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CROSS REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Patent Application Serial No. 60/223,945 of Philip Martens filed Aug 9, 2000.
BACKGROUND OF THE INVENTION
The benefits of weight lifting exercises in terms of building and maintaining strength, body toning, and general health and endurance, are well known. Free weights are frequently used. Free weights include barbells and hand weights known as dumbbells. The classic dumbbell is a weight exercise device with a short hand grip or bar connected to weights at either end. The dumbbell is meant for use with a single hand. The weight is usually fixed but is sometimes adjustable through addition or subtraction of increments of weight. A dumbbell inventory typically includes pairs of dumbbells of various weights ranging from one to twenty pounds or more. Another type of dumbbell is the block style dumbbell of the type sold under the trademark Powerblock®.
Weight training machines are frequently used in addition to, or instead of, free weights. The weight training machine safely mimics, to some extent, barbell-type weight lifting. It also permits the user to engage in types of weight resistance exercises not available through the use of free weights alone. The “weight” resistance of the machine is provided by means of a stack of weights, springs, elastic bands, shock absorbers, or even the user's own body weight.
The preferred resistance structure for such machines is weights. These take the form of several hundred pounds of stacked weights that are dedicated to the singular purpose of providing resistance for the weight training machine. The weights are permanently or semi-permanently attached to the remainder of the machine. This makes the machine heavy and hard to move. The weight increments are relatively large, whereby a user may tend to overload, which can lead to injury. The weights add to the expense of the machine, even while an inventory of dumbbell weights may be available. The machine weights can contribute to stress on the floor or other supporting surface.
The other resistance means indicated are generally less desirable than weights but are preferred where either cost and/or weight are factors. For example, in home units, cost is generally considered a factor to the purchaser, and weight becomes a factor in shipping the unit and in subsequent storage by the user. Elastic bands wear out. Springs will fatigue. As is the case with a spring, the resistance offered by an elastic band is not constant but varies proportionate to the amount of deflection. Adjustment ability is limited.
SUMMARY OF THE INVENTION
The invention pertains to a weight lifting exercise machine that employs dumbbells for the weight resistance and for incremental weight adjustment. Dumbbells are particularly suitable. They are often available at the exercise location for free weight exercise use, typically in equal weight pairs. Typically the weight range of dumbbells is three pounds to one hundred pounds, although it can be more. The use of dumbbells or other hand weights on the weight lifting machine of the invention eliminates the need for a separate stock of dedicated machine weights.
The weight lifting machine includes an overall frame that stands on the floor, and at least one upright support post or guide rail. A dumbbell weight carrier is assembled to the guide rail for up and down movement. The carrier includes one or more receptacles to engage the dumbbells, and a carriage connected to the receptacles for movement on the guide rail. Dumbbells can be loaded and unloaded on the dumbbell carrier. The carrier can be connected to a cable, such as a wire rope, a chain or combination thereof. The other end of the cable is connected to a weight handle to be engaged by the exercising person in lifting or lowering the carrier against gravity. Depending on the configuration of the machine, the weight handle is engaged by the hands, feet, legs or the like, to accomplish an exercise routine. In doing so, the weight carrier is lifted and lowered along the guide rail.
In one form of the invention, the weight handle is connected to the carrier through a pulley system of one or more pulleys that conveniently position the weight handle relative to the user, for example, proximate a bench. The carrier will typically be adapted to carry dumbbells and have a bracket to receive and hold a plurality of dumbbells. There may be one or more dumbbell carriers that move on one or more guide rails. A second weight handle may be connected to the carrier for versatility of the machine.
The weight lifting machine can include a bench to support the user, lying or sitting, while engaging the weight handle in a pulling action against the weight resistance. The bench can optionally be pivotally connected to the machine frame so as to be folded into the overall frame of the machine during non-use to save room. In another form of the invention, the user engaging the weight handle lifts against the weight resistance, as when doing squats or military presses.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front perspective view of one form of a weight lifting exercise machine according to the invention;
FIG. 2 is a side plan view of the weight lifting exercise machine of FIG. 1;
FIG. 3 is a rear perspective view of the weight lifting exercise machine of FIG. 1;
FIG. 3A is a view of the exercise machine of FIGS. 1 through 3 showing the seat support beam pivoted up and out of the way;
FIG. 4 is a perspective view of the dumbbell carrier of the weight lifting exercise machine of FIG. 1 with a portion broken away for purposes of illustration;
FIG. 4A is a perspective view like that of FIG. 4 showing an alternative dumbbell carrier configuration having two vertical guide rails;
FIG. 5 is a top view of the dumbbell carrier of FIG. 4;
FIG. 6 is an enlarged sectional view of a portion of the dumbbell carrier of FIG. 5 taken along the line 6 — 6 thereof;
FIG. 7 is a rear perspective view of a weight lifting exercise machine according to another form of the invention;
FIG. 8 is a perspective view of a weight lifting exercise machine according to a yet further form of the invention;
FIG. 8A is a modification of the form of the invention shown in FIG. 8;
FIG. 9 is a perspective view of the dumbbell carrier of the weight lifting exercise machine of FIG. 7; and
FIG. 10 is a front perspective view of a weight lifting exercise machine according to a still further form of the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to the drawings, there is shown in FIGS. 1 through 3 a weight lifting exercise machine according to one form of the invention, indicated generally at 10 . Machine 10 has an overall frame 11 with a first upright member comprised as a support and guide rail 12 ; and a second upright front support member 14 . An overhead beam 15 connects the upper ends of the support members 12 , 14 and overhangs the front support member 14 . A frame stand includes a horizontal lateral leg 16 connected to a longitudinal horizontal leg 18 in a “T” shape. The lower ends of the support members 12 , 14 are connected to the longitudinal leg 18 . A foot brace 25 is assembled to the end of the leg 18 opposite its connection to the lateral leg 16 .
An exercise station includes an horizontal bench support beam 20 pivotally connected to and extending forward from the lower portion of the second upright structural member 14 . The outer end of the support beam 20 is connected to a vertical leg 21 attached to a horizontal leg 29 . A weight bench includes a seat 22 attached to the support beam 20 , and a backrest 23 . Backrest 23 is positioned adjacent to seat 22 and is connected at one end to a hinge structure 24 so that it can be pivoted up and down, or from the upright position shown in FIGS. 1 through 3, to a flat horizontal position. The back rest 23 is held upright by a U-shaped rod 26 that interconnects with notches in a positioning bracket 27 .
A dumbbell carrier is assembled to the guide rail 12 for up and down sliding movement on the guide rail. As shown in FIGS. 1 through 3, carrier 30 carries a dumbbell weight 31 . The structure of carrier 30 is more particularly shown in FIGS. 4 and 5. The carrier 30 has dumbbell racks or receptacles comprised as a pair of brackets 33 , 34 positioned in back to back relationship and separated by a carriage structure. Each bracket has a plurality of openings for receipt of the bar of a dumbbell. First bracket 33 has side plates 35 , 36 connected by a back plate 38 . A first side plate 35 has a series of vertically spaced, hook-shaped edge openings 39 A, 40 A, 42 A. Second side plate 36 has a corresponding plurality of edge openings 39 B, 40 B, 42 B. Each of the edge openings defines a pocket for receipt of a section of a dumbbell bar. The bar of the dumbbell is engageable in a pair of corresponding openings. A plurality of such bars can be accommodated by each bracket. The openings are upwardly open and hook-shaped to inhibit unintended disengagement of the bar from the bracket. The second bracket 34 similarly has side plates 43 , 44 and a back plate 46 . The second bracket 34 also has a plurality of hook-shaped edge openings arranged in corresponding pairs.
The first and second carrier brackets 33 , 34 are connected to a carriage structure for movement up and down the guide rail 12 . This carriage structure includes the backplates 38 , 46 of the brackets 33 , 34 , and sidewall structures 47 , 48 . Each of the sidewall structures 47 , 48 includes a channel shaped member connected to the backplates 38 , 46 of brackets 33 , 34 by nut and bolt assemblies 50 . The backplates and sidewall structures form a guide opening 54 that is slightly oversized with respect to the cross-sectional dimensions of the guide rail 12 . This permits up and down sliding movement of the dumbbell carrier 30 on the guide rail 12 . Downward movement of the carrier 30 is stopped by stop members 57 .
Means can be provided, if necessary, to facilitate movement of the carrier 30 on guide rail 12 , such as rollers, grease, or the like. As shown, pads of low friction material are in place to facilitate movement of carrier 30 on rail 12 . Referring to FIG. 6, sidewall structure 48 has an end wall 49 and a short overlapping interior wall 51 . A slide pad 52 of Teflon® or similar low friction material is fastened to interior wall 51 in confronting relationship to rail 12 . In like fashion, slide pads 53 are fastened to the interior surfaces of the back plates 38 , 46 of brackets 33 , 34 .
As shown in FIG. 2, the standard dumbbell 31 has end weights 55 connected by a dumbbell bar 56 . The hook-shaped openings or pockets 39 , 40 , 42 are adapted to secure the dumbbell bar 56 in place. A number of dumbbells can be stacked in the bracket. As shown in FIG. 4, the carrier can accommodate six dumbbells, three in each bracket. More or less could be provided. Dumbbells of various weights can be loaded on to the carrier 30 according to the exercise prerogative of the user. For example, two forty-pound dumbbells can be loaded onto the carrier 30 , along with two ten-pound dumbbells and one five-pound dumbbell for a total loaded weight of 105 pounds plus the weight of the carrier 30 . Weight increments can be added and subtracted according to the weights of the various dumbbells available.
Referring again to FIGS. 1 through 3, a main weight handle 58 is connected to the carrier 30 so that movement of the weight handle 58 moves the carrier 30 against the influence of gravity. The connection between the weight handle and the carrier can be a system of levers, linkages, cables, belts, a combination thereof, or other such connecting means capable of transmitting a tension force. In the embodiment shown in FIGS. 1 through 3, the weight handle is connected to the carrier 30 through a cable and pulley system. The cable can be wire, rope, chain, or the like or any combination thereof, capable of transmitting a tension force.
The weight handle is readily detachable and interchangeable with other weight handles. For example, another weight handle can be shorter, or fashioned of rope. A weight handle could be fashioned as a head harness for neck exercise, or as a harness to fit other body parts according to the specialized exercise routine.
A main cable 59 is fastened at one end to an eye clip 60 that is attached to the carrier 30 (FIG. 4 ). The other end of main cable 59 is fastened to another eye clip 62 that is centrally attached to the weight handle 58 . The intermediate segment of main cable 59 is trained over a pulley system which includes first, second and third pulleys, 63 , 64 and 65 , that are mounted in the overhead beam 15 . The overhead beam 15 can be a box beam with downwardly open slots so that pulley axles can be mounted between the sidewalls and carry pulleys as shown. The beam 15 extends forward from the front support member 14 . The weight handle 58 is positioned off of the forward tip of overhead beam 15 where it can be pulled away from overhead beam 15 in an action that lifts the carrier 30 along the guide rail 12 . Return movement of the weight handle 58 is stopped by the overhead beam 15 .
Bench support beam 20 is removable from the overall frame 11 when not in use in order to provide clearance for the exercising person so approach the weight handle 58 standing. The inside end of beam 20 has a bracket 67 that engages a segment of the second support member 14 of frame 11 . A pin 68 passes through aligned holes in the bracket 67 and support member 14 to secure the beam in place. The support beam is removable simply by removal of the pin 68 and moving the beam 20 away from the frame. Additionally, bench support beam can be pivoted upwardly about pin 68 as shown and described with respect to FIG. 3 A.
A secondary weight handle system lends versatility to the machine 10 . A secondary cable 71 is connected at a fixed end to frame 11 as at leg 18 of the frame stand. The opposite end of secondary cable 71 is connected to a second weight handle 72 . A pulley block 74 carries an upper pulley 75 and a lower pulley 76 . A segment 59 A of the main cable 59 is trained over upper pulley 75 . The segment 59 A is located between the first and second pulleys 63 , 64 of the pulley system of the first weight handle 58 . The secondary cable 71 is trained over the lower pulley 76 of pulley block 74 . A sixth pulley 78 is mounted at the lower end of the second support post 14 of frame 11 . A seventh pulley 79 is mounted in the vertical leg 21 that is attached to the support beam 20 . The secondary cable 71 extends from the lower pulley 76 to the sixth pulley 78 and then over the seventh pulley 79 to the connection at the second weight handle 72 .
The second weight handle 72 shown in the configuration of FIGS. 1 through 3 is adapted for engagement by the ankles and lower legs of the exercising person. Leg pads 81 , 82 are fastened to the ends of the second weight handle 72 . The second weight handle 72 is connected to the lower end of a pivot arm 83 . Pivot arm 83 is pivotally connected to the upper end of a support member 85 . The lower end of support member 85 is fastened to the end of the horizontal support beam 20 . A padded support bar 86 is also connected to the support member 85 .
The second weight handle 72 is engagable by the legs and ankles of the exercising person. The exercising person can be sitting on the seat 22 facing the support member 85 . The ankles engage the pads 81 , 82 on the second weight handle 72 in a lifting motion. This lifts the carrier 30 through the secondary cable 71 . Alternatively, the exercising person can stand facing the machine and engage the back of the ankle on one of the pads 81 , 82 one leg at a time. From FIGS. 1 through 3, it may easily been seen that the second weight handle 72 could be configured to be manually grasped by the exercising person and lifted to mimic lifting a barbell. FIG. 3A shows an embodiment of the invention of the form shown in FIGS. 1 through 3 wherein the bench support beam 20 is pivoted about the pin 68 to a position up against the second support member 14 and out of the way. A strap 73 or other suitable holding structure secures the bench support in the stored position. A secondary weight handle 72 A is available at the lower end of the second support member 14 . A foot brace 25 is assembled to the end of the leg 18 for use by a sitting exercising person.
Another form of the invention is shown in FIG. 7 and indicated generally at 10 A. The machine 10 A is like the machine 10 shown in FIGS. 1 through 3 with the exception of a modified dumbbell carrier 30 A. The machine 10 A has a frame 11 including a first upright guide post and rail 12 , a second upright support member 14 , and an overhead horizontal beam 15 . Frame 11 is supported on a stand which includes horizontal legs 16 , 18 . A support beam 20 carries a seat 22 with a back rest 23 . A weight handle 58 is connected through a cable 59 to the carrier 30 A. A second weight handle 72 is connected by a secondary cable 71 to the weight carrier 30 A for manipulation as described above.
The carrier 30 A differs from the carrier 30 in that it only has a single receptacle bracket for engagement of dumbbells. The carrier 30 A has a bracket 88 with side plates 89 , 90 that have vertically spaced, hook-shaped edge openings arranged in pairs for receipt of dumbbell handles. The bracket 88 has a back plate 92 that together with sidewall structure 93 forms a carriage up and down movement on the guide rail 12 . Dumbbells like the dumbbell 94 can be loaded on the carrier 88 according to the weight preference of the exercising person.
FIG. 4A shows another weight carrier-guide rail configuration wherein two guide rails are provided. Many existing weight machines currently employ a weight system using a pair of parallel guide rails, whereby the present invention can be retrofitted to such machines. The weight carrier is shown generally at 30 B and a pair of vertical guide rails are shown in phantom at 12 B and 12 C. The weight carrier 30 B has a top plate 37 fastened between the side walls 46 A, 47 A. Top plate 37 has a pair of guide rail mounting openings 41 A, 41 B. The guide rails 12 B, 12 C are engaged in the openings 41 A, 41 B for up and down movement of the carrier on the guide rails.
FIG. 8 shows a yet further form of the invention indicated generally at 10 B. The form of the invention at 10 B differs from the earlier form of the invention indicated generally at 10 in FIGS. 1 through 3 in the structure of the dumbbell carrier and in the configuration of the exercise station. Otherwise the machines are the same. Machine 10 B has a frame 11 that includes a first support member or guide rail 12 and a second upright support member 14 connected by an overhead beam 15 . Legs 16 and 18 stabilize the frame. A dumbbell carrier 30 B is connected to the main cable 59 that is trained over pulleys attached to the overhead beam 15 and then to the main weight handle 58 .
The dumbbell carrier 30 B is adapted to carry hand weights or dumbbells having a box-like configuration, of the type sold under the trademark Powerblock®. The dumbbell carrier 30 B is more particularly shown in FIG. 9 . The dumbbell carrier 30 B includes a carriage structure to straddle and ride along the guide rail 12 . The carriage structure includes lateral side wall structures 96 , 97 connected to back plates 98 , 99 by bolts 116 . A pair of receptacle baskets 101 , 102 are connected respectively to the back plates 98 , 99 . Each basket 101 , 102 is adapted to carry one or more of the block style dumbbells 100 . For example, the basket 101 has a flat base or tray 104 connected to a back wall 103 which is in turn connected to a back plate 98 by bolts 108 . Basket 101 has inclined side walls 105 , 106 and a front lip 107 for confining weights placed on the tray 104 of the basket 101 . An eye clip 110 is connected to the dumbbell carrier 30 B for connection to the main cable 59 of machine 10 B.
Referring back to FIG. 8, the exercise station 112 includes a pair of horizontal, parallel tracks 113 , 114 and a seat assembly 115 mounted for sliding of movement on the tracks. Seat assembly 115 faces frame 11 and is adapted to travel back and forth on the tracks relative to the frame. Foot supports 117 , 118 are mounted at the inward ends of the tracks 113 , 114 . Suitable connecting structure 119 releasably connects the tracks 113 , 114 and the foot supports to the frame 11 .
A secondary weight handle 121 is connected to the free end of the secondary cable 71 where it is trained over the pulley 78 assembled in the second frame support member 14 . The inward limit of travel of the secondary weight handle 121 is the second support member 14 . Pulling on the secondary weight handle 121 away from the frame 11 raises the weight carrier 30 B and any weights carried thereon through the secondary cable 71 trained over the pulley block assembly 74 .
