mean ± s . e . m , and shown in the graph in fig2 c . n = 8 per group . * p & lt ; 0 . 004 . ** p & lt ; 0 . 001 . 4t1 cells ( 1 × 10 6 cells / mouse ) were orthotopically implanted into female balb / c mice and tumors were allowed to establish for 14 days . animals then received mst - 205 daily by i . p . injection for 14 days . mst - 205 was delivered in a vehicle comprised of 37 . 5 % peg400 , 12 . 5 % ethanol and 50 % saline . tumor growth was monitored 2 times per week by caliper - based measurement . treatment initiation and termination are indicated by arrows . vehicle - treated animals served as controls . n = 8 for each group . * p & lt ; 0 . 01 , ** p & lt ; 0 . 003 , compared to vehicle controls . results are shown in fig3 . while specific embodiments of the invention have been described and illustrated , such embodiments should be considered illustrative of the invention only and not as limiting the invention as construed in accordance with the accompanying 1 . maresca , a . ; temperini , c . ; vu , h . ; pham , n . b . ; poulsen , s . a . ; scozzafava , a . ; quinn , r . j . ; supuran , c . t . non - zinc mediated inhibition of carbonic anhydrases : coumarins are a new class of suicide inhibitors . j . am . chem . soc . 2009 , 131 , 3057 - 3062 . 2 . supuran , c . t . carbonic anhydrases : novel therapeutic applications for inhibitors and activators . nat . rev . drug discov . 2008 , 7 , 168 - 181 . 3 . vu , h . ; pham , n . b . ; quinn , r . j . direct screening of natural product extracts using mass spectrometry . j . biomol . screen . 2008 , 13 , 265 - 275 . 4 . a ) supuran , c . t . carbonic anhydrases as drug targets — general presentation . in drug design of zinc - enzyme inhibitors : functional , structural , and disease applications , supuran , c . t . ; 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10 . b ) supuran , c . t . ; di fiore , a . ; de simone , g . carbonic anhydrase inhibitors as emerging drugs for the treatment of obesity . expert opin . emerg . drugs . 2008 , 13 , 383 - 392 ; 11 . a ) minakuchi , t . ; nishimori , i . ; vullo , d . ; scozzafava , a . ; supuran , c . t . molecular cloning , characterization and inhibition studies of the rv1284 β - carbonic anhydrase from mycobacterium tuberculosis with sulfonamides and a sulfamate . j . med . chem . 2009 , 52 , 2226 - 2232 ; 11 . b ) nishimori , i . ; minakuchi , t . ; vullo , d . ; scozzafava , a . ; innocenti , a . ; supuran , c . t . carbonic anhydrase inhibitors . cloning , characterization and inhibition studies of a new β - carbonic anhydrase from mycobacterium tuberculosis . j . med . chem . 2009 , 52 , 3116 - 3120 . 12 . s . m . sethna , n . m . shah the chemistry of coumarins . chem . rev . 1945 , 36 , 1 - 62 . 13 . maresca a , supuran c t . coumarins incorporating hydroxy - and chloro - moieties selectively inhibit the transmembrane , tumor - associated carbonic anhydrase isoforms ix and xii over the cytosolic ones i and ii . bioorg med chem . lett . 2010 aug . 1 ; 20 ( 15 ): 4511 - 4 . 14 . winum , j - y ., poulsen , s . a . ; supuran c . t . therapeutic applications of glycosidic carbonic anhydrase inhibitors . med . res . rev . 2009 , 29 , 419 - 35 . 15 . maresca , a ; temperini , c ; pochet , l ; masereel , b ; scozzafava , a ; and supuran , c . deciphering the mechansim of carbonhic anhydrase inhibition with coumarins an thiocoumarins . j med chem 2010 , 53 , 335 - 344 . | 0 |
in one aspect , the invention relates to methods of preparing a long acting anesthetic . construction of the anesthetic will be described . experimentation to insure the anesthetic lasts over 30 hours will also be detailed . the following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds , compositions , and biomaterials and / or methods claimed herein are made and evaluated , and are intended to be purely exemplary of the invention and are not intended to limit the scope of what the inventors regard as their invention . three compounds were used including bupivacaine hydrochloride : 1 - butyl - n -( 2 , 6 - dimethylphenyl )- 2 - piperidinecarboxamide and hyaluonan : ( also called hyaluronic acid or hyaluronate ) an anionic , non - sulfated glycosaminoglycan distributed widely throughout connective , epithelial , and neural tissues , and fibrinogenor coagulation factor i , which is a soluble 340 kd plasma glycoprotein required for normal platelet function and wound healing . the composite anesthetic composition was made with powdered bupivacaine ( 40 mg ) was mixed with fibrinogen ( 40 mg ) with a magnetic stir bar . hyaluronan ( 16 mg ) was then added to the bupivacaine / fibrinogen mixture and placed in an ultrasound sonicator for final mixing followed by a vacuum to remove excess air . special testing containers were constructed with a mid polyurethane shelf to centralize the compounds within a test tube , allowing them to bathe in two ml of release medium . simulated body fluid ( sbf ) was selected as the release medium , rather than serum , which contains potential binding proteins . each specimen was initially bathed with two ml of sbf . at the end of each time period , the specimen was withdrawn and replaced with fresh sbf . release fluid was replaced at every time point and saved for bupivacaine quantification analysis . release profile experiments were conducted on four bupivacaine composites . the composite combinations were selected based on their low energy bonding characteristics that would result in the best sustained - releasing profiles . the four groups were group 1 : bupivacaine + hyaluronan , group 2 : bupivacaine + hyaluronan + fibrinogen , group 3 : bupivacaine + heparin , and group 4 : bupivacaine + heparin + fibrinogen . in each of the four composites 40 mg of powdered bupivacaine was used . other combinations were added to the bupivacaine as follows : 16 mg of hyaluronan , 40 mg of heparin , and 40 mg of fibrinogen . initially , the powdered bupivacaine was mechanically mixed with one or two of the other compounds with a magnetic stir - bar . eight ml of normal saline was added to replicate a 0 . 5 % solution that is used in the clinical setting . each composite was then placed in an ultrasound sonicator , followed by a vacuum to remove excess air . the four composites were then ready for testing . all four composites were tested in an identical manner for three different trials ( n = 3 ). a control of 0 . 5 % bupivacaine without additives was also included in each trial . there were fifteen time periods for each of the 15 specimens , totaling 225 elute samples . after all samples were collected , an ultraviolet - visible spectrophotometer was used to determine the concentration of bupivacaine in each of the elute samples . specific wavelength for absorption of bupivacaine was found in the 280 nanometers range . serial bupivacaine dilutions were created in order to generate standard curves to assist in calculating accurate bupivacaine concentrations . this required a calculation of the linear regression analysis for best fit . once all concentrations were known , data interpretation was accomplished . statistical analysis was completed by anova f - test for all combinations . a student t - test was then run on those found to be significant after anova screening . statistical significance was determined by a p value & lt ; 0 . 05 . based on the releasing data , the best combination was the hyaluronan - fibrinogen - bupivacaine combination . statistical analysis comparing all combinations demonstrated a statistically significant difference between hyaluronan / fibrinogen / bupivacaine combination and the heparin / bupivacaine composite ( p & lt ; 0 . 0415 ). a separate method to analyze the releasing profile was completed . this data examined the total amount of bupivacaine released over the entire study period . a comparison between the control and the hyaluronan / fibrinogen / bupivacaine composite was made . the total concentrations released were nearly equal after comparing the areas under the curves . a similar amount of drug is released , maintaining the same toxicity potential ; however , bupivacaine is released at a slower rate in the hyaluronan / fibrinogen / bupivacaine composite . | 0 |
in the following descriptions of the invention , terms such as “ front ,” “ back ,” “ top ,” “ bottom ,” “ side ,” and the like are used herein merely for ease of description and refer to the orientation of the components as shown in the figures . generally , the present invention may be briefly described as follows . referring first to fig1 and 2 , a preferred embodiment of an integrated pressure sense element assembly 100 of the present invention is shown . the sense element assembly 100 comprises two assemblies — a substrate assembly 102 and a diaphragm assembly 104 . the substrate assembly comprises a substrate 106 , a cp electrode 108 , a cr electrode 110 and a sealing layer 112 . in a preferred embodiment , the sealing layer 112 is a frit . however , any other material that provides a hermetic seal and provides for thermal expansion can be used . the cp electrode 108 is preferably elliptical in shape as shown more fully in fig3 and is connected to cp terminal 114 . the cr electrode 110 is also preferably elliptical in shape and is substantially an annular ring surrounding the cp electrode 108 as shown in fig1 and 3 . in a preferred embodiment , the cr electrode 110 is c - shaped . however , the cr electrode 110 may be a complete annulus surrounding the cp electrode 108 providing that there is an electrical connection possible directly with the cp electrode 108 without touching the cr electrode 110 . the cr electrode 110 is connected on one end 116 to a cr terminal 118 . the cp electrode 108 is connected to the cp terminal 114 by a conductor which extends from the cp electrode 108 and through the gap between the two ends 116 and 122 of the cr electrode 110 . in a preferred embodiment , a guard electrode 120 is provided which is connected from cr terminal 118 around cp terminal 114 to end 122 of the cr electrode 108 . the reason for this guard electrode 120 is to protect , or isolate the cp electrode that when the sensor is operational , there should be no temperature effect that affects the relative capacitance of the cp 108 and cr 110 electrodes . in an preferred embodiment in which a frit is used , the frit layer 112 will become di - electric after it is fired . thus , it will respond to outside temperature changes by a change in the dielectric constant . therefore , if the areas covered by the frit are different , as the temperature changes , the capacitances as measured at cp 108 and cr 110 electrodes will deviate from one another making the sensor less accurate . if the cr 110 and cp 108 electrodes have substantially the same area covered by the frit layer 112 then there will be very little capacitance deviation between the two electrodes . thus , in a preferred embodiment a guard electrode 120 is placed around the terminal 114 of the cp electrode 108 to act as a shield so that the only capacitance that the cp electrode 108 will be exposed to will be the capacitance created by the cr electrode 110 . in addition , if the sensor is exposed to high frequency signals , without the guard electrode 120 , terminal 118 would act like an antenna causing the sensitivity of the sensor to decrease . however , it is to be understood that the guard electrode 120 can be omitted . as shown in fig3 , in a preferred embodiment of the present invention , the cp 108 and cr 110 electrodes are fabricated by printing the cp and cr electrodes onto the substrate 106 so that they are off center on the substrate 106 . because they are elliptical in shape , by placing them off center onto the substrate 106 , the electrodes 108 and 110 can be fabricated on a larger area while still retaining sufficient space between the perimeter of the outer cr electrode 110 and the circumference of the substrate to be fused together . thus , when the diaphragm 104 and the substrate 102 assemblies layers are fused together , there is still enough space for the sealing layer 112 so that an effective seal is still possible . in a preferred embodiment , the elliptical electrodes are shaped such that the outer electrode 110 will provide essentially the same outside exposed area as the inner electrode 108 . further , in a preferred embodiment , the major diameter of the outer electrode 110 is no more than approximately twenty percent ( 20 %) larger than the minor diameter so that the increase in stress caused by the non - circular shape will remain negligible but the sensitivity to pressure will be nearly increased proportionally to the increased size of the major diameter of the outer electrode . accordingly , this configuration allows a more sensitive sensor assembly to be packaged in a smaller diameter housing . the substrate assembly preferably is fabricated by printing the cp 108 , cr 110 and guard 120 electrodes and the cr 118 and cp 114 terminals onto the substrate 106 , drying and firing them , printing the sealing layer 112 , drying the seal to drive off any volatile organic binders to leave a material that is approximately the consistency and hardness of chalk . referring again to fig1 - 3 , the diaphragm assembly 104 is shown comprising a diaphragm 120 , a ground electrode 122 having a terminal 126 connected thereto and a sealing layer 124 . a shield electrode which is on the bottom of the diaphragm assembly is not shown . in a preferred embodiment , the ground 122 and shield ( not shown ) electrodes and their terminals are fabricated by printing them onto the diaphragm 120 so that the electrodes are centered on the diaphragm 120 and correspond to the outer perimeter of the cr electrode 110 . thereafter , the electrodes are dried then fired . once the electrodes have cooled , the sealing layer 124 is printed and dried to drive off any volatile organic binders to leave a material that is approximately the consistency and hardness of chalk . the sense element 100 is completed when the substrate 102 and diaphragm 104 assemblies are fused together by aligning them along alignment notches 130 and 136 and then firing them so that the sealing layers 112 and 124 melt and fuse the assemblies 102 and 104 together . in a preferred method of the present invention , either the sealing layer 112 on the substrate assembly 102 or the sealing layer 124 on the diaphragm assembly 104 is fired prior to joining the assemblies together . the firing is done to partial completion so that the sealing layer will still have a coarse texture . after the sealing layer has cooled , the two assemblies 102 and 104 are then joined together by firing . this reduces the amount of outgassing during the joining process and it produces a stronger and less porous bond , reducing the chance of leakage in the final product . in a preferred embodiment , the sealing layer 112 is non - symmetrical due to the elliptical shapes of the electrodes 108 and 110 . since the sealing layers 112 and 124 provide support for the both the diaphragm 120 and the substrate 106 during the firing process and control the final gap between the electrodes , the sealing layers 112 and 124 must be held as constant and uniform as possible . to overcome the lack of symmetry , the sealing layers 112 and 124 are fabricated so that they have gaps 140 and 142 to balance out each sealing area so as to improve slumping when the layers of the sensor assembly 100 are fused together . this way , the centroid of each of the sealing layers 112 and 124 are kept as close as possible to the geometric center of the diaphragm 120 . another feature that is offered is the placement of an additional terminal 144 on the ground electrode . this way , it does not matter on which side of the diaphragm 120 that the ground electrode 122 is placed during fabrication so long as the shield electrode ( not shown ) is placed on the opposite side and they are connected through via holes 146 a or 146 b . the substrate 106 is manufactured so that it has 3 holes 150 a , b and c corresponding to terminals 114 , 118 , and 126 of the cp , cr and ground electrodes 108 , 110 and 122 , respectively . in addition , each of the sealing layers 112 and 124 also have holes therein which correspond to terminals 114 , 118 , and 124 of the cp , cr and ground electrodes . once the assemblies are aligned to be fused together , the holes in the substrate 106 and in the sealing layers 112 and 124 are also aligned and filled with conductive epoxy to provide the necessary conduit for the electrical connections . it will be understood that in the present invention , the sensitivity of the sense element 100 will increase without having to increase the overall size of the housing . those skilled in the art will understand that this type of sensor can be used in the automotive , airplane , heating , ventilating , and air conditioning systems ( hvac ) industries , among other applications . the embodiments described above are exemplary embodiments of the present invention . those skilled in the art may now make numerous uses of , and departures from , the above - described embodiments without departing from the inventive concepts disclosed herein . thus , the construction of the embodiments disclosed herein is not a limitation of the invention . accordingly , the present invention is to be defined solely by the scope of the following claims . | 7 |
the instant invention for electronic slip power control for a wound rotor induction motor ( wrim ) is shown in fig1 . before describing the fig1 embodiment reference will first be made to the prior art embodiment shown in fig2 . the control system shown in fig2 is for an automatically torque regulatedac adjustable speed drive . a wound rotor induction motor , indicated generally at 10 , comprises a stator 12 and a rotor 14 . the stator 12 is connected to a three - phase supply through primary protection and disconnect equipment shown symbolically at 16 . a bank of power factor correction capacitors 18 may be included if desired . the rotor is connected to slip rings shown symbolically at 20 , 22 and 24 . the slip rings 20 , 22 , 24 are connected to a three - phase full - wave rectifier , comprising a six - diode bridge section indicated generally at 26 , which is rated for the rotor output . the output of the full - wave rectifier 26 is applied to ac smoothing filter indicated generally at 28 . the filter 28 isconnected across an inverter bank comprising silicon controlled rectifiers ( scr &# 39 ; s ) indicated generally at 30 . a transformer , indicated generally at 32 , has a three - phase primary winding 34 and a three - phase secondary winding 36 . the transformer 32 is optional and is used where it is necessary to match the output of inverter 30 to the available ac power supply . the inverter bank 30 comprises six substantially identical siliconcontrolled rectifiers ( scr &# 39 ; s ) only one of which will be identified . each scr comprises an anode 38 , a cathode 40 and a gate 42 . the scr &# 39 ; s are firedby the application of a gating signal to one of the gates such as 42 . the gating of the inverter bank 30 is through feedback and trigger circuits indicated symbolically at 44 . the useful load indicated symbolically at 46is coupled to a tachometer generator 48 which develops a signal proportional to the speed of the load 46 and sends it via line 50 to the feedback and trigger circuit 44 . a torque transducer shown symbolically at52 develops a torque feedback signal which is sent by line 54 to the feedback and trigger circuit 44 . briefly , the ac voltage induced in the wrim rotor 14 is rectified in the full - wave bridge 26 to a dc level , which is fed through the filter 28 directly to the inverter 30 . the scr inverters are triggered at an inverting rate established by the frequency of the three - phase line so that the inverter output is maintained at constant frequency . the ac single phase tachometer generator 48 provides an indication of output motor speed . the tap - on resistor 52 senses the rectified current in the rotor secondary circuit , and provides a signal which is a function of the torque developed by the induction motor 10 . together the two feedback signals are summed to provide signals to the trigger circuitry 44 for controlling the inverter firing angles and therefore the inverter regenerative output voltage and power . upon energizing the system by closing the primary protection and disconnect equipment 16 , both the motor10 and the transformer 32 are energized -- the system is ready to be started . initially no current flows in the rotor 14 since the inverter 30 is not operating and hence no torque or motor rotation results . by turning on theinverter 30 at its full voltage output , the system will be operational , butthe motor 10 will not develop any torque until the voltage is reduced to a level that will permit rotor current to flow . as the voltage output of inverter 30 is reduced , current is permitted to flow in the rotor circuit since its voltage output ( which is rectified to dc by the three - phase full - wave bridge 26 ) is greater than the counter voltage being developed by the inverter 30 . the mechanical outputs of the motor -- both torque and speed -- are controlled over its entire range of operation by varying the voltage output of inverter 30 from maximum opposing voltage to a minimum or zero voltage output . since horsepower is a direct function of torque and speed ( i . e ., horsepower = kts ), when the applied torque of the load momentarily goes down thus tending to increase the speed , the feedback control circuitry 44 gates the scr &# 39 ; s of the inverter 30 so as to regenerate more ac power to the three - phase supply , thereby restoring the applied torque to the rotor 14 and maintaining the same speed and torque on the motor 10 . in the invention of fig1 the equipment which is the same as that of fig . 2 has been identified with the same numerals . the control system of fig1 is the same as that of fig2 except that the inverter now comprises two sections , indicated generally at 56 and 58 , each comprising six scr &# 39 ; s . additionally , the transformer 60 now comprises secondaries 62 and 64 connected to the outputs of the inverters 56 and 58 respectively . the primary 66 of transformer 60 is connected to the three - phase power supply . the inverter 58 is shunted by a disconnect switch shown symbolically at 68 . the inverters 56 and 58 are usually rated at half the voltage capacity of the rotor 14 , and the voltage matching transformer 60 is a three - winding unit , i . e ., one primary 66 and two secondary windings 62 , 64 . the operation of the system of fig1 is as follows . when starting , both inverter 56 and inverter 58 are at full voltage . as the motor current ( torque ) and speed are increased , the inverter 58 is reduced toward zero voltage output . during this period inverter 56 is held at maximum voltage output . when inverter 58 reaches zero voltage output , the shorting switch 68 ( connected across its output ) is closed , and inverter 58 is then shorted out and eliminated for the remainder of system operation . ( the shorting switch 68 is again opened during stopping as will be explained ). the system will then operate exactly as described in connection with fig2 control being realized by means of the single inverter 56 , that is , full voltage output from the inverter 56 will give 50 % speed , and reducingthis voltage output to zero will permit increasing the motor speed to the top rating of the motor 10 . in stopping the induction motor 10 , the output of inverter 56 is increased from its then operating value to its full or 100 % magnitude . the shorting switch 68 is then opened and inverter 58 is now back on the line at zero output voltage . once the shorting switch 68 has been opened , ( transferringrotor current to the inverter 58 ), the output of inverter 58 is increased from its zero output level to its maximum value , causing the motor 10 to be brought to a stop . thus the rotor current ( torque ) is reduced to zero by virtue of opposing voltage supplied by the inverters 56 and 58 in series , i . e ., inverter 56 at maximum voltage added to the increasing voltage output from the inverter 58 . the advantages of the fig1 arrangement over the prior art are many . by reason of the fact that two inverters are used , the voltage rating of eachinverter can be one - half that of the single inverter system of the prior art shown in fig2 . however , it should be noted at this point that this one - half rating for the inverters is not a requirement in the practice of this invention . thus , the first inverter need have only a voltage rating sufficient to satisfy the expected running range for the wound rotor motor , with the second inverter ( the one which is shorted out ) having a voltage rating of sufficient magnitude to satisfy the additional capacity requirements imposed by starting and stopping service . this results in lower inverter losses since lower voltage rated scr &# 39 ; s can be used . secondly , the matching transformer 60 can have a reduced rating -- up to as much as 43 % by proper selection of the secondary windings 62 and 64 . for example : the primary winding rating is required to match only the kva rating of inverter i , since when both secondaries are in use , in the speed range from 0 to 50 % of rated speed , only 25 % of rotor current needs to be handled . thus , the transformer rating by comparison with the normal 100 % speed range , two - winding unit , is greatly reduced . thirdly , by reducing the inverter ratings to one - half that of the rotor rating for the operating range , the kvar &# 39 ; s generated by the inverter 56 attop speed are one - half those generated by the full - range unit ( i . e ., inverter 30 of fig2 ) and the power factor correction capacitor bank 18 ( when required ) may be reduced to approximately one - half the value of the power factor correction capacitor bank 18 used with the single inverter offig2 . further , by using a reduced rating for the inverter 56 , the harmonic currents flowing into the power source will be reduced since they are proportional to rating of the inverter used . thus , the multiple inverter , multiple secondary winding transformer arrangement of fig1 provides all the advantages of the full - range ( 0 - 100 %) electronic slip power control of fig2 with lower equipment cost , higher efficiency of operation , and reduced power source disturbance . | 7 |
in one aspect of the present disclosure , there is provided a conjugated polymer containing an ethynyl crosslinking group and its use . the conjugated polymer material has a conjugated backbone structure and a functionalized ethynyl crosslinking group as side chain . the present disclosure will now be described in greater detail with reference to the accompanying drawings so that the purpose , technical solutions , and technical effects thereof are more clear and comprehensible . it is to be understood that the specific embodiments described herein are merely illustrative of , and are not intended to limit , the disclosure . the present disclosure provides a conjugated polymer containing an ethynyl crosslinking group , having the following structure : wherein , x and y are mole percentages and x + y = 1 ; ar1 and ar2 in multiple occurrences are the same or different and independently selected from an aryl or a heteroaryl group ; and , r3 is a linking group . as used herein , the term “ small molecule ” refers to a molecule that is not a polymer , oligomer , dendrimer , or blend . in particular , there is no repetitive structure in small molecules . the molecular weight of the small molecule is no greater than 3000 g / mole , more preferably no greater than 2000 g / mole , and most preferably no greater than 1500 g / mole . as used herein , the term “ polymer ” includes homopolymer , copolymer , and block copolymer . in addition , in the present disclosure , the polymer also includes dendrimer . the synthesis and application of dendrimers are described in dendrimers and dendrons , wiley - vch verlag gmbh & amp ; co . kgaa , 2002 , ed . george r . newkome , charles n . moorefield , fritz vogtle . the term “ conjugated polymer ” as defined herein is a polymer whose backbone is predominantly composed of the sp2 hybrid orbital of carbon ( c ) atom . some known non - limiting examples are : polyacetylene and poly ( phenylene vinylene ), on the backbone of which the c atom can also be optionally substituted by other non - c atoms , and which is still considered to be a conjugated polymer when the sp2 hybridization on the backbone is interrupted by some natural defects . in addition , the conjugated polymer in the present disclosure may also comprise aryl amine , aryl phosphine and other heteroarmotics , organometallic complexes , and the like . in the present disclosure , the terms such as polymerid , polymeride , and polymer have the same meaning and are interchangeable in use . in some embodiments , the polymers described in one aspect of the disclosure have a molecular weight ( mw ) of no smaller than 10000 g / mole , more preferably no smaller than 50000 g / mole , more preferably no smaller than 100000 g / mole , and most preferably no smaller than 200000 g / mol . in some preferred embodiments , the polymers described in one aspect of the disclosure are provided , wherein ar1 and ar2 are the same or different in multiple occurrences and independently selected from any one of the following structural groups : an cyclic aromatic group , including any one of benzene , biphenyl , triphenyl , benzo , fluorene , indenofuorene , and derivatives thereof ; and , a heterocyclic aromatic group , including triphenylamine , dibenzothiophene , dibenzofuran , dibenzoselenophen , furan , thiophene , benzofuran , benzothiophene , benzoselenophene , carbazole , indolocarbazole , pyridylindole , pyrrolodipyridine , pyrazole , imidazole , triazole , oxazole , thiazole , oxadiazole , oxatriazole , dioxazole , thiadiazole , pyridine , pyridazine , pyrimidine , pyrazine , triazine , oxazine , oxathiazin , oxadiazine , indole , benzimidazole , indoxazine , bisbenzoxazole , isoxazole , benzothiazole , quinoline , isoquinoline , cinnoline , quinazoline , quinoxaline , naphthalene , phthalein , pteridine , xanthene , acridine , phenazine , phenothiazine , phenoxazine , benzofuropyridine , furodipyridine , benzothienopyridine , thienodipyridine , benzoselenophenopyridine , selenophenodipyridine , and the like , or a combination thereof , or a combination thereof . in some embodiments , the ar1 , ar2 cyclic aryl groups and heterocyclic aryl groups may be further optionally substituted , wherein the substituents may be hydrogen , deuterium , alkyl , alkoxy , amino , alkenyl , alkynyl , aralkyl , heteroalkyl , aryl and heteroaryl , or a combination thereof . typically , the conjugated polymer comprises at least one backbone structural unit . the backbone structural unit is typically a π - conjugated structural unit with relatively large energy gap , also referred to as backbone unit , which may be selected from monocyclic or polycyclic aryl or heteroaryl . in the present disclosure , the conjugated polymer may comprise two or more backbone structural units . typically , the content of the backbone structural unit may be no smaller than 40 mol %, more preferably no smaller than 50 mol %, more preferably no smaller than 55 mol %, and most preferably no smaller than 60 mol %. in a preferred embodiment , the polymer according to one aspect of the disclosure is provided , wherein ar1 may be a polymer backbone structural unit that is any one selected from the group consisting of benzene , biphenyl , triphenyl , benzo , fluorene , indenofuorene , carbazole , indolocarbazole , dibenzosilole , dithienocyclopentadiene , dithienosilole , thiophene , anthracene , naphthalene , benzodithiophene , benzofuran , benzothiophene , benzene and selenophene and its derivatives , or a combination thereof . “ polymer backbone ” refers to a chain having the largest number of chain units or repeating units in a polymer chain with a branched ( side chain ) structure . in some embodiments , the polymers of the present disclosure have hole - transport properties . in a preferred embodiment , the polymer according to one aspect of the disclosure is provided , wherein ar2 may be selected from units having hole - transport properties , and a hole - transport unit may be preferably any one selected from the group consisting of aromatic amines , triphenylamine , naphthylamine , thiophene , carbazole , dibenzothiophene , dithienocyclopentadiene , dithienosilole , dibenzoselenophen , furan , thiophene , benzofuran , benzothiophene , benzoselenophene , carbazole , indolecarbazole , and their derivatives , or a combination thereof . in another preferred embodiment , ar2 may have the structure represented by chemical formula 2 : wherein ar 1 , ar 2 , ar 3 in multiple occurrences are independently the same or different : ar 1 is selected from a single - bond or mononuclear or polynuclear aryl or heteroaryl , wherein the aryl or heteroaryl may be optionally substituted with other side chains . ar 2 is selected from mononuclear or polynuclear aryl or heteroaryl , wherein the aryl or heteroaryl may be optionally substituted with other side chains . ar 3 is selected from mononuclear or polynuclear aryl or heteroaryl , wherein the aryl or heteroaryl may be optionally substituted with other side chains . ar 3 may also be linked to other parts of chemical formula 2 by a bridging group . the preferred structural unit represented by chemical formula 2 is chemical formula 3 ar 4 , ar 6 , ar 7 , ar 10 , a 11 , ar 13 , and ar 14 are defined in the same way as ar 2 in chemical formula 2 , ar 5 , ar 8 , ar 9 , and ar 12 are as defined in the same way as ar 3 in chemical formula 2 . ar 1 - ar 14 in chemical formula 2 and chemical formula 3 may be preferably selected from the group consisting of phenylene , naphthalene , anthracene , fluorene , spirobifluorene , indenofuorene , phenanthrene , thiophene , pyrrole , carbazole , binaphthalene , dehydrophenanthrene , and the like , or a combination thereof . particularly preferred alternatives of the structural units represented by chemical formula 2 and chemical formula 3 are listed in table 1 . each of these compounds may be optionally substituted with one or more substituents , and r is a substituent . wherein d 1 and d 2 may be independently the same or different in multiple occurrences and may be selected from any of the following functional groups or any combinations thereof : thiophene , selenophene , thieno [ 2 , 3b ] thiophene , thieno [ 3 , 2b ] thiophene , dithienothiophene , pyrrole , and aniline , all of which functional groups may be optionally substituted by any group below : halogen , — cn , — nc , — nco , — ncs , — ocn , scn , c (═ o ) nr 0 r 00 , — c (═ o ) x , — c (═ o ) r 0 , — nh 2 , — nr 0 r 00 , sh , sr 0 , — so 3 h , — so 2 r 0 , — oh , — no 2 , — cf 3 , — sf 5 , silyl or carbyl or hydrocarbyl having 1 to 40 c atoms , wherein r 0 and r 00 are substituent groups . ar 15 and ar 16 may be independently selected from the same or different forms in multiple occurrences and may be selected from mononuclear or polynuclear aryl or heteroaryl and may be optionally fused to their respective adjacent d 1 and d 2 . n1 - n4 may be independently selected from an integer from 0 to 4 . preferably , ar 15 and ar 16 in the materials represented by chemical formula 4 are selected from phenylene , naphthalene , anthracene , fluorene , spirobifluorene , indenofuorene , phenanthrene , thiophene , pyrrole , carbazole , binaphthalene , dehydrophenanthrene , or a combination thereof . the unit having the hole - transport property may correspond to the hole - transport material htm in oled . suitable organic htm materials may optionally comprise compounds having the following structural units : phthlocyanine , porphyrine , amine , aryl amine , triarylamine , thiophene , fused thiophene such as dithienothiophene and dibenzothiphene , pyrrole , aniline , carbazole , indolocarbazole , and their derivatives , or a combination thereof . examples of cyclic aryl amine - derived compounds that may be used as htm include , but not limited to , the general structure as follows : wherein each ar 1 to ar 9 may be independently selected from : cyclic aryl groups such as benzene , biphenyl , triphenyl , benzo , naphthalene , anthracene , phenalene , phenanthrene , fluorene , pyrene , chrysene , perylene , azulene ; and heterocyclic aryl groups such as dibenzothiophene , dibenzofuran , furan , thiophene , benzofuran , benzothiophene , benzoselenophene , carbazole , pyrazole , imidazole , triazole , isoxazole , thiazole , oxadiazole , oxatriazole , dioxazole , thiadiazole , pyridine , pyridazine , pyrimidine , pyrazine , triazine , oxazine , oxathiazin , oxadiazine , indole , benzimidazole , indoxazine , bisbenzoxazole , benzisoxazole , benzothiazole , quinoline , isoquinoline , cinnoline , quinazoline , quinoxaline , naphthalene , phthalein , pteridine , xanthene , acridine , phenazine , phenothiazine , phenoxazine , dibenzoselenophene , benzoselenophene , benzofuropyridine , indolocarbazole , pyridylindole , pyrrolodipyridine , furodipyridine , benzothienopyridine , thienodipyridine , benzoselenophenopyridine , and selenophenodipyridine ; groups comprising 2 to 10 ring structures which may be the same or different types of cyclic aryl or heterocyclic aryl and are bonded to each other directly or through at least one of the following groups , for example : oxygen atom , nitrogen atom , sulfur atom , silicon atom , phosphorus atom , boron atom , chain structure unit , and aliphatic cyclic group ; and wherein each ar may be further optionally substituted , and the substituents may optionally be hydrogen , alkyl , alkoxy , amino , alkene , alkyne , aralkyl , heteroalkyl , aryl and heteroaryl . in one aspect , ar 1 to ar 9 may be independently selected from the group consisting of : wherein n is an integer of 1 to 20 ; x 1 to x 8 are ch or n ; ar 1 is as defined above . additional non - limiting examples of cyclic aryl amine - derived compounds may be found in u . s . pat . no . 3 , 567 , 450 , u . s . pat . no . 4 , 720 , 432 , u . s . pat . no . 5 , 061 , 569 , u . s . pat . no . 3 , 615 , 404 , and u . s . pat . no . 5 , 061 , 569 . suitable non - limiting examples of htm compounds are set forth in the following table : the htm described above may be incorporated into the polymer of the present disclosure by a hole - transport structural unit . in some embodiments , the polymers of the present disclosure have electron - transport properties . in a preferred embodiment , according to one aspect of the present disclosure , wherein ar2 may be selected from units having electron - transport properties , and preferred electron - transport units may be any one selected from the group consisting of pyrazole , imidazole , triazole , oxazole , thiazole , oxadiazole , oxatriazole , dioxazole , thiadiazole , pyridine , pyridazine , pyrimidine , pyrazine , triazine , oxazine , oxathiazin , oxadiazine , indole , benzimidazole , indoxazine , bisbenzoxazole , isoxazole , benzothiazole , quinoline , isoquinoline , cinnoline , quinazoline , quinoxaline , naphthalene , phthalein , pteridine , xanthene , acridine , phenazine , phenothiazine , phenoxazine , benzofuropyridine , furodipyridine , benzothienopyridine , thienodipyridine , benzoselenophenopyridine , and selenophenodipyridine , or a combination thereof . the unit having the electron - transport characteristics may correspond to the electron - transport material etm in the oled . etm is also sometimes called n - type organic semiconductor material . in principle , examples of suitable etm materials are not particularly limited and any metal complexes or organic compounds may be used as etm as long as they have electron - transport properties . preferred organic etm materials may be selected from the group consisting of tris ( 8 - quinolinolato ) aluminum ( alq3 ), phenazine , phenanthroline , anthracene , phenanthrene , fluorene , bifluorene , spiro - bifluorene , phenylene - vinylene , triazine , triazole , imidazole , pyrene , perylene , trans - indenofluorene , cis - indenonfluorene , dibenzol - indenofluorene , indenonaphthalene , benzanthracene and their derivatives , or any combination thereof . in another aspect , compounds that may be used as etm may be molecules comprising at least one of the following groups : wherein r 1 may be selected from the group consisting of : hydrogen , alkyl , alkoxy , amino , alkene , alkyne , aralkyl , heteroalkyl , aryl and heteroaryl , wherein , when they are aryl or heteroaryl , they may have the same meaning as ar 1 in htm as described above ; ar 1 - ar 5 may have the same meaning as ar 1 in htm as described above ; n is an integer from 0 to 20 ; and x 1 - x 8 may be selected from cr 1 or n . non - limiting examples of suitable etm compounds are listed in the following table : the etm described above may be incorporated into the polymer of the present disclosure by an electron - transport structural unit . the conjugated polymer containing an ethynyl crosslinking group of structural chemical formula 1 according to one aspect of the present disclosure is provided , wherein r3 is a linking group . in a preferred embodiment , r3 may be selected from alkyl , alkoxy , amino , alkenyl , alkynyl , aralkyl , heteroalkyl , aryl and heteroaryl having from 2 to 30 carbon atoms . in some embodiments , r3 is a non - conjugated linking group , preferably any one selected from the group consisting of alkyl , alkoxy , amino , alkenyl , alkynyl , aralkyl , heteroalkyl , or a combination thereof . in some preferred embodiments , r3 is a conjugated linking group , preferably selected from c1 to c30 alkyl , c1 to c30 alkoxy , benzene , biphenyl , triphenyl , benzo , thiophene , anthracene , naphthalene , benzodithiophene , aryl amine , triphenylamine , naphthylamine , thiophene , carbazole , dibenzothiophene , dithienocyclopentadiene , dithienosilole , dibenzoselenophen , furan , thiophene , benzofuran , benzothiophene , benzoselenophene , carbazole , furan and the like , or a combination thereof . non - limiting examples of a suitable linking group r3 with a crosslinkable group are listed in the following table : in a preferred embodiment , the conjugated polymer of the present disclosure may have the general chemical formula 5 below : where x , y and z are mol % which are greater than 0 and x + y + z = 1 , and ar2 - 1 has the same meaning as ar2 described above . in a more preferred embodiment , the conjugated polymer as described above is provided , wherein at least one of ar1 , ar2 and ar2 - 1 is selected as a hole - transport unit and at least one selected as an electron - transport unit . 1 ) ar2 - 1 is selected as an electron - transport unit , ar2 is selected as a hole - transport unit ; 2 ) ar1 is selected as a backbone structural unit having electron - transport property , ar2 - 1 is selected as a hole - transport unit , and ar2 is selected as a hole - transport unit , 3 ) ar2 - 1 is selected as a light emitting unit ( including singlet emitter and triplet emitter ), and ar2 is selected as a hole - transport unit ; 4 ) ar2 - 1 is selected as a hole - transport unit , ar2 is selected as an electron - transport unit . in some preferred embodiments , the crosslinking group may be present in an amount of not greater than 50 mol %, more preferably not greater than 40 mol %, more preferably not greater than 30 mol %, and most preferably not greater than 20 mol %. a general synthetic process of a conjugated polymer containing the ethynyl crosslinking group may be : first synthesizing a monomer with a functionalized ethynyl crosslinking group , and then producing the conjugated polymer containing the ethynyl crosslinking group using polymerization processes such as transition metal catalyzed coupling ( suzuki polymerization , heck polymerization , sonogashira polymerization , still polymerization ) and the witting reaction . the reaction duration , reaction temperature , monomer ratio , reaction pressure , solubility , amount of catalyst , ligand ratio , phase transfer catalyst , and other parameters may be manipulated to control the molecular weight and dispersion coefficient of the polymer . the synthesis route may be as follows : a general synthetic process of a multi -( ternary or above ) conjugated polymer containing ethynyl crosslinking group may be : first synthesizing a monomer with a functionalized ethynyl crosslinking group , and then producing the conjugated polymer containing the ethynyl crosslinking group with multiple species f monomers ( three kinds or above ) using polymerization processes such as transition metal catalyzed coupling ( suzuki polymerization , heck polymerization , sonogashira polymerization , still polymerization ) and the witting reaction . the reaction duration , reaction temperature , monomer ratio , reaction pressure , solubility , amount of catalyst , ligand ratio , phase transfer catalyst , and other parameters may be manipulated to control the molecular weight and dispersion coefficient of the polymer . the synthesis route may be as follows : for some special polymer reaction , the ethynyl crosslinking group is sensitive to some of the specific chemical reagents , temperature and so on used in the polymer reaction process , which may initiate reaction of the ethynyl group . for example , if the temperature required for the polymerization reaction exceeds 180 ° c . or even higher than 280 ° c ., or 380 ° c ., the crosslinking groups of the conjugated polymer side chains are relatively active at high temperature and result in polymerization reaction of the ethynyl crosslinking groups to each other , generating an insoluble and infusible polymer with no solution processing characteristics . therefore , under the special polymerization conditions , the terminal hydrogen atoms on the ethynyl crosslinking group may be first protected to reduce its chemical reactivity . the most common protecting group for the terminal hydrogen atom of the ethynyl crosslinking group may be trimethylsilyl ( tms ). after formation of a trimeryl - containing polymer precursor , the polymer precursor may be treated with an alkali solution for some time to generate the targeted conjugated polymer , i . e ., the conjugated polymer containing the ethynyl crosslinking group . the optimized conjugated polymer synthesis route is shown in the following figure : the synthetic route of the conjugated organic monomer containing an ethynyl crosslinking group may be as shown below , but is not limited to the use of the following route to synthesize the target compound . the starting material a ( commercial chemical reagents or synthesized via chemical processes ) may be obtained by electrophilic optional substitution reaction ( e . g ., halogenation such as chlorination , bromination , iodination ) to obtain compound b . and the compound b can react with trimethylsilyl acetylene in a sonogashira coupling reaction catalyzed by pd — cu co - catalyst to yield compound c . the trimethylsilyl protective functional group may be removed from the compound c in an alkaline solution to produce the target compound d . in order to facilitate understanding of the conjugated polymer containing an ethynyl crosslinking group according to the present disclosure , examples of the conjugated polymers containing an ethynyl crosslinking group are given below , but are not limited thereto . the conjugated polymers containing the ethynyl crosslinking group listed herein have a distinct feature that the ethynyl group is linked to the backbone of the conjugated polymer directly or linked by a chain of conjugated aryl ring or heterocyclic aryl ring . the present disclosure also provides a mixture which may comprise a polymer according to one aspect of the disclosure , and at least another organic functional material . the organic functional material may include hole ( also referred to as electron hole ) injecting or transport material ( him / htm ), hole - blocking material ( hbm ), electron - injection or transport material ( eim / etm ), electron - blocking material ( ebm ), organic host material ( host ), singlet emitter ( fluorescent emitter ), multiplet emitter ( phosphorescent emitter ), especially light - emitting organometallic complexes . non - limiting examples of various organic functional materials are described , for example , in wo2010135519a1 , us20090134784a1 , and wo 2011110277a1 . the organic functional material may be a small - molecule polymeric material . the following is a more detailed description the organic functional material ( but not limited thereto ). htm has been described earlier and will be further discussed below . suitable organic him / htm materials for use in one aspect of the present disclosure may include any one of the compounds having the following structural units : phthalocyanines , porphyrins , amines , aryl amines , biphenyl triaryl amines , thiophenes , thiophenes such as dithiophenethiophene and thiophthene , pyrrole , aniline , carbazole , indeno - fluorene , and derivatives thereof . other suitable hims also include : fluorocarbon - containing polymers ; polymers comprising conductive dopants ; conductive polymers such as pedot / pss ; self - assembled monomers such as compounds comprising phosphonic acid and silane derivatives ; metal oxides , such as moox ; metal complex , and a crosslinking compound , or a combination thereof . other examples of metal complexes that may be used as htm or him may include , but are not limited to , the general structure as follows : m may be metal having an atomic weight greater than 40 ; ( y 1 - y 2 ) is a bidentate ligand , wherein y 1 and y 2 are independently selected from c , n , o , p , and s ; l is an auxiliary ligand ; m is an integer from 1 to the maximum coordination number of the metal ; m + n is the maximum coordination number of the metal . in one embodiment , ( y 1 - y 2 ) may be a 2 - phenylpyridine derivative . in another embodiment , ( y 1 - y 2 ) may be a carbene ligand . in another embodiment , m may be selected from ir , pt , os , and zn . in another aspect , the homo of the metal complex is greater than − 5 . 5 ev ( relative to the vacuum level ). etm has been described earlier and will be further discussed below . examples of eim / etm material used in one aspect of the present disclosure are not particularly limited , and any metal complex or organic compound may be used as eim / etm as long as they can transfer electrons . preferred organic eim / etm materials may be selected from the group consisting of tris ( 8 - quinolinolato ) aluminum ( alq3 ), phenazine , phenanthroline , anthracene , phenanthrene , fluorene , bifluorene , spiro - bifluorene , phenylene - vinylene , triazine , triazole , imidazole , pyrene , perylene , trans - indenofluorene , cis - indenonfluorene , dibenzol - indenofluorene , indenonaphthalene , benzanthracene and their derivatives , or any combination thereof . the hole - blocking layer ( hbl ) used in one aspect of the present disclosure is typically used to block holes from adjacent functional layers , particularly light - emitting layers . in contrast to a light - emitting device without a barrier layer , the presence of hbl usually leads to an increase in luminous efficiency . the hole - blocking material ( hbm ) of the hole - blocking layer ( hbl ) requires a lower homo than the adjacent functional layer , such as the light - emitting layer . in a preferred embodiment , the hbm has a greater energy level of excited state than the adjacent light - emitting layer , such as a singlet or triplet , depending on the emitter . in another preferred embodiment , the hbm has an electron - transport function . typically , eim / etm materials with deep homo levels may be used as hbm . on the other hand , examples of metal complexes that may be used as eim / etm may include , but are not limited to , the following general structure : ( o — n ) or ( n — n ) is a bidentate ligand , wherein the metal coordinates with o , n , or n , n ; l is an auxiliary ligand ; and m is an integer whose value is from 1 to the maximum coordination number of the metal . in another preferred embodiment , the organic alkali metal compound may be used as the eim . in the present disclosure , the organic alkali metal compound may be understood as a compound having at least one alkali metal , i . e ., lithium , sodium , potassium , rubidium , and cesium , and further comprising at least one organic ligand . non - limiting examples of suitable organic alkali metal compounds used in one aspect of the present disclosure may include the compounds described in u . s . pat . no . 7 , 767 , 317 b2 , ep 1941562b1 and ep 1144543b1 . the preferred organic alkali metal compound may be a compound of the following formula : wherein r 1 has the same meaning as described above , and the arc represents two or three atoms and the bond to form a 5 - or 6 - membered ring with metal m when necessary , while the atoms may be optionally substituted with one or more r 1 ; and wherein m is an alkali metal selected from lithium , sodium , potassium , rubidium , and cesium . the organic alkali metal compound may be in the form of a monomer , as described above , or in the form of an aggregate , for example , two alkali metal ions with two ligands , 4 alkali metal ions and 4 ligands , 6 alkali metal ions and 6 ligand , or in other forms . the preferred organic alkali metal compound may be a compound of the following formula : wherein , the symbols used are as defined above , and in addition : o , each time it may be the same or different , selected from 0 , 1 , 2 , 3 or 4 ; and p , each time it may be the same or different , selected from 0 , 1 , 2 or 3 . in a preferred embodiment , the alkali metal m is selected from the group consisting of lithium , sodium , potassium , more preferably lithium or sodium , and most preferably lithium . in a preferred embodiment , the organic alkali metal compound is used in the electron - injection layer , and more preferably the electron - injection layer consists of the organic alkali metal compound . in another preferred embodiment , the organic alkali metal compound is doped into other etms to form an electron - transport layer or an electron - injection layer , more preferably an electron - transport layer . non - limiting examples of a suitable organic alkali metal compound are listed in the following table : examples of a triplet host material used in one aspect of the present disclosure are not particularly limited and any metal complex or organic compound may be used as the host material as long as its triplet energy is greater than that of the light emitter , especially a triplet emitter or phosphorescent emitter . examples of metal complexes that may be used as triplet hosts may include , but are not limited to , the general structure as follows : wherein m may be a metal ; ( y 3 - y 4 ) may be a bidentate ligand , y 3 and y 4 may be independently selected from c , n , o , p , and s ; l may be an auxiliary ligand ; m may be an integer with the value from 1 to the maximum coordination number of the metal ; and , m + n is the maximum number of coordination of the metal . in a preferred embodiment , the metal complex which may be used as the triplet host has the following form : ( o — n ) may be a bidentate ligand in which the metal is coordinated to o and n atoms . in one embodiment , m may be selected from ir and pt . non - limiting examples of organic compounds that may be used as triplet host are selected from : compounds containing cyclic aryl groups , such as benzene , biphenyl , triphenyl , benzo , and fluorene ; compounds containing heterocyclic aryl groups , such as triphenylamine , dibenzothiophene , dibenzofuran , dibenzoselenophen , furan , thiophene , benzofuran , benzothiophene , benzoselenophene , carbazole , indolocarbazole , indolopyridine , pyrrolodipyridine , pyrazole , imidazole , triazole , oxazole , thiazole , oxadiazole , oxatriazole , dioxazole , thiadiazole , pyridine , pyridazine , pyrimidine , pyrazine , triazine , oxazine , oxathiazin , oxadiazine , indole , benzimidazole , indoxazine , bisbenzoxazole , isoxazole , benzothiazole , quinoline , isoquinoline , cinnoline , quinazoline , quinoxaline , naphthalene , phthalein , pteridine , xanthene , acridine , phenazine , phenothiazine , phenoxazine , benzofuropyridine , furodipyridine , benzothienopyridine , thienodipyridine , benzoselenophenopyridine , and selenophenodipyridine , or a combination thereof ; and groups containing 2 to 10 ring structures , which may be the same or different types of cyclic aryl or heterocyclic aryl and are linked to each other directly or by at least one of the following groups , such as oxygen atom , nitrogen atom , sulfur atom , silicon atom , phosphorus atom , boron atom , chain structure unit , and aliphatic ring , wherein each ar may be further optionally substituted and the substituents may be any one of hydrogen , alkyl , alkoxy , amino , alkene , alkyne , aralkyl , heteroalkyl , aryl and heteroaryl , or a combination thereof . in a preferred embodiment , the triplet host material may be selected from compounds comprising at least one of the following groups : r 1 - r 7 may be independently selected from the group consisting of hydrogen , alkyl , alkoxy , amino , alkene , alkyne , aralkyl , heteroalkyl , aryl and heteroaryl , which may have the same meaning as ar 1 and ar 1 described above when they are aryl or heteroaryl ; n may be an integer from 0 to 20 ; x 1 - x 8 may be selected from ch or n ; and x 9 may be selected from cr 1 r 2 or nr 1 . non - limiting examples of suitable triplet host material are listed in the following table : examples of singlet host material used in one aspect of the present disclosure are not particularly limited and any organic compound may be used as the host as long as its singlet state energy is greater than that of the light emitter , especially the singlet emitter or fluorescent light emitter . non - limiting examples of organic compounds used as singlet host materials may be selected from : cyclic aryl compounds , such as benzene , biphenyl , triphenyl , benzo , naphthalene , anthracene , phenalene , phenanthrene , fluorene , pyrene , chrysene , perylene , azulene ; heterocyclic aryl compounds , such as triphenylamine , dibenzothiophene , dibenzofuran , dibenzoselenophen , furan , thiophene , benzofuran , benzothiophene , benzoselenophene , carbazole , indolocarbazole , indolopyridine , pyrrolodipyridine , pyrazole , imidazole , triazole , isoxazole , thiazole , oxadiazole , oxatriazole , dioxazole , thiadiazole , pyridine , pyridazine , pyrimidine , pyrazine , triazine , oxazine , oxathiazin , oxadiazine , indole , benzimidazole , indoxazine , bisbenzoxazole , isoxazole , benzothiazole , quinoline , isoquinoline , cinnoline , quinazoline , quinoxaline , naphthalene , phthalein , pteridine , xanthene , acridine , phenazine , phenothiazine , phenoxazine , benzofuropyridine , furodipyridine , benzothienopyridine , thienodipyridine , benzoselenophenopyridine , and selenophenodipyridine ; and groups comprising 2 to 10 ring structures , which may be the same or different types of cyclic aryl or heterocyclic aryl and are linked to each other directly or by at least one of the following groups , such as oxygen atom , nitrogen atom , sulfur atom , silicon atom , phosphorus atom , boron atom , chain structure unit , and aliphatic rings . in a preferred embodiment , the monomorphic host material may be selected from compounds comprising at least one of the following groups : r 1 may be independently selected from the group consisting of hydrogen , alkyl , alkoxy , amino , alkene , alkyne , aralkyl , heteroalkyl , aryl and heteroaryl ; ar 1 is aryl or heteroaryl and has the same meaning as ar 1 defined in the htm above ; n is an integer from 0 to 20 ; x 1 - x 8 is selected from ch or n ; x 9 and x 10 are selected from cr 1 r 2 or nr 1 . non - limiting examples of a suitable singlet host material are listed in the following table : the hole - blocking layer ( hbl ) used in one aspect of the present disclosure is typically used to block holes from adjacent functional layers , particularly light - emitting layers . in contrast to a light - emitting device without a barrier layer , the presence of hbl usually leads to an increase in luminous efficiency . the hole - blocking material ( hbm ) of the hole - blocking layer ( hbl ) requires a lower homo than the adjacent functional layer , such as the light - emitting layer . in a preferred embodiment , the hbm has a greater energy level of excited state than the adjacent light - emitting layer , such as a singlet or triplet , depending on the emitter . in another preferred embodiment , the hbm has an electron - transport function . in one embodiment , the hbm used comprises the same molecules as the host material in the light - emitting layer . in another preferred embodiment , the hbm may be selected from compounds comprising at least one of the following groups : wherein n may be an integer from 0 to 20 ; l may be an auxiliary ligand ; and m may be an integer from 1 to 3 . the singlet emitter used in one aspect of the present disclosure tends to have a longer conjugate π - electron system . to date , there have been many examples , such as , but not limited to , any one of styrylamine and its derivatives or combinations thereof , and any one of indenofluorene and its derivatives or combinations thereof . in a preferred embodiment , the singlet emitter may be selected from the group consisting of monostyrylamines , distyrylamines , tristyrylamines , tetrastyrylamines , styrylphosphines , styryl ethers , and arylamines , or combinations thereof . mono styrylamine refers to a compound which comprises an unsubstituted or optionally substituted styryl group and at least one amine , most preferably an aryl amine . distyrylamine refers to a compound comprising two unsubstituted or optionally substituted styryl groups and at least one amine , most preferably an aryl amine . ternarystyrylamine refers to a compound which comprises three unsubstituted or optionally substituted styryl groups and at least one amine , most preferably an aryl amine . quaternarystyrylamine refers to a compound comprising four unsubstituted or optionally substituted styryl groups and at least one amine , most preferably an aryl amine . preferred styrene is stilbene , which may be further optionally substituted . the corresponding phosphines and ethers are defined similarly to amines . aryl amine or aromatic amine refers to a compound comprising three unsubstituted or optionally substituted cyclic or heterocyclic aryl systems directly attached to nitrogen . at least one of these cyclic or heterocyclic aryl systems is preferably selected from fused ring systems and most preferably has at least 14 aryl ring atoms . among the preferred examples are aryl anthramine , aryl anthradiamine , aryl pyrene amines , aryl pyrene diamines , aryl chrysene amines and aryl chrysene diamine . aryl anthramine refers to a compound in which a diarylamino group is directly attached to anthracene , most preferably at position 9 . aryl anthradiamine refers to a compound in which two diarylamino groups are directly attached to anthracene , most preferably at positions 9 , 10 . aryl pyrene amines , aryl pyrene diamines , aryl chrysene amines and aryl chrysene diamine are similarly defined , wherein the diarylarylamino group is most preferably attached to position 1 or 1 and 6 of pyrene . non - limiting examples of singlet emitter based on vinylamine and arylamine are also preferred examples which may be found in the following patent documents : wo 2006 / 000388 , wo 2006 / 058737 , wo 2006 / 000389 , wo 2007 / 065549 , wo 2007 / 115610 , u . s . pat . no . 7 , 250 , 532 b2 , de 102005058557 a1 , cn 1583691 a , jp 08053397 a , u . s . pat . no . 6 , 251 , 531 b1 , us 2006 / 210830 a , ep 1957606 a1 , and us 2008 / 0113101 a1 . non - limiting examples of singlet light emitters based on distyrylbenzene and its derivatives may be found in , for example , u . s . pat . no . 5 , 121 , 029 . further preferred singlet emitters may be selected from the group consisting of : indenofluorene - amine , indenofluorene - diamine , benzoindenofluorene - amine , benzoindenofluorene - diamine , dibenzoindenofluorene - amine , and dibenzoindenofluorene - diamine . other materials useful as singlet emissors include , but are not limited to , polycyclic aryl compounds , especially any one selected from the derivatives of the following compounds : anthracenes such as 9 , 10 - di - naphthylanthracene , naphthalene , tetraphenyl , phenanthrene , perylene such as 2 , 5 , 8 , 11 - tetra - t - butylatedylene , indenoperylene , phenylenes such as 4 , 4 ′-( bis ( 9 - ethyl - 3 - carbazovinylene )- 1 , 1 ′- biphenyl , periflanthene , decacyclene , coronene , fluorene , spirobifluorene , arylpyren ( e . g ., us20060222886 ), arylenevinylene ( e . g ., u . s . pat . no . 5 , 121 , 029 , u . s . pat . no . 5 , 130 , 603 ), cyclopentadiene such as tetraphenylcyclopentadiene , rubrene , coumarine , rhodamine , quinacridone , pyrane such as 4 ( dicyanoethylene )- 6 -( 4 - dimethylaminostyryl - 2 - methyl )- 4h - pyrane ( dcm ), thiapyran , bis ( azinyl ) imine - boron compounds ( us 2007 / 0092753 a1 ), bis ( azinyl ) methene compounds , carbostyryl compounds , oxazone , benzoxazole , benzothiazole , benzimidazole , and diketopyrrolopyrrole , or combinations thereof . non - limiting examples of some singlet emitter material may be found in the following patent documents : us 20070252517 a1 , u . s . pat . no . 4 , 769 , 292 , u . s . pat . no . 6 , 020 , 078 , us 2007 / 0252517 a1 , and us 2007 / 0252517 a1 . non - limiting examples of suitable singlet emitters are listed in the following table : the triplet emitter used in one aspect of the present disclosure is also called a phosphorescent emitter . in a preferred embodiment , the triplet emitter may be a metal complex of the general formula m ( l ) n , wherein m may be a metal atom ; l may be a same or different ligand each time it is present , and may be bonded or coordinated to the metal atom m at one or more positions ; n may be an integer greater than 1 , preferably 1 , 2 , 3 , 4 , 5 or 6 . alternatively , these metal complexes may be attached to a polymer by one or more positions , most preferably through an organic ligand . in a preferred embodiment , the metal atom m may be selected from the group consisting of transition metal elements or lanthanides or actinides , preferably ir , pt , pd , au , rh , ru , os , sm , eu , gd , tb , dy , re , cu or ag , and particularly preferably os , ir , ru , rh , re , pd , or pt . preferably , the triplet emitter comprises a chelating ligand , i . e ., a ligand , coordinated to the metal by at least two bonding sites , and it is particularly preferred that the triplet emitter comprises two or three identical or different bidentate or multidentate ligand . chelating ligands help to improve stability of metal complexes . non - limiting examples of organic ligands may be selected from the group consisting of phenylpyridine derivatives , 7 , 8 - benzoquinoline derivatives , 2 ( 2 - thienyl ) pyridine derivatives , 2 ( 1 - naphthyl ) pyridine derivatives , or 2 phenylquinoline derivatives . all of these organic ligands may be optionally substituted , for example , optionally substituted with fluoromethyl or trifluoromethyl . the auxiliary ligand may be preferably selected from acetylacetonate or picric acid . in a preferred embodiment , the metal complex which may be used as the triplet emitter may have the following form : wherein m is a metal selected from the group consisting of transition metal elements or lanthanides or actinides ; ar 1 may be the same or different cyclic group each time it is present , which comprises at least one donor atom , that is , an atom with a lone pair of electrons , such as nitrogen atom or phosphorus atom , which is coordinated to the metal through its ring group ; ar 2 may be the same or different cyclic group comprising at least one c atom and is coordinated to the metal through its ring group ; ar 1 and ar 2 are covalently bonded together , wherein each of them may carry one or more substituents which may also be joined together by substituents ; l may be the same or different at each occurrence and is an auxiliary ligand , preferably a bidentate chelating ligand , and most preferably a monoanionic bidentate chelating ligand ; m is 1 , 2 or 3 , preferably 2 or 3 , and particularly preferably 3 ; and , n is 0 , 1 , or 2 , preferably 0 or 1 , particularly preferably 0 . non - limiting examples of triplet emitter materials that are extremely useful may be found in the following patent documents and references : wo 200070655 , wo 200141512 , wo 200202714 , wo 200215645 , ep 1191613 , ep 1191612 , ep 1191614 , wo 2005033244 , wo 2005019373 , us 2005 / 0258742 , wo 2009146770 , wo 2010015307 , wo 2010031485 , wo 2010054731 , wo 2010054728 , wo 2010086089 , wo 2010099852 , wo 2010102709 , us 20070087219 a1 , us 20090061681 a1 , us 20010053462 a1 , baldo , thompson et al . nature 403 , ( 2000 ), 750 - 753 , us 20090061681 a1 , us 20090061681 a1 , adachi et al . appl . phys . lett . 78 ( 2001 ), 1622 - 1624 , j . kido et al . appl . phys . lett . 65 ( 1994 ), 2124 , kido et al . chem . lett . 657 , 1990 , us 2007 / 0252517 a1 , johnson et al ., jacs 105 , 1983 , 1795 , wrighton , jacs 96 , 1974 , 998 , ma et al ., synth . metals 94 , 1998 , 245 , u . s . pat . no . 6 , 824 , 895 , u . s . pat . no . 7 , 029 , 766 , u . s . pat . no . 6 , 835 , 469 , u . s . pat . no . 6 , 830 , 828 , us 20010053462 a1 , wo 2007095118 a1 , us 2012004407a1 , wo 2012007088a1 , wo2012007087a1 , wo 2012007086a1 , us 2008027220a1 , wo 2011157339a1 , cn 102282150a , wo 2009118087a1 . non - limiting examples of suitable triplet emitter are given in the following table : in some embodiments , the organic functional materials described above , including him , htm , etm , eim , host , fluorescent emitter , and phosphorescent emitters , may be in the form of polymers . in a preferred embodiment , the polymer suitable for the present disclosure is a conjugated polymer . in general , the conjugated polymer may have the general formula : wherein b , a may be independently selected as the same or different structural elements in multiple occurrences . b : a π - conjugated structural unit with relatively large energy gap , also referred to as backbone unit , which may be selected from monocyclic or polycyclic aryl or heteroaryl , preferably in the form of benzene , biphenylene , naphthalene , anthracene , phenanthrene , dihydrophenanthrene , 9 , 10 - dihydrophenanthroline , fluorene , difluorene , spirobifluorene , p - phenylenevinylene , trans - indenofluorene , cis - indenofluorene , dibenzol - indenofluorene , indenonaphthalene and derivatives thereof , or a combination thereof . a : a π - conjugated structural unit with relatively small energy gap , also referred to as a functional unit , which , according to different functional requirements , may be selected from the above - mentioned hole - injection or hole - transport material ( him / htm ), hole - blocking material ( hbm ), electron - injection or electron - transport material ( eim / etm ), electron - blocking material ( ebm ), organic host material ( host ), singlet emitter ( fluorescent emitter ), multiplet emitter ( phosphorescent emitter ), or a combination thereof . non - limiting examples of light - emitting polymers are disclosed in wo2007043495 , wo2006118345 , wo2006114364 , wo2006062226 , wo2006052457 , wo2005104264 , wo2005056633 , wo2005033174 , wo2004113412 , wo2004041901 , wo2003099901 , wo2003051092 , wo2003020790 , wo2003020790 , us2020040076853 , us2020040002576 , us2007208567 , us2005962631 , ep201345477 , ep2001344788 , and de102004020298 . in another embodiment , the polymers suitable for the present disclosure may be non - conjugated polymers . the nonconjugated polymer may be the backbone with all functional groups on the side chain . non - limiting examples of such nonconjugated polymers for use as phosphorescent host or phosphorescent emitter materials may be found in patent applications such as u . s . pat . no . 7 , 250 , 226 b2 , jp2007059939a , jp2007211243a2 and jp2007197574a2 . non - limiting examples of such nonconjugated polymers used as fluorescent light - emitting materials may be found in the patent applications jp2005108556 , jp2005285661 , and jp2003338375 . in addition , the non - conjugated polymer may also be a polymer , with the conjugated functional units on the backbone linked by non - conjugated linking units . non - limiting examples of such polymers are disclosed in de102009023154 . 4 and de102009023156 . 0 . the present disclosure also provides a formulation which may comprise a conjugated organic polymer as described in one aspect of the present disclosure and at least one organic solvent . examples of the organic solvents include , but are not limited to , methanol , ethanol , 2 - methoxyethanol , dichloromethane , trichloromethane , chlorobenzene , o - dichlorobenzene , tetrahydrofuran , anisole , morpholine , toluene , o - xylene , m - xylene , p - xylene , 1 , 4 - dioxahexane , acetone , methyl ethyl ketone , 1 , 2 - dichloroethane , 3 - phenoxytoluene , 1 , 1 , 1 - trichloroethane , 1 , 1 , 2 , 2 - tetrachloroethane , ethyl acetate , butyl acetate , dimethylformamide , dimethylacetamide , dimethyl sulfoxide , tetrahydronaphthalene , naphthane , indene and / or their formulations . in a preferred embodiment , the formulation according to one aspect of the disclosure is a solution . in another preferred embodiment , the formulation according to one aspect of the disclosure is a suspension . the formulation in the examples of the present disclosure may comprise an organic mixture from 0 . 01 to 20 wt %, more preferably from 0 . 1 to 15 wt %, more preferably from 0 . 2 to 10 wt %, and most preferably from 0 . 