In use of the machine 10 B, the exercising person optionally engages either the main weight handle 58 or the secondary weight handle 121 . When engaging secondary weight handle 121 , the exercising person is seated on the seat assembly 15 with feet engaging the foot supports 117 , 118 . The exercising person engages the secondary weight handle 121 and pulls it away from the frame 11 , continuing the exercise routine by moving the secondary weight handle 121 away from and toward the frame 11 against the weight offered by the dumbbell carrier 30 B. A collection of one or more dumbbells is assembled on the trays of the baskets 101 , 102 .
FIG. 8A shows a modification of the exercising machine of FIG. 8 . The sliding seat assembly has been removed and a short seat assembly 109 has been installed. Short seat assembly is assembled to the second support member 14 beneath the main weight bar 58 . Hold down pads 111 are also assembled to the second support member 14 positioned for engagement by the thighs of the exercising person seated on short seat assembly 109 and pulling on weight handle 58 .
A still further form of a weight lifting exercise machine according to the invention is shown in FIG. 10 and indicated generally at 124 . The machine 124 includes an overall frame 125 that is relatively tall and open at the front. A stand for frame 125 includes front legs 126 , 127 and back legs 133 , 136 . Each of the front legs 126 , 127 has a front foot 129 , 130 engaging the supporting surface, and a horizontal section 131 , 132 extending rearward from the foot. Back legs 136 , 133 connect respectively at the base of each to the horizontal sections 131 , 132 of the front legs 129 , 130 . Back legs 136 , 133 are connected brace 138 . Each back leg 136 , 133 extends upwardly and is inclined forwardly, terminating in an upper horizontal section 134 , 135 . The ends of the upper sections 134 , 135 are connected by an overhead beam 137 .
First and second generally vertical guide rails 141 , 143 carry first and second weight carriers 149 , 150 . Weight carriers 149 , 150 ride up and down on the guide rails 141 , 143 . A weight handle 145 is connected at first and second ends respectively to the first and second carriers. The weight carriers can be loaded with dumbbells as the dumbbell 153 . The weight handle 153 is lifted against the weight resistance of the carriers and any weights carried by the carriers.
A first vertical track member 139 is parallel to and spaced from the first guide rail 141 . A second such track member 142 is disposed in similar fashion to the second guide rail 143 . The guide rails and track members are connected to the horizontal leg sections 134 , 135 of the back legs, at their upper ends. The lower ends are connected to the horizontal sections 131 , 132 of the front legs. Each of the track members has a vertical slot facing the corresponding guide rail. Ends of the weight handle 145 have first and second guide members 146 , 147 , that have pegs or fingers 148 , 152 that ride in the slots of the track members for safety and stability when lifting and lowering the weight handle 145 .
In use of the embodiment of the invention shown in FIG. 10, a plurality of dumbbells are loaded onto the weight carriers 149 , 150 to achieve a desired total weight. The exercising person stands in front of the frame 125 and grasps the weight handle 145 . Frame 125 is relatively tall so as to permit the exercising person to stand under the overhead beam 137 . The exercising person lifts the weight handle 145 against the weight afforded by the dumbbells located on the weight carriers. The exercising person can engage in weight lifting exercises of the type normally accomplished with a barbell. The path of the weight handle is confined to up and down movement, a safety consideration. | A weight lifting exercise machine that uses dumbbell weights for the weight resistance and for incremental weight adjustment. Dumbbells are particularly suitable since they are usable both as free weights and as incremental weights for the exercise machine. The machine includes an overall frame that stands on the floor, and at least one vertical guide rail attached to the frame. A dumbbell weight carrier is a assembled to the guide rail. The dumbbell weight carrier has a carriage that engages the guide rail. A dumbbell receptacle is attached to the carriage. The dumbbell receptacle can hold a plurality of dumbbell weights selected according to the overall weight desired by the exercising person. A weight handle is connected to the dumbbell weight carrier. The exercising person engages the weight handle and moves it against the weight resistance of the weight carrier and dumbbell weights loaded thereon. | 0 |
BACKGROUND OF THE INVENTION
The present invention relates to a hand-propelled lawn mower that is also a physical exercise appliance which is constructed so as to indicate exercise data, including exercise period of time, speed, calories burned, load pushed, pulse rate, and the like of the user during the mowing of a lawn with the mower.
Hand propelled lawn mowers of various types have been well known for many years. Stationary exercise apparatus on which an exercise computer and display is mounted that measures time, distance, calories burned, pulse rate, and the like are also well known. Additionally, various non-stationary exercise apparatus are known, most often bicycles, have had such computers mounted thereon to measure similar functions are known.
SUMMARY OF THE INVENTION
This invention relates to hand propelled lawn mowers in general and to exercise equipment in general and the use of such hand-propelled lawn mower as a apparatus for exercise that yields quantifiable results of exercise engaged in by a user. A standard, reel-type, hand-propelled lawn mower is preferably used of which the present design modifies or adds to the handle to provide a load sensor that senses the load placed by the user on the mower handle as the lawn mower is propelled across a lawn. Additionally, a speed sensor is used that determines the speed of the lawn mower as it crosses a lawn. The output from the load sensor and speed sensor are input into an exercise computer that tracks time spent and calculates, for example, calories burned and has a read-out that includes, for example, load, calories burned, speed, distance travelled, time of exercise, and the like.
It is therefore an object of the present invention to provide a lawn mower combined with an exercise calculating apparatus.
It is a further object of the present invention to provide a lawn mower combined with an exercise computer and display apparatus that includes sensors including means to determine load placed on the lawn mower by a user.
It is a further object of the present invention to provide a lawn mower combined with an exercise computer and display apparatus that includes sensors including means to determine load placed on the lawn mower by a user that is displayed on the display apparatus.
It is a further object of the present invention to provide a lawn mower combined with an exercise computer and display apparatus that includes sensors including means to determine velocity of the lawn mower.
It is a still further object of the present invention to provide a lawn mower combined with an exercise computer and display apparatus where the exercise computer and display indicates velocity of the lawn mower.
It is a further object of the present invention to provide a lawn mower combined with an exercise computer and display apparatus where the exercise computer and display calculates estimated calories burned by the user based on the load placed on the handles of the lawn mower and the distance travelled.
It is a still further object of the present invention to provide a lawn mower combined with an exercise computer and display apparatus where the exercise computer and display indicates estimated calories burned by the operator of the lawn mower.
It is a still further object of the present invention to provide a lawn mower combined with an exercise computer and display apparatus where the exercise computer and display displays time spent exercising.
It is a still further object of the present invention to provide a lawn mower combined with an exercise computer and display apparatus where the exercise computer and display displays distance travelled while pushing the lawn mower.
Other objects and advantages of the present invention will become apparent from the following description taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front view of a lawn mower with exercise computer and display in accordance with one embodiment of the present invention.
FIG. 2 is a side view of the lawn mower with exercise computer and display of FIG. 1.
FIG. 3 is a top view of a strain gauge for use with a means to determine load on the handle of the lawn mower of FIG. 1.
FIG. 4 is a top view of an exercise computer and display as used in the lawn mower of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now in detail to the drawings, wherein like reference numerals indicate like elements throughout the several views, there is shown in FIGS. 1 and 2 a lawn mower with exercise computer and display 10 in accordance with one preferred embodiment of the present invention. The lawn mower with exercise computer and display 10 comprises a hand-propelled lawn mower 20, a means to determine the velocity 30 of the lawn mower 20, a means to determine load 40 placed on the handle 22 of the lawn mower 20 and an exercise computer and display apparatus 50.
The hand propelled lawn mower 20 can be of a manual type, for example a standard reel-type manual lawn mower as depicted in FIGS. 1 and 2, or possibly a power-type lawn mower with a gas or electric engine (not shown). For the sake of obtaining maximum exercise, the manual reel-type lawn mower is more desirable than a power mower in that lawn mowers of this type generally require more effort to propel across a lawn, thus providing for more exercise.
The means to determine velocity 30 of the lawn mower 20 across a lawn may preferably be of a type typically known for electronic bicycle speedometers. Here, the lawn mower would include a pair of velocity determining means 30A, 30B which cooperate with one another for producing electrical revolution signals in the form of electrical pulses. One of the velocity determining means would be a passive element 30A carried by one of the lawn mower wheels 25, 26, for example the right wheel 26 in FIG. 1. This could be magnet as depicted in FIG. 1 mounted to a side edge of the wheel 26. The other of the pair of velocity determining means could be pick-up means 30B mounted on a stationary point on the frame 24 of the lawn mower 20, adjacent (at one point every time the wheel rotates) the passive means 30A on the wheel which responds to turning of the passive means 30A when it passes the pick-up means 30B and thereby produces an electrical signal.
The pick-up 30B means can take the form of an electrical switch capable of responding to movement of the passive means 30A each time it crosses the pickup means 30B to produce an electrical pulse for each revolution of the wheel 26. It would also be possible for the pickup means 30B to be an induction coil.
The pulsing signal is then electronically transported to the exercise computer and display apparatus 50 described below by wire 32. The signal then enters into the computer and display apparatus 50 which calculates the speed of the lawn mower 20 based on a known circumference or diameter of the wheel 26. The computer and display apparatus 50 has capacity to calculate forward or reverse speed of the lawn mower 20 and calculate total distance traveled. The computer and display apparatus 50 can also take this information and, using the additional factor of time which is determined by the computer, determine average speed, top speed, and the like.
The means to determine velocity 30 of the lawn mower can be any other type known in the art, for example, that shown and described in U.S. Pat. No. 4,071,892, the complete reference of which is incorporated by reference into the present specification, and is not limited to the embodiment described above.
The means to determine load 40 again can be any such means known in the art that can provide an electrical signal through wire 44 that is proportional to the load placed on the handle 22 of the lawn mower 20. Preferably, the means to determine load is one or more simple strain gauge load cells 42 (see FIG. 3) that determine load based on a minute deflection of the handle 20 of the lawn mower. The geometry and location of such a strain gauge load cell can easily be determined by one skilled in the art. Such a strain gauge cell eliminates pivot maintenance and moving parts of a more complicated spring-type means to determine load and provides an electrical output which can be used for direct input into the exercise computer and display apparatus 50. Such a load cell signal output can also easily be calibrated for different handles 22 and work by a user can also be easily calculated.
The load signal enters the computer where it can be displayed and/or enters a calculation for calories burned, and the like.
Alternatively, any means to determine load as is known in the art may be used, such as a spring type mechanical linkage means. However, this type would typically be less desirable due to the increased number of moving parts, particularly in the dirty environment in which a lawn mower operates. Additionally, here, added means to provide an electrical signal must also be provided.
The exercise computer and display apparatus 50 has input means to take the output of the means to determine velocity and the means to determine load, as described above, and enter them into the exercise computer and display apparatus to determine and display various exercise parameters useful to an operator of the lawn mower. The exercise computer and display apparatus has a built-in clock that is used for display and to determine the value of some of the parameters. These parameters may include, but are not be limited to, distance traveled estimated work expended (for example, estimated calories) speed, load on the handles, time spent exercising.
Finally, the present apparatus can be made an after-market add-on in which just the computer, means to determine velocity and means to determine load are sold for installation by a user on any hand-propelled lawn mower. In this case calibration of the means to determine load and the means to determine speed would have to be accomplished by the user.
It will be recognized by those skilled in the art that changes may be made in the above described embodiments of the invention without departing from the broad inventive concepts thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but is intended to cover all modifications which are within the scope and spirit of the invention as defined by the appended claims. | A physical exercise apparatus including a hand-propelled lawn mower having an exercise computer for selectively displaying exercise data including speed and the like thereon obtained while mowing a lawn. | 8 |
FIELD OF THE INVENTION
The present invention concerns streptavidin muteins, a process for the production of such proteins by means of recombinant DNA technology as well as the use of these streptavidin muteins for the isolation, purification and determination of biological substances, in particular of other recombinant proteins.
BACKGROUND AND PRIOR ART
Nowadays the biotin/streptavidin system is a generally known binding system in molecular biology the importance of which has increased considerably in recent years and which is used in various fields of application. In doing so one utilizes the specific affinity between biotin and streptavidin which, together with an affinity constant of the order of 1013, is one of the most stable known non-covalent interactions.
Important conventional applications are for diverse separation and detection methods usually using biotinylated enzymes or/and antibodies in various variations. Examples are for example ELISA, Western blot etc. A prerequisite for such methods is that the reagent or enzyme used in a biotinylated form in the method must firstly be obtainable in a pure form in order to be able to carry out the biotinylation which takes place in a chemical reaction.
However, for certain applications a biotinylation is not possible or at least not in a simple manner such as for example when detecting and purifying recombinantly produced proteins which have previously not yet been isolated. Therefore in the past methods for modifying the biotin/streptavidin system have been sought in order to extend its range of application.
A successful approach has been to produce peptide ligands which also have a specific binding affinity for streptavidin. Suitable peptide ligands and corresponding fusion proteins are disclosed in DE-OS 42 37 113. The advantage of these peptide ligands compared to biotin is essentially that their coding sequence is linked at the DNA level with the gene of a desired protein and can subsequently be coexpressed together with that of the protein by which means a recombinant protein labelled with the peptide ligand, i.e. fused thereto, is formed. Due to the small size of the peptide ligands and the fact that they can be attached to the N- or C-terminus of the desired protein, i.e. in areas which often are not of major importance for the structure and biochemical function of the protein, it is generally also not necessary to again cleave off the peptide ligand after its isolation and before using the protein for other purposes so that this also results in a more economical process. Indeed no case is yet known in which a cleavage would have been necessary. If nevertheless cleavage should be necessary, this can be accomplished by inserting a protease cleavage site between the binding peptide and protein sequence.
Such peptide ligands which are suitable are described in detail for example in Schmidt and Skerra, Protein Eng. 6 (1993), 109-122 and J. Chromatogr. A 676 (1994), 337-345 as well as in Schmidt et al., J. Mol. Biol. 255 (1996), 753-766.
Advantages of the streptavidin peptide ligand system are that the purification of recombinant proteins becomes possible at all and that this purification can be achieved for example by affinity chromatography under very mild elution conditions since the bound peptide ligand as part of the recombinant protein is displaced competitively by biotin or derivatives thereof. In addition the peptide ligand enables the recombinant protein to be for example detected by Western blot, ELISA or by immune microscopy using suitable streptavidin conjugates.
A disadvantage of this system has previously been its relatively low affinity. An affinity constant of 2.7×10 4 M -1 has been determined by means of isothermal titration calorimetry for the complex between streptavidin and the peptide ligand referred to as strep-tag (Ala Trp Arg His Pro Gln Phe Gly Gly (SEQ ID NO: 1)). Although there were indications that the binding could be somewhat stronger for a fusion protein containing the peptide ligand, it is desirable to have a system with a fundamentally improved affinity.
Hence the object of the invention was to optimize the streptavidin/peptide ligand system with regard to binding strength.
After initial experiments had been carried out to further optimize the sequence of the peptide ligand, it had to be assumed that the peptide ligand according to DE-OS-4237113 already apparently represented an optimum and thus this approach was less promising.
Once the crystal structure of the streptavidin/peptide ligand complex was available in high resolution, a better understanding was gained of the molecular interactions and the structural characteristics (Schmidt et al. (1996), supra) but no clear information could be obtained from these structural data on whether and in which manner a modification of the peptide sequence or of streptavidin could be carried out in a rational manner to improve the affinity and hence to achieve the initial objective.
In an evolutionary research approach it has now been surprisingly found that the binding affinity for the streptavidin/peptide ligand system can be improved by mutation in the region of the amino acid positions 44 to 53 of streptavidin.
SUMMARY OF THE INVENTION
Thus a subject matter of the present invention is a polypeptide selected from muteins of streptavidin which is characterized in that it (a) contains at least one mutation in particular an amino acid substitution in the region of the amino acid positions 44 to 53 with reference to the amino acid sequence of wild type-(wt)-streptavidin (nomenclature according to Argarana et al., Nucleic Acids Res. 14 (1986), 1871-1882) and (b) has a higher binding affinity than wt-streptavidin for peptide ligands comprising the amino acid sequence Trp-Xaa-His-Pro-Gln-Phe-Xaa-Xaa (SEQ ID NO: 16) in which X represents an arbitrary amino acid and Y and Z either both denote Gly or Y denotes Glu and Z denotes Arg or Lys.
The streptavidin muteins of the present invention can correspond to the amino acid sequence of wt-streptavidin outside of the region of the amino acid positions 44 to 53. On the other hand the amino acid sequence of the muteins according to the invention can also be different to the wt-streptavidin sequence outside the region of the amino acids 44 to 53. Such variants of th e streptavidin sequence include naturally occurring as well as artificially produced variants and the modifications are understood as substitutions, insertions, deletions of amino acid residues as well as N- or/ and C-terminal additions.
The term "higher binding affinity" refers within the sense of the present application to a complex composed of a streptavidin mutein according to the invention and a peptide ligand according to DE-OS-4237113 and can be determined by standard methods such as ELISA, fluorescence titration or titration calorimetry. The binding affinity determined in this manner is specified by parameters such as affinity and dissociation constants or thermodynamic parameters. The increase of the binding affinity which is obtained with a streptavidin mutein modified according to the invention within the region of the amino acid positions 44 to 53 compared to the corresponding unmodified streptavidin is in general at least a factor of 5, preferably at least a factor of 10 and more preferably at least a factor of 20. Preferred streptavidin muteins according to the invention comprise at least one mutation in the region of the amino acid positions 44 to 47.
Preferred streptavidin muteins according to the invention are derived from streptavidin variants which are shortened at the N- or/and the C-terminus. The minimal streptavidins which are N- and C-terminally shortened known from the state of the art are particularly preferred. A preferred polypeptide according to the present invention comprises outside of the mutagenized region the amino acid sequence of a minimal streptavidin which begins N-terminally in the region of the amino acid positions 10 to 16 and terminates C-terminally in the region of the amino acid positions 133 to 142. The polypeptide particularly preferably corresponds to a minimal streptavidin outside of the mutation region which comprises an amino acid sequence from position Ala 13 to Ser 139 and optionally has an N-terminal methionine residue. In this application the numbering of amino acid positions refers throughout to the numbering of wt-streptavidin (Argarana et al., Nucleic Acids Res. 14 (1986), 1871-1882).
Streptavidin muteins according to the invention that are especially preferred are characterized in that at position 44 Glu is replaced by a hydrophobic aliphatic amino acid e.g. Val, Ala, Ile or Leu, at position 45 an arbitrary amino acid is present, at position 46 an aliphatic amino acid and preferably a hydrophobic aliphatic amino acid is present or/and at position 47 Val is replaced by a basic amino acid e.g. Arg or Lys and in particular Arg. Streptavidin muteins in which the aliphatic amino acid at position 46 is Ala i.e. there is no substitution at position 46, or/and in which the basic amino acid at position 47 is Arg or/and in which the hydrophobic aliphatic amino acid at position 44 is Val or Ile have a particularly high affinity for the peptide ligand with the sequence WSHPQFEK (strep-tag II) described by Schmidt et al., Supra.
Specific examples of streptavidin muteins according to the invention have the sequences Val 44 -Thr 45 -Ala 46 -Arg 47 (SEQ ID NO: 6) or Ile 44 -Gly 45 -Ala 46 -Arg 47 (SEQ ID NO: 8) in the region of the amino acid positions 44 to 47.
For practical considerations it is desirable to have a further ligand which, due to a higher binding affinity or/and when present at higher concentrations, can detach the binding of the previously defined peptide ligands (according to DE-OS-4237113) from the streptavidin mutein according to the invention. In this manner it is possible to release bound peptide ligands or proteins to which a peptide ligand is fused under very mild elution conditions. Hence under this aspect the present invention concerns those streptavidin muteins according to the invention whose binding affinity for peptide ligands is such that they can be competitively eluted by other streptavidin ligands e.g. biotin, iminobiotin, lipoic acid, desthiobiotin, diaminobiotin, HABA (hydroxyazobenzene-benzoic acid) or/and dimethyl-HABA. The use of coloured substances such as HABA has the advantage that the elution can be checked visually.
However, irrespective of this, the binding affinity of the streptavidin mutein for peptide ligands is, as defined above, higher than that of the underlying wt-streptavidin. The binding affinity expressed as an affinity constant is thus greater than 2.7×10 4 M -1 with reference to the peptide ligand Ala Trp Arg His Pro Gln Phe Gly Gly (also referred to as strep-tag in the following) shown in SEQ ID NO:1 and greater than 1.4×10 4 M -1 with reference to the peptide ligand Trp Ser His Pro Gln Phe Glu Lys (also referred to as strep-tag II in the following) shown in SEQ ID NO:2 i.e. greater than the published values for the complex formation of the respective peptide ligands with wt-streptavidin (within the limits of error). In general the affinity constant for the strep-tag II is at least a factor of 10, preferably a factor of 10 to 200 higher than the respective values for wt-streptavidin.
It may be preferable for certain detection methods to use the streptavidin muteins of the present invention in a labelled form. Accordingly a further subject matter of this invention is a polypeptide according to the invention which is characterized in that it carries at least one label. Suitable labelling groups are known to a person skilled in the art and comprise the usual radiolabels, fluorescent labels, luminescent labels and chromophore labels as well as substances and enzymes which generate a substrate that can be determined in a chemical or enzymatic reaction. In this connection all labels known for wt-streptavidin can also be coupled to the streptavidin muteins according to the invention.
A further aspect of the present invention concerns a nucleic acid which comprises a sequence coding for the streptavidin. Such a nucleic acid is optionally operatively linked to a sequence coding for a signal peptide and, in a particular embodiment, the sequence coding for the signal peptide is the sequence for the OmpA signal peptide. Moreover it is also possible to use other signal peptides and this may even be preferable especially depending on the expression system or host cell used. A large number of such signal peptides are known in the state of the art and will not be elucidated in detail here. However, cytoplasmic expression is preferred i.e. with a start methionine instead of the signal sequence (cf. Schmidt and Skerra (1994), supra).
A further aspect of the present invention concerns a vector which contains at least one copy of an aforementioned nucleic acid in an operatively functional environment. An operatively functional environment is understood as those elements which enable, favour, facilitate or/and increase the expression, i.e. transcription or/and a subsequent processing, of the mRNA. Examples of such elements are promoters, enhancers, transcription initiation sites and termination sites, translation initiation sites, polyA-sites etc.
The vector is selected depending on the intended expression system and for this single copy plasmids, multi-copy plasmids as well as vehicles which facilitate an integration of the nucleic acid into the host genome come into consideration. A large number of suitable vectors are known from the state of the art and will not be described in detail here. They optionally contain standard elements used for vectors such as resistances, selection markers or/and elements which for example enable an amplification of the nucleic acid or the induction of expression.
A further aspect of the present invention concerns a cell which is transformed or transfected with such a vector which carries as an insert at least one copy of a nucleic acid sequence coding for a streptavidin mutein according to the invention. The selection of the cell is not particularly critical and in general it is possible to use any cells that are suitable for such purposes. Prokaryotic as well as eukaryotic cells and yeasts come into consideration. For practical reasons prokaryotic cells are generally preferred and in particular E. coli for the expression of an unglycosylated protein as in the present case.
Yet a further aspect of the present invention concerns a process for the production of a streptavidin mutein according to the invention which is characterized by the following steps:
(a) transforming a suitable host cell with a vector which contains a nucleic acid coding for the streptavidin mutein,
(b) culturing the host cell under conditions in which an expression of the streptavidin mutein takes place,
(c) isolating the polypeptide.
With respect to the production process it must be noted that the streptavidin muteins according to the invention may have a toxic effect due to their ability to bind to endogeneous cell biotin. Hence when culturing the host cell the conditions should be selected such that the expression product that forms is either transported from the inside of the host cell used for example into the periplasma or into the culture medium by means of a suitable signal sequence or it aggregates inside the cell in the form of insoluble inclusion bodies. In the former case the streptavidin mutein according to the invention can be isolated from the periplasmic cell fraction or the cell supernatant whereas in the latter case step (c) of the process according to the invention comprises the lysis of host cells, the isolation of the streptavidin mutein in the form of inclusion bodies and the renaturation of the streptavidin mutein. In this case E. coli is preferred as the host cell.
The practical applications for the streptavidin muteins or the streptavidin mutein/peptide ligand system according to the invention are essentially the same as those for conventional streptavidin/biotin or streptavidin/peptide ligand systems. There are advantages especially in situations in which a higher binding strength is desired than that between native streptavidin and peptide ligand or in situations in which it is not possible to biotinylate a substrate of interest or is less easy than the corresponding linkage to a peptide ligand.
The advantages over the conventional streptavidin/biotin system apply in particular to affinity chromatography and in purification, isolation or determination methods for recombinant proteins. Accordingly the invention also concerns the use of a streptavidin mutein according to the invention in a method for the isolation, purification or detection of a protein that is fused with a peptide sequence of the formula Trp-Xaa-His-Pro-Gln-Phe-Xaa-Xaa (SEQ ID NO: 16) in which X represents an arbitrary amino acid and Y and Z either both denote Gly or Y denotes Glu and Z denotes Arg or Lys wherein a liquid containing the protein to be isolated or purified is contacted with the optionally immobilized streptavidin mutein under suitable conditions in order to bind the peptide sequence to the streptavidin mutein, the resulting complex is separated from the liquid and the protein is released from the complex or detected. The peptide sequence is particularly preferably selected in the form of strep-tag or strep-tag II. The peptide sequence is preferably fused to the N- or/and C-terminus of the protein. The streptavidin mutein can be bound to a solid phase or can be capable of binding to it.
An advantage of utilizing the streptavidin mutein/peptide ligand system according to the invention in an isolation or purification method is that very mild conditions can be used to elute the fusion protein carrying the peptide ligand. Hence it is possible to incubate a solid phase coupled to the streptavidin mutein, such as for example an affinity chromatography column to which the fusion protein has been adsorbed, with an adequate concentration of a ligand selected from biotin and derivatives thereof in order to release the fusion protein from the complex. In this connection the use of desthiobiotin has proven to be particularly advantageous.
The streptavidin muteins according to the invention can be used in detection methods in an essentially similar manner to the corresponding methods that are known for conventional streptavidin. A further application is the qualitative or quantitative determination of a protein which is fused with a peptide sequence of the formula Trp-Xaa-His-Pro-Gln-Phe-Xaa-Xaa (SEQ ID NO: 16) in which X represents an arbitrary amino acid and Y and Z either both denote Gly or Y denotes Glu and Z denotes Arg or Lys, wherein the protein to be determined is contacted under suitable conditions with a labelled streptavidin mutein in order to bind the peptide sequence to the streptavidin mutein and the label is determined. Such a determination method can for example be carried out qualitatively to detect proteins in Western blots or quantitatively as an ELISA. Suitable labels are all known radioactive and non-radio-active labelling groups e.g. luminescent groups, enzymes, metals, metal complexes etc. The streptavidin can be directly labelled e.g. by covalent coupling. However, indirect labels such as labelled anti-streptavidin antibodies or biotinylated enzymes etc. can also be used.
A further subject matter of the invention is the use of the streptavidin muteins according to the invention to immobilize a protein which is fused with a peptide sequence Trp-Xaa-His-Pro-Gln-Phe-Xaa-Xaa (SEQ ID NO: 16) in which X represents an arbitrary amino acid and Y and Z either both denote Gly or Y denotes Glu and Z denotes Arg or Lys. This immobilization is preferably carried out on solid phases coated with streptavidin muteins such as microtitre plates, microbeads made of organic or paramagnetic materials or sensor chips.
In addition it is of course also possible to use the streptavidin muteins according to the invention in a conventional streptavidin/biotin (derivative) system. In other words this means the use of the streptavidin muteins according to the invention to determine or isolate substances which carry a group capable of binding to streptavidin. If only a part of the wt-streptavidin is replaced by the streptavidin muteins according to the invention, particular effects can be achieved in this connection via the formation of mixed tetramers.
Yet a further aspect of the invention also concerns a reagent kit which contains a streptavidin mutein according to the invention and optionally standard buffer and auxiliary substances and additives. Such a reagent kit is in particular intended to be used in one of the isolation, purification or determination methods described above. However, the kit is also suitable for other methods in which the conventional streptavidin/biotin system is used e.g. for nucleic acid hybridization assays or immunoassays. The reagent kit can contain the streptavidin mutein according to the invention in a solid phase-bound or/and labelled form.
The invention is further elucidated by the following examples and the attached figures in which:
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 shows a schematic drawing of the vector pASK75-SAp;
FIG. 2 is a graph which shows the binding affinity of recombinant wt-streptavidin compared to streptavidin muteins according to the invention in an ELISA;
FIG. 3 shows the binding affinity of recombinant wt-streptavidin compared to a streptavidin mutein according to the invention in a fluorescence titration and
FIG. 4 shows the purification of a strep-tag fusion protein using a streptavidin mutein by affinity chromatography.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 shows the expression vector pASK75-SAp which contains a sequence coding for a minimal streptavidin (Ala 13 to Ser 139 ), a sequence coding for the OmpA signal peptide as well as the tetracyclin promoter/operator (tet P/O ) for transcription regulation.
Other labelled regions of the vector are the intergenic region of the filamentous phage f1 (f1-IG), the origin of replication (ori), the β-lactamase gene (bla) for ampicillin resistance, the tetracyclin repressor gene (tetR) and the lipoprotein transcription terminator (t lpp ).
The hybrid structural gene containing the coding sequences for the signal peptide and minimal streptavidin begins at the XbaI site and extends downstream to the HindIII site. The junction between the signal sequence and streptavidin is at the StuI/PvuII site. The SacII site which was used to insert the mutated streptavidin gene sequences is also shown.
FIG. 2 shows the improved affinity of the streptavidin muteins according to the invention for the peptide ligand strep-tag II in an ELISA. For this rows of an ELISA plate were each coated with equivalent concentrations of a recombinant wt-streptavidin (rhombus), the mutein "1" (circle) or "2" (square) or only saturated with BSA (cross). After saturating and washing the wells were incubated with a purified fusion protein consisting of bacterial alkaline phosphatase (PhoA) and strep-tag II at the concentrations shown in the graph. After washing to remove unbound protein, the activity of the bound PhoA-strep-tagII fusion protein was measured in the presence of p-nitrophenyl phosphate. The data were fitted by non-linear regression by the least squared error method. The following K d values were obtained: 0.21 μM for mutein "1"; 0.30 μM for mutein "2"; 18 μM for recombinant wt-streptavidin.
FIG. 3 is a graph which shows the binding affinity of recombinant wt-streptavidin compared to streptavidin muteins according to the invention in a fluorescence titration.
A solution of wt-streptavidin (rhombus), the mutein "1" (circle) or "2" (square) was titrated with a solution of the synthesized strep-tag II peptide which was derivatized N-terminally with anthranilic acid and the fluorescence of the tryptophan and tyrosine residues was measured (excitation at 280 nm; emission at 340 nm). The experimental conditions are described in example 6. A K D value for the peptide complex of 13.0±1.3 μM for wt-streptavidin was determined by non-linear regression of the data points according to the theory of simple complex formation whereas the mutants "1" and "2" had K D values of 1.37±0.08 μM and 1.02±0.04 μM respectively.
FIG. 4 shows the purification of the fusion protein composed of bacterial alkaline phosphatase and strep-tag II by affinity chromatography using the immobilized streptavidin mutein "1" according to the invention.
FIG. 4 shows the elution profile (based on the absorbance of the eluate at 280 nm) when purifying the fusion protein composed of bacterial alkaline phosphatase and strep-tag II by affinity chromatography from the bacterial periplasmic cell extract using the immobilized streptavidin mutein "1". The experimental conditions are described in example 4. After removing the host proteins by washing with chromatography buffer, it was eluted successively with solutions of diamino-biotin (dab), desthiobiotin (dtb) and biotin. The bound fusion protein was almost quantitatively eluted in the presence of desthiobiotin. Subsequent analysis by SDS polyacrylamide gel electrophoresis showed an almost complete purity of the protein isolated in this manner.
The invention is further elucidated by the following sequence protocol:
SEQ ID NO. 1: shows the amino acid sequence of the peptide ligand strep-tag,
SEQ ID NO. 2: shows the amino acid sequence of the peptide ligand strep-tag II,
SEQ ID NO. 3/4: show the nucleotide and amino acid sequence of wt-streptavidin in the region of amino acids 44-47,
SEQ ID NO. 5/6: show the nucleotide and amino acid sequence of the streptavidin mutein 1 in the region of amino acids 44-47,
SEQ ID NO. 7/8: show the nucleotide and amino acid sequence of the streptavidin mutein 2 in the region of amino acids 44-47,
SEQ ID NO. 9: shows the nucleotide sequence of the oligonucleotide primer P1,
SEQ ID NO. 10: shows the nucleotide sequence of the oligonucleotide primer P2,
SEQ ID NO. 11: shows the nucleotide sequence of the oligonucleotide primer P3,
SEQ ID NO. 12: shows the nucleotide sequence of the oligonucleotide primer P4,
SEQ ID NO. 13: shows the nucleotide sequence of the oligonucleotide primer P5,
SEQ ID NO. 14: shows the nucleotide sequence of the oligonucleotide primer P6 and
SEQ ID NO. 15: shows the nucleotide sequence of the oligonucleotide primer P7.
SEQ ID NO. 16: shows a general formula for muteins described herein.
SEQ ID NO: 17 shows the wild type sequence of streptavidin.
EXAMPLES
General methods
DNA manipulations were carried out by conventional genetic engineering methods (see e.g. Sambrook et al., Molecular Cloning. A Laboratory Manual (1989), Cold Spring Harbor Press). In general the E. coli K12 strain JM83 (Yanisch-Peron et al., (1985), Gene 33, 103-119) was used for cloning and expression with the exception of the expression under the control of the T7 promoter which was carried out according to Schmidt and Skerra (1994), supra. Sequencings were carried out by plasmid sequencing according to the standard dideoxy technique using the T7 sequencing kit from Pharmacia, Freiburg. The primers and oligonucleotides were synthesized using an Applied Biosystems DNA synthesizer.
Example 1
Preparation of an expression bank for streptavidin muteins
In order to construct the vector pASK75-SAp which carries the gene sequence coding for a minimal streptavidin fused to the coding sequence of the OmpA signal peptide (cf. FIG. 1), the sequence coding for minimal streptavidin was amplified by PCR from the expression vector pSA1 (Schmidt and Skerra, (1994), supra) using the primers P1 and P2:
P1: 5'-GAG ATA CAG CTG CAG AAG CAG GTA TCA CCG GCA C (SEQ ID NO. 9) and
P2: 5'-CGG ATC AAG CTT ATT AGG AGG CGG CGG ACG GCT TCA C (SEQ ID NO. 10)
and Taq DNA polymerase, the reaction product was purified by gel electrophoresis, cleaved with PvuII and HindIII and ligated into the vector fragment of pASK75 cleaved with StuI and HindIII. The complete nucleotide sequence of pASK75 is stated in DE-A-44 17 598.1. The vector generated in this manner pASK75-SAp contains a DNA sequence which codes for the OmpA signal peptide fused to minimal streptavidin beginning at Ala 13 .