25 to 5 wt %. the present disclosure also provides the use of said formulation as a coating or printing ink in the preparation of organic electronic devices , and particularly preferably by means of printing or coating in a preparation process . among them , suitable printing or coating techniques may include , but are not limited to , ink - jet printing , typography , screen printing , dip coating , spin coating , blade coating , roll printing , torsion printing , lithography , flexography , rotary printing , spray coating , brush coating or pad printing , slit type extrusion coating , and so on . preferred are inkjet printing , screen printing and gravure printing . the solution or suspension may additionally comprise one or more components such as surface active compounds , lubricants , wetting agents , dispersing agents , hydrophobic agents , binders , etc ., for adjusting viscosity , film forming properties , improving adhesion , and the like . for more information about printing techniques and their requirements for solutions , such as solvent , concentration , viscosity , etc ., see handbook of print media : technologies and production methods , edited by helmut kipphan , isbn 3 - 540 - 67326 - 1 . based on the above polymers , the present disclosure also provides use of the polymers as described above , i . e . application of the polymers to an organic electronic device , which may be selected from , but not limited to , organic light emitting diodes ( oled ), organic photovoltaics ( opvs ), organic light emitting cells ( oleec ), organic field effect transistor ( ofet ), organic light emitting field effectors , organic lasers , organic spin electron devices , organic sensors , and organic plasmon emitting diodes , especially oled . in a particularly preferred embodiment , the polymer according to one aspect of the present disclosure is used in an electron - transport layer , especially a hole - transport layer , of an organic electronic device . the present disclosure further provides an organic electronic device which may comprise at least one polymer as described above . typically , such an organic electronic device may comprise at least a cathode , an anode , and a functional layer between the cathode and the anode , wherein the functional layer may comprise at least one of the polymers as described above . in a preferred embodiment , the above - described organic electronic device is an electroluminescent device , which may include a substrate , an anode , at least one light - emitting layer , and a cathode . in a particularly preferred embodiment , the organic electronic device described above may be an oled . the substrate may be opaque or transparent . transparent substrates may be used to make transparent light - emitting components . see , for example , bulovic et al ., nature 1996 , 380 , p 29 , and gu et al ., appl . phys . lett . 1996 , 68 , p 2606 . the substrate may be rigid or flexible . the substrate may be plastic , metal , semiconductor wafer or glass . most preferably the substrate has a smooth surface . substrates free of surface defects are particularly desirable . in a preferred embodiment , the substrate is flexible and may be selected from polymer films or plastic , with a glass transition temperature ( tg ) of 150 ° c . or above , more preferably above 200 ° c ., more preferably above 250 ° c ., and most preferably above 300 ° c . non - limiting examples of suitable flexible substrates are poly ( ethylene terephthalate ) ( pet ) and polyethylene glycol ( 2 , 6 - naphthalene ) ( pen ). the anode may comprise a conductive metal or a metal oxide , or a conductive polymer . the anode may easily inject holes into the hole - injection layer ( hil ) or the hole - transport layer ( htl ) or the light - emitting layer . in one embodiment , the absolute value of the difference between the work function of the anode and the homo energy level or the valence band energy level of the emitter in the light - emitting layer or of the p - type semiconductor material of the hil or htl or the electron - blocking layer ( ebl ) may be smaller than 0 . 5 ev , more preferably smaller than 0 . 3 ev , and most preferably smaller than 0 . 2 ev . non - limiting examples of anode materials may include , but are not limited to , al , cu , au , ag , mg , fe , co , ni , mn , pd , pt , ito , aluminum - doped zinc oxide ( azo ), and the like . other suitable anode materials are known and may be readily selected for use by one of ordinary skill in the art . the anode material may be deposited using any suitable technique , such as suitable physical vapor deposition , including rf magnetron sputtering , vacuum thermal evaporation , electron beam ( e - beam ), and the like . in some embodiments , the anode may be patterned . the patterned ito conductive substrate is commercially available and may be used to fabricate the device according to the disclosure . the cathode may comprise a conductive metal or a metal oxide . the cathode may easily inject electrons into the eil or etl or directly into the light - emitting layer . in one embodiment , the absolute value of the difference between the work function of the cathode and the lumo energy level or the valence band energy level of the emitter in the light - emitting layer or of the n - type semiconductor material of the electron - injection layer ( eil ) or the electron - transport layer ( etl ) or the hole - blocking layer ( hbl ) may be smaller than 0 . 5 ev , more preferably smaller than 0 . 3 ev , and most preferably smaller than 0 . 2 ev . in principle , all of the material that may be used as the cathode of an oled may serve as a cathode material for the device of the present disclosure . examples of the cathode material may include , but are not limited to , any one of al , au , ag , ca , ba , mg , lif / al , mgag alloys , baf2 / al , cu , fe , co , ni , mn , pd , pt , ito , or a combination thereof . the cathode material may be deposited using any suitable technique , such as suitable physical vapor deposition , including rf magnetron sputtering , vacuum thermal evaporation , electron beam ( e - beam ), and the like . oleds may also comprise other functional layers such as hole - injection layer ( hil ), hole - transport layer ( htl ), electron - blocking layer ( ebl ), electron - injection layer ( eil ), electron - transport layer ( etl ), and hole - blocking layer ( hbl ), or a combination thereof . materials suitable for use in these functional layers are described in detail in wo2010135519a1 , us20090134784a1 , and wo2011110277a1 . in a preferred embodiment , in the light emitting device according to one aspect of the present disclosure , the light - emitting layer thereof may be prepared by printing with the formulation of the present disclosure . the light emitting device according to one aspect of the present disclosure may have a light emission wavelength between 300 and 1000 nm , more preferably between 350 and 900 nm , and more preferably between 400 and 800 nm . the disclosure also provides the use of organic electronic devices according to one aspect of the disclosure in a variety of electronic devices including , but not limited to , display devices , lighting devices , light sources , sensors , and the like . the disclosure also provides an electronic device comprising an organic electronic device as described in an aspect of the disclosure , including , but not limited to , display devices , lighting devices , light sources , sensors , and the like . the disclosure will now be described with reference to the preferred embodiments , but the disclosure is not to be construed as being limited to the following examples . it is to be understood that the appended claims are intended to cover the scope of the disclosure . those skilled in the art will understand that modifications can be made to various embodiments of the disclosure with the teaching of the present disclosure , which will be covered by the spirit and scope of the claims of the disclosure . to a 250 ml three - necked round bottom flask , 26 . 40 g ( 0 . 1 mol ) of 2 , 5 - dibromo - p - xylene and 24 . 39 g ( 0 . 2 mmol ) of phenylboronic acid was added . 250 ml of toluene was added and stirred to dissolve , followed by 50 ml water and 21 . 2 g na 2 co 3 ( 0 . 2 mol ), stirring all solids were dissolved . 0 . 5 ml of aliquat 336 and 75 mg of tetra ( triphenylphosphine ) palladium catalyst ( 0 ) (( pph 3 ) 4 pd ) were added and flushed with protective nitrogen gas for 10 min before heated to reflux ( 92 - 100 ° c .). after refluxing for 20 min , the nitrogen gas was turned off and the system kept sealed , reflexing and reacting overnight . the reaction solution was extracted with toluene ( 50 ml × 4 ) after cooling , and the organic phase was combined and successively washed with saturated solution of nacl and water . white crystal 22 . 48 g was obtained by evaporation of the solvent and drying , with the theoretical value of 25 . 84 g and a yield rate of about 87 %. m . p . 180 - 181 ° c . ( lit . 180 ° c . ), 1 h nmr ( cdcl 3 , 400 mhz , ppm ): δ 7 . 44 - 7 . 30 ( m , 10h ), 7 . 14 ( s , 2h ), 2 . 26 ( s , 6h ). to a 250 ml three - necked round bottom flask , 12 . 92 g ( 0 . 05 mol ) of 2 , 5 - diphenyl - p - xylene and 250 ml of pyridine was added under mechanical stirring to dissolve , followed by 30 ml of water and 39 . 51 g of kmno 4 ( 0 . 25 mol ). it was heated to reflux ( about 105 - 110 ° c .) for 2 h , during which it was cooled after every 30 min of refluxing and added with 60 ml of water and 15 . 59 g of kmno 4 ( 0 . 1 mol ), repeated for four times in total . afterwards , it was cooled after every 6 h of refluxing and added with 60 ml of water , repeated for four times in total . after the reaction , filtration was done when hot . the filter cake was rinsed with boiling water ( 1000 ml × 4 ), the filtrate was combined , and the solvent was evaporated to about 100 ml , to which 50 ml of concentrated hydrochloric acid was added . after cooling , filtration , and washing with cold water , it was dried in vacuo to give 9 . 21 g of white solid , with the theoretical value of 15 . 92 and a yield rate of about 57 . 9 %. m . p . 281 - 282 ° c . ( lit . 282 ° c . ), 1 h nmr ( dmso - d 6 , 400 mhz , ppm ): δ 7 . 67 ( s , 2h ), 7 . 46 - 7 . 38 ( m , 10h ). to a 500 ml three - necked round bottom flask , 100 ml of concentrated sulfuric acid was added , followed by slow addition of 3 . 18 g of 2 , 5 - diphenylcarbodiimide ( 0 . 01 mol ) under stirring . reaction was allowed under room temperature for 0 . 5 h and followed by the addition of 5 - 10 drops of fuming sulfuric acid . after 6 h of reaction , the reaction solution was poured into ice - water mixture and stirred with a glass rod . the mixture was filtered by suction , rinsed with a large amount of water , and dried to give a dark red solid of 1 . 95 g , with the theoretical value of 2 . 82 g and a yield rate of about 69 %. m . p .& gt ; 300 ° c . ( lit .& gt ; 300 ° c . ), 1 h nmr ( cdcl 3 , 400 mhz , ppm ): δ 7 . 79 ( s , 2h ), 7 . 68 ( d , j = 7 . 36 hz , 2h ), 7 . 57 - 7 . 51 ( m , 4h ), 7 . 37 - 7 . 29 ( m , 2h ). to a 500 ml three - necked round bottom flask , 5 . 64 g of 6 , 22 - indolifluinedione ( 0 . 02 mol ) was added , and then slowly 300 ml of diethylene glycol and 4 ml of hydrazine hydrate ( 85 %) successively added with stirring , followed by 28 . 10 g of koh ( 0 . 5 mol ) ground into fine powder . after flushing with protective nitrogen gas for 10 min , it was heated to reflux ( 195 ° c .) for reaction of 48 h , before the mixture was cooled and poured into a mixed solution of crushed ice / concentrated hydrochloric acid ( v : v = 8 : 1 ), while stirring with a glass rod . the mixture was filtered by suction , washed with water , and dried to obtain a yellowish gray solid of 2 . 29 g , with the theoretical value of 5 . 09 g and a yield rate of 45 %. m . p . 300 - 301 ° c . ( lit . 300 - 302 ° c . ), 1 h nmr ( dmso - d 6 , 400 mhz , ppm ): δ 8 . 09 ( s , 2h ), 7 . 93 ( d , j = 7 . 4 hz , 2h ), 7 . 59 ( d , j = 7 . 4 hz , 2h ), 7 . 39 ( t , j = 7 . 4 hz , 2h ), 7 . 31 ( t , j = 7 . 4 hz , 2h ), 3 . 99 ( s , 4h ). to a 250 ml three - necked round bottom flask , a stir bar and 1 . 27 g of indenofuorene ( 6 ) were added , and a high vacuum piston ( paraffin seal ) was placed in the middle while rubber stoppers were place on both sides . the flask was heated with a blower while being evacuated with an oil pump . 100 ml of dry thf was added to the flask with a syringe . 6 ml of 2 . 87 m n - butyllithium ( 17 . 22 mmol ) was added dropwise to the flask using a syringe under stirring at − 78 ° c . and reacted under nitrogen protection for 1 h . the system was allowed to warm up to room temperature for 30 min of reaction and then cooled to − 78 ° c . 3 . 82 g of 1 - bromooctane ( n - c 8 h 17 br , 20 mmol ) was added with a syringe , reacted at room temperature for 1 h at − 78 ° c ., spontaneously warmed up to room temperature , and reacted overnight . the reaction was quenched by the addition of about 30 ml of water . the reaction solution was extracted with petroleum ether ( 50 ml × 4 ). the organic phase was combined and dried over anhydrous na 2 so 4 . the solvent was evaporated before purification by column chromatography ( 100 - 200 mesh silica gel / petroleum ether ). recrystallization from methanol gave 1 . 45 g of beige crystals , with the theoretical value of 3 . 52 g and a yield rate of about 47 . 7 %. 1 h nmr ( cdcl 3 , 400 mhz , ppm ): δ 7 . 72 ( d , j = 6 . 8 hz , 2h ), 7 . 58 ( s , 2h ), 7 . 33 - 7 . 24 ( m , 6h ), 1 . 99 ( t , j = 8 . 0 hz , 8h ), 1 . 12 - 0 . 98 ( m , 24h ), 0 . 76 - 0 . 59 ( m , 20h ); 13 c nmr ( cdcl 3 , 100 mhz , ppm ): δ 151 . 08 , 149 . 92 , 141 . 48 , 140 . 50 , 126 . 59 , 122 . 81 , 119 . 30 , 113 . 81 , 54 . 66 , 40 . 67 , 31 . 50 , 29 . 69 , 23 . 67 , 22 . 51 , 13 . 96 . to a 250 ml three - necked round bottom flask , a stir bar , 7 . 03 g of 6 , 6 , 12 , 12 - tetraoctylindenofuorene ( 10 mmol ), and 100 ml of ccl4 were added , dissolved by stirring . 40 g al 2 o 3 / cubr ( 0 . 25 mol ) was added for reaction under refluxing for 18 h . the reaction mixture was filtered and the filtrate was washed with water and dried over anhydrous na 2 so 4 . the solvent was evaporated and the resulting solid was recrystallized in methanol to give 3 . 73 g of white crystals with the theoretical value of 8 . 61 g and a yield rate of about 43 . 3 %. 1 h nmr ( cdcl 3 , 400 mhz , ppm ): δ 7 . 57 ( d , j = 8 . 4 hz , 2h ), 7 . 52 ( s , 2h ), 7 . 45 ( s , 2h ), 7 . 44 ( d , j = 8 . 4 hz , 2h ), 1 . 97 ( t , j = 8 . 2 hz , 8h ), 1 . 11 - 0 . 96 ( m , 24h ), 0 . 75 - 0 . 58 ( m , 20h ); 13 c nmr ( cdcl 3 , 100 mhz , ppm ): δ 153 . 12 , 149 . 68 , 140 . 12 , 139 . 72 , 129 . 69 , 125 . 97 , 120 . 73 , 120 . 63 , 113 . 84 , 55 . 13 , 40 . 60 , 31 . 58 , 29 . 71 , 23 . 76 , 22 . 62 , 14 . 11 . to a 250 ml three - necked round bottom flask , a stir bar was added , and a high vacuum piston was placed in the middle while rubber stoppers were place on both sides . the flask was heated with a blower while being evacuated with an oil pump . a solution of 4 . 31 g of 2 , 8 - dibromo - 6 , 6 , 12 , 12 - tetraoctylindenofuorene ( 5 mmol ) in 120 ml of thf was added to the flask using a syringe and stirred at − 78 ° c . for 20 min . then , 6 ml of 2 . 87 m n - butyllithium ( 17 . 22 mmol ) was added dropwise with a syringe , reacted under protective nitrogen gas for 2 h . 5 ml of 2 - isopropyl - 4 , 4 , 5 , 5 - tetramethyl - 1 , 3 , 2 - dioxaborane was added dropwise with a syringe , reacted at − 78 ° c . for 2 h and then allowed to warm up to room temperature for reaction overnight . the reaction was quenched by adding 10 ml of water to the flask . the reaction was extracted with ether ( 50 ml × 4 ). the organic phase was combined and dried over anhydrous na 2 so 4 . the solvent was evaporated before purification by column chromatography ( 100 - 200 mesh silica gel / ethyl acetate v : v = 9 : 1 ) to give 1 . 18 g of white crystals , with the theoretical value of 4 . 78 g and the yield rate of about 24 . 7 %. 1 h nmr ( cdcl 3 , 400 mhz , ppm ): δ 7 . 75 ( d , j = 7 . 7 hz , 2h ), 7 . 71 ( d , j = 7 . 3 hz , 2h ), 7 . 70 ( s , 2h ), 7 . 59 ( s , 2h ) 4 . 19 ( t , j = 5 . 3 hz , 8h ), 2 . 08 ( t , j = 5 . 3 hz , 4h ), 2 . 01 ( q , j = 6 . 4 hz , 8h ), 1 . 07 - 0 . 96 ( m , 24h ), 0 . 68 ( t , j = 7 . 0 hz , 12h ), 0 . 58 ( t , j = 6 . 7 hz , 8h ); 13 c nmr ( cdcl 3 , 100 mhz , ppm ): δ 150 . 49 , 150 . 15 , 143 . 94 , 140 . 83 , 132 . 35 , 127 . 75 , 118 . 59 , 114 . 17 , 61 . 99 , 54 . 58 , 40 . 64 , 31 . 51 , 29 . 71 , 27 . 42 , 23 . 65 , 22 . 52 , 13 . 96 . to a 500 ml three - necked round bottom flask , 49 g of triphenylamine ( 0 . 2 mol ) was added , 300 ml of n , n - dimethylformamide was added slowly with stirring , and 34 . 10 g ( 0 . 2 mol ) of n - bromosuccinimide ground into fine power was added in several batches . the reaction was performed under nitrogen protection at room temperature in the dark for 48 h . after cooling , it was poured into crushed ice and extracted three times with dichloromethane . the organic phases were combined and washed three times with water . 200 - 300 mesh silica gel column was used for separation , while the eluent was for petroleum ether . the product was 58 g with a yield rate of 90 %. to a 500 ml three - necked round bottom flask , 4 - bromotriphenylamine ( 12 . 00 g , 40 . 00 mmol ), cui ( 0 . 052 g , 0 . 28 mmol ), ( ph 3 p ) 2 pdcl 2 ( 0 . 475 g , 0 . 68 mmol ), 200 ml of degassed toluene , and 60 ml of degassed diisopropylamine were added under stirring to dissolve and mix evenly . a solution of trimethylethynylsilane ( 4 . 32 g , 44 . 0 mmol ) in diisopropylamine ( 30 ml ) was added dropwise under argon at room temperature . after the dropwise addition , the temperature of the reaction solution was raised to 70 ° c . and the reaction was carried out under argon for 6 hours . the reaction progress was monitored by thin layer chromatography . after completion of the reaction , the reaction solution was cooled to room temperature , and the impurities such as solid salt were removed by filtration . the crude product was separated and purified by column chromatography ( silica gel column , with eluent as petroleum ether ), and further recrystallized from methanol to give a white solid which was filtered and dried in vacuo to give 9 . 58 g of a yield rate of 70 %. to a 500 ml three - necked round bottom flask , 6 g of 4 - trimethylsilylethynyltriphenylamine ( 0 . 02 mol ) was added , 300 ml of n , n - dimethylformamide was added slowly with stirring , and 6 . 810 g ( 0 . 04 mol ) of n - bromosuccinimide ground into fine power was added in several batches . the reaction was performed under nitrogen protection at room temperature in the dark for 48 h . after cooling , it was poured into crushed ice and extracted three times with dichloromethane . the organic phases were combined and washed three times with water . 200 - 300 mesh silica gel column was used for separation , while the eluent was for petroleum ether . the product was 5 . 6 g with a yield rate of 90 %. in a 25 ml two - necked round bottom flask , 195 mg ( 0 . 5 mmol ) of monomer 4 , 4 - dibromo - 4 ′- trimethylsilyl ethynyltriphenylamine , 418 mg ( 0 . 5 mmol ) of monomer 2 , 8 - bis ( 4 , 4 , 5 , 5 - tetramethyl - 1 , 3 , 2 - dioxaborolane - diyl )- 6 , 6 , 12 , 12 - tetraoctylindenofuorene , 10 mg of pd ( pph 3 ) 4 , 10 ml of degassed toluene , 4 ml of degassed tetrahydrofuran , and 2 ml of a 20 wt % aqueous solution of tetraethylammonium hydroxide were added , homogenized , and flushed with argon for 15 minutes . the reaction was carried out under argon protection at 110 ° c . for 24 hours , followed by the successive addition of 50 μl of bromobenzene to reflux for 2 hours and 20 mg of phenylboronic acid to reflux for 2 hours . after the reaction was completed and cooled to room temperature , the reaction solution was added dropwise to methanol for precipitation . the resulting flocculent precipitate was filtered , dried in vacuo , and the resulting polymer was redissolved in about 30 ml of tetrahydrofuran . the resulting tetrahydrofuran solution was filtered through a polytetrafluoroethylene ( ptfe ) filter having a pore size of 0 . 45 m , distilled under reduced pressure , concentrated , and added dropwise to methanol for precipitation . the precipitate was dried in vacuo to give 392 mg of pale yellow solid with a yield rate of 74 %. gpc ( tetrahydrofuran , polystyrene standard sample ) mn = 21 000 g mol − 1 , pdi = 1 . 8 . to a solution of polymer p1 ( 392 mg ) in tetrahydrofuran ( 200 ml ), 15 ml of 20 wt % potassium hydroxide aqueous solution was added , followed by the addition of 20 ml of methanol to dilute the reaction solution . the reaction was stirred under argon at room temperature for 1 hour . after completion of the reaction , the reaction solution was poured into ice water and extracted with trichloromethane . the oil layers were washed with water , saturated sodium chloride aqueous solution and concentrated to obtain a crude product . the crude product was separated and purified by column chromatography ( silica gel column , with eluent as petroleum ether ) and further recrystallized in methanol to give a white solid , which was filtered and dried in vacuo to give a yield of 352 mg with a yield rate of 80 %. gpc ( tetrahydrofuran , polystyrene standard sample ) mn = 21 000 g mot − 1 , pdi = 1 . 8 . the polymer p2 prepared in example 1 was used as a hole - transport material in an organic / polymer electroluminescent device o / pleds ( ito anode / hole - transport layer / light - emitting layer / electron - transport layer / aluminum cathode ). the ito conductive glass and block resistors of about 20 ohm / cm square were pre - cut into 15 mm × 15 mm square piece , ultrasonically cleaned successively with acetone , micron - level semiconductor special detergent , deionized water , and isopropyl alcohol , flushed with nitrogen , and placed in the oven for later use . prior to use , the ito glass pieces were bombarded by plasma for 10 minutes in an oxygen plasma etch instrument . pedot : pss dispersion in water ( about 1 %) clevios ™ pedot : pss a14083 was used as a buffer layer in a high - speed spin coating ( kw - 4a ), the thickness depending on the solution concentration and rotation speed , monitored in real time by a surface profiler ( tritek alpha - tencor - 500 type ). after film formation , the residual solvent was removed in a constant - temperature vacuum oven . the thickness of the pedot : pss film on the ito substrate was 80 nm thick . the polymer p2 synthesized in example 1 was dissolved in a toluene solution at a concentration of 5 mg / ml . the polymer p2 was spin - coated on a pedot : pss film , and the thickness was 20 nm . the reaction was heated to 200 ° c . for 30 min on a hot plate , so that the substance p2 underwent a crosslinking reaction . the polymer p2 film was then rinsed with toluene and the thickness was determined to be 18 - 19 nm , indicating that the crosslinking reaction was effective and the solification of polymer p2 film was relatively complete . the fluorescent conjugated polymer p - ppv ( p - ppv is a green - emitting material ) or meh - ppv ( meh - ppv is an orange - red emitting material ) was weighed in a clean bottle , transferred to a film - specific glove box under nitrogen protection , dissolved in toluene , and filtered through a 0 . 45 micron filter . the fluorescent polymer was spin - coated on the hole - transport layer of the polymer p2 film , and the optimal thickness of the polymer light - emitting layer was 80 nm . the film thickness was measured using an alpha - tencor - 500 surface profiler . then , about 2 - 5 nm csf was applied under vacuum deposition conditions as an electron - injection / transporting layer . aluminum ( 100 nm ) was vacuum evaporated on the electron - transport layer as a cathode . the light emitting area of the device has a region masked by the ito interaction cover with an area determined to be 0 . 04 square centimeters . all preparation procedures were carried out in a glove box in a nitrogen atmosphere . the current - voltage characteristics , light intensity , and external quantum efficiency of the device were measured by the keithley236 current - voltage measurement system and a calibrated silicon photodiode . | 2 |
this invention is surgical instruments for stabilizing - the beating heart and methods for their use . the means for stabilizing the beating heart are comprised of several alternative structures which engage the surface of the heart to stabilize the beating heart during coronary surgery . the instruments provide the capability to exert and maintain a stabilizing force on the heart by contacting the heart with the stabilizing means and by fixing the position of the stabilizing means throughout the duration of a surgical procedure . the instruments and methods of the invention are preferably used for stabilization of the beating heart during a minimally invasive coronary artery bypass graft ( cabg ) operation which has been specially developed to facilitate placement of a bypass graft without cardioplegia or cardiopulmonary bypass . although the means for stabilizing the beating heart can be applied in different surgical contexts , the devices described herein are most advantageously employed in a cabg procedure wherein only one or two incisions are placed in the chest . the structure of the stabilizing means may be described by several structural embodiments which stabilize the beating heart while the minimally invasive surgical procedure is performed . the stabilizer means may also advantageously function in a multiple component system containing a retractor , an occluder , a surgical blower or suction device , an apparatus for holding the source artery , such as a lima holder , or other like devices to enable a surgeon to more efficiently complete the anastomosis . while the devices disclosed herein each use mechanical means to stabilize the beating heart , certain embodiments are designed to operate on the entire heart while others have more localized effect and may be applied to the area immediately proximate to a structure such as the target artery of the anastomosis . in each instance , the beating heart is effectively stabilized at the area where a surgical procedure is to be performed . surgical access to the beating heart may be achieved by several conventional cardiac surgical procedures which have been developed for traditional bypass surgery . the surgeon may obtain the advantages provided by the invention in any procedure where the bypass is achieved on the beating heart . when access to the beating heart is achieved by a sternotomy , the length of the sternum is separated to expose the surface of the heart . preferably , the surgeon takes additional measures to restrict the movement at the entire heart within the chest cavity . for example , an inflatable cushion with straps or laces may be inserted beneath or surrounding the heart . additionally , when the pericardium is available , the pericardium may be incised and used to position the beating heart . when the pericardium is available , the surgeon can use the pericardium to raise and rotate the beating heart within the chest cavity and maintain the position by suturing the pericardium to the periphery of the incision . in the preferred embodiment , minimally invasive access to the beating heart is achieved by a thoracotomy , which is usually created in the left side of the chest by a vertical incision between the ribs , insertion of a retractor between the ribs , followed by spreading of the ribs and securing the retractor in an open position to provide access to the source artery and the target coronary artery . the use of the pericardium to position the beating heart as described above is particularly advantageous when the less invasive thoracotomy is used to provide access to the heart . an incision is created in the pericardium which is then sutured to the periphery of the thoracotomy . in this configuration , the pericardium acts as a restraining sac to keep the beating heart in a desired orientation to achieve the anastomosis . the means for stabilizing the beating heart is introduced through the opening created by the thoracotomy and is brought into contact with the heart . the surgeon applies a stabilizing force to the heart via the stabilizing means which may then be fixed in place by attachment to a fixed support . when the rib retractor or platform is fixed in an open position to expose the heart , the retractor platform may also provide an advantageous stable support structure to which the stabilizing means may be affixed . when the position of the stabilizing means is fixed by attachment to a stable support or to the retractor platform , the stabilizing force is maintained for the duration of the procedure . although the particular source and target artery of the anastomosis are determined clinically , common minimally invasive bypass procedure on the beating heart comprises an anastomosis which forms a connection between the left internal mammary artery ( lima ) as the source artery and the left anterior descending artery ( lad ) as the target artery . the lima to lad anastomosis is used as an example herein but it is readily appreciated that the techniques and instruments described herein may be applied to other procedures depending on the clinical diagnosis . to complete the anastomosis , the surgeon must dissect a portion of the lima by separating it from the internal chest cavity . once dissection of the lima is achieved , the surgeon may attach the dissected lima to the target cardiac artery , in this example , the lad . in this example , the stabilizing means of this invention would be used to stabilize the beating heart during at least the portion of the procedure during which the surgeon completes the anastomosis to the lad . the structure of the portion of the stabilizing means which contacts the heart includes an inflatable member , a platform which may be substantially planar or which may be contoured to fit conformingly on the surface of the heart , one or more contact members which exert a stabilizing force on the heart proximate to the site of the anastomosis , a pair of contact members which may be plates or rectangular members which are placed on either side of the target coronary artery at the site of the anastomosis and which may have a friction or tissue spreading means associated therewith . the stabilizing means may also include a shaft means having several alternative embodiments to facilitate adjusting the position and orientation of the instrument . for example , the shaft means may have an adjustable length and the axis of the shaft means may have at least one ball joint disposed within its length such that the orientation of the shaft means relative to another structure such as the contact members on the retractor may be continuously varied . as is apparent from the description of the several embodiments , each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope of the invention . referring to fig1 a stabilizing means is comprised of one or more , and preferably two , contact members 1 , which are attached to a rigid , or semi - rigid connecting shaft 2 which is in turn connected to shaft means 3 . the contact members 1 may be substantially planar or may be slightly curved to conform to the shape of the heart . the contact members 1 may have any of several alternate shapes including cylindrical members formed into a u - shape or may comprise a pair of substantially parallel members spaced apart in a parallel configuration such that a target artery can be positioned between the contact members . the shape of the contact members may be varied depending on the clinical assessment by the surgeon , the design of the other features of the stabilizing means , or the design of other instruments used to complete the anastomosis . in some embodiments , as described herein , the . contact members 1 may have apertures , openings or attachments to facilitate connection with sutures or other devices to achieve the requisite stabilization . in a preferred embodiment , a pair of substantially planar rectangular contact members 1 are attached at one end to a continuous connecting shaft 2 and are oriented in a substantially parallel fashion such that a target cardiac artery is positioned therebetween and passes along the length of the contact members 1 when the stabilizing means engages the heart . see fig9 a - c . while the contact members 1 may each be connected to the connecting shaft 2 at one end , with the connecting shaft 2 operably attached to shaft means 3 , the configuration of the connecting shaft 2 relative to the contact members 1 may be altered depending on the configuration of the contact members 1 and the clinical aspects of the procedure . for example , the connecting shaft may be continuous to connect with the contact members 1 without touching the artery or may include an additional member which may be operated to contact the target artery positioned between the contact members 1 , see fig8 to occlude the passage of blood through the target artery . the contact members 1 , connecting shaft 2 and shaft means 3 may be composed of any non - toxic material such as a biocompatible plastic or stainless steel , having sufficient tensile strength to withstand a stabilizing force exerted on the heart via manipulation of the shaft means 3 to cause the contact members 1 to exert a stabilizing force on the beating heart . the shaft means 3 may be a simple rigid post or may be comprised of a multi - component system designed to be adjustable in length and orientation at least one point along its length . thus , the length of the shaft means 3 and the orientation of the contact members 1 at the distal ( lower ) end of the shaft means 3 can be altered by the surgeon . preferably , the length and orientation at the shaft means 3 relative to the contact members 1 can be adjusted by controls located at the proximate ( upper ) end of shaft means 3 . this design provides the advantage that the surgeon can introduce the stabilizing means to the beating heart by placing the contact members 1 on the surface of the heart , exerting a stabilizing force , and then locking the contact members 1 in place relative to the shaft means 3 . furthermore , the surgeon may then lock the shaft means 3 into a fixed position by attachment to a stable support such as the retractor , thereby maintaining the stabilizing force for the duration of the procedure . in one embodiment , the shaft means 3 has a housing 11 whose overall length is adjustable by a telescoping release 4 operated by an annular thumbscrew 10 which tightens about the housing 11 . the position and orientation of the contact members 1 relative to the shaft means 3 is adjustable by virtue of a locking ball joint 5 which is interposed between the connecting shaft 2 and which is located at the distal end of shaft means 3 . the locking ball joint 5 allows the position of the shaft means 3 to be positioned with three degrees of freedom relative to the contact members 1 . referring again to fig1 a locking ball joint 5 is provided by including a block 6 within the shaft means 3 which conformingly contacts the ball joint 5 and fixes the position of the ball joint 5 . block 6 is compressed against ball joint 5 when a threaded push block 7 is connected to a long allen 9 is actuated by means such as a thumbscrew 8 at the upper end of the shaft means 3 . in operation , a rotation of the top thumbscrew 8 loosens the lower ball joint 5 to allow continuous positioning of the shaft means 3 relative to the contact members 1 , and a counterrotation locks the ball joint 5 into place , fixing the position of the contact members 1 relative to shaft means 3 . the upper end of shaft means 3 may also have associated therewith an upper ball joint 13 such that the shaft means 3 can be oriented with three degrees of freedom relative to a fixed support such as a retractor . the position and orientation of the shaft means 3 may thus be fixed relative to the stable support by a locking latch 14 or other conventional mechanism which prevents movement of the upper ball joint . either the shaft means 3 or the retractor may contain the locking latch 14 surrounding the upper ball joint 13 or any like fixture to firmly attach the shaft means 3 to a stable support , e . g ., an anchor portion 15 extending from the retractor ( not shown ). referring to fig1 b , the contact members 1 preferably have friction means 4 associated with their bottom surface 5 such that the contact members 1 more securely engage the beating heart when a stabilizing force is exerted on the shaft means 3 . the friction means 4 preferably comprises a textured surface covering the bottom surface 5 of the contact member 1 , and may be comprised of several bio - compatible substances such as a textured rubber , textured or ridged aluminum , stainless steel or the like . as noted above , at the upper end of the shaft means 3 , the shaft means 3 may be attached to a fixed support , such as by anchor portion 15 , which may be any surface or structure which does not move with the beating heart . for example , the shaft means 3 may be attached to a fixture on the retractor system used to spread the ribs for access to the heart or may be attached to a fixed structure such as the surgical table or associate aperture which is not connected to the patient . in a preferred embodiment , the shaft means 3 is directly attached to a component of the retractor system which is designed to receive the shaft means 3 and to maintain the position and orientation of the shaft means 3 during the procedure . the shaft means 3 may also be attached , to or comprised of , a conformable arm which is used to position the stabilizing means against the heart and then to lock the stabilizing means in place once a stabilizing force has been exerted . the conformable arm is flexible and lockable and may have several configurations including a plurality of links , segments , or universal joints in serial configuration and having a cable fixture passed through the interior of the links which cause the entire conformable arm to become rigid by tightening the cable fixture . also , the conformable arm may be comprised of a synthetic gel or polymer contained within a conformable cylindrical housing and which becomes rigid upon exposure to light or heat , such as the commercially available dymax 183 - m . where the shaft means 3 is further comprised of the conformable arm , the conformable arm may be attached directly to the connecting shaft 2 or the contact members 1 . referring to fig2 the stabilizer - means may also be comprised of a single shaft means 3 connected to each contact member 1 . in a preferred embodiment , the shaft means 3 are interconnected at an intermediate pivot point 16 which permits the contact members 1 to be continuously positioned in parallel fashion relative to one another . the proximate ( upper ) portion of the individual shaft means 3 may have grips adapted to be grasped by the hand or may have an anchor portion 15 for attachment to a retractor or other fixed support . as with the other embodiments described herein , the length of the shaft means 3 may be adjustable by a conventional telescope configuration . in such a configuration , a first shaft 18 has a partially hollow segment 17 adapted to receive the complimentary portion of the second shaft 19 . either first 18 or second 19 shafts may be connected to the contact members 1 and may each have a conventional locking mechanism ( not shown ). the shaft means may also have a tensioning spring mechanism having an axis 21 which is displaced between a portion of the shaft means 3 affixed to the contact members 1 and the remainder of the shaft means 3 . in this configuration , the contact members 1 remain tensioned against the heart proximate to the anastomosis site when the proximal end of the shaft means 3 is affixed to a stable support . the shaft means may also comprise an interlocking mechanism 18 to fix the position of a single shaft 18 relative to the other . this embodiment also preferably has a friction means 4 as described above attached to each contact member 1 . an additional advantage of this embodiment is derived from the capability to move the contact members 1 apart from one , another in a parallel configuration . thus , the contact members 1 can first be positioned to engage the surface of the heart tissue , followed by the application of a stabilizing force in combination with spreading of the proximate ( upper ) end of the shaft means 3 . application of a stabilizing force causes the tissue on either side of the target artery to be stabilized . by coincidentally spreading the proximate portion of the shaft means 3 , the tissue engaged by the contact members 1 is stretched to provide stabilization and improved exposure of the target coronary artery . referring to fig3 the contact members 1 may be further comprised of a spring - tensioned frame 21 having a movable frame extension 22 which may have pins or an associated friction means 4 to engage the tissue proximate to the target artery . the movement of the frame extension 22 is tensioned by a spring means 23 which draws the frame extension 22 toward the contact member 1 after the frame extension 22 has been manually positioned to engage the tissue . the use of this embodiment of the invention is the same as is described for the other embodiments herein , with the frame extension 22 providing improved exposure of the target artery . as with the other embodiments of the invention disclosed herein , the contact members 1 may be attached at one end by a connecting shaft 2 which is attached to a shaft means 3 as described above . the connecting shafts 2 may also be positioned relative to one another by a conventional threaded post 24 with a positioning thumbscrew 25 . referring to fig4 this embodiment of the stabilizing means is comprised of an elongated sheath member 26 which wraps around the heart in a strap - like fashion to restrict the motion of the heart . this embodiment is particularly useful when access to the beating heart is provided by a sternotomy . the sheath member 26 is positioned to surround the heart and manipulated so that each end of the sheath member 26 extends out of the chest cavity through a the stemotomy . if desired , at least one end of each sheath member 26 is attached to the retractor to secure the position of the sheath member 26 . the sheath member 26 may have a plurality of support attachments 27 which engage the exterior of the heart to hold it in place . at the point where the support attachments 27 contact the surface of the heart , the support attachments 27 may have friction means 4 attached to the surface which is in direct contact with the heart . the support attachments 27 may have or be comprised of inflatable members 28 which cushion the heart against the sheath member 26 , and absorb the motion of the heart while it is stabilized . where the sheath member 26 has a plurality of inflatable members 28 , the sheath member 26 is preferably further comprised of at least one lumen 29 for introduction of air or a biocompatible fluid to the inflatable members 28 , which may be inflated separately or simultaneously . in the former instance , a separate lumen 29 is provided for each inflatable member 28 . the insertion of the sheath member 26 into the chest cavity should be performed while the inflatable members 28 are deflated and is achieved manually or by a conventional guide and / or guidewire . each of the support attachments 27 may be permanently attached to the sheath member 26 or may slide along the length of the sheath member 26 . alternatively , alone or in combination with at least one other inflatable member 28 , an inflatable member 28 may be positioned immediately proximate to the target coronary artery to achieve a more localized stabilization . the inflatable member 28 is positioned to lie next to , or may surround , the target coronary artery and may have openings or apertures placed in the body of the member through which surgical procedures are performed . referring to fig5 the stabilizer means may comprise at least one stabilizer plate which is attached to a stable support and which may be used with a lever member for improving exposure at the target artery while the anastomosis is completed . in this embodiment , the means for stabilizing the beating heart comprises a left and right stabilizing plate 30 , 31 which are oriented to exert a downward force on the tissue at either side of the target artery at the anastomosis site and which may be substantially planar or may be curved to conform to the surface of the heart . one or both of the stabilizing plates 30 , 31 may have an edge 27 deflected downward along its length so that the edge 27 depresses the tissue proximate to the artery to increase the exposure of the artery during the completion of anastomosis . preferably , the edge 27 of the stabilizing plates 30 , 31 has a separate lever member 33 running substantially parallel to the artery and on both sides thereof . the top portion of each lever member 33 contacts the underside of the stabilizing plates 30 , 31 . in this embodiment , the lever member 33 is substantially cylindrical , traverses the stabilizing plate along its length , and is oriented to be parallel to the edge 27 of the stabilizing plate 30 , 31 . the lever member 33 is fixed in place , and may be affixed to the heart by a suture . in such a configuration , each of the stabilizing plates 30 , 31 , which is in contact with the lever member 33 along its length , contacts the heart such that the edge 27 depresses the tissue on both sides of the target coronary to restrict the movement of the beating heart . the stabilizing plates 30 , 31 can be attached to one another or can move independently as desired . opposite the edge 32 , at a point separate from the lever member 33 , the stabilizing 30 , 31 plate is connected to a shaft means 3 which holds the stabilizing plate 30 , 31 in position and which may be manipulated relative to the lever member 33 to cause the edge 27 to engage the heart . the shaft means 3 is preferably affixed to each stabilizing plate 30 , 31 at a point opposite the edge 27 and removed from the point where the lever member 33 contacts the stabilizer plate 30 , 31 at a location to maximize leverage when the stabilizer plates 30 , - 31 are drawn upwards at the point of attachment of the shaft means 3 . the shaft means 3 may be constructed as described elsewhere herein and should be of sufficient length to facilitate manipulation of the shaft means 3 by the surgeon . as noted , the shaft means may also be attached to the retractor to fix movement of the stabilizing plates 30 , 31 during the procedure . in a preferred embodiment , the length of the shaft means 3 is adjustable relative to the retractor or other stable support . for example , the shaft means 3 may be telescopic as described above or may be comprised of a hollow post 34 which receives a rigid shaft 35 which is in turn fixed to the retractor . the rigid shaft 35 may also be substantially hollow and may have a suture or other line 36 passed therethrough and which also passes through the length of the hollow post 34 . in this configuration , one end of the suture or line 36 is attached to the stabilizing plate 30 , 31 and the other end extends through the hollow post 34 or the rigid shaft 35 to a position where it may be manipulated by the surgeon . the position of the stabilizing plate 30 , 31 may thereby be remotely actuated . by drawing tension on the suture or line 36 , the stabilizing plate 30 , 31 pivots about the lever member 33 and the edge 32 of the stabilizer plates 30 , 31 depress the tissue on either side of the target artery . referring to fig6 this embodiment of the invention is a means for stabilizing the beating heart wherein the shaft means is comprised of a flexible , lockable arm 37 having a plurality of interconnecting links 38 which allow positioning of the flexible arm 37 in every direction until the desired configuration is achieved at which point the flexible arm 37 may be locked into fixed configuration by tightening a cable fixture ( not shown ) attached to a cable 39 running axially through the interconnecting links 38 . each interconnecting link is comprised of a ball portion 38 a and a receiving portion 38 b such that the ball portion 38 fits conformingly within the receiving portion 38 b . the proximate ( uppermost ) end of the flexible , lockable arm 37 can be attached to a stable support , or to the retractor . in a preferred embodiment , the flexible , lockable arm 37 is a series of interconnecting links 38 having a cable 39 running through the center of each interconnecting link 38 such that when tension is exerted on the cable 39 , the flexible , lockable arm 37 is fixed in a rigid position . fig6 also shows an embodiment of the invention wherein the contact members 1 are comprised of a pair of substantially parallel elements 1 a , 1 b which are positioned to receive a simple snap fixture 40 which is affixed to the surface of the heart . in this embodiment , the snap fixture 40 is positioned between the two parallel elements 1 a , 1 b of the contact member 1 , in order to fix the position of the heart tissue relative to the contact members 1 . as in the above embodiment , the contact members 1 are preferably oriented in a substantially parallel fashion with the target artery of the anastomosis passing therebetween . the snap fixtures 40 are affixed to the heart by a suture , wherein the suture line 41 may then also be attached to the contact member 1 via a notch , which may form a one - way locking mechanism to secure the suture line 41 , or may be attached to a circular . post disposed in the body of the contact member 1 . the suture line 41 then may be tied through the notch or to the post in the contact member 1 to more tightly secure the heart to the contact member 1 . an additional advantage of this embodiment is that the stabilizing means is actually affixed to the cardiac tissue via the suture line 41 , such that when the heart is moving laterally or downward the artery being stabilized remains immobile . referring to fig7 a stabilizing means 60 is comprised of a substantially planar and substantially rigid surface 62 having a centrally disposed opening 61 in which the target artery of the anastomosis is positioned longitudinally through the opening . at either or both ends of the centrally disposed opening 61 , an occluder 63 extends below the surface 62 and engages the target artery to substantially reduce or eliminate the flow of blood through the artery . the occluder is a rigid member having a smooth outer surface for contacting and depressing the target artery without damaging the tissue . the planar surface 62 of the stabilizing means also has an aperture 64 comprising an opening which traverses the entire planar surface 62 so that the anastomosis can be passed through the aperture 64 when the anastomosis is completed . the planar surface 62 may also provide a mounting surface for springed tissue retractors 65 comprising a coiled spring 66 attached to the planar surface at one end and having a hook or pin 67 at the opposite end to engage and spread the tissue proximate to the anastomosis site to improve the exposure of the target artery . the planar surface 62 is attached to a post 69 which may be attached to a stable support such as the rib retractor as shown in fig9 b . the planar surface 62 may also have at least one port 70 for receiving a suture line . referring to fig8 the stabilizing means may have operably associated therewith an artery occluder 42 , which is preferably attached to the contact members 1 or to the connecting shaft 2 . the artery occluder 42 may comprise a semi - rigid member which has a blunt portion 43 , which may be positioned such that the blunt portion 43 engages the target artery 55 and compresses the target artery 55 to a point causing occlusion of the target artery 55 passing between the contact members 1 such that the blood flow through the artery is substantially reduced or eliminated . preferably , the occluder 42 has a shaft portion 44 which traverses the connection shaft 2 such that the blunt portion 43 of the occluder 43 may move from above the level of the target artery 55 to a point sufficient to occlude the blood flow . referring to fig9 a , the means for stabilizing the beating heart 54 of the invention is shown in use together with a rib retractor 50 and additional apparatus 51 , 52 which may be used during the beating heart cabg procedure . in use , the blades 53 of the retractor separate the ribs , thereby providing an access space for the introduction of surgical instruments , including the stabilizing means 54 of the invention . the stabilizing means 54 is thus brought into contact with the heart such that the contact members are proximate to the target artery 55 . once the stabilizing force has been exerted , sufficient to minimize the motion of the beating heart , the stabilizing means 54 is fixed in place , preferably by attachment to the rib retractor 50 . referring to fig9 b , the stabilizing means 54 is an embodiment substantially as described above and shown in fig1 which is comprised of a pair of rectangular , substantially planar contact members 1 which are placed proximate to a target artery 55 . the shaft means 3 is conformable such that it may be conveniently attached to the rib retractor 50 . as shown in fig9 b , the surgeon may readily adjust the orientation and positioning of the contact members 1 relative to the shaft means 3 while the stabilizing means 54 is in continuous contact with the heart by manipulating the thumbscrew 8 at the proximal end of the instrument . [ 0050 ] fig9 c shows a later stage of the procedure at a point where the anastomosis is being completed by suturing at target artery 55 . the stabilizing means 54 thus maintains a stabilizing force at the anastomosis site for the duration of the procedure . referring to fig1 , as noted above , attachment to a rib retractor is a preferred technique for fixing the position and orientation of the stabilizing means . the stabilizing means of the invention may therefore advantageously attached to a fixture attached to a rib retractor 50 or may be configured to be directly incorporated into the body of a portion of the rib retractor 50 . a surgical rib retractor 50 is generally comprised of a body 54 having blades 53 attached thereto , which engage the ribs and spread the ribs when the retractor 50 is operated to move the blades 53 apart from one another . the space created by the retracted blades 53 provides access to the heart . thus , once the retractor 50 is locked into the open position , the stabilizing means may be applied to the heart and a stabilizing force maintained at the site of the anastomosis by fixing the position and orientation of the shaft means 3 relative to the rib retractor 50 . referring to fig1 , the shaft means 3 traverses the width of the body 54 of the retractor 50 and is held in place by an upper plate 57 and a lower plate 58 having circular openings 59 therein through which the shaft means 3 passes and which maintain the position 6 f a sphere 56 positioned between the upper plate 57 and lower plate 58 . the size of the openings 59 is larger than the diameter of the shaft means 3 but smaller than the largest diameter of the sphere 56 . thus , the shaft means 3 passes through the sphere 56 and may pivot about a point approximately at the center of the sphere 56 . referring to fig1 and 12 , because the available access and working space for the surgeon may be limited , certain embodiments of the invention may be contained substantially within the chest cavity . preferably , the stabilizing means is connected to the bottom of the rib retractor 50 on each side of the opening created by spreading the ribs using the rib retractor 50 . referring to fig1 , rib retractor 50 is shown in an open position whereby blades 53 engage and spread the ribs . a pair of stabilizing bars 72 having a conventional ratchet means 73 attached at the end thereof are positioned beneath the retractor . the ratchet means 73 is comprised of a plurality of teeth 74 on the stabilizing bars 72 and a ratcheting aperture 75 permitting one - way passage of the stabilizing bars 72 unless released by a release mechanism . the stablizing bars 72 are curved downward such that as the bars are advanced through the ratchet means 73 , the lowermost portion 76 of the stablizing bars 72 engages the beating heart proximate to the anastomosis site . referring to fig1 , the orientation of the portion of the stabilizing means which engages the heart relative to the rib retractor 50 is similar to the embodiment shown in fig1 . in this embodiment , a contact member 1 is attached on opposite ends to at least two malleable supports 80 which are in turn attached to the rib retractor 50 . the malleable supports 80 are preferably made of stainless steel bands which are woven in a mesh or have a repeating serpentine configuration to allow for substantial expansion within the chest cavity . this configuration yields a malleable support 80 with sufficient tensile strength to maintain a stabilizing force at the anastomosis site while allowing the surgeon to manipulate the malleable supports within the chest cavity to achieve the desired orientation relative to the beating heart . the particular examples set forth herein are instructional and should not be interpreted as limitations on the applications to which those of ordinary skill are able to apply this invention . modifications and other uses are available to those skilled in the art which are encompassed within the spirit and scope of the following claims . | 0 |
the present invention will now be described more fully with reference to the accompanying drawings , in which preferred embodiments of the invention are shown . this invention may , however , be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein . rather , these embodiments are provided so that this disclosure is thorough and complete and fully conveys the concept of the invention to those skilled in the art . hereafter , the embodiments of the present invention shall be described in detail with the accompanying drawings . according to the embodiments of the present invention , there is provided a phase - change memory element where the first electrode used as a heating layer and the second electrode which is opposite to the first electrode are formed with layers of the same height , and a memory layer which is formed by a phase - change material placed between the side surface of the first and second electrodes which face each other . for such a phase - change memory element , the contact surface between the first electrode used as a heating layer and the memory layer is dependent on the side width of the first electrode , while , the area of the side surface of the first electrode is determined by the width and the thickness of the first electrode , which will be formed during a patterning process . accordingly , despite of the limitation of the patterning process , the contact surface of the first electrode could be formed with a very small with the aid of actually the thickness of the first electrode . the thin thickness of the first electrode can be realized during a deposition process beyond the limitation of the patterning process . therefore , the volume of a phase - change region which is dependent on the contact surface can be very small , and accordingly a phase - change memory element operation using a low current is possible . now , the phase - change memory element and a method of manufacturing the same shall be described in detail according to the preferred embodiments of the invention . fig1 a through 7b are general views of a phase - change memory element and the method of manufacturing the same according to the first embodiment of the present invention . fig1 a is a plan view showing the step of forming the first electrode pad 20 and the second electrode pad 30 on a first insulating layer 10 , and fig1 b is a cross sectional view according to a cutting - plane line 1 – 1 ′ of fig1 a . referring to fig1 a and 1b , the first insulating layer 10 is mounted on a semiconductor substrate ( not shown ) where a transistor element or diode element constituting a circuit for an addressing or memory operation . the integration of a transistor or diode on a semiconductor substrate for the operation of a phase - change memory element can be realized by a known process . a first contact hole through the first insulating layer 10 is formed on the first insulating layer 10 using a photo lithography process in order to form an electrical connection with the circuit . thereafter , a film of a conductive material , for example , a metal or other conductive material is deposited on the first insulating layer 10 and then a first interconnection contact 25 is formed to fill the first contact hole is etched back or flattened . the first connection contact 25 plays the role of an electrical connection between the first electrode and the transistor element . the first interconnection contact 25 can be formed by a semiconductor process known as a plug process , however , it also can be formed by filling the first contact hole with an electrode pad layer in the deposition process of the pad layer followed by . in a case when the first interconnection contact 25 is formed by a known plug process , the electrode pad layer is formed by the deposition of a metal or conductive film on the first connection contact 25 and the first insulating layer 10 . the electrode pad layer can be formed of a different material from or the same material as that of the first interconnecting contact 25 . afterward , by means of patterning the electrode pad layer , the first electrode pad 20 and the second electrode pad 30 , which is opposite to the first electrode pad 20 , are formed . in this way , since the first electrode pad 20 and the second electrode pad 30 are formed in one process , the first electrode pad 20 and the second electrode pad 30 substantially have the same height facing sidely each other . fig2 a is a plan view of an electrode layer 40 and fig2 b is a cross sectional view cut according to a cutting - plane line 2 – 2 ′ of fig2 a . referring to fig2 a and 2 b , an electrode layer 40 is deposited to cover the first electrode pad 20 and the second electrode pad 30 . thereafter , the electrode layer 40 is patterned so that the portion of the electrode layer 40 , which is between the first electrode pad 20 and the second electrode layer pad , has narrower width than the width of the first electrode pad 20 or the second electrode pad 30 . this electrode layer 40 can work as a diffusion barrier layer , and can also be used as a heating layer for heating the phase - change material so as to cause phase change or transformation . particularly , the portion deposited on the first electrode pad 20 works as the heating layer . the electrode layer 40 is formed of a conductive film , such as titanium aluminium nitride ( tialn ), titanium silicon nitride ( tisin ), or titanium carbon nitride ( ticn ). meanwhile , as shown in fig2 a , it is preferable that patterning is performed such that the width of the electrode layer 40 between the first electrode pad 20 and the second electrode pad 30 is narrower than the width of the first electrode pad 20 or / and the second electrode pad 30 . it is more preferable that the width sided to the first electrode pad 20 is narrower than that of the second electrode pad 30 side , since the electrode layer 40 existing above the first electrode pad 20 actually plays as a heating layer . in other words , the purpose of performing the above process is to make the volume of the phase change region small enough to confine to the contacting surface between the first electrode , which will be formed of a part of electrode layer 40 , and the phase change material by allowing more current to concentrate onto the portion of the electrode layer 40 covering the first electrode pad 20 than the contacting surface of the phase change layer , that is , the memory layer . fig3 a is a plan view explaining the step of dividing the electrode layer 40 and fig3 b is across sectional view according to the cutting plane line 3 – 3 ′ of fig3 a . referring to fig3 a and 3b , a second insulating layer 50 is formed on the electrode layer 40 , and a second contact hole 55 is formed on the electrode layer 40 using the photolithography process . the second contact hole 55 is formed to expose a portion of the first insulating layer 10 between the first electrode pad 20 and the second electrode pad 30 so as to separate the electrode layer 400 in fig2 a into the first electrode 41 located on the first electrode pad 20 and the second electrode 45 located on the second electrode pad 30 . for complete separation , the width of the second contact hole 55 is formed wider than the electrode layer 40 portion between the first electrode pad 20 and the second electrode pad 30 . here , as shown in fig3 a , a side surface of the first electrode 41 is exposed as a portion of side wall of the second contact hole 55 . the side surface of the narrow width portion 43 of the first electrode pad 20 side of the electrode layer 40 is exposed the side wall of the second contact hole 55 . while the material used for the second insulating layer 50 mentioned above , it is preferable to be formed of a silicon oxide layer ( sio 2 ), which has good coherence , for semiconductor manufacturing process , and in order to obtain a higher thermal insulating characteristic , a low thermal conductivity material such as bpsg , could be used . fig4 is a cross - sectional view showing the step of depositing of a memory layer 60 between the first electrode 41 and the second electrode 45 . referring to fig4 , a memory layer 60 is formed in the second contact hole 55 by depositing a phase - change material so as to contact the first electrode 41 and the second electrode 45 which are exposed to the second contact hole 55 . as shown in fig4 , the memory layer 60 could be deposited as a liner form without completely filling the second contact hole 55 . a chalcogenide alloy , for example , an alloy of ge — sb — te which is widely used for phase change material , could be used as a material for the memory layer 60 . fig5 a is a plan view showing the step of patterning the memory layer pattern 65 and fig5 b is a cross sectional view according to the cutting - plane line 5 – 5 ′ of fig5 a . referring to fig5 a and 5b , the deposited memory layer 60 is extended over the second insulating layer 50 according to the characteristics of deposition ; however , the patterning is performed to form a memory layer pattern 65 by a selective removal of such extended portion . for example , the memory layer 60 is etched back or cmp ( chemical mechanical polishing ) to form the memory layer pattern 65 as a ring shape on the side wall of the second contact hole 55 as shown in fig5 a . also , such patterning may be performed by a photolithography process . patterning by a combination of the cmp and photolithography processes enhances the uniformity of the shape of the memory layer pattern 65 . fig6 is a cross - sectional view showing the step of forming a third insulating layer 70 on the memory pattern 65 . as shown in fig6 , the third insulating layer 70 , which is formed of a silicon oxide layer , is formed on the second insulating layer 50 . fig7 a is a plan view showing the step of forming an upper electrical line 80 connected to the second electrode 45 , and fig7 b is a cross sectional view according to cutting - plane line 7 – 7 ′ of fig7 a . referring to fig7 a and 7b , through the third insulating layer 70 , a third contact hole 83 is formed to expose the second electrode 45 selectively , and then an electric line layer filling the third contact hole 83 is deposited . thereafter , the upper electric line 80 is connected electrically with the second electrode 45 through a second connecting contact 81 which is a portion filling the third contact hole 83 . here , the upper electric line 80 can be made of a conductive metal layer , such as aluminum ( al ) or titanium tungsten ( tiw ). as foregoing descriptions , a phase - change memory element can be formed by the process and steps according to the preferred embodiments of the present invention as suggested in fig7 a and 7b , since the first electrode 41 and the second electrode 45 are formed with the same layer . a phase - change layer , that is , a memory layer pattern 65 , which is located between the first electrode 41 and the second electrode 45 , contacts a side surface of the relatively narrow width of the first electrode which is exposing to the side wall of the second contact hole 55 . accordingly , the contacting surface between the memory layer pattern 65 and the first electrode 41 is confined to the side surface of the narrow width of the first electrode 41 . because the first electrode 41 is actually used as a heating layer , the operation volume is substantially confined to the portion of the memory layer pattern 65 adjoining the side surface of the narrow width portion 43 of the first electrode 41 . the width of the narrow width portion 43 of the first electrode 41 is dependent on the photolithography process but the thickness substantially is dependent on the thickness of the deposition of the electrode layer 40 which is for the first electrode 41 . at present time , the photolithography process has a limitation in patterning ; however , the layer thickness by deposition can be achieved far beyond the limitation of the photolithography process , and has enabled the obtaining further thinner and better in uniformity . in other words , it is possible to control the thickness of the thin film much thinner than the width of the first electrode layer , and to achieve a higher uniformity . therefore , the contacting surface of the memory layer pattern 65 with the narrow width portion 43 of the first electrode 41 can be very small and be controlled with very high uniformity . fig8 a and 8b are the general views of a phase - change memory element and manufacturing method thereof according to the second embodiment of the present invention . referring to fig8 a and 8b , as explained in fig3 a and 3b according to the first embodiment , after separation of the first electrode 41 and the second electrode 45 is performed by the installation of the second contact hole 55 , the memory layer can be formed by filling the second contact hole 55 . then , after flattening the upper surface of the memory layer using cmp process so as to expose the upper surface of the second insulating layer , a memory layer patterning 67 can be formed to completely fill the second contact hole 55 . besides above , there are various ways of forming a phase - change region , for example , patterning using the photolithography process after deposition of phase - change material , and the like . however , in all cases , the actual volume of a phase - change region is confined to the contact surface with the cross - section of the first electrode 41 . according to the embodiments of the present invention , in order to have very small volume of phase change region during operation , the phase change region can be confined to the contacting surface of the memory layer with the side surface of the first electrode which is used for heating layer . since the area of the side surface of the first electrode depends on the thickness of the layer of the first electrode , it is possible to control the volume of a phase - change region in accordance with the thickness of the first electrode . the thickness of a thin film can be controlled smaller size than the width formed by the photolithography process , and the thickness can be controlled with a higher uniformity . as a consequence , it is possible to manufacture a phase - change memory element capable of low power operation , and , especially , to manufacture a semiconductor substrate or wafer which has uniform characteristics as a whole . also , it is possible to minimize the number of masks required in the manufacturing process , thereby decreasing process costs , and it enables manufacture of a high integrated memory device . this invention may , however , be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein . rather , these embodiments are provided so that this disclosure is thorough and complete and fully conveys the concept of the invention to those skilled in the art . | 7 |
hereinafter , a semiconductor device according to a first embodiment is described with reference to fig1 . as illustrated in fig1 , a semiconductor device 1 according to the first embodiment has a circuit board 2 . a semiconductor chip 3 is mounted on the top surface ( i . e ., a semiconductor chip mounting surface ) of the circuit board 2 . two connection pads 4 are formed on both sides of the semiconductor chip 3 . a solder ball 5 is mounted on each connection pad 4 . a molding resin layer 7 is formed on the top surface of the circuit board 2 so as to cover the semiconductor chip 3 and to upwardly expose the solder balls 5 through vias 6 , respectively . the top surfaces of the solder balls 5 are put into a clean state when a copper support plate ( to be described below ) is removed by etching . thus , there is no resin residue of the molding resin layer 7 . plural connection terminals 8 are formed on the bottom surface of the circuit hoard 2 . a solder ball 9 is mounted on each connection terminal 8 . next , a manufacturing method for the above - mentioned semiconductor device 1 is described hereinafter with reference to fig2 a to 4c . referring to fig2 a to 2i , first , a solder ball mounting portion 11 , on which the solder ball 5 is to be mounted , is formed on a copper support plate 10 ( see fig2 a ). a method for forming the solder ball mounting portion 11 is described in detail with reference to fig3 a to 3d . first , a copper thin plate k is prepared as illustrated in fig3 a , and a photoresist film 12 is formed entirely on the top surface of the copper thin plate k as illustrated in fig3 b . then , the photoresist film 12 is partially covered with a mask to open the part other than a part corresponding to each solder ball mounting portion 11 , and the exposure and development are performed as normal . consequently , as illustrated in fig3 c , only the part of the copper thin plate k , which corresponds to each solder ball mounting portion 11 , is covered with the photoresist film 12 . then , a so - called “ half etching ” is performed by immersing the copper thin plate k in copper etching solution . consequently , the non - covered parts of the copper thin plate k are etched to be thin , while the covered parts of the copper thin plate k corresponding to the solder ball mounting portions 11 are maintained . then , the resist film 12 is peeled . thus , as illustrated in fig3 d , the copper support plate 10 having the solder ball mounting portions 11 is formed from the copper thin plate k . turning back to fig2 b , after the solder ball mounting portions 11 are formed on the copper support plate 10 , a solder ball 5 is mounted on each solder ball mounting portion 11 by performing solder reflowing . then , flip chip mounting is performed on the circuit board 2 ( see fig2 c ), so that semiconductor chips 3 are mounted on the top surface of the circuit board 2 ( see fig2 d ). the copper support plate 10 is faced to the circuit board 2 so that the solder balls 5 respectively abut the connection pads 4 , and solder reflowing is performed to thereby respectively solder - connect the solder balls 5 to the connection pads 4 , as illustrated in fig2 e . then , as illustrated in fig2 f , the space between the mounting surface of the circuit board 2 and the copper support plate 10 is filled with epoxy resin by a so - called transfer molding method . thus , the molding resin layer 7 is formed . thereafter , etching is performed using , e . g ., alkali etchant ( manufactured by meltex incorporated ( trade name is “ a process ”) to selectively remove only the copper support plate 10 ( see fig2 g )). in this state , the vias 6 are formed in the molding resin layer 7 along the shapes of the solder ball mounting portions 11 formed on the copper support plate 10 . further , the top surfaces of the solder balls 5 are brought into a clean state by the etchant when the copper support plate 10 is removed by etching , and there is no resin residue of the molding resin layer 7 . solder reflowing may be additionally performed . then , a solder ball 9 is mounted on each connection terminal 8 formed on the bottom surface of the circuit board 2 , as illustrated in fig2 h . then , the circuit board 2 is cut at positions p illustrated in fig2 i via a blade into individual separated pieces , thereby manufacturing individual separated semiconductor devices 1 . in each semiconductor device 1 , the top portion of the solder hall 5 , which is exposed from each via 6 formed in the molding resin layer 7 , functions as a mounting terminal for connecting other circuit boards and the like . as illustrated in fig4 a to 4c , another package substrate 13 is stacked on the above - mentioned semiconductor device 1 , thereby forming a pop structure . hereinafter , a method for stacking another package substrate 13 on the semiconductor device 1 is described with reference to fig4 a to 4c . as illustrated in fig4 a to 4c , a solder ball 14 is mounted on each connection terminal formed on the bottom surface of the package substrate 13 . first , as illustrated in fig4 a , the solder balls 14 on the package substrate 13 are faced to the solder balls 5 on the semiconductor device 1 , respectively . and , as illustrated in fig4 b , the solder balls 14 are arranged in the vias 6 from which the solder balls 5 are exposed , respectively . thus , the package substrate 13 is pre - stacked on the semiconductor device 1 . then , the solder reflowing is performed so that the solder balls 14 on the package substrate 13 and the solder balls 5 on the semiconductor device 1 are respectively melt - connected to each other , as illustrated in fig4 c . on this occasion , the solder balls 14 on the package substrate 13 can easily be arranged in the respective vias 6 formed in the molding resin layer 7 of the semiconductor device 1 because the inverted - cone - like vias 6 expose the respective solder balls 5 . consequently , the package substrate 13 can be mounted easily and surely on the semiconductor device 1 . according to the first embodiment , when the copper support plate 10 is removed by etching , the top portion of each solder ball 5 , which is exposed from an associated one of the vias 6 formed in the molding resin layer 7 of the semiconductor device 1 , is maintained in a clean state in which no residue of the molding resin layer 7 remains . consequently , the wettability of each solder ball 5 is enhanced . thus , the solder balls 5 and the solder balls 14 are surely connected , respectively , and the electrical connection between the semiconductor device 1 and the package substrate 13 is enhanced . next , a semiconductor device according to a second embodiment is described hereinafter with reference to fig5 to 9c . as illustrated in fig5 , a semiconductor device 21 according to the second embodiment has a circuit board 22 . a semiconductor chip 23 is mounted on the top surface ( i . e ., a semiconductor chip mounting surface ) of the circuit board 22 . two connection pads 24 are formed on both sides of the semiconductor chip 23 . a solder ball 25 is mounted on each connection pad 24 . a molding resin layer 27 is formed on the top surface of the circuit board 22 so as to cover the semiconductor chip 23 and to upwardly expose the solder balls 25 through vias 26 , respectively . a metal plating film m formed by a method to be described below is formed on and covers the top surface of each solder ball 25 exposed from an associated one of the vias 26 formed in the molding resin layer 27 . plural connection terminals 28 are formed on the bottom surface of the circuit board 22 . a solder ball 29 is mounted on each connection terminal 28 . next , a manufacturing method for the above - mentioned semiconductor device 2 is described hereinafter with reference to fig6 a to 8d . referring to fig6 a to 6i , first , a solder ball mounting portion 31 , on which the solder ball 25 is to be mounted , is formed on a copper support plate 30 ( see fig6 a ). the metal plating films m are formed to cover the top surfaces of the solder ball mounting portions 31 , respectively . a method for forming such a solder ball mounting portion 31 , and a method for forming metal plating film m on the solder ball mounting portion 31 are described in detail with reference to fig7 a to 7h . first , a copper thin plate k is prepared as illustrated in fig7 a , and a photoresist film 32 is formed entirely on the top surface of the copper thin plate k as illustrated in fig7 b . then , the photoresist film 32 is partially covered with a mask to open the part other than a part corresponding to each solder ball mounting portion 31 , and the exposure and development are performed as normal . consequently , as illustrated in fig7 c , only the part of the copper thin plate k , which corresponds to each solder ball mounting portion 31 , is covered with the photoresist film 32 . then , a so - called “ half etching ” is performed by immersing the copper thin plate k in copper etching solution . consequently , the non - covered parts of the copper thin plate k are etched to be thin , while the covered parts of the copper thin plate k corresponding to the solder ball mounting portions 31 are maintained . then , the resist film 32 is peeled . thus , as illustrated in fig7 d , the copper support plate 30 having the solder ball mounting portions 31 is formed from the copper thin plate k . next , as illustrated in fig7 e , an electrodeposited resist film 33 prepared from acrylic polymer is formed on the entire surface of the copper support plate 30 . then , the top surface of the copper support plate 30 , on which the solder ball mounting portions 31 are formed , is covered with a mask , and the exposure and development are performed as normal . consequently , as illustrated in fig7 f , an opening 34 is fowled in the electrodeposited resist film 33 correspondingly with the solder ball mounting portions 31 . then , as illustrated in fig7 g , the metal plating film m is formed on each solder hall mounting portion 31 through the opening 34 . the metal plating film m have a four layer structure formed of a gold plating film m 1 , a palladium plating film m 2 . a nickel plating film m 3 . and a palladium plating film m 4 arranged in this order outwardly from the side of the solder ball mounting portion 31 ( see fig8 a to 8d ). in order to form such a metal plating film m , first , the copper support plate 30 , on which the electrodeposited resist film 33 having the opening 34 is formed , is immersed in a gold plating bath for a given time . a plating solution retained in the gold plating bath is made up of 50 grams ( g )/ liter ( l ) of potassium citrate , and 50 g / l of tripotassium citrate . consequently , a first layer formed of a gold plating film m 1 is formed on the solder ball mounting portion 31 . next , the copper support plate 30 with the gold plating film m 1 is immersed in a palladium plating bath for a given time . a plating solution retained in the palladium plating bath is made up of 150 g / l of potassium phosphate , and 15 of pd ( nh 3 ) 4 cl 2 . consequently , a second layer formed of a palladium plating film m 2 is formed on the gold plating film m 1 . next , the copper support plate 30 with the gold plating film m 1 and the palladium plating film m 2 is immersed in a nickel plating bath for a given time . a plating solution retained in the nickel plating bath is made up of 320 g / l of nickel sulphamate . consequently , a third layer formed of a nickel plating film m 3 is formed on the palladium plating film m 2 . finally , the copper support plate 30 with the first layer , i . e ., the gold plating film m 1 , the second layer , i . e ., the palladium plating film m 2 , and the third layer , i . e ., the nickel plating film m 3 is immersed in a palladium plating bath for a given time . a plating solution retained in this palladium plating bath is made up of 150 g / l of potassium phosphate , and 15 g / l of pd ( nh 3 ) 4 cl 2 . consequently , a fourth layer formed of a palladium plating film m 4 is formed on the nickel plating film m 3 . after the metal plating film m configured by the gold plating film m 1 , the palladium plating film m 2 , the nickel plating film m 3 and the palladium plating film m 4 is formed on the solder ball mounting portion 31 , the electrodeposited resist film 33 is removed by etching . thus , the copper support plate 30 in which the metal plating films m are respectively formed on the solder ball mounting portions 31 is obtained , as illustrated in fig7 h . turning back to fig6 b , after the solder ball mounting portions 31 each having the metal plating film m are formed on the copper support plate 30 , a solder ball 25 is mounted on each solder ball mounting portion 31 by performing solder reflowing . in the copper support plate 30 , as shown in fig8 a , the metal plating film m initially has the four layer structure formed of the gold plating film m 1 , the palladium plating film m 2 , the nickel plating film m 3 , and the palladium plating film m 4 arranged from the side of the solder ball mounting portion 31 . and , the solder reflowing is performed by melting the solder balls 25 at a temperature equal to or higher than the melting point , as illustrated in fig8 b . consequently , a solder alloy of the solder ball 25 and the nickel plating film m 3 is formed . the outermost palladium plating film m 4 is formed at the time of reflowing in order not only to prevent the oxidation of the nickel plating film m 3 , but also to contribute to the enhancement of wettability when being melt into the solder alloy . after the solder alloy is formed , the gold plating film m 1 and the palladium plating film m 2 maintain a two layer structure without change , and serves to prevent the oxidation of a nickel alloy . then , flip chip mounting is performed on the circuit board 22 ( see fig6 c ), so that semiconductor chips 23 are mounted on the top surface of the circuit board 22 ( see fig6 d ). the copper support portion 30 is faced to the circuit board 22 so that the solder balls 25 respectively abut the connection pads 24 , and solder reflowing is performed to thereby respectively solder - connect the solder balls 25 to the connection pads 24 , as illustrated in fig6 e . then , as illustrated in fig6 f , the space between the mounting surface of the circuit board 22 and the copper support plate 30 is filled with epoxy resin by a so - called transfer molding method . thus , the molding resin layer 27 is formed . fig8 c schematically illustrates this state . in fig8 c , illustration of the connection pad 24 is omitted . thereafter , etching is performed using , e . g ., alkali etchant ( manufactured by meltex incorporated ( trade name is “ a process ”) to selectively remove only the copper support plate 30 ( see fig6 g )). at that time , as illustrated in fig8 d , only the copper support plate 30 is removed by etching . the gold plating film m 1 and the palladium plating film m 2 that are formed on the solder ball mounting portion 31 maintain the two layer structure and remain at the side of the solder ball 25 so that the outer surfaces of the gold plating film m 1 are respectively exposed from the vias 26 formed in the molding resin layer 27 . when the copper support plate 30 is removed by etching , the surface of each gold plating film m 1 is put into a clean state by etchant . thus , there is no resin residue of the molding resin layer 27 . also in fig8 d , illustration of the connection pad 24 is omitted . solder reflowing may be additionally performed . then , a solder ball 29 may be mounted on each connection terminal 28 formed on the bottom surface of the circuit board 22 , as illustrated in fig6 h . then , the circuit board 22 is cut at positions p illustrated in fig6 i via a blade into individual separated pieces , thereby manufacturing individual separated semiconductor devices 21 . in each semiconductor device 21 , the gold plating film m 1 exposed from each via 26 formed in the molding resin layer 27 functions as a mounting terminal for connecting other circuit boards and the like . as illustrated in fig9 a to 9c , another package substrate 33 is stacked on the above - mentioned semiconductor device 21 , thereby forming a pop structure . hereinafter , a method for stacking another package substrate 33 on the semiconductor device 21 is described with reference to fig9 a to 9c . as illustrated in fig9 a to 9c , a solder ball 34 is mounted on each connection terminal formed on the bottom surface of the package substrate 33 . first , as illustrated in fig9 a , the solder balls 34 on the package substrate 33 are faced to the gold plating films m 1 on the semiconductor device 21 , respectively . and , as illustrated in fig9 b the solder balls 34 are arranged in the vias 26 from which the gold plating films m 1 formed on the top surfaces of the solder balls 25 are exposed . thus , the package substrate 33 is pre - stacked on the semiconductor device 21 . then , the solder reflowing is performed so that the solder balls 34 on the package substrate 33 and the solder balls 25 on the semiconductor device 21 are respectively melt - connected to each other with the gold plating film m 1 and the nickel plating film m 2 , as illustrated in fig9 c . on this occasion , the solder balls 34 on the package substrate 33 can easily be arranged in the respective vias 26 formed in the molding resin layer 27 of the semiconductor device 21 because the inverted - cone - like vias 26 expose the respective solder balls 25 . consequently , the package substrate 33 can be mounted easily and surely on the semiconductor device 21 . according to the second embodiment , the metal plating film m having at least three layers of the gold plating film m 1 , the nickel plating film m 2 , and the palladium plating film m 3 are formed on the solder ball mounting portions 31 . in addition , after the copper support plate 30 is removed by etching , the metal plating films m remain at the side of the solder balls 25 . the nickel plating film m 2 and the gold plating film m 1 formed on the top portion of each solder ball 25 , which is exposed from an associated one of the vias 26 formed in the molding resin layer 27 , is maintained in a clean state in which there is no residue of the molding resin layer 27 , when the copper support plate 30 is subjected to etching . consequently , the wettability of each solder ball 25 is enhanced . thus , the solder balls 25 and the solder balls 34 are surely connected , respectively , and the electrical connection between the semiconductor device 21 and the package substrate 33 is enhanced . the above - described embodiments are not limited to the above - described devices / methods as they are , and various improvements and modifications can be made without departing from the scope of the invention . for example , in the second embodiment , the metal plating films m ( each having the four layer structure formed of the gold plating film m 1 , the palladium plating film m 2 , the nickel plating film m 3 , and the palladium plating film m 4 ) are respectively formed on the solder ball mounting portions 31 of the copper support plate 30 . after the solder balls 25 are connected to the metal plating films m by solder reflowing ( see fig6 a and 6b ), the solder balls 25 are connected to the connection pads 24 on the circuit board 22 ( see fig6 e ). however , the manufacturing method according to the invention is not limited thereto . the method illustrated in fig1 a to 10i can be employed . as illustrated in fig1 a to 10i , the metal plating films m ( each having the four layer structure formed of the gold plating film m 1 , the palladium plating film m 2 , the nickel plating film m 3 , and the palladium plating film m 4 ) are respectively formed on the solder ball mounting portions 31 of the copper support plate 30 ( see fig1 a ). then . each solder ball 25 is mounted on and connected to an associated connection pad 24 formed on the circuit board 22 through solder reflowing ( see fig1 d ). thereafter , each solder ball mounting portion 31 formed on the copper support plate 30 is connected to an associated solder ball 25 by solder reflowing ( see fig1 e ). fig1 a to 11d schematically illustrate the above method . in fig1 a to 11d , illustration of the connection pad 24 is omitted . as illustrated in fig1 a , the metal plating film m formed on the copper support plate 30 initially has the four layer structure formed of the gold plating film m 1 , the palladium plating film m 2 , the nickel plating film m 3 , and the palladium plating film m 4 arranged from the side of the solder ball mounting portion 31 . after the metal plating film m formed on the solder bah mounting portion 31 of the copper support plate 30 is connected to the solder ball 25 formed on the circuit board 22 , as illustrated in fig1 b , the solder ball 25 is melted at a temperature equal to or higher than the melting point and subjected to solder reflowing . thus , a solder alloy of the solder ball 25 , the outermost palladium plating film m 4 , and the next nickel plating film m 3 is formed , while the palladium plating film m 2 and the gold plating film m 1 maintain their structure without change . in addition , according to the so - called transfer molding method , the space between the mounting surface of the circuit board 22 and the copper support plate 30 is tilled with epoxy resin . thus , the molding resin layer 27 is formed ( see fig1 c ). thereafter , etching is performed with alkali etchant to selectively remove only the copper support plate 30 ( fig1 d ). thus , only the copper support plate 30 is removed by etching . the gold plating film m 1 and the palladium plating film m 2 formed on the solder ball mounting portion 31 maintain a two layer structure and remain at the side of the solder ball 25 . a surface of the gold plating film m 1 existing on an outer side of the plating film m is exposed from each via 26 formed in the molding resin layer 27 and put into a clean state by etchant when the copper support plate 30 is removed by etching . thus , there is no residue of the molding resin layer 7 . and , the wettability of each solder ball 25 is enhanced . thus , the solder balls 25 and the solder balls 34 are surely connected , respectively , and the electrical connection between the semiconductor device 21 and the package substrate 33 is enhanced . the semiconductor device 21 and the manufacturing method therefor illustrated in fig1 a to 11d are similar to those according to the second embodiment except the above - mentioned differences . thus , the description of similar respects therebetween is omitted . in the first and second embodiments , the solder balls 9 , 29 are mounted on the connection terminals 8 , 28 formed on the bottom surface of the circuit board 2 , 22 , respectively . however , if the semiconductor devices 1 and 21 are used in a land grid array ( lga ) structure , it is unnecessary that the solder balls 9 and 29 are mounted on the connection terminals 8 and 28 , respectively . according to the first and second embodiments , the semiconductor chips 3 , 23 are mounted on the circuit boards 2 , 22 by flip chip mounting . the cases to which the first and second embodiments can be applied are not limited thereto . the first and second embodiments can be applied to the cases where the semiconductor chip is connected to the circuit hoard by wire bonding , and where the semiconductor device of the so - called chip stack type , in which two semiconductor chips are respectively stacked at upper and lower positions , is configured so that the upper semiconductor chip is mounted on the circuit board by wire bonding , and that the lower semiconductor chip is mounted thereon by flip chip mounting . according to the first and second embodiments , the metal plating film m has the four layer structure formed of the gold plating film m 1 , the palladium plating film m 2 , the nickel plating film m 3 , and the palladium plating film m 4 . the structure of the metal plating film m is not limited thereto . the metal plating film m may have a three layer structure formed of e . g ., a set of a gold plating film , a nickel plating film , and a palladium plating film , or a set of a gold plating film , a palladium plating film , and a gold plating film . according to the first and second embodiments , the metal plating film is formed by plating . however , for example , the metal film may be formed by another method such as sputtering . according to the first and second embodiments , the solder balls 5 , 25 are formed as the mounting terminals on the copper support plate 10 , 30 or on the circuit board 22 ( connection pad 24 ) by solder reflowing . however , instead of the solder balls , mounting terminals may be formed , for example , by printing solder paste on the connection pad 24 . instead of the solder balls 5 , 25 , cu - core solder balls ( solder coated cu balls ) may be used . | 7 |
fig1 is a cross - sectional view of the tensioner . tensioner 100 comprises a pulley 7 which engages a belt ( not shown ) to thereby provide a belt tension or load . pulley 7 is journalled to arm 6 with a bearing 11 . pulley is engaged with the bearing outer race . bearing 1 comprises a ball bearing as shown , but could also comprise a needle bearing or other suitable bearing known in the art . arm 6 is biased by torsion spring 3 thereby urging a pulley 7 into engagement with a belt which applies a tensile load to the belt . torsion spring 3 is operationally disposed between base 1 and arm 6 . arm 6 pivots about shaft 2 . pivotal movement of arm 6 allows the tensioner to compensate for any changes in belt length as the belt stretches over time and as the drive length changes from thermal expansion . arm 6 pivots about a low - friction bushing 10 about shaft 2 . shaft 2 is press fit into base 1 and extends normally from base 1 . eccentric adjuster 8 is also press fit to the end of shaft 2 opposite base 1 . eccentric adjuster 8 is used to rotate the tensioner into proper engagement with the belt during installation . eccentric refers to the center of hole 21 not being coaxial with a center of rotation of pulley 7 or of arm 6 . eccentric adjuster 8 is used to properly load the belt with a predefined tension by compensating for all component and system tolerances . a tool ( not shown ) engages the adjuster at tool receiving portion 82 . it is locked in place once the belt is installed by fully engaging a fastener inserted through a hole 21 , 81 into a mounting surface . to minimize the amount of arm oscillation or movement during operation friction damping is used . excessive arm motion induced by the engine vibration could cause the belt to jump a tooth or “ ratchet ”. tooth jump or ratcheting of the belt causes a loss of synchronization between the driven and driving shaft ( s ) of the belt . wave spring 5 is disposed between damping member 13 and arm 6 . wave spring 5 imparts a normal force upon damping member 13 . damping member 13 bears frictionally upon base 1 , thereby damping an oscillation of arm 6 . damping member 13 is generally a toroid in shape , but may also be disk shaped . torsion spring 3 is compressed between arm 6 and pad 12 . pad 12 is mechanically engaged with base 1 wherein tangs 120 engage each side of a tab 41 . being thus engaged pad 12 is constrained against rotation relative to base 1 . fig2 is an exploded view of the tensioner . damping member 13 creates friction damping between arm 6 and base 1 . damping disk 9 is also used to create friction damping between arm 6 and eccentric adjuster 8 . frictional surface engages eccentric adjuster 8 . damping member 13 and damping disk 9 are disposed on axially opposite ends of arm 6 . damping member 13 and damping disk 9 each move rotationally with arm 6 , while base 1 and eccentric adjuster 8 are fixed to the mounting surface , such as an engine ( not shown ). pulley surface 71 may be flat , multi - ribbed or toothed to accommodate a suitable belt . an end 31 of spring 3 engages tab 41 , wherein tab 41 acts as a reaction point on base 1 . the other end 32 of spring 3 engages arm 6 . rotation of arm 6 is limited by stops 63 coming into contact with a tab 41 . fig2 b is a side view of the wave spring . the wave spring comprises multiple coils 51 . each coil comprises undulations wherein each coil comes into contact with an adjacent coil at a limited number of locations approximately 120 ° apart . this description is not intended to limit the coil design of the spring . each spring may have more or fewer undulations per coil depending on design requirements . it may also comprise one or more coils . in an alternate embodiment the wave spring comprises only one coil with ends joined . fig3 is an exploded view of the tensioner . torque from arm 6 is transferred through keyway 61 to tab 130 thereby causing damping member 13 to move in locked unison with arm 6 . keyway 61 is disposed at an axial end of arm 6 . base 1 comprises tabs 41 ( three are shown ) which extend in a substantially axial direction . torque from arm 6 is transferred through keyways 62 . keyways 62 are disposed at an axial end of arm 6 opposite keyway 61 . damping disk 9 comprises a tab 91 which extends in the axial direction . tab 91 engages a keyway 62 . rotation of arm 6 causes locked rotation of damping disk 9 through interaction of keyway 62 and tab 91 . damping member 13 and damping disk 9 are loaded normally by compression of wave spring 5 thereby creating normal force friction . this arrangement compensates for wear and assembly tolerances . wave spring 5 is captured between damping member 13 and arm 6 in a receiving portion 63 . spring 5 rotates with arm 6 ensuring that relative motion only occurs between damping member 13 and base 1 , as well as only between damping disk 9 and eccentric adjuster 8 . spring 5 is shown as a wave spring which is preferred due to its spring rate characteristic and area of surface contact . fig2 b is a side view of the wave spring . in this embodiment spring 5 comprises multiple coils or volutes , each having a wave profile . this allows suitable control of the axial ( or normal ) force relative to the tolerances of the tensioner assembly . the force of the wave spring in combination with the compression of torsion spring 3 , and further in conjunction with the coefficient of friction of mating parts determines the damping level of the tensioner assembly . in alternate embodiments spring 5 may comprise a single coil wave spring . the coefficient of friction of the various mating parts is as follows : damping member 13 and damping disk 9 may comprise any known frictional material used in a tensioner damping application , including oil resistant metals and polymers . alternate embodiments may produce sufficient axial force by use of the torsion spring 3 in compression without use of the wave spring . fig6 is a chart illustrating the spring rate ( k ) as a function of spring height . total compression is indicated for each spring type , namely , spring washer , wave spring and compression or torsion spring . fig4 is a cross - sectional view of an alternate embodiment . fig5 is an exploded view of the alternate embodiment in fig4 . fig4 and 5 describe an alternate embodiment where a spring loads two damping disks , 18 , 19 , that are fixed to rotate together thereby preventing the need to fix the damping disks to the arm 20 to be dampened . damping disk 18 is in frictional contact with a static component , base 11 , and the damping disk 19 is in frictional contact with the moving member , arm 20 , to dampen the movement of the arm 20 . eccentric adjuster 15 is an eccentric that is used to move the tensioner into proper engagement with the belt during installation . eccentric refers to the center of hole 150 not being coaxial with a center of rotation of pulley 15 or of arm 12 . eccentric adjuster 15 is used to load the belt with a predetermined tension . eccentric adjuster 15 is used only during belt installation and is locked in place once the belt is installed by fully engaging a fastener ( not shown ) through a hold 150 with a mounting surface . the fastener may comprise a bold or any other suitable fastener know in the art . pulley 14 engages a belt to provide belt tension or load . pulley 14 is journalled to arm 20 about a bearing 141 , pulley 14 is engaged with the bearing outer race . bearing 141 comprises a ball bearing as shown , but could also comprise a needle bearing or other suitable bearing know in the art . arm 20 is biased by torsion spring 13 thereby urging pulley 14 into a belt ( not shown ). pivotal movement of arm allows the tensioner to compensate for any changes in belt length as the belt stretches over time and as the drive length changes from thermal expansion or as engine load and therefor belt load changes . arm 20 pivots about a low - friction bushing 16 on shaft 12 . shaft 12 is fixed to base 1 . motion of arm 20 is damped by frictional contact with damping disk 19 . damping disk 19 is pressed into arm 20 by o - ring 17 . o - ring 17 comprises an elastomeric material and is used as a compressible resilient member to apply a normal force to damping disk 19 and damping disk 18 . o - ring 17 could be replaced by a wave spring , a compression spring , a belleville spring , or other compressible resilient member having spring characteristics known in the art . damping disk 18 is pressed by o - ring 17 into base 11 . base 11 is fixed to a mounting surface such as an engine ( not shown ). frictional surface 193 engages arm 20 . frictional surface 183 engages base 11 . damping is created by the resistant torque created by the frictional force of the contact between damping disk 18 and base 11 , and damping disk 19 and arm 20 . each tab 181 on damping disk 18 fits between two cooperating lug ( s ) 191 on damping disk 19 . this arrangement fixes damping disk 18 and damping disk 19 so there is no relative rotation between the two but allows movement between these two components in the axial direction . movement in the axial direction allows o - ring 17 to apply a preload force to both damping disks 18 , 19 and to compensate for manufacturing tolerances and wear . a lip 182 on each tab 181 engages a cooperating rim 192 on damping disk 19 to limit the relative axial movement of the damping disks 18 , 19 by locking them together . the assembly of damping disk 18 and damping disk 19 “ floats ” between the arm 20 and base 11 . neither damping disk 18 nor damping disk 19 are rotationally fixed to base 11 or arm 20 . retainer 21 holds the assembly together axially . retainer 21 is fixed to eccentric adjuster 15 and engages shaft 12 to hold the assembly axially . fig7 is a detail of the retainer and adjuster . retainer 21 holds the assembly together when the tensioner is not mounted to an engine . retainer 21 is attached to adjuster 15 by engagement of posts 151 and holes 211 and prongs 212 . the two posts 151 prevent retainer 21 from rotating and prongs 212 retain retainer 21 on posts 151 . fig1 is a detail of the retainer in fig7 . fig8 is a detail of the retainer on the adjuster . the sub - assembly of retainer 21 and adjuster 15 is inserted into shaft 12 . tabs 213 are resiliently bent inward during assembly to allow retainer 21 to pass through the bore of shaft 12 . receiving portions 152 provide a space into which tabs 213 are bent . a circumferential groove 121 in shaft 12 allows tabs 213 to resiliently expand outward to lockingly engage shaft 12 . fig9 is a detail of the assembled shaft and adjuster . relative axial movement of adjuster 15 and shaft 12 is restricted by interaction between the wall of groove 121 and the radially expanded tabs 213 . fig1 is a cross sectional view of the shaft . although a form of the invention has been described herein , it will be obvious to those skilled in the art that variations may be made in the construction and relation of parts and method without departing from the spirit and scope of the invention described herein . | 5 |
the present invention is as described herein below , including detail to exemplary embodiments of the invention . examples of these exemplary embodiments are illustrated in the accompanying drawings . while the invention is described in conjunction with these embodiments , it will be understood that it is not intended to limit the invention to the described embodiments . rather , the invention is also intended to cover alternatives , modifications , and equivalents as one of ordinary skill in the art understands the invention . in the following description , specific details are set forth in order to provide a thorough understanding of the present invention . the present invention may be practiced without some or all of these specific details . in other instances , well - known aspects have not been described in detail in order not to unnecessarily obscure the present invention . in this specification and the appended claims , the singular forms “ a ,” “ an ,” and “ the ” include plural references unless the context clearly dictates otherwise . unless defined otherwise , all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this invention belongs . the invention is directed to cargo handling services and systems , including online trace and track features with complete shipment information , auto - notification of import cargo status , quick online payment for import service charge and storage , instant bar - coded cargo pickup authorization pass , carrier certificate in soft copy , among other features . these features are discussed below in connection with the assignee of the present patent application &# 39 ; s use of the “ epic ” engine , “ epic 1 ,” “ epic 2 ,” and “ epic 3 .” the “ epic ” engine is a single point of entry for airline related messaging including ffm , fwb , fhl and fsn . these and other acronyms herein are well understood in the industry and defined or explained further in the publication by the international air transport association (“ iata ”) “ iata freight forwarder - carrier — ground handling agent communication functional specifications ,” (“ iata functional specifications ”), dated sep . 29 , 2008 , which is available at the website : http :// www . iata . org / sitecollectiondocuments / documents / ia taffcarrierghafunctional specificationsv07 . pdf . the entire contents of the iata functional specifications publication is incorporated herein by reference . for completeness some key definitions are provided . all documents indicated may refer to electronic documents . electronic documents include documents , forms , and messages received by or directly entered into the epic system . non - electronic documents , such as an unmessaged documents , for example an awb not entered into epic , may be entered and become part of the epic system . cargo data shared among stakeholders includes : an airway bill , a piece count , discrepancy , weight , dimensions , a signed approval of freight tendered , a confirmation of a truck driver from a stored comparison photo , flight number , flight arrivals , flight departures , incoming flights , outgoing flights , a photo documenting freight condition , screening steps taken , buildup data , breakdown data , and special handling requirements and codes . an air waybill (“ awb ”) is a document made out by or on behalf of the shipper , which evidences the contract between the shipper and airline ( s ) for the carriage of cargo over the routes of the airline ( s ). a consignment is one or more pieces of goods accepted by the airline from one shipper at one time and at one address , receipted for in one lot , and moving on one air waybill or one shipment record to one consignee at one destination address . for purposes of this application , consignment is also referred to a cargo and freight . a flight manifest contains the details of consignments loaded onto a specified flight . a freight forwarder is the party arranging the carriage of goods including connected services and / or associated formalities on behalf of a shipper or consignee . a ground handling agent is the entity authorized to act for or on behalf of the carrier , for accepting , handling , loading / unloading , transiting , or dealing with cargo , passengers and baggage . a house waybill (“ hwb ”) is a document made out by an agent / consolidator specifying the contract between the shipper and the agent / consolidator for the arrangement of carriage of goods . a house manifest is a document containing the same information as a cargo manifest and additional details on freight amounts , etc . a receipt for the cargo ( also known as “ cargo receipt ”) is a document , which is provided to the shipper , upon shipper &# 39 ; s request , by the carrier creating a shipment record as a substitution for the issuance of an air waybill and which permits identification of the shipment . a shipment record is any record of the contract of carriage preserved by carrier , evidenced by means other than an awb . the shipment record is initiated by the fwb information and confirmed or modified by the subsequent fsu ( rcs ). fsu / rcs would only modify the information regarding total number of pieces (“ piece count ”), weight , and volume amount of the shipment (“ dimensions ”). an ffm message provides the details of consignments loaded onto a specified flight . an fhl message ( type i ) provides a checklist of freight forwarder hwb associated with a master awb . an fhl message ( type 2 ) provides details of one hwb consignment for the carrier to provide customs with advance information based on the hwb information provided by the origin freight forwarder . the message containing the hwb data may be sent by the origin freight forwarder and may be updated by the origin ground handler . an mb message is used to transmit a complete set of awb data in accordance with the iata cargo services conference resolutions . the message containing the awb data may be sent by the origin freight forwarder and may be updated by the origin ground handler to include data , such as weight , number of pieces , volumes . an fsu ( rcs ) message is used to notify / update interested parties with a change of status of a specified consignment as recorded in the system of a handling party . the rcs specifies that the consignment has been physically received from the shipper and is considered by the carrier as ready for carriage on this date at this location . stakeholders may include : the cargo shipper , customs broker , consignee , cargo receiver , trucker and / or trucking company , freight forwarder at origin , air carrier , air carrier &# 39 ; s offices at origin , air carrier &# 39 ; s offices at destination , ground handling operations / agent at origin , or ground handling operations / agent at destination . a carrier simply transports goods , for example : a trucker , train , airplane , etc . a ground handling agent processes inbound and outbound information regarding the physical flow of the consignments . messages entering the epic engine are interpreted and made available through the system and computer - implemented method of the present invention . epic , the customer service portal , is a web based application that is accessed via the internet for online payment and access to data . a user / stakeholder must successfully login to epic . fig1 shows the user login screen display . fig2 illustrates the initial screen display , epic payable items , following a successful user login . the user is directed to navigation tabs , buttons , and shortcuts along the top of the initial screen display . fig3 is an illustration of epic navigation tabs , buttons , and shortcuts . the displayed navigation tabs include tracking , epayment , report , myprofile , and administration . the epayment navigation tab displays all items in the payment process including : unpaid , paid but not picked up , and delivered . the user &# 39 ; s screen is filtered by clicking on the various buttons at the top of the screen . various parts of the application are accessed by clicking on the tabs . these buttons used for filtering are only accessible when the user is in the epayment tab . alternatively , the user may click on the payable items shortcut . there is a list of shortcut items on the left the left hand side of the screen . these shortcuts include payable items , which lists shipments in various stages of payment ; view cart , which contains the user &# 39 ; s shopping cart items for when the user is ready to pay ; prepaid balance , which is a view of the user &# 39 ; s balance and further containing the option to replenish the account ; and a payment history , showing all receipts . fig4 shows a navigation portion of the screen with filtering by an airport code tab . the tracking navigation tab displays all shipments paid or open and allows the user to print carrier certificates for all user consigned messaged shipments . many airlines provide freight messaging ( ffm , fwb , fhl and fsn ). freight messaging is received on flight lift off from the point of origin . after receiving messaging , a user may access to a number of features , including : click and pay , trace and track , online carrier certificates , and customs release interpretation . a user is able to pay for shipments prior to a time when messaging arrives through the input awb ( s ) manually and pay feature . while the present invention envisions 100 % industry participation , unmessaged airlines likely will be carriers . unmessaged simply means that freight messaging is not directly entered into epic . yet , a user manually entering the awb information . once entered , the user may pay for all of his shipments and perform any other task online through epic . the report navigation provides detail and summary reports of paid items . all users have access to the report paid and waiting to be picked up . this is the same information that appears in the epayment tab . but this information is conveniently combined in one report . there are several financial reports that are available as well . the user must have advanced access granted from a super admin user to access financial reports . the financial reports include both summary and detail reports . summary reports are available by airline and by user . detail reports are available by airline , by user , by payment type , and by master / house awb . all reports can be exported to excel . fig6 shows a report screen of epayment tab information consolidated in a single report . the my profile navigation tab permits the user to change a password and update the user profile . fig7 displays a my profile epayment user summary screen . the administration navigation tab is only visible to super admin level users . only online users with super admin or admin privileges can see this tab . there are three main user types . first , super admin user has full access to epic and is responsible for setting up users and users &# 39 ; rights . the super admin can change individual user &# 39 ; s rights and provide individual operators with access to certain features , including , for example : financial reports and the ability to pay isc . fig8 displays an administration super admin user &# 39 ; s setup screen . second , an accounting user of epic has full access with the exception of user management rights . finally , operator users have online payment access and operating reports only . fig9 displays an administration operator access screen . a search box is also visible on the initial navigation page . fig5 shows a search screen with searching options dropdown menu . the dropdown menu allows a user to search according to one of five criteria . first , the master awb dropdown selection is used to search a return for a particular master awb . second , the airline code dropdown selection allows the user to filter the view and show only bills for a particular airline based on the associated airline prefix . third , the house awb dropdown selection permits a search and return based on a particular house awb . fourth , return all bills for a particular flight number , regardless of the date . finally , a user may also search based on an arrival date . when the user first enters epic , a list of shipments with messaging received that have not been yet been paid for will appear . the user may click and pay for these shipments . instead , for example , if it is not a simple bill , the user may choose to pay by either master or house . fig1 shows a paying isc screen . a user can automatically calculate storage and select a storage date from the drop down . the user may also add storage to most pre - existing shipments by clicking on the ‘ more ’ button , entering pickup date , and the amount . the ‘ more ’ button can be used as needed for additional storage . fig1 shows a paying storage screen . under the epayment edit tool , a user may add house awbs and move pre - paid isc payments . if the house is paid , but not picked up , you can move the associated isc payment to any of the other houses under the same master awb . fig1 displays an epayment edit shipment screen . after selecting items , the user clicks the add to cart button . a user &# 39 ; s items will be added to the cart . if a user would like to delete the item from the cart and return it to the open items list as payable , the delete check box is clicked and then the modify cart appears . when ready to pay the view cart button is clicked . fig1 shows user cart screen . storage and isc items are listed as separate items . until fully paid , the shipment remains in the open items section . other stakeholders will be able to select the messages for payment while it is in the cart . other users will be notified the subject messages are “ in cart ” and payment options for them are not available . when a user is ready to pay the pay now button is clicked . the user have the option to select his own reference number for each awb item in the cart and then select his payment option . payment options include , but are not limited to : paying by credit card , paying by e - check , and paying by pre - paid account . the most convenient way to pay is to establish a prepaid account . this is a pool of funds available to users to make payments from . it can be used to pay for both isc and storage . to pay a balance , simply select payment option and hit verify . as long as there are enough funds in the account , the transaction will be processed . to see the balance history click on the shortcut for prepaid balance . a receipt will be emailed to the main contact . the user may receive an email by entering an additional address . as discussed above , to pay for a shipment on one of the unmessaged airlines , a user can click on the button input awb ( s ) manually and pay . fig1 shows a payment screen for an unmessaged shipment . to pay for an unmessaged shipment , a user should select based the corresponding airline prefix . an optional 2nd code may be entered as necessary . these codes include : the awb , the house awb , the flight number , and the arrival date . also as indicated above , a user has the option to search and pay for messaged shipments prior to message arrival . fig1 shows an epayment screen utilizing the search and pay for messaged shipments . a user can enter payments for master bills prior to their arrival using the input awb ( s ) manually and pay feature . once the messaging arrives the awb data is updated to your record and the user is able to use this feature for house awbs . the search and pay feature also allows a particular user to pay for shipments not consigned to that particular user . enter the whole master awb into the search field and the bill will be presented for payment . a user may also pay for partial shipments as they come in or once they all arrive . fig1 shows a pay for partial shipments screen . the user is charged isc once and storage for the whole shipment based on the portion of the whole that is selected . storage is based on the total kilos for all parts being picked up and the arrival date of the flight . isc is only charged once per master or house awb . online payment as described above , eliminates the need for physical checks and simplifies the terminal service process . access to online receipts provides the benefit of having one copy used by all the people all the time . additional features include : auto - notification , bar - code pickup pass , and trace and track . auto - notification allows a user to choose to receive pre - alerts and reminders sent via email or wireless device from the point of shipment arrival to the cargo pickup . bar - code pickup pass permits the user to receive payment receipt and pickup confirmation code generated online . bar - code pickup pass results in faster cargo recovery for all stakeholders . finally , trace and track , where a user may view complete shipment information and status , filtered according to parameters , includes : simple awb , location , payment , consolidation , partial payment , proof of delivery , inbound shipment , freight condition , piece count , weight , customs release , and discrepancy . trace and track provides access cargo information from anywhere anytime . epic 2 , the mobile warehouse management system , provides additional functionality and features , including automation of the delivery of and capture of information from the cargo handling warehouse . epic 2 reconfigures the cargo handling and optimizes the processes between the office and the warehouse , resulting in increased efficiencies . epic 2 enables tablet - aided acceptance of cargo , buildup , breakdown , and delivery . furthermore , epic 2 empowers workforce by connecting cargo and data together resulting in process efficiency , quality improvement , increased productivity , sla / c2k compliance , and enhanced employee satisfaction . epic 2 provides auto dlv messaging to meet real - time c2k compliance with accurate truck waiting time . epic 2 automatically prepares bcl to provide quicker cargo processing time and throughput . finally , epic 2 provides auto customs release to minimize the risk of customs fines and penalties . warehouse transportation vehicle ( s ), such as a forklift , are outfitted with mounting devices to a hold a smartdevice . other comparable devices with an apple ios or android os mobile device offering advanced capabilities , including personal computer - like functionality ( pc - mobile handset convergence ) or a palmtop computer may also be employed . the mounting device keeps the ipad protected , and accessible to the staff in a safe way . the staff sign into the smartdevice and application to retrieve information about incoming or outgoing freight . they also capture all information regarding the freight required for handling . warehouse staff are presented with a prioritized list of freight arriving at the warehouse for an import breakdown . fig1 shows a screen displaying a prioritized list of freight arriving at the warehouse . as the freight is broken down on to skids , the agent enters piece counts and locations for those skids . the agent also notes any discrepancies . warehouse staff are presented with a list of truckers that have checked in and are waiting to pick - up their freight for the import delivery . fig1 shows a screen displaying list of truckers that have checked in and are waiting to pick - up their freight . once a trucker is selected , they can see what freight it is and where it is located in the warehouse for retrieval . the warehouse agent uses the smartdevice and application to note cargo data . they also check the id of the driver against the id appearing digitally in the system . warehouse staff are presented with a list of truckers that have checked in and are waiting to drop - off their freight . once a trucker is selected , they can initiate the capture of critical acceptance cargo data . warehouse staff select the flight they are performing a build up for and then create skids right in the application in an export build up . a skid is a temporary storage location for cargo , for example a pallet . fig1 displays a screen showing an online freight build up and creating of a pallet . freight is added to the pallet with simple clicks . all critical build up data is captured including piece count , weights , dimensions , and special handling codes . a build up tag is printed out wirelessly by the scale to be attached to the freight . supervisors are provided with a smartdevice with an app installed that will allow them to capture condition of the freight whether it is good or bad . for example , after freight is built up it is photographed to show it is in good condition and built properly . or if freight arrives damaged it is photographed . all photos are associated with the freight and retrievable through our software . as discussed above , for airlines that do not provide message data , the information may be entered manually . epic 2 provides an import awb capture tool that allows stakeholders to quickly capture awb data electronically . fig2 shows an online tool allowing agents to capture awb data electronically for airlines that do not provide message data . once entered , the awb is now treated as messaged and is used throughout the system . all office related export awb acceptance data is captured through the epic system . fig2 illustrates a display of all captured office related export acceptance data . the capture data includes : awb and flight data , trucker identification , security checks , etc . once captured , this data then becomes available throughout the system and enables a paperless export acceptance process . the import manager is a centralized view of all import processes being captured in the warehouse or in the office . fig2 shows a real - time centralized view of all import processes captured in a warehouse or office . the manager displays status of the breakdown , discrepancies , nomination requests and notification status . similarly , the export manager is a centralized view of all export processes being captured in the warehouse or in the office . fig2 illustrates a real - time centralized view of all export processes being captured in the warehouse or in the office . the manager displays status of the outgoing flight including booking , acceptance , buildup and departure . the export flight manager also creates and sends export flight messaging to the airline handling system , such as ffm to make the build - up process faster in the office as well . the user also sees important information about freight being built that have special handling codes associated with them . fig2 shows the airline portal allowing customers access to their flight data , the epic airline portal . this portal allows airline carrier customers access to their flight data . data is presented in a user friendly way , in that data is consolidated into powerful business reports and can be easily filtered based on parameters . inbound shipments can be tracked down to the proof of delivery where the user can actually see which trucker picked up the freight and when . epic 3 provides several additional features and functions , such as dock management , a manager module , airline portal plus , and epic cloud . dock door management maximizes use of the dock doors to reduce the trucker waiting time as much as possible . the trucker engagements starts in the parking lot where the employee will be equipped with a smartdevice and application to identify the trucker and capture basic details to alert the warehouse staff of his arrival and what to prepare for . the trucker is then assigned a door based on complexity of the shipment they are dropping off or picking up and what is currently happening at each dock door . for facilities that are not busy , the freight can start to be retrieved and staged before the trucker is even walking through the traffic doors to check in . a qualifying trucker can skip the manual check - in process altogether and go straight to the dock door . for busier facilities , freight will move through faster with less unnecessary waiting by the trucker . the manager module provides warehouse managers a smartdevice application , so that the manager can set priorities for staff , complete shift reporting , fill out accident or incident reports , capture images , monitor the operations and communicate with staff and customers . airline portal plus includes an engine allowing airlines to forward all of the flight data , even for stations that are not handled in order that they can achieve reporting across their entire enterprise . epic cloud is a commerce platform for the air cargo community where partners can pay each other or transact with each other . social network features such as user profiles , online presence , and document sharing will be part of the applications . | 6 |
the examples described and drawings rendered are illustrative and are not to be read as limiting the scope of the invention as it is defined by the appended claims . below , the same reference characters are used for identical components in the different views of the figures . the illustrations in the figures are diagrammatic and not to scale . in fig1 , the system element 1 comprises a suction chamber 2 which is used for generating a suction stream and which is a generally known component , known by a person of ordinary skill in the art . the system element 1 further comprises a transport device 3 that encloses lateral walls of the suction chamber 2 . as shown in fig1 , the transport device 3 comprises a first roller 4 and a second roller 5 , where the rollers are arranged at opposite lateral surfaces of the suction chamber 2 and contact the respective lateral surface . according to the embodiment , pulleys 6 for driving the rollers 4 , 5 and thus for driving the system element 1 are arranged on the respective end regions 4 a , b and 5 a , b of the first and second rollers 4 , 5 . the pulley 6 and the rollers 4 , 5 are firmly connected to an axle 12 , as shown in fig4 , so that the running belt 7 is not subjected to unnecessary deformation as a result of torque transmission , but may instead carry out its sealing function without hindrance . as an alternative , a drive belt ( not shown ), may be used and is driven by a motor ( not shown ) and is connected to the pulley 6 , to drive the running belt 7 , such that a torque acts on the rollers 4 , 5 , and so that the system element may be moved . according to the embodiment , the suction chamber 2 is supported by the rollers 4 , 5 such that rotation of the rollers 4 , 5 may be possible and the suction chamber 2 may be safely held to the rollers 4 , 5 . according to the embodiment , the running belt 7 is made from a flexible material so that the running belt 7 may carry out its sealing function . as shown in fig1 , the embodiment comprises two running belts 7 a , 7 b that may establish contact with opposite lateral surfaces of the suction chamber 2 , where the lateral surfaces are not the same as the lateral surfaces that are contacted by the rollers 4 , 5 . as shown in fig1 , the end regions 4 a , 5 a of the rollers 4 , 5 are connected by way of the running belt 7 a , and the end regions 4 b , 5 b of the rollers 4 , 5 are connected to each other by a separate running belt 7 b . both belts are examples of a connection element . with reference to fig2 and 3 , the function of the system element 1 according to fig1 is described . fig2 shows a diagrammatic lateral view of the system element , according to fig1 , in a state in which the suction chamber 2 generates a suction stream , wherein the system element 1 is sucked to a surface 8 of a workpiece 9 . as shown in fig2 , in this suction state , the flexible running belt 7 b ( and the running belt 7 a that is not visible in this view ) conforms to the curved surface 8 of the workpiece 9 . fig2 shows guide discs 11 around where the running belt 7 b has been placed . fig3 shows a front view of the sucked in system element , according to fig2 . the diagram shows that in the sucked in state , the running belts 7 a , b may conform with the surface 8 of the workpiece 9 , and that the rollers 4 , 5 may be made from a correspondingly elastic flexible material . fig4 shows a diagrammatic partial lateral view of a detail of the system element 1 according to fig1 . as shown in fig4 , the running belt 7 is placed around a guide disc 11 . the guide disc 11 is connected to an axle 12 which extends from the roller 5 towards the outside . by way of a sliding bearing or ball bearing 13 , a connection 14 is supported by the axle 12 . the connection 14 is preferably rigid and bears or supports the suction chamber ( not shown ). according to the preferred embodiment , the rigid connection 14 comprises a first part 15 , that extends so as to be substantially parallel in relation to the axle 12 and the roller 5 , and a second part 16 and a third part 17 which extend substantially perpendicularly from the first part 15 in the direction of the axle 12 . the free ends of the first and second parts 16 , 17 are supported by the axle 12 via the sliding bearings or ball bearings 13 . the first and second parts 16 , 17 of the connection 14 are spaced apart from each other , and the pulley 6 is arranged between the first part 16 and the second part 17 , as shown in fig4 . during the transport of the suction chamber 2 over the workpiece 9 , the suction device 2 is supported by the rollers 4 , 5 . to this effect , the axle bearing 12 of the rollers 4 , 5 is rigidly connected to the suction chamber 2 as described above . expediently , attachment of the axle bearing 12 is further to the outside than the position of the running belts 7 such that the axle bearing arrangement may not be in the way of automatic sealing between the running belts 7 and the rollers 4 , 5 . the rigid connection 14 of the axle bearings 12 and the suction chamber 2 comprises an opening 18 , through which the upper part of the running belts 7 may move . in an inoperative position , e . g . while a transported tool is in operation , attachment of the suction device may also be possible by way of additional suction cups or by way of full contact of the suction device in that the rigid connection to the rollers is undone . thus , the running belts 7 a , 7 b , which may serve as connection elements , and the rollers 4 , 5 , which may serve to generate forward movement of the system element 1 , may conform to the curved surface 8 of the workpiece 9 when the suction chamber 2 generates a suction stream , so that a good negative pressure is generated between the suction chamber 2 and the surface 8 of the workpiece 9 , where negative pressure makes possible reliable adhesion of the system element 1 to the surface 8 of the workpiece 9 . in this way a tool ( not shown ) that is coupled in any desired manner to the system element may reliably be conveyed to a desired position on the surface of the workpiece 9 , where the tool may be positioned . although not shown in the figures , a transport system according to the invention may comprise a plurality of system elements 1 . for example , the shape of the suction chamber 2 is not limited to a square or rectangular shape but instead may comprise any form with any number of lateral surfaces , but it may be ensured that each lateral surface is contacted either by a roller or by a running belt so as to ensure that adequate negative pressure is generated for adhesion of the system element 1 . furthermore , the running belt 7 may also be designed as some other connection element that interconnects the end regions of the rollers and contacts a lateral surface of the suction chamber 2 . in this case , the drive of the system element 1 takes place by applying a torque to any one of the rollers 4 , 5 ( or to both ) without the need for pulleys 6 . as an alternative , the running belts 7 may be made from a suitable material and may have a suitable shape so that forward movement of the system element may by said running belts 7 alone , wherein the rollers 4 , 5 are idle rollers . the system element may be used in many sectors , for example , in aircraft construction , shipbuilding or in any other sectors where a tool has to be reliably transported over a curved surface of a workpiece and has to be positioned thereon , wherein the term “ tool ” also refers to a component , robot or a workpiece to be transported . furthermore , the system element may of course also be used on horizontal or flat surfaces . it should also be mentioned that “ comprising ” does not exclude any other elements or steps , and that “ a ” or “ an ” does not exclude a plurality . it should furthermore be noted that characteristics or steps described with reference to one of the above embodiments may also be used in combination with other characteristics or steps of other above - described embodiments . the reference symbols in the claims should not be understood in a restrictive sense . alternative combinations and variations of the examples provided will become apparent based on this disclosure . it is not possible to provide specific examples for all of the many possible combinations and variations of the embodiments described , but such combinations and variations may be claims that eventually issue . | 1 |
in the following detailed description of the invention , numerous specific details are set forth in order to provide a thorough understanding of the invention . however , the invention may be practiced without these specific details . in other instances well known methods , procedures , and / or components have not been described in detail so as not to unnecessarily obscure aspects of the invention . fig1 schematically shows a part of a data processing system , e . g . a system used in a mobile phone comprising a transmitter 10 and a receiver 20 . the transmitter 10 may be any data producing device , e . g . a baseband processor , a storage or a camera chip . the receiver 20 may be any data receiving device , e . g . a processor , or another storage . the transmitter 10 transmits data frames to the receiver 20 via data link 30 . the receiver 20 can communicate error messages to the transmitter 10 via return data link 40 . although in the embodiment shown the transmitter 10 and the receiver 20 are directly coupled , they may alternatively be coupled via one or more intermediary nodes . fig2 schematically shows an example of a data frame exchanged between the transmitter and the receiver . the data frames comprise control data as well as user data . the control information serves to control a proper transfer of the user data ( payload pl ). the control data includes at least a frame sequence number fs , and may further include for example a start of frame sof marker , an end of frame marker eof , and a traffic class indicator tc ( e . g . indicating high / low priority data traffic , isochronous traffic or best effort traffic ). furthermore redundant data crc may be present to verify correctness of the user data and / or control data . the frame sequence number fs is shown to be part of the data frame trailer , but it may also be part of the frame header . fig3 shows in more detail a transmitter according to the present invention . the transmitter includes a production module 11 for producing at least one data frame for transmission . the production module 11 may for example be an input buffer that temporarily stores data frames received from an external source 12 as shown dashed in the embodiment of this figure . alternatively the production module may for example generate the data frames itself , e . g . from signal provided by a sensor , or antenna . the at least one data frame includes a sequence number , user data and an error - detection code . the transmitter further includes a retransmission buffer 13 for temporarily storing the at least one data frame . a controller 14 configures the retransmission buffer 13 for retransmission and selects which of the production module 11 and the retransmission buffer 13 is used for supplying the data frames for transmission . the outputs of the production module 11 and of the retransmission buffer 13 are coupled to a multiplexor 15 , controlled by the controller 14 to select one of the outputs for providing a data frame for transmission to the receiver 20 . the operation of the controller 14 is shown in more detail in fig4 . at startup ( step s 4 _ 1 ) the controller initializes the following variables : therein the variables oldest_seq and newest_seq respectively indicate the sequence number of the oldest data frame and the newest data frame in the retransmission buffer . the variables rd_ptr and wr_ptr respectively indicate the retransmission buffer locations that are currently read from and written to . the variable empty indicates whether data frames are available in the retransmission buffer . frame_start [ ] is a table comprising for each data frame x the location of the first word of said data frame in the retransmission buffer 13 . in step s 4 _ 2 the controller waits for one of the following conditions to occur : a new word of a data frame becomes available for transmission ( c 4 _ 1 ). in that case the data frame is added to the retransmission buffer in action s 4 _ 3 . this action is described in more detail with reference to fig5 a and 5b . an error message ( nac ) is received ( c 4 _ 2 ) that indicates the sequence number seq of the last correctly received data frame . in that case all the data frames up to and including the reported frame sequence number seq are discarded , and the retransmission buffer read pointer is moved at the beginning of the first unacknowledged data frame in action s 4 _ 4 . this action is described in more detail with reference to fig6 . the event get_replay_word is received during a replay ( c 4 _ 3 ). this results in receiving a word from the retransmission buffer 13 . when all the data from the retransmission buffer 13 has been resent , a flag is set . this action c 4 _ 3 is described in more detail in fig7 . fig5 a and 5b are described now in more detail . in the embodiment shown data frames can comprise a variable number of words , and the production module 11 indicates the last word by a flag last_in_frame . the data frames are added word by word wr_word to the retransmission buffer 13 . first , in step s 5 _ 1 it is verified whether the retransmission buffer 13 is full . the retransmission buffer 13 is full if the value of the write pointer wr_ptr is equal to the value of the read pointer rd_ptr and the flag empty is false . if indeed the retransmission buffer 13 is full , the oldest data frame in the retransmission buffer is therefore removed in action s 5 _ 2 . this action , which is illustrated in more detail in fig5 b , includes steps s 5 _ 3 , s 5 _ 4 , s 5 _ 5 . in step s 5 _ 3 the index indicating the oldest data frame in the retransmission buffer 13 is incremented : in step s 5 _ 4 the read pointer is updated : this pointer rd_ptr addresses the first word of this new oldest data frame in the retransmission buffer 13 . after the read pointer is updated it is verified in step s 5 _ 5 whether removing the data frame resulted in an empty retransmission buffer 13 . this is the case if the read pointer equals the write pointer : the full - buffer test s 5 _ 1 may be repeated . this may for example be necessary if a new data frame is larger than the oldest data frame stored in the retransmission buffer 13 . after the full - buffer test s 5 _ 1 and the possible oldest - frame removal s 5 _ 2 , the word to be , written wr_word is inserted in the retransmission buffer at the wr_ptr position in step s 5 _ 6 , the wr_ptr pointer is incremented to the next retransmission buffer location in step s 5 _ 7 , and the empty flag is set to false in step s 5 _ 8 , because at least the current word wr_word is in the retransmission buffer 13 . in step s 5 _ 9 it is determined whether a new data frame has been completely stored in the retransmission buffer 13 , by inspecting the value of the flag last_word_in_frame provided by the production module 11 . if it is determined in step s 5 _ 9 that a new data frame has been completely stored in the retransmission buffer 13 it is also necessary to update information about the start of the next data frame . the number of data frame entries is limited . accordingly in step s 5 _ 10 it is verified whether all numbers are in use . in this particular example , the least significant bits of the sequence number are used to identify a data frame in the retransmission buffer 13 . e . g ., if there are 8 bits used for the sequence number , the least significant 4 bits can be used to maintain 16 data frame entries . the following test reveals whether a data frame entry is in use : if this is the case , in step s 5 _ 11 , worked out in fig5 b , the oldest data frame is removed from the retransmission buffer 13 to make space for the new data frame . the start of the newest data frame is calculated in step s 5 _ 12 by : subsequently the index pointing to the newest data frame is incremented in step s 5 _ 13 : when a negative acknowledge nac is received , the data transmitter 10 prepares the retransmission buffer 13 for retransmission , as shown in more detail in fig6 . first in step s 6 _ 1 it is checked if the reported sequence number seq is actually stored in the retransmission buffer . this is the case if : if so , in step s 6 _ 2 all the data frames up to and including the data frame with number seq are removed from the retransmission buffer . accordingly the variable oldest_seq is updated as : and in step s 6 _ 3 the new read pointer is updated as : in step s 6 _ 4 the currently being transmitted data frame is also removed from the retransmission buffer . removal is achieved by incrementing the write pointer wr_ptr to the start of the next data frame : in step s 6 _ 5 the replay pointer is set to the beginning of the oldest data frame : retransmission continues ( see fig7 ), until the replay pointer is equal to the write pointer . this is verified in step s 7 _ 1 . every time a word is requested , this is delivered from the replay_ptr position in the retransmission buffer ( step s 7 _ 2 ), and replay_ptr is incremented in step s 7 _ 3 . subsequently the replayed word of the frame is transmitted ( s 7 _ 4 ). if all the buffer has been replayed ( replay_ptr == wr_ptr ), a message is issued in step s 7 _ 5 that normal operation mode is assumed again ( s 4 _ 2 , fig4 ). fig8 schematically illustrates a receiver 20 of a data processing system according to the invention . the receiver 20 includes an input 21 for receiving the at least one data frame . the input 21 is coupled to a channel decoder module 22 that decodes the data from a 9 bit communication format into an 8 bit internal data format . a next module 23 converts this 8 bit internal data format into data having a further 17 bit internal format . the 17 bit data is supplied to the receive buffer 24 and to a crc - module 25 that compares the value of the crc data in the data frame with the value of the crc data calculated from the user data in the data frame . the receiver further has an error detection module 26 for detecting an error in the at least one data frame . the error detection module 26 may for example detect the following errors . an invalid symbol was received in the physical layer of the protocol . in the embodiment shown this is reported by a signal err_sym9b from the channel decoder module . a crc error occurs in the data frame ( likely caused by a bit flip ). in the embodiment shown this type of error is reported by a signal err_crc from the crc - module 25 . a sequence number error may be reported if the sequence number of a data frame does not logically follow from the sequence number of a previous data frame . an rx buffer overflow err_buf_overflow may also be a cause for an error message . the error detection module 26 here functions as the module for signaling an error message . in case an error is detected , the error detection module 26 requests via req_nac that an error indication message is sent to the transmitter 10 . the message req_nac includes information indicative for the sequence number of the last correctly received data frame . such indicative information is preferably the sequence number itself of the last correctly received data frame . alternatively it is for example the sequence number of the first data frame received with errors . this is however not always possible , as the detected errors may not necessarily be associated with a data frame . they can be associated with e . g ., a control frame , or an invalided idle symbol . the receiver 20 in the data processing system further includes a timer 27 that indicates the amount of time lapsed from the moment the error message req_nac transmission is initiated . after expiry of a predetermined amount of time it provides a signal expire to the error detection module 26 . in response to this signal the error detection module 26 initiates a new transmission of an error message . the error detection module 26 further may initiate a resynchronization of the connection to the transmitter with a signal req_link_sync . fig9 schematically illustrates a finite state machine for operation of a receiver 20 according to the invention . in this scheme the oval blocks indicate a state . the indented rectangular blocks indicate a detected condition , and the unindented rectangular blocks indicate an action state s 9 _ 1 is the initial state of the receiver 20 after reset . from that state it transfers to state s 9 _ 2 , which is maintained as long as no errors are detected . condition c 9 _ 3 implies an error is detected . in that case actions a 9 _ 4 and a 9 _ 5 are carried out . action a 9 _ 4 is the communication of a message req_nac to notify the transmitter 10 of the data frame of the sequence number of the last correctly received data frame . action a 9 _ 5 is starting the timer 27 to measure the waiting time for a response of the transmitter 10 to said message . state s 9 _ 6 is a waiting state wherein the receiver waits for a response of the receiver . during said waiting stage s 9 _ 6 the following conditions may occur : c 9 _ 7 : the receiver 20 receives a replay of data frames by the transmitter . in that case the timer may optionally be stopped to save power ( in action a 9 _ 8 ) and the receiver 20 assumes the no - error state s 9 _ 2 . the replay detection may consist of detecting a valid data and / or control frame , or detecting the link resynchronization at the physical layer . c 9 _ 9 : the timer 27 expires . in this case the actions a 9 _ 10 , a 9 _ 11 and a 9 _ 12 are performed . action a 9 _ 10 is a resynchronization of the data link 40 from the receiver 20 to the transmitter 10 . this action is followed by action a 9 _ 11 , which is the transmission of a new negative acknowledgement message which includes a flag to request the data frame transmission link to be resynchronized . as action a 9 _ 12 additionally the timer 27 is started again . following the actions a 9 _ 10 , a 9 _ 11 and a 9 _ 12 the receiver 20 assumes the waiting state s 9 _ 6 , wherein it waits again for the retransmission of data frames by the transmitter 10 . c 9 _ 14 : another error is detected . in this case , the no error indication message is further sent to the transmitter to prevent an avalanche of error messages to the transmitter when for example the link is out of sync , and with every symbol an error is likely to be detected . as a result , the receiver 20 returns directly to state s 9 _ 6 , wherein it waits for a retransmission of data frames or another response of the transmitter . as indicated by the dashed box in fig8 an error counter 28 may be used , instead of a timer 27 to initiate a second error indication message transmission . when an error indication message is transmitted by the receiver , the error counter is initialized to count the detected errors up to a predetermined value . when this value of errors is reached , the same actions as for the timer expiration are taken ( e . g ., link resynchronization a 9 _ 10 and initiating a second error indication message transmission a 9 _ 11 ), after which the error counter is reinitialized and again set to count detected errors . the error counter may stop counting errors when a response c 9 _ 7 from the transmitter is observed . fig1 shows a first example of a communication between a transmitter 10 and a receiver 20 in a data processing system according to the invention . at time t 1 the transmitter 10 transmits a data frame . this data frame is received at time t 2 by the receiver 20 . in this example the receiver detects that an error occurs in the time interval tl - t 2 . in response thereto , at time t 3 , it transmits an error message nac to notify the transmitter 10 of the data frame of the occurrence of the error . the error message includes at least information relating to the sequence number of the last correctly received data frame . the message is received at time t 4 by the transmitter 10 , and triggers a retransmission of one or more data frames at time t 5 . at time t 6 the receiver detects the retransmission and stops it the timer . fig1 shows a second example of a communication between a transmitter 10 and a receiver 20 in a data processing system according to the invention . until time t 5 the second example is equivalent to the first one . however , in the example shown , a further error occurred during the transmission of the retransmitted one or more data frames , and an error is detected at t 6 , however , no error message nac is reported back to the transmitter 10 as the timer is still running . as soon as the timer expires at t 7 , the data link 40 from the receiver 20 to the transmitter 10 is synchronized . alternatively , immediate resynchronization upon detection of the error is an option . however , the bit error rates are expected to be much higher ( e . g ., once every second ) than the synchronization error rates ( e . g ., once every hour ). the link resynchronization is only needed for synchronization errors , not for bit errors . as a result , usually the system will recover from the error without link resynchronization ( see fig1 ), and , therefore , there is no need to resynchronize the link with the first error detection . however , in the more rare cases that the system was not able to recover from error after the timer expires , it can be assumed that the link is out of sync and it may be resynchronized immediately . after synchronization of the data link 40 at time t 8 the receiver 20 transmits a new error message . this error message is received at t 9 by the transmitter 10 . in response thereto the transmitter first synchronizes the data link 30 from the transmitter 10 to the receiver 20 , and subsequently at time t 10 retransmits one or more data frames . at time t 11 the receiver 20 notices that the retransmission is started , and stops its timer 27 . it is remarked that the scope of protection of the invention is not restricted to the embodiments described herein . parts of the system may implemented in hardware , software or a combination thereof . neither is the scope of protection of the invention restricted by the reference numerals in the claims . the word ‘ comprising ’ does not exclude other parts than those mentioned in a claim . the word ‘ a ( n )’ preceding an element does not exclude a plurality of those elements . means forming part of the invention may both be implemented in the form of dedicated hardware or in the form of a programmed general purpose processor . the invention resides in each new feature or combination of features . | 7 |