A plasmid bank with DNA sequences which code for streptavidin derivatives mutagenized in the region of amino acid positions 44 to 47 (with reference to wt-streptavidin) was prepared by PCR amplification of pASK75-SAp using the following primers P3 and P4:
P3: 5'-TCG TGA CCG CGG GTG CAG ACG GAG CTC TGA CCG GTA CCT ACN N(C/G)N N(G/T)N N(C/G)N N(G/T)G GCA ACG CCG AGA GCC GCT AC (SEQ ID NO. 11) and
P4: 5'-CGG ATC AAG CTT ATT AGG AGG CGG CGG ACG GCT TCA C (SEQ ID NO. 12).
DNA sequences were generated in this manner which contained 32-fold degenerated codons for each of all the 20 amino acids or a stop codon at each of the four positions 44 to 47. In addition a KpnI restriction site was generated at the site in the region of the codons for the amino acids 41/42. The resulting PCR products were purified by gel electrophoresis, cleaved with SacII and HindIII and ligated into the correspondingly cleaved vector fragment of pASK75-SAp.
E. coli JM83 cells were transformed with the vector mixture using the calcium chloride method (Sambrook et al., 1989).
Example 2
Identification of streptavidin muteins with an increased binding affinity for peptide ligands
In order to identify streptavidin muteins with an increased binding affinity for peptide ligands, a fusion protein was prepared comprising the alkaline phosphatase of E. coli (PhoA) and the strep-tag II peptide (WSHPQFEK) which was attached to its C-terminus. For this the complete phoA gene including its own signal sequence and translation initiation region was amplified by PCR according to a method published by Skerra (Nucleic Acids Res. 20 (1992), 3551 to 3554) from chromosomal E. coli K12 W3110 DNA (Bachmann, Bacteriol. Rev. 36 (1972), 525-557) using the phosphorothioate primers P5 and P6 and pfu DNA polymerase:
P5: 5'-TAA TGT TCT AGA ACA TGG AGA AAA TAA AGT GAA ACA AAG GAC (SEQ ID NO. 13) and
P6: 5'-GCT AGG CGG TTT CAG CCC CAG AGC GGC TTT C (SEQ ID NO: 14).
The PCR product obtained in this manner was purified and cleaved with the restriction enzyme XbaI. This DNA fragment was then inserted in several steps into the plasmid pASK75-strepII (constructed from pASK75 by site-specific mutagenesis using the oligodeoxynucleotide P7 5'-CAC AGG TCA AGC TTA TTA TTT TTC GAA CTG CGG GTG AGA CCA AGC GCT GCC TGC (SEQ ID NO. 15) while replacing the region between XbaI and Eco47III to obtain the expression plasmid pASK75-PhoA strep II.
The protein production took place in 2 l LB medium containing 100 μg/ml ampicillin in which the gene expression was induced at A 550 =0.5 by addition of 0.2 μg/ml anhydrotetracyclin. The induction was carried out overnight at a temperature of 37° C. The PhoA/strep-tag II fusion enzyme was then purified from the periplasmic cell fraction by streptavidin affinity chromatography using diaminobiotin as the eluting agent according to the procedure of Schmidt and Skerra (1994), supra. Due to the presence of Zn(II) ions and Mg(II) ions in the active centre of the enzyme the chromatography buffer contained no EDTA.
The plasmid bank obtained in example 1 was plated out on a hydrophilic GVWP membrane (Millipore, Eschborn) which had been placed on an Agar plate containing LB medium which contained 100 μg/ml ampicillin. The membrane was incubated for 7 to 8 hours at 37° C. until colonies became visible.
Then a second membrane was prepared, an Immobilon-P membrane (Millipore, Eschborn) which was coated for ca. 6 hours with anti-streptavidin immunoglobulin (Sigma, Deisenhofen) at a concentration of 720 μg/ml in PBS (4 mM KH 2 PO 4 , 16 mM Na 2 HPO 4 , 115 mM NaCl) and afterwards was blocked for ca. 2 hours in 3% w/v bovine serum albumin (BSA), 0.5% v/v Tween in PBS.
This second membrane was placed on a M9 minimal agar plate which contained 100 μg/ml ampicillin and 0.2 μg/ml anhydrotetracyclin. Subsequently the GVWP membrane with the colonies on the upper side was placed on the second membrane and the relative positions of the two membranes was marked. After incubation overnight at room temperature the upper membrane with the colonies was removed and stored on a fresh LB ampicillin agar plate at 4° C. The second membrane was also removed from the agar plate and washed three times for 1 minute while shaking in PBS/Tween (0.1% v/v Tween in PBS). Subsequently the membrane was admixed with 10 ml fresh PBS/Tween solution containing the purified PhoA/strep-tagII fusion protein (ca. 1-2 μg/ml). After incubating for one hour at room temperature it was washed again twice in PBS/Tween and twice in PBS buffer. The signal generation took place for 1 to 2 hours in the presence of 10 ml AP buffer (100 mM Tris, pH 8.8, 100 mM NaCl, 5 MM MgCl 2 ) with addition of 30 μl bromo-chloro-indolylphosphate (BCIP) (50 mg/ml in dimethylformamide) and 5 μl nitroblue tetrazolium (NBT) (75 mg/ml in 70% v/v dimethylformamide). The colour spots which formed in this process were assigned to corresponding colonies on the first membrane. After isolation and culture of these clones, two streptavidin muteins "1" and "2" were identified. The nucleotide and amino acid sequences in the mutagenized region for wt-streptavidin and for the muteins were as follows:
______________________________________wt-streptavidin GAG TCG GCC GTC (SEQ ID NO. 3) Glu.sup.44 Ser.sup.45 Ala.sup.46 Val.sup.47 (SEQ ID NO. 4) mutein "1" GTC ACG GCG CGT (SEQ ID NO. 5) Val Thr Ala Arg (SEQ ID NO. 6) mutein "2" ATC GGT GCG AGG (SEQ ID NO. 7) Ile Gly Ala Arg (SEQ ID NO. 8)______________________________________
Example 3
Production of streptavidin muteins on a preparative scale
The known expression system for recombinant minimal streptavidin (Schmidt and Skerra (1994), supra) was used to produce streptavidin muteins on a preparative scale. For this the major part of the coding region was removed from the vector pSA1 which contains the coding region of wt-streptavidin and the T7 promoter by using the singular SacII and HindIII restriction sites and replaced by the corresponding regions from the mutated pASK75-SAp plasmids. wt-streptavidin and the streptavidin muteins were subsequently expressed in the form of cytoplasmic inclusion bodies, solubilized, renatured and purified by fractional ammonium sulphate precipitation as described by Schmidt and Skerra (1994) supra. The purity of the proteins was checked by SDS-PAGE using the discontinuous buffer system of Fling and Gregerson (Anal. Biochem. 155 (1986), 83-88). Characterization of the purified proteins that were dialysed against water by electrospray ionisation mass spectrometry yielded masses of 13334 for the recombinant wt-streptavidin (theoretical 13331.5), 13371 for mutein "1" (theoretical 13372.6) and 13344 for mutein "2" (theoretical 13342.5).
Example 4
Affinity chromatography
The streptavidin muteins prepared in example 3 and wt-streptavidin were coupled to NHS-activated Sepharose 4B (Pharmacia Freiburg) at a loading of 5 mg protein per ml swollen gel (Schmidt and Skerra, 1994, supra). After blocking the remaining active groups overnight with 100 mM Tris/HCl, pH 8.0, 2 ml of the gel was placed in a column with a diameter of 7 mm. In order to examine the behaviour of the streptavidin muteins immobilized in this manner in the affinity purification of strep-tag or strep-tagII-carrying fusion proteins, the recombinant protease inhibitor cystatin (Schmidt and Skerra 1994, supra) which was either fused to strep-tag or strep-tagII as well as the PhoA/strep-tagII fusion protein mentioned above were used. The fusion proteins were produced in an expression system by secretion into the periplasmic space and the periplasmic cell fraction was prepared as described in Schmidt & Skerra (1994), supra.
The chromatography was carried out in the presence of 100 mM Tris/HCl, pH 8.0 containing 1 mM EDTA (except in the case of PhoA) at a flow rate of ca. 20 ml/h and the eluate absorbance was measured at 280 nm. After applying a sample of 10 ml corresponding to the periplasmic cell fraction of 1 l E. coli culture medium, the column was washed until the absorbance at 280 nm had reached the base line. Afterwards bound protein was eluted step-wise by applying 10 ml each of diaminobiotin, desthio-biotin and biotin (all from Sigma, Deisenhofen) at a concentration of 2.5 mM in chromatography buffer and in the stated order.
It turned out that, in contrast to wt-streptavidin, the use of diaminobiotin did not lead to an elution in the case of the streptavidin muteins. When the biotin derivative desthiobiotin, which binds with a higher affinity to streptavidin, was used an elution with a sharp maximum was also achieved in the case of the muteins. This was quantitative since in the subsequent elution with biotin essentially no amounts of fusion protein could be detected in the eluate (cf. FIG. 4).
Example 5
ELISA
An ELISA was carried out to determine the binding affinity of the streptavidin muteins for the peptide ligand strep-tagII.
The wells of a 96-well microtitre plate (Becton Dickinson Co., Oxnard, Calif.) were coated overnight with 100 μl of a solution of recombinant wt-streptavidin or the muteins "1" or "2" at a concentration in each case of 100 μg/ml in 50 mM NaHCO 3 , pH 9.6. The wells were then blocked for 2.5 hours with 3% w/v BSA, 0.5% v/v Tween in PBS. After washing three times with PBS/Tween, 50 μl of the same buffer was added to each well. 20 μl from a solution of 20 μl of 4.85 μM purified and dialysed PhoA/strep-tag II fusion protein plus 30 μl PBS/Tween was added to the first well of each row and mixed. A dilution series was set up in the other wells of a row by pipetting 50 μl (from a total of 100 μl) out of the first well and mixing it with the contents (50 μl) of the next well in the same row etc. In this manner concentrations of the fusion protein between 970 nM in the first well of each row and 0.19 nM in the tenth well were obtained.
After incubating for one hour the solutions were removed and the wells were each washed twice with PBS/Tween and with PBS. Subsequently 100 μl of a solution of 0.5 mg/ml p-nitrophenyl phosphate in 1 mM ZnSO 4 , 5 mM MgCl 2 , 1 mM Tris/HCl, pH 8.0 was pipetted into each well. The activity of the bound fusion protein was measured using a SpectraMAX 250 photometer (Molecular Devices, Sunnyvale, Calif.) as an absorbance change at 410 nm per time.
The data were evaluated assuming a single binding equilibrium between streptavidin (mutein) monomers (P) and the PhoA/strep-tag II fusion protein (L) which yielded a dissociation constant K D =[P] [L]/[P.sup.. L]. Under the condition that [P] TOT =[P]+[P.sup.. L] and that [L] is very much larger than [P.sup.. L] so that [L] TOT is approximately the same as [L] [P.sup.. L]=[L] TOT [P] TOT /(K D +[L] TOT applies for the amount of bound fusion protein. FIG. 2 shows a graph of the experimental results obtained.
It can be seen from the binding curves that the two streptavidin muteins have a very similar affinity for the strep-tap II fusion protein which is more than an order of magnitude higher than the affinity of wt-streptavidin.
Example 6
Fluorescence titration
In order to determine the dissociation constant of the 1:1 complex of the streptavidin muteins (considered as a monomer) and the peptide ligands, a fluorescence titration was carried out with the strep-tag II synthesized by peptide chemistry.
The peptide with the sequence Abz-Trp-Ser-His-Pro-Gln-Phe-Glu-Lys-COOH (SEQ ID NO: 6, with N-terminal Abz added thereto) (Abz represents o-aminobenzoic acid i.e. anthranilic acid) was synthesized stepwise on a solid phase from Fmoc-protected amino acids according to methods known to a person skilled in the art in the order C-terminus to N-terminus wherein Abz was coupled in the last step as a Boc-protected derivative. The peptide was subsequently cleaved from the carrier and freed of the protecting groups. After purification by HPLC the mole mass was confirmed by means of field desorption mass spectrometry.
The fluorescence titration was carried out with an LS50 fluorescence spectrophotometer from the Perkin Elmer Company (Langen) in a 1.sup.. 1 cm 2 quartz cuvette which was thermostated at 25° C. The wavelengths for excitation and emission were 280 nm and 340 nm respectively with a respective slit width of 5 nm. 2 ml of the solution of wt-streptavidin or the muteins "1" and "2", which were prepared as described in example 3 and had been dialysed against 1 mM EDTA, 100 mM Tris/HCl pH 8.0, were placed in the cuvette at a concentration of 1 μM (determined by absorbance photometry for the respective monomer using an extinction coefficient of .di-elect cons. 280 =40455 M -1 cm -1 ). Then volumes of 1 μl or 4 μl of a 0.5 mM solution of the peptide in the same buffer were repeatedly added by pipette (a total of 40 μl) and after mixing with a stirring bar the fluorescence intensity was read. The data were evaluated as described in FIG. 3.
__________________________________________________________________________# SEQUENCE LISTING - - - - <160> NUMBER OF SEQ ID NOS: 17 - - <210> SEQ ID NO 1 <211> LENGTH: 9 <212> TYPE: PRT <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: BINDING <223> OTHER INFORMATION: Binding ligand for strept - #avidin - - <400> SEQUENCE: 1 - - Ala Trp Arg His Pro Gln Phe Gly Gly 1 5 - - - - <210> SEQ ID NO 2 <211> LENGTH: 8 <212> TYPE: PRT <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: BINDING <223> OTHER INFORMATION: Binding ligand for strept - #avidin - - <400> SEQUENCE: 2 - - Trp Ser His Pro Gln Phe Glu Lys 1 5 - - - - <210> SEQ ID NO 3 <211> LENGTH: 12 <212> TYPE: DNA <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: CDS <223> OTHER INFORMATION: Synthesized - - <400> SEQUENCE: 3 - - gagtcg gccg tc - # - # - # 12 - - - - <210> SEQ ID NO 4 <211> LENGTH: 4 <212> TYPE: PRT <213> ORGANISM: Streptomyces avidinii <220> FEATURE: <223> OTHER INFORMATION: Amino acids 44-47 of w - #ild type streptavidin - - <400> SEQUENCE: 4 - - Glu Ser Ala Val - - - - <210> SEQ ID NO 5 <211> LENGTH: 12 <212> TYPE: DNA <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: CDS <223> OTHER INFORMATION: Synthesized - - <400> SEQUENCE: 5 - - gtcacggcgc gt - # - # - # 12 - - - - <210> SEQ ID NO 6 <211> LENGTH: 4 <212> TYPE: PRT <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: MUTAGEN <223> OTHER INFORMATION: Mutagen of amino acids - #44-47 of wild type streptavidin - - <400> SEQUENCE: 6 - - Val Thr Ala Arg - - - - <210> SEQ ID NO 7 <211> LENGTH: 12 <212> TYPE: DNA <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: CDS <223> OTHER INFORMATION: Synthesized - - <400> SEQUENCE: 7 - - atcggtgcga gg - # - # - # 12 - - - - <210> SEQ ID NO 8 <211> LENGTH: 4 <212> TYPE: PRT <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: MUTAGEN <223> OTHER INFORMATION: Mutagen of amino acids - #44-47 of wild type streptavidin - - <400> SEQUENCE: 8 - - Ile Gly Ala Arg - - - - <210> SEQ ID NO 9 <211> LENGTH: 34 <212> TYPE: DNA <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: primer.sub.-- .sub.-- bind <223> OTHER INFORMATION: primer for sequence encod - #ing streptavidin - - <400> SEQUENCE: 9 - - gagatacagc tgcagaagca ggtatcaccg gcac - # -# 34 - - - - <210> SEQ ID NO 10 <211> LENGTH: 37 <212> TYPE: DNA <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: primer.sub.-- .sub.-- bind <223> OTHER INFORMATION: primer for sequence encod - #ing streptavidin - - <400> SEQUENCE: 10 - - cggatcaagc ttattaggag cgggcggacg gcttcag - #- # 37 - - - - <210> SEQ ID NO 11 <211> LENGTH: 74 <212> TYPE: DNA <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: primer.sub.-- .sub.-- bind <223> OTHER INFORMATION: degenerate primer sequence - #for use inencoding mutations in <223> OTHER INFORMATION: amino acids 44-47 of s - #treptavidin. "n" isused at positions <223> OTHER INFORMATION: 42,43,45,46,48,49,51 and 52. - # In each case,"n" can be a, c, <223> OTHER INFORMATION: t, or g. - - <400> SEQUENCE: 11 - - tcgtgaccgc gggtgcagac ggagctctga ccggtaccta cnnsnnknns nn -#kggcaacg 60 - - ccgagagccg ctag - # - # - # 74 - - - - <210> SEQ ID NO 12 <211> LENGTH: 37 <212> TYPE: DNA <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: primer.sub.-- .sub.-- bind <223> OTHER INFORMATION: Primer sequence used in - #connection with SEQID NO: 12 to <223> OTHER INFORMATION: generate mutations of str - #eptavidin - - <400> SEQUENCE: 12 - - cggatcaagc ttattaggag cgggcggagc gcttcac - #- # 37 - - - - <210> SEQ ID NO 13 <211> LENGTH: 42 <212> TYPE: DNA <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: primer.sub.-- .sub.-- bind <223> OTHER INFORMATION: Primer for encoding fusio - #n protein of E.coli alkaline <223> OTHER INFORMATION: phosphatase and SEQ ID - #NO: 2 - - <400> SEQUENCE: 13 - - taatgttcta gaacatggag aaaataaagt gaaacaaagg ac - # - # 42 - - - - <210> SEQ ID NO 14 <211> LENGTH: 31 <212> TYPE: DNA <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: primer.sub.-- .sub.-- bind <223> OTHER INFORMATION: Primer used with SEQ I - #D NO: 13 - - <400> SEQUENCE: 14 - - gctaggcggt ttragcccca gagcgg cttt c - # - # 31 - - - - <210> SEQ ID NO 15 <211> LENGTH: 54 <212> TYPE: DNA <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: primer.sub.-- .sub.-- bind <223> OTHER INFORMATION: Used for site directed - #mutagenesis ofsequences generated <223> OTHER INFORMATION: by SEQ ID NOS: 13 & - # 14. - - <400> SEQUENCE: 15 - - cacaggtcaa gcttattatt tttcgaactg cgggtgagac caagcgctgc ct - #gc 54 - - - - <210> SEQ ID NO 16 <211> LENGTH: 8 <212> TYPE: PRT <213> ORGANISM: Artificial sequence <220> FEATURE: <221> NAME/KEY: VARIANTS <222> LOCATION: Positions 2, 7 & 8 <223> OTHER INFORMATION: First Xaa (position 2) - #is any amino acid. Second Xaa <223> OTHER INFORMATION: (position 7), is Gly o - #r Glu. Third Xaa (position 8) is <223> OTHER INFORMATION: Gly, Arg or Lys. Secon - #d Xaa must be Glywhen third Xaa <223> OTHER INFORMATION: is Gly, and must be - #Glu when third Xaa isArg or Lys - - <400> SEQUENCE: 16 - - Trp Xaa His Pro Gln Phe Xaa Xaa 1 5 - - - - <210> SEQ ID NO 17 <211> LENGTH: 159 <212> TYPE: PRT <213> ORGANISM: Streptomyces avidinii - - <400> SEQUENCE: 17 - - Asp Pro Ser Lys Asp Ser Lys Ala Gln Val Se - #r Ala Ala Glu AlaGly 1 5 - # 10 - # 15 - - Ile Thr Gly Thr Trp Tyr Asn Gln Leu Gly Se - #r Thr Phe Ile Val Thr 20 - # 25 - # 30 - - Ala Gly Ala Asp Gly Ala Leu Thr Gly Thr Ty - #r Glu Ser Ala Val Gly 35 - # 40 - # 45 - - Asn Ala Glu Ser Arg Tyr Val Leu Thr Gly Ar - #g Tyr Asp Ser Ala Pro 50 - # 55 - # 60 - - Ala Thr Asp Gly Ser Gly Thr Ala Leu Gly Tr - #p Thr Val Ala Trp Lys 65 - #70 - #75 - #80 - - Asn Asn Tyr Arg Asn Ala His Ser Ala Thr Th - #r Trp Ser Gly Gln Tyr 85 - # 90 - # 95 - - Val Gly Gly Ala Glu Ala Arg Ile Asn Thr Gl - #n Trp Leu Leu Thr Ser 100 - # 105 - # 110 - - Gly Thr Thr Glu Ala Asn Ala Trp Lys Ser Th - #r Leu Val Gly His Asp 115 - # 120 - # 125 - - Thr Phe Thr Lys Val Lys Pro Ser Ala Ala Se - #r Ile Asp Ala Ala Lys130 - # 135 - # 140 - - Lys Ala Gly Val Asn Asn Gly Asn Pro Leu As - #p Ala Val Gln Gln 145 1 - #50 1 - #55__________________________________________________________________________ | The invention concerns a polypeptide selected from muteins of streptavidin which is characterized in that it (a) contains at least one mutation in the region of the amino acid positions 44 to 53 with reference to wild type-(wt)-streptavidin and (b) has a higher binding affinity than wt-streptavidin for peptide ligands comprising the amino acid sequence Trp-X-His-Pro-Gln-Phe-Y-Z in which X represents an arbitrary amino acid and Y and Z either both denote Gly or Y denotes Glu and Z denotes Arg or Lys. In addition nucleic acids coding for the polypeptide, a vector containing this nucleic acid, a cell transfected with the vector as well as the use of a polypeptide in a method for the isolation, purification or determination of proteins are disclosed. Yet a further subject matter is a reagent kit containing the polypeptide. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to a piston for internal combustion engines, and more particularly is directed to the piston-ring groove of a piston of aluminium alloy, which has good wear resistance.
2. Description of the Prior Art
In general, the piston-ring groove of a piston for an internal combustion engine is not only exposed to a high temperature, but also mechanically worn due to friction between the piston and a piston ring, so that blow-by is caused, and the consumption of lubricant increases. Thus, the life of the engine is shortened.
In case of a diesel engine in which abrasion on the piston-ring groove is very large, the piston is cast in special cast iron so as to reduce the abrasion. Further, it is disclosed in Japanese Laid Open Patent No. 53-31014 how to make aluminium alloy forming the piston body, penetrate into porous metal which is embedded around the piston-ring groove, when the piston is cast under high pressure.
Moreover, in Japanese Laid Open Patent Nos. 59-21393, 59-218341, and 59-212159, it is disclosed to increase the wear resistance of the piston ring groove reinforced by porous metal made of Fe, Ni, Cu or the like, in which hard intermetallic compound of porous metal and aluminium is produced by heat treatment.
The invnetors of this application found such facts that (1) the kind of the porous material influences in a process of forming an intermetallic compound of the porous material with aluminium, and (2) cracks are initiated in brittle portions of the formed intermetallic compound when the piston is repeatedly heated of long duration.
If a volumetric ratio V f of the porous metal ring is rather small, there is no detrimental effect on the piston even if the cracks are produced in the intermetallic compound. However, if the volumetric ratio of the porous metal ring increases, the cracks in the intermetallic compound will propagate in the aluminium alloy matrix at the boundary area between aluminium alloy matrix and the reinforced area with porous metal, resulting in the fall-out of the reinforced area from the piston body.
Moreover, there is another problem when the piston-ring groove is reinforced with the porous material. Even if the volume of the intermetallic compound is increased while keeping the volumetric ratio of the porous metal ring small, the wear resistance of the reinforced area is far less than the conventional Ni-resist ring carrier. In order to increase the wear resistance of the reinforced area with the porous metal to the acceptable level for heavy duty diesel engines, the volumetric ratio of the porous metal ring should be more than 20%. However, the reinforced area with such a high porous metal ratio can easily fall out from the piston, as mentioned already.
OBJECT AND SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to increase the wear resistance of the piston ring groove by porous metal without making use of the intermetallic compound, and to offer the method to avoid cracking and falling-out of the reinforced area, so that the reinforcing method of the piston ring groove with the porous metal ring can be applied without failure for heavy duty engines.
Another object of the invention is to provide a piston for internal combustion engines which is excellent in machinability and wear resistance, so that it becomes easy to manufacture the piston, and further, the life of the engine can be prolonged.
In accordance with an aspect of this invention, an aluminium alloy piston for internal combustion engine is reinforced with a porous metal ring cast in through squeeze casting process, whereby at least the surface layer of the porous metal contains more than 10% chromium by weight and the layer thickness is more than 0.001 mm. The chromium containing layer suppresses the formation of the brittle intermetallic compound of aluminium and reinforcing metal, thus preventing from cracking in the intermetallic compound and increasing the wear resistance of the piston ring groove. The formation of the brittle intermetallic compound can be suppressed, whether chromium is contained only on the surface layer of the porous metal or chromium is contained uniformly in the porous metal. In order to increase the wear resistance of the reinforced piston ring groove, it is preferable that the chromium content is more than 15% by weight and that the thickness of the layer containing more than 15% chromium is bigger than 0.003 mm.
Whether chrome is contained only in the interface layer of the porous metal, or whether chrome is uniformly contained in the whole layer of the porous metal, it gives scarcely any influence on the formation of the intermetallic compound, but the more chrome is contained the better the abrasion resistance becomes, and it is preferable that the layer contains more than 15% Cr and is more than 0.003 mm in thickness. Further, the layer may contain 100% Cr.
It is preferable that the volumetric ratio V f of the porous metal falls between 10 to 60%. When V f is less than 10%, the abrasion resistance is scarcely improved, and when V f is more than 60%, it becomes difficult to completely fill the pores of the porous metal with aluminium unless the preheating temperature is raised. However, at the high preheating temperature, the undesirable compound of the porous metal with aluminium is apt to be produced in the interface part of the composite layer.
The porous metal may be either of carbon steel, alloy steel, nickel alloy or Monel metal, and chromium can be diffused in the porous metal through a chromizing process. In another case, chromium containing porous metal can be produced through powder metallurgy, e.g. using austenitic stainless steel powders. Further, the chromium layer can be plated on the porous metal.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front view, partly broken away and in section, of a piston made of aluminium alloy and used for internal combustion engines in which this invention is to be applied.
FIG. 2 is a micrograph of the reinforced ring groove area with a conventional porous metal of Nickel;
FIGS. 3 and 4 are photographs of an X-ray micro analizing of the reinforced ring groove area with a conventional porous nickel metal ring;
FIGS. 5 through 7 are photographs of an X-ray micro analizing of the reinforced ring groove area with an embodiment of this invention;
FIG. 8 is a diagram of the result of abrasion tests of pistons; and
FIG. 9 is a diagram showing the thickness of a compound of iron with aluminium.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to the drawings and initially to FIG. 1, a piston 1 has a top piston-ring groove 2 surrounded with a composite layer 3, whereby the piston-ring groove 2 is strengthened. The composite layer 3 comprises an annular member made of cellular nickel (manufactured by "Sumitomo-Denko" Co., Ltd. and identified by a registered trademark "Celmet"). The annular member is so formed by press work as to have a volumetric ratio V f of 30% after making composite with aluminium alloy. Further, another annular member is prepared, in which a cemented chrome layer of about 0.03 mm thickness is formed at a surface of the above annular member by means of chromizing.
The two kinds of annular members are positioned in respective molds. Molten aluminium alloy of a 740-degree centigrade temperature is poured into the respective molds, and then pressed under the pressure of 800 Kg/cm 2 . Thus, each of the annular members becomes the composite layer 3 by penetration of aluminium alloy. The piston 1 made thereby receives a solid solution treatment at temperature of 495° C. for five hours, and an artificial aging at temperature of 200° C. for five hours. Thereafter specimens are cut out of the piston 1, and their microstructures are observed.
FIG. 2 is a micrograph of the composite layer 3, in which a reaction layer of nickel with aluminium has been formed. FIGS. 3 and 4 show results of quantitative analyses of nickel and aluminium observed with an X-ray analyser incorporated in a scanning type electron microscope. It will be seen from the results that there exists a pure nickel layer at the central part of the composite layer, but there is formed a compound layer of nickel with aluminium at the surface of the composite layer, since the amount of aluminium increases with the approach of the surface of the composite layer.
FIGS. 5 to 7 show results of observing, with the X-ray analyser, the composite layer comprising the other annular member, at the surface of which the cemented chrome layer of 0.003 to 0.005 mm thickness is formed by means of chromizing. It will be seen from the results that aluminium has not penetrated the inner part of the annular member due to formation of the chrome layer.
In the meanwhile, when an internal combustion engine is operated for five hundred hours under the alternation of full-load maximum speed running and non-load running to expose pistons of the engine to cyclic heat loads, cracks are apt to be initiated in an interface layer of the piston body of aluminium alloy, and the composite layer, the volumetric ratio V f of which is more than 20%. In tests described hereinafter, the cyclic heat loads are substituted by the alternation of heating the piston at temperature of 500° C., and being suddenly immersed in the water of normal temperature in order to simplify the tests.
Two pistons using the annular members of porous metal (one is chromized, and the other is not chromized) are compared by impregnating method, and it is found that the porous metal and the piston body of aluminium alloy are completely separated n their interface which is formed in the piston using the annular member not to be chromized, whereas there is no crack initiated in the piston using the annular member to have been chromized.
Moreover, the two pistons are tested by an Ogoshi's abrasion testing machine. According to FIG. 8 which shows the test results, it is found that the wear resistance of the piston using the annular member to have been chromized is improved.
THE SECOND EMBODIMENT
Another embodiment in which the porous metal is formed by sintering will be hereinafter described. Three kinds of mixtures obtained by adding 5%, 10% and 20% Cr to mild steel powder are heated to produce three kinds of sinters, the volumetric ratio V f of which is 50%. Three kinds of composite layers formed by means of pressure casting receive a solid solution treatment at temperature of 495° C. for five hours, and an artificial aging at temperature of 200° C. for five hours. Then, the thickness of a compound of iron with aluminium is measured, and a relation of the thickness to chrome contents is shown in FIG. 9.
After three repetitions of an alternation heated at temperature of 500° C., and suddenly immersed in the water of normal temperature, it is found that the composite layer and the piston body of aluminium alloy are separated in their interface which is formed in the piston using the sinter which contains no chrome, whereas there is no crack initiate in the piston using the sinter which contains 10% Cr.
THE THIRD EMBODIMENT
An additional abrasion test is made for a composite layer based on a cellular metal of type 316 stainless steel (containing 16 to 18% Cr), the volumetric ratio V f of which is 50%. According to a test result shown in FIG. 8, the composite metal of this type is less in amount of abrasion than that based on the member of cellular nickel, since its volumetric ratio V f is larger.
Moreover, after three repetitions of the alternation heated at temperature of 500° C., and suddenly immersed in the water of normal temperature, it is found that there is no crack initiated in the interface of the composite layer and the base portion of aluminium alloy.
Various modifications are possible within the scope of the appended claims, for example, the porous metal may be plated with chrome, or chrome may be uniformly contained in the porous metal, if the amount of chrome is more than 10%. | A piston for internal combustion engines has a piston-ring groove which is strengthened with a composite layer based on porous metal which is embedded around the piston-ring groove. The porous metal contains at least more than 10% Cr, and the volumetric ratio of the porous metal is between 8 to 70%, so that even though the engine is put in action under high heat loads, no crack is initiated in the piston. | 5 |
INTRODUCTION AND BACKGROUND
The present invention relates to novel, single-component, humidity-curing caulking and sealing substances based on mercapto-terminated polymers and/or oligomers, so-called polysulfides.
Compositions known in the art are extendable at room temperature and cure into a rubber-elastic product; they are highly significant in industrial sealing and bonding applications wherein the bonding or sealing site must be elastic.
The materials are mostly used in the form of two-component systems; namely, the compound with terminal mercapto groups on one hand and the oxidizer on the other are packed and stored separately, and then the two components are mixed together shortly before use. For simpler and more reliable applications, more and more users increasingly desire single-component compounds; that is, mixtures that are capable of remaining stable in storage which simultaneously contain the polymer and the oxidizer and which will harden when put to use upon contact with the atmospheric humidity at room temperature.
Single-component systems based on such various oxidizers as alkaline earth peroxide, zinc peroxide, chromate, alkali permanganate or lead dioxide are known. Each such system offers specific advantages, but also incurs specific drawbacks. At present, the best industrial single-component caulking and sealing substances based on mercapto-ended compounds contain manganese dioxide as the oxidizer.
In their cured state, the compositions based on manganese dioxide are soft, permanently elastic substances nevertheless exhibiting high resiliency properties, and even when aging, they undergo no significant stiffening.
Regrettably, however, manganese dioxide does not permit the manufacture of white compounds. This drawback is a significant problem because the user, and in particular the architect, increasingly needs white, single-component sealants.
Corresponding single-component systems are already known whereby white substances can be prepared.
Illustratively U.S. Pat. No. 3,349,047 discloses white polysulfide masses using an alkaline earth peroxide, as a rule calcium peroxide, as a latent hardener. However such substances have been found to be too stiff after curing for many applications. The attempt already has been made to lower the elastic modulus of these substances by simultaneously employing monofunctional mercapto compounds as so-called chain stoppers. Problems arise, however, as this entails reduction of the internal strength and resiliency of the product.
Other white products are known. Thus, U.S. Pat. Nos. 3,275,579; 3,402,155; 3,499,864 and German OLS 18 00 982; 20 62 259 and 21 07 971 disclose white, single-component polysulfides containing zinc oxide or zinc peroxide as hardeners. While they differ always in the kind of activator used for the oxidizer, they nevertheless all share the same basic difficulty; that is, the cured substances harden further by undesired secondary reactions during aging and become too stiff. Moreover, this problem cannot be overcome by adding plasticizers to the composition.
SUMMARY OF THE INVENTION
Accordingly, one object of the invention is to create white single-component sealing compositions based on mercapto-terminated polymers and/or oligomers which upon contact with atmospheric humidity will cure to form a soft-elastic product having good recovery and where the aging of the cured compound so formed is free of significant undesired rigidification.
In attaining the above and other objects of the invention, one feature resides in providing single-component, humidity-curing sealing compositions on mercapto-terminated polymers and/or oligomers and latent hardeners which substances are substantially free of water, and containing an effective amount of an alkali perborate monohydrate to serve as the latent hardener. These compositions further contain barium oxide or strontium oxide as the accelerator in a sufficient amount to function as such. Fillers and plasticizers can also be present and are selected so that their aqueous slurries or aqueous extracts are neutral or alkaline. In addition, the compositions have a heavy-metal content for the total mixture which is less than 0.01%. In more detail it has been found that the content of the alkali perborate monohydrate should not exceed the stoichiometrically required amount by more than 3 g/100 g of the mercapto-terminated polymer and/or oligomer.
It has further been found that single-component sealing compositions are especially useful when they additionally contain 0.05-2% by weight of a complexing agent. Representative of such agents is an alkali salt of ethylene diaminotetraacetic acid or of nitrilotriacetic acid. Still further examples of the complexing agent is an alkali polyphosphate, as well as N-salicylidene ethylamine, N,N'-disalicylidene ethylene, N,N'-disalycidene triethylene diamine.
A further feature of the invention resides in a process for preparing the foregoing caulking and sealing compositions comprising intensively mixing together mercapto-terminated polymers and/or oligomers, and at least one of the group of fillers, plasticizers, and dessicants and, optionally, at least one of the group of solvents, coupling agents, pigments, complexing agents, accelerators, thixotropizing agents and retarders. The resulting mixture contains less than 0.01% of heavy metals. The mixing is carried out intensively under vacuum. The resulting dry mixture is then mixed with a paste that is independently made by mixing alkali perborate and barium oxide or strontium oxide with plasticizers.