referring particularly to fig1 the reference numeral 10 generally designates an array of hydraulic transmission control elements for regulating the engagement and disengagement of friction clutch 12 and band brake 14 to effect shifting between a pair of forward transmission speed ratios . in a typical application , a 1 : 1 or direct ratio ( 3rd ) is provided with engagement of the clutch 12 , and an underdrive ratio ( 2nd ) is provided with engagement of the band brake 14 . thus , a 2 - 3 upshift is achieved through concurrent disengagement of band brake 14 and engagement clutch 12 , while a 3 - 2 downshift is achieved through concurrent disengagement of clutch 12 and engagement band brake 14 . as explained below , this invention concerns the engagement of band brake 14 to effect a 3 - 2 downshift . the illustrated hydraulic elements include a positive displacement mechanically driven hydraulic pump 16 , a pressure regulator valve 18 , a force motor controlled line pressure bias valve 20 and limit valve 22 , an operator manipulated manual valve 24 , a solenoid controlled 2 - 3 shift valve 26 , a clutch apply servo 28 , a fluid restriction circuit 30 , and a band apply servo 32 . the pump 16 receives hydraulic fluid at low pressure from the fluid reservoir 40 , and supplies line pressure fluid to the transmission control elements via output line 42 . pressure regulator valve 18 is connected to the pump output line 42 and serves to regulate the line pressure and torque converter feed pressure ( cf ) by returning a controlled portion of the line pressure to reservoir 40 via the line 44 . the pressure regulator valve 18 is biased at one end by orificed line pressure in line 46 and at the other end by the combination of a spring 48 and a controlled bias pressure in line 50 . the controlled bias pressure is supplied by the line pressure bias valve 20 which develops pressure in relation to the current supplied to electric force motor 52 , the force motor 52 being hydraulically balanced by the pressure in bias chamber 54 . line pressure is supplied as an input to bias valve 20 via line 54 and the limit valve 22 . an accumulator 56 connected to the bias pressure line 50 serves to stabilize the bias pressure . with the above - described valving arrangement , it will be seen that the line pressure of the transmission is electrically regulated by force motor 52 . in the event of an interruption of electrical power to the force motor 52 , the bias pressure in line 50 assumes a maximum value , thereby forcing maximum line pressure . the friction clutch 12 and band brake 14 are activated by conventional fluid servos 28 and 32 , respectively . the servos 28 and 32 , in turn , are connected to a fluid supply system comprising the manual valve 24 , the 2 - 3 shift valve 26 , and the fluid restriction circuit 30 . the manual valve 24 develops a supply pressure d32 for the 2nd and 3rd forward speed ranges of the transmission in response to driver positioning of the transmission range selector lever 60 . the d32 pressure , in turn , is supplied via line 62 to the shift valve 26 and fluid restriction circuit 30 for application to the servos 28 and 32 . the shift valve 26 is spring - biased against a controlled bias pressure developed by the solenoid 64 , the valve 26 being illustrated in its activated state . in the illustrated state , the shift valve 26 supplies d32 supply pressure to the clutch servo 28 via line 66 and to a release chamber 68 of band brake servo 32 via line 70 . in the deactivated state , the lines 66 and 70 are exhausted via exhaust port 72 . the fluid restriction circuit 30 comprises a first orifice 80 connecting the d32 supply pressure line 62 to an apply chamber 82 of band brake servo 32 , and a solenoid operated flow control valve 84 . the flow control valve 84 is selectively controlled to connect a second orifice in parallel with the first orifice 80 , the second orifice being defined by the valve seat 86 . the flow control valve 84 includes a pintle armature 88 which is normally retracted from the seat / orifice 86 by a return spring ( not shown ) to connect the second orifice in parallel with the first orifice 80 , and a solenoid 90 which when electrically activated ( energized ) extends the pintle armature 88 into engagement with the seat / orifice 86 . thus , fluid pressure is supplied to the servo inlet chamber 82 via the parallel combination of orifices 80 and 86 when solenoid 90 is deactivated , and via the orifice 80 alone when solenoid 90 is activated . the deactivated condition thereby defines a high flow state , while the activated condition defines a low flow state . as described below , the valve 84 is controlled to its high flow state at the initiation of a 3 - 2 downshift , and is controlled to its low flow state after a determined delay time td . the servo 32 includes a post 92 fastened to a diaphragm 94 which is axially displaceable within the servo housing . a pair of springs 96 and 98 reacting against the housing of servo 32 urge the diaphragm 94 and hence the post 92 downward , as viewed in fig1 to release the band brake 14 . the spring forces may be aided by fluid pressure in release chamber 68 or opposed by fluid pressure in apply chamber 82 . reference numeral 100 designates a computer - based control unit which develops suitable electrical control signals for the force motor 52 and the solenoids 64 and 90 in response to a variety of vehicle and powertrain parameters , represented by the input lines 102 . the line pressure control of force motor 52 is essentially continuous during operation of the transmission , ensuring that the developed pressure is sufficient to prevent clutch slippage during steady state operation , and providing shift quality control during shifting . the control of solenoids 64 and 90 , on the other hand , pertain strictly to shifting and are discrete or on - off in nature . in 2nd ratio operation , the shift valve solenoid 64 is deactivated so that the clutch servo 28 and the band brake servo release chamber 68 are vented through shift valve exhaust port 72 . the servo apply chamber 82 is maintained at d32 supply pressure via fluid restriction circuit 30 , overcoming the spring bias to extend the servo post 92 and engage the band brake 14 . when a 2 - 3 upshift is required , the control unit 100 activates the shift valve solenoid 64 to connect the d32 supply pressure to clutch servo 28 and the release chamber 68 of band brake servo 32 via orifice 29 . this pressure balances the apply chamber pressure , allowing the springs 96 and 98 to stroke the diaphragm 94 , retracting the post 92 as the apply chamber fluid is displaced through the fluid restriction circuit 30 and into the pressure control line 62 . during this operation , the solenoid 90 is deactivated , and the flow control valve 84 is in its high flow state . the pressure in the clutch servo 28 builds as a function of the spring rates and orifices , engaging the clutch 12 as the band brake is released . this is a conventional band - to - clutch wash - out upshift . when a 3 - 2 downshift is required , the control unit 100 determines a delay time td for the flow control valve 84 , and deactivates the shift valve solenoid 64 to vent the fluid in clutch servo 28 and band brake servo release chamber 68 . the determination of delay time td is described below in reference to fig3 . the combination of the line pressure ( d32 ) and the effective orifice size of fluid restriction circuit 30 determines the fluid flow rate into servo apply chamber 82 , which in turn , determines the stroke time of the servo post 92 . once the shift is complete , there is no flow through the fluid restriction circuit 30 , and the solenoid 90 is deactivated . the graph of fig2 illustrates the relationship between the stroke time of band brake servo 32 and the transmission line pressure , with and without activation of the flow control valve solenoid 90 . when the solenoid 90 is activated and the supply pressure can only pass through orifice 80 , the relationship is given by the &# 34 ; 1 orifice &# 34 ; trace 110 . as one would expect , increasing line pressure increases the fluid flow , thereby decreasing the stroke time ; similarly , decreasing line pressure decreases the fluid flow , thereby increasing the stroke time . when the shuttle valve solenoid 90 is deactivated and the supply pressure can pass through the valve seat orifice 86 as well as the orifice 80 , the relationship is given by the &# 34 ; 2 orifice &# 34 ; trace 112 . the parallel combination of orifices 86 and 80 permits increased flow , resulting in reduced stroke time for a given line pressure . the graph of fig2 also shows that the range of available stroke times depends on the transmission line pressure . at pressure pl , for example , the shortest stroke time tmin is achieved by maintaining the high flow ( two orifice ) state throughout the shift , while the longest stroke time tmax is achieved by maintaining the low flow ( one orifice ) state throughout the shift . stroke times between tmin and tmax are obtained , according to this invention , by initiating the shift in the high flow state and switching to the low flow state after a determined delay time td . of course , a zero delay time would result in a stroke time of tmin , and a long delay time would result in a stroke time of tmax . as the line pressure increases above pl , both tmin and tmax decrease ; as the line pressure decreases below pl , both tmin and tmax increase since the same considerations which generally dictate an increase in stroke time dictate a decrease in line pressure , and vice versa , the range of available stroke times ( tmax - tmin ) is generally adequate to achieve optimum shift timing control . the primary control parameters for both line pressure and stroke time are vehicle speed and transmission input torque , as typically represented by engine throttle position . as the vehicle speed increases , it is generally advantageous to decrease line pressure to reduce spin losses , and to increase the downshift stroke time so that the input speed can substantially reach the 2nd ratio speed by the time the band brake 14 engages . as the input torque increases , it is generally advantageous to increase the line pressure to prevent steady state clutch slippage , and to decrease the downshift stroke time to limit the energy absorbed by the on - coming band brake . the above considerations , at least with respect to stroke time , are reflected in the 3 - d look - up table representation of fig3 . thus , for a given engine throttle position , the desired delay time td decreases with increasing vehicle speed to provide increasing servo stroke time . for a given vehicle speed , the desired delay time td increases with increasing engine throttle position to provide decreasing servo stroke time . in the above described mechanization , it is most convenient to address the effects of line pressure variations by empirically determining and storing delay time values into the look - up table of fig3 . that is , the delay time values which are empirically found to achieve the desired stroke times in various operating conditions of the powertrain are stored in a look - up table or data array as a function of the corresponding engine throttle position vs . vehicle speed test points . delay times for engine throttle position vs . vehicle speed operating points between empirically determined values are determined by interpolation . factors compensating for the effects of temperature and altitude variations may also be taken into account . in the preferred embodiment of this invention , a second look - up table or data array is provided for the storage of adaptive corrections to the table depicted in fig3 . as explained below in connection with fig4 and 6b , the performance of the transmission control in the course of normal 3 - 2 downshifts is measured and compared to a reference indicative of high quality shifting . if the measured value significantly deviates from the reference value , the control unit develops or updates a delay time adaptive correction term td ( adapt ) for the operating point in effect during the shift . in the next 3 - 2 downshift at such operating point occurs , the delay time will be determined as a combined function of the base delay time td ( base ) from the table of fig3 and the adaptive correction term td ( adapt ) from the adaptive table , so that the shift quality will be improved . a 3 - 2 downshift according to this invention is depicted in graphs a - e of fig4 on a common time base . graph a depicts the transmission speed ratio nt / no ; graph b depicts the torque capacity of the 3rd clutch 12 ; graph c depicts the stroke or displacement of servo 32 ; graph d depicts the torque capacity of the 2d band brake 14 ; and graph e depicts the energization state of the flow control valve solenoid 90 . initially , the shift valve solenoid 64 is energized to engage 3rd clutch 12 , and the flow control valve solenoid 90 is deenergized , defining a high flow state . the shift is initiated at time t0 with the deenergization of shift valve solenoid 64 and the determination by control unit 100 of a flow control valve delay time td . the deenergization of shift valve solenoid 64 quickly reduces the torque capacity of 3rd clutch 12 , as indicated in graph b . shortly thereafter at time t1 , the input speed , and therefore the ratio nt / no , increases toward the 2nd ratio , as indicated in graph a . the control unit 100 detects the change in speed ratio nt / no as indicated in graph e , and starts a delay timer for comparison with the determined delay time td . also , approximately at time t1 , the flow of fluid through orifices 80 and 86 begins to stroke the servo post 92 , as indicated in graph c . this displaces the fluid in servo release chamber 68 into the 3rd clutch exhaust circuit , slowing the release of 3rd clutch 12 , as indicated in graph b . in view of the above , it will be recognized that conditions other than a change in the speed ratio nt / no may be used to initiate the measured delay time . for example , the delay time could be initiated in response to a detected initial displacement of the servo post 92 , or the deenergization of shift valve 64 . at time t2 , the delay timer count reaches the determined delay time td , and the control unit 100 energizes the flow control valve solenoid 90 as indicated in graph e . this closes the orifice 86 , decreasing the flow to servo apply chamber 82 , and reduces the rate of displacement of servo post 92 , as indicated in graph c . at time t3 when the servo 32 is almost fully stroked , the torque capacity of 2nd band brake 14 quickly increases , as indicated in graph d . when the fully stroked position is reached at time t4 , the remaining fluid pressure in 3rd clutch servo 28 quickly exhausts through orifice 72 , fully releasing the 3rd clutch 12 , as indicated in graph b . at this point , the ratio change is completed , as indicted in graph a . shortly thereafter at time t5 , the flow control valve solenoid 90 is deenergized in preparation for the next shift . as indicated in reference to fig3 the above - described control is carried out essentially open - loop in that a predetermined delay time is used to control the operation of flow control valve 84 during the course of a shift . however , it is recognized that it may be desirable to trim the empirically determined delay times to compensate for part - to - part tolerance variations and other variations which occur over time . the control unit 100 continues to monitor specified parameters in the course of the shift to detect an aberration which indicates an inappropriate delay time td . one such indication is engine flare , as indicated by the broken line 114 in graph a of fig3 . this condition occurs if the stroke time is too long . if this condition is detected , the solenoid 90 is immediately deenergized to return the flow control valve 84 to the high flow state , and an adaptive delay term td ( adapt ) for increasing the delay time is determined and stored in the adaptive table referenced above in relation to fig3 . a further indication of a delay time aberration is the shift time . this condition occurs if the stroke time is too short , as indicated by the broken line 116 in graph a of fig3 . this condition is detected by comparing a measure of the shift time to a reference shift time stref based on vehicle speed nv . if the measured shift time is significantly shorter than the reference shift time , an adaptive delay term td ( adapt ) for decreasing the delay time is determined and stored in the adaptive table . flow diagrams representative of computer program instructions for carrying out the control of this invention with the apparatus of fig1 are depicted in fig5 and 6a - 6b . the flow diagram of fig5 represents a main or executive computer program which is periodically executed in the course of vehicle operation in carrying out the control of this invention . the block 230 designates a series of program instructions executed at the initiation of each period of vehicle operation for setting various terms and timer values to an initial condition . thereafter , the blocks 232 - 234 are executed to read the various inputs referenced in fig1 and to determine the desired speed ratio rdes . the desired ratio rdes may be determined in a conventional manner as a predefined function of engine throttle position tps and output vehicle speed nv . if the actual ratio ract -- that is , no / nt -- is equal to the desired ratio rdes , as determined at block 238 , the blocks 243 and 244 are executed to deenergize the flow control valve solenoid 90 and to determine the desired line pressure lpdes . in this case , the desired line pressure lpdes is determined as a function of throttle position and output speed , and also is adjusted based on the desired ratio rdes and an adaptive corrective term pad . the adaptive correction term pad may be generated during upshifting , based on shift time , as set forth in u . s . pat . no . 4 , 283 , 970 to vukovich et al . issued aug . 18 , 1981 , and assigned to the assignee of this invention . if an upshift is required , as determined by blocks 238 and 240 , the blocks 242 and 244 are executed to perform suitable upshift logic in addition to determining the desired line pressure lpdes as described above . if a downshift is required , as determined by blocks 238 and 240 , the blocks 246 and 248 are executed to determine the desired line pressure lpdes and to perform the downshift logic . in this case , the desired line pressure is determined as a function of throttle position , output speed , the pre - shift or old ratio rold , and the adaptive correction term pad , as indicated at block 246 . as indicated at block 248 , the downshift logic is set forth in further detail in the flow diagram of fig6 a - 6b . in any case , the block 250 is then executed to convert the desired line pressure lpdes to a solenoid duty cycle lp ( dc ), to output the duty cycle lp ( dc ) to force motor 52 , and to output discrete solenoid states to the solenoids 64 and 90 . referring now to the downshift logic flow diagram of fig6 a - 6b , the block 252 is first executed to determine the required states of the various shift valve solenoids . as indicated above , the present invention concerns the 2 - 3 shift valve solenoid 64 , which is activated to initiate a 2 - 3 upshift and deactivated to initiate a 3 - 2 downshift . if the shift is a 3 - 2 downshift , as detected at block 254 , the blocks 256 - 274 are executed to determine the required state of flow control valve solenoid 90 as a function of the vehicle speed nv and engine throttle position tps , as described above in reference to fig3 - 4 . when the transmission speed ratio nt / no first starts to increase toward 2nd , as determined by blocks 256 - 258 , the blocks 260 - 262 are executed to look up the delay time td as a function of measured vehicle speed and engine throttle position values nv , tps , to look up a reference shift time stref as a function of the vehicle speed nv , and to reset the delay timer . as indicated at block 260 , the delay time td is comprised of two components : a base delay time td ( base ) and an adaptive delay time td ( adapt ). thereafter during the shift , execution of the blocks 260 - 262 is skipped , as indicated by the flow diagram line 263 . until the delay timer reaches the determined delay time td , or unless engine flare is observed , as determined by blocks 264 and 270 , the remainder of the routine is skipped . once the delay timer reaches the determined delay time td , the block 266 is executed to energize the flow control valve solenoid 90 . the adaptive delay time functions are set forth in fig6 b , which is a continuation of the flow diagram of fig6 a . if engine flare is observed , by detecting an unexpected increase in the ratio nt / no , for example , the blocks 272 - 274 are executed to deenergize the flow control solenoid 90 and to increment or update the adaptive delay time value td ( adapt ) for the vehicle speed vs . engine throttle position operating point used at block 260 . the amount of the increase may be fixed or variable as a function of the amount or timing of the observed flare . if the ratio change is almost complete and the delay timer is significantly less than the the reference shift time value stref , as determined at blocks 276 - 278 , the block 280 is executed to decrement or update the adaptive delay time value td ( adapt ) for the vehicle speed vs . engine throttle position operating point used at block 260 . as with the adaptive increase of td ( adapt ), the amount of the adaptive decrease may be fixed or variable as a function of the deviation of the actual shift time ( delay timer ) from the reference shift time stref . while illustrated in reference to a wash - out shift arrangement , it will be appreciated that the engagement rate control of the present invention will find application in the engagement of any torque transmitting device having a member which is displaced by a servo in relation to the volume of fluid directed to an apply chamber thereof . it is expected that various other modifications to the illustrated embodiment will occur to those skilled in the art as well , and it should be understood that controls incorporating such modifications may fall within the scope of the present invention , which is defined by the appended claims . | 8 |
hereinafter reference will now be made in detail to various embodiments of the present invention , examples of which are illustrated in the accompanying drawings and described below . while the invention will be described in conjunction with exemplary embodiments , it will be understood that present description is not intended to limit the invention to those exemplary embodiments . on the contrary , the invention is intended to cover not only the exemplary embodiments , but also various alternatives , modifications , equivalents and other embodiments , which may be included within the spirit and scope of the invention as defined by the appended claims . it is understood that the term “ vehicle ” or “ vehicular ” or other similar term as used herein is inclusive of motor vehicles in general such as passenger automobiles including sports utility vehicles ( suv ), buses , trucks , various commercial vehicles , watercraft including a variety of boats and ships , aircraft , and the like , and includes hybrid vehicles , electric vehicles , plug - in hybrid electric vehicles , hydrogen - powered vehicles and other alternative fuel vehicles ( e . g ., fuels derived from resources other than petroleum ). as referred to herein , a hybrid vehicle is a vehicle that has two or more sources of power , for example both gasoline - powered and electric - powered vehicles . the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention . as used herein , the singular forms “ a ,” “ an ” and “ the ” are intended to include the plural forms as well , unless the context clearly indicates otherwise . it will be further understood that the terms “ comprises ” and / or “ comprising ,” when used in this specification , specify the presence of stated features , integers , steps , operations , elements , and / or components , but do not preclude the presence or addition of one or more other features , integers , steps , operations , elements , components , and / or groups thereof . as used herein , the term “ and / or ” includes any and all combinations of one or more of the associated listed items . unless specifically stated or obvious from context , as used herein , the term “ about ” is understood as within a range of normal tolerance in the art , for example within 2 standard deviations of the mean . “ about ” can be understood as within 10 %, 9 %, 8 %, 7 %, 6 %, 5 %, 4 %, 3 %, 2 %, 1 %, 0 . 5 %, 0 . 1 %, 0 . 05 %, or 0 . 01 % of the stated value . unless otherwise clear from the context , all numerical values provided herein are modified by the term “ about ”. according to one aspect , the present invention provides a method for preparing lactide , including : ( a ) adding an ionic solvent to lactic acid oligomers , wherein the lactic acid oligomers are any synthesized through the polymerization of lactic acid monomers ; and ( b ) synthesizing lactide from the lactic acid oligomers added to the ionic solvent by regulating a temperature and / or a pressure , preferably be regulating both temperature and pressure . according to an exemplary embodiment of the present invention , the polymerization of lactic acid monomer in the step ( a ) is carried out at a temperature of about 120 to 300 ° c . under a pressure of about 1 to 500 mmhg for about 1 to 5 hours . however , the various conditions suitable for lactide synthesis ( e . g ., temperature , pressure and time ) can vary , and thus the conditions for polymerization can include all the conditions involved in the polymerization process where lactic acid monomers are converted into lactic acid oligomers . as such , while the above noted range is preferable , the temperature is not limited to the defined conditions . in an exemplary embodiment of the present invention , the synthesis of lactide in the step ( b ) is carried out at a temperature of about 100 to 1000 ° c . under a pressure of about 1 to 600 mmhg for about 1 to 5 hours . in an exemplary embodiment of the present invention , the ionic liquid is used for the purpose of ensuring stability at a high temperature condition during the step of preparing lactide . since there is no upper limit to a boiling point of the ionic liquid , and the thermal degradation thereof easily occurs at a high temperature , it is possible to ensure stability of a solvent even at a high temperature . in one example of the present invention , the ionic solvent suitable for the lactide synthesis includes 1 - butyl - 1 - methyl - azepanum bis ( trifluoromethylsulfonyl ) imide ; 1 - butyl - 1 - methyl - azepanum dicyanamide ; 6 - azonia - spiro [ 5 , 6 ] dodecan bis ( trifluoromethylsulfonyl ) imide ; 6 - azonia - spiro [ 5 , 6 ] dodecan dicyanamide ; 1 - benzyl - 3 - methylimidazolium chloride 1 - butyl - 1 , 3 - dimethylpiperidinium bis ( trifluoromethylsulfonyl ) imide ; 1 - butyl - 1 , 3 - dimethylpiperidinium dicyanamide ; 1 - butyl - 3 - methylimidazolium bis ( trifluoromethylsulfonyl ) imide ; 1 - hexyl - 3 - methylimidazolium chloride ; 1 - ethyl - 3 - methylimidazolium bis ( trifluoromethylsulfonyl ) imide ; 1 - butyl - 3 - methylimidazolium tetrafluoroborate ; 1 - ethyl - 3 - methylimidazolium acetate ; 1 - ethyl - 3 - methylimidazolium thiocyanate ; 1 - ethyl - 3 - methylimidazolium ethylsulfate ; n , n - dimethylethanolamine acetate and combinations thereof , but is not limited thereto . any known ionic solvent can be used , with preferred ionic solvents being those that have a boiling point of about 200 ° c . or greater , which is the temperature at which reaction yield increases . as such , reaction yield can be increased while ionic solvent is removed and recovered . in addition , in the case where the synthetic reaction is carried by adding lactic acid oligomers to an ionic solvent , it is possible to reduce the amount of the ionic solvent . generally , the present invention adds the ionic solvent in a low amount of about 20 parts by weight based on 100 parts by weight of the lactic acid oligomers , while still making it possible to synthesize lactide at a high yield . while the present method allows for the addition of such small amounts of ionic solvent , there is no limitation to the amount of ionic solvent added . thus , for example , it is possible to synthesize lactide by reacting lactic acid oligomers in the presence of an excessive amount of ionic solvent . in an exemplary embodiment of the present invention , when the lactic acid oligomers are used in the step ( a ), lactide can be synthesized by using the lactic acid oligomers having a molecular weight of about 600 to 9000 g / mol . in an exemplary embodiment of the present invention , a catalyst is further added to the step of lactide synthesis . any suitable catalysts can be used in the method of the present invention and preferably , the catalyst is selected from the group consisting of al ( iso - pro ) 3 ; al ( ethyl acetoacetate ) 3 ; al ( alo ( iso - pro )) 3 ; ti ( iso - pro ) 4 ; ti (( iso - pro ) 2 ( acethylacetonate )) 2 ; ti ( acethylacetonate ) 4 ; zn ( hexanoate ) 2 ; zn ( stearate ) 2 ; zn ( naphthenate ) 2 ; zncl 2 ; zno ; zr ( n - pro ) 4 ; zro ( stearate ) 2 ; zr ( acethylacetonate ) 4 ; zr ( n - buo ) 3 ( acethylacetonate ); zro ( aco ) 2 ; zro ( oh ) 2 ; zro 2 ; sn ( octoate ) 2 ; and combinations thereof . in general , any catalysts that include a metal such as ti , zn , zr , sn or al and are capable of increasing a reaction yield can be used . in an exemplary embodiment of the present invention , it is possible to continuously synthesize lactide by sequentially adding the lactic acid oligomers after the synthesis of lactide is completed . further , according to the present method , the ionic liquid does not participate in the synthetic reaction , and thus , it can be used sequentially in the following continuous reactions . because the ionic liquid exists in a liquid state at room temperature , simple washing of a reactor can be optionally carried out by using the ionic liquid as a medium . the term “ simple washing ” as used herein refers to simple rinse - out rather than a complicated washing of the whole reactor that is typically required of a reactor in which lactide is prepared . therefore , the present invention provides an eco - friendly method for preparing lactide which is characterized by minimizing unnecessary processing , such as reactor washing , and which reduces the amount of a solvent used in the reaction . the following examples illustrate the invention and are not intended to limit the same . lactic acid oligomers were prepared by using lactic acid monomer at 150 ° c ., 0 . 3 atm ( 228 mmhg ) for 2 hours , and then , based on 100 parts by weight of the lactic acid oligomers that would be converted into lactide , 50 parts by weight of 1 - butyl - 3 - methylimidazolium chloride as an ionic liquid were added thereto . after that , 0 . 05 parts by weight of zno as a catalyst was added to the resulting mixture based on 100 parts by weight of the lactic acid oligomers , followed by performing the synthetic reaction of lactide at 150 ° c ., 0 . 05 atm ( 38 mmhg ) for 2 hours . after the synthetic reaction was completed , lactide was obtained with a yield of 80 % or greater , and the reaction was progressed continuously . lactic acid oligomers were prepared by using lactic acid monomers at 150 ° c ., 0 . 3 atm ( 228 mmhg ) for 2 hours , followed by introducing the lactic acid oligomers into a reactor where lactide was synthesized by using 1 - butyl - 3 - methylimidazolium chloride . under the same conditions of lactide synthesis as described in example 1 , lactide was continuously synthesized for 2 hours . after the synthetic reaction was completed , lactide was obtained as the amount of the lactic acid oligomers added thereto ( i . e ., lactide was produced in about the same amount as the lactic acid oligomers used ). in particular , the lactide was produced with a yield of greater than about 80 % of the amount of oligomer added after the production of the first lactide . lactide was synthesized according to the same conditions as described in example 1 except that lico 3 was used as a catalyst . after the synthetic reaction was carried out 2 hours , lactide was synthesized with a yield of 85 % or greater ( wherein the yield is the amount of lactide synthesized based on the amount of lactic acid oligomers used ). lactide was synthesized according to the same conditions as described in example 1 except that 1 - butyl - 3 - methylimidazolium chloride as an ionic liquid was used in an amount of 30 pats by weight based on 100 parts by weight of the lactic acid oligomers . after the synthetic reaction was carried out 2 hours , lactide was synthesized with a yield of 80 % ( based on the amount of lactic acid oligomers added ). lactic acid oligomers were prepared by using lactic acid monomers at 150 ° c ., 0 . 3 atm ( 228 mmhg ) for 2 hours , and zno as a catalyst was added thereto in an amount of 0 . 05 wt % based on the amount of lactic acid oligomers . the resulting mixture was subjected to a lactide synthetic reaction at 150 ° c ., 0 . 05 atm . the synthetic reaction was carried out 1 hour , but there was little synthetic reaction . the yield ( lactide ) of the synthesis was about 15 % ( based on the amount of lactic acid oligomer added ), and the majority reaction product was lactic acid ( i . e . a majority of the remaining 85 % produced by the reaction ). in particular , 15 % of lactide was produced from the initial input of oligomers and most of the remainder is present in the oligomer state . after the reaction according to comparative example 1 was completed , the resulting mixture was subjected to a further reaction at 160 ° c . for 3 hours . as a result , about a 15 % yield of lactide was synthesized ( based on the amount of lactic acid oligomer added ). however , no additional synthetic reaction occurred . lactic acid oligomers were prepared by using lactic acid monomer at 150 ° c ., 0 . 3 atm ( 228 mmhg ) for 2 hours , and zno as a catalyst was added thereto in an amount of 0 . 05 wt % based on the amount of lactic acid oligomer . the resulting mixture was subjected to a lactide synthetic reaction at 205 ° c . and 0 . 05 atm or lower . after the synthetic reaction was carried out 2 hours , lactide was synthesized with a yield of 80 % ( based on the amount of lactic acid oligomers added ). as demonstrated , the preparation method of the present invention was capable of consecutively synthesizing lactide with a yield of about 85 % or greater ( based on the amount of lactic acid oligomers added ) at a reaction temperature of about 150 ° c . on the other hand , the preparation method according to comparative examples was capable of merely synthesizing lactide with a yield of about 15 % at a reaction temperature of about 160 ° c . in a non - consecutive manner , and could only non - consecutively synthesize lactide with a yield of 85 % of greater at a reaction temperature of about 205 ° c . the invention has been described in detail with reference to exemplary embodiments thereof . however , it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention , the scope of which is defined in the appended claims and their equivalents . | 2 |
for the envisaged therapeutical uses , hgf from different sources can be used , for example from animal or human organs or from prokaryotic or eukaryotic cells transformed with genes coding for hgf . by the term hgf , an activated form of hgf is obviously meant , such as described in example 1 and 6 . the use of human recombinant hgf is preferred , but the invention also applies to all the possible variants of hgf , including any deletion and / or substitution mutant forms . the hepatocyte growth factors will be formulated in dosage forms suitable to the administration of protein substances . the formulations of the invention therefore will be administered preferably by the parenteral route and they can be prepared using conventional techniques and excipients , as described for example in remington &# 39 ; s pharmaceutical sciences handbook , mack pub . co ., n . y ., usa . anyhow , other administration routes already suggested for protein active principles , such as the nasal , sublingual , rectal and oral routes , cannot be excluded . for the latter , the active principle will suitably be protected from metabolic degradation making use of known techniques , for example the inclusion in liposome vesicles . the hgf dosage , according to the invention , may vary within wide ranges , for example from about 0 . 01 mg to about 10 mg of hgf , one or more times daily . the following examples further illustrate the invention . full - length hgf cdna was cloned from human liver mrna and inserted into the baculovirus transfer vector pvl1393 ( invitrogen , san diego , calif .). the recombinant vector was cotransfected with the bsul - digested bacpak6 viral dna ( clontech laboratories , palo alto , calif .) into spodoptera frugiperda insect cells ( sf9 ) by the lipofectin procedure ( gibco - brl , gaithersburg , md .). positive clones were identified and purified by dot - blot hybridization and plaque assay . the recombinant virus was used to infect sf9 cells with dilutions of 10 - 1 , 10 - 2 , 10 - 3 , 10 - 6 . after one week , the infected cell extracts were blotted on a nylon filter and probed with radiolabelled full - length human hgf cdna . the viruses containing the hgf cdna gene were subsequently purified by plaque assay . single viral clones were isolated and used for large scale infection of sf9 cells . the recombinant factor was purified by affinity chromatography on heparin ( biorad laboratories , hercules , calif . ), according to the procedure published by weidner et al ., 1990 , with some modifications . sf9 spodoptera frugiperda cells were grown at 27 ° c . in serum - free sf900 medium ( gibco ltd , scotland ). exponentially growing cultures were infected by adding the viral stock in serumfree culture medium , and the cells were grown for 3 days . the culture medium was then collected and was incubated overnight in the presence of 3 % foetal calf serum at 37 ° c ., to ensure full activation of the precursor ; it was then spun at 300 × g for 15 min , to remove cellular debris , and cleared by centrifugation at 10 , 000 × g for 1 h . the supernatant was buffered to ph = 7 . 4 with tris , supplemented with a mixture of protease inhibitors ( 1 mm pmsf , 50 μg / ml leupeptin , 10 μg / ml aprotinin , 4 μg / ml pepstatin ) and the detergent chaps to a final concentration of 0 . 2 % w / v , filtered on a 0 . 45 μm pore tuffryn membrane filter ( gelman sciences , ann arbor , mich .) by vacuum suction , cooled to 4 ° c . and applied to a 5 ml heparin - agarose column assembled in an fplc apparatus in the cold room with a loading rate of 8 ml / h . the column was sequentially washed with 0 . 15 m nacl , 50 mm tris - hcl ph = 7 . 4 , 0 . 2 % chaps and 0 . 5 m nacl , 50 mm tris - hcl ph = 7 . 4 , 0 . 2 % chaps until the eluant absorbance returned to the baseline . bound materials were eluted with a linear gradient from 0 . 5 m to 1 . 8m nacl over 8 h in 50 mm tris - hcl ph = 7 . 4 , chaps 0 . 2 %, with a flow rate of 0 . 2 ml / min , and 2 ml fractions were collected . the starting material , the column breakthrough and washings , and the eluted fractions , were scored for the content of hgf by the mdck scattering assay ( weidner et al ., 1990 ; naldini et al ., 1992 ). the fractions containing the peak of hgf activity , eluting at approximately 1m nacl , were pooled , concentrated with a diafiltration device with 30 , 000 molecular weight cut off ( amicon div ., grace industrial , switzerland ), checked for biological activity on mdck cells , and purity by sds - page and protein stains , to give pure hgf with an average yield of the procedure of 150 μg from 700 ml of culture supernatant . production of human recombinant pro - hgf in insect cells . hgf cdna was cloned from human liver mrna ( naldini et al ., 1991a ) and inserted as a bamhi - ecori fragment into the baculovirus transfer vector pvl1393 ( invitrogen ). the recombinant vector was co - transfected with the bsui - digested bacpak6 viral dna ( clontech ) into spodoptera frugiperda insect cells ( sf9 ), by the lipofectin procedure . positive viral clones isolated by dot - blot hybridization and plaque assay were used for large scale infection . hgf was obtained from culture supernatant of sf9 infected cells 72 hours post - infection , by affinity chromatography on a heparin - sepharose fplc column ( biorad ), eluted with a linear 0 . 5 - 1 . 8 m nacl gradient . the unprocessed recombinant factor ( pro . sup .• hgf ) was detected by comassie blue staining as a band of 90 kda in sdspage . protein concentration was estimated by comassie blue staining and comparison with a standard curve obtained with increasing amounts of bovine serum albumin . the effect of hgf on the growth and differentiation of hematopoietic progenitors was evaluated in colony formation assays . heparinized samples of bone marrow , fetal umbilical cord blood and adult peripheral blood , obtained from volunteers , were diluted with an equal volume of phosphate buffered saline ( pbs ), and separated by ficoll - hypaque 1077 sd ( pharmacia ) density gradient centrifugation at 550 g for 30 minutes . light - density mononuclear cells ( ld - mc ) were collected , washed twice in pbs and resuspended in iscove modified dulbecco &# 39 ; s medium ( imdm ) ( gibco ) supplemented with 5 % fetal calf serum ( fcs ). mononuclear adherent cells were then removed by a two steps incubation of 30 minutes each in plastic flasks at 37 ° c . mononuclear non - adherent cells ( mnac ) were incubated with neuraminidase - treated sheep erythrocytes for 15 minutes at 37 ° c ., centrifuged and incubated for 45 minutes at 4 ° c . t - lymphocyte - depleted mnac were separated by ficoll - hypaque 1077 sd ( pharmacia ) density gradient centrifugation . t - lymphocyte - depleted mnac were then incubated for 45 minutes at 4 ° c . with the following antibodies : anti - cd3 , anti - cd4 , anti - cd8 , anticd11 , anti - cd19 , anti - cd57 ; most of the remaining b - and t - lymphocytes , monocytes and granulocytes were thus removed by incubation for 45 min . at 4 ° c . with immunomagnetic beads coated with anti - mouse igg ( m - 450 dynabeads , dynal ), subsequently collected by a magnet ( mpc - 1 dynabeads , dynal ). a positive selection of the cd34 + cells was then performed : cells were incubated with an antibody anti - cd34 ( my - 10 ; technogenetics ) for 45 minutes at 4 ° c ., then for 45 minutes at 4 ° c . with immunomagnetic beads coated with anti - mouse igg ; a 4 : 1 beads / cell ratio was found to provide the best recovery . cd34 + cells bound to the beads were then collected by a magnet and resuspended in imdm supplemented with 10 % fcs . an overnight incubation at 37 ° c . was then performed ; to allow cd34 + cells detachment , the beads were subjected to shearing forces by repeated flushing through a pasteur pipette . further details about the negative / positive double selection procedure used have been published previously ( bagnara et al ., 1991 ). the recovered cells were morphologically unidentifiable blast elements on may - grunwald - giemsa staining , slightly contaminated by promyelocytes . flow cytometry analysis indicated that the percentage of cd34 + cells in the selected cell preparations varied between a minimum of 30 % ( when the starting material was bone marrow ) and a maximum of 50 % ( when the starting material was peripheral blood ). contamination by cd4 +, cd2 +, cd16 + or cd19 + cells was constantly below 1 %. the colony assay for erythroid burst - forming units and for multipotent colony - forming units ( cfu - gemm ) was performed according to iscove et al ., 1974 . cord blood , bone marrow or peripheral blood cd34 + cells were plated in 24 - well cell culture clusters ( costar ), at a density of 2 . 5 × 10 3 cells / well , in a medium containing imdm , 30 % fcs , 2 × 10 - 4 m hemin , 5 × 10 - 5 β - mercaptoethanol and 0 . 9 % methylcellulose . the cells were stimulated with the following growth factors alone or in combination : epo 2 ng / ml , il - 3 2 ng / ml , gh - csf 50 ng / ml , scf 20 ng / ml , pro - hgf 2 , 10 or 40 ng / ml . colonies scored positive only when dark - red and containing more than four aggregates . the assay for the 14 - day granulo - monocyte colony - forming units ( cfu - gm ) was performed as previously described ( iscove et al ., 1971 ). cord blood , bone marrow or peripheral blood cd34 + cells were plated in 24 - well cell culture clusters ( costar ), at a density of 2 . 5 × 10 3 cells / well , in a medium containing imdm , 20 % fcs , 0 . 3 % noble agar ( difco ) and the following growth factors alone or in combination : il - 3 2 ng / ml , gm - csf 50 ng / ml , scf 20 ng / ml , pro - hgf 2 , 10 or 40 ng / ml . for the megakaryocyte colony - forming unit ( cfu - meg ) assay , plasma clot assay was performed according to vainchenker et al ., 1979 . cord blood , bone marrow or peripheral blood cd34 + cells were plated in 24 - well cell culture clusters ( costar ), at a density of 2 . 5 × 10 3 cells / well , in a medium containing imdm , 20 mg / ml l - asparagine ( sigma ), 3 . 4 mg / ml cacl 2 , 10 % bovine plasma citrated ( gibco ), 1 % detoxified bovine serum albumin ( bsa , fraction v chon ) ( sigma ), 10 % of heat - inactivated human ab serum and the following growth factors alone or in combination : il - 3 2 ng / ml , gm - csf 50 ng / ml , scf 20 ng / ml , pro - hgf 2 , 10 or 40 ng / ml . after 12 days of incubation , the plasma clot was fixed in situ with methanol - acetone 1 : 3 . for 20 minutes , washed with pbs and air dried . fixed plates were stored at - 20 ° c . until immunofluorescence staining was performed ; cfu - meg colonies were scored as aggregates of 3 - 100 cells intensively fluorescent to monoclonal antibody cd41 ( immunotech ) directed against the iib / iiia glycoprotein complex . binding was shown by fluorescein - conjugated goat anti - mouse ig ( becton dickinson ). the results are schematized in fig1 and 2 , and they show that , in the presence of standard concentrations of erythropoietin ( 2 ng / ml ), hgf dramatically increased the number of colonies derived from the bfu - e precursors ( fig1 ). hgf also stimulated the growth of colonies derived from multipotent cfu - gemm progenitors . the number of colonies was comparable to that obtained by combining known hemopoietic factors such as gm - csf and interleukin - 3 ( gasson , 1991 ; miyajima et al ., 1993 ). it should be noted , however , that the hgf effect was restricted to the stimulation of cfu - gemm and bfu - e . neither granulo - monocytic nor megakaryocytic colonies were ever observed in response to hgf . the response to hgf was dose - dependent and could be observed at concentrations of hgf as low as 5 pm both in erythroid and multipotent colonies ( fig2 ). the hgf action was also studied on cd34 + foetal hematopoietic progenitors , enriched from human umbilical cords blood . it is known that this population contains a percentage of primitive stem cells higher than the population purified from adult bone marrow or peripheral blood ( broxmeyer et al ., 1992 ; lu et al ., 1993 ). as observed in the case of adult hematopoietic progenitors , hgf stimulated both bfu - e and cfu - gemm derived colonies . in the presence of both hgf and stem cell factor ( scf ), a significant increase in the number of cfu - gemm - derived colonies was observed ( fig3 ). in this case , fewer erythroid colonies could be seen compared to those developed in the cultures stimulated by hgf alone . this suggests that the combination of hgf and scf preferentially affects proliferation of multipotent progenitors . the erythroid colonies grown in the presence of both growth factors were extremely large and showed a high hemoglobin content . the size of cfu - gemm derived colonies grown in these conditions was also increased and , within each colony , the erythroid lineage was predominant . in these assays hgf did not synergize with gm - csf and interleukin - 3 , either tested individually or in combination . expression of the hgf receptor in a subpopulation of adult hematopoietic progenitors ( cd34 +). the presence of hgf receptor at the surface of hematopietic progenitors was studied by flow cytometry analysis of bone marrow and peripheral blood mononuclear cells . monoclonal antibodies directed against extracellular epitopes of the hgf receptor β chain were used . a small but clearly identifiable subpopulation of bone marrow cells stained positive for the hgf receptor ( table ). ______________________________________ phenotype positive cells % ______________________________________a . unfractionated hgf - r + 0 . 6 ± 0 . 1 bone marrow hgf - r +/ cd34 + 0 . 3 ± 0 . 05 hgf - r +/ cd34 - 0 . 3 ± 0 . 1 hgf - r +/ scf - r + 0 . 2 ± 0 . 1 hgf - r +/ scf - r - 0 . 4 ± 0 . 1 b . cfu - gemm - derived hgf - r + 15 . 3 ± 1 . 5 colonies c . bfu - e - derived hgf - r + 9 . 7 ± 1 . 2 colonies______________________________________ about half of the cells expressing the hgf receptor also co - expressed the cd34 marker and could thus be identified as hematopoietic - progenitors . as described above , hgf synergized with the scf in stimulating the growth and differentiation of cfu - gemm derived colonies . in line with this observation , a subpopulation of cells co - expressing the hgf and the scf receptors was identified using a monoclonal antibody against extracellular epitopes of the scf receptor . similar results were obtained by flow cytometry analysis of cd34 + progenitors circulating in the peripheral blood . flow cytometry analysis with anti - hgf - receptor antibodies was also performed on cells harvested from the colonies developed in vitro in response to hgf . the table shows that hgf - receptor positive cells were present . expression of hgf and its receptor during the embryonal development of hematopoietic cells . the expression of the hgf receptor was studied in embryonal hematopoietic cells by in situ hybridization of histological sections of mouse embryos . using an antisense met probe , the hgf receptor mrna could be clearly detected in megaloblastic cells located within the cavity of the developing heart and aorta from 10 - 10 . 5 days post coitum . specific mrna could be detected in the hepato / biliary primordium , which at this stage contains hemopoietic precursors . in this developing organ erythroid islands showed a higher levels of hgf receptor mrna , compared with the level of expression observed in the surrounding hepatocytes . from 11 days post coitum the hematopoietic embryonal liver also expressed hgf mrna . in order to prove the mobilization of the bone marrow hemopoietic precursors at the peripheral blood , the murine model has been used . balb / c mice were treated subcutaneously for 4 days with hgf at varied concentrations or with control preparations . at the end of the treatment , mice were killed , the circulating leukocytes were counted and hemopoietic colonies from peripheral blood were cultured . in hgf - treated mice , contrary to the untreated controls , an about 60 % increase in circulating leukocytes was observed as well as an increase in the colonies obtainable from peripheral blood . this phenomenon has an intensity comparable with that of g - csf , already described and used to mobilize bone marrow hematopoietic precursors ( janssen , w . e ., et al ., prog . clin . biol . res . 389 : 429 - 39 ). using in the colony formation assay on cd34 + cells of example 3 equimolecular amounts of activated hgf , obtained according to example 1 , instead of pro - hgf , statistically similar results have been obtained in the colonies count as shown in the enclosed fig4 . 1 . bagnara , g . p ., g . zauli , l . vitale , p . rosito , v . vecchi , g . paolucci , g . c . avanzi , u . ramenghi , f . timeus , and v . gabutti , 1991 . in vitro growth and regulation of bone marrow enriched cd34 + hematopoietic progenitors in diamond - blackfan anemia . blood . 78 ; 2203 - 2210 . 2 . boccaccio , c ., g . gaudino , g . gambarotta , f . galimi , and p . m . comoglio . 1994 . hepatocyte growth factor receptor expression is inducible and is part of the delayed - early response to hgf . j . biol . chem . in press . 3 . bottaro , d . p ., j . s . rubin , d . l . faletto , a . m . l . chan , t . e . kmiecick , g . f . vande woude , and s . a . aaronson . 1991 . identification of the hepatocyte growth factor receptor as the c - met proto - oncogene . science . 251 : 802 - 804 . 4 . broxmeyer , h . e ., hangoc , g ., cooper , s ., riberio , c ., greaves , v ., yoder , m ., wagner , j ., vadhan - raj , s ., benninger , l ., rubinstein , p ., and randolph brown e . 1992 . growth characteristics and expansion of human umbilical cord blood and estimation of its potential for transplantation in adults . proc . natl . sci . ( usa ) 89 : 4109 - 4113 . 5 . broxmeyer , e . h ., r . maze , k . miyazawa , c . carow , p . c . hendrie , s . cooper , g . hangoc , s . vadham - raj , and l . lu . 1992 . the c - kit receptor ands its ligand , steel , as regulators of hemopoiesis . cancer cells . 3 : 480 - 487 . 6 . bussolino , f ., m . f . di renzo , m . ziche , e . bocchietto , m . oliviero , l . naldini , g . gaudino , l . tamagnone , a . coffer , and p . m . comoglio . 1992 . hepatocyte growth factor is a potent angiogenic factor which stimulates endothelial cell motility and growth . j . cell . biol . 119 : 629 - 641 . 7 . clark , s . c ., and r . kamen . 1987 . the human hematopoietic colony - stimulating factors . science . 236 : 1229 - 1237 . 8 . di renzo , m . f ., r . p . narsimhan , m . olivero , s . bretti , s . giordano , e . medico , p . gaglia , p . zara , and p . m . comoglio . 1991 . expression of the met / hgf receptor in normal and neoplastic human tissues . oncogene . 6 : 1997 - 2003 . 9 . galimi , f ., brizzi , m . f ., comoglio , p . m ., 1993 . the hepatocyte growth factor and its receptor . stem cells ii suppl 2 , 22 - 30 . 10 . gasson , j . 1991 . molecular physiology of granulocyte - macrophage colony - stimulating factor . blood . 77 : 1131 - 1145 . 11 . gherardi , e ., j . gray , m . stoker , m . perryman , and a . furlong . 1989 . purification of scatter factor , a fibroblast basic protein that modulates epithelial interactions and movement . proc . natl . acad . sci . usa . 86 : 5844 - 5848 . 12 . giordano , s ., c . ponzetto , m . f . di renzo , c . s ., cooper , and p . m . comoglio . 1989a . tyrosine kinase receptor indistinguishable from the c - met protein . nature . 339 : 155 - 156 . 13 . giordano , s ., m . f . di renzo , r . narshimhan , c . s . cooper , c . rosa , and p . m . comoglio . 1989b . biosynthesis of the protein encoded by the c - met proto - oncogene . oncogene . 4 : 1383 - 1388 . 14 . giordano , s ., z . zhen , e . medico , g . gaudino , f . galimi , and p : m : comoglio . 1993 . transfer of the motogenic and invasive response to scatter factor / hepatocyte growth factor by transfection of the human c - met protooncogene . prac . natl . acad . sci . usa . 90 : 649 - 653 . 15 . grant , d . s ., h . k . kleinman , i . d . goldberg , m . bhargava , b . j . nickoloff , j . l . kinsella , p . j . polverini , and e . m . rosen . 1993 . scatter factor induces blood vessel formation in vivo . proc . natl . acad . sci . usa . 90 : 1937 - 1941 . 16 . halaban , r ., j . f . rubin , y . fusanaka , m . cobb , t . boulton , d . faletto , e . rosen , a . chan , k . yoko , w . white , c . cook , and g . moellmann . 1992 . met and hepatocyte growth factor / scatter factor signal transduction in normal melanocytes and melanoma cells . oncogene . 7 : 2195 - 2206 . 17 . iscove , n . n ., s . senn , j . e till , and e . a . mcculloch . 1971 . colony formation by normal and leukemic human marrow cells in culture : effect of conditioned medium from human leukocytes . blood . 37 : 1 - 5 . 18 . iscove , n . n ., f . sieber , and h . winteralter . 1974 . erythroid colony formation in cultures of mouse and human bone maroow : analysis of the requirement for erythropoietin by gel filtration and affinity chromatography on agarose - concanavalin a . j . cell . physiol . 83 : 309 - 320 . 19 . kan , m ., g . h . zhang , r . zarnegar , g . michalopoulos , y . myoken , w . l . mckeehan , and j . l . stevens . 1991 . hepatocyte growth factor / hepatopoietin a stimulates the growth of rad kidney proximal tubule epithelial cells ( rpte ), rat nonparenchymal liver cells , human melanoma cells , mouse keratinocytes and stimulates anchorage - independent growth of sv40 - transfomed rpte . biochem . biophys . res . commun . 174 : 331 - 331 . 20 . kmiecik , t . e ., i . r . kelleer , e . rosen , and g . f . vande woude . 1992 . hepatocyte growth factor is a synergistic factor for the growth of hematopoietic progenitor cells . blood . 16 : 2454 - 2457 . 21 . koury , m . j ., and m . c . bondurant . 1990 . erythropoietin retards dna breakdown and prevents programmed death in erythroid progenitor cells . science . 248 : 378 - 381 . 22 . lu , l ., m . xiao , r . n . shen , s . grisby , and h . e . broxmeyer . 1993 . enrichment , characterization and responsiveness of single primitive cd34 + human umbilical cord blood hematopoietic progenitors with high proliferative and replating potential . blood . 81 : 41 - 48 . 23 . matsumoto , k ., hashimoto , k . yoshikaua , and t . nakamura . 1991 . marked stimulation of growth and motility of human keratinocytes by hepatocyte growth factor . exp . cell . res . 196 : 114 - 120 . 24 . metcalf , d . 1984 . the hemopoietic colony stimulating factors . elsevier , amsterdam . 25 . metcalf , d . 1987 . the molecular control of cell division , differentiation , commitment and maturation in hemopoietic cells . nature . 339 : 27 - 30 . 26 . michalopoulos , g . k . 1990 . liver regeneration : molecular mechanisms of growth control . faseb j . 4 : 176 - 187 . 27 . miyajima , a ., a . l . mui , t . ogorochi , and k . sakamaki . 1993 . receptors for granulocyte - macrophage colony - stimulating factor , interleukin - 3 and interleukin - 5 . blood . 82 : 1960 - 1974 . 28 . miyazawa , k ., h . tsubouchi , d . naka , k . takahashi , h . okigaki , n . arakaki , h . nakayama , s . hirono , o . sakiyama , k . takahashi , e . godha , y . daikuhara , and n . kitamara . 1989 . molecular cloning and sequence analysis of cdna for human hepatocyte growth factor . biochem . biophys . res . commun . 163 : 967 - 973 . 29 . montesano , r ., k . matsumoto , t . nakamura and l . orci . 1991 . identification of a fibroblast - derived epithelial morphogen as hepatocyte growth factor . cell . 67 : 901 - 908 . 30 . nakamura , t ., t . nishizawa , m . hagiya , t . seki , m . shimonishi , a . sugimura , k . tashiro , and s . shimizu . 1989 . molecular cloning and expression of human hepatocyte growth factor . nature . 342 : 440 - 443 . 31 . naldini , l ., m . weidner , e . vigna , g . gaudino , a . bardelli , c . ponzetto , r . narshimhan , g . hartmann , r . zarnegar , g . michalopoulos , w . birchmeier , and p . m . comoglio . 1991a . scatter factor and hepatocyte growth factor are indistinguishable ligands for the met receptor . embo j . 10 : 2867 - 2878 . 32 . naldini , l ., e . vigna , r . p . narshiman , g . gaudino , r . zarnegar , g . michalopoulos , and p . m . comoglio . 1991b . hepatocyte growth factor ( hgf ) stimulates the tyrosine kinase activity of the receptor encoded by the proto - oncogene c - met . oncogene . 6 : 501 - 504 . 33 . park , m ., m . dean , k . kaul , m . j . braun , m . a . gonda , and g . f . vande woude . 1987 . sequence of met protooncogene cdna has features characteristic of the tyrosine kinase family of growth - factor receptors . proc . natl . acad . sci . usa . 84 : 6379 - 6383 . 34 . pepper , m . s ., k . matsumoto , t . nakamura , l . orci , and r . montesano . 1992 . hepatocyte growth factor increases urokinase - type plasminogen activator ( μ - pa ) and μ - pa receptor expression in madin - darby canine kidney epithelial cells . j . biol . chem . 267 : 20493 - 20496 . 35 . prat , m ., r . p . narsimhan , t . crepaldi , m . r . nicotra , p . g . natali , and p . m . comoglio . 1991a . the receptor encoded by the human c - met oncogene is expressed in hepatocytes , epithelial cells and solid tumors . int . j . cancer . 49 : 323 - 328 . 36 . rubin , j . s ., a . m . l . chan , d . p . bottaro , w . h . burgess , w . g . taylor , a . c . cech , d . w . hirschfield , j . wong , t . hiki , p . w . finch , and s . a . aaronson . 1991 . a broad - spectrum human lung fibroblast - derived mitogen is a variant of hepatocyte growth factor . proc . natl . acad . sci . usa . 88 : 415 - 419 . 37 . sonnenberg e ., d . meyer , k . m . weidner , and c . birchmeier . 1993 . scatter factor / hepatocyte growth factor and its receptor , the c - met tyrosine kinase , can mediate a signal exchange beyween mesenchyme and epithelia during mouse development . j . cell . biol . 123 : 223 - 235 . 38 . sporn , m . b ., and a . b . roberts . 1992 . transforming growth factor - β : recent progress and new challenges . j . cell . biol . 119 : 1017 - 1021 . 39 . stern , c . d ., g . w . ireland , s . e . herrick , e . gherardi , j . gray , m . perryman , and m . stoker . 1990 . epithelial scatter factor , and m . stoker . 1990 . epithelial scatter factor , and m . stoker . 1990 . epithelial scatter factor and development of the chick embryonic axis . 110 : 1271 - 1284 . 40 . stoker , m ., e . gherardi , m . perryman , and j . gray . 1987 . scatter factor is a fibroblast - derived modulator of epithelial cell mobility . nature . 327 : 239 - 242 . 41 . vainchenker , w ., j . bouquet , j . guichard , and j . breton - gorius . 1979 . megakaryocyte colony formation from human bone marrow precursors . blood 59 : 940 - 945 . 42 . weidner , k . m ., j . behrens , j . vandekerckove , and w . birchmeier . 1990 . scatter factor : molecular characteristics and effect on the invasiveness of epithelial cells . j . cell . biol . 11 : 2097 - 2108 . 43 . weidner , k . m ., n . arakaki , j . vandekerchove , s . weingart , g . hartmann , h . rieder , c . fonatsch , h . tsubouchi , t . hishida , y . daikuhara , and w . birchmeier . 1991 . evidence for the identity of human scatter factor and hepatocyte growth factor . proc . natl . acad . sci . usa . 88 : 7001 - 7005 . | 0 |
the novel features believed characteristic of the invention are set forth in the appended claims . the invention will best be understood by reference to the following detailed description of illustrated embodiments when read in conjunction with the accompanying drawings , wherein like reference numerals and symbols represent like elements . fig1 - 3 together refer to an aromatherapy face mask , hereinafter referred to as face mask 10 . the face mask 10 has a face shield 12 that is infused with aromatherapy oils 30 and has two ear loops 26 coupled at opposite ends of the face shield 12 . fig1 is a perspective view of an embodiment of the face mask 10 of the present invention . in this embodiment , the face shield 12 is rectangular and the two ear loops 26 extend from opposite ends of the rectangular face shield 12 . each ear loop 26 has a first end coupled to a top corner 16 of the rectangular face shield 12 and a second end coupled to a bottom corner 18 of the rectangular face shield 12 . it should be clearly understood , however , that substantial benefit may be derived from the ear loops 26 being coupled to other suitable portions of the face shield 12 . the face mask 10 may also have a moldable nose piece 28 coupled along a top edge 14 of the rectangular face shield 12 . referring to fig2 , the face shield 12 is shown having three layers . the first layer 20 and the third layer 24 are both fluid - resistant . the second layer 22 is absorptive and is infused with essential aromatherapy oils 30 ( see fig1 ). here , the nose piece 28 is shown being coupled between the second layer 22 and the third layer 24 . fig3 shows the face mask 10 of fig1 in use by a user 32 . in this embodiment , the user 32 is a health care provider . however , it should be clearly understood that substantial benefit may be derived from a user 32 that is not a health care provider . the absorptive second layer 22 of the face shield 12 is infused with aromatherapy oils 30 . the user 32 will wear the face mask 10 by placing the third layer 24 of the face shied 12 against his / her face and looping the ear loops 26 around the user &# 39 ; s 32 ears . the user 32 will breathe in the scent of the aromatherapy oils 30 thus affecting the mood of the user 32 . the affect that the scent of the aromatherapy oils 30 have on the user 32 depends upon the scent of the oils 30 . some scents will affect the mood of the user 32 . for example , vanilla scent will have a soothing and calming effect , sweet orange scent will promote happiness and reduce anxiety , grapefruit scent will induce euphoria and relieve performance anxiety , and chamomile will promote peace and reduce tension . lemon scent will be refreshing and uplifting to the user 32 . and a combination of lavender and vanilla scents will help combat stress and relieve tension . other scents may be useful in combating symptoms of the user 32 . for example , peppermint scent may soothe a headache or clear the user &# 39 ; s 32 sinuses . a combination of lemon , grapefruit , and geranium scents will activate and balance the mind and emotions , and may help clear the user &# 39 ; s 32 head . while the invention has been particularly shown and described with reference to preferred embodiments thereof , it will be understood by those skilled in the art that the foregoing and other changes in form and details may be made therein without departing from the spirit and scope of the invention . | 0 |