Now it was found that a storage-stable mixture is achieved if an anhydrous, mercapto-terminated polymer and/or oligomer and, optionally, water-free fillers and additives and plasticizers are mixed with sodium- or potassium-perborate monohydrate and if this mixture is stored tightly against air and humidity, provided the individual components of the mixture are selected such that the content of heavy metals in the total mixture be less than 0.01%.
If the mixture does contain such plasticizers and fillers and additives that their aqueous slurries or their aqueous extracts are neutral or alkaline, then this mixture will form in air (of at least 50% relative humidity) a thin skin within about two hours and will cure fully within a few days. All liquid polymers on oligomers or mixtures of oligomeric and polymeric compounds with at least two terminal mercapto groups, for instance polysulfide polymers, polymeric thioethers and the like are suitable for the sealants of the invention. These polymeric and oligomeric are well known in the art.
Preferred liquid, mercapto-terminated components suitable for purposes of the invention are polysulfide polymers and oligomers of the general formula HS--(RSS) n --RSH, where n is between 5 and 25 and R denotes an alkyl-, alkylether- or alkylthioether-residue. The preferred residue R is a bis-ethyl-formal residue of formula:
--C.sub.2 H.sub.4 --O--CH.sub.2 --O--C.sub.2 H.sub.4 --.
Depending on the value of n and the size of the residue R, the molecular weight of these compounds will be between 500 and 8,000. These polysulfide compounds exhibit a room-temperature viscosity of 0.5 to 80 Pa.s.
Potassium and sodium perborate monohydrate can be used as alkali perborates. It was found that neither the tetra nor the tri-hydrate of the perborates nor sodium perborate anhydrite (oxoborate) are suitable for the substances of the invention. The amount of perborate used must correspond at least to the stoichiometric quantity required for the oxidation-formation of disulfide bridges from the mercapto-groups.
It is conventional industrial practice to add to such polymer mixtures an excess amounting to a multiple of the stoichiometrically required amount of oxidizer in order to enhance the rate of curing. It was found with respect to the present invention that the curing rate is much less dependent than heretofore expected on the excess of perborate. Instead attention must be paid to the fact that perborates, being susceptible oxidizers, easily dissociate. Accordingly, the quantity of the alkali perborate monohydrate used should not exceed the stoichiometrically required amount by more than 2 g/100 of mercapto-terminated polymer and/or oligomer.
In the manner of any other conventional sealant, the compositions of the present invention in addition to the polymer-hardener system also contain significant amounts of plasticizers, fillers and additives. These additional components (plasticizers, fillers and additives) are well known in the polysulfide sealant polymer art and any suitable ones can be used for purposes of this invention. The amounts of these ingredients to be used are also known in the art. Because these sealant composition are storage-stable mixtures which harden when exposed to humidity, they must be substantially free of water. In other words, the initial products must be essentially water-free and may be dried further when mixed (under vacuum). Ordinarily the plasticizers and liquid mercapto-terminated polymers or oligomers contain about 0.1-0.3% water. The water content of conventional, commercial, dry-stored fillers is in the range of 0.2-0.5%.
It was found in accordance with the present invention that the single-component system of the invention is not unduly susceptible to humidity, so that only moderate drying is required, which can be skipped, if commercial dessicants are used adequately. On the other hand the system of the invention also behaves in a generally known way, namely that storage stability will be better with lower mixture water content in the mixture. It was found that for a water content of 0.15-0.2% in the mixture the storage stability will be 4 weeks at 70° C. and the curing rate (23° C.; relative humidity 50%) is 0.5 mm/d.
The system of the invention is more sensitive to and reacts far more sharply to traces of heavy metals or their salts, which may be present in the mercapto-terminated polymers and additives, most of all in the fillers. The presence of traces of heavy metals tends to increase during mixing caused by the abrasion in the apparatus of the mixer.
Heavy metals in this sense are the metals of the 1st, 6th, 7th, and 8th secondary groups of the Periodic System of Elements, and in particular iron, cobalt, nickel, copper, vanadium, manganese, molybdenum or tungsten. Such heavy metals or heavy metal ions catalyze the decomposition of the perborate during the storage of the sealant and thereby reduce the storage stability of the composition. It was found that single-component caulking and sealing compounds based on mercapto-terminated polymers and/or oligomers wherein the alkali perborate monohydrate is present as a latent hardener may contain up to 0.01% of heavy metal. Only when the sum of the catalytically active heavy metals exceeds 0.01% will the storage stability be significantly reduced. While the substance then remains extrudable, it no longer cures when exposed to humidity.
When the components are being compounded together, individual components are permitted to contain a higher proportion of heavy metal provided the stated amount not be exceeded in the full mixture. This is significant in that many natural fillers contain heavy metals, in particular iron, from 0.02-0.04% and may indeed be used in the compositions of the invention as long as the total content of heavy metals is not exceeded.
It was found furthermore that adding 0.05-2% by weight of a complexing agent to the composition of the invention improves storage stability. In particular it was found that the proportion of heavy metal introduced by abrasion of the mixer apparatus may be neglected if a complexing agent is added. Effective complexing agents illustratively are alkali phosphates, the tetracetylethylene diamine, alkali salts of ethylene diamino-tetraacetic acid or nitrilo triacetic acid, or compounds of the N-salicylidene-ethylamine type or N-N'-disalicylidene-ethylene- or triethylene-diamine.
Only neutral of basic (alkaline) fillers and additives may be used in the invention. The measure of this acidity or alkalinity is the pH value of a 10% aqueous solution of a slurry as regards fillers and solid additives, or the pH value of an aqueous solution or extract as regards liquid additives. If the pH value of such a solution or slurry or extract is equal to or larger than 7, then the tested filler or additive may be used. There are a few exceptions in the form of retarders present in low amounts, for instance oleic acid, stearic acid, salicylic acid, citric acid, nitrilo-triacetic acid or ethylene-diamino tetraacetic acid, with the latter possibly also being simultaneously complexing agents and retarders. Such materials are well known in the art.
Suitable illustrative fillers are clays, dolomite, titanium dioxide, barytes, cellulose or polyamide powders. Useful solid additives are, illustratively, alkaline earth oxides or hydroxides, molecular-sieve powders, flowers of sulfur, bentonite and possibly pigments, reaction accelerators or stabilizers. Examples of liquid additives are solvents, plasticizers such as phthalates, benzoic-acid esters, hydrogenated ter-phenyls or polyethers of high boiling points, coupling agents or liquid stabilizers, dessicants or anti-precipitants.
The sealant compositions of the invention are prepared by intensively mixing conventional, mercapto-terminated polymers and/or oligomers, fillers, plasticizers, dessicants and possibly solvents, coupling agents, pigments, complexing agents, accelerators, retarders and thixotropic agents, which together contain less than 0.01% of heavy metals. Preferably the mixing operation is carried out in vacuum, drying taking place simultaneously in order to control moisture.
Independently of the above, alkali perborate and barium oxide or strontium oxide are made into a paste together with or separately from plasticizers and any further additives. The resulting paste is then mixed with the mixture containing the polymer and/or the oligomer.
As a result of the process described above, a white injectable caulking and sealing composition is then obtained, which will be storage-stable at room temperature for several months if air is excluded. Upon contact with humid air, the composition hardens within a few days into a rubber-elastic product. This cured sealant exhibits neither discoloration nor yellowing (DIN 18540) upon aging, nor does its elastic modulus significantly increase.
DETAILED DESCRIPTION OF INVENTION
The following examples serve to illustrate details of the invention.
EXAMPLE 1
The polymer used in Example 1 is a polysulfide with the average structure:
HS--(C.sub.2 H.sub.4 --O--CH.sub.2 --OC.sub.2 H.sub.4 --SS) .sub.22 --C.sub.2 H.sub.4 --O--CH.sub.2 --O--C.sub.2 H.sub.4 SH
and with about 0.5% crosslinking. Its mean molecular weight is 4,000 and its viscosity is about 35-45 Pa.s at 27° C. All quantitative data refer to parts or percent by weight.
A base mixture consisting of:
1000 parts polymer as defined above,
370 parts benzylbutylphthalate,
800 parts clay
350 parts titanium dioxide (alkaline),
5 parts sodium phosphate,
20 parts molecular-sieve powder 3A,
25 parts bentonite (Bentone SD-2),
5 parts toluene
are intensively mixed for 10 minutes in a planetary mixer in vacuum (600 Pa).
The mixture so prepared has a water content of 0.15% and a content in heavy metals of about 0.005%.
235 g of a paste are added to the above mixture, wherein the paste consists of the following components which are mixed in a triple roller blender
10 parts barium oxide,
30 parts sodium perborate monohydrate,
35 parts chalk,
160 parts plasticizer.
The thixotropic substance so prepared is divided into several portions used int he tests below:
(a) One portion is stored in a sealed tube at 70° C. After three week's storage, the substance is still suitable.
(b) One portion is extended to form test samples (15×15×50 mm) in accordance with DIN 18540 and is stored in the open at 23° C. and 50% relative humidity. After 100 minutes the substance exhibits a thin, tack free skin. After 1 day, the skin is 1 mm thick. After 30 days, the sample has cured into a rubber-elastic body.
The tests below are carried out by means of the samples cured under (b):
______________________________________Tensile stress at 100% elongation after curing: 0.2 N/mm.sup.2Recovery after 1 h elongation at 100%: 85%Modulus at 100 elongation and -20° C.: 0.26 N/mm.sup.2Modulus at 100% elongation after 0.3 N/mm.sup.2aging (DIN 18540):Discoloration after aging: none.______________________________________
EXAMPLES 2 and 3
Single-component sealant compositions with the mercapto-terminal polymers below are prepared in a manner similar to that of Example 1 except as noted:
Again white substances curing in humid air but storage-stable when air is excluded are obtained, which neither rigidify nor yellow with aging.
The mercapto-terminated polymer used in Example 2 is an oligomeric polysulfide with the average structure below:
HS--(C.sub.2 H.sub.4 --O--CH.sub.2 --O--C.sub.2 H.sub.4 --SS) --C.sub.2 H.sub.4 --O--CH.sub.2 --O--C.sub.2 H.sub.4 SH
having about 2% crosslinking. Its mean molecular weight is about 1,000 and its viscosity at 27° C. is 0.7-1.2 Pa.s.
Because of the higher content in SH groups, 470 g of the paste cited in example 1 are added.
The mercapto-terminated polymer used in Example 3 is a polymeric mercaptan with the average structure below: ##STR1## where R is an aryldiamide group.
Further variations and modifications of the foregoing will be apparent to those skilled in the art and are intended to be encompassed by the claims appended hereto.
German priority application No. P 38 09 104.6 is relied on and incorporated herein. | Single-component sealing compositions based on mercapto-terminated polymers and/or oligomers and latent hardeners are disclosed. The substances are substantially water-free and the hardeners are alkali perborate monohydrates. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
This is a Continuation-in-part of Ser. No. 612,546, filed Sept. 11, 1975, now abandoned, which in turn was a continuation of Ser. No. 455,362, filed Mar. 27, 1974, now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to lubricants for sewing threads and primarily to a nonflammable lubricant for use on a sewing thread employed in manufacturing nonflammable garments.
In the past, there have been a number of problems associated with the manufacture of nonflammable apparel, not the least of which related to the sewing thread employed in manufacturing such garments. Sewing threads generally require some type of lubrication in order to sew properly and to protect the thread from deteriorating due to the heat of friction created as the thread passes through the needle of the sewing machine. Most lubricants known in the trade today, however, are flammable and even the small amount of lubricant used, which may constitute from 2 to 10% of the total weight of the sewing thread, is so flammable that flammability of the seam occurs with the result that the original object, i.e. to have a nonflammable garment, is for all practical purposes destroyed.
This problem is further complicated by the fact that sewing threads currently in use for manufacturing nonflammable garments are generally of synthetic materials which exhibit thermoplastic properties. Such threads require even better lubrication than natural threads to ensure against needle burn.
It is therefore necessary and desirable in the manufacture of nonflammable apparel, to employ a sewing thread lubricated with an nonflammable lubricant. Such nonflammable lubricants known to the inventor in the past have been ordinary lubricants such as esters, mineral oils, paraffins, and other fatty acid derivities which, although flammable in themselves, can be rendered non-flammable by the addition of fire-retardant materials such as compounds of halogens and phosphorous. These materials are only make-shifts, however, and the actual lubrication component is itself still flammable. Furthermore, the nonflammable portion of the combination generally has substantial nonlubricating properties which limits the lubrication value of the composite lubricant, since the nonflammable portion often comprises as much as 8 or 10% of the total mixture.
In view of these difficulties with known lubricants, it was desirable to find a lubricant that had both lubricating and flame-retardant properties. It was discovered by this inventor that certain halogenated alkanes had these properties, i.e. superior lubricity and inherent nonflammability.
SUMMARY OF THE INVENTION
Broadly stated, this invention comprises a flame-retardant yarn or thread primarily for use in sewing flame-retardant apparel and the like. The flame-retardant capability of the yarn or thread is imparted primarily by a flame-retardant lubricant which consists of one or more mono- or di- halo alkanes having from ten to thirty carbon atoms, where the halogen is either chlorine or bromine.
BRIEF DESCRIPTION OF THE DRAWING
FIGS. 1A - 1F are graphs (the ordinates and abscissas of which are all the same) of the maximum char length of a seam sewn in various fabrics with the lubricated sewing threads of this invention;
FIG. 2 is a graph of the average residual flame time of a 100% polyester batiste fabric seamed with the lubricated sewing threads of this invention; and
FIG. 3 is a graph of the average residual flame time of a 100% nylon tricot fabric seamed with the lubricated sewing threads of this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
It was initially discovered by this inventor that brominated octadecane, and monobromo-octadecane in particular, had the desired properties for use as a flame-retardant lubricant for sewing threads.
Octadecane is a classic paraffin and is a lubricant in its own right because it happens to have those physical properties that make it a lubricant. It is a normal paraffin which is slick, like grease, but yet has certain other properties, such as the ability to disperse itself well along a thread structure and to be applied easily to thread to enhance the sewing capability of the thread. When bromine is attached to normal octadecane, the resulting compound becomes nonflammable because bromine is a well known fire retardant and its presence in almost any material in sufficient amounts will render an otherwise flammable compound nonflammable. It was also found that bromine in a compound with octadecane does not detract from the lubricating value of the latter, contrary to the addition of flame-retardant materials to other lubricants.
Thus bromo-octadecane can be applied to thread as is, with no further additions, from either a solvent application, the solvent being expected to evaporate before the possible introduction of flame, or from a hot melt by a kiss roll. Since octadecane melts at a fairly low temperature, it can be applied as a 100% compound from hot melt. In a preferred embodiment, the hot melt process was employed to topically apply the monobromo-octadecane to 100% polyester thread in an amount of 10% by weight of the thread. In general, the amount of lubricant applied depends on the type of sewing operation and is not critical although ranges of 2 to 10% by weight of the thread or yarn are common.
Subsequent experiments conducted by this inventor resulted in a finding that additional brominated or chlorinated alkanes, having a carbon chain length of from about 10 to about 30 carbon atoms, also had the desired lubricity and nonflammability properties. In the course of research conducted for this invention, the materials listed in TABLE I below were found to be particularly advantageous and useful.
TABLE I______________________________________LUBRICANT MATERIAL CODE______________________________________Mixed bromo alkanes C.sub.10 thru C.sub.22 Br 10/221, bromo decane Br 101, bromo dodecane Br 121, bromo tetradecane Br 141, bromo hexadecane Br 16mixed bromo hexadecane & octadecane Br 16/181, bromo octadecane Br 181, bromo eicosane Br 201, bromo docosane Br 22mixed brominated alkenes (avg. C.sub.24 - C.sub.28) Br 24/281, 10, dibromo decane Br.sub.2 10-A1, 2, dibromo decane Br.sub.2 10-Bmixed dibrominated alkenes Br.sub.2 20/24 (avg. C.sub.20 - C.sub.24)mixed dibrominated alkenes Br.sub.2 24/28 (avg. C.sub.24 - C.sub.28)1, chloro dodecane Cl 121, chloro octadecane Cl 181, chloro docosane Cl 22mixed part. chlorinated alkenes Cl 24/28 (avg. C.sub.24 - C.sub.28)1, 10, dichloro decane Cl.sub.2 10______________________________________
Among many others, one of the best methods for the preparation of alkyl bromides, albeit expensive, is the reaction of hydrobromic acid with the alcohol of the required alkyl compound. By this means, for example, octadecyl bromide can be obtained by the direct reaction of hydrobromic acid with octadecanol; this, in fact, is how much of the material used in the research for this invention was made.
A second method, more attractive economically and from the standpoint of obtaining raw materials more easily, is the bromination with pure bromine of an unsaturated material. Thus, for example, bromine will react directly with normal octadecene to produce both primary and secondary octadecyl bromide. The relative proportion of the primary and secondary bromide can be controlled by the reaction conditions.
Materials used in the research for this invention were made by both these methods. The raw materials used in these methods are available commercially; the alkyl halides used in this invention are manufactured by, for example, Humphrey Chemical Company, Devine Street, North Haven, Conn. 06473.
The actual composition of mixed olefins is not always consistent, but generally it is a distribution of carbon chain lengths from very small amounts of the lower number through larger amounts of the principal numbers into smaller amounts of the larger numbers. For practical purposes, though, the mixed brominated alkenes simply result in mixed alkyl halides. The mixed bromo alkanes C 10 through C 22 (Br 10/22) was made from pure materials to show that a mixture of a number of various chain length halides also results in a usable material.
All of the lubricants listed in Table I can be applied to a sewing thread in the same manner as described above with respect to monobromo-acetadecane.
Probably the most definite indication that these materials may be used as thread lubricants is in the actual application of the materials to 100% polyester spun sewing thread, that product being used to make seams. One of the measures of a lubricant for sewing thread would be the coefficient of friction produced by that thread as it passed over metal. Table II shows the amount of finish which was applied to a thread, and the coefficient of friction produced by passing that thread over a metal pin. Three known thread lubricants, Proctol 4101 (P4101), paraffin wax (wax), and dimethyl polysiloxane (SIL), were tested and compared with the flame-retardant lubricant materials of this invention. Proctol 4101, which is a commercially available material for threads suitable for flame-retardant sewing, and has been used by a large segment of the industry, is included as a control to show that the alkyl halides of this invention are equal to that material which is already used commercially. All of the coefficients of friction of the alkyl halides of this invention are in a range which would make acceptable lubricants; the new materials are, in many cases, better lubricants. To show that these materials may be applied from normal kiss roll applications in industrial practice, the viscosity of the materials are also shown in Table II.
TABLE II______________________________________Amount of CoefficientFinish Applied of VISCOSITYCode To Thread Sample Friction CPS Temp (° C)______________________________________P4101 10.9% 0.130 19.0 25wax 17.0 0.098 17.0 190SIL 8.8 0.119 359.7 25Br 10/22 3.4 0.082 11.5 25Br 10 10.6 0.111 8.0 25Br 12 11.9 0.101 11.0 25Br 14 13.2 0.098 12.0 25Br 16 6.8 0.102 12.5 25Br 16/18 11.8 0.122 12.5 25Br 18 10.2 0.095 2.4 100Br 20 9.3 0.087 3.2 100Br 22 11.4 0.162 3.9 100Br 24/28 10.6 0.074 6.2 100Br.sub.2 10-A 11.6 0.123 10.0 25Br.sub.2 10-B 11.8 0.136 11.0 25Br.sub.2 20/24 12.2 0.130Br.sub.2 24/28 12.7 0.136 7.2 100Cl 12 11.0 0.128 12.0 25Cl 18 12.5 0.107 16.0 25Cl 22 9.7 0.160 4.1 100Cl 24/28 11.9 0.145 6.0 100Cl.sub.2 10 11.8 0.127 15.0 25______________________________________
In order to demonstrate that the materials of this invention do indeed contribute to the nonflammability of seams, sewn according to the Department of Commerce test number FF-3-71, seams were made in five different types of fabric used in commerce, and were subjected to char length (CL) and residual flame time (RFT) tests. A description of the flammability test method specified in DOC FF-3-71 can be found in Jakes et al, "A Primer on Seam Flammability," Bobbin, December, 1974. All of the seams were Stitch Type 503 and Seam Type SSal (described in Federal Standard No. 751a). Also, a fabric was made by knitting the sewing thread to demonstrate its nonflammable properties. The results of all of these tests can be seen in Table III. The test fabrics were:
A. 100% polyester batiste
B. Flame retardant 100% cotton flannel
C. Flame retardant acetate brushed knit
D. 100% dynel knit
E. 100% nylon tricot
F. Self fabric knitted from thread
TABLE III__________________________________________________________________________A B C D E FLubricant CL RFT CL RFT CL RFT CL RFT CL RFT CL RFT__________________________________________________________________________P4101 3.5 2.5 2.4 0.0 2.4 0.0 1.8 0.0 2.7 0.0 3.1 0.0wax *BEL 25.5 2.4 0.0 3.2 0.0 1.5 0.0 3.0 20.5 3.3 0.0SIL BEL 85.0 2.0 0.0 3.3 0.0 1.6 0.0 2.9 27.0 2.9 27.0Br 10/22 2.7 9.0 1.8 0.0 3.4 0.0 1.5 0.0 2.6 7.0 3.0 0.0Br 10 3.5 8.0 2.3 0.0 3.8 0.0 1.8 0.0 2.9 0.0 3.3 0.0Br 12 2.6 2.0 2.1 0.0 3.7 0.0 1.8 0.0 3.2 0.0 3.4 0.0Br 14 3.0 1.0 1.8 0.0 2.8 7.0 2.0 0.0 2.9 0.0 2.7 0.0Br 16 2.8 2.0 1.9 0.0 2.9 0.0 2.2 0.0 2.8 3.0 3.1 0.0Br 16/18 3.2 13.0 1.5 1.5 2.5 0.0 1.5 0.0 3.1 6.5 2.4 0.0Br 18 2.6 1.0 1.5 0.0 2.3 3.0 1.4 0.0 3.3 10.0 3.3 0.0Br 20 2.4 2.0 1.9 0.0 3.4 1.5 1.7 0.0 2.5 0.0 2.6 0.0Br 22 3.0 0.0 2.2 0.0 2.5 0.0 1.5 0.0 2.8 0.0 2.9 0.0Br 24/28 2.7 1.5 2.1 1.0 2.8 1.0 1.8 0.0 3.0 1.5 2.9 0.0Br.sub.2 10-A 3.2 8.0 2.5 2.0 3.0 2.0 1.6 0.0 3.0 0.0 3.0 0.0Br.sub.2 10-B 3.0 0.0 3.0 0.0 2.8 0.0 1.7 0.0 2.9 0.0 3.1 0.0Br.sub.2 24/28 2.8 0.0 3.0 0.0 3.6 0.0 1.8 0.0 4.2 41.0 2.9 0.0Cl 12 3.2 9.0 2.3 1.5 3.2 0.0 1.9 0.0 3.3 0.0 2.8 0.0Cl 18 3.4 13.5 2.5 1.5 3.2 17.5 1.6 0.0 2.9 3.0 3.1 0.0Cl 22 2.1 1.5 2.6 2.0 2.9 29.0 1.7 0.0 2.8 13.0 3.1 0.0Cl 24/28 3.2 0.0 BEL 0.0 3.0 0.0 2.2 0.0 3.5 0.0 3.1 0.0Cl.sub.2 10 3.6 17.0 2.3 2.0 3.0 2.0 1.8 0.0 3.1 2.0 3.0 0.0__________________________________________________________________________ CL = CHAR LENGTH (inches) RFT = RESIDUAL FLAME TIME (seconds) *BURNED ENTIRE LENGTH
In the Department of Commerce test, one of the reasons for failure is the char length. Normally, out of a five specimen burning, no char length can be greater than the entire length of the sample, which is 10 inches, nor can the average of the five be greater than 7 inches. Therefore, the average char length can be used as an indication of the effectiveness of nonflammability of thread finishes. It can be seen from the graphs of FIGS. 1A-F that, in most of the fabrics tried, the thread is of such little importance that it has no pronounced effect on seam flammability. However, in the 100% nylon tricot, and 100% polyester batiste, the lubricants which do not have nonflammable properties (i.e., wax and SIL) exhibit a detrimental effect on the flammability of the seam.
Another indication of flammability under DOC FF-3-71 is residual flame time, which is the actual time that the flame continues in the drip after the removal of the ignition. In order to demonstrate the effectiveness of the flame-retardant lubricants of this invention, FIGS. 2 and 3 show the average residual flame times for the two fabrics already demonstrated to be critical. These clearly indicated that waxy materials, or silicone, which are commonly used, are unsatisfactory for use as flame-retardant lubricants for threads seaming these materials.
At this point, it is important to point out that, in many fabrics, the nonflammable properties of the fabric itself are sufficient to counteract any flammability of the thread used in the seaming of these fabrics. This means that, for many purposes, threads of any description would be found suitable, at least statistically. However, in critical fabrics, the use of a thread with nonflammable lubricant is indicated, and of course, this lubricant is always indicated when sewing garments of a nonflammable nature, since the influence of thread and seams is never clear-cut enough to positively determine beforehand that a thread of a flammable nature may be used.
It should also be pointed out that it is well-known in the trade, especially after being demonstrated in work done by Spivak et al at the University of Maryland, on the seaming of nonflammable garments, that the actual type of seam, the density of the resulting seam, the type of stitch and the density of thread in the stitch, also effect flammability. There are other types of seams in which thread is even more critical, those being seams in which the proportion of thread to fabric becomes very large, such as a "flatlock." In these cases, the use of a sewing thread treated with a flame-retardant lubricant may be particularly important.
It is to be understood that various modifications in the structural details of the preferred embodiment described herein may be made within the scope of this invention and without departing from the spirit thereof. It is intended that the scope of this invention shall be limited solely by the hereafter appended claims. | A flame-retardant yarn or thread containing a flame-retardant lubricant which consists of one or more mono- or di-chloro alkanes or one or more mono- or di-bromo alkanes, wherein the alkanes have ten to 30 carbon atoms. | 3 |
[0001] This application claims the benefit of U.S. Provisional Application Ser. No. 61/225,158, filed on Jul. 13, 2009, entitled “Corner Hanger,” which application is hereby incorporated herein by reference.
TECHNICAL FIELD
[0002] This invention relates generally to building structures and, more particularly, to interchangeable devices to ornament framing structures.
BACKGROUND
[0003] Generally, framing structures, such as doors and windows, have a decorative piece of trim nailed into place. The trim services to cover gap between the wall and the framing structure, thereby providing a more aesthetically pleasing appearance. While the trim is more aesthetically pleasing, many times it is desirable to provide different appearances.
[0004] One solution to this is to replace the trim as desired. This solution, however, is difficult and time-consuming. Replacing the trim requires the trim to be cut to the precise size, nailing the trim in place, caulking the joints, and painting the trim and wall surfaces.
[0005] Another solution is placing a wallpaper-type border around the trim. This solution involves affixing a decorative strip with an adhesive. While this solution provides a decorative border, changing or removing the wallpaper-type border may also be difficult and time-consuming as the wallpaper-type border is affixed by glue.
[0006] Yet another solution is to paint a decorative scene directly on the wall itself around the trim. This solution is time-consuming to put up in the first place as well as replacing it. This solution may also be expensive if it is necessary to hire a painter to create the painting.
SUMMARY
[0007] These and other problems are generally reduced, solved or circumvented, and technical advantages are generally achieved, by embodiments of the present invention, which provides interchangeable devices to ornament a framing structure.
[0008] In an embodiment, interchangeable corner hanger devices to ornament protruding corner structures are provided. The interchangeable corner hanger devices include a horizontal portion and a vertical portion. The horizontal portion is designed to rest on an exposed edge of the corner structure, and the vertical portion is designed to hang over the corner structure and rest against a wall upon which the corner structure is attached. The vertical portion has a length sufficient to stabilize the corner hanger without the use of other adhesives or attachments.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] For a more complete understanding of the present invention, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
[0010] FIGS. 1-15 illustrate embodiments of corner hangers having various shapes.
DETAILED DESCRIPTION
[0011] The making and using of the presently preferred embodiments are discussed in detail below. It should be appreciated, however, that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are merely illustrative of specific ways to make and use the invention, and do not limit the scope of the invention.
[0012] FIG. 1 illustrates an interchangeable corner hanger 102 placed on a corner structure 104 protruding from a supporting wall 103 in accordance with an embodiment, wherein the corner hanger 102 is shaped as a dog such that the leg of the dog hangs over a corner of the corner structure 104 to provide stability. In this embodiment, the corner structure 104 is illustrated as trim around a doorway for illustrative purposes only. In other embodiments, the corner structure 104 may be trim around a window, a mirror, a light plate switch, or the like. The corner hanger 104 may be formed of any suitable material, such as wood, plastic, or the like, and be of any suitable thickness. In an embodiment in which the corner structure 104 is trim around a doorway, the corner hanger 102 is formed of wood having a thickness of about one-eighth of an inch.
[0013] The corner hanger 102 has a horizontal portion 106 and a vertical portion 108 . The horizontal portion 106 has one or more contact points 107 designed to rest upon an upper surface 112 of the corner structure 104 . While the embodiment illustrated in FIG. 1 illustrates that substantially all of a bottom surface 110 of the corner hanger 102 contacts the upper surface 112 of the corner structure 104 , in other embodiments, portions of the bottom surface 110 may have multiple contact points such that not all of the bottom surface 110 contacts the upper surface 112 of the corner structure 104 .
[0014] The vertical portion 108 extends over a corner of the corner structure 104 and provides stability and balance to the corner hanger 102 , allowing the corner hanger 102 to stay in place without need of fasteners, such as glue, Velcro, nails, screws, or the like. By extending a portion of the corner hanger 102 over the corner of the corner structure 104 in the manner illustrated in FIG. 1 , the center of gravity is effectively lowered relative to the upper surface 112 of the corner structure 104 . It has been found that in this manner, it allows the corner hanger 102 to remain in place, even over a door trim with the door being repeatedly slammed shut. Without the vertical portion 108 , the center of gravity would be considerably higher and provides a much less stable structure. In an embodiment, the center of gravity is lower than about two inches above the upper surface 112 of the corner structure 104 . For example, in an embodiment, the center of gravity is lower than the upper surface 112 of the corner structure 104 .
[0015] The vertical portion 108 may further rest against the supporting wall 103 , such that the supporting wall 103 provides an anti-tipping effect. As can be appreciated, a structure comprising only the horizontal portion has a fulcrum or point of rotation along a joint between the contact points 107 and the upper surface 112 of the corner structure 104 and, as a result, could easily tip over. The vertical extension of the vertical portion 108 , however, restricts the tipping motion, because as the horizontal portion 106 tips, the vertical portion 108 is “pushed into” the wall. In this manner, as the wall prevents the vertical portion 108 from rotating into the wall, the horizontal portion 106 is prevented from tipping over.
[0016] It should be appreciated that the larger the vertical portion 108 is relative to the horizontal portion 106 , the more stable the corner hanger 102 may be. Further, it should be noted that the vertical height of the horizontal portion 106 also affects the stability, wherein the greater the vertical height of the horizontal portion 106 , the less stable. Accordingly, the greater the vertical height of the horizontal portion 106 , it may be desirable to increase the size of the vertical portion 108 .
[0017] Embodiments of the corner hanger 102 may be easily replaced to provide different themes to a room. For example, seasonal themes may be used for Valentine's Day, Easter, Christmas, Halloween, Fourth of July, Thanksgiving, and the like, throughout the year.
[0018] FIGS. 2-11 are examples of types of corner hangers that may be used in accordance with various embodiments. Referring first to FIG. 2 , the corner hanger 102 has a shape of a snake, wherein the head of the snake is elevated above the upper surface 112 of the corner structure 104 . Further, FIG. 2 illustrates that the entirety of the vertical portion 108 does not necessarily rest against the corner structure. For example, the curve of the snake around the corner of the corner structure 104 extends past the corner, thereby leaving a gap between the corner structure 104 and the corner hanger 102 . The lower portion of the snake rests against the trim, thereby aiding in providing a solid, stable base.
[0019] In FIG. 3 , the corner hanger 102 has a shape of a sleeping baby, wherein a head and body of the sleeping baby rests on the upper surface 112 of the corner structure 104 , and feet of the sleeping baby hang over the corner of the corner structure 104 to provide stability.
[0020] FIG. 4 illustrates the corner hanger 102 shaped as a boy with angel wings. Similar to the embodiment illustrated in FIG. 3 , the legs hang over the corner of the corner structure 104 to provide support. FIG. 4 also illustrates an embodiment in which multiple contact points 107 are used for the interface between the horizontal portion 106 and the corner structure 104 .
[0021] FIG. 5 illustrates the corner hanger 102 shaped as an elephant in which a trunk of the elephant hangs over the edge to provide support. FIG. 5 also illustrates that embodiments may be designed such that the vertical portion 108 does not directly contact portions of the corner structure 104 . As illustrated below with reference to FIGS. 12 and 13 , in some embodiments at least a portion of the vertical portion 108 contacts the corner structure 104 .
[0022] FIGS. 6 and 7 illustrate the corner hanger 102 as a bear and a girl, respectively, with angel wings. Similar to the embodiment illustrated in FIG. 4 , the legs hang over the corner of the corner structure 104 to provide support.
[0023] FIGS. 8 and 9 illustrate various corner hangers of a cat, wherein FIG. 8 is illustrated to hang from the right side and FIG. 9 is designed to hang from the left side. It should also be noted that the vertical portion of the cat in FIG. 8 comprises the back legs of the cat, while the vertical portion of the cat in FIG. 9 comprises the tail.
[0024] FIGS. 10 and 11 illustrate that embodiments of the corner hanger 102 may use shapes or configurations other than animals or people. For example, in the embodiment illustrated in FIG. 10 , the word “Peace” is used, wherein the “P” hangs over the edge to provide stability. FIG. 10 further illustrates that a flat edge is not necessarily present to rest against the top surface of the corner structure 104 . FIG. 11 illustrates a similar embodiment in which the corner hanger 102 is shaped as the word “Joy,” wherein the “y” hangs over the corner of the corner structure 104 . In these embodiments, the corner hanger has multiple points of contact.
[0025] FIG. 12 illustrates the corner hanger 102 shaped as a giraffe. In this embodiment, the corner hanger 102 is designed such that the vertical portion 108 of the corner hanger 102 contacts the corner structure 104 to keep the corner hanger 102 from rotating and swinging off of the corner structure 104 . In particular, the single, relatively small, contact point 107 of the giraffe acts as a point of rotation aided by the weight of the giraffe's body hanging over the corner of the corner structure. The giraffe rotates thus until the one or more portions of the vertical portion 108 of the giraffe contacts the corner structure 104 .
[0026] FIGS. 13-15 illustrate embodiments of the corner hanger 102 wherein the horizontal portion 106 is small compared to the overall size of the corner hanger 102 . For example, in FIG. 13 , the horizontal portion 106 comprises only a hand of a monkey, while remaining portions of the body of the monkey hang over the corner of the corner structure 104 . Similarly, in FIG. 14 , the dog is hanging by only the lower portions of the back legs of the dog, and in FIG. 15 , an elf hangs only by the lower legs.