for further illustrating the invention , experiments detailing a method for manufacturing a compound refractive lens for focusing x - rays in two dimensions are described below . it should be noted that the following examples are intended to describe and not to limit the invention . as shown in fig1 a - 2 b , a method for manufacturing a compound refractive lens for focusing x - rays in two dimensions , the method comprising the following steps : 1 ) preparation of a mother lens for the compound refractive lens for focusing x - rays : a ) using a glass substrate - chrome material to prepare a photolithographic mask of the mother lens by using an electron beam lithography ; the photolithographic mask of the mother lens comprising a plurality of first parabola - shaped holes and a plurality of square holes arranged coaxially at intervals ; a cross section of each of the first parabola - shaped holes being formed by connecting openings of two symmetrical parabolas ; equation of the two parabolas of the first parabola - shaped hole being represented by x 2 = 2rz , in which , r representing radius of curvature at the vertex of the parabolas ; x and z representing an x axis and a z axis in a rectangular coordinate system , respectively , as shown in fig1 ; a major axis and a minor axis of the first parabola - shaped hole being calculated by the above equation ; the number of the square holes being n , and a side length of the square hole being 1 + δ ; b ) cleaning a glass substrate ; c ) depositing a copper , aluminum , or gold film on the cleaned glass substrate as an electroforming cathode film using a sputtering method or an evaporation method ; d ) spin coating a layer of a bp212 positive photoresist on the electroforming cathode film ; baking , and curing the positive photoresist ; e ) spin coating a layer of a su - 8 photoresist having a thickness of 1 on the bp212 positive photoresist ; f ) exposing , developing , and hardening the coated su - 8 photoresist , and using the photolithographic mask of the mother lens prepared in step a ); g ) washing a first sample piece obtained from step f ), and removing an exposed bp212 positive photoresist from an upper surface ; h ) placing the first sample piece treated by step g ) in an electroforming solution for electroforming ; and the electroforming material being copper , nickel , iron , or chromium ; i ) taking the first sample piece out of the electroforming solution when a thickness of the electroforming metal is the same as the thickness of the su - 8 photoresist , that is 1 ; and washing the first sample piece to remove remaining electroforming solution ; j ) immersing the first sample piece in an acetone solution ; removing the bp212 positive photoresist and the su - 8 photoresist adhering on it to yield the mother lens of the compound refractive lens for focusing x - rays ; 2 ) preparation of a daughter lens for the compound refractive lens for focusing x - rays : k ) using a glass substrate - chrome material to prepare a photolithographic mask of the daughter lens by using the electron beam lithography ; the photolithographic mask of the daughter lens comprising a clamping arm and a plurality of square embedded lens bodies coaxially arranged on the clamping arm ; the number of the square embedded lens bodies is n , which is the same as the number of the square holes of the mother lens ; each of the square embedded lens bodies comprising a second parabola - shaped hole having a cross section formed by connecting openings of two symmetrical parabolas ; equation of the two parabolas of the second parabola - shaped hole being represented by y 2 = 2rz , in which , r representing radius of curvature at the vertex of the parabolas ; y and z representing a y axis and the z axis in a rectangular coordinate system , respectively , as shown in fig1 ; a major axis and a minor axis of the second parabola - shaped hole being calculated by the above equation ; a center of the second parabola - shaped hole and a center of the square embedded lens body coincide ; the square embedded lens body has a side length of 1 ; the square embedded lens body and the clamping arm are integrated as a whole body ; and a thickness of the clamping arm being t ; l ) cleaning a silicon substrate ; m ) spin coating a layer of bp212 photoresist on a surface of the cleaned silicon substrate ; and pre - baking to yield a second sample piece ; n ) depositing a copper , aluminum , or gold film on the second sample piece obtained from step m ) as an electroforming cathode film using the sputtering method or the evaporation method ; o ) spin coating a layer of kmp c5315 photoresist on the second sample piece from step n ); p ) spin coating a layer of su - 8 photoresist having a thickness of 1 on the second sample piece from step o ); q ) exposing , developing , and hardening the coated su - 8 photoresist , and using the photolithographic mask of the daughter lens prepared in step k ); r ) removing an exposed kmp c5315 photoresist from an upper surface using a degumming agent of kmp c5315 ; s ) placing the second sample piece treated by step r ) in an electroforming solution for electroforming ; and the electroforming material being copper , nickel , iron , or chromium but different from the material of the electroforming cathode film ; t ) taking the second sample piece out of the electroforming solution when a thickness of the electroforming metal is the same as the thickness of the su - 8 photoresist , that is 1 ; and washing the second sample piece to remove remaining electroforming solution ; u ) immersing the second sample piece in an acetone solution ; removing the kmp c5315 photoresist and the su - 8 photoresist adhering on it , and meanwhile removing the bp212 photoresist and the silicon substrate ; v ) removing the electroforming cathode film from the second sample piece after treatment of step u ) using a method of chemical etching to yield the daughter lens of the compound refractive lens for focusing x - rays ; and w ) placing the mother lens and the daughter lens beneath a microscope , finding and clamping the clamping arm of the daughter lens , aligning the square embedded lens bodies of the daughter lens with the square holes of the mother lens , respectively , for allowing the first parabola - shaped holes and the second parabola - shaped holes to form an orthogonal structure and allowing the n square embedded lens bodies of the daughter lens to fit the n square holes of the mother lens , respectively ; and inserting and pressing the square embedded lens bodies into the corresponding square holes , respectively . a distance between the center of the first parabola - shaped hole and the center of the square hole in step a ) is 1 . a distance between adjacent square embedded lens bodies in step k ) is 1 . the compound refractive lens for focusing x - rays of the example comprises : the glass substrate , the mother lens disposed on the glass substrate , and the daughter lens embedded in the mother lens ( as shown in fig1 ). the glass substrate functions a base of the compound refractive lens for focusing x - rays , and the manufacturing of the mother lens is performed on the glass substrate . the mother lens comprises a body material of the mother lens , and the first parabola - shaped cavities and the square cavities arranged in order at intervals on the body material . the square cavities are used for accommodating the daughter lens . the daughter lens comprises the clamping arm and the embedded lens bodies . the embedded lens bodies are in the square shapes ; and a second parabola - shaped cavity is disposed in a center of each of the square embedded lens bodies . the embedded lens bodies of the daughter lens are inserted into the square cavities of the mother lens from an upper of the mother lens . the first parabola - shaped cavity of the mother lens and a paraboloid of the second parabola - shaped cavity of the daughter lens achieve the refraction of the x - ray to focus the x - ray radiation along the minor axis of the parabola . the 2d focusing function of the compound refractive lens for focusing x - rays of the invention is realized by a plurality of the 2d focusing and refractive unit ( as shown in fig1 c ) which is formed by two perpendicularly arranged parabolas ( one is along a y axis , and the other is along an x axis ). an incident light of x - ray beam is radiated on the compound refractive lens for focusing x - rays along a z axis of a coordinate system , after being refracted by a plurality of the 2d focusing and refractive units , the x - ray exits from the compound refractive lens for focusing x - rays to form a 2d focal spot . a major axis of the first parabola - shaped hole and the second parabola - shaped hole is 42 μm , a minor axis is 32 μm , l is 50 μm , δ is 1 μm , n is 20 , and t is 50 μm . the material of the electroforming cathode film is copper ; and the electroforming material is nickel . as shown in fig1 a - 2 b , manufacturing steps of the compound refractive lens for focusing x - rays in two dimensions are the same as that of example 1 , except that a major axis of the first parabola - shaped hole and the second parabola - shaped hole is 242 μm , a minor axis is 222 μm , l is 250 μm , δ is 2 μm , n is 100 , and t is 100 μm . the material of the electroforming cathode film is aluminum ; and the electroforming material is nickel . as shown in fig1 a - 2 b , manufacturing steps of the compound refractive lens for focusing x - rays in two dimensions are the same as that of example 1 , except that a major axis of the first parabola - shaped hole and the second parabola - shaped hole is 200 μm , a minor axis is 180 μm , l is 210 μm , δ is 1 . 5 μm , n is 80 , and t is 80 μm . the material of the electroforming cathode film is gold ; and the electroforming material is iron . while particular embodiments of the invention have been shown and described , it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects , and therefore , the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention . | 6 |
please refer to fig3 through fig5 . fig3 through fig5 are perspective diagrams showing the means of fabricating a transistor containing suicides according to the present invention . as shown in fig3 , a substrate 200 is first provided and a gate structure having a gate dielectric layer 202 and a gate 204 is formed over the surface of the substrate 200 , in which the gate 204 is composed of conductive materials such as doped polysilicon . next , a lightly doped ion implantation is performed to implant a light dopant ( not shown ) into two sides of the substrate 200 corresponding to the gate 204 to form a source / drain extension region 210 by utilizing the gate 204 as a mask . next , a liner 206 , such as a silicon oxide layer , is deposited around the gate structure and a spacer 208 is formed over the surface of the liner 206 , in which the spacer 208 is composed of a silicon oxide offset spacer and a silicon nitride spacer . next , a heavily doped ion implantation is performed to implant a heavy dopant ( not shown ) into the substrate 200 to form a source / drain region 212 with heavier dopant concentration by utilizing the gate 204 and the spacer 208 as a mask . next , a thermal annealing process utilizing a temperature ranging from 1000 ° c . to 1020 ° c . is performed to activate the dopants within the substrate 200 and repair the damage of the crystal lattice structure of the substrate 200 during the ion implantation process . next , a low temperature selective epitaxial growth ( seg ) is performed to form an epitaxial layer 216 over the surface of the source / drain extension region 210 and the source / drain region 212 , in which the epitaxial layer 216 is composed of silicon germanium , as shown in fig4 . next , another ion implantation process is performed to implant a retarded dopant 214 , such as fluoride ions , nitrogen , and oxygen , into the junction area between the epitaxial layer 216 and the source / drain region 212 and the gate 204 to form a retarded interface layer . alternatively , depending on the retarded property of the dopants , a surface treatment , such as an ion implantation process , a plasma treatment , or a gas or liquid treatment containing high concentration dopants with retarded property can be performed on the surface of the gate 204 , the source / drain extension region 210 , and the source / drain region 212 to form the retarded interface layer containing dopants with retarded effects before performing the low temperature selective epitaxial growth to form the epitaxial layer 216 . next , a surface cleaning process is performed to completely remove the native oxides and other impure materials remaining on the surface of the epitaxial layer 216 and a sputtering or deposition process is performed to form a metal layer ( not shown ) on the epitaxial layer 216 , in which the metal layer is composed of cobalt , titanium , nickel , platinum , palladium , and molybdenum . subsequently , as shown in fig5 , a rapid thermal process ( rtp ) is performed to react the metal layer with the epitaxial layer 216 deposited earlier to form a silicide layer 220 over the top of the gate 204 and the source / drain region 212 and the non - reacted portion of the metal layer is removed afterwards . since the dopants are implanted into the surface of the gate 204 and the source / drain region 212 via the ion implantation process performed earlier , the reaction between the metal layer and the epitaxial layer 216 will ideally stop at the retarded interface layer . in other words , the present invention is able to effectively utilize the location of the retarded interface layer and the thickness of the epitaxial layer 216 to accurately control the thickness and depth of the silicide layer 220 , thereby adjusting the contact resistance and improving conventional problems such as junction leakage , which is caused by an overly short distance between the source , drain , and substrate of the pn junction and the silicides , and nickel silicide piping effect , which is caused by the approach of suicides into the channel area during silicide reactions . additionally , since the epitaxial layer 216 will be reacted completely to form the silicide layer 220 , the present invention is able to replace the selectively epitaxial growth ( seg ) process described earlier with a low temperature selective polysilicon growth process to form a polysilicon layer over the surface of the source / drain extension region 210 and the source / drain region 212 . as shown in fig5 , after the fabrication process is completed , a transistor 222 having silicide structure is obtained , in which the transistor 222 includes a substrate 200 , a gate 204 formed on the substrate 200 , a gate dielectric layer 202 formed under the gate 204 , a spacer 208 formed over the surface of the sidewall of the gate 204 , a liner 206 formed between the sidewall of the gate 204 and the spacer 208 , and a suicide layer 220 formed on top of the gate 204 and two sides of the substrate 200 corresponding to the spacer 208 . additionally , a source / drain region 212 and a source / drain extension region 210 are formed within the substrate 200 . preferably , a retarded dopant 214 is included between the source / drain region 212 and the silicide layer 220 to form a retarded interface layer , in which the dopant is implanted by an ion implantation process and fluoride ions , nitrogen , and oxygen are utilized as the ion source . overall , the advantage of the present invention is to perform an ion implantation process before or after disposing an epitaxial layer on the top of the gate and the surface of the source / drain region . eventually , the retarded dopant injected is to be utilized as a retarded interface layer to stop the reaction of the salicide fabrication , thereby improving problems such as junction leakage , which is caused by an overly short distance between the source , drain , and substrate of the pn junction and the silicides , and nickel silicide piping effect , which is caused by the approach of suicides into the channel area during silicide reactions . additionally , a thicker epitaxial is formed over the surface of the gate and the source / drain region as the epitaxial layer will be reacted into a silicide layer in the final stage of the process , thereby reducing the sheet resistance of the source / drain region . consequently , the present invention is able to obtain a field effect transistor with much better ultra shallow junction structure and source / drain region with lower sheet resistance . those skilled in the art will readily observe that numerous modifications and alterations of the device and method may be made while retaining the teachings of the invention . accordingly , the above disclosure should be construed as limited only by the metes and bounds of the appended claims . | 7 |
the present invention describes an apparatus that permits the planting of salmonid and other fish eggs in stream and lake beds without the necessity of complex channels and permanent facilities such as hatchery buildings . also included is a method of planting fish eggs including salmon eggs without the use of difficult to prepare trenches and settling ponds . referring to fig1 the article of this invention is comprised of a hopper or bin 1 used as a receptacle for fertilized fish eggs . this hopper has an opening at its base 2 which permits the fertilized eggs to flow from the hopper . to regulate the flow of fertilized salmon eggs from the hopper and to prevent upflowing of water during flushing control valve 3 is utilized . the hopper 1 is connected with central chamber 4 . this chamber 4 has a pair of lateral openings 5 and 6 . lateral opening 6 is capped by cap 7 to prevent leakage of water . water is pumped from a water source , usually from upstream by means of a pump ( not shown ), into lateral opening 5 of central chamber 4 though perforations 8 . in order to regulate the flow of water , control valve 9 is employed . from the central chamber 4 the water , followed by the fertilized eggs , exits through opening 10 into a length of rigid hollow tubing 11 having a pointed base 12 for easy insertion into the stream bed substrates . during operation , valve 3 is in a closed position , while water is pumped into the hollow chamber 4 and is diverted down through the length of rigid hollow tubing 10 . the pressure of the water flushes the stream bed intragravel fines to loosen the gravel and remove life - smothering sediments . through the hydraulic pumping action , the device easily works its way into the gravel . when the apparatus is being used for desiltation and flushing alone , higher water flows are often desirable . in that case , the main valve is opened wide and the pump achieves maximum rpm . during egg deposition , however , water flows are restricted and probing is executed so as to prevent flushing out of previously deposited eggs in gravels adjacent to the planting plot . thus , once an appropriate depth is reached and proper flushing of the silt and fines from the substrate has been achieved , the control valve 9 is placed in a reduced flow or closed position . fertilized salmon eggs are introduced into the hopper 1 and permitted to flow down rigid hollow tube 11 by opening control valve 3 . once the eggs have settled to the base of tube 11 , the apparatus is gently withdrawn from the substrate permitting the eggs to mix with the gravel . a detailed view of the preferred embodiment of the present invention wherein a plurality of planters are joined to permit a multiplicity of simultaneous plantings is shown in fig2 . in this embodiment there is exhibited a plurality of interconnected hoppers 20 - 23 preferably 2 to 6 with splash baffles 24 - 26 containing , preferably , periodically placed , 3 / 16 inch perforations at the point of connection . these hoppers have an opening at their respective bases 27 - 30 . attached to each hopper opening between the hopper and the hollow chamber 35 - 38 are control valves 31 - 34 . each chamber has a pair of lateral openings 39 - 40 , 41 - 42 , 43 - 44 , 45 - 46 . lateral opening 39 is capped by cap 47 . opening 40 of chamber 35 is connected to opening 41 of chamber 36 . opening 42 of chamber 36 is connected to opening 43 of chamber 37 and opening 44 of chamber 37 is attached to opening 45 . joinder may be accomplished by any appropriate means provided it is sufficiently strong to withstand the pressure exerted by the water without leaking . water is pumped into lateral opening 46 from the water source . flow of the water is regulated by control valve 48 . these valves can be , for example , either a ball or gate valve . connected to the base of each central chamber 35 - 38 is a length of rigid hollow tubing 49 - 52 . this tubing is preferably 1 inch diameter polyvinyl chloride ( pvc ) pipe , however , other suitable materials may be employed . in order to prevent distortion of the rigid tubing during insertion , 4 - way &# 34 ; t &# 34 ; stiffness 53 - 56 may be employed . however , suitable reinforcement may be obtained from numerous other materials . during operation , after the water has been pumped through the device and has sufficiently loosened the gravel and removed sediment , the eggs in each hopper may be planted in unison or each bin may be planted in succession depending upon the operator &# 39 ; s preference . the operation of the multiple planting device is the same as the single device . fig3 is a cutaway view of a hollow chamber 36 shown in fig2 giving a detailed view of the interior with the perforations 57 . these perforations permit water to flow through the hollow tubing but prevent the fertilized eggs from becoming entrapped in the central chamber . the splash baffles 24 between hoppers 20 and 21 are also shown . the article of the present invention and the accompanying method may be used to plant in either stream beds or lake beds . in addition to salmon , this invention is useful in the planting of eggs of other salmonid species such as trout and steelhead . besides the two primary functions of the salmonid egg planting device , hydraulic flushing of sediments and deposition of fertilized salmonid eggs , this invention is instrumental in the removal of redeposited siltation on the surface of the stream bed after egg deposition and the injection of nutrients into the water and / or incubation gravel . also the invention may be used in the removal of adult predators and larvae predators either prior to deposition or during incubation . by repeating this sequence of flushing and deposition , the stream or lake bed can be seeded to any desired egg density . the density , however , is dependent upon substrate geomorphology which includes , for example , the following variables , rubble size , size / abundance ratios and the composition of the rubble , depth and degree of aqueous irrigation in the substrate , dissolved oxygen content of the irrigating waters , the species of fish involved , biological oxygen demand of the substrate , amount and form of water flow on the stream bed surface and the dynamics of upwelling intragravel water . at the present time established known figures for egg densities which result in successful fry survival exceed 7 , 000 eggs per square meter . the use of this apparatus allows for adding an additional dimension to salmonid egg planting : multiple depth planting . estimates of potential densities in excess of 25 , 000 eggs per cubic meter for ideal gravels have been suggested . thus , greater production of salmon may be obtained from physically limited spawning areas . as water intake is generally from an upstream source the flushing and planting proceeds in a downstream progression . the insertion of a venturi valve at any point in the pump &# 39 ; s exhaust stem to the main water control valve air may be introduced into the system . the resulting venturi effect gives additional lifting quality to the flushing process . in order to test for favorable water flow during sequential egg deposition , a 2 inches diameter pvc pipe is inserted into the substrate at the desired planting depth . when the probing activities are too close together , water is forced through the gravel raising the water level in the 2 inch tube . when no detectable change in the water level occurs , appropriate waterflow and separation of the egg deposition sites will have been achieved for the specific gravel composition and conditions of that portion of the stream bed . once a satisfactory determination has been achieved , egg deposition may proceed . however , it is advantageous to repeat the test should changes in resistance to probe insertion or change in gravel size be noticed . choice of the appropriate stream bed spawning environment is primarily dependent upon the natural history and physiological requirements of each species . pink salmon ( onchorynchus gorbuscha ) are capable of spawning on tidal flats where the water &# 39 ; s salinity varies with every tide . pink salmon are more resistant to the repeated salt water flushes that are associated with high tidal action wherein king salmon ( onchorynchus tshawytscha ) eggs are intolerant to salt water . the benefits attendant to the use of this invention are numerous . an important factor is that artificial fertilization avoids gamete retention , other social responses that inhibit spawning and wasting viable gametes , etc . also , a favorable planting depth may be easily achieved so that problems caused by scouring , frost , and predators may be avoided . furthermore , the invention allows for multi - level egg deposition while still permitting the upper gradient of the substrate to be utilized for natural spawning . while other methods of mechanical egg planting show successful egg to fry survival ratios none have the benefit of a highly effective flushing action to remove sediment , exactness of deposition , and the patterned deposition permitted by this invention . this invention , by permitting in - stream planting avoids the ecological and other problems incumbent in diverting stream flow , slowing or controlling water volume or the construction of expensive incubation channels . however , where an incubation channel has been constructed this invention may be used to increase yield of salmon fry . while this invention has been described by reference to the preferred embodiments thereof , it will be understood that the invention is not limited thereto , but only to the lawful scope of the appended claims . | 8 |
referring to the drawings generally , wherein like reference numerals designate the same or functionally similar elements throughout the several drawings , and to fig1 in particular , there is shown a schematic sectional side view of a first embodiment of the present invention , drawn to a radiant synthesis gas cooler , generally designated 10 . the synthesis gas cooler 10 is typically a cylindrical vessel having its longitudinal axis oriented vertically . in this embodiment , the cooler 10 is provided with hot synthesis gas 12 from a gasifier ( not shown ) at an inlet 14 provided at the top of the cooler 10 . the gas 12 enters an inner flue or enclosure region 16 provided within the cooler 10 . the inner flue is defined by inner enclosure wall 18 , preferably cylindrical in shape , and comprised typically of fluid - cooled tubes . the working fluid within the tubes may be water , steam or a mixture thereof . in addition to the fluid - cooled tubes forming the inner enclosure wall 18 , the inner flue 16 is also provided with a plurality of fluid - cooled , wing wall surfaces 20 which are internally suspended within the cooler 10 so that a significant portion of the wing walls 20 are exposed to the incoming synthesis gas 12 , thereby heating the working fluid ( again water , steam or a mixture thereof ) conveyed through the wing walls 20 . the wing walls 20 are generally constructed as a planar bank of tubes provided adjacent to one another , and are provided with inlet and outlet manifolds or headers 22 which distribute or collect the working fluid conveyed through the wing walls 20 . the number and arrangement of the wing walls 20 provided would be determined by heat transfer and other requirements . thus , while fig2 illustrates an arrangement of six ( 6 ) wing walls 20 arranged around the vertical longitudinal axis of the cooler 10 , a greater or fewer number of wing walls 20 may be provided to suit particular heat transfer and cooling requirements . as the hot synthesis gas 12 flows down through the inner flue 16 , it is cooled by the inner enclosure wall 18 and the wing walls 20 , and at a bottom region 24 of the inner flue 16 the synthesis gas 12 turns upwardly substantially 180 degrees through one or more openings 26 provided in the inner enclosure wall 18 and then into an outer flue or enclosure region 28 defined by the inner enclosure wall 18 and a similarly constructed outer enclosure wall 30 . the outer flue 28 thus has a substantially annular shape . manifolds or headers 32 may be provided to facilitate formation of these openings 26 , if necessary . the synthesis gas 12 is then conveyed upwardly through the outer flue 28 , through one or more openings 34 , and then out of the cooler 10 via synthesis gas outlet 36 . the distance between the inner enclosure wall 18 and the outer enclosure wall 30 , as well as the distance between the outer enclosure wall 30 and a shell 38 forming the cooler 10 will be of a size sufficient to provide access and inspection when the cooler 10 is out of service . the enclosure walls 18 , 30 forming the inner and outer flues 16 , 28 , respectively , will preferably be provided as independent fluid circuits to provide for individual lifting , removal and inspection . all water / steam generating surface will be arranged to provide for natural circulation , avoiding the need for a forced circulating system with circulation pumps . solids entrained in the hot synthesis gas 12 flowing downwardly through the inner flue 16 will tend to fall out of the synthesis gas 12 at the bottom region 24 where the synthesis gas 12 makes an approximately 180 degree turn upwardly into the outer flue 28 . the solids fall into a water bath 38 provided at a lower portion of the cooler 10 , thereby permitting the solids to be cooled and removed via solids outlet 40 . sootblowers 42 may be provided at the openings 26 provided at the bottom region 24 where the synthesis gas 12 makes the 180 degree turn into the outer flue 30 , if required to prevent pluggage from accumulated solids . the combination of the inner and outer flues 16 , 28 , with the wing walls 20 located within the inner flue 16 , results in an overall height of the cooler 10 that is substantially less than with either construction individually . providing independent inner and outer flues 16 , 28 with space for lifting and removal while accommodating the wing wall headers 22 and connections thereto ( not shown ) inside the inner flue 16 will require a novel inner flue 16 design , particularly at the bottom of the inner flue 16 . depending upon the amount of heat in the synthesis gas 12 provided to the cooler 10 , additional heating surface may be required , and a second embodiment of the present invention to accomplish this task is illustrated in fig3 . as those skilled in the art will appreciate , the second embodiment shares several design features with the first embodiment of fig1 , and in particular also provides an arrangement of convection heating surface 50 arranged within the outer flue 28 as shown . this convection heating surface 50 can be water or steam cooled , and comprised of one or more banks of tubes arranged so that the synthesis gas 12 flows over the outside of the tubes . the banks of convection heating surface 50 may be provided within the outer flue 28 anywhere around the perimeter of the cooler 10 . in one specific feature of this embodiment , the convection heating surface 50 may employ the same fluidic circuitry ( an integrated cooling approach ) as is employed in the steam generating surface comprising the inner and outer enclosure walls 18 , 30 , respectively , thus eliminating the need for a separate cooling system . alternatively , a separate fluidic circuit may be employed for the convection heating surface 50 . synthesis gas 12 , after flowing over the convection heating surface 50 , exits the outer flue 28 via openings 34 , and exits the cooler via gas outlet 36 . sootblowers 52 can be provided to clean the convection heating surface 50 to prevent pluggage . the convection heating surface 50 eliminates the need for a convection cooler component separate and detached from the radiant cooler 10 , as well as the otherwise attendant connecting flues with turns , pressure vessel containment for same and , in the case of the aforementioned integrated cooling approach , a separate cooling system . the synthesis gas 12 flowing from the radiant cooling section ( the inner flue 16 ) upwardly over the convection heating surface 50 located within the outer flue 28 travels substantially in a straight line , minimizing gas turbulence at the inlet to the outer flue 28 . this minimizes the potential for uncontrollable ash pluggage , and permits the ability to provide sootblowers 52 adjacent the convection heating surface 50 to clean same . this design is especially advantageous as compared to the turbulence and attendant uncontrollable pluggage problems typically encountered at the abrupt entrance to tubes at the inlet tubesheet of a fire tube cooler design . if desired , a further simplification of the structures and equipment employed in a gasification system can be accomplished by means of a third embodiment of the present invention , as illustrated in fig4 . as shown therein , this arrangement extends the tubes comprising the enclosure wall 18 , and which defines the inner flue 16 , upwardly to form an integral , fluid - cooled gasifier enclosure region 60 in an upper region of the cooler 10 . the integral gasifier 60 is thus positioned within the cooler 10 to provide the synthesis gas 12 to the inner flue 16 . the tubes forming the enclosure wall 62 of the gasifier enclosure region 60 would have a refractory coating 64 to protect the surface of the tubes from molten slag and to maintain the gasifier enclosure region 60 environment at temperatures sufficient for the proper gasification reactions to occur . this gasifier enclosure region 60 according to the present invention overcomes the problems associated with uncooled , refractory gasifiers , as well as the prior art for cooled gasifiers . the present invention improves on prior cooled gasifier designs by integrating the cooling circuitry for the gasifier enclosure region 60 into the same fluid - cooled circuitry as that provided for the radiant cooler 10 , eliminating the need for a separate cooling system . this design also recovers the heat rejected from the gasifier enclosure region 60 and transfers it into the gasification plant &# 39 ; s steam / water system , thereby improving efficiency and providing modest fuel cost savings over the life of the unit . the above discussion of each of the three design embodiments list the technical advantages of each over the prior art . from a commercial perspective , the combined inner / outer flue with wing wall design concept substantially reduces cost by significantly reducing the overall height of the radiant synthesis gas cooler . these cost reductions are obtained not just from the reduced cost of the outer vessel , but also from transportation costs , fuel piping costs , steel structure costs , and costs to construct the component on site . providing separable inner and outer flues minimizes maintenance costs . this is important with a gasification process cooler , which experiences a more aggressive corrosion environment and requires more maintenance over time than combustion gas coolers used in a conventional pulverized coal plant . the incorporation of the convection heating surface integrally within the radiant cooler enclosures eliminates the cost of a separate component . the cost savings are substantial here as well , because in addition to saving on an extra pressure vessel there are also savings in reduced gas flue and steam / water piping costs , steel structure costs and construction costs . the savings from higher availability on solid fuel , due to reduced or eliminated convective cooler plugging , can be more than the entire capital cost of a convective cooler over the life of the unit . the incorporation of an integral , cooled gasifier provides modest cost savings over separate cooled gasifiers by eliminating the need for separate pressure vessels and some of the cooling circuitry . while it may be somewhat more expensive in capital cost as compared to an uncooled gasifier , it is believed that the higher availability using solid fuels will be substantial , greatly exceeding any capital cost difference . the cost savings from combining some or all of the three design concepts to allow elimination of a spare component train are significant . again , these savings expand beyond just the extra components to include all the supporting equipment and steel structures surrounding the components and the construction costs associated with building it . it will thus be appreciated that an important , fundamental improvement provided by the present invention involves consolidating individual components into one integrated component to make it compact , low cost , more reliable , and more maintainable . while specific embodiments of the invention have been shown and described in detail to illustrate the application of the principles of the invention , those skilled in the art will appreciate that changes may be made in the form of the invention covered by the following claims without departing from such principles . in some embodiments of the invention , certain features of the invention may sometimes be used to advantage without a corresponding use of the other features . accordingly , all such changes and embodiments properly fall within the scope of the following claims . | 2 |
please refer to fig3 . a typical computer 10 has a screen 15 , a keyboard device 31 , some function keys 33 , a motherboard ( not shown ), a memory ( not shown ), etc . please refer to fig4 . fig4 shows a first embodiment of a signal noise reduction system 20 in the computer 10 . the signal noise reduction system 20 comprises a signal generating element 30 and a digital chip 40 . the signal generating element 30 , such as the keyboard device 31 or the function keys 33 , is electrically connected to the at least one digital chip 40 ( such as a keyboard control chip 41 , which is basically pins of a gpio ). please refer to fig5 . fig5 is a flowchart of a method of signal noise reduction according to the present invention . this flowchart describes the signal processing performed by the signal generating element 30 and a connection line 21 of the digital chip 40 . samples shown in fig1 indicate the signals generated by the signal generating element 30 ; “ sample 1 ” indicates the first signal , “ sample 2 ” indicates the second signal , and so on . debouncehigh , debouncelow and stablesignal are variables of the logical operations , wherein stablesignal indicates signals confirmed by the digital chip 40 . please refer to fig6 and fig7 for further description of the signal processing . an and logical operation is performed on the received recent signal and “ n ” previous signals ; in this embodiment , n = 2 , so 3 samples are selected ; the corresponding formula is : please refer to fig6 . in the logical operation for sample 1 , sample 2 and sample 3 , since each of sample 1 , sample 2 and sample 3 are “ 1 ”, debouncehigh ( 3 )= 1 . in the logical operation for sample 2 , sample 3 and sample 4 , since sample 4 = 0 , debouncehigh ( 4 )= 0 . step 301 indicates that only when all samples are “ 1 ”, then debouncehigh is “ 1 ”; under any other condition debouncehigh is “ 0 ”. the above - mentioned “ n ” can be other values , but is preferably between 1 and 5 . for example , when n = 1 , the corresponding formula is : an or logical operation is performed on the received recent signal and “ n ” previous signals ; the corresponding formula is : please refer to fig6 . in the operation for sample 1 , sample 2 and sample 3 , since all of sample 1 , sample 2 and sample 3 are “ 1 ”, debouncehigh ( 3 )= 1 . in the operation for sample 4 , sample 5 and sample 6 , since sample 4 , sample 5 and sample 6 are all “ 0 ”, debouncelow ( 6 )= 0 . step 302 indicates that only when all samples are “ 0 ”, then debouncelow is “ 0 ”, and under any other condition debouncelow is “ 1 ”. an or logical operation is performed with the previous confirmed signal and result from step 301 , and then an and logical operation is performed on the result from logical operation 302 and the result from step 302 ; the corresponding formula is please refer to fig6 . for example , in order to calculate stablesignal ( 3 ), assuming stablesignal ( 2 )= 1 ( which means the previous confirmed signal was “ 1 ”), stablesignal ( 3 )=( 1 or 1 ) and ( 1 )= 1 , so the new confirmed signal is 1 . by way of further example , stablesignal ( 6 )=( 1 or 0 ) and ( 0 )= 0 , which indicates that the previous confirmed signal was “ 1 ”, and the new confirmed signal is 0 . the formulas in the above - mentioned description may be explained as follows . step 301 and step 302 may be explained as : checking whether received recent signals and “ n ” previous signals are all consistent digital logical operations . debouncehigh is used for checking whether all samples are 1 , and debouncelow is used for checking whether all samples are 0 . when all samples are 1 ( the signals are consistent ), debouncehigh = 1 and debouncelow = 1 ; when all samples are 0 ( the signals are consistent ), debouncehigh = 0 and debouncelow = 0 . when the signals are not consistent ( some samples are “ 1 ”, some samples are “ 0 ”), debouncehigh = 0 and debouncelow = 1 . step 303 may be described as determining a new confirmed signal with digital logical operations based upon the previous confirmed signal and the results from step 301 and step 302 , using the following two conditions : condition 1 : if step 301 and step 302 find consistent signals , then the new confirmed signal is set to the recent signals and the previous confirmed signal is ignored . and regardless of whether stablesignal ( the previous confirmed signal ) is “ 1 ” or “ 0 ”, the new confirmed signal is “ 1 ”. and regardless of whether stablesignal ( the previous confirmed signal ) is “ 1 ” or “ 0 ”, the new confirmed signal is “ 0 ”. condition 2 : if step 301 and step 302 find non - consistent signals , the new confirmed signal is set to the previous confirmed signal . that is , it is noted that , since the signals are not consistent , debouncehigh = 0 and debouncelow = 1 may be assumed . please refer to fig6 . when the signals are not consistent , such as when sample 2 = 1 , sample 3 = 1 and sample 4 = 0 : please refer to fig7 . when the signals are not consistent , such as when sample 2 = 0 , sample 3 = 0 and sample 4 = 1 : please refer to fig8 . fig8 shows a second embodiment of a signal noise reduction system in a computer according to the present invention . a difference between this embodiment and the first embodiment is that there is more than one signal generating element ; for example , three signal generating elements 30 a , 30 b , 30 c are all connected to the same digital chip 40 . please refer to fig9 . fig9 shows a third embodiment of a signal noise reduction system in a computer according to the present invention . a difference between this embodiment and the first embodiment is that the signal generating element 30 may be a south bridge chip 32 ( or a north bridge chip ), which means that non - gpio pins can be used in the technology of the present invention . please refer to fig1 . fig1 shows a signal noise reduction system performing logical operations to a plurality of pins . for example , when processing eight pins p 1 ˜ p 8 , stablesignal for each pin can be calculated simultaneously . for example , an 8 bit system can calculate 8 pins simultaneously , and a 16 bit system can calculate 16 pins simultaneously , which is an advantage of the present invention . the above - mentioned logical operations can be executed by the digital chip 40 . although the present invention has been explained in relation to its preferred embodiment , it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the invention as hereinafter claimed . for example , when debouncehigh = 1 , there is no need to calculate debouncelow , and stablesignal may simply be set to “ 1 ”; and when debouncelow = 0 , stablesignal may be directly set to “ 0 ”. of course , utilizing a logical “ if ” operation may reduce efficiencies , therefore , the embodiment of the present invention do not use the logical “ if ” operation . | 7 |
in accordance with one embodiment , there is provided a wound healing composition and the method of use of the composition on a patient &# 39 ; s skin or wound . this product accelerate healing and restoration of a wound . in accordance with another embodiment , there is provided a method of use of the composition that is a photodynamic technique whereby the composition is activated by light providing a beneficial effect on the skin or wound and promoting healing . the composition and method may be used to treat injuries to the different layers of the skin , including incisions , lacerations , abrasions , puncture wounds , penetrations wounds , gunshot wounds , contusions , hematomas and crushing injuries . lesions to muccosae may also be treated with the composition of the present invention , which may be used for example , to treat pathological lesions of the oral mucosa , such as periodontitis , ulcers , and cold sores ( orafacial herpes ). the composition comprises a number of active principles selected from groups of possible components . these various active principles each have their mechanism of action . the composition comprises oxidants as a source of oxygen radicals . peroxide compounds are oxidants that contain the peroxy group ( r — o — o — r ) which is a chainlike structure containing two oxygen atoms , each of which is bonded to the other and a radical or some element . suitable oxidants for preparation of the active medium include , but are not limited to : hydrogen peroxide ( h 2 o 2 ) is the starting material to prepare organic peroxides . h 2 o 2 is a powerful oxidizing agent , and the unique property of hydrogen peroxide is that it breaks down into water and oxygen and does not form any persistent , toxic residual compound . hydrogen peroxide for use in this composition can be used in a gel , for example with 6 % hydrogen peroxide a suitable range of concentration over which hydrogen peroxide can be used in the present composition is from about 3 . 5 % to about 6 %. urea hydrogen peroxide ( also known as urea peroxide carbamide peroxide or percarbamide ) is soluble in water and contains approximately 35 % hydrogen peroxide . carbamide peroxide for use in this composition can be used as a gel , for example with 16 % carbamide peroxide that represents 5 . 6 % hydrogen peroxide . a suitable range of concentration over which urea peroxide can be used in the present composition is from about 10 % to about 16 %. urea peroxide brakes down to urea and hydrogen peroxide in a slow - release fashion that can be accelerated with heat or photochemical reactions . the released urea [ carbamide , ( nh 2 )], is highly soluble in water and is a powerful protein denaturant . it increases solubility of some proteins and enhances rehydration of the skin and / or mucosa . benzoyl peroxide consists of two benzoyl groups ( benzoic acid with the h of the carboxylic acid removed ) joined by a peroxide group . it is found in treatments for acne , in concentrations varying from 2 . 5 % to 10 %. the released peroxide groups are effective at killing bacteria . benzoyl peroxide also promotes skin turnover and clearing of pores , which further contributes to decreasing bacterial counts and reduce acne . benzoyl peroxide breaks down to benzoic acid and oxygen upon contact with skin , neither of which are toxic . a suitable range of concentration over which benzoyl peroxide can be used in the present composition is from about 2 . 5 % to about 5 %. inclusion of other forms of peroxides ( e . g . organic or inorganic peroxides ) should be avoided due to their increased toxicity and their unpredictable reaction with the photodynamic energy transfer . the photoactivators transfer light energy to the oxidants . suitable photoactivators can be fluorescent dyes ( or stains ), although other dye groups or dyes ( biological and histological dyes , food colorings , carotenoids ) can also be used . combining photoactivators may increase photo - absorbtion by the combined dye molecules and enhance absorption and photo - biomodulation selectivity . this creates multiple possibilities of generating new photosensitive , and / or selective photoactivator mixtures . a advantageous characteristic of a photoactivator is increased fluorescence . in the present invention , re - emission of light in the green to yellow spectrum would be advantageous , since it is a deep penetrating wavelength range , with deep absorption by the blood . this confers a strong increase on the blood flow , vasodilation and angiokinetic phenomena . suitable photoactivators include , but are not limited to : the xanthene derivative dyes have been used and tested for a long time worldwide . they display low toxicity and increased fluorescence . the xanthene group consists of 3 sub - groups that are : a ) the fluorenes ; b ) fluorones ; and c ) the rhodoles . the fluorenes group comprises the pyronines ( e . g . pyronine y and b ) and the rhodamines ( e . g . rhodamine b , g and wt ). depending on the concentration used , both pyronines and rhodamines may be toxic and their interaction with light may lead to increased toxicity . similar effects are known to occur for the rhodole dye group . fluorescein is a fluorophore commonly used in microscopy with an absorption max of 494 nm and an emission max . of 521 nm . the disodium salt of fluorescein is known as d & amp ; c yellow 8 . it has very high fluorescence but photodegrades quickly . in the present composition , mixtures of fluorescein with other photoactivators such as indocyanin green and / or saffron red powder will confer increased photoabsorption to these other compounds . eosins group comprises eosin y ( tetrabromofluorescein , acid red 87 , d & amp ; c red 22 ) with an abs max 514 - 518 nm , stains cytoplasm of cells , collagen , muscle fibers and red blood cells intensely red ; and eosin b ( acid red 91 , eosin scarlet , dibromo - dinitrofluorescein ), with the same staining characteristics as eosin y . eosin y , eosin b , or a mixture of both can be used because of their sensitivity to the light spectra used : broad spectrum blue light , blue to green light and green light . their tissue and biofilm staining properties and their low toxicity are also advantageous . both eosin y and eosin b stain red blood cells and thus confer to the composition of the present invention haemostatic ( controls the flow or stops the flow of blood ) properties as well as increase the selective targeting of light to the soft tissues of the lesion or wound during the application of the composition . phloxine b ( 2 , 4 , 5 , 7 tetrabromo 4 , 5 , 6 , 7 , tetrachlorofluorescein , d & amp ; c red 28 , acid red 92 ) is a red dye derivative of fluorescein which is used for disinfection and detoxification of waste water through photooxidation . it has an abs . max . of 535 - 548 nm . it is also used as an intermediate for making photosensitive dyes and drugs . erythrosine b ( acid red 51 , tetralodofluorescein ) is a cherry - pink coal - based fluorine food dye used as a biological stain , and a biofilm and dental plaque disclosing agent , with max . abs . 524 - 530 nm in aqueous solution . it is subject to photodegradation . erythrosine is also used in some embodiments due to its photosensitivity to the light spectra used and its ability to stain biofilms . inclusion of erythrosine should be favored when using the composition in deep pockets of infected or contaminated tissue , such as periodontal pockets in periodontal therapy . rose bengal ( 4 , 5 , 6 , 7 tetrachloro 2 , 4 , 5 , 7tetraiodofluorescein , acid red 94 ) is a bright bluish - pink biological dye with an absorption max of 544 - 549 nm , that has been used as a dye , biological stain and diagnostic aid . also used in synthetic chemistry to generate singlet from triplet oxygen . merbromine ( mercurochrome ) is an organo - mercuric disodium salt of fluorescein with an abs . max . of 508 nm . it is used as an antiseptic . the azo ( or diazo -) dyes share the n - n group , called azo the group . they are used mainly in analytical chemistry or as food colorings and are not fluorescent . suitable azo dyes include : methyl violet , neutral red , para red ( pigment red 1 ), amaranth ( azorubine s ), carmoisine ( azorubine , food red 3 , acid red 14 ), allura red ac ( fd & amp ; c 40 ), tartrazine ( fd & amp ; c yellow 5 ), orange g ( acid orange 10 ), ponceau 4r ( food red 7 ), methyl red ( acid red 2 ), murexide - ammonium purpurate . dye molecules commonly used in staining protocols for biological materials can also be used as photoactivators . suitable biological stains include : saffranin ( saffranin o , basic red 2 ) is also an azo - dye and is used in histology and cytology . it is a classic counter stain in a gram stain protocol . fuchsin ( basic or acid ) rosaniline hydrochloride ) is a magenta biological dye that can stain bacteria and has been used as an antiseptic . it has an abs . max . 540 - 555 nm . 3 , 3 ′ dihexylocarbocyanine iodide ( dioc6 ) is a fluorescent dye used for staining cell &# 39 ; s endoplasmic reticulum . vesicle membranes and mitochondria . it shows photodynamic toxicity ; when exposed to blue light , has a green fluorescence . carminic acid ( acid red 4 , natural red 4 ) is a red glucosidal hydroxyanthrapurin naturally obtained from cochineal insects . indocyanin green ( icg ) is used as a diagnostic aid for blood volume determination , cardiac output , or hepatic function . icg binds strongly to red blood cells and when used in mixture with fluorescein , it increases the absorption of blue to green light . saffron red powder is a natural carotenoid - containing compound . saffron is a spice derived from crocus sativus . it is characterized by a bitter taste and iodoform or hay - like fragrance ; these are caused by the compounds picrocrocin and saffranal . it also contains the carotenoid dye crocin that gives its characteristic yellow - red color . saffron contains more that 150 different compounds many of them are carotenoids : mangicrocin , reaxanthine ; lycopene , and various α - and β - carotenes , that show good absorption of light and beneficial biological activity . also saffron can act as both a photo - transfer agent and a healing factor . saffron color is primarily the result of α - crocin ( 8 , 8 diapo - 8 , 8 - carotenoid acid ). dry saffron red powder is highly sensitive to fluctuating ph levels and rapidly breaks down chemically in the presence of light and oxidizing agents . it is more resistant to heat . data show that saffron has anticarcinogenic , immunomodulating and antioxidant properties . for absorbance , it is determined for the crocin specific photon wavelength of 440 nm ( blue light ). it has a deep red colour and forms crystals with a melting point of 186 ° c . when dissolved in water it forms an orange solution . crocetin is another compound of saffron that was found to express an antilipidermic action and promote oxygen penetration in different tissues . more specifically it was observed an increased oxygenation of the endothelial cells of the capillaries . an increase of the oxygenation of muscles and cerebral cortex was observed and led to an increased survival rate in laboratory animals with induced hemorrhagic shock or emphysema . anatto a spice contains as main constituent ( 70 - 80 %) the carotenoid bixin which displayed relevant antioxidative properties . fucoxanthine is a constituent of brown algae with a pronounced ability for photosensitization of red - ox reactions . healing factors comprise compounds that promote or enhance the healing or regenerative process of the tissues on the application site of the composition . during the photoactivation of the composition , there is an increase of the absorption of molecules at the treatment site by the skin or the mucosa . an augmentation in the blood flow at the site of treatment is observed for an extent period of time . an increase in the lymphatic drainage and a possible change in the osmotic equilibrium due to the dynamic interaction of the free radical cascades can be enhanced or even fortified with the inclusion of healing factors . suitable healing factors include , but are not limited to : hyaluronic acid ( hyaluronan , hyaluronate ): is a non - sulfated glycosaminoglycan , distributed widely throughout connective , epithelial and neural tissues . it is one of the primary components of the extracellular matrix , and contributes significantly to cell proliferation and migration . hyaluronan is a major component of the skin , where it is involved in tissue repair . while it is abundant in extracellular matrices , it contributes to tissues hydrodynamics , movement and proliferation of cells and participates in a wide number of cell surface receptor interactions , notably those including primary receptor cd44 . the hyaluronidases enzymes degrade hyaluronan . there are at least seven types of hyaluronidase - like enzymes in humans , several of which are tumor suppressors . the degradation products of hyaluronic acid , the oligosaccharides and the very - low molecular weight hyaluronic acid , exhibit pro - angiogenic properties . in addition , recent studies show that hyaluronan fragments , but not the native high molecular mass of hyaluronan , can induce inflammatory responses in macrophages and dendritic cells in tissue injury . hyaluronic acid is well suited to biological applications targeting the skin . due to its high biocompatibility , it is used to stimulate tissue regeneration . current studies evidenced hyaluronic acid appearing in the early stages of healing to physically create room for white blood cells that mediate the immune response . it is used in the synthesis of biological scaffolds for wound healing applications and in wrinkle treatment . glucosamine : is one of the most abundant monosaccharides in human tissues and a precursor in the biological synthesis of glycosilated proteins and lipids . it is commonly used in the treatment of osteoarthritis . the common form of glucosamine used is its sulfate salt . glucosamine shows a number of effects including an anti - inflammatory activity , stimulation of the synthesis of proteoglycans and the synthesis of proteolytic enzymes . a suitable range of concentration over which glucosamine can be used in the present composition is from about 1 % to about 3 %. allantoin : is a diureide of glyosilic acid . it has keratolytic effect , increases the water content of the extracellular matrix , enhances the desquamation of the upper layers of dead ( apoptotic ) skin cells , and promotes skin proliferation and wound healing . also , saffron can act as both a photo - transfer agent and a healing factor . chelating agents can be included to promote smear layer removal in closed infected pockets and difficult to reach lesions ; act as a metal ion quencher and as a buffer . suitable chelating agents include , but are not limited to : ethylenediaminotetraacetic acid ( edta ): it is an aminoacid , used to sequester di - and trivalent metal ions . edta binds to metals via 4 carboxylate and 2 amine groups . edta forms especially strong complexes with mn ( iii ), fe ( iii ), cu ( iii ), co ( iii ). prevents collection of the platelets and blood clots formation . it is used in the endodontic therapy as a smear layer removal agent during instrumentation . it is used to buffer solutions . ethylene glycol tetraacetic acid ( egta ) is related to edta , but with a much higher affinity for calcium than for magnesium ions . it is useful for making buffer solutions that resemble the environment inside living cells and is often employed in dentistry , more specifically endodontics , in the removal of smear layer . lipolysis stimulating factors can be included for use of the composition in cosmetic applications , such as wrinkle treatment . caffeine , and the metabolic derivative of caffeine paraxanthine can increase in the lipolysis process to releases glycerol and fatty acids into the blood stream . the wound healing composition may also contain one or more hydrophilic gelling agent . the hydrophilic gelling agent enhances the consistency of the composition and contributes to facilitating the application of the composition to the skin or wounded area . also , when used with hydrogen peroxide ( h 2 o 2 ), it may contribute to the slow the release of the h 2 o 2 , and provide a more immediate reaction because pure h 2 o 2 can be used directly . suitable hydrophilic gelling agent include , but are not limited to glucose , modified starch , methyl cellulose , carboxymethyl cellulose , propyl cellulose , hydroxypropyl cellulose , carbopol ® polymers , alginic acid , sodium alginate , potassium alginate , ammonium alginate , calcium alginate , agar , carrageenan , locust bean gum , pectin , and gelatin . the inclusion of suitable photosensitive compounds and activation with a light source of a proper wavelength , leads to the acceleration in the breakdown process of the source of peroxide ( the oxidant ) and the other reactions that take place , via a photodynamic phenomenon . the included dyes are illuminated by photons of a certain wavelength and excited to a higher energy state . when the photoactivators &# 39 ; excited electrons return to a lower energy state , they emit photons with a lower energy level , thus causing the emission of light of a longer wavelength ( stokes shift ). in the proper environment , much of this energy transfer is transferred to oxygen or the reactive hydrogen peroxide and causes the formation of oxygen radicals , such as singlet oxygen . the singlet oxygen and other reactive oxygen species generated by the activation of the composition are thought to operate in a hormetic fashion . that is , a health beneficial effect is brought about by the low exposure to a normally toxic stimuli ( e . g . reactive oxygen ), by stimulating and modulating stress response pathways in cells of the targeted tissues . endogenous response to exogenous generated free radicals ( reactive oxygen species ) is modulated in increased defense capacity against the exogenous free radicals and induces acceleration of healing and regenerative processes . furthermore , activation of the composition will also produce an antibacterial effect . the extreme sensitivity of bacteria to exposure to free radicals makes the composition of the present invention a de facto bactericidal composition . possible mechanism of action should be a fortified redox signalling phenomenon resulting in accentuated signal transduction process in which cells convert one kind of signal into another ; activated “ second messengers ” induce a “ signal cascade ” beginning with a relatively small stimulus that elicits a large response via biologically monitored amplification of such signals . these complex mechanisms act possibly involving angiogenic phenomena via growth factor activation . this method could be described as a form of photodynamic therapy . however , unlike other photodynamic techniques , where the photoactoactivators are incorporated in the tissue structure . in the present method , the photoactive material is in simple contact with the tissue and acts when activated by light , as a “ photodynamic device ” that chemically interacts with the tissue . additionally , the actinic light penetrates the tissue , and the light that is emitted by the photoactivator ( light of a longer wavelength ) is also absorbed by the tissue . any source of actinic light can be used . any type of halogen , led or plasma arc lamp , or laser may be suitable . the primary characteristic of suitable sources of actinic light will be that they emit light in a wavelength ( or wavelengths ) appropriate for activating the one or more photoactivators present in the composition . in one embodiment , an argon laser is used . in another embodiment , a potassium - titanyl phosphate ( ktp ) laser ( e . g . a greenlight ™ laser ) is used . in yet another embodiment , a led photocuring device is the source of the actinic light . in yet another embodiment , the source of the actinic light is a source of visible light having a wavelength between 400 and 600 nm . furthermore , the source of actinic light should have a suitable power density . suitable power density for non - collimated light sources ( led , halogen or plasma lamps ) are in the range from about 900 mw / cm 2 to about 2000 mw / cm 2 . suitable power density for laser light sources are in the range from about 0 . 5 mw / cm 2 to about 0 . 8 mw / cm 2 . the duration of the exposure to actinic light will be dependent on the surface of the treated area , and on the type of lesion , trauma or injury that is being treated . the photoactivation of the composition may take place within seconds or even fragment of seconds , but a prolonged exposure period is beneficial to exploit the synergistic effects of the absorbed , reflected and reemitted light on the composition of the present invention and its interaction with the tissue being treated . in one embodiment , the time of exposure to actinic light of the tissue , skin or wound on which the wound healing composition has been applied is a period between 60 second and 5 minutes . in another embodiment , the time of exposure to actinic light of the tissue , skin or wound on which the wound healing composition has been applied is a period between 60 seconds and 5 minutes per cm 2 of the area to be treated , so that the total time of exposure of a 10 cm 2 are would be between 10 minutes and 50 minutes . in yet another embodiment , the source of actinic light is in continuous motion over the treated area for the appropriate time of exposure . in yet another embodiment , multiple applications of the wound healing composition and actinic light are performed . in some embodiments , the tissue , skin or wound is exposed to actinic light at least two , three , four , five or six times . in some embodiments , a fresh application of the wound healing composition is applied before exposure to actinic light . an exemplary wound healing composition was prepared by mixing the following components : the oxidant ( 4 ml ) and healing factors ( 1 . 5 ml ) were mixed and the combined with the photoactivators ( 1 ml ). the resulting composition was applied to the skin of a wounded patient , and activated with actinic light provided by a led photocuring device ( blue light ). the composition was removed following treatment . an second exemplary wound healing composition was prepared by mixing the following components : the oxidant ( 4 ml ) and healing factors ( 1 . 5 ml ) were mixed and the combined with the photoactivators ( 1 ml ). the resulting composition was applied to the skin of a wounded patient , and activated with actinic light provided by a led photocuring device ( blue light ). the composition was removed following treatment . this second exemplary composition is using the fluorescein dye as a photoactivator to other dyes ( indocyanine green and saffron red powder ) present in the composition . the addition of a small amount of fluorescein to the indocyanine green and saffron red powder solution caused reemission of light at wavelengths that activated the other dye compounds and improved the treatment by increasing the established clinical absorption / reemission criteria . indocyanine green binds well to hemoglobin and helps the selective energy absorption by the tissues and also helps targeting these tissues with the generated free radical cascades . also , this photoactivators mixture is able to render saffron red fluorescent , which again improves both the photodynamic and biostimulating phenomena . the toxicity of the photoactivators eosin y and erythrosine b was evaluated by measuring the cytotoxicity of these compounds on human cells . hep g2 human hepatocellular carcinoma cells with an epithelial morphology were treated for 24 hours with increasing concentrations ( 0 . 001 to 100 μm ) of eosin y or erythrosine b , and the cellular survival was evaluated . increasing concentrations of either eosin y ( fig1 ) or erythrosine b ( fig2 ) did not affect cellular viability when compared to untreated cells . straurosporine ( sts ) was used as a positive control for inducing cellular mortality and caused a dose - dependent effect ( fig1 and 2 ). similar results were obtained by measuring cell death by release of lactate dehydrogenase ( ldh ). therefore , neither eosin y or erythrosine b caused increased cellular mortality . random skin flaps in rat were used to study the wound healing procedures , for evaluating the benefits of ischemic and pharmacologic preconditioning methods on skin flap survival , applying blood flow assessment technologies on flaps , demonstrating the effects of vascular shunts and the studies on skin flap viability . the random skin flap model was used to study the effect of the comosition of the present invention on skin flap survival and associated modulations contributing to healing process . excision wound of 1 cm in width by 2 cm in length were cut dorsally on the midline of the back , 2 cm below the interior angle of the scapulae . the skin was cut with a surgical blade , the panniculus carnosus and a 0 . 5 cm layer subcutaneous to the panniculus camosus was excised from the wound edges . the wound was next photographed with an 8 mm by 8 mm size marker . one gram of the wound healing composition was applied to the wound ( 0 . 5 g / cm 2 ) and irradiated with a blue led light during 3 minutes . excisions were performed on rats ( n = 2 per group ) as described above in example iv , and the excisions were treated or not with a single application of 1 gram of a wound healing composition comprising the oxidant ( carbamide peroxide ) and a photoactivator mixture containing eosin y , erythrosine b and saffron red powder . the excisions were irradiated with a led light ( blue light ) for 3 minutes . the percentage of wound closure was evaluated ( fig3 ) over a ten - day period following treatment . animals treated with the composition showed a more rapid wound closure over the initial first three - day period following treatment . excision were performed on rats ( n = 2 per group ) as described above in example iv , and the excisions were treated or not with a single application of 1 gram of a wound healing compositions comprising : ( a ) the oxidant ( carbamide peroxide ) and a photoactivator mixture containing eosin y , and erythrosine b ; ( b ) the oxidant ( carbamide peroxide ) and a photoactivator mixture containing eosin y , erythrosine b and saffron red powder , or ( c ) the oxidant ( carbamide peroxide ) and a photoactivator mixture containing eosin y . erythrosine b , saffron red powder and indocyanine green . the excisions were irradiated with a led light ( blue light ) for 3 minutes . the percentage of wound closure was evaluated daily for four days ( fig4 ). animals treated with compositions ( a ) and ( b ) showed improved wound closure over the four - day period following treatment . the addition of indocyanine green in composition ( c ) repressed the wound healing effect observed for compositions ( a ) and ( b ). excision were performed on rats ( n = 2 per group ) as described above in example iv , and the excisions were treated or not with a single application of 1 gram of a wound healing composition comprising the oxidant ( carbamide peroxide ) and a photoactivator mixture containing eosin y and erythrosine b . the excisions were irradiated with a led light ( blue light ) for 3 minutes . the percentage of wound closure was evaluated ( fig5 ) over a twelve - day period . animals treated with the composition showed a more rapid wound closure over the first seven - day period following treatment . using a template of 3 cm by 9 cm ( 3 × 9 ) in plexiglas , a flap was traced on the dorsal skin with a surgical marker , taking as limits the inferior angles of the scapulae and the superior bones of pelvis . a pure random pattern flap with cranial base was cut using sterile techniques and elevated through deep fascia , including superficial fascia , panniculus carnosus , the subcutaneous tissue and skin . to minimize wound contraction and simulating the human condition , a 0 . 5 cm subcutaneous layer of panniculus carnosus from the wound edges was removed . during one hour , an impermeable barrier ( e . g . a silicone sheeting ) was placed between the flap and its donor site to eliminate the possibility of wound bed support . the sheet was then removed , the flap returned to its original position and the flap edges were surgically closed using 4 / 0 nylon suture in an interrupted fashion . immediately following flap closure , flap pedicle were coated with 13 . 5 g of gel formulation ( 0 . 5 g / cm 2 ) and irradiated . the controls did not receive any treatment . care was taken to distribute ointment evenly along the entire flap . gel formulation was prepared the same day of the experiment . for gel + light group the animals were treated with gel formulation , the flap was irradiated for 3 minutes with a led lamp . excision were performed on rats ( n = 2 per group ) as described above , and the excisions were treated or not with the gel formulation , and irradiated with a led light ( blue light ) as described in example viii . the results demonstrate a direct correlation of necrosis from fluorescein injection and direct visualization . biopsies were evaluated for changes in histology . data from the treated group demonstrate a clinically significant 1 . 5 times reduction in necrosis , ( percent necrosis , mean , sd of 45 . 7 (± 17 . 36 ) vs . 30 . 42 (± 20 . 18 ), in the control and treatment groups respectively ). now referring to fig7 a , the clinical evaluation of necrosis following flap surgery , in the control and treatment group shows that higher necrosis is observed on the control group versus the treatment group . hematoxylin and eosin staining of biopsies from the control and treatment group ( fig7 b ) reveal that greater vascular recruitment occurs in the treated group ( see black arrows therein ). masson trichrome staining for the assessment of collagen fibril deposition ( fig7 c ) at a 40 × magnification shows that new collagen deposition is occurring in the treatment group vs the control group . the photodynamic treatment using photoactivators and wavelength specific light aimed at increasing the viability of the skin flap by stimulating the vascular recruitment of collaterals in flaps to improve the loco - regional state of the new wound , including the formation of new collagen therein . the embodiments and examples presented herein are illustrative of the general nature of the subject matter claimed and are not limiting . it will be understood by those skilled in the art how these embodiments can be readily modified and / or adapted for various applications and in various ways without departing from the spirit and scope of the subject matter disclosed claimed . the claims herof are to be understood to include without limitation all alternative embodiments and equivalents of the subject matter hereof . phrases , words and terms employed herein are illustrative and are not limiting . where permissible by law , all references cited herein are incorporated by reference in their entirety . it will be appreciated that any aspects of the different embodiments disclosed herein may be combined in a range of possible alternative embodiments , and alternative combinations of features , all of which varied combinations of features are to be understood to form a part of the subject matter claimed . | 0 |
in order to provide a clearer and consistent understanding of the specification and claims , including the scope to be given such terms , the following definitions are provided . &# 34 ; actin - binding compound &# 34 ; is meant to include any compound , and especially any protein ( or peptide ), which is capable of binding actin so as to modify any of actin &# 39 ; s many functions , including suppressing the ability of actin monomers to polymerize into filaments . when administered to a subject in need of treatment , the actin - binding compounds of the invention are substantially free of natural contaminants which associate with such compound either in vivo ( in a prokaryotic or eukaryotic ) host , or in vitro ( as a result of a chemical synthesis ). such compounds include , but are not limited to extracellular actin - binding proteins such as gelsolin and dbp , and intracellular actin - binding proteins such as those most abundant in cells ( for example , myosins , tropomyosins , profilin and cofilin ) and those most abundant in non - muscle cells . actin - binding compounds within the scope of the methods of the invention also include but are not limited to a ) actin - binding compounds that predominantly sequester actin monomers , that is , bind monomers in a complex which is resistant to polymerization ( for example , dbp , profilin , depactin , cofilin , and dnaase i ); b ) actin - binding compounds which sequester monomers and possess filament severing activity ( for example , gelsolin , villin , fragmin and severin ; c ) actin - binding compounds that predominantly block the ends of actin filaments and prevent the exchange of monomers with that end ( for example , capping protein , β - actinin , and acumentin ); and d ) actin - binding nonproteinaceous molecules that have such effects on actin ( for example , cytochalasin or biologically - active derivatives thereof , that block the ends of actin filaments ). if desired , such compounds may be administered in the form of a pharmaceutically acceptable salt to the animal . by the term &# 34 ; thrombotic event &# 34 ; is meant any vascular condition in which vascular occlusion , thrombosis , infarction or other biological perturbation results in fibrinolysis . the term &# 34 ; animal &# 34 ; is meant to include all animals in which the accumulation of free actin or actin filaments in the bloodstream or extracellular space would be detrimental to the physiology of the animal . foremost among such animals are humans ; however , the invention is not intended to be so limiting , it being within the contemplation of the present invention to treat any and all animals which may experience the beneficial effect of the invention . an &# 34 ; efficacious amount &# 34 ; of an actin - binding compound is one which is sufficient to reduce or eliminate toxic effects of actin in an animal . a material is said to be &# 34 ; substantially free of natural contaminants if it has been substantially purified from materials with which it is normally and naturally found before such purification . examples of natural contaminants with which actin - binding compounds might be associated are : non - actin - binding peptides , carbohydrates , glycosylated peptides , lipids , membranes , etc . a material is said to be substantially free of natural contaminants if those contaminants normally and naturally found with the substance in vivo or in vitro are substantially absent from a sample of the material . by &# 34 ; substantially absent &# 34 ; is meant that such contaminants are either completely absent or are present at such low concentrations that their presence ( 1 ) does not interfere with the desired therapeutic effect of the active agent ( herein the actin - binding compound ) in the preparation when such preparation is administered to an animal and ( 2 ) does not harm the animal as the result of the administration of such preparation . the term &# 34 ; administration &# 34 ; is meant to include introduction of actin - binding compounds to an animal by any appropriate means known to the medical art , including , but not limited to , enteral and parenteral ( e . g ., intravenous ) administration . the term &# 34 ; pharmaceutically acceptable salt &# 34 ; is intended to include salts of the actin - binding compounds of the invention . such salts can be formed from pharmaceutically acceptable acids or bases , such as , for example , acids such as sulfuric , hydrochloric , nitric , phosphoric , etc ., or bases such as alkali or alkaline earth metal hydroxides , ammonium hydroxides , alkyl ammonium hydroxides , etc . the term &# 34 ; pharmaceutically acceptable vehicle &# 34 ; is intended to include solvents , carriers , diluents , and the like , which are utilized as additives to preparations of the actin - binding compounds of the invention so as to provide a carrier or adjuvant for the administration of such compounds . the term &# 34 ; treatment &# 34 ; or &# 34 ; treating &# 34 ; is intended to include the administration of actin - binding compounds to a subject for purposes which may include prophylaxis , amelioration , prevention or cure of actin related disorders . the term &# 34 ; fragment &# 34 ; is meant to include any portion of a molecule which provides a segment of an actin - binding compound which is capable of binding actin monomers ; the term is meant to include actin - binding fragments which are made from any source , such as , for example , from naturally - occurring peptide sequences , synthetic or chemically - synthesized peptide sequences , and genetically engineered peptide sequences . further , if such fragment is a peptide , a fragment of a peptide of such actin - binding protein is meant to include to any variant of the actin - binding protein . a &# 34 ; variant &# 34 ; of a compound such an actin - binding compound is meant to refer to a compound substantially similar in structure and biological activity to either the native compound , or to a fragment thereof . the biological activity of the compounds of the invention is their ability to bind actin and modify it into a form which is less toxic to an animal than unmodified actin . such modification may be the result of the binding of the compounds per se or the result of a chemical or enzymatic reaction which results from such binding . a &# 34 ; functional derivative &# 34 ; of an actin binding compound is a derivative which possesses a biological activity that is substantially similar to the biological activity of the actin - binding compound . by &# 34 ; substantially similar &# 34 ; is meant activity which is quantitatively different but qualitatively the same . for example , a functional derivative of an actin - binding protein of the invention would contain the same amino acid backbone as an actin - binding protein but also contains other modifications such as post - translational modifications such as , for example , bound phospholipids , or covalently linked carbohydrate , depending on the necessity of such modifications for the performance of the diagnostic assay or therapeutic treatment . as used herein , the term is also meant to include a chemical derivative of an actin binding compound . such derivatives may improve the compound &# 39 ; s solubility , absorption , biological half life , etc . the derivatives may also decrease the toxicity of the molecule , or eliminate or attenuate any undesirable side effect of the molecule , etc . derivatives and specifically , chemical moieties capable of mediating such effects are disclosed in remington &# 39 ; s pharmaceutical sciences ( 1980 ). procedures for coupling such moieties to a molecule are well known in the art . the term &# 34 ; functional derivative &# 34 ; is intended to include the &# 34 ; fragments ,&# 34 ; &# 34 ; variants ,&# 34 ; &# 34 ; analogues ,&# 34 ; or &# 34 ; chemical derivatives &# 34 ; of a molecule . an &# 34 ; analog &# 34 ; of the actin - binding compounds of the invention is meant to refer to a compounds substantially similar in function to either the native actin - binding compound or to a fragment thereof . for example , an analog of an actin - binding protein is a protein which does not have the same amino acid sequence as an actin - binding protein but which is sufficiently homologous to an actin - binding protein so as to retain the biological activity of such actin - binding protein . the methods of the invention are based , in part , upon the observation that secondary injury of the lung and / or kidney often results when , in response to inflammation or injury elsewhere in the body , complexes of actin with the actin - binding proteins gelsolin and dbp appear in the blood and the levels of free gelsolin and dbp in the plasma are significantly depressed . knowing that infusions of free , extracellular actin are toxic to the lung and kidneys , and inhibit fibrinolysis , the inventor made the observation that it is the uncomplexed actin in the blood which is responsible for the secondary tissue injury to the lungs and kidney . the inventor made the further unique observation that tissue injury and inflammation may saturate the host &# 39 ; s ability to complex and remove such toxic , free extracellular actin . the inventor then drew the conclusion that amelioration of the toxic effects of extracellular actin , and especially , cytoprotective effects to the lung and / or kidney may be provided by administering sufficient amounts of an actin - binding compound to the subject to complex or otherwise modify the extracellular actin into a non - toxic monomeric form . the particular actin - binding molecules that are the subject of the methods of the invention are purified native and recombinant actin - binding proteins , and other non - proteinaceous actin - binding molecules , and biologically - active fragments thereof , which are characterized by the presence of unique actin binding domains which possess the biological activity of being able to sequester actin in a monomeric form or rapidly to disaggregate or depolymerize actin filaments or to cover sites on free actin that are toxic to host cells . individual actin - binding domains possessing this biological activity may also be produced by synthetic , enzymatic , proteolytic , chemical or recombinant dna methods . in a preferred embodiment , gelsolin , dbp , or actin - binding fragments thereof , or , a combination of gelsolin and dbp and / or actin - binding fragments thereof , are provided to the subject in need of treatment . plasma gelsolin , ( also called brevin , or actin depolymerizing factor ) and dbp , ( also called gc globulin ) are the two high affinity actin - binding proteins that exist in plasma . high affinity actin - binding proteins bind actin with a k d of less than 10 - 8 . both gelsolin and dbp bind to actin in serum and have actin depolymerizing activity . dbp preferentially binds monomeric actin while gelsolin preferentially binds actin filaments . gelsolin is a multifunctional actin - binding protein obtained from mammalian cytoplasm and extracellular fluids . plasma gelsolin differs from cellular gelsolin only by the addition of 25 amino acids at the amino terminus of the molecule and both gelsolins are the product of a single gene . plasma gelsolin has three actin - binding sites and binds with high affinity to either g - actin or f - actin . plasma gelsolin binds a second actin molecule with a higher affinity than it binds a first actin molecule , and thus preferentially forms 2 : 1 complexes over 1 : 1 complexes and binds filaments in preference to monomers . when added to f - actin , plasma gelsolin severs the filament in a nonproteolytic manner and remains bound to one end of the newly formed filament . if free gelsolin molecules are present , they will sever the actin filament successively until only 2 : 1 actin - gelsolin complexes are present , thereby rapidly depolymerizing the filament . free and complexed ( to actin ) gelsolin molecules differ in their functional properties . although free gelsolin can sever actin filaments , actin - gelsolin complexes cannot . gelsolin &# 39 ; s primary function in the plasma is to sever actin filaments . if gelsolin is present in excess of actin , only gelsolin - actin complexes result ; if actin is in excess , there are free actin oligomers and gelsolin - actin complexes . the actin severing occurs by way of a nonproteolytic cleavage of the noncovalent bond between adjacent actin molecules . gelsolin &# 39 ; s severing activity is activated by micromolar ca 2 ++ and has been shown to be inhibited by phosphatidyl inositol , bisphosphate ( pip2 ) and phosphatidyl inositol monophosphate ( pip ). since extracellular ca 2 ++ concentrations are at millimolar levels and extracellular fluids do not normally contain pip or pip 2 in a form that inhibits gelsolin , plasma gelsolin is constitutively active in extracellular fluids . dbp has a single actin binding site and binds constitutively to monomeric but not f - actin . in one embodiment , efficacious levels of actin - binding compounds are administered so as to provide therapeutic benefits against the secondary toxic effects of excessive extracellular actin . by &# 34 ; efficacious levels &# 34 ; of actin - binding compounds is meant levels in which the toxic effects of free extracellular actin are , at a minimum , ameliorated . by &# 34 ; excessive &# 34 ; extracellular actin is meant an amount of extracellular actin which exceeds the ability of the plasma proteins to bind and clear the actin from extracellular fluids without secondary tissue damage or toxic effects . by &# 34 ; secondary &# 34 ; tissue damage or toxic effects is meant the tissue damage or toxic effects which occur to otherwise healthy tissues , organs , and the cells therein , due to the presence of excessive extracellular actin in the plasma , usually as a result of a &# 34 ; primary &# 34 ; tissue injury elsewhere in the body . in the methods of the invention , infusion of actin - binding compounds , such as , for example , gelsolin , dbp , or actin - binding fragments thereof results in a ) binding to actin monomers so as to prevent their condensation into actin filaments , and / or b ) cleavage of actin filaments to the monomeric state , and / or c ) enhanced clearance of such actin complexed to actin - binding protein or fragments thereof from the circulation or extracellular tissue environment . actin - binding compounds may be conjugated , either chemically or by genetic engineering , to fragments of other agents which provide a targeting of such actin - binding compound to a desired site of action . actin - binding compounds or active fragments thereof which possess the ability to transport across the renal glomerulus filter may be used to reduce actin toxicity to the kidney . actin - binding compounds which have a molecular weight less than 65 kd may be expected to cross the renal glomerulus filter and thus be capable of neutralizing toxic effects of filtered actin ; such compounds may also more easily penetrate plugs of actin lodged in capillaries of any organ or in the extracellular space . alternatively , other compounds may be conjugated , either chemically or by genetic engineering , to the actin - binding compound or active fragment thereof , so as to enhance or provide additional properties to such actin binding compound , especially properties which enhance the compound &# 39 ; s ability to promote relief of actin &# 39 ; s toxic effects . for example , because actin promotes intravascular blood coagulation and inhibits fibrinolysis , by conjugating tissue plasminogen activator and / or an antithrombin such as hirudin or active fragments thereof to the actin - binding compound one can target a fibrinolytic agent to the sites where tissue injury released actin which promoted intravascular blood coagulation . amounts and regimens for the administration of actin - binding compounds can be determined readily by those with ordinary skill in the clinical art of treating actin - related disorders , tissue injury and inflammation . generally , the dosage of actin - binding compound treatment will vary depending upon considerations such as : type of actin - binding compound employed ; age ; health ; conditions being treated ; kind of concurrent treatment , if any , frequency of treatment and the nature of the effect desired ; extent of tissue damage ; gender ; duration of the symptoms ; and , counterindications , if any , and other variables to be adjusted by the individual physician . dosage can be administered in one or more applications to obtain the desired results . the dosage can be calculated in the following manner . the normal blood gelsolin concentration is 2 . 4 μm ( 2 . 4 μmol / l ), and the normal blood dbp concentration is 5 μm ( 5 μmol / l ). thus , the total blood actin - binding capacity ( abc ) is approximately 7 . 5 μmol / l . the blood volume is 6 % of the body weight , hence a 70 kg person has 4 . 2 liters of blood and thus ( 4 . 2 l × 7 . 5 μmol / l ) 31 . 5 μmols abc . since dbp and gelsolin are distributed throughout the extracellular space ( which is 10 % of the body weight , the body contains ( 7 . 5 × 7 ) 52 . 5 μmols abc . it may be desired to administer between 32 and 53 μmols of an actin binding compound ( or 0 . 46 μmol / kg body weight ) to cover total complexing or depletion of endogenous abc . since 0 . 425 mg of actin is equal to 1 μmol , and since there is 4 . 86 mg actin per gram of skeletal muscle , each gram of muscle contains 11 . 3 μmol actin , or 4 . 6 grams of muscle destruction could neutralize total body abc . however , because the toxic effects of actin are presumably local ( e . g ., inhibition of clot lysis ), sequestered or kinetically determined ( e . g ., actin permeates an organ faster than binding proteins neutralize it ), it is likely that a theoretically minimum dose will have to be adjusted upward in order to achieve kinetically favorable therapeutic effects . the kinetic effect can be important , for example , since hemolysis of about half of erythron , which should liberate only 4 . 2 μmol of actin , reduces the plasmia gelsolin concentration by half acutely ( smith et al . blood 72 : 214 - 2181 ( 1988 )), suggesting slow equilibration between extravascular and blood compartments . conversely , a therapeutically effective state , capable of breaking up local deposits of actin , may be achievable only by a transient pulse of a high concentration of actin - binding molecules . the compounds of the invention can be administered in any appropriate pharmacological carrier for administration . they can be administered in any form that effects prophylactic , palliative , preventative or curing conditions of tissue injury in humans and animals . preparations of the actin - binding proteins of the invention for parenteral administration includes sterile aqueous or non - aqueous solvents , suspensions and emulsions . examples of non - aqueous solvents are propylene glycol , polyethylene glycol , vegetable oil , fish oil , and injectable organic esters . aqueous carriers include water , water - alcohol solutions , emulsions or suspensions , including saline and buffered medical parenteral vehicles including sodium chloride solution , ringer &# 39 ; s dextrose solution , dextrose plus sodium chloride solution , ringer &# 39 ; s solution containing lactose , or fixed oils . intravenous vehicles include fluid and nutrient replenishers , electrolyte replenishers , such as those based upon ringer &# 39 ; s dextrose and the like . the actin - binding proteins of the invention may also be administered by means of pumps , or in sustained - release form , especially , when the primary injury is prolonged or delayed rather an acute . an example in which the primary injury is often prolonged or delayed rather than acute is a myocardial infarction wherein the damage to the heart muscle is not revealed ( or persists ) until days after the primary heart attack . the actin binding molecules of the invention may also be delivered to specific organs in high concentration by means of suitably inserted catheters , or by providing such molecules as a part of a chimeric molecule ( or complex ) which is designed to target specific organs . administration in a sustained - release form is more convenient for the patient when repeated injections for prolonged periods of time are indicated . for example , it is desirable to administer the actin - binding proteins of the invention in a sustained - release form when the methods of the invention are being used to treat a genetic or chronic disease based upon an actin - related disorder so as to maximize the comfort of the patient . the actin - binding proteins of the invention can be employed in dosage forms such as tablets , capsules , powder packets , or liquid solutions for oral administration if the biological activity of the protein is not destroyed by the digestive process and if the characteristics of the compound allow it to be absorbed across the intestinal tissue . the pharmaceutical compositions of the present invention are manufactured in a manner which is in itself know , for example , by means of conventional mixing , granulating , dragee - making , dissolving , lyophilizing or similar processes . the compositions of the present invention , in and of themselves , find utility in the control of actin - induced physiological damage , be it chronic or acute . the compositions of the invention direct the body &# 39 ; s own mechanisms for dealing with excess actin in the bloodstream or extracellular tissues to its maximum potential . in intravenous dosage form , the compositions of the present invention have a sufficiently rapid onset of action to be useful in the acute management of potential tissue damage . additionally , a low potency version is useful in the management of mild or chronic actin - related disorders . in addition , the compositions of the present invention provide requisite reagents for the laboratory assay of actin levels in an animal &# 39 ; s bloodstream or extracellular tissues . actin - binding proteins which are substantially free of natural contaminants can be isolated and purified from their natural or recombinant sources in accordance with conventional conditions and techniques in the art previously used to isolate such proteins , such as extraction , precipitation , chromatography , affinity chromatography , electrophoresis , or the like . one of skill in the art can identify the actin - binding domain ( s ) of an actin - binding compound using techniques known in the art , without undue experimentation , and such domains are preferred in the methods of the invention . for example , derivatives of the native actin - binding proteins , or , derivatives of recombinantly produced actin - binding proteins , can be made by proteolytic cleavage of the full - length actin - binding protein with common proteases , such as , for example , trypsin , chymotrypsin , and subtilisin . affinity chromatography with actin - derivatized resins may be used to assay such fragments for their actin - binding ability . when identification of compounds or fragments thereof which possess actin - severing activity is desired , such compounds or fragments can also be identified using techniques known in the art , for example , by following the rate of depolymerization of pyrene - labeled f - actin . further , such fragments may be identified by their homology to other known actin - binding or actin - severing domains wherein it may be predicted that function will follow homology . for example , it is known that severin , gelsolin and villin , and especially amino acid residues 40 - 351 in severin and amino acid residues 63 - 383 in gelsolin , show extensive homology in the domain responsible for f - actin severing activity . the n - terminal half of gelsolin , for example , an n - terminal tryptic fragment known as ct45 , is capable of severing f - actin and contains two actin binding sites . one of these sites resides in a chymotryptic fragment , ct15n ( human gelsolin residues 24 - 150 ), which binds the ends of actin monomers and filaments with high affinity ; the other site is contained in the adjacent fragment ct28n ( residues 151 - 406 ), which binds to the side of f - actin in a polyphosphoinositide - regulated manner . neither of the fragments sever actin filaments by themselves . the smallest gelsolin polypeptide which is capable of severing f - actin encompasses residues 25 - 165 of plasma gelsolin . efficacious amounts of ct45 which are substantially free of natural contaminants can be administered to a patient who has had a severe myocardial infarction or other thrombotic event for a time and period throughout which damage to the heart or tissue is revealed . the amount of the peptide to be administered may be determined after assaying the ratio of total to bound gelsolin in the patient &# 39 ; s plasma to determine the fraction of the total gelsolin which has already been saturated with actin released by the dying heart cells and calculating the amount needed to , at a minimum , supply enough actin - binding capability to return this ratio to levels found in healthy individuals . further , indicators of renal damage such as the patient &# 39 ; s bun and creatinine levels may be closely monitored and the dose of the actin - binding molecule adjusted higher , if necessary , if such indicators reveal that renal damage may be occurring . thus , the present invention may be used to administer actin - binding compounds to animals in levels sufficient to either a ) prevent actin filament formation and / or b ) process actin filaments to a &# 34 ; stable &# 34 ; monomeric state , in amounts sufficient to treat and / or prevent undesirable physiological effects of free actin accumulation or release in the bloodstream . further , compounds such as actin - binding proteins are highly conserved among species and can be easily isolated in large quantities from nonhuman ( bovine , porcine ) plasma and / or muscle tissues and fragments of these proteins can be chemically or enzymatically prepared by techniques well - known in the art . thus such actin - binding compounds can be administered to a subject in need of the therapeutic methods of the invention without provoking a severe immune response . all references cited in this application are incorporated herein by reference . having now generally described the invention , the following examples further describe the materials and methods used in carrying out the invention . the examples are not intended to limit the invention in any manner . an efficacious amount of an actin - binding compound , for example ct45 , or a peptide containing residues 25 - 165 of plasmia gelsolin , which binds g - and f - actin with high affinity , and which is capable of actin - filament severing and is substantially free of natural contaminants , in a pharmaceutically acceptable vehicle , is administered to a subject that has recently undergone massive trauma , acute hemolysis or rhabdomyloysis due to any cause . the amount of the actin - binding molecule to be given , and the duration of therapy , may be determined by monitoring depletion of extracellular actin - binding capacity through measurements of total plasma gelsolin concentrations or of actin gelsolin complexed in the plasma . if necessary , endogenous gelsolin can easily be differentiated from a therapeutic fragment of gelsolin by monoclonal antibodies directed to epitopes in different domains of the native gelsolin molecule , such antibodies are known in the art . ( chaponnier et al . j . cell biol . 103 : 1473 - 1481 ( 1986 )). in addition , by monitoring pulmonary functions , for example , by measurement of arterial blood oxygenation , and / or renal function , for example , by measurement of serum bun and creatinine concentrations , the dosage of actin - binding compound is adjusted to therapeutic levels . an efficacious amount of an actin - binding molecule is given to patients who have sustained an acute myocardial infarction due to coronary artery thrombosis , prior to or simultaneous with administration of a thrombolytic agent . this is done because plasma gelsolin levels have been known to decrease , progressively following acute myocardial infarction and because actin has been shown to inhibit plasmin , the enzyme activated by all thrombolytic treatments . it is also done because all fibrinolytic therapies currently in existence have had a finite failure rate , that is , arterial patency is not achieved or else reocclusion occurs . to the extent that this failure is caused by inhibition of plasmin generated endogenously or as a result of thrombolytic therapy by free actin emerging from necrotic atheromatous plaques or from infarcted myocardial tissue , actin - binding molecule therapy is directed against this mechanisms of failure . now having fully described this invention , it will be understood by those with skill in the art that the scope may be performed within a wide and equivalent range of condition , parameters , and the like , without affecting the spirit or scope of the invention or of any embodiment thereof . | 6 |
fig1 is a block diagram of a program and system information protocol ( psip ) data generator according to the invention in the context of system 100 that can produce an advanced television standards committee ( atsc ), standard a / 65 , compliant digital television ( dtv ) signal . the system 100 of fig1 includes : a psip generator 102 according to the invention ; sources of data upon which the psip generator operates , such as a source 108 of listing service data , a source 110 of traffic system data and a source 112 of other data ; a multiplexer 114 to incorporate the psip data from the psip generator 102 into an a / 65 - compliant dtv signal ; and a source 116 of audio data , video data , etc . in fig1 , the psip generator 102 includes an interface unit 104 and a non - uniform interval calculation unit 106 . the psip generator 102 according to the invention can be implemented by adapting a well known psip generator according to the discussion herein . an example of a known psip generator is the psip builder pro brand of psip generator manufactured and sold by triveni digital inc . the psip builder pro itself is based upon a programmed pc having a pentium type of processor using the microsoft windows nt4 . 0 operating system . the software can be written in the java language . the other blocks of fig1 correspond to known technology . in fig1 , the invention has been depicted in the context of a digital television broadcast such as a terrestrial broadcast , and more particularly one that is compliant with the advanced television standards committee ( atsc ), where each event is a program , and the schedule data is psip data . however , the invention is readily applicable to any television format , e . g ., analog terrestrial , analog cable , digital cable , satellite , etc ., for which an electronic schedule is maintained and corresponding data is sent to a receiver for the purpose of presenting an electronic program guide ( epg ) to a viewer . the units 104 and 106 within the psip generator 102 do not necessarily correspond to discrete hardware units . rather , the units 102 and 104 can represent functional units corresponding to program segments of the software that can embody the invention . the interface unit 104 can generate a graphical user interface ( gui ) that operates to receive at least one , issuance parameter for like psip tables ( e . g ., etts or eits ) that do not all have an issue interval assigned by the a / 65 standard . such an interface will be described in more detail below with regard to fig2 . the non - uniform interval calculation unit 106 is operable to determine non - uniform issuance intervals for ones of the like psip tables that do not have an assigned interval , based upon the issuance parameter ( s ) received via the interface unit 104 . fig2 is an example image of a dialog window 200 ( a gui ) that can be generated by the interface unit 104 according to the invention . in fig2 , the dialog window 200 can include : a cycle time settings tab 202 ; a miscellaneous settings tab 204 ; a ftp periodic update controls tab 206 ; an “ apply settings ” button 226 ; a “ defaults ” button 228 ; a “ refresh ” button 230 ; and a “ close ” button 232 . the position of the cursor can be indicated via the reverse highlighting 234 . the cycle time settings tab 202 can include a “ cycle times ( in seconds ) for eits :” region 208 , a “ cycle times ( in seconds ) for psip tables :” region 210 , a “ cycle times ( in seconds ) for psi tables :” region 212 and a “ cycle times ( in seconds ) for etts .” region 214 . it is well known that eits carry program schedule information including program title information and program start information . each eit covers a three - hour time span . etts carry text messages associated with the eits , e . g ., program description information for an eit . in fig2 . the “ cycle times ( in seconds ) for eits :” region 208 of the dialog window 200 can include : a box 216 in which a user can enter a fixed interval for the eit 0 table ; a box 218 in which a user can enter an increment for the eit k table ; and a box 220 in which a user can enter a maximum number of eit tables that are to be sent . usually , the number entered in box 220 will be far smaller than the maximum number of eit tables permitted by the a / 65 standard . also , in fig2 . the “ cycle times ( in seconds ) for etts :” region 214 can include : a box 222 in which a user can enter a fixed interval for the ett 0 table ; and a box 224 in which a user can enter an increment for the ett k table . the non - uniform interval calculation unit 106 can receive the values in the boxes 216 , 218 , 220 , 222 and 224 from the regions 208 and 214 , respectively , and use them to determine the non - uniform issuance intervals of , e . g ., the eit and ett tables . further discussion of the operation of the unit 106 is couched in a particular non - limiting example , for simplicity . the a / 65 standard recommends a time interval for outputting the zeroith event information table ( eit ), i . e ., eit 0 , but provides no guidelines regarding eit 1 through eit 128 . for the rating region table ( rrt ), the a / 65 standard recommends a value only for the output frequency of rrt 1 . and no recommendation is made regarding the output frequencies of any of the extended text tables ( etts ). under the a / 65 standard , it is left to the discretion of the operator of a psip data generation system to select the frequency of table output for the unmentioned tables . the operator could specify an entry for each group of tables , but that would be burdensome because it would require a total of over 500 entries . a simple solution to the problem of unspecified output frequencies would be to set each type of table to the same output frequency , but that creates a problem in that the guidelines for bandwidth specified by the a / 65 standard would be exceeded . a further consideration to solve the problem , namely of how to insert the least amount possible of meta data into the dtv signal and yet still achieve an a / 65 compliant dtv signal , is : how closely in time to the present moment does each table relate ? that is , table types such as the eit describe event information up to two weeks into the future . a user of an electronic program guide that receives such table types will typically want to view event information concerning only the next 24 - 48 hours . users typically do not look farther into the future than this because ( at least in part ) the event schedule information two weeks into the future is much more likely to change than is event schedule information concerning the next 24 - 48 hours , i . e ., the farther into the future . the less reliable the event information becomes . care must be exercised so as not to set the intervals to be too infrequent . this is because the dtv receiver can become stalled waiting for a table to arrive . if the dtv receiver is stalled for 0 . 5 seconds , a user might not notice or object if she did . but such a delay of , e . g ., 4 - 5 seconds probably would be noticed by , and probably would annoy , the user . this reinforces the need to set short intervals for near term events because users are likely to want to display epg information about them . again , the invention , in part , provides an interface unit 104 that defines parameters that the non - uniform interval calculation unit 106 then can use to generate the time intervals between tables of the same type . typically ( but not necessarily ) the function performed by the unit 106 will be linear , e . g ., with a defined start interval ( the root_time ) and an increment interval ( increment_time ). for example , if the user desires eit 0 to be output every half second ( root time ) with each succeeding eit 0 to be output 0 . 25 seconds less frequently than the preceding eit , namely eit i the user would enter 0 . 5 seconds as the root_time in box 216 and 0 . 25 seconds as the increment_time in box 218 . the function for each table eit - i interval would then be : for example , eit 12 can be output every 0 . 5 sec +( 0 . 25 sec * 12 )= 3 . 5 seconds , which is less frequent than eit 0 . obviously , other examples are possible , e . g ., the increment_time for each of different groups of like tables can be set . a similar calculation for etts can be performed by the unit 106 . the invention has at least the following advantages : 1 ) it provides an easy way of entering the interval times for the tables : 2 ). it defines the interval times for like tables that are not all fixed to a constant interval ; and 3 ) it provides an interval function that increases the interval for tables that represent information further out in time . the invention being thus described , it will be obvious that the same may be varied in many ways . such variations are not to be regarded as a departure from the spirit and scope of the invention , and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims . | 7 |
fig1 shows an exploded view of the inventive socket assembly 11 comprising a base 12 and a cover 14 both of which are formed or molded of a suitable relatively rigid insulative material such as plastic . the socket 11 includes a central passage 15 for mounting onto the terminal pin portion of the neck of a television picture tube , not shown . the terminal pins generally labeled 16 extend downwardly for purposes of connecting the socket assembly 11 to suitable electrical and electronic circuitry , as is known . a conductor plate or ring 30 , in substantially a semi - circle shape , conforms to the shape of a horizontal planar surface 22 on base 12 and is securely embedded as by molding , as is well - known , slightly beneath the surface 22 . conductor plate 30 includes a terminal tab 31 for connecting through an electrical lead 32 to ground reference . openings 33 are formed in surface 22 to selectively expose sections of the ring 30 to provide one part of an arc gap as will be explained . the pins 16 extend upwardly through suitable apertures 18 in base 12 and are bent over to have a portion 21 which extends horizontally over respective spark gap openings 33 formed on surface 22 . pin portions 21 each include a dimple protrusion 23 which extends downwardly toward , but spaced from , ring 30 . this provides the gap across which the low voltage arcing occurs ; as is well - known in the art . the base plate 12 is generally in an irregular circular form , in plan view , as is the entire assembly 11 . the base 12 includes an upwardly extending peripheral wall 29 which is irregular in height . the cover 14 includes a peripheral wall 24 which mates with and encircles wall 29 . the top 25 of cover 14 comprises two stepped planar surfaces which conform to and provide a cover for base 12 . the periphery of opening 15 in base 12 includes one or more positioning notches 28 on its circumference for properly indexing the socket assembly 11 on the neck of the associated tube . the wall 24 of cover 14 includes vertically extending flexible latches 26 which mate with , or are received by respective positioning catches or shoulders 27 formed on the periphery of the base 12 . the ends 33 of the pins 16a which extend to the periphery of opening 15 provide electrical contact with the picture tube pins . pin contact ends 33 are bifurcated and are in the form of a spring - biased and centrally cantilevered structure similar to that described in u . s . pat . no . 3 , 733 , 522 assigned to the same assignee as the present invention . a portion of base 12 extends vertically to form a housing 40 which is substantially rectangular in plan view , on one side of base 12 . housing 40 contains or encloses the high voltage spark gap devices , see also fig2 . housing 40 is divided into two similar but separate chambers or compartments 41 and 42 for housing or containing two distinct but similar set of spark gap electrodes . fig2 shows a cross - sectional view of the housing 40 and one set of the spark gap ball electrodes 43 and 44 in chamber 41 . each ball electrode is substantially hemi - spherical and includes a central nipple 60 which extends toward the other electrode ; this provides a reliable spark gap initiating point . as seen in fig1 the housing 40 includes a central air space 45 formed by dielectric walls or barrier 46 and 47 . the combination of the foregoing dielectric barrier walls and the air spaces therebetween provide improved thermal and dielectric characteristics for the socket assembly 11 substantially according to the concepts described in u . s . pat . no . 3 , 771 , 024 and assigned to the same assignee as the present invention . the chamber 41 tends to maintain the atmosphere therein constant and stable such that the spark gap formed between the two opposed electrodes 43 and 44 maintain a more constant arcing level . it has been found that in certain multipotential applications , it is necessary that the spacing between pairs of ball electrodes be adjusted to arc at different high voltage ranges . thus , in the embodiment shown , ball electrodes 43 and 44 are spaced at a greater distance than the electrodes in compartment 42 to accommodate a larger operating or arcing voltage . as shown in fig2 the ball electrode 43 is embedded or formed in a plastic plug 51 which conforms to the periphery of the chamber 41 , and is received in chamber 41 . the electrode 43 is connected as by lead 62 to the pin 16a and to the high voltage conductor 59 . chamber 41 includes an interior peripheral ledge 63 in which a hollow cup shaped ring spacer 64 is positioned . spacer 64 includes an inwardly extending rim 65 for purposes to be described . the plug 51 including ball electrode 43 rests on the top of spacer 64 . the lower electrode 44 is embedded in the bottom of chamber 41 and its lower surface is open to the surroundings . a vent hole 66 vents the interior of chamber 41 to the surroundings . electrode 44 is connected through lead 67 to ground reference . an important feature of the invention are the structures shown in fig2 which provides a corona disruption capability . since corona precedes dielectric breakdown , a corona discharge adversely affects and changes the selected and pre - established voltage breakdown or arcing potential , between the electrodes . it has been found that with ball electrodes positioned in chamber 41 having smooth sides , a corona discharge path initiated at one electrode extends or moves along the walls of the chamber and thence tends to reduce the arcing potential between the two electrodes . as shown by the dashed lines 69 in fig2 the rim or shoulder 65 on spacer 64 provides an effective barrier which interrupts the corona ionizing path track to thereby inhibit corona discharge . in effect the rim 65 provides a shadow area , indicated as x , from electrodes 43 or 44 to the wall of the chamber 41 , which tends to inhibit establishing a corona discharge along the wall of the chamber . while the invention has been particularly shown and described with reference to a preferred embodiment 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 . | 7 |
in both of the semiconductor devices shown in fig1 and 2 , multiple semiconductor materials are integrated to form the device on a si substrate 10 and 20 respectively . it should be noted that both fig1 and fig2 are diagrammatic and are not drawn to scale , the dimensions of the thicknesses of the various layers of semiconductor materials being exaggerated for greater clarity . corresponding parts in both figures are given the same hatching and generally have the same references numerals but separated by ten , for example the si substrate in fig1 has the reference numeral 10 whereas in fig2 the si substrate has the reference numeral 20 . in both fig1 and fig2 , the semiconductor device comprises a cmos device wherein both an n - mosfet device n and a p = mosfet device p are formed on the same si substrate 10 , 20 . in the first embodiment shown in fig1 , the substrate also comprises a layer 11 of gap provided over a base si layer 10 to provide insulation and to reduce thermal problems caused by self - heating and the n and p devices are formed on the layer 11 . each of the n and p devices comprises a channel of appropriate type conductivity semiconductor material 12 , 13 respectively formed on the layer 11 and separated by an isolation region 14 . in fig1 , the first , n - type conductivity semiconductor material used for the channel 12 of the n device also comprises silicon and the second p - type conductivity semiconductor material used for the channel 13 of the p device comprises a silicon - germanium alloy . the manner in which this cmos device is manufactured will now be described with reference to fig3 . after provision of the si substrate 10 , the gap layer 11 is first grown on the si layer 10 . over this , a second thin si layer 12 is then grown to form part of the first channel material for the n - mosfet device n . the second thin si layer 12 can be p - type doped in - situ during an epitaxy growth step . the thickness of this second si layer 12 may be between 10 nm and 20 nm . since a high crystalline quality undoped gap layer , 11 and the second si layer 12 can be directly grown in a single growth step on a si substrate 10 using either molecular beam epitaxy or vapor phase epitaxy or a metalorganic chemical vapour deposition ( mocvd ) technique , a reduction in the fabrication time and cost of a wafer as compared to the conventional but tedious simox or wafer bonding processes used in soi type devices can be achieved . the thickness of the gap layer 11 may be between 50 nm and 150 nm . essentially , therefore , a complete base structure comprising the layers 10 , 11 , and 12 with an excellent interface quality in the si / gap interface can be epitaxially grown initially in a single epitaxy growth step ( step 1 ). the second si layer 12 is then dry etched at a place where the p - mosfet device p is to be defined ( step 2 ). in order to form the p - mosfet device p , a si0 . 75ge0 . 25 layer 13 is then epitaxially grown , which may be between 10 nm and 30 nm thick and n - type doped in - situ during epitaxy growth step ( step 3 ). the composition of ge in this layer may be tuned ( x = 0 . 2 − 0 . 3 ) to match the lattice constant exactly with that of the gap layer 11 beneath it . an isolation region 14 is then defined first by anisotropically etching the si layer 12 and the si0 . 75ge0 . 25 layer 13 to separate these layers and then by depositing silicon nitride ( si3n4 ) or sio2 by a conventional cvd technique ( step 4 ). gate oxide layers 15 are then formed over the layers 12 and 13 ( step 5 ). these layers 15 may be thermally grown and may typically comprise sio2 or another high - k material such as tantalum oxide ( tao5 ), hafnium oxide ( hf02 ) or other suitable gate dielectric material . gate electrode layers 16 are then deposited ( step 6 ) and may be of polysilicon or any other suitable metal with the desired work function . the p and n doping in the channel layers 12 and 13 and the gate work function , i . e . the gate material , will define the threshold voltage of the device . once the gate electrode layers 16 have been deposited , the source - drain regions can be formed ( steps 7 and 8 ). preferably , nitride spacer layers 17 are first deposited around the gate region formed by the gate oxide layers 15 and the gate electrode layers 16 ( step 7 ). these nitride spacers may be between 25 nm and 100 nm thick . after this a source - drain implant step is performed . these implants may comprise arsenic ( as ) for the n - mosfet device n and boron ( b ) for the p - mosfet device p . finally , the source - drain contact layers 18 of any suitable metal are deposited ( step 8 ). turning now to the embodiment shown in fig2 , again a gap layer 21 is first grown on a si substrate 20 . however , in this embodiment , the channel layer 22 of the n - mosfet n is composed of gaas material and the channel layer 23 of the p - mosfet p is composed of a si0 . 75ge0 . 25 material . as discussed above , one problem associated with the growth of gaas on a gap / si substrate 21 , 20 is lattice mismatch between the si and gaas layers . this problem is overcome in the present embodiment by using intermediate layers 29 and 30 , each of which comprises a superlattice stack of between four and six layers . the manner in which this cmos device is manufactured will now be described with reference to fig4 . the first layer 29 is laid down over the gap layer 21 and comprises alternating layers of gap and gaasp each being between 5 nm and 10 nm thick and left undoped . the second layer 30 is laid down over the layer 29 and comprises alternating layers of gaasp and gaas , again each being between 5 nm and 10 nm thick and left undoped . each layer 29 , 30 may be grown between four and six times to absorb the lattice mismatching . initially , a base structure b comprising the si layer 20 , the gap layer 21 , the intermediate layers 29 and 30 , and the first channel layer 22 of the n - mosfet n is first grown in a single epitaxy step ( step 1 ) using either a molecular beam epitaxy ( mbe ) or a metalorganic chemical vapor deposition ( mocvd ) technique . the top gaas channel layer 22 may be intrinsically p - type doped to a desired value to form a p - well for the n - mosfet n . the thickness of gaas channel layer is preferably between 10 nm and 20 nm thick and the thickness of the gap layer 21 is preferably between 50 nm and 150 nm . once the base structure b has been formed , a portion of the top gaas layer 22 is dry etched at a place where the p - mosfet p is to be formed ( step 2 ). a si0 . 75ge0 . 25 layer 23 is then epitaxially grown ( step 3 ). this layer 23 is preferably between 10 nm and 30 nm thick and n - type doped in - situ during the epitaxy growth step . as in the first embodiment , the composition of the ge may be tuned ( x = 0 . 2 − 0 . 3 ) to match the lattice constant exactly with the gap layer 21 underneath . an isolation region 24 is then defined first by anisotropically etching the gaas layer 22 and the si0 . 75ge0 . 25 layer 23 to separate these layers and then by depositing silicon nitride or silicon dioxide by a conventional cvd technique ( step 4 ). the gate dielectric materials are then grown ( step 5 ). unlike the first embodiment shown in fig1 , in this embodiment these materials may be different . the gaas channel 22 of the n - mosfet n may be covered with a gallium oxide ( gao ) dielectric layer 25 that is be thermally grown or deposited to a thickness selected for a desired device performance . however , the si0 . 75ge0 . 25 material forming the channel layer 23 of the p - mosfet p is covered by a conventional sio2 dielectric material 31 , which is also thermally grown or deposited to a thickness selected for a desired device performance . other high - k materials , such as tao5 , hf02 or any other gate dielectric material may also be used for p - mosfet p . once the dielectric layers 25 and 31 have been formed , the gate electrode layers 26 are then deposited ( step 6 ) and may be of polysilicon or any other suitable metal with a desired work function . the electrode material may be the same for both the n - and p - mosfet devices n and p . the p and n doping in the top channel layers 22 and 23 and the gate work function , i . e . the gate material , will define the threshold voltage of the device . once the gate electrode layers 26 have been formed , the source - drain extensions may be implanted and are preferably arsenic ( as ) for the n - mosfet n and boron ( b ) for the p - mosfet p . as in the first embodiment , nitride spacer layers 27 are then deposited around the gate regions ( step 7 ). the nitride spacer layers 27 are preferably between 25 nm and 100 nm thick . finally , the source - drain metal contact layers 28 of any suitable metal are then deposited ( step 8 ). | 7 |
referring to the drawings in detail , and initially to fig1 - 5 , a shift arrangement 10 for a bicycle according to the present invention , includes a housing 16 to be secured to a handlebar 12 of a bicycle by a clamp 14 . for discussion hereafter , reference to an inner facing side or inner facing surface will refer to the side or surface facing the rider , and reference to an outer facing side or outer facing surface will refer to the side or surface facing away from the rider . specifically , housing 16 includes a first half housing shell 18 and a second half housing shell 20 secured to first half housing shell 18 so as to encase the assembly for effecting gear shifting . as shown best in fig5 - 8 , first half housing shell 18 includes a planar circular outer wall 22 having an annular inturned flange 24 at the periphery thereof . three equiangularly spaced ears 26 extend outwardly from annular inturned flange 24 , each ear 26 having a threaded opening 28 therein facing second half housing shell 20 . a central opening 30 is provided in planar outer wall 22 , with central opening 30 having a slightly oval or oblong configuration . two raised stops 32 and 34 extend inwardly from planar outer wall 22 at the edge of central opening 30 , with stops 32 and 34 being about 100 degrees apart around central opening 30 . an arcuate guide wall 36 is also provided on the inside surface of planar outer wall 22 between stops 32 and 34 and spaced away from central opening 30 . a gap 35 is provided between the end of arcuate guide wall 36 and stop 34 , the purpose for which will become apparent from the discussion hereafter . as best shown in fig5 and 9 - 14 , second half housing shell 20 also includes a planar substantially circular outer wall 40 having an annular inturned flange 42 at the periphery thereof . an annular wall 44 extends outwardly from the periphery of annular inturned flange 42 , with three equiangularly spaced ears 46 extending outwardly from annular wall 44 . each ear 46 has a through bore 48 therein . in this regard , bolts 50 ( fig1 ) extend into through bores 48 and are threadedly received in threaded openings 28 to secure second half housing shell 20 to first half housing shell 18 , with annular wall 44 seating on inturned flange 24 . annular inturned flange 42 includes an outwardly extending nose 52 of a generally frusto - conical configuration with a slight taper extending therefrom , and with a central bore 54 extending therethrough in communication with the interior of housing 16 . as shown in fig1 , nose 52 cooperates with cable adjust collar 56 , with the derailleur cable 57 extending through cable adjust collar 56 and nose 52 into the interior of housing 16 , as will be explained in greater detail hereafter . a cylindrical boss 58 extends inwardly from the center of the inner facing surface of circular outer wall 40 and has a substantially trapezoidal shaped upper end 60 with the longer side of substantially trapezoidal shaped upper end 60 being rounded , although the present invention is not limited to this shape . a central opening 61 is provided through cylindrical boss 58 and substantially trapezoidal shaped upper end 60 , and smaller offset openings 63 and 65 are provided in substantially trapezoidal shaped upper end 60 . a slight depression 62 is formed near the periphery of circular outer wall 40 at the inner facing surface thereof at a position approximately 70 degrees offset from nose 52 in the counterclockwise direction of fig1 , with a through opening 64 formed in the center of slight depression 62 . a raised projection 66 is formed to one side of depression 62 in the counterclockwise direction of fig1 , at the inner facing surface of circular outer wall 40 and at the inner facing surface of annular inturned flange 42 , and includes a threaded opening 68 therein . raised projection 66 includes a triangular shaped projection 70 extending inwardly from annular inturned flange 42 . a substantially triangular recess 72 is formed in the inner facing surface of annular inturned flange 42 directly behind slight depression 62 , and extends upwardly to annular wall 44 . a circular opening 74 extends into the bottom wall of recess 72 . a u - shaped recess 76 is formed in the inner facing surface of annular inturned flange 42 to the opposite side of slight depression in the clockwise direction of fig1 , and extends the entire height thereof . lastly , a through opening 78 extends through annular inturned flange 42 , substantially diametrically opposite u - shaped recess 76 . referring now to fig4 , 5 and 15 - 18 , a slide or mounting element 80 as part of a mounting arrangement 79 for the shift lever to be discussed hereafter , is slidably mounted to planar circular outer wall 22 of first half housing shell 18 . specifically , slide 80 includes a circular disc 82 having a circular boss 84 extending from the center of the outer facing surface of circular disc 82 . boss 84 is cut away to define a slightly raised pedestal 86 and raised walls 87 a and 87 b extending upwardly therefrom with a generally outer circular footprint . raised walls 87 a and 87 b define a large rectangular open area 88 between raised walls 87 a and 87 b , which is in communication with a small rectangular open area 90 between raised walls 87 a and 87 b through an intermediary curved open area 92 between raised walls 87 a and 87 b , all above slightly raised pedestal 86 . a central threaded opening 94 is provided on the outer facing surface of circular disc 82 at the center thereof . a cylindrical projection 96 is provided on the outer facing surface of circular disc 82 , adjacent to small rectangular open area 90 and at a lower height than slightly raised pedestal 86 . an annular advance roller 97 ( fig1 ) is rotatably mounted on cylindrical projection 96 , and is adapted to fit through gap 35 . the opposite inner facing surface of slide 80 includes an elongated recess 98 having a flat end 100 at one end thereof and extends in the same lengthwise direction as large rectangular open area 88 and centered therewith . a triangular recess 102 is provided to one side of elongated recess 98 and includes a guide wall 103 as will be discussed in greater detail hereafter . a further recess 104 is provided on the opposite side of elongated recess 98 for the purpose of reducing material . in addition , a slightly arcuate raised wall 106 extends upwardly from the inner facing surface of slide 80 at a position generally inline with elongated recess 98 but near the opposite periphery of circular disc 82 . a further slightly arcuate raised wall 108 of lesser dimensions than slightly arcuate raised wall 106 extends upwardly from one outer circumferential corner of slightly arcuate raised wall 106 . slide 80 is slidably mounted to planar circular outer wall 22 of first half housing shell 18 such that the outer facing surface of slide 80 rests against the inner facing surface of first half housing shell 18 and such that raised walls 87 a and 87 b extend through central opening 30 . a shift lever 110 , as shown in fig5 and 19 , is attached to the outer facing surface of slide 80 , to the outside of first half housing shell 18 . specifically , lever 110 has a generally human leg shaped appearance , with an upper leg section 112 connected to a lower leg section 114 at an angle of about 140 degrees through a knee section 116 , with the free end of lower leg section 114 including a foot 118 extending approximately at a right angle from lower leg section 114 . upper leg section 112 includes a main body 120 having dimensions corresponding to the dimensions of large rectangular open area 88 of slide 80 and fits therein . the free end of upper leg section 112 tapers down through an arcuate reducing section 122 to a reduced dimension rectangular parallelepiped section 124 . arcuate reducing section 122 has dimensions corresponding to the dimensions of intermediary curved open area 92 of slide 80 and fits therein , and rectangular parallelepiped section 124 has dimensions corresponding to small rectangular open area 90 and fits thereon . in this position , a through bore 126 in main body 120 is in coaxial alignment with central opening 94 of slide 80 . a rivet , bolt or the like ( not shown ) extends through bore 126 and central opening 94 to fixedly secure shift lever 110 to slide 80 . it will therefore be appreciated that rotation of shift lever 110 around the axis of through bore 126 results in corresponding rotation of slide 80 relative to first half housing shell 18 . in addition , since raised walls 87 a and 87 b have a generally outer circular footprint , and since central opening 30 of first half housing shell 18 has a slightly oval or oblong configuration , raised walls 87 a and 87 b can slide within central opening 30 . thus , when shift lever 110 is pushed by the user in an axial direction thereof , from the outer surface of foot 118 , as shown in fig4 , raised walls 87 a and 87 b slide within central opening 30 . referring now to fig5 , 20 and 21 , a post sleeve 130 as a rotatable element of an actuating arrangement is provided in the housing 16 against the inner facing surface of slide 80 . specifically , post sleeve 130 includes a thin generally circular plate 132 having two ears 134 and 136 extending outwardly in the plane of plate 132 and separated by an angle of about 100 degrees . a boss 138 is provided at the outer end of one ear 134 and has a post 140 extending therefrom at right angles to the plane of plate 132 , while a post 142 extends from the other ear 136 on the opposite side of plate 132 . an annular groove 141 is provided around post 140 near the free end thereof . a small opening 143 is provided on the opposite surface of ear 136 . in addition , plate 132 includes a central through bore 144 . a center shaft 146 as part of the mounting arrangement 79 is fixed in central opening 61 of cylindrical boss 58 and extends through bore 144 . the free end of center shaft 146 has a post sleeve roller 145 ( fig4 ) thereon which slidably fits within elongated recess 98 and which permits center shaft 146 to rotate therein . a compression spring 147 ( fig4 and 16 ) or other suitable spring member is fit within elongated recess 98 between flat end 100 thereof and post sleeve roller 145 to normally bias post sleeve roller 145 away from flat end 100 . post sleeve 130 is rotatably mounted on center shaft 146 such that post 142 extends within triangular recess 102 of slide 80 . an annular advance roller 148 is rotatably mounted on post 142 and is adapted to be guided along guide wall 103 of slide 80 , as will be discussed hereafter , during sliding movement of raised walls 87 a and 87 b within central opening 30 . advance roller 148 is shown disengaged from post 142 in fig3 merely for better illustration purposes . as shown in fig5 and 22 , a coiled torsion shift lever return spring 131 is mounted against the inner facing surface of post sleeve 130 . the inner end of shift lever return spring 131 is bent to form a bent spring projection 133 that is fixed in offset opening 63 , while the outer end of shift lever return spring 131 is bent to form a bent spring projection 135 that is fixed in small opening 143 provided in ear 136 of post sleeve 130 . in this manner , shift lever return spring 131 functions to normally bias post sleeve 130 in the clockwise direction of fig3 . as a result , annular roller 148 mounted on post 142 functions to rotate slide 80 and shift lever 110 therewith . as shown best in fig3 , 5 and 23 - 28 , a triple gear pulley 150 is rotatably mounted on cylindrical boss 58 of second half housing shell 20 at the inner facing surface of shift lever return spring 131 . triple gear pulley 150 includes a generally cylindrical body 152 having a central through bore 153 through which cylindrical boss 58 extends . cylindrical body 152 has a centrally located annular cable guiding groove 154 around the outer circumference thereof around which derailleur cable 57 extends . a pointed triangular nose 156 extends outwardly from the outer periphery of cylindrical body 152 and intersects with cable guiding groove 154 . triangular nose 156 includes a cylindrical recess 158 at one side which extends partly therethrough , and an elongated slot 160 at the opposite side which extends into open communication with cylindrical recess 158 . triangular nose 156 , as shown in fig4 , is normally oriented in a lower position to the right side thereof . in this manner , cable 57 enters housing 16 and extends within cable guiding groove 154 from a position slightly to the left of triangular nose 156 , and through elongated slot 160 and cylindrical recess 158 . a cylindrical plug 162 ( fig4 ) is fixed to the free end of cable 57 that extends through cylindrical recess 158 , and is fit within cylindrical recess 158 so as to secure the free end of cable 57 to triple gear pulley 150 at pointed triangular nose 156 . a small opening 157 is provided in the inner facing surface adjacent triangular nose 156 . it will be appreciated that cable guiding groove 154 divides the outer circumference of triple gear pulley 150 into an inner circumferential section and an outer circumferential section . a first set of inner gear teeth 164 extend from the inner circumferential section and a second set of outer gear teeth 166 extend from the outer circumferential section , respectively , both starting from a position immediately above triangular nose 156 and extending upwardly and around triple gear pulley 150 to a position approximately diametrically opposite to triangular nose 156 . it will be appreciated that inner gear teeth 164 have a generally symmetrical trapezoidal appearance , while outer gear teeth 166 each have the same inclination in a direction toward triangular nose 156 and have a greater pitch than gear teeth 164 . as a result , and as will be appreciated from the discussion hereafter , gear teeth 166 are slightly offset from gear teeth 164 . a third set of outer gear teeth 168 extend around the outer circumferential section from a position slightly spaced from the end of the second set of outer gear teeth 166 to a position adjacent to the opposite side of triangular nose 156 . gear teeth 168 have a generally symmetrical trapezoidal appearance . as shown in fig5 and 29 , a coiled torsion gear return spring 165 is mounted between second half housing shell 20 and triple gear pulley 150 . the inner end of gear return spring 165 is bent to form a bent spring projection 167 that is fixed in offset opening 65 of second half housing shell 20 , while the outer end of gear return spring 165 is bent to form a bent spring projection 169 that is fixed in small opening 157 adjacent triangular nose 156 of triple gear pulley 150 . in this manner , gear return spring 165 functions to normally bias gear return spring 165 in the counterclockwise direction of fig4 . as shown best in fig3 - 5 , 30 and 31 , a pawl flange 170 is fixed to the outer facing surface of second half housing shell 20 . pawl flange 170 includes a plate 171 having a main section 172 and a finger section 174 extending therefrom . finger section 174 includes a through bore 176 through which a bolt 178 ( fig3 and 4 ) extends from the outer facing side thereof into threaded engagement with threaded opening 68 to fixedly secure pawl flange 170 to second half housing shell 20 . pawl flange 170 further includes a short post 180 extending from the inner facing surface thereof at a left end position of main section 172 of plate 171 and a tall post 182 extending from the inner facing surface thereof at a lower position on main section 172 of plate 171 . as shown in fig3 - 5 , 32 and 33 , a hold pawl 184 as part of an actuating arrangement is rotatably mounted on tall post 182 of pawl flange 170 . hold pawl 184 includes a pawl lever 186 having a substantially central through bore 188 which is mounted on tall post 182 . a downwardly inclined pawl catch 190 is provided at one end of pawl lever 186 for engaging with gear teeth 166 of triple gear pulley 150 , to be described hereafter . further , a post 192 extends from the outer facing surface of pawl lever 186 at the end thereof opposite pawl catch 190 for engagement with the upper arcuate surface of further slightly arcuate raised wall 108 . as shown in fig3 - 5 and 34 , a main pawl 194 as part of an actuating arrangement is then rotatably mounted on long post 182 of pawl flange 170 on top of hold pawl 184 . main pawl 194 includes a pawl lever 196 having an upper engagement surface 197 and a through bore 198 at one end by which main pawl 194 is mounted on tall post 182 . a downwardly inclined pawl catch 200 is provided at an opposite end of pawl lever 196 for engaging with gear teeth 164 of triple gear pulley 150 , to be described hereafter . further , a post 202 extends from the outer facing surface of pawl lever 196 at the end thereof adjacent pawl catch 200 for engagement with the upper arcuate surface of slightly arcuate raised wall 106 . a main pawl spring 204 normally biases pawl catch 200 into engagement with gear teeth 164 , as shown in fig3 and 4 . specifically , main pawl spring 204 includes a cylindrical base 206 with a central through bore 208 through which tall post 182 extends . a first spring arm 210 extends from cylindrical base 206 at the inner facing end thereof and engages with the inner surface of annular inturned flange 42 . a second l - shaped spring arm 212 extends from cylindrical base 206 at the outer facing end thereof and engages with upper engagement surface 197 of pawl lever 196 . as a result , when an external force is applied to remove pawl catch 200 from gear teeth 164 , spring arms 210 and 212 are tensioned , so that when the external force is removed , spring arms 210 and 212 force main pawl 194 in the counterclockwise direction of fig1 to force pawl catch 200 into engagement with gear teeth 164 . as shown in fig3 - 5 , 36 and 37 , an advance pawl 214 as part of an actuating arrangement is rotatably mounted on post 140 of post sleeve 130 . advance pawl 214 includes a pawl lever 216 having a lower engagement surface 217 and a through bore 218 at one end by which advance pawl 214 is mounted on post 140 of post sleeve 130 . an upwardly inclined pawl catch 220 is provided at an opposite end of pawl lever 216 for engaging with gear teeth 168 of triple gear pulley 150 , to be described hereafter . an advance pawl spring 222 normally biases pawl catch 220 into engagement with gear teeth 168 , as shown in fig3 , 4 and 38 . specifically , advance pawl spring 222 includes a cylindrical base 224 with a central through bore 226 mounted on boss 138 of post sleeve 130 below advance pawl 214 . a first l - shaped spring arm 228 extends from cylindrical base 224 at the outer facing end thereof and engages with the side edge of thin generally circular plate 132 of post sleeve 130 . a second l - shaped spring arm 230 extends from cylindrical base 224 at the inner facing end thereof and engages with lower engagement surface 217 of advance pawl 214 . as a result , when an external force is applied to remove pawl catch 220 from gear teeth 168 , spring arms 228 and 230 are tensioned , so that when the external force is removed , spring arms 228 and 230 force advance pawl 214 in the counterclockwise direction of fig3 to force pawl catch 220 into engagement with gear teeth 168 . as shown in fig3 - 5 and 39 , an advance pawl retaining ring 232 is snap fit onto post 140 of post sleeve 130 , and is held in annular groove 141 thereof , in order to retain advance pawl 214 and advance pawl spring 222 in position . further , as shown in fig5 and 40 , a return spring spacer 234 is mounted on substantially trapezoidal shaped upper end 60 of cylindrical boss 58 between post sleeve 130 and triple gear pulley 150 . specifically , return spring spacer 234 includes a substantially circular plate 236 with a center substantially trapezoidal shaped through bore 238 of the same shape and dimensions as substantially trapezoidal shaped upper end 60 so as to fit therearound . as a result , return spring spacer 234 is not rotatable . an arcuate flange 240 extends in a coplanar manner from the edge of circular plate 236 for an angle of approximately 90 degrees , and has opposite inclined 242 and 244 . in operation , in the neutral or rest position in which no gear change occurs , pawl catch 220 of advance pawl 214 sits on arcuate flange 240 of return spring spacer 234 and is thereby out of engagement with gear teeth 168 . at this time , also , pawl catch 200 of main pawl 194 is biased by main pawl spring 204 into engagement with gear teeth 164 so that the particular gear of the derailleur stays in position . hold pawl 184 is not biased into engagement with gear teeth 166 , but may fall into one of these teeth by means of gravity . for shifting in a direction to pull cable 57 in a first shifting direction denoted by arrow 101 , the person rotates shift lever 110 in a first pivoting direction of arrow 246 in fig4 , that is , in the counterclockwise direction thereof . because slide 80 is fixed to shift lever 110 , slide 80 also rotates in the same counterclockwise direction of fig3 . in this position , compression spring 147 maintains the centered position of slide 80 . the amount of rotation of slide 80 is limited by advance roller 97 between stops 32 and 34 of first half housing shell 18 . in addition , advance of first roller 97 , during the initial rotation , is rotated to a position away from gap 35 , and in front of arcuate guide wall 36 , which prevents linear movement of shift lever 110 , that is , which only allows rotational movement thereof . arcuate guide wall 36 and advance roller 97 form a limiting arrangement 99 for preventing the substantially linear sliding movement of slide 80 upon movement of the single lever 110 in the first pivoting direction , that is , these elements form arrangement 99 for limiting movement of the single lever only in a rotational direction . further , because advance roller 148 abuts against guide wall 103 of slide 80 , post sleeve 130 also rotates in this counterclockwise direction . during this movement , advance pawl 214 rotates with post sleeve 130 and thereby moves past arcuate flange 240 of return spring spacer 234 . as a result , advance pawl 214 is no longer restrained by arcuate flange 240 and is biased by advance pawl spring 222 into engagement with gear teeth 168 . continued rotation causes advance pawl 214 to thereby rotate triple gear pulley 150 in the counterclockwise direction of fig3 in order to pull cable 57 . during this movement , main pawl 194 is caused to move out of a gear tooth 164 by the force of this rotation and against the force of main pawl spring 204 , and then be forced into engagement of the next gear tooth 164 by spring 204 . since shift lever 110 can be rotated a distance to effect up to four gear shiftings in a single movement , main pawl 194 would repeat this operation , that is , be moved out of one gear tooth 164 and into the next gear tooth 164 , and so on , during this gear shifting operation . in like manner hold pawl 184 would perform a similar operation since it is not restrained at all . when the rotational force on shift lever 110 is released , post sleeve 130 is biased in the clockwise direction by shift lever return spring 131 . because advance roller 148 abuts against guide wall 103 of slide 80 , slide 80 and shift lever 110 also rotate in this clockwise direction . because of the configuration of pawl catch 220 of advance pawl 214 , pawl catch 220 is caused to move in and out of gear teeth 168 during this return movement . in other words , advance pawl 214 is configured to move triple gear pulley 150 only in the counterclockwise direction . it is note that the tension on cable 57 would normally force triple gear pulley 150 back in the clockwise direction . however , to retain triple gear pulley 150 is this changed gear position , main pawl 194 engages gear teeth 164 and holds triple gear pulley 150 in position , because there is no rotational force of advance pawl 214 on triple gear pulley 150 . in this regard , cable 57 is pulled to effect a shifting operation in first direction denoted by arrow 101 . for shifting in the opposite direction , the person linearly moves shift lever 110 in the direction of arrow 248 in fig4 in a second substantially linear direction . preferably , there is no rotational movement of shift lever 110 , that is , movement is purely linear . since slide 80 is fixed to shift lever 110 , slide 80 also moves in this linear direction . as such , advance roller 97 on slide 80 moves through gap 35 on first half housing shell 18 . specifically , post sleeve or second roller 145 around the free end of center shaft 146 slidably moves within elongated recess 98 of slide 80 against the force of compression spring 147 . in addition , advance roller 148 rides along guide wall 103 of slide 80 . this arrangement of post sleeve roller 145 within elongated recess 98 of slide 80 and advance roller 148 riding along guide wall 103 of slide 80 together form an arrangement 199 for limiting movement of the single lever in a linear direction . it will be appreciated , however , that post sleeve 130 does not slide and is therefore stationary at this time . as a result , advance pawl 214 is restrained by arcuate flange 240 of return spring spacer 234 , and is thereby out engagement with gear teeth 168 during this entire shifting operation . during this sliding movement , slightly arcuate raised wall 106 of slide 80 engages post 202 of main pawl 194 to move downwardly inclined pawl catch 200 out of engagement with gear teeth 164 of triple gear pulley 150 . at the same time , slightly arcuate raised wall 108 abuts post 192 of hold pawl 184 to move downwardly inclined pawl catch 190 into engagement with gear teeth 166 of triple gear pulley 150 . therefore , at this time , triple gear pulley 150 is held in position only by hold pawl 184 . the spacing or pitch of gear teeth 166 is greater than the width of pawl catch 190 so that , during this initial engagement , triple gear pulley 150 is caused , by the pull force from cable 57 , to rotate slightly in the clockwise direction of fig3 by a slight distance equal to the difference between the spacing or pitch of gear teeth 166 and the width of pawl catch 190 , until pawl catch 190 abuts against the edge of the respective gear tooth 166 to hold triple gear pulley 150 in position . when the linear force applied to shift lever 110 is released , compression spring 147 forces slide 80 to move linearly to its original position . as a result , slightly arcuate raised wall 108 no longer abuts post 192 of hold pawl 184 , whereby downwardly inclined pawl catch 190 can be moved out of engagement with gear teeth 166 of triple gear pulley 150 . this occurs by reason of the tension on cable 57 moving triple gear pulley 150 in the clockwise direction of fig3 , whereby hold pawl 184 is forced by this rotation out of engagement with gear teeth 166 . at the same time , slightly arcuate raised wall 106 of slide 80 no longer engages post 202 of main pawl 194 , whereby main pawl spring 204 forces main pawl 194 to move in the counterclockwise direction of fig3 . however , triple gear pulley 150 already rotated slightly in the clockwise direction of fig3 , as described above . as a result , there is no gear tooth 164 for main pawl 194 to engage . therefore , triple gear pulley 150 starts to rotate in the clockwise direction of fig3 by reason of the tension on cable 57 , until downwardly inclined pawl catch 200 of main pawl 194 engages the next tooth 166 and is forced into this next tooth 166 by main pawl spring 204 in order to hold triple gear pulley 150 in this position . as a result , cable 57 is released to effect a shifting operation in a second opposite direction denoted by arrow 103 in fig4 . it will be appreciated that various modifications can be made to the invention within the scope of the claims . for example , rather than shift lever 110 moving only in a linear direction during the reverse shifting operation , it can move in a slightly arcuate path in which it also rotates slightly while moving linearly . further , it is possible to effect the linear movement of shift lever 110 after shift lever 110 is first rotated a small distance . in this regard , reference in the claims to substantially linear covers all of these arrangements . having described specific preferred embodiments of the invention with reference to the accompanying drawings , it will be appreciated that the present invention is not limited to those precise embodiments and that various changes and modifications can be effected therein by one of ordinary skill in the art without departing from the scope or spirit of the invention as defined by the appended claims . | 8 |
in fig1 designates generally a load vehicle of an arbitrary kind , which is equipped with a goods elevator in the form of a rear mounted elevator generally designated by 2 . a frame or chassis of the vehicle is designated by 3 . the elevator 2 comprises a base portion or attachment box 4 which is secured to the vehicle frame 3 , e . g . through welding or riveting . to this base portion 4 are connected two arms 6 which are pivotable about hinges 5 of the base portion 4 and only one of which is visible in fig1 since the other is disposed at the opposite side of the vehicle . the arms 6 are , in turn , at their ends facing away from the hinges 5 connected to a load carrier 7 , preferably in the form of a plate extending substantially over the whole width of the vehicle . each of the pivotable arms 6 is adapted to co - operate with a first piston - cylinder mechanism 8 which is pivotable about a second hinge 9 of the base portion 4 and connected to the load carrier 7 at a bracket 10 . it is obvious that the load carrier 7 can be raised and lowered to a desired level through pivoting the arms 6 through extension and retraction respectively of the piston rod in the piston - cylinder mechanism 8 . to provide for the pivoting or tilting of the load carrier 7 between the raised vertical position shown by dash lines and a lowered position , e . g . horizontal or inclined upwardly or downwardly from the horizontal direction , a second pair of piston - cylinder mechanisms 11 is provided which are at one end pivotally connected to the base portion 4 by hinges 12 , and at the opposite end likewise pivotally connected to the load carrier or plate 7 . on the pivoting arm 6 there may preferably be provided a drive - in guard of the kind known per se . now reference is made to fig2 which shows more in detail one of the two piston - cylinder mechanisms 11 comprised in the goods elevator for the pivoting or tilting of the plate 7 . a piston - rod 14 in this mechanism is slidably movable relative to an associated piston 15 , but is by means of a driver uniformly movable together with the piston between the starting position 15 and an intermediate position determined by a stop 16 limiting the travel of the piston 15 , the piston rod 14 being movable relative to the piston 15 between said intermediate position and a position furthermost extended out of the cylinder 17 . said driver consists in this case of the interior portion 18 of the piston 15 , engaging or being engaged by and thereby co - operating with a shoulder 19 formed in the transition between a piston rod portion having a greater diameter than the piston rod portion 21 . as shown in fig2 a support ring 22 may , if desired , be provided between the shoulder 19 and the piston 15 . the above - mentioned stop 16 comprises one or a plurality of stiff or rigid members which are exclusively attached to a flank wall 23 of the cylinder 17 , in fact the flank wall 23 through which the piston rod 14 extends . in this case the stop 16 consists simply of a tube which is secured , e . g . by welding , to the inner side of the flank wall 23 . the flank wall 23 is dismountably or detachably secured to the remaining portion of the cylinder 17 . more particularly the flank wall 23 is formed as a robust ring , which is secured inside one end of the cylinder 17 by means of a locking ring 24 . the wall or ring 23 has , on one hand , an exterior seal 25 to the inner side of the cylinder 17 , and , on the other , an interior seal 26 to the body surface of the piston rod 14 . both of these seals 25 and 26 consist preferably of o - rings . further , the flank wall 23 comprises preferably a wiper designated by 27 . the operation chamber of the cylinder 17 located at the left - hand side of the piston 15 in fig2 is designated by 28 . into the operating chamber 28 a conduit 29 opens which is connected to an arbitrary pressure medium source not shown in the drawings . the mechanism may operate either with a pneumatic or a hydraulic pressure medium , while it is here preferred to use a hydraulic medium . according to the invention the piston - cylinder mechanism 11 includes a spring 30 tending , when the piston rod 14 is in its position furthermost extending out of the cylinder 17 , to move the piston rod 14 in a direction towards its initial position . in this case the spring 30 consists of a compression spring , preferably a helical compression spring , which is adapted , when the piston rod 14 approaches its position furthermost extending out of the cylinder 17 , to be compressed between on one hand a first part fixed to the piston rod 14 , and on the other a second portion being at least during the compression phase fixed or stationary relative to the cylinder 17 . in the embodiment shown , the compression spring 30 is lodged in the operating chamber 28 of the cylinder 17 , said above - mentioned first part that provides the compression of the spring 30 consisting of a ring 31 disposed at or adjacent the inner end of the piston rod 14 , while the second part consists of the piston 15 . to accommodate the spring 30 a seat 32 is recessed into the piston 15 . the ring 31 is retained in place or positioned by a locking ring 33 . according to the invention the length of the spring 30 is equal to and preferably less than the difference between the travel of the piston rod 14 and the travel of the piston 15 , whereby the spring 30 will operate solely during the movement of the piston rod 14 relative to the piston 15 . the piston 15 has in a conventional manner , an exterior seal 34 sealing to the inner side of the cylinder 17 , besides which an interior seal 35 is provided to seal to the body surface of the piston rod portion 21 . in practice leakage of hydraulic liquid might occur from the operation chamber 28 through any of the seals 34 and 35 into the cylinder base 36 . to collect such leaking liquid a return conduit 37 is provided which opens behind the front edge of the stop 16 and conveys the liquid back to the pressure medium source of the mechanism . the mechanism is in a conventional manner provided with two pivot bearings 38 ; one disposed at one flank of the cylinder 17 and the other disposed at the free end of the piston rod 14 . to ensure that the pressure of the pressure medium can be brought to bear on the end surface 42 of the piston rod 14 at the position of the piston rod 14 furthermost inserted into the cylinder , a stop lug 44 is provided on the piston rod 14 in order to provide a space between the remaining end surface 42 of the piston rod 14 and the end wall 40 of the cylinder 17 . this may instead thereof also be effected by providing a stop , not shown , for the plate 7 of the goods elevator , i . e . said stop will ensure that the end surface 42 of the piston rod will not at the lower position of the goods elevator plate 7 come into contact with the cylinder end wall 40 . at the free end of the piston rod 14 may as shown in fig2 a protective cover 39 be provided . in fig2 the piston rod 14 is shown in a bottom position having the stop lug 44 of the piston rod 14 abutting on the end wall 40 of the cylinder 17 . in this position the plate 7 of the goods elevator is lowered into a position of maximum inclination to the horizontal direction ( see fig1 ). to pivot the plate 7 upwardly hydraulic liquid is supplied by the conduit 29 into the operation chamber 28 . of course , there is no seal around the ring 31 and there is sufficient clearance for the passage of fluid . the pressure of the hydraulic liquid introduced into the operation chamber 18 will act on the end surface 41 of the piston 15 , and on the end surface 42 of the piston rod 14 , the piston 15 and piston rod 14 then moving due to the driver arrangement 18 - 19 to the right hand in fig2 with an even , relatively low speed . after the piston 15 and piston rod 14 have moved a length corresponding to the distance between the end surface 43 of the piston 15 and the front edge of the stop tube 16 further movement of the piston 15 is stopped . the travel that the piston 15 and the piston rod 14 performed in this action corresponds to what is required to pivot the plate 7 from the downwardly inclined position into the position inclined upwardly from the horizontal direction , shown by full lines in fig1 . by a continued pumping of hydraulic liquid into the operation chamber 28 the piston rod 14 alone is capable of moving further . by the fact that the piston 15 is now stationary the partial pressure on the end surface 42 of the piston rod 14 will increase . this on the condition of a constant or unchanged supply of hydraulic liquid into the operation chamber 28 . as a consequence of the increased partial pressure on the piston rod 14 the same will move at a speed depending on the ratio between the cross sectional area of the piston rod 14 and the cross sectional area of the piston 15 . the smaller the cross sectional area of the piston rod 14 is in relation to the cross sectional area of the piston 15 , the greater the speed increase will be . it will be obvious from the above that the piston rod 14 , during the swivelling up of the plate 7 from the position inclined upwardly from the horizontal direction into the vertical position corresponding to the position of maximum projection of the piston rod 14 , will move considerably swifter than during swivelling within the lower range of movement . during the later phase of the movement of the piston rod 14 out of the cylinder 17 the spring 30 will be compressed by the ring 31 and obtain a maximum spring force when the piston rod 14 attains its extreme position . when the load plate 7 is to be lowered from its vertical raised position , the spring 30 will , as soon as the hydraulic pressure ceases , swiftly and positively activate the piston rod 14 through the spring 30 in such a manner that the piston rod will be moved into the cylinder and the plate 7 pivoted somewhat from the vertical position . thereby an initial pivoting of the plate 7 will be obtained so as to supply thereto , through its proper weight , a torque that swings the plate 7 swiftly and efficiently down into the position inclined upwardly from the horizontal direction shown with full line in fig1 . it is understood that by selection of the length of the stop 16 in relation to the positioning of the driver shoulder 19 it will be possible to vary the position of the plate 7 in which a change in the movement speed is desired . it will be understood that the invention is not limited solely to the embodiment described and shown in the drawings . thus the piston - cylinder mechanism according to the invention is not only applicable in connection with goods elevators and other lifting devices but as well in any context whatsoever wherein a variation of the movement speed of the piston rod 14 of the mechanism is desired . further , the invention is not limited to a piston - cylinder mechanism , the piston 15 of which can be supplied with two different movement velocities solely . it is thus conceivable to provide in one and the same cylinder , two or a plurality of telescopically or otherwise slidable piston rods , each having a piston co - operating with a particular stop . thereby the speed variation will be possible to obtain not only in one but in two or more steps . likewise a plurality of modifications of the embodiment shown in fig2 may be undertaken . the spring 30 may , for example , be lodged in the space 36 instead of in the operation chamber 28 , and it is also conceivable to use tension springs instead of compression springs . the design of the stop 16 may be varied in various manners though it is preferable to attach the same to the dismountable flank wall 23 . the stop lug 44 is shown in the example as a body projecting from the end surface 42 of the piston rod 14 to the end of utilizing the pressure of the pressure medium to operate actively on the end surface 42 in the retracted position of the piston - cylinder mechanism , but it may possibly be replaced by a convexity in the end surface 42 of the piston rod . various other modifications are possible within the scope of the appended claims . | 1 |
referring to fig1 filter body 1 contains two similar cylindrical filtering apertures disposed side by side , one of which is shown sectioned at 2 . the filtering apertures contain conically hollowed - out end caps 3 , 4 , 5 and 6 which are bolted onto filter body 1 by means of bolts , one of which is shown at 7 and each end cap carries a perforated supporting disk , two of which are shown at 8 and 9 , each provided with numerous , aligned perforations such as 10 and 11 . suitable filters 12 and 13 made , for example , from woven steel cloth pass between each pair of supporting disks . manifold 14 , provided with band heaters one of which is shown at 15 and a pressure transducer 16 , carries molten plastic and feeds it to the two filtering chambers via two valves 17 and 18 which are actuated when desired by means of a double - ended pneumatic cylinder 19 . each filtering aperture is provided with a purge valve such as 20 and 21 . filtered plastic , which has passed through either filter 12 or filter 13 , is collected by means of manifold 22 which is heated by means of band heaters , one of which is shown at 23 and with a further pressure transducer 24 ; plastic enters and leaves the apparatus in the direction of a -- a . in operation , with both filters 12 and 13 substantially unclogged as determined by the pressure difference measured by the transducers 16 and 24 , valves 17 and 18 are open and valves 20 and 21 are closed so that substantially molten plastic -- provided for example by an extruder feeding manifold 14 -- is filtered simultaneously in both filtering chambers and is collected by manifold 22 and passed , for example , to a granulator . when the difference between the pressures upstream and downstream of the filters reaches a pre - set limit one of the inlet valves associated with one of the two filtering chambers , say 17 is closed and the associated purge valve communicating with the same filtering chamber , here 20 is opened . substantially molten plastic driven by the downstream pressure within manifold 22 flows through one of the filters , here 12 , in a direction opposite to that which the plastic follows during filtering and a proportion of the impurities collected on filter 12 will be dislodged and carried out of the filtering chamber through purge valve 20 . when the bulk of the collected impurities has been disposed of , purge valve 20 is closed again and filtering re - commences through both filters . when the difference between the upstream and downstream pressures rises again to the pre - set limit , the other filter , here 13 , situated in the neighboring filtering chamber is similarly cleaned by the removal of contaminants using counterflow through purge valve 21 . this sequence of filtering and purging operations is repeated a number of times until following a purging operation the difference between the upstream and downstream pressures no longer returns to a sufficiently low value , indicating that filter cleaning is no longer efficient enough . at this stage plastic flow to one filtering chamber is shut off by means of , for example , valve 17 and , with both purge valves 20 and 21 closed and while filtering proceeds through filter 13 , filter 12 is moved through filtering chamber 2 in a manner similar to that described in gb - a - 1181075 but with one important difference : since filtering does not proceed across the filter being moved there is here no pressure differential across the moving filter 12 which can , accordingly , move easily and free of friction against the two perforated supporting disks 8 and 9 despite the severe clogging which filter 12 will by now be subject to . having moved filter 12 , valve 17 is reopened and valve 18 is closed , with purge valve 21 still closed , so that filter 13 can be moved in turn with no pressure differential across it whilst filter 12 is filtering . thereafter filtering again proceeds with both valves 17 and 18 open until there is sufficient clogging to require cleaning the filters once again by counterflow . it will be seen that , unlike using apparatus described in gb - a - 1181075 , the present apparatus does not provide constant pressure conditions in operation but , with the use of suitable automatic supervisory controls monitoring its two pressure transducers , it does permit continuously filtering even heavily contaminated plastic materials without requiring operator supervision until its filter supply is exhausted and owing to its filters being moved in the absence of differential pressure across the moving filter , it can operate using inexpensive , lightly constructed filters ; since these filters are continuously cleaned their useful life is greatly extended leading to further economies of operation . an important feature of the apparatus is the provision of novel flow valves for the plastic such as 17 , 18 and particularly 20 and 21 which must control the flow of plastic with a highly concentrated impurity content without requiring service over very long periods of continued operation . such a valve will be described in better detail with reference to fig2 and 3 . the valve consists of a body 25 , through which normally molten plastic flows in the direction b , which is provided with a side chamber 26 containing a piston 27 which can be reciprocated by means such as pneumatic cylinder 19 of fig1 or , in the case of high extrusion pressures , by other means such as a hydraulic cylinder . valve body 25 can be heated by means of heaters 28 , 29 , 30 , 31 and 32 and cooled by means of coolant flow through channels such as 33 , 34 and 35 ; cylindrical side chamber 26 is cooled by the flow of a suitable coolant such as water flowing in the annular space 36 surrounding it so that a substantially rigid plastic plug 37 forms in it , acting as a pressure seal . this plug is delimited on one side by the valve body and on the other side by operating piston 27 . when the valve is to be open flow channel 38 within its body is kept at a temperature at which the plastic being processed can flow . neck 39 situated between the now hot body 25 and the cold side chamber is of a reduced cross - section so as to minimize heat conduction . when it is desired to close the valve , piston 27 is moved so as to force plug 37 into flow channel 38 , closing it and valve body 25 is cooled so as to keep plug 37 sufficiently rigid and in situ . reopening the valve is achieved by reheating valve body 25 so that its contents remelt and piston 27 is withdrawn to its original , outer position as shown . fresh , hot plastic now enters sidechamber 26 and a new plug 37 begins to form . it will be seen that , since the valve achieves its tight shutoff without the necessity of metal - to - metal contact and re - forms its tight , sealing abutment every time it is operated it can tolerate the presence of even large and abrasive contaminants such as metal swarf or pebbles which , if they are located in the flow channel when the valve is shut , become imbedded in the plug forming the seal without impairing its operation . the temperature of the inner end of plug 37 , next to the valve body , can be adjusted by making neck 39 longer or shorter and the wall of the neck thicker or thinner : it is advantageous to allow that inner end to remain moderately warm so that it remains pliable enough to facilitate this embedment . the speed with which the valves can be operated is an important parameter of the apparatus described since it defines the worst - case contamination which the apparatus can still cope with and this speed depends on the time taken to cool plug 37 . one way of hastening this consists in making the sidechamber cross - section , and hence plug 37 , flat so that the core of its cross - section is more accessible to cooling . another way is shown in fig4 where piston 27 is provided with a pin 40 made from a material of good thermal conductivity such as a metal ; this helps the cooling of plug 37 from within and it also supports plug 37 when it is thrust into flow channel 38 : it is however best to make pin 40 sufficiently short so that it does not enter channel 38 too far and makes no contact with particulate contaminants carried in the flow . another way of speeding up valve operation consists in providing the valve with more than one side channel and hence , more than one plug ; these plugs can then close the flow in the valve in turn so that one plug operates while another is being formed . a two - side - chambered valve is shown in fig5 and 6 which operates like that described above but can achieve a faster repetition rate . pistons 40 and 41 , situated in side chambers flanking valve body 44 are taking turns closing valve bore 45 . both pistons 40 and 41 are pulled outwards while the valve is open and valve body 44 is kept heated by heaters such as 47 . when the valve is to close , one of the pistons is pushed inward , assuming the position of piston 41 so that the plug formed in side chamber 43 , not shown , is forced into bore 45 closing the valve ; the heaters 47 in valve body 44 are switched off and a suitable coolant such as water is circulated in coolant channels such as 46 so as to stabilize the cold plug in the valve body . meanwhile a fresh plastic plug is cooling in chamber 42 whose piston 40 is in its outer position as shown . the valve is reopened to flow by reheating it and by stopping coolant flow in its coolant channels such as 46 and piston 41 is withdrawn : however no sooner has plastic flow resumed through valve bore 45 it can , if desired , be stopped once more by actuating piston 40 whilst a fresh plastic plug is forming in side chamber 43 . it will be clear that more than two side chambers can be employed if an even faster repetition rate is desired . pistons 40 and 41 of the valve arrangement shown in fig5 and 6 can also be actuated by a common means as shown in fig1 . pistons 40a and 41a are both fastened to a frame 101 which is reciprocated by a double - acting pneumatic or hydraulic cylinder 102 which is fastened to valve body 44a by means of struts 102a . clearly two valves such as 44a can also be utilized in place of valves 17 and 18 if faster repetition is required . the valve arrangement shown in fig1 is actuated by valve operating means 19 situated between the valves 17 and 18 . an alternative arrangement in which the operating means are situated outside the valves is shown in fig1 and 15a . valves 17a and 18a here have their pistons 97a and 97b oriented outward and fastened to frame 93 which is reciprocated by hydraulic cylinders 94 and 95 actuated in turn , the hydraulic cylinders being fastened to supporting struts 96 which are affixed to body 1 by means not shown . fig7 and 8 represent an axial section taken in direction b -- b of fig1 and an end view seen from the direction c , with manifold 14 and valves 17 and 18 removed for clarity ; purge valve 20 is shown as a revolved section . body 1 is heated to processing temperature by heaters such as 46 and during filtering plastic flows through chamber 2 in the direction a ; purge valve 20 is closed at that time . filter 12 is cleaned in situ when required by closing the inflow of plastic from manifold 14 and by opening purge valve 20 in the manner disclosed above ; during this phase plastic flows into chamber 2 in a direction opposite to a and , having transversed supporting disks 8 and 9 and filter 12 , this flow leaves chamber 2 through channel 47 and valve 20 , taking with it impurities collected by the filter opposite apertures such as 10 . when sufficient cleaning has taken place purge valve 20 is closed once more and filtering recommences . it is found that after a number of such cleaning operations this process becomes progressively less efficient and eventually it becomes necessary to introduce a fresh filter part into chamber 2 . this is carried out by first stopping the inflow of plastic into chamber 2 by closing valve 17 , and , with purge valve 20 still closed , filter 12 is then moved in a manner generally described in gb - a - 1181075 while sealing plugs , formed from the plastic being filtered , are maintained in ports 48 and 49 respectively where filter 12 enters and leaves filter body 1 , by suitable thermal control means as disclosed e . g . in gb - a - 1181075 ; however since there is no plastic flow through filter 12 at that time this movement takes place substantially free of frictional resistance . filter advance involves extrusion of the sealing plug in the outlet port 49 . this outlet port is of greater cross - sectional area than the inlet port 48 , so that there is a net force assisting extrusion , arising from the pressure of material in the passage which is connected to the outlet of the other passage . preferably the entire contaminated portion of filter within the passage is replaced . filter cleaning is alternated between the two filtering chambers as is also the replacement of filters ; pressure fluctuations due to these operations can be lessened by utilizing more than two filtering chambers . fig7 shows a filtering chamber with two discrete perforated disks 9 and 8 flanking filter 12 and supporting it during filtering and backflushing respectively . fig1 and 17a show an arrangement in which a supporting structure taking the place of disk 8 is formed by cutting grooves 105a to 105i in filter body 1a ; walls such as 105 situated between these grooves support filter 12a during backflushing . plastic material to be filtered enters along channel 111 and , when this channel is closed during backflushing , the contaminants accumulated on filter 12a within grooves 105 are carried out of filter body 1a along channel 109 . fig9 and 11 represent an axial section taken in direction b -- b , an axial section taken at right angles in the direction d -- d and a side view taken in the direction c respectively of half or filter body 1 provided with a means of purging chamber 2 alternative to valve 20 . pocket 50 consists of two zones 51 and 52 thermally separated by neck 53 . inner zone 51 is provided with heaters 52 and 53 , coolant channels 54 and 55 and outer zone 52 has an internal constriction and is provided with heater 56 . during filtering in chamber 2 both zones 51 and 52 are kept cooled so that the plastic within them becomes sufficiently rigid to seal chamber 2 and so prevent any loss of plastic . when it is desired to clean filter 12 heater 56 close to the constriction is heated and it softens the plastic in the pocket in the vicinity of the constriction sufficiently to permit outward movement of the plug situated within pocket 50 ; this movement is accompanied by a flow of plastic in the opposite sense to a and this flow passes through filter 12 , taking with it impurities collected on the filter next to the apertures such as 10 in disk 8 and carrying them into pocket 50 through channel 57 . frictional resistance to the movement of the contents of the pocket may be lessened by heating inner zone 51 also , sufficiently to bring about a detachment from the inner walls of zone 51 and to lessen frictional drag but not so greatly as to unduly hasten the movement of the plug . when a sufficient amount of contaminants has been drawn into pocket 50 , a similar amount having been removed from it simultaneously , heating of both zones is stopped and cooling is resumed and subsequently movement of the plug ceases ; filtering is then resumed again through chamber 2 . when the removal of comparatively small amounts of impurities suffices to clean the filters sufficiently then a short purge valve shown in fig1 may be employed . when larger amounts of contaminants must be disposed of at a time this valve will be elongated as shown in fig1 . heaters 90a and cooling channels 90b are provided here in both sections of the valve so that the movement of the plug containing impurities can be swiftly arrested by recooling , the coolant channel near the constriction being particularly effective . the valve is provided with an adaptor section 91 securable to filter body 1 and at the other extremity the end of the constriction is shown at 90e . an axial section of a diverter valve suitable for regulating the flow of highly contaminated plastic without requiring external means of power such as hydraulics is shown in fig1 . the diverter consists of an actuator which utilizes the molten plastic being filtered as its working fluid and two valves such as 17 and 18 in an in - line configuration . the tubular actuator is divided by annular necks 59 and 60 , which serve to reduce thermal conduction , into a central zone 58 and outer zones 63 and 64 . the central zone 58 is cooled by means of a coolant , such as water , flowing in channels 61 and 62 while the two outer zones 63 and 64 are heated to a temperature at which the plastic being processed is substantially fluid by means of heaters 65 , 66 , 67 and 68 . in use , the actuator contains plastic which is substantially fluid in outer zones 63 and 64 but is sufficiently rigid in central zone 58 to act as a part of a hydraulic piston . the actuator is flanked on each side by a valve of the kind described above ; their side chambers 69 and 70 being here cooled by a suitable coolant such as water circulating in channels 71 and 72 . the actuator contains three perforated pistons , two of which are shown at 73 and 74 , fastened to piston rod 75 and all three are embedded in fully or at least sufficiently rigid plastic plugs , two of which are contained in the respective side chambers of the two valves flanking the actuator and the third , 74 in a plastic plug of a larger diameter situated in central zone 58 of the actuator . outer zone 63 is provided with two valves 76 and 77 each consisting of a chamber having a small bore such as 80 communicating with the bore of outer zone 63 and both valves are also provided with temperature control means such as heaters 81 and coolant channels 82 . outer zone 64 is likewise provided with similar valves 78 and 79 ; in use these valves are open when sufficiently heated to permit the passage of substantially molten plastic under pressure and closed when cold enough to render plastic material contained in them sufficiently rigid so as to resist flow . valves 77 and 79 are connected to manifold 14 and valves 76 and 78 are open to the atmosphere ; it will be seen that when valve 76 is heated and valve 77 cooled then outer zone 63 will contain plastic at atmospheric pressure and when valve 76 is cooled and valve 77 heated then it will contain plastic at the pressure present in manifold 14 . like considerations apply to outer zone 64 . piston rod 75 may be moved to one side by releasing the plastic pressure in the heated outer zone of the actuator on that side and by pressurizing the plastic in the heated outer zone on the opposite side of the actuator , this being brought about by rendering the plastic within two of valves 76 , 77 , 78 and 79 sufficiently rigid by cooling and rendering it sufficiently fluid by heating it in the other two . by reversing the thermal status of these four valves piston rod 75 and the three pistons keyed to it will be moved in the opposite sense . it will be seen that since the outer pistons adjoin the plastic plugs formed within the cooled sidechambers 69 and 70 of the two valves flanking the actuator , such as valve 17 these two valves will be suitably operated by the actuator , the operating force available depending on the ratio of the cross - sectional areas of pistons 74 and 73 . care must be taken that the two valves 76 and 77 serving outer zone 63 are not open simultaneously , the channel such as 80 to be closed being cooled first : in this way the plastic contained in that channel can be made sufficiently rigid while it is at rest so as to close that channel before the other channel communicating with the same outer zone is opened by heating . in this manner there is negligible plastic flow through the channel to be closed and therefore little heat is carried into it by plastic flow so that the closing of the channel by external cooling is facilitated . fig1 shows a schematic plan view of apparatus according to the invention comprising two extruders 83 and 84 which carry filtering chambers 85 and 86 respectively . the filtered plastic passes from these to a common collecting duct 87 and thence to , for example a pelletizer , in the direction of arrow d . certain known features of the apparatus disclosed herein , such as the details of the inlet and outlet ports , are disclosed in gb - a - 1181075 , the contents of which are incorporated herein by way of reference . in an example of filtering using the above filtering equipment polypropylene resin at about 200 degrees centigrade is made to flow through twin filtering chambers using 6 &# 34 ; diameter supporting plates such as 9a ; the initial pressure drop across clean filters such as 12 and 13 is typically between 250 and 500 psi . depending on filter construction and the flow rate and viscosity of the polymer . filtering is continued until the pressure drop across the filters reaches about 3000 psi . when backflushing is initiated ; thereafter the pressure drop again returns to near its initial value . after repeated cycles the instantaneous pressure drop after backflushing gradually rises . it will be found that the rate of filter clogging , as indicated by following the pressure drop , is not constant but increases more and more rapidly at higher levels of clogging and at the same time , the efficiency of filter cleaning decreases as seen from the pressure drop immediately following backflushing . for a given filter construction and depending also on the kind of impurities encountered a given value of the pressure drop following backflushing will be found , such as 2000 psi . in the example given , where it becomes necessary to change the filter areas in use so as to avoid having to backflush faster than the valves can cope with ; after introducing fresh filter areas the initial pressure drop across the filters returns once more to 250 to 500 psi . a practical limit is set on the pressure drop at which the filters are renewed by , in particular , the shortest time period during which the more frequently occurring backflushing operation can be carried out and this depends mainly on the cooling of the plastic plugs utilized to control flow in the valves . in the above example a satisfactorily hard polypropylene plug of 1 inch diameter will be formed in 10 to 12 minutes , utilizing cooling water at ambient temperature ; these plugs can then be sufficiently softened to be removed in about 1 . 5 to 2 minutes . in general workable flat plugs can be constructed to respond in half these times but the thicknesses that can be used depend on the mechanical strength of the plastic being filtered and the pressure differential which must be supported . finally , while a filter body has been shown as one embodiment with two side - by - side filtering apparatus served by a manifold , the present invention contemplates the use of any number of filtering apertures arranged in any arrangement provided that they are in a parallel flow configuration . the control of heating and cooling means and mechanical traction described above is preferably accomplished by electrical switchgear activated and controlled by a programmable computer . a flow chart showing steps involved in a suitable computer program is shown in fig1 and 19 . the operation of a filtering system according to the invention under computer control involves detecting the pressure drop across the filters , valve cooling and polymer plug forming in the valves , timing of a suitable period to facilitate plug forming , closing the valves either by cooling alone or by accompanying mechanical traction , heating the valve bodies in order to open them , moving the filters so as to introduce fresh filter parts and controlling the filter lengths so introduced , keeping track of which filtering chamber is to be operated next and which actuator ( in the case of double - acting actuators , which side of any actuator ) is to be powered next and in what sequence so that the backflushing and filter renewal operations are fully controlled and properly coordinated . filter movement may be controlled using a servo system of known art ( u . s . pat . no . 3783355 ) or by actuating an automatic cutter at the emerging filter end and detecting the position of the cut end by means of a photoelectric cell : in this way the filtering operation can be fully automated . in a similar way the semi - solid or solid plastic plug carrying the contaminants emerging from the purge valve can be severed and the position of the cut end can be likewise detected ; where the contaminants are carried out in a largely fluid stream timing the open period of the valve will suffice . during purging through valve 20 contaminants carried in polypropylene the removal of as little as 215 grs . ( less than half a pound ) sufficed to adequately clean the filter area , depending somewhat on filter construction and the nature of the contaminants . turning to the flowcharts of fig1 and 19 , the steps listed correspond to successive computer operations and are aimed at detecting the pressure drop across the filters , actuating the required heating , cooling and tractive steps according to a predetermined time schedule as well as severing the emerging polymer plugs and obtaining positional information of the cut ends . the term &# 34 ; initialize &# 34 ; refers to the establishment of known initial conditions in the apparatus and storing the data required for operating it . the term &# 34 ; side &# 34 ; refers to a selected filter and its associated valves , &# 34 ; counter &# 34 ; is an internal reminder keeping track of filter movement , &# 34 ; toggle &# 34 ; refers to changing the filter selected or the sense of actuator movement for the next operation . &# 34 ; photocells &# 34 ; are devices detecting the position of the emerging polymer plugs and &# 34 ; cutters &# 34 ; are devices such as pneumatically reciprocated motorized circular saws which severe these plugs ; the use of methods less prone to causing accidents such as detecting holes drilled in the plugs rather than severing the plugs are also anticipated . | 1 |
the system as described herein comprises a comprehensive color video display system for operation with two sources of image data , one of which may be a conventional digital image generator , referred to here simply as a processor 10 . for descriptive purposes , a matrix memory 12 included in the system is separately shown , and comprises a 512 column × 512 row matrix memory , each location storing a 7 bit pixel and thus capable of 128 color combinations or grey scale levels . the analog image source is , in this example , a closed circuit tv camera 14 , while the output display is to be generated on a tv monitor 16 including a crt 17 and synchronizing circuits 18 . the system is maintained in synchronism by conventional means which are not significant to the inventive concept and the details of which have accordingly been omitted for simplicity . broadly speaking , however , the processor 10 clock may serve as the master synchronizing signal reference for the timing of data transfer and for vertical and horizontal scanning purposes in the video devices . the presence of the memory 12 enables the system to effect precise synchronization between the image signal trains . in the figures , the use of multiple lines between functional elements is designated by the employment of a diagonal across the line accompanied by a numeral or other notation indicating the number of lines that are there represented . the digital image signal train is applied from the matrix memory 12 to an address register 20 , the output signals ( seven parallel lines ) from the address register 20 being applied through a decoder 22 to a table look - up device or memory 24 . inasmuch as the system operates essentially in real time and data is transferred on a serial basis , read control and bit timing signals that may be applied to the different functional units have been omitted for simplicity . the output of the decoder 22 comprises 27 , or a total of 128 , output lines to address a corresponding number of word storage locations in the table look - up memory 24 . the storage locations contain 4 bits each of red , green and blue color data and may also include 4 bits of control data although in the present example the control data used is primarily that contained in the analog signal channel . the table look - up memory 24 may comprise a prewired or program addressable type of storage , such as a read only memory , or a randomly addressable memory that may be distructively read but immediately rewritten . the 16 output bits from the memory 24 , comprising the 12 color bits ( and the 4 control bits where these are used ), are applied to an output register 26 , with the 4 control bits being converted to signals on 1 of 16 output lines in a control decoder 28 . the color bits may be applied to what is here called a &# 34 ; digital dimmer &# 34 ; 30 , which actually comprises a separate divider for each of the 4 bit color signals , and which can be set to divide each signal by unity , three - fourths , one - half , or one - quarter , so as to reduce the intensity of the signal . for this purpose , a &# 34 ; division control &# 34 ; input is utilized , and this may comprise either a manually selectable switch , processor control signals , or two selected bits in the control signal from the table look - up memory 24 may be used for this purpose . the three sets of 4 color input signals , with or without the optional digital dimming function , are applied to the arithmetic and logic unit 32 , which unit is also referred to herein as containing digital bit mixers . the arithmetic and logic unit 32 is described in greater detail hereafter in conjunction with fig2 . corresponding sets of color intensity signals are also derived in an analog channel commencing with the closed circuit tv 14 , signals from which are applied through an amplifier to a video analog signal digitizer 42 . in the digitizer 42 , a fixed number of adjustable signal amplitudes are utilized to define the grey scale range , from minimum to maximum . a chain of precision resistors 44a , 44b , 44c . . . 44p are coupled to a high and low voltage source respectively . the high voltage source is selectable in level , and provided by a first digital register 46 , here referred to as a &# 34 ; high number register &# 34 ;, which is settable to a selected value either by switch control or by program control to represent a desired maximum voltage for the voltage divider chain of resistors 44 . the output from the high number register 46 is transformed into a corresponding analog level by a first digital - to - analog converter 48 . similarly , the minimum potential to be established for the other end of the voltage divider chain is provided by a low number register 50 controlling an associated digital - to - analog converter 52 . by moving the maximum and minimum values further apart , the digital increments defined by the voltage divider chain are increased but a greater range is covered , while the converse may also be established . because the absolute values of the limits may be moved up or down concurrently , both threshold values and the degree of resolution of the grey scale may be changed by the digitizer 42 . taps taken from the successive intermediate points of the voltage divider chain are applied to individual inputs of a series of comparators 54a , 54b , 54c . . . 54o , comprising operational amplifiers arranged as threshold sensitive devices which give a binary output signal to indicate whether the applied signal is above or below a preselected level . the outputs of the comparators 54 are applied to a holding register 56 . the 15 comparators 54 that are coupled between the midpoints of the resistors 44 in the voltage divider chain provide inputs through the holding register 56 to a priority encode circuit 60 which provides 4 bits of parallel encoded data with , for example , 1111 representing the maximum value and all voltage levels above that value , and 0000 defining the minimum value and all voltage levels in the subband below it . these parallel signals are applied to a second table look - up memory 62 having 16 words of 16 bits each , with 4 bits each being devoted to the red , green and blue colors respectively , and 4 bits being devoted to control data . an address encoder 64 is employed to select the appropriate word . the control data groupings have been labeled &# 34 ; and &# 34 ;, &# 34 ; or &# 34 ;, &# 34 ; add &# 34 ;, &# 34 ; subtract &# 34 ;, &# 34 ; block a &# 34 ;, &# 34 ; block b &# 34 ;, and &# 34 ; average &# 34 ; but with 4 different bits up to a total of 16 different functions are available . the table look - up function here performed provides a conversion to pseudocolor from grey scale black and white , either derived from the closed circuit tv 14 or from some other source , so that the ability to discriminate is substantially greater than with a single color . output signals from the memory 62 are applied through an output register 66 to the arithmetic and logic unit 32 for the 12 color signals , and to a second control decoder 68 , for the control signals . both sets of control signals or combination bits from the decoders 28 and 68 are applied to a multiplexer 70 , along with another set of signals from a mode register 72 . the mode register 72 , which may be manually set or operated under program control to generate functional control signals , provides the equivalent of a static or external control for the system . whichever set , or combination of parts of sets , of control signals is utilized under selection control at the multiplexer 70 , the sixteen output lines from the multiplexer govern the functions performed within the arithmetic and logic unit 32 . the output signals from the arithmetic and logic unit 32 comprise the digital , 4 bit valued , signals for red , green and blue respectively , and these are applied to intensity control circuits 76 in the tv monitor 16 . the intensity control circuits 76 include digital - to - analog converters and conventional amplification circuits for modulation of display color intensity . details of the arithmetic and logic unit 32 are shown in part in fig2 which fragment relates only to the 16 possible control functions that may be exercised for each bit value of each color , such as the four bits r 1 , r 2 , r 3 and r 4 for each channel ( a & amp ; b ). in fig2 the functions have been designated in various ways , but all represent some type of arithmetic or logic operation . the four depicted bit mixers 80 , 81 , 82 , 83 each contain like functional gates or circuits , although only the r 1 bit mixer 80 is shown in some detail . thus for the logical &# 34 ; and &# 34 ; function , the two input signals r 1a and r 1b are applied to a three input and gate 86 that also receives a control signal to effect the designated function for the same picture element . for the next picture element , the &# 34 ; or &# 34 ; function provided by the circuit 87 may be desired , and the second control line is actuated , so that the circuit 87 responds to a signal on either input line . similarly , exclusive - or and other logical functions may also be defined . also included in this example are an add / subtract circuit 88 , circuits 90 and 91 for blocking the a and b signals respectively , a circuit 92 for averaging the two signals , and , by way of illustration , an arbitrary function designated simply as &# 34 ; function 16 &# 34 ;. where full addition , subtraction or averaging of each 4 bit value with a corresponding 4 bit color value is to be effected , conventional circuits providing carry between adder stages will be desired . where the blocking signal function is employed , the corresponding input signal is simply gated off . although the circuits are separately shown for ease of understanding , it will be apparent that these and many other functions could be established by a microprogram and that where hard wired circuits are to be used conventional logical design would substantially reduce the number of gating elements utilized . the operation of the system may perhaps best be visualized initially in terms of the concurrent generation of two color images , each consisting of an array of distributed pixels derived from a sequence of coded bit - valued representations . the 7 bit digital characters from the processor 10 provide extremely finely resolved grey scale values which are used to address a corresponding word location in the table look - up memory 24 . the chosen word location contains three different digitized color values , each 4 bits long , and may also contain the control or combinational bits , although others are used in this particular example . the output from the table look - up memory 24 is provided essentially in real time and represents the pseudocolor conversion of the input . great variety is possible because of the number of words available in this memory , which permits essentially all colors , including white , to be generated , and with a wide range of intensities . concurrently , the analog signal from the cctv source 14 is converted digital grey scale values at the comparators 54 , in relation to increments within a range established by the high and low number registers 46 , 50 respectively . although a lower number of grey scale values is available ( in this example ) the ability to shift limits and adjust increments within the limits enables the contrast and intensity of the analog input to be altered to best advantage . when this input is converted to pseudocolor in the associated table look - up memory 62 , it is read out concurrently with the accompanying control bit patterns in a coded sequence , and again in essentially real time fashion . both digital coded sequences of color values for a pixel are then combined in dynamic dependence on the control signal pattern for the same pixel , within the arithmetic and logic unit 32 . although the analog channel is used for data dependent control in this example , the groups of combination bits taken from the other image input , or static control bits may be taken from the mode register 72 , as selected at the multiplexer 70 . substantial advantages for video display systems are realized from the real time digitizing and generation of color - valued signals which are then dynamically combined in a data dependent manner . the use of a table look - up memory in each image signal path transforms each image to a more readily interpreted form , even if the type of control remains static ( e . g . if the whole images merely are combined in additive fashion ). the ability of the video analog signal digitizer to alter the range and resolution of the grey scale permits selective modifidation of the video input for advantageous display purposes but is not required for use of the invention . however various advantages are derived , because low level backgrounds may be eliminated , or the contrast in a scene having low level illumination may be substantially enhanced . it is more significant , however , that dynamic control on a pixel - by - pixel basis enables different parts of an image to be colored in advantageous and different ways depending on data content and relationships . referring to fig3 a , which represents a relatively simple condition , it may be seen that a background of a pure color a is to be viewed except where a pure color b from the other input exceeds a minimal level . thus , as shown , in writing color b there is no mixing with color a , and the region of color b can be of varying intensity ( as can the region of color a , although this is not shown ). consequently a line drawn in color b ( e . g . red ) appears to cut through the background of color a ( e . g . green ) and no color mixing results . of course , the &# 34 ; pure &# 34 ; colors need not be a primary red , green or blue , but can be any appropriate color of the spectrum including white . fig3 a thus represents a blocking function , and could be accompanied by concurrent conversion of pure color b to a maximum level wherever it is to be written . fig3 b shows that the blocking function can be independent of background , in that the varying intensity region of color b can be written without color mixing against a background of colors a , c and d generated during the pseudocolor transformation . because of the dynamic control of increments of picture area , further variations may be introduced , based upon the intensity of one or the other of the images . thus as seen in fig3 c , where color a is of less than a certain threshold in intensity , pure color b may be superimposed on a background of color a by blocking color a . at or above the chosen threshold for color a , the colors may be mixed ( additively or subtractively ) to give a different effect . as an extension of this capability , adding , blocking and subtracting functions can be used at different regions all dependent upon the intensity level of the signal in the channel corresponding to color a , as shown in fig3 d . a typical specific example of how signals may variably be combined based upon the data content in the signals themselves involves the display of digitally generated characters and vectors on a map reference which may be derived from a closed circuit tv monitor . lines and patterns of varying intensity are generated by the digital source but for best comprehension of the display it is not suitable to simply additively combine the signals . this would result in the lines having both different intensities and varying colors along their lengths . it is also not satisfactory for all purposes simply to block one of the signals so as to permit the lines to stand out more clearly , because there can be significant variations in the digital input . it may be desired to show only the highest intensity lines , and to leave the map image at its appropriate intensity where lines are not to be shown . in accordance with the invention these and other functions can be performed automatically and in real time . in order to provide a display in which characters and vectors generated in the digital channel starting with the processor 10 are uniquely presented relative to an analog image starting with the cctv 14 , a prearranged combination of control bits and color bit values is entered into the video look - up table 62 . the video analog signal digitizer 42 is set to appropriate maximum and minimum values , and it is assumed that a pseudocolor analog display of three different colors is to be generated . it is also assumed for this example that the digitally generated images will be arithmetically combined in each of the separate color regions . thus , the entry into the video look - up table 62 may employ the &# 34 ; add &# 34 ; function and provide a red color output in the address range of 0 to 5 , may employ the green color output and the &# 34 ; subtract &# 34 ; control function in the address range of 6 to 10 , and the blue color output together with the &# 34 ; add &# 34 ; control function for addresses from 11 to 15 . concurrently , the digital input is converted to a single color , or to a number of colors in a prearranged format in the video look - up table 24 . as the analog signals are digitized , a pseudocolor output is generated consisting of the three selected colors in different areas . these areas are overwritten by the digitally generated patterns in different colors . consequently , outstanding or significant features can readily be identified against the background . in this example and in example iii , it is assumed for convenience that the control bits are included in the video look - up table 24 in the digital channel instead of the video look - up table 62 in the analog channel . in this example , it is desired to provide sharply visible digitally generated characters and vectors against the analog pseudocolor image background . if the digital signal is divided into eight principal increments ( 0 to 7 ) and it is desired to display the digital signal clearly whenever the digital value is at increment levels 6 and 7 , then the entries in the video look - up table 24 are written as follows : consequently , the pseudocolor image of the map will appear at its normal intensity except where the digital lines are sufficiently bright , at which regions the digital lines will appear in full brightness , without color mixing with the pattern of the map . furthermore , the map display is generated throughout in pseudocolor in accordance with any rule that is established and entered into the second video look - up table 62 . obviously the options of having the map only in graduated tones of one color and having the superimposed digitally generated line patterns in one color , or in different colors , are readily available . consider another situation in which the analog signal has been converted to three color signals , red , green and blue , each with intensity values of 0 to 15 . the digital signal initially has intensity values of 0 to 127 , but is applied to the table look - up memory 24 so as to generate a pseudocolor signal of corresponding intensity variations , but in three different colors , each scaled from 0 - 15 . however , in this situation it is desired that when the grey scale intensity value of the digital signal is in excess of level 10 ( or 11 - 15 ), then the digital pseudocolor signal will override the analog signal , which will be blocked out , but otherwise the two signals will be summed and divided by two , or averaged . for these purposes , the control bit entries in the video look - up table memory 24 are set as follows : under these circumstances , if the pseudocolor output for the digital input is green for all addresses , then green lines will show on the screen for signal levels of digital input in the 11 - 15 range . however , for signal levels from the digital input of 1 - 10 , mixtures of the green digital input and the analog signal input , whatever color it is , will appear on the screen . thus wherever the analog signal is red , weaker green lines drawn on top will appear to be yellowish or orange in color . thus , depending on the input signal levels , one pattern can be seen through the other . although a number of variations and modifications have been described herein , it will be appreciated that the invention is not limited thereto but encompasses all forms and expedients within the scope of the appended claims . | 6 |
all references , including publications , patent applications , and patents , cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein . the use of the terms “ a ” and “ an ” and “ the ” and similar referents in the context of describing the invention ( especially in the context of the following claims ) are to be construed to cover both the singular and the plural , unless otherwise indicated herein or clearly contradicted by context . the terms “ comprising ,” “ having ,” “ including ,” and “ containing ” are to be construed as open - ended terms ( i . e ., meaning “ including , but not limited to ,”) unless otherwise noted . recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range , unless otherwise indicated herein , and each separate value is incorporated into the specification as if it were individually recited herein . all methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context . the use of any and all examples , or exemplary language ( e . g ., “ such as ”) provided herein , is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed . no language in the specification should be construed as indicating any non - claimed element as essential to the practice of the invention . preferred embodiments of this invention are described herein , including the best mode known to the inventor for carrying out the invention . variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description . the inventor expects skilled artisans to employ such variations as appropriate , and the inventor intends for the invention to be practiced otherwise than as specifically described herein . accordingly , this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law . moreover , any combination of the above - described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context . unless defined otherwise , all technical and scientific terms used herein have the meaning commonly understood by a person skilled in the art to which this invention belongs . the specimen culture vehicle ( scv ) for microbiology specimens of the present invention is an automated device , which in one aspect is designed to be used as a component of a microbiology automation platform ( map ), described below . the scv and the map can be integrated to physically process specimens facilitated by a software scheduling and routing system through a series of steps involving : ( i ) pre - identification ; ( ii ) identification ; and ( iii ) post - identification processing of the specimen . the pre - identification can include , but is not limited to , growth and isolation , fixation , amplification , separation , and staining . the identification phase can include , but is not limited to , visual inspection and identification , uv / visible and mass spectrometry , enzyme - linked immunosorbent assay ( elisa ), immunoassay , and other biochemical methodologies . the post - identification phase can include , but is not limited to , holding for additional testing , storage , retrieval , and archiving . shown in fig1 - 3 is one embodiment of a specimen culture vehicle ( scv ) device for microbiology specimens , in both assembled and exploded views . in this embodiment , the scv 10 is shown to include a housing comprising a top shell 11 and a bottom shell 12 . preferably , the overall shape of the scv housing is spherical , the diameter of which is preferably smaller than 8 . 9 cm . the scv is preferably designed to fit in a typical hospital pneumatic tube transport system , and also to fit in a standard - sized biohazard transport bag . the bottom surface 13 of the housing is molded generally flat so that the scv remains upright , and is not subject to tipping over . because of its flat top and bottom surfaces , the scv is stackable and rackable . the integrity of the media , diluent , and specimen is maintained while held in the scv regardless of the physical orientation of the scv . the scv &# 39 ; s “ shell ” housing is preferably constructed of rigid plastic ( for example , polycarbonate ), and more preferably of injection molded plastic . as such , it is designed to protect the inoculated growth chambers in case of impact or if the scv is dropped . moreover , the scv &# 39 ; s physical composition is designed to withstand cleaning with standard laboratory cleaning solutions , and is designed to withstand adverse environmental conditions of temperature , humidity , stress , air particulates , and pressure . the scv material should preferably withstand temperatures of about 0 ° c . to about 50 ° c . and a relative humidity of about 15 % to about 80 % for about 180 days , while maintaining specimen integrity and preventing leakage , evaporation , desiccation or aerosolization of the specimen , media , or diluent ( s ). the scv physical composition should preferably support storage temperatures post - analysis of about 4 ° c . to about 8 ° c . for about 1 week . the scv construction materials are chosen so that they will maintain the integrity of the media and organisms to be isolated . the scv should withstand the range of mechanical forces and pressures to which it reasonably can be expected to be subjected without breakage or leakage . moreover , the materials selected for the scv structure , including its mechanisms , seals , and gaskets , should not interfere ( chemically or otherwise ) with the internal mechanisms , seals , growth media or microbiological specimen . nor should the materials selected for the seals and gaskets degrade significantly within the shelf life of the scv . preferably , the plastic structure should be able to have adhesive labels applied to it . the top shell 11 of the housing is formed to include a pair of exteriorly - exposed cylindrical cavities 14 , 15 for respectively receiving a specimen input chamber ( syringe ) 16 and a diluent chamber ( syringe ) 17 . the specimen input chamber 16 is designed to prevent leakage , aerosolization or cross - contamination , and is covered with a screw - top lid 18 . the lid 18 has a permeable aperture 19 ( conforming to standard industry requirements governing the use of these types of closures ) that allows a needle ( or canula ) to penetrate it while retaining the specimen within the chamber , and preventing air and possible contaminants from entering . the lid 18 for the specimen input chamber also has some feature ( not shown ) that indicates if the specimen has been tampered with . the specimen input chamber 16 is preferably clear on at least one side so that the integrity of the specimen can be observed by the operator from the exterior of the scv . in general , the specimen input chamber 16 is large enough to accept all standard sized swabs , and it is designed to contain preferably , at minimum , 4 . 0 ml of liquid sample and an additional 2 . 0 ml of fluid in case the operator applies diluent to the chamber . the specimen input chamber is designed to account for any losses due to dead volume and / or any volume changes due to temperature changes . the diluent chamber 17 contains a diluent ( preferably about 2 . 0 ml of 0 . 9 % saline ) that can be added to the specimen . a finger - operated plunger 20 permits the operator to apply a selective amount of the diluent to the specimen input chamber 16 . the diluent chamber 17 is designed to account for losses due to dead volume and volume changes due to temperature changes , and is designed to prevent leakage , aerosolization , tampering or cross - contamination . the specimen input chamber 16 and the diluent chamber 17 both are coupled through small apertures in the top shell 11 to an input manifold 21 . the input manifold 21 comprises a specimen port 22 , a diluent port 23 and an output port 24 , all connected by an internal fluid duct . an internal check valve 25 ( see fig4 ) in the fluid duct between the specimen input chamber 16 and the diluent chamber 17 prevents backflow of specimen into the diluent chamber . the output port 24 of the input manifold 21 is fluidly coupled via flexible tubing ( not shown ) to a first t manifold 26 , comprising first and second input ports 27 , 28 and an output port 29 ( all connected by an internal t - shaped fluid duct ). flow of the specimen / diluent mixture from the input manifold 21 to the first input port of the t manifold 26 is restricted by a shuttle valve mechanism 30 . in one embodiment , this mechanism comprises a sliding shuttle 31 , a cam 32 mounted on a rotatable shaft 33 , and a finger - operable control handle 34 . upon rotation of the handle ( which extends outside the scv housing ) by the operator , the shaft and cam are rotated , sliding the shuttle and thus opening or closing the valve mechanism 30 . a rehydrating water chamber 35 is fluidly coupled to the second input port of the t manifold 26 via flexible tubing ( not shown ) and an elbow manifold 36 . the elbow manifold 36 comprises an internal fluid duct with a check valve 37 ( see fig4 ) to prevent the specimen / diluent mixture from back flowing to the water chamber 35 . the water chamber 35 preferably contains distilled water for the purpose of rehydrating the culturing media in the growth chambers . in one embodiment , the amount of distilled water is 7 . 250 ml , plus an amount to make up for any dead volume losses . optionally , the rehydrating water chamber has a plunger 35 a ( see fig4 ) that is accessible on the exterior of the scv housing by the operator , whereby the operator can selectively control the amount of water introduced into the system . from the first t manifold 26 , the specimen / diluent / water mixture flows via a flexible tube ( not shown ) to a second t manifold 38 , comprising an input port 39 and first and second output ports 40 , 41 ( all connected by an internal t - shaped fluid duct ). this second t manifold includes an internal check valve 42 ( see fig4 ) to prevent backflow of the mixture . the pair of output ports 40 , 41 in the second t manifold 38 feed the specimen / diluent / water mixture ( via a pair of flexible tubes — not shown ) into an actuator which facilitates the flow of the mixture throughout the scv &# 39 ; s fluid circulation system . in the embodiment illustrated in fig1 - 3 , this actuator is a dual , low - pressure , rotary peristaltic pump 43 having a pair of input ports and a pair of output ports . as is well - known in the art , a peristaltic pump comprises a flexible tube fitted inside a circular pump casing , and a rotor with one or more rollers ( or wipers ) that intermittently compress the flexible tube as the rotor turns . the portion of the tube under compression closes , thus forcing fluid inside the tube to be pumped through the tube to an outlet port of the pump . as the tube opens to its natural state after the passing of a roller , fluid flow is induced into the inlet port of the pump . a dual peristaltic pump , such as used in the present embodiment , has a pair of compressible tubes and a pair of different rotor mechanisms , thus permitting pumping of fluids at two different rates as the rotors turn . the rotors of the dual peristaltic pump 43 are driven by a crank mechanism 44 having a drive shaft 45 and a crank handle 46 mounted on the surface of the scv housing . when the operator turns the crank handle in a clockwise direction , the rotors turn and the specimen / diluent / water mixture is drawn through the pump . it will be noted in the illustrated embodiment that flow of both the specimen / diluent mixture and the rehydrating water via separate flexible tubes to the first t manifold 26 ( and then on to the second t manifold 38 and the peristaltic pump 43 ) is restricted by a dual shuttle valve 50 . this valve is only opened upon turning by the operator of the crank mechanism 44 ( specifically , by the rotation of a tumbler 47 attached as part of the crank mechanism and its resultant movement of the shuttle valve &# 39 ; s armature 51 , cam mechanism 52 and shuttle 53 ). accordingly , it is impossible for any of the specimen / diluent mixture or the rehydrating water to reach either the pump or the growth chambers until the operator actuates the scv by turning the crank mechanism 44 . in an alternate embodiment ( not shown ), the scv includes a rotary motor within the housing and a rotatable crank mechanism coupled between the motor and the peristaltic pump . thus , rather than being operated by hand - cranking , the pump is operated when the motor is powered . power for the motor can be supplied either by a battery source within the scv housing or by a source external to the housing ( such as by plugging the scv into a vehicle power source during transport ). it will also be appreciated that the scv can comprise other types of pumps well known to persons skilled in the art . specimen / diluent / water mixture exiting the first output port of the pump travels via a flexible tube ( not shown ) to a first inlet of a growth chamber manifold 55 . in this manifold , the first inlet connects to a first fluid duct which branches into seven separate ducts ( each with its own backflow - preventing check valve 56 — see fig4 ), whereby the specimen / diluent / water mixture is directed to as many as seven of the eight growth chambers 60 a - g . likewise , specimen / diluent / water mixture exiting the second output port of the pump travels via another flexible tube ( not shown ) to a second inlet of the growth chamber manifold 55 . the second inlet connects to a second fluid duct ( with its own backflow - preventing check valve 56 ) which directs the specimen / diluent / water mixture to the eighth of the eight growth chambers 60 h . ideally , the eight growth chambers are visible to the operator through an orifice 70 in the top shell 11 of the housing so that the integrity of the media within the chambers can be observed and the amount of specimen / diluent / water mixture introduced into the chambers can be observed and controlled . in one embodiment of the scv , the eight growth chambers consist of one specifically for viral culture and six or seven chambers for bacteriology or mycology . if only six chambers are utilized for bacteriology or mycology , the remaining chamber is saved for future expansion and does not contain culturing media . the viral growth chamber contains , preferably , 0 . 50 ml of specimen and liquid media , specifically for viral culture ( total volume is determined as follows : 0 . 25 ml liquid media + 0 . 25 ml specimen ). the other seven growth chambers can contain , preferably , 1 . 05 ml of specimen and liquid media ( total volume is determined as follows : 1 . 00 ml liquid media + 0 . 05 ml specimen ). more specifically , the scv contains media suitable for the preservation and cultivation of all pathogenic bacteria , mycology , and viruses . the media selected for the scv meets the criteria of encouraging growth in a maximum amount of organisms with a minimum number of separate media . the culturing media does not consist of caustic or dangerous chemicals which will hinder the operation of the scv , and for pcr considerations the media does not contain any dna or rna fragments , or dead organisms . the media , when liquid , is transparent , which is necessary for turbidity checks ( or other growth checks ). preferably , the media contained in the growth chambers of the scv comprises tryptic trypticase soy media ; tryptic soy agar w 5 % sheep blood ; thioglycollate media ; chocolate ii agar ; bcye agar base ; viral transport medium ; selective 7h11 agar ; as separate media , or as any mixtures thereof . as will be appreciated , scvs can be manufactured with different combinations of growth media , thus providing different culturing choices to an operator to best match the circumstances of a particular biospecimen collection occurrence . the media is preferably lyophilized . once rehydrated , the media has the proper ph . optionally , one of the growth chambers ( specifically the chamber containing thioglycollate media ) has the capability of having the oxygen removed from the chamber to promote the growth of anaerobic organisms . the other growth chambers ( all except the one containing thioglycollate media ) should contain enough oxygen to promote the growth of aerobic organisms . the scv is manufactured sterile or the scv is sterilized prior to leaving the manufacturing facility . the culturing media and diluent are dispensed into the scv during the manufacture of the scv . importantly , the culturing media is sterile when inserted into the growth chambers of the scv , or the media is sterilized during the scv sterilization process mentioned above . the scv includes eight extraction portals — in the form of an eight - node plate 80 ( each node backed by a flexible septum 81 penetrable by a hypodermic needle )- that allow media containing the specimen sample to be withdrawn quickly and easily . these portals also allow multiple samples to be drawn over a period of time . each of the portals is connected fluidly to a separate one of the eight growth chambers 60 a - h via respective flow ducts in the growth chamber manifold 55 , eight flexible tubes ( not shown ), and respective flow ducts in an output manifold 82 . an output shuttle valve 83 simultaneously controls the flow of specimen / media samples through the eight flexible tubes . samples therefore can only be extracted from the scv when the valve handle 84 and connected cam mechanism 85 have been rotated 90 °, thus permitting the shuttle 86 to slide and opening the flexible tubes for fluid flow from the respective growth chambers . the valve handle 84 is configured and positioned so that it can be manipulated by either a human operator or a robotic unit in an automated analyzing platform . optionally , the scv is equipped with one or more indicators that show if temperature , pressure , aerobic / anaerobic conditions , shock exposure , and radiation exposure tolerances have been breached . moreover , the scv can have some type of indicator ( e . g ., broken safety seal ) to notify the user of potential contamination of the device prior to use . the internal temperature of each of the growth chambers can be dynamically adjustable to promote optimum growth of the microorganisms . in that case , each growth chamber may have a temperature sensor , and there is an electronic feedback loop for the purpose of maintaining a specific temperature range ( in other words , a thermostat or similar device ). the scv also has at least one electrically powered “ heater ” and / or “ chiller ”, for the purpose of creating an optimum growing environment . preferably , this heater or chiller is a well - known type of solid - state thermoelectric module , such as a peltier device 90 ( see fig4 ). accordingly , the scv requires a power source for any sensors , any associated leds , and the heater or chiller . in one embodiment , the scv does not require external power sources , and all on - board electronic devices and batteries preferably have a shelf life greater than 12 months . in an alternate embodiment , the scv has a power port which can readily be connected to an external power source ( such as a portable battery or a vehicle power outlet ). the scv is marked with a unique labeling that establishes the relationship of the patient and ordering event to the specimen acquired . this labeling can include conventional barcode , rfid tagging , similar techniques , or combinations thereof . for a barcode identification system , the hibcc standard is generally followed . for an rfid identification system , appropriate standards can be followed from iso / iec , ieee and ansi . an rfid tag preferably contains a data storage medium that will allow digital data to be written to it , stored on it and read from it , as defined by the version of the data storage medium . this identification “ links ” the particular specimen and the results of its analysis to the original patient , source , and presumptive diagnosis . the orders placed for analysis and the corresponding results are linked to the analysis of the scv contents and either stored with the specimen and / or transmitted via interface to a host information system , such as a laboratory information system ( lis ) or laboratory information management system ( lims ) that will store the patient demographics and test results or forward these results and patient demographics to other interfaced systems . the minimum identification information required by the microbiology laboratory and map on the scv is preferably stored in human - readable ( e . g ., label ) form , as well as in digital format . for example , a label on the scv should contain , for traceability purposes , some or all of the following : information regarding lot number , serial number , product identification number , manufactured date and expiration date . and the label on the scv should have an area on which an operator can hand write data . the handwritten portion of the scv &# 39 ; s label should include space for a patient name , a patient unique identifier or date of birth , the collection time and date , the name of the person collecting the specimen , and the specimen type . the information stored digitally on the scv is preferably accessible in the absence of the map by means of devices such as pc - based or hand - held readers . communication to the scv is performed through the scv &# 39 ; s identification system . the scv &# 39 ; s identification system comprises two parts : one that is physically attached to the scv at all times and another part that can read or acknowledge the existence of the part attached to the scv . the communication to the scv follows approved standards of communication . the scv is designed for single use , and is preferably disposable . thus , the scv should be capable of being sterilized for disposal using standard laboratory methodologies ( such as by lethal ionizing radiation ). sterilization of the scv should not degrade the scv &# 39 ; s construction materials , valving or internal mechanisms , nor should it hinder the readability of the written or digital information stored thereon . the scv can be disposed by using standard laboratory methodologies , including incineration . in an alternative embodiment of the scv , rather than having growth chambers of the type shown in fig1 - 3 , slots are provided within the housing for receiving a plurality of micro - lab plates ( such as are available commercially from micronics , inc .). the plates either can be preselected and installed in the scv during manufacture or can be “ field ” selected so that an operator can spontaneously configure the scv to best fit the circumstances of a biospecimen collection occurrence . each plate 100 ( fig5 ) comprises an inlet port 101 that , when the plate is installed within the scv , fluidly connects to one of the fluid ducts within the scv &# 39 ; s growth chamber manifold 55 , at least one outlet port 102 that fluidly connects to one of the scv &# 39 ; s extraction portals , and a series of interconnecting channels and chambers between the inlet and outlet ports for containment of culturing media and other substances deemed useful for the growth and preparation of the biospecimen . for example , appropriate substance can be provided in a plate to de - salt the cultured biospecimen ( thus rendering it more suitable for subsequent mass spectrometry analysis ). the scv is intended to integrate to an automated analyzing platform . the devices and methods of the present invention therefore preferably include a microbiology automation platform ( map ) and microbiology analyzers and the platform to which they interface . the map of the present invention is meant to automate the processes of the user ( operator ) whether or not there is physical hardware in place to do the actual manipulation of the cultured biospecimen . workflow logic determines and drives the series of steps required for a particular specimen . various workstations perform the designated procedure on the specimen and return it to the control of the platform following the procedure . the workstations can optionally be an automated instrument or a human user ( e . g ., medical technician ). in one example , the microbiology automation platform is a hybrid of a traditional laboratory information system ( lis ) and a laboratory device . the platform receives orders and order updates from an lis and sends results to an lis , but it does not manipulate patient information or perform other functions traditionally performed by an lis . it is possible to transmit data from the platform to national databases for the tracking of pathogenic outbreaks and trends in infectious diseases . such systems are associated , for example , with state health laboratories , health and human services at the state and national level , and the centers for disease control and prevention databases . the scv is designed with a physical feature that ensures proper orientation into the map . more specifically , the scv has an elongated slot 88 formed extending across the bottom shell 12 of the housing ( see fig1 and 3 ) that ensures its proper orientation on a conveyor track 110 used to automatically move one or more scvs to and through various analyzing workstations 111 - 114 within the map . when the scv is properly oriented in the map , the data storage medium ( i . e ., barcode or rfid tag ) is accessible to and readable by appropriate identification readers , the eight extraction portals on the scv are accessible to the medical device workstations performing the preparatory or analysis steps , and the valve handle 84 on the scv is easily accessible and manageable by robotic units in the map , as well as by manual operation . the graphic presentation of data on the map preferably includes : a windows ®- based color gui , message logging , status reporting , trending , management reports , epidemiology reports , images , inventory , quality control , and instrument utilization reports . the map preferably supports within the same configuration multiple pre - processing components , multiple detection components , multiple identification components , and multiple susceptibility components . referring now to fig6 , a schematic diagram of scv ( and biospecimen ) movement throughout the laboratory automation system is shown . this system operates as described in u . s . pat . no . 5 , 614 , 415 , the entirety of which is incorporated herein by reference . the scv ( with cultured biospecimen ) arrives at a specimen receiving station 120 , where the scv is loaded onto a conveyor track system designated generally at 110 . at specimen receiving station 120 , the scv is given an identification code which correlates with the scv and the biospecimen to be analyzed , so that the scv and biospecimen may be directed throughout the laboratory automation system , even when the scv is removed from the conveyor track for specific testing at a workstation . as shown in fig6 , conveyor track system 110 is preferably a continuously moving conveyor which will move scvs in a generally closed loop system . at receiving station 120 , the scv assignment is entered into the map &# 39 ; s cpu 130 to determine which workstations the biospecimen must utilize , the order in which the stations are to be utilized , the priority of the particular analyses to be conducted or steps to be taken , and any other pertinent information with respect to priority or turnaround time . entry of this information may be as easy as scanning the rfid tag or barcode of the scv . as represented by the double - headed arrows in fig6 , it will be appreciated that the cpu communicates ( wirelessly or by hard wire connection ) with each of the workstations 111 - 114 and the receiving station 120 . while fig6 shows only four specific workstations 111 - 114 , a conventional clinical laboratory could have a wide variety of such stations throughout a facility . the closed loop system of conveyor track 110 permits a biospecimen to stop at any given workstation in any desired order . thus , if time constraints require that the analysis of workstation 113 be performed first , and that an analysis of workstation 111 be performed at some time after the analysis of workstation 113 , the scv containing the biospecimen can travel on conveyor track 110 past workstations 111 and 112 , directly to workstation 113 , for immediate analysis . the scv is then reintroduced onto the conveyor track 110 to follow the closed loop around to the next workstation assigned to the biospecimen . once all desired analyses have been completed , the scv ( with any remaining cultured or original biospecimen ) is forwarded to a specimen archiving station 115 for removal from the conveyor track 110 and appropriate storage . the map supports the maintenance of a portion of the original biospecimen that is not contaminated or altered during processing and , therefore , is maintained for quality assurance purposes and / or confirmatory testing . the dispensing of the biospecimen / media combination from the extraction portals on the scv is preferably performed automatically by the map &# 39 ; s workstation equipment ( including robotic extraction probes or needles ), but it can also be done manually . the map equipment checks specimen volume prior to testing to ensure sufficient quantity for the testing to be performed , and the map continuously tracks the amount of specimen processed from the scv in order to determine availability of specimen volume for further testing . the map equipment also is capable of re - closing the scv after specimen has been removed or reagents / diluents have been added . the devices and methods of the present invention also include software . thus , the map can be configured to perform many different functions , as desired by a particular clinical facility . for example , the map has the capability to dynamically change the processing steps to completion of the specimen analysis based on information either received with the order or through information associated with the current status of the specimen . the map is developed with a rules engine that drives the logic of processing steps based upon microbiology standards in practice . this rule set is user configurable to mimic the current standard operating procedures of the microbiology laboratory staff . the map has the capability of sending revised or additional orders to a host system through a standard data communications interface 135 . the map is developed with on - line specimen tracking . specimen status is presented to the user interface in a graphical presentation . specimen status preferably includes : estimated time of testing completion , turn - around - time reporting , logging of any event where the scv is manually removed from the system , and a logging of the duration of time the scv spends at any sub - process in the system . the map records a complete processing history for each scv processed , including maintaining the data relationship between the scv ( the primary specimen ) and any aliquots ( secondary specimens ) that are created from the original scv specimen . data stored on the map are accessible remotely . the map contains an event monitoring , recording , and notification system . the map software supports auto - verification of patient results . the map software automatically accepts or rejects a specimen result based on a series of user - defined rule sets . rules for test scheduling and routing changes are customizable based on laboratory operational , business , and clinical objectives . the map can optionally have the capability to automatically prepare specimen and accompanying paperwork to refer specimens to public health entities . similarly , the map can optionally support the collection and reporting of data for peer - to - peer quality assurance programs ( and thus can optionally have the capability of maintaining various quality assurance reports on - line ). it is to be understood that this invention is not limited to the particular devices , methodology , protocols , subjects , or reagents described , and as such may vary . it is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only , and is not intended to limit the scope of the present invention , which is limited only by the claims . other suitable modifications and adaptations of a variety of conditions and parameters , obvious to those skilled in the art of microbiological diagnostics , are within the scope of this invention . | 2 |
the present invention , which provides a self - aligned soi body capacitor and a method of fabricating the same , will now be described in greater detail by referring to the drawings that accompany the present application . the drawings are provided herein for illustrative purposes and thus they are not drawn to scale . in fig1 – 20 , the structure through various processing steps is illustrated in different views . drawing a represents a top - down view where cross - sections a — a and b — b , and in some instances c — c , are shown . drawing b is a cross sectional view along the line a — a , drawing c is a cross sectional view along the line b — b , and drawing d is a cross sectional view along the line c — c . “ a — a ” is a cross section in a vertical cutting a plane parallel to a wordline location , and through the center of the wordline location . “ b — b ” is a cross section in a vertical cutting plane parallel to a bitline location , and through the center of the bitline location . “ c — c ” is a cross section in a vertical cutting plane parallel to a bitline location , and through a capacitor plate . the process of fabricating a self - aligned soi body capacitor begins by first providing the structure 10 shown in fig1 a – 1c . the structure 10 includes a si - on - insulator ( soi ) substrate 12 , a patterned material stack 20 located on an upper surface of the soi substrate 12 and a patterned resist 30 located on an upper surface of the patterned material stack 20 . the soi substrate 12 includes a semiconductor layer 14 , a buried insulating layer 16 and a si - containing layer 18 . the semiconductor layer 14 of the soi substrate 12 comprises any semiconductor material known in the art . illustrative examples of semiconductor materials that can be employed as the semiconductor layer 14 include , but are not limited to : si , sic , sige , sigec , ge alloys , gaas , inas , inp as well as other iii / v or ii / vi compound semiconductors . typically , the semiconductor layer 14 is a si - containing semiconductor such as , si , sic , sige , or sigec . the thickness of the semiconductor layer 14 is inconsequential to the present invention . the buried insulating layer 16 is typically comprised of an oxide , nitride , oxynitride or multilayers thereof . more typically , the buried insulating layer 16 is comprised of an oxide . the thickness of the buried insulating layer 16 may vary depending on the origin of the layer . typically , however , the buried insulating layer 16 has a thickness from about 5 to about 500 nm , with a thickness from about 50 to about 200 nm being more highly preferred . the si - containing layer 18 of the soi substrate 12 is comprised of a silicon containing semiconductor including , for example , si , sic , sige , or sigec . the si - containing layer 18 of the soi substrate 12 is preferably monocrystalline . the thickness of the si - containing layer 18 may vary depending on the technique that was used in forming the soi substrate 12 . typically , the si - containing layer 18 of the soi substrate 12 has a thickness from about 2 to about 300 nm , with a thickness from about 5 to about 150 nm being more highly preferred . the crystal orientation of the semiconductor layer 14 and the si - containing layer 18 may be the same or different , with the same crystal orientation being typical for soi substrates made by separation of silicon by ion implantation of oxygen ( simox ). illustratively , the crystal orientation of layers 14 and 18 are typically chosen from ( 100 ), ( 110 ) or ( 111 ). the si - containing layer 18 of the soi substrate 12 can be unstrained , strained or a combination thereof . the soi substrate 12 shown in fig1 a – 1c can be fabricated using techniques that are well known in the art . for example , the soi substrate 12 may be formed by an ion implantation process referred to as simox in which ions such as oxygen ions are implanted into a starting wafer and thereafter the ion implanted wafer is subjected to an annealing process that causes the formation of the buried insulating layer 16 within the substrate . alternatively , the soi substrate 12 can be formed by a layer transfer process that includes wafer bonding . the patterned material stack 20 shown in fig1 a – 1c comprises at least three layers , with a fourth layer being optional . the bottom most layer of material stack 20 is a nitride layer 22 . an optional oxide marker layer 24 may be located on the nitride layer 22 . the purpose of using the optional oxide marker layer 24 will be discussed in relation to fig1 a – 10c . a polysilicon layer 26 may be located on the oxide marker layer 24 , if present , or on the nitride layer 22 . the uppermost layer of the material stack 20 comprises a nitride layer 28 . the thickness of the patterned material stack 20 may vary depending on the number of layers within the stack . typically , the overall thickness of the patterned material stack 20 is from about 20 to about 600 nm , with a thickness from about 35 to about 300 nm being more typically . this overall thickness for the patterned material stack 20 includes a thickness for the nitride layer 22 from about 5 to about 200 , preferably from about 10 to about 100 nm , a thickness for the optional oxide marker layer 24 from about 3 to about 10 , preferably , from about 4 to about 8 nm , a thickness for the polysilicon layer 26 from about 5 to about 200 , preferably from about 10 to about 100 nm , and a thickness for the nitride layer 28 from about 5 to about 200 , preferably from about 10 to about 100 nm . the patterned resist 30 is comprised of a conventional photoresist material and its thickness is well known to those skilled in the art . the patterned material stack 20 is formed by first forming the various material layers using one or more conventional blanket deposition techniques such as , for example , chemical vapor deposition ( cvd ), plasma enhanced chemical vapor deposition ( pecvd ), evaporation , chemical solution deposition , or atomic layer deposition . the polysilicon layer 26 can be formed by a cvd process . in addition to deposition processes , the various insulating layers of the material stack 20 can be formed by thermal means including oxidation and nitridation . a combination of the aforementioned techniques can also be used . after forming the various layers of the material stack , a resist is applied to the uppermost layer of the material stack 20 utilizing a conventional deposition process such as , for example , spin - on coating , and then the resist is subjected to a conventional lithographic process . the lithographic process includes exposing the resist material to a pattern of radiation and developing the resist utilizing a conventional developer . after the resist has been patterned , the pattern is transferred into the material stack , stopping on the upper surface of the soi substrate 12 , i . e ., on top of the si - containing layer 18 , utilizing one or more , preferably one , etching process . the etching process used to pattern the material stack includes a dry etching process ( including reactive ion etching , ion beam etching , plasma etching or laser ablation ), wet etching , or a combination thereof . preferably , the etching used to pattern the material stack comprises anisotropic reactive ion etching wherein the chemistry of the etchant is changed to selectively etch the exposed material layer . the patterned resist 30 can , in some embodiments , be removed from the structure following the formation of the patterned material 20 utilizing a conventional resist stripping process . prior to forming the material stack on the soi substrate , a pre - implant step is performed in which ions ( n - or p - type ) are implanted through the si - containing layer 18 and the buried insulating layer 16 stopping within the upper surface of the semiconductor layer 14 . that is , a heavily doped ( on the order of about 1 × 10 19 atoms / cm 3 or greater ) region ( not shown in the drawings ) can be formed at or near the interface between the buried insulating layer 16 and the semiconductor layer 14 . the dopant polarity of the heavily doped region is selected to be the same as the dopant polarity of the polysilicon body capacitor sidewall plate , to be subsequently formed and contacted to the substrate . this heavily doped region in the semiconductor layer 14 beneath the buried insulating layer 16 will serve to distribute the voltage that is applied to the sidewall plates , by enhancing conduction near the semiconductor layer 14 / buried insulating layer 16 interface . note that in fig1 a – 1c the patterned material stack 20 protects portions of the si - containing layer 18 , while leaving other portions of the si - containing layer 18 exposed . also , the patterned material stack 20 defines ( i . e ., covers ) the active region in which the transistor of the inventive structure will be subsequently formed . the optional oxide maker layer 24 is shown in fig1 a – 1c and is not shown again in the remaining drawings . next , and as shown in fig2 a – 2c , exposed portions of the si - containing layer 18 , not protected by the patterned material stack 20 , are then etched using the upper patterned nitride layer 28 as an etch mask . this etching step removes all the exposed portions of the si - containing layer 18 , stopping on the upper surface of the buried insulating layer 16 . the etching step is performed utilizing an etching process such as anisotropic reactive ion etching that selectively removes the si - containing layer 18 . if the patterned resist 30 was not previously stripped from the structure , it can be removed following this etching process . note that in fig2 a – 2c the si - containing layer 18 is patterned such that the sidewalls thereof all substantially aligned with the sidewalls of the patterned material stack 20 . moreover , in fig2 a – 2c , portions of the buried insulating layer 16 , not directly beneath the patterned material stack 20 , are now exposed . a dielectric 32 is then formed on the exposed sidewalls of the etched si - containing layer 18 as well as the exposed sidewalls of the polysilicon layer 26 . the dielectric 32 serves as the insulator between the sidewall plate ( to be subsequently formed ) of the body capacitor and the remaining si - containing layer 18 ( which will form the body of a mosfet ). the dielectric 32 may comprise sio 2 , silicon oxynitride , or a high k material ( k greater than 4 . 0 , preferably greater than 7 . 0 ) such as , for example , al 2 o 3 or ta 2 o 5 . the dielectric 32 , which can be formed by a variety of techniques including deposition ( such as , for example , cvd or pecvd ) or thermal ( such as oxidation or oxynitridation ), has a thickness from about 2 to about 20 nm . more typically , the dielectric 32 has a thickness from about 3 to about 6 nm . the structure including the dielectric 32 that is formed on the exposed sidewalls of the remaining si - containing layer 18 and the polysilicon layer 26 is shown , for example , in fig3 a - 3c . fig4 a – 4c show the structure that is formed after an insulating material 34 , such as an oxide , is formed over the surface of the exposed buried insulating layer 16 and atop the patterned material stack 20 . any conventional deposition process such as cvd or pecvd can be used to form a layer of the insulating material 34 . after forming the insulating material 34 , the insulating material 34 is planarized so that an upper surface of the insulating material 34 is coplanar with the upper surface of the polysilicon layer 26 of the patterned material stack 20 . that is , a planarization process such as chemical mechanical polishing ( cmo ) and / or grinding is used to provide a structure as shown in fig5 a – 5c in which the upper surface of the insulating material 34 is substantially planar to the upper surface of the polysilicon layer 26 . it is noted that the planarization process used in this step of the present invention removes the upper nitride layer 28 of the patterned material stack 20 . as shown in fig5 a – 5c , isolation regions 34 are formed adjacent to the remaining portions of layers 26 , optionally 24 , 22 and layer 18 . a pad nitride layer 36 is then deposited by conventional techniques over the planarized structure shown in fig5 a – 5c providing the structure shown , for example , in fig6 a – 6c . the pad nitride layer 36 is a relatively thick layer since it determines the height of the wordline wiring to be subsequently formed . typically , the pad nitride layer 36 has a thickness from about 30 to about 150 nm . stripes ( i . e ., openings or troughs ) 38 are then formed through the pad nitride layer 36 stopping on the upper surface of the polysilicon layer 26 in the active region ( see fig7 c ) and on the surface of insulating material 34 in the region that lies to the periphery of the active region ( see fig7 b ). the stripes 38 are formed by lithography and etching . the etching step is performed by utilizing an anisotropic reactive ion etch for silicon nitride that is selective to silicon and silicon oxide . the stripes 38 define the location of the sidewall capacitor plates , which will be self - aligned to the body ( i . e ., the remaining si - containing layer 18 ), and the location of the wordline gate conductors . both the sidewall capacitor plates and the wordlines are self - aligned to each other since they will be defined by and registered to the same structural features ( i . e ., through the opening in the pad nitride layer 36 ). the structure including the stripes 38 is shown , for example , in fig7 a – 7c . the exposed surfaces of the insulating material 34 outside of the active region shown along line a — a are then etched by a dry etching process such as anisotropic reactive ion etching through layer 34 and the underlying buried insulating layer 16 stopping on the upper surface of semiconductor layer 14 . the etching process used in this step of the present invention , which provides the structure shown in fig8 a – 8c , is selective to silicon and silicon nitride . in fig8 b , reference numeral 40 is used to define the recessed region formed by this step of the present invention ; note that no etching occurs in the active area during this step of the present invention , since it is protected by either polysilicon layer 26 or pad nitride 36 . the recessed region 40 and the stripes 38 are then filled with a conductor 42 and then the conductor 42 is planarized to the upper surface of pad nitride 36 providing the structure shown in fig9 a – 9c . the filling process includes any conventional deposition process , while planarization is performed utilizing cmp and / or grinding . the conductor 42 comprises a metal , a metal alloy , a metal silicide , polysilicon or a combination thereof . preferably , polysilicon is used as the conductor 42 . when polysilicon is used as the conductor 42 , it is typically formed using an in - situ doping deposition process . the polysilicon is doped with the same dopant polarity as the buried layer that was previously formed into the semiconductor layer 14 as described in connection with the structure shown in fig1 a – 1c . preferably , the dopant polarity of the polysilicon conductor 42 and of the deep implant region described above in fig1 a – 1c are p - type since a p - type workfunction for the capacitor plate will result in maximum body hole concentration , for the nmosfets in this exemplary embodiment . the exposed conductor 42 is then etched selective to nitride and oxide , recessing the top surface of the conductor 42 slightly below the top surface of the si - containing layer 18 . see , for example , the structure shown in fig1 b . in this step , all the exposed conductor 42 over the active region as well as portions of the polysilicon layer 28 are removed which exposes a top surface of nitride layer 22 . see , for example , the structure shown in fig1 c . in embodiments in which the optional oxide marker 24 is present in the structure , and when that layer is reached during the course of etching the conductor 42 in the active region , the oxide signature is detected to indicate that the remaining amount of conductor 42 to be etched is slightly thicker than the lower nitride layer 22 . the use of the optional oxide marker layer 24 results in excellent control of the depth of the conductor recess below the top surface of the si - containing layer 18 . the recessed conductor forms the sidewall plate conductors 42 ′. next , and as shown in fig1 a – 11b , an oxide layer 44 having a precisely controlled thickness is formed over the top surface of the recessed conductor 42 ′. this oxide layer serves as an insulating layer between the body capacitor plate and the subsequently formed overlying wordline conductor . the oxide layer 44 is formed utilizing an oxidation process to a thickness from about 5 to about 20 nm . the surface of the si - containing layer 18 in the active region ( see , fig1 c ) is protected during this thermal oxidation step by the nitride layer 22 . oxide layer 44 is however formed on the exposed sidewalls of polysilicon layer 26 in the active region . the exposed nitride layer 22 in the active region that overlays the si - containing layer 18 is then removed , preferably with an anisotropic etch to minimize undercutting of the nitride layer 22 elsewhere on the si - containing layer 18 . at this point in the process , channel doping ( not shown ) may be introduced into the exposed portions of the si - containing layer 18 using conventional ion implantation techniques . a screen oxide ( also not shown ) may optionally be formed prior to the implantation process and thereafter removed . the resultant structure that is formed after the foregoing step of removing the exposed nitride layer 22 overlaying the si - containing layer 18 is shown in fig1 a – 12c , for example . reference numeral 45 is used to denote the openings formed during this step of the present invention . a transfer gate dielectric 46 is then formed on the exposed surface of si - containing layer 18 through opening 45 . the transfer gate dielectric 46 comprises an oxide , oxynitride or a high k ( k greater than 4 . 0 , preferably greater than 7 . 0 ) dielectric . the thickness of the transfer gate dielectric 46 is typically from about 1 to about 10 nm . any conventional deposition process or thermal process can be used to form the transfer gate dielectric 46 . fig1 a – 13c show the structure after the transfer gate dielectric 46 has been formed . fig1 a – 14c shows the structure after wordline gate conductor 48 and an insulating cap 50 are formed . specifically , the wordline gate conductor 48 is formed through the opening 45 atop the transfer gate dielectric 46 by deposition . following the deposition process , the wordline gate conductor 48 is planarized to the upper surface of the pad nitride layer 36 . the planarized wordline gate conductor 48 is then recessed utilizing a timed etching process such as reactive ion etching . the wordline gate conductor 48 is comprised of a conductive material including , for example , a metal , metal alloy , metal silicide , polysilicon or any combination thereof . the insulating cap 50 , typically an oxide , is then deposited and planarized utilizing conventional processes well known in the art . the exposed pad nitride layer 36 is then removed utilizing a well known etching method such as , for example , hot phosphoric acid or reactive ion etching , exposing the polysilicon layer 26 and insulating material 34 . the resultant structure is shown in fig1 a – 15c . the exposed polysilicon layer 26 over the active region is then removed by etching , e . g ., reactive ion etching , thus exposing the nitride layer 22 over the active region . the structure formed after this step of the present invention has been performed is shown , for example , in fig1 a – 16c . at this point of the inventive process , an oxide spacer 52 is formed on each sidewall of the wordline conductor 48 . the purpose of the spacer 52 is to slightly widen the footprint of the wordline to avoid any possibility of etching into the seam between the wordline and the oxide layer 44 over the body capacitor plate 42 ′ when the nitride layer 22 is subsequently removed . if the spacer 52 was not present at this time , there would be a remote possibility that the etch to remove the lower nitride layer 22 may damage the protective oxide layer 44 between the wordline 48 and the body capacitor plate 42 ′. the oxide spacer 52 is formed using well known methods such as deposition of a conformal cvd oxide film , followed by an anisotropic etch . fig1 a – 17c show the structure including the oxide spacer 52 . the exposed lower nitride layer 22 over active si - containing layer 18 is then removed , for example , by reactive ion etching , stopping on the si - containing layer 18 surface outside of the wordlines 48 . the resultant structure in shown , for example , in fig1 a – 18c . a silicon nitride etch chemistry is typically employed to avoid erosion of the insulating material 34 and the insulating cap 50 . conventional processing follows , with formation of oxide spacers ( if not previously formed ), and source / drain implantation . since the sidewall plates 42 ′ and the source / drain diffusions 54 to be subsequently formed in the next processing step ( see fig1 a – 19c ) are each separately self - aligned with the wordline troughs 38 , they are self - aligned with each other . the self - alignment of the sidewall plates 42 ′ and the source / drain diffusions 54 is not taught or suggested in any prior art soi body capacitor known to the applicants of the present invention . source - drain implants ( including any extensions and halos ) and anneals are now done forming at least the source - drain diffusions 54 shown in fig1 a – 19c . fig2 a – 20d exemplify a typical layout of a portion of the 1 t - capacitorless memory array with self - aligned sidewall body plates 42 ′. specifically , in fig2 a – 20d , a structure including two transistors that share a common bitline diffusion 54 bl in the memory array is illustrated . the source line diffusion shown in these drawings are labeled as 54 sl . the structure shown in fig2 a – 20d includes source - line ( sl ) conductors 56 that are formed adjacent to selected wordlines using well known metal deposition and damascene processes . an interlayer dielectric ( ild , not shown ) is then typically deposited . bitline studs 58 are formed to selected diffusions , and bitline conductors 60 are formed using standard methods . higher level insulating and wiring layers are then formed to complete the fabrication of the chip . several specific layouts and technology options for a memory array employing the self - aligned body - capacitor will be shown next . it is noted that in the present invention , the wordlines lie perpendicular to the bitlines and arrays of transistors are arranged in rows and columns . note that a new cross - section ( c — c ) has been added in fig2 . c — c is a cut parallel to b — b but passing through the capacitor plate 42 ′ of the self - aligned body capacitor . a phantom of the soi region ( i . e ., si - containing layer 18 ) and source - drain diffusions 54 has also been incorporated into cross - sectional view c - c to illustrate the location of the capacitor plate 42 ′ with respect to the diffusions 54 in the si - containing layer 18 , as well as the wordline conductor 48 . it is emphasized that the edges of the capacitor plate 42 ′, the wordline conductor 48 , and the diffusions 54 are all self - aligned and are not subject to alignment tolerance . the above discussion , in reference to fig1 – 20 , illustrates the various processing steps that are used in fabricating the inventive self - aligned soi body capacitor structure shown in fig2 . fig2 and 22 illustrate some cell layouts that can include the inventive structure shown in fig2 . in fig2 and 22 , like reference numerals are used to describe the components that are present in the structure shown in fig2 . a first exemplary layout of a portion of an array of cells employing the inventive self - aligned soi body capacitor illustrated in fig2 is shown in fig2 . specifically , fig2 illustrates an open bitline architecture design where each wordline 48 gates a cell in each crossing bitline 60 . locations of the sidewall capacitor plate 42 ′, self - aligned to the wordlines and diffusions , are delineated by the dashed line rectangular regions . this embodiment defines continuous stripes of soi ( running horizontally in fig2 ). rows of soi stripes are separated by the inventive capacitor plate and regions of sti . bodies of adjacent mosfets sharing the same soi stripe are isolated by source - drain diffusions , which extend all the way to the box ( as previously described by the process flow ). if the technology were designed to use shallow source - drain diffusions that extend only partly to the box body charge of adjacent mosfets would not be isolated . in that case sti would be needed to provide isolation between bodies of mosfets sharing a common bitline . the case of source - drain diffusions extending partly to the box is discussed in fig2 . specifically , fig2 illustrates a second exemplary layout of a portion of an array of cells employing the inventive self - aligned soi body capacitor . in the folded bitline architecture design shown in fig2 , each wordline 48 gates a cell in alternate crossing bitlines . locations of the sidewall capacitor plate , self - aligned to the wordlines and diffusions 60 , are delineated by the - dashed line rectangular regions . regions of soi ( i . e ., the active si - containing layer 18 ) are indicated by rectangles bordered by dotted lines . these regions are labeled with reference numeral 100 in fig2 . a plurality of isolation regions ( i . e ., stis ) isolates soi regions that lie under each bitline . each one of the plurality of isolated soi regions contains a single mosfet with a single bitline contact diffusion on a first end and a single source line ( sl ) contact diffusion on a second end of said isolated soi region . corresponding soi regions in adjacent rows jog laterally by 1 minimum feature dimension ( 1f ), thus resulting in the folded bitline layout . since this second exemplary layout uses intervening sti to isolate bodies of mosfets sharing a common bitline , there is no restriction on the source - drain diffusion depth . no art has been found which illustrates a folded bitline layout for a body - charge storage type of memory device . all the known art for this type of cell employ continuous stripes of soi , thus necessitating deep diffusions . it may be advantageous to employ shallow diffusions for improved scalability . while the present invention has been particularly shown and described with respect to preferred embodiments thereof , it will be understood by those skilled in the art that the foregoing and other changes in forms and details may be made without departing from the spirit and scope of the present invention . it is therefore intended that the present invention not be limited to the exact forms and details described and illustrated , but fall within the scope of the appended claims . | 7 |
referring now to fig1 a leadscrew assembly 10 is illustrated comprising a leadscrew 12 and a leadscrew drive nut 14 mounted on the leadscrew . a coupling of the present invention , for transferring motion from the drive nut 14 to a movable carriage , not shown , comprises a coupler member or plate 16 which is disposed around and connected to the drive nut , such as by mating threads 18 . a carriage plate 20 , or a member which can be connected to , or be part of , and move with the carriage , is also disposed in spaced relationship around the leadscrew in spaced relation to the coupler plate 16 . an intermediate member 22 , which in this embodiment is comprised of two mating plates 24 and 26 , is also disposed in spaced relationship around the leadscrew between the coupler plate 16 and the carriage plate 20 . the intermediate member 22 is connected to the coupler plate 16 by a first connecting means such as a pair of flexure members 28 which are fixed at opposite ends to both the intermediate member and the coupler plate . the flexure members are connected to the coupler plate at a pivot axis 30 which is substantially perpendicular to the axis 32 of the leadscrew , and are fixedly connected at the intermediate member end . a second pair of flexure members 34 connect the intermediate member 22 to the carriage plate 20 . the second pair of flexure members are also rigidly connected to the intermediate member end and are connected to the carriage plate at a pivot axis 36 , which is substantially perpendicular to the leadscrew axis and also substantially perpendicular to pivot axis 30 . thus , the second pair of flexure members is oriented 90 ° to the first pair . as illustrated , the intermediate member 22 is formed of two mating plates 24 and 26 which rigidly hold the ends of both pairs of the flexure members when the plates are tightly fastened together by means of screws or the like , not shown . the flexure assembly must be very stiff in the direction of the leadscrew axis and about the leadscrew axis . by flexing , the flexure members permit relative movement of the intermediate member rotationally about axes 30 and 36 , as well as perpendicularly to these axes . the flexure members have a sufficiently high aspect ratio of length to diameter that they permit the intermediate member 22 to move in the plane perpendicular to the leadscrew axis without permitting movement along the leadscrew axis . the flexure members must be stout enough that they will not buckle under the load being transferred form the leadscrew drive nut to the carriage , yet they must permit the small transverse motion of the leadscrew without transferring that motion to the carriage . thus , the coupler of the present invention prevents the transfer of the once - per - revolution errors in the leadscrew to the carriage . a first alternative embodiment is illustrated in fig2 similar to the embodiment of fig1 wherein similar components are identified with similar reference numbers with the prefix &# 34 ; 2 &# 34 ;. in this embodiment both pivot axes 230 and 236 are located in the same plane in intermediate member 222 . although the construction of this embodiment may be a bit more complex , the location of both pivot axes in the same plane prevents the introduction of induced motion , such as transverse motion caused by motion about a pivot axis . a second alternative embodiment is illustrated in fig3 similar to the embodiment of fig1 wherein similar components are identified with similar reference numbers with the prefix &# 34 ; 3 &# 34 ;. in this embodiment the intermediate member 322 , the flexure members 328 and 334 , and the connecting means for the carriage 320 , are all formed from a single sheet of folded sheet metal , for example . such a construction is very simple and economic to form , and yet provides all of the features and advantages of the preferred embodiment . a third alternative embodiment is illustrated in fig4 similar to the embodiment of fig1 wherein similar components are identified with similar reference numbers with the prefix &# 34 ; 4 &# 34 ;. in this embodiment , the coupling is folded so that the length thereof is substantially reduced . moreover , this embodiment provides a common plane for the pivot axes , such as provided by the embodiment illustrated in fig2 except that the common plane passes through the coupling member and the carriage connecting means which are also co - planar . fig5 and 7 illustrate variations of the formed sheet metal coupler construction of fig3 . the structure shown in fig5 is for a folded coupler similar to fig4 except that the pivot axes are not in a common plane . the structure shown in fig6 is for the folded coupler of fig4 . the structure shown in fig7 is for a coupler like that shown in fig2 wherein the pivot axes are in a common plane in the intermediate member 622 . fig8 illustrates the use of the coupler of the present invention as a flexible shaft coupling . in this application , the coupler member 816 is connected to an input shaft ( not shown ), and the connecting means 820 is connected to an output shaft ( not shown ). with the present coupler , movement of the input shaft transverse to its axis will not be imparted to the output shaft while transmitting the rotation of the input shaft to the output shaft . still further , it will be appreciated that the intermediate member can be connected directly to either drive nut or to the carriage without the need for a coupler member or a connector member so long as the form of the connection between the intermediate member and the drive nut or the carriage is the same as that described for the connection between the intermediate member and the coupler and the connector member , i . e . so long as the connection provides the same freedom of movement between the two members as well as the same constraints . it will thus be seen that the present invention provides a simple , inexpensive leadscrew coupling which corrects for lead screw drunkenness without the need to specify extremely accurately manufactured , and thus very expensive , lead screws for use in systems sensitive to such errors , such as scan printing apparatus . by compensating for once per revolution lead screw errors , the present invention permits the use of much less expensive lead screws . the invention has been described with reference to specific preferred embodiments and variations thereof , but it will be understood that other variations and modifications can be effected within the spirit and scope of the invention , which is defined by the following claims . | 8 |
hereunder , referring to the attached drawings , there are described embodiments in which a rotatively - operated electronic component according to the present invention is applied to a portable phone . as shown in fig1 the portable phone 1 includes a body case 2 made of synthetic resin , where various kinds of members are housed or mounted . at the upper part of the body case 2 , an antenna 3 is installed to be extracted or stowed freely , and through the antenna 3 transmission and reception of radio waves are conducted with base stations . at the front upper part of the body case 2 is installed a speaker 4 as an electro - acoustic conversion means . when calling , a voice of a called party is outputted from this speaker 4 . at the front lower part of the body case 2 is installed a microphone 5 as an acoustic - electronic conversion means . when calling , voice of a user is collected by this microphone 5 . at somewhat upper position from the front center of the body case 2 is installed a liquid crystal display ( lcd ) 6 as a display means capable of displaying various kinds of information such as receiving condition of radio waves , the amount of battery remaining , telephone numbers of called parties , registered contents as a telephone directory ( telephone numbers and names of called parties or the like ), outgoing and incoming history , and other kinds of registered contents . at the front lower half of the body case 2 , various operation keys 7 are installed as operating means . by pressing these operation keys 7 , input of various instructions , texts or the like may be performed . further , at the upper part of the left side surface of the body 2 , a jog dial 8 is installed as a different switch apparatus from the operation keys 7 . by rotating this jog dial 8 , menus displayed on the liquid crystal display 6 , scrolling display of various items such as a list of outgoing and incoming history , telephone number list or the like , and a cursor for selecting items , etc ., may be displayed . by the pushing operation ( pushing - in operation ) of the jog dial 8 to the internal direction of the body case 2 , the items displayed on the liquid crystal display 6 may be decided or executed . furthermore , selection or execution of the designated items may also be conducted by moving the jog dial 8 to the rear side of the portable phone along the side surface of the body case 2 to provide the pivoting operation ( push - down operation ) about the pivot axis parallel to the rotation plane of the jog dial 8 and orthogonal to the pushing - in direction , or by moving the jog dial 8 to the opposite direction of the push - down operation , namely , by moving it to the front side of the portable phone along the side surface of the body case 2 to provide the pivoting operation ( push - up operation ) about the pivot axis parallel to the rotation plane of the jog dial 8 and orthogonal to the pushing direction . various operations may be provided . for example , once decided items may be cleared by the push - up operation , and a hierarchy of the menu may be raised by one level during display of the menu or a display of a menu ( called catch menu hereafter ) by which a user is allowed to select procedures such as hold - on of call , microphone - off or the like when calling may be actuated during calling by the push - down operation . as shown in fig2 the jog dial 8 essentially consist of a disc member 9 , a detection circuit 10 , and a first to a third switches 11 , 12 and 13 . when the rotating operation is performed with the disc member 9 , its rotation direction and rotation angle are detected by the detection circuit 10 , and the result of the detection is outputted to a control means described later . when the disc member 9 is pushed into the interior of the body case 2 by the pushing operation , the first switch 11 is operated , and when the push - down operation is performed with the disc member 9 , the second switch 12 is operated , and when the push - up operation is performed with the disc member 9 , the third switch 13 is operated . the control means described later is operable to recognize operating condition of these switches , and to conduct various controls in accordance with the rotation direction and the rotation angle of the disc member 9 and the operating condition of the first to the third switches 11 , 12 and 13 . as shown in fig3 the disc member 9 is supported by a base member 14 made of insulation material to be rotative and movable to the pushing direction , namely , to an arrow a direction in fig3 . more specifically , an intermediate supporting plate 15 is supported by the base member 14 with freely pivoting , and the disc member 9 is supported at the position near the pivot edge of the intermediate supporting plate 15 . the intermediate supporting plate 15 is impelled to move to a clockwise direction shown in fig3 by a spring member ( not shown ), namely , to an arrow cw direction in fig3 whereby pivoting to the clockwise direction cw is made to stop at the initial position as shown in fig3 . at the rear side of the intermediate supporting plate 15 of the base member 14 , an intermediate operation element 16 having the shape of a letter l from side - view is supported with freely pivoting . at the position facing the rear edge 16 a of the intermediate operation element 16 of the base member 14 , the first switch 11 is disposed . accordingly , when the disc member 9 is pushed to the pushing - in direction a , the intermediate supporting plate 15 pivots to the counterclockwise direction , namely , to the arrow ccw direction in the drawing , against the impelling force of the spring member ( not shown ), so that the disc member 9 appears to move to the pushing - in direction a apparently . when the intermediate supporting plate 15 pivots to the counterclockwise direction ccw , a front edge 16 b of the intermediate operation element 16 is pressed by a rear edge 15 a of the intermediate supporting plate 15 , and the intermediate operation element 16 is pivoted such that the rear edge 16 a moves to the first switch 11 , and pushes down the first switch 11 , whereby a signal is outputted to the effect that the push - down operation is conducted by the first switch 11 . when the force of pushing the disc member 9 to the pushing - in direction a is removed , the intermediate supporting plate 15 pivots to the clockwise direction cw by the impelling force of the spring member and returns to the initial position . on the base member 14 , two supported pieces 14 a , 14 a are formed , each protruding to the opposite directions with respect to the direction orthogonal to the pushing - in direction a and parallel to the rotation plane of the disc member 9 . fig3 shows that the disc member 9 is supported by the intermediate supporting plate 15 which is freely pivoting , but the disc member may also be supported by an intermediate supporting plate which , when being pushed , slides straight to the pushing - in direction a with respect to the base member . as shown in fig5 the disc member 9 consists of two discs , namely , a stationary fixed disc and a rotating disc which is disposed coaxially with the fixed disc and rotative with respect to the fixed disc . at the portion near the rim of the rotating disc facing the fixed disc , there exist a pair of counter electrodes , each being spaced and facing in the direction of the radius . these counter electrodes contact on - the - slide with pairs of counter electrodes formed at the portion near the rim of the fixed disc . the counter electrodes of the fixed disc , both in the outer and in the inner circumference , are disposed in a little displacement with respect to the circumferential direction . for example , when the counter electrodes of the rotating disc contact the counter electrodes of the fixed disc , and by putting the counter electrodes of the rotating disc to be at grounding potential , rotating angle may be detected by counting the number of times when the counter electrodes of the rotating disc fall to the grounding potential . regarding the counter electrodes of the fixed disc , those of the outer circumference and the inner circumference are disposed in a little displacement with respect to the circumferential direction , so that the electrodes which earlier fall to the grounding potential according to the direction of rotation are different between those of the outer circumference and those of the inner circumference . such being the case , rotation direction may be detected according to which electrodes fall earlier to the grounding potential . therefore , by detecting by means of the detection circuit 10 the number of times when the counter electrodes fall to the grounding potential and which electrodes of the outer or inner circumference fall earlier to the grounding potential , a control means described later may know the rotation direction and the rotation angle of the disc member 9 , thereby capable of performing the required control . as shown in fig5 - 7 , the body case 2 is formed with a front case 2 f and a rear case 2 r . in the rear case 2 r is formed a placement unit 17 of the jog dial 9 . the placement unit 17 is formed long recessed in the lateral direction , and a notch 17 a is opened at the side surface in the left side . at the side walls 17 b and 17 c facing each other at the top and the bottom of the placement unit 17 , are provided pivoting fulcrums 18 . the pivoting fulcrum 18 is composed of two supporting pieces 19 , 19 ′, each facing spaced in the longitudinal direction , namely , to arrows b and c directions in fig1 and position control pieces 20 , 20 ′, each located at the left and right sides of the two supporting pieces 19 , 19 ′. the surfaces of the supporting pieces 19 , 19 ′ facing with each other are formed to shape protruded curve surfaces 19 a , 19 a ′ viewing in the vertical direction , namely , viewing in arrows d and e directions in fig1 . the space of the most narrow portion between the two protruded curve surfaces 19 a and 19 a ′ is made to be the same as or a slightly larger than a thickness f of the supported piece 14 a of the base member 14 of the jog dial 9 . the space between the two position control pieces 20 and 20 ′ is made to be a little larger than a width g of the supported piece 14 a . the supported piece 14 a of the base member 14 is respectively inserted between the supporting pieces 19 and 19 ′ of the respective pivoting fulcrum 18 , and sandwiched by the respective protruded curve surfaces of 19 a , 19 a ′, and a portion of the disc member 9 is made to protrude outside the body case 2 through the notch 17 a . movement thereof in the lateral direction is controlled by the position control pieces 20 , 20 ′. within the rear case 2 r , at the opposite surface to the surface of the base member 14 which supports the disc member 9 , namely , at the position facing the rear surface 14 b is disposed the second switch 12 . at the position facing the disc member 9 of the front case 2 f is disposed the third switch 13 . accordingly , by rubbing with a finger pad or the like the portion of the disc member 9 protruding outside the body case 2 to move upward , namely , to an arrow d direction in fig1 or to the rear side direction , namely , to an arrow e direction in fig1 the disc member 9 is rotated to be able to output a signal in accordance with its rotating direction and rotating angle , and by pushing to an arrow a direction , the first switch 11 is pushed down to be able to output the adapted signal . by pushing to the rear side direction with the finger pad or the like the portion of the disc member 9 protruding outside the body case 2 , namely , by pushing to an arrow c direction , the disc member 9 and the base member 14 supporting thereof are made to pivot to the rear side direction about the supported pieces 14 a serving as pivoting fulcrums supported by the supporting pieces 19 , 19 ′, whereby the second switch 12 is pushed down with the rear surface 14 b of the base member 14 to output the adapted signal . furthermore , by pushing to the front side direction with the finger pad or the like the portion of the disc member 9 protruding outside the body case 2 , namely , by pushing to an arrow b direction , the disc member 9 and the base member 14 supporting thereof are made to pivot to the front side direction about the supported pieces 14 a serving as pivoting fulcrums supported by the supporting pieces 19 , 19 ′, whereby the third switch 13 is pushed down with the front surface of the disc member 9 to be able to output the adapted signal . moreover , the space between the control pieces 20 and 20 ′ is made a little larger than the width g of the supported piece 14 a of the base member 14 , so that the supported piece 14 a may move freely within the space surrounded by these control pieces 20 , 20 ′ and the supporting pieces 19 , 19 ′ without being provided with stress , whereby occurrence of plastic deformation on the supported piece 14 a and the other parts of the base member 14 may be prevented . next , referring to fig2 there is described an outline of the circuit configuration of the portable phone 1 according to the present invention . firstly , command information inputted from the above - described various means such as operation keys 7 or the jog dial 8 is inputted to a cpu ( central processing unit ) 21 . the cpu 21 , based on the inputted command information , controls an lcd driver circuit 22 and displays on the liquid crystal display 6 various information according to the command information ( for example , telephone number being inputted , menu items , or outgoing history , telephone directory information or the like ). the cpu 21 , based on command information being inputted , controls a transmission - reception circuit unit 23 to execute various processing according to the command information such as call processing , call closing processing or the like . furthermore , the cpu 21 accesses a ram ( random access memory ) 24 which is a first storage means and makes it store designated information , or accesses an eeprom ( electrically erasable and programmable read only memory ) 25 which is a second storage means to make it store various information such as outgoing history or telephone directory list which do not want to be erased when power is tuned off . the cpu 21 is made to execute each control described above based on program code stored in a rom ( read only memory ) 26 . under control of the cpu 21 , the transmission reception circuit unit 23 is made to transmit control signal via the antenna 3 to conduct the call processing , and to receive incoming call signal from the base station via the antenna 3 to notify the cpu 21 about the incoming call . when calling , the transmission - reception circuit unit 23 also transmits a voice signal inputted from the microphone 5 after performing designated signal processing , or demodulates the voice signal after performing designated signal processing for a reception signal to output to the speaker 4 . the jog dial 8 of the portable phone 1 may provide respective command information according to the rotating operations of the disc member 9 , the pushing - in operation of the disc member 9 , the pivoting operation in the push - down direction of the disc member 9 and the pivoting operation in the push - up direction of the disc member 9 . accordingly , various instruction operation may be performed with the jog dial 8 by operating the disc member 9 into the five directions . functions conventionally allocated to the other operation keys , for example , clear of the decided item , shift - up of a menu hierarchy by one level , display of the catch menu during calling , etc ., may be performed by operating only the jog dial 8 and not using the other operation keys 7 . accordingly , it is possible to perform instruction operations with a finger of the thumb or the forefinger while holding the phone in a hand , thereby extremely increasing convenience of handling . fig8 shows another example of a jog dial 8 a . in the embodiment described above , the second and the third switches 12 , 13 are disposed in positions to sandwich the disc member 9 , and there is an advantage that the space produced by disposition of the three switches may be made compact . in the present invention , the second and the third switches 12 , 13 are not necessarily disposed in the positions to sandwich the disc member 9 . in the jog dial 8 a of fig8 the disc member 9 is supported on the base member 27 capable of rotating and moving to the pushing - in direction , namely , to an arrow a direction in the drawing , which is the same as the jog dial 8 of the embodiments described above . on the base member 27 is supported a first switch ( not shown ) which is operated by pushing the disc member 9 to an arrow a direction . the base member 27 is made longer in the pushing - in direction . at about the midpoint thereof , protruding supported pins 28 ( one of them is shown ) are provided . in the housing member , protruding supporting pieces 29 , 29 ′ are provided . in supporting holes 29 a , 29 a ′ of the protruding supporting pieces 29 , 29 ′, the supported pins 28 , 28 ′ of the base member 27 are supported allowing free pivoting movement . sandwiched between the front side direction edge of the base member 27 , namely , a position corresponding to the edge of the side where the disc member 9 is supported , and the backward edge ( the other side of the front side edge ) of the base member 27 , switches 30 , 31 are disposed at the positions respectively corresponding to the edge of the side where the disc member is supported and to the edge of the opposite side , sandwiching the supported pins 28 . the switches 30 , 31 are further supported by a flexible printed board 32 , and the switch 30 serves as the second switch and the switch 31 serves as the third switch . in the jog dial 8 a , in addition to the rotating operation of the disc member 9 to two directions and the pushing - in operation of the disc member 9 , the push - down operation of the disc member 9 , namely , the operation to ove the disc member 9 to the arrow c direction in the drawing is made to pivot the base member 27 to push the second switch with the front side edge of the base member 27 . also , the push - up operation of the disc member 9 , namely , the operation to move the disc member 9 to the arrow b direction in the drawing is made to pivot the base member 27 to push the third switch 31 with the backward edge of the base member 27 . accordingly , also with the switch apparatus of this example , a variety of instruction operations may be performed by operating only the disc member 9 . any of the shapes and the configurations of each part illustrated in the described embodiments and the examples thereto shows only an embodying example in carrying out the present invention , and it is to be understood that the technical scope of the present invention shall not be interpreted in a limited sense by these examples . | 7 |
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