[0027] In embodiments such as those illustrated in FIGS. 12-15 , the center of gravity is sufficiently close to the vertical surface of the corner structure 104 such that the corner hanger 102 does not rotate off the corner structure 104 . For example, in an embodiment the center of gravity is within two inches of the vertical surface of the corner structure 104 .
[0028] Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, and composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed, that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps. | In an embodiment, an interchangeable corner hanger to ornament framing protruding corner structures is provided. The interchangeable corner hanger includes a horizontal portion and a vertical portion. The horizontal portion is designed to rest on an exposed edge of a corner structure, and the vertical portion is designed to hang over the corner of the corner structure and rest against a wall upon which the trim is attached. The vertical portion has a length sufficient to stabilize the corner hanger without the use of other adhesives or attachments. | 8 |
This is a continuation of application Ser. No. 08/226,632, filed Apr. 12, 1994, now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to dissipation of thermal energy generated by electronic devices. More particularly, it relates to miniaturized heat sink apparatus for dissipating thermal energy generated by semiconductor devices and the like into the surrounding environment and to methods of making such apparatus.
U.S. Pat. No. 4,884,331--Hinshaw describes heat sinks which have been successfully Used for semiconductor device packages. These heat sinks are generally quite small and are primarily designed for computer applications. Fans have been used in conjunction with such heat sinks to form miniature thermal cooling modules.
Other prior art apparatus generally comprises a plurality of thin parallel fins or pins longitudinally bonded within a rectangular housing. The housing may also comprise a compression chamber for reducing air into the fin section in order to provide a uniform flow of air through the fins.
A pin fin heat sink must be machined and requires several minutes per part to produce. Therefore, the labor cost for a pin fin heat sink is high. It is an object of the present invention to provide a stamped and formed heat sink which is considerably less expensive than a pin fin heat sink.
SUMMARY OF THE INVENTION
In accordance with the present invention, a heat sink has a face for attachment to an electronic device and stamped and formed heat dissipation elements extending from the edges of the base perpendicular to the base. The heat dissipation elements have openings for the flow of air through the body of the heat sink. The heat sink can be used either with a fan or in open air flow.
The heat dissipation elements are formed for an interference fit with a fan for forcing air through the heat dissipation elements. The fan can be snapped into the body of the heat sink for ease of assembly. Because it can be assembled without the use of screws or other attachment devices, the heat sink is more economical of manufacture. In the heat sinks of the prior art described above, screws are used to attach the fan to the heat sink, sometimes necessitating machining away pin fins and drilling and tapping a hole in the base of the heat sink for screw attachment.
The heat sink of the present invention also has the advantage that, in case of fan failure in the field, a new fan can be easily snapped into the old heat sink without the use of tools.
The stamped and formed heat sink of the present invention is considerably cheaper than a pin fin heat sink because it can be made in a progressive die in a punch press. The presses can be run from between 60 and 120 strokes per minute. A part is produced with every stroke. On the other hand, a pin fin heat sink must be machined and requires several minutes, per part, to produce. Therefore, the labor cost for the pin fin heat sink is considerably higher than that of the present invention. Also, more material is used in a pin fin heat sink than in a stamped and formed heat sink of the present invention.
SHORT DESCRIPTION OF THE DRAWINGS
FIG. 1 shows one embodiment of a heat sink of the present invention;
FIG. 2 shows an embodiment with plastic snap clips on the fan body to secure the fan to the body of the heat sink;
FIG. 3 shows an embodiment in which the fan snaps in from the side of the heat sink;
FIG. 4A is a top plan view of a heat sink;
FIGS. 4B, 4C and 4D are back, side and front elevation views, respectively, of the heat sink of FIG. 4A;
FIG. 4E is a view on the section 1--1 of FIG. 4A;
FIG. 5 shows the heat sink of the present invention with a pin grid array and a socket;
FIG. 6A is a top plan view of another embodiment of the invention;
FIG. 6B is a side view of FIG. 6A;
FIG. 6C is a section on the line 2--2 of FIG. 6A;
FIG. 6D is a view on the line 3--3 of FIG. 6A;
FIG. 7A shows a top view of the die section of a progressive die and punch; and
FIG. 7B shows a progression strip of the heat sink being formed from coil stock.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, a heat sink comprises a thermally conductive body with a base 11. The underside of the base 11 is a face adapted for attachment to an electronic device package.
Stamped and formed heat dissipation elements 12, 13 and 14 extend from the edges of the base perpendicular to the base. These elements have openings 15 for the flow of air into the body of the heat sink. The heat dissipation element 16 has a height which is lower than the heat dissipation elements 12-14.
A fan 17 forces air through the heat dissipation elements toward the base 11. The heat dissipation elements 12-14 are formed for an interference fit with the fan 17 so that the fan can be snapped into the body of the heat sink.
Fingers 18, or detents, are formed from slots in the heat dissipation elements 12-14. The fingers 18 have beveled leading edges. As the fan is snapped into the body from the top, the beveled leading edges follow the contour of the fan. The fingers 18 are deformed, and they snap back into position to securely hold the fan in the body of the heat sink.
FIG. 2 shows an embodiment with plastic snap clips 19 on the fan body. The clips 19 at the rear of the fan pop into the holes 20 and the clips 19 at the front of the fan snap under the fingers 21 at the front of the heat sink body.
In FIG. 3, the fan 17 snaps into the body from the front. The fingers 22 are bent in to fit the curvature of the fan housing. The ledge 23 on the fan slides under the fingers 22 to prevent the fan from being lifted out. The curved part of the fan springs the fingers outward and the fingers fit against the fan. In the embodiments described so far, there is an interference with other items on top of the CPU. Therefore, the heat sink must be smaller than the fan in that area. Normally, the heat sink would be as large or larger than the fan.
FIGS. 4A-4E show an embodiment in which portions 24 and 25 of heat dissipation elements 12 and 14 are bent into the center of the body at an angle of 45°. These portions 24 and 25 provide better thermal performance and direct air swirling within the heat sink. The portions 24 and 25 form ledges on which the fan rests. The front edge of the fan rests on the top edge of the heat dissipation element 16 which has a lower height.
FIG. 5 is an exploded view of a heat sink in accordance with the present invention, with a pin grid array 26 and a socket 27 of the type supplied by AMP, Inc. A spring attachment 28 hooks under the catch 29 on the socket to secure together the package. Other means of attaching the heat sink to the electronic package can be used. A spring of the type shown in the publication AMP, Inc. Low Insertion Force (LIF) PGA socket for Intel 486DX2 CPU device Supplement 65238, issued April 1992, can be used to secure the stamped and formed heat sink to a socket. A single leaf of the spring can be used for attaching. The advantage of attaching the heat sink to ears on the socket is that the entire assembly of heat sink, microprocessor, and socket is held together. As heat sinks become larger and have more mass, heat sinks sometimes need to be assembled to the socket to pass shock and vibration tests.
FIGS. 6A, 6B, 6C and 6D show another modification of the stamped and formed heat sink which includes gull wing heat dissipation elements 30 and 31 extending from base 11. This heat sink is made by the die of FIG. 7A. A clip 32 secures the heat sink to a transistor.
FIG. 7A is a top view of a progression die which is used to form the heat sink of FIG. 6A-6D. FIG. 7B shows a progression strip for forming the heat sink of FIGS. 6A-6D. The die section of FIG. 7A has twelve stations which correspond with the twelve sections of the progression strip shown in FIG. 7B. The progression strip matches up with holes and slots in the die section of FIG. 7A. The top portion, or punch section, of the die is not shown. Upon each closure of the punch section on the die section, a stamped and formed heat sink is formed and the strip is advanced by one station. Stations numbers 4, 5 and 6 bend the clip 32 over. Station No. 1 forms the gull wings 33 and 34 and cuts the part away from the strip of coil stock. Sheets and strips of thermally conductive stock can also be used to form the heat sink.
While a particular embodiment of the invention has been shown and described, various modifications are within the true spirit and scope of the invention. The appended claims are, therefore, intended to cover all such modifications. | A stamped and formed heat sink has a thermally conductive body including a base having a face adapted for attachment to an electronic device package. Stamped and formed heat dissipation elements extend from the edges of the base perpendicular to the base. The heat sink is formed in a progressive punch and die press so that a heat sink is produced on every stroke. | 7 |
BACKGROUND OF INVENTION
1. Field of the Invention
The present invention generally relates to a woven fabric for use in a paper, cellulose or board manufacturing machine that is seamed by interlocking loops along each of two fabric edges to form an endless woven fabric.
2. Description of the Prior Art
As will be known to those skilled in the art, papermaking machines generally include three sections which are referred to as the forming, press and dryer sections. A felt is generally employed to transport the formed, wet sheet through the press and dryer sections of the papermaking equipment. The felt must be particularly adapted to specific conditions encountered in papermaking.
Typically, such felts include a supporting base, such as a woven fabric, and a paper carrying or supporting layer fixed to the base. The paper carrying or supporting layer is generally softer and smoother than the base layer. The support layer is often a non-woven batt material which has been affixed to the base and has homogeneous characteristics as to permeability, compaction and drainage. Slight irregularities or imperfections in the support layer are undesirable in virtually all papermaking operations. Inconsistencies in the felt thickness, gauge or weight can cause undesirable vibrations during operation of the equipment.
In press fabrics, the batt material is often anchored to a base fabric which is provided with end loops to join the fabric. Many of these fabrics are woven as endless loops in patterns that provide the seaming loops at each end of the fabric. Standard woven loop base constructions frequently include two layers of weft yarns in a low density, symmetrical construction. However, these base fabrics typically provide limited batt anchorage and sheet support due to low surface contact area. This necessitates the use of a third, topical laminate structure, having a higher density of weft or warp yarns. The laminate is generally bound to the primary base by means of filament entanglement during a post weaving needling process. This process can be costly and time consuming.
Another problem associated with endlessly woven seamed fabrics is seaming of the fabric. Standard endlessly woven loop seam products are made with stacked weft pairs, formed by looping around a forming monofilament. A common problem associated with this type of loop formation is non-uniform loop alignment, both in the vertical and horizontal axis, when the forming wire is removed. This misalignment creates a seam that is difficult to mesh.
FIGS. 1-3 show representative loop misalignments experienced in common prior art endlessly woven seams. Generally, as a loom weaves the loops in an endless weave construction, it naturally offsets the returning weft position slightly from its outgoing weft position. It is possible to maintain the weft yarns in a stacked relationship throughout the fabric through the balanced weave of the warp yarns. However, the last warp yarn 2 does not have a balancing yarn on one of its sides and, therefore, an unbalanced crimp force is applied to the weft yarns in the loop area, as shown by the arrows in FIG. 2 . As a result, the two weft yarn passes which form each loop are not balanced by warps and the loops tend to be misaligned.
A similar misalignment of the loops occurs in flat woven fabrics wherein the tie back portion of the warp yarn is offset from the outgoing portion of the warp yarn during loop formation.
The present invention combines two high density structures during the weaving process, with the primary base construction being used to form endless type seam loops. This is achieved by means of unique weave patterns that stitch in a higher density weft layer of yarns to provide greater batt anchorage and maintain a stacked weft arrangement in the base for uniform, vertically aligned, loop formation.
SUMMARY OF THE INVENTION
The present invention generally relates to a papermaker's fabric of a type having a system of primary machine direction yarns which form seaming loops at each end of the fabric. The fabric also includes a system of secondary machine direction yarns and a system of cross-machine direction yarns. The cross-machine direction yarns are interwoven with the primary and secondary systems of machine direction yarns in a weave pattern that provides adjacent balancing yarns that maintain the seam loops in substantially vertical alignment. A method of forming the papermaker's fabric is also provided.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top plan view of prior art end loops.
FIG. 2 is an elevation view of the prior art end loops along the line 2 — 2 in FIG. 1 .
FIG. 3 is a side elevation view of the prior art end loops along the line 3 — 3 in FIG. 1 .
FIG. 4 is a schematic perspective view of a portion of the fabric according to the present invention.
FIG. 5 is an end elevation view of a portion of the fabric according to the present invention.
FIG. 6 is a schematic view showing the weaving progression of the weft yarns.
FIG. 7 shows a position of the weft yarn after the fabric of FIG. 6 is removed from the loom and opened.
FIG. 8 is a cross section taken along the line 8 - 8 in FIG. 6 .
FIG. 9 is a weave pattern diagram for the preferred embodiment of the base fabric of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The preferred embodiment will be described with reference to the drawing figures wherein like numerals represent like elements throughout.
Referring to FIGS. 4 and 5 the preferred fabric 100 generally comprises a base fabric 110 with batt material 112 attached thereto. The base fabric 110 comprises three layers of machine direction (MD) yarns 114 , 116 and 118 interwoven with a system of cross-machine direction (CMD) yarns 120 . MD layers 114 and 116 are woven in stacked pairs and form seam loops 122 at each end of the base fabric 110 . The third layer MD yarns 118 extend above MD layers 114 and 116 and are substantially parallel thereto. In the preferred embodiment, two third layer MD yarns 118 are provided for every pair of stacked MD yarns 114 and 116 .
The fabric 110 is preferably endless woven using a two shuttle loom. The first shuttle weaves the lower and intermediate MD layers 114 and 116 and the second shuttle weaves the upper MD layer 118 . As shown in FIG. 6, the base fabric 110 is woven on the loom doubled over upon itself. That is, the base fabric 110 is woven with an upper weaving layer 130 and a lower weaving layer 132 which are opened after weaving as shown in FIG. 7 to provide a base fabric 110 which is approximately twice the length of the fabric on the loom. Reference to position of the yarns relative to one another is the relative position after the fabric is opened, unless otherwise specified.
The CMD yarns 120 interweave with all three MD yarn layers 114 , 116 and 118 . As shown in FIGS. 5 and 8, the CMD yarns 120 preferably include two CMD subsystems 120 a, b. Upper CMD subsystem yarns 120 a weave exclusively with the middle and upper MD layers 116 and 118 and the lower CMD subsystem yarns 120 b weave exclusively with lower and middle MD layers 114 and 116 .
The base fabric 110 has a weave which preferably repeats on sixteen (16) CMD yarns and thirty-two (32) MD yarns. As shown in FIG. 8, CMD yarns 1 , 4 , 5 , 8 , 12 , 13 and 16 make up the upper CMD subsystem 120 a and CMD yarns 2 , 3 , 6 , 7 , 10 , 11 , 14 and 15 make up the lower CMD yarn subsystem 120 b. The upper CMD subsystem yarns 120 a weave exclusively with the intermediate and upper layer MD yarns 116 and 118 . Each upper subsystem CMD yarn 120 a preferably weaves, relative to the intermediate and upper MD layers 116 , 118 , over two, under four, over two and under four in a given repeat. For example, as shown in FIG. 8, warp yarn 16 weaves over MD yarns 4 and 5 , under MD yarns 8 , 12 , 13 and 16 , over MD yarns 20 and 21 , and under MD yarns 24 , 28 , 29 and 32 . The lower CMD subsystem yarns 120 b preferably weave in a standard “N” pattern relative to the lower and intermediate MD layers 114 , 116 . For example, CMD yarn 14 weaves over weft yarns 5 and 6 , between MD yarns 13 and 14 , under MD yarns 21 and 22 , and between MD yarns 29 and 30 in a given repeat.
As can be seen in FIG. 8, the intermediate MD yarns 116 interweave with both CMD subsystem layers 120 a,b, to integrate the fabric. This weave pattern integrates the three MD layers 114 , 116 , 118 while maintaining the seam loops 122 in substantial vertical alignment. Loop alignment is maintained by the balanced weave of the end upper CMD yarn 120 a which counterbalances the unbalanced crimp force of the end lower CMD yarn 120 b.
The fabric 110 may be flat woven or endless woven. The preferred method of endless weaving the fabric 110 will be described with reference to FIGS. 6-9. FIG. 9 shows a weave pattern diagram for the base fabric 110 wherein the filled boxes indicate where a warp yarn or cord is over a respective weft yarn. Weaving of the fabric will be described with reference to positioning of the cords only, but it will be understood that the warp heddles are positioned for each shuttle pass in accordance with the desired weave pattern.
The base fabric 110 is preferably woven using a two shuttle loom. Referring to FIGS. 6-9, the first shuttle is thrown across the loom with all of the cords LC, RC 1 , and RC 2 lowered. The right cord RC 1 is then raised and the first shuttle is thrown back across the loom, thereby looping around the end right cord RC 1 . This first shuttle pass is depicted as 1 and 2 in FIG. 6 . The end right cord RC 1 remains raised and the second shuttle is thrown across the loom from the side opposite the first shuttle. The three left cords LC, RC 1 , and RC 2 are raised as the second shuttle is thrown back across the loom. This second shuttle pass is depicted as 3 and 4 in FIG. 6 . The first shuttle then weaves weft yarns 5 and 6 . The left cord LC and the inner right cord RC 2 are raised and the first shuttle is thrown across the loom. All three cords LC, RC 1 , and RC 2 are raised and the first shuttle is thrown back across the loom, thereby weaving weft yarns 5 and 6 in the lower fabric layer and looping around the end right cord RC 1 . To weave weft yarn 7 , both right cords RC 1 and RC 2 are raised and the second shuttle is thrown across the loom. The left cord LC and the end right cord RC 1 are raised and the second shuttle is thrown back across the loom to weave weft yarn 8 . At the transition of each shuttle back to the upper weaving layer 130 , a turning fold is formed as is known in endless weaving. The shuttles weave in the same pattern across the width of the fabric 110 with the heddles being adjusted to provide the desired weave pattern.
To open the fabric 110 after the desired width is formed, the right end cord RC 1 is removed and the left and inner right cords LC and RC 2 are replaced with yarns consistent with the remainder of the warp yarns. Removal of RC 1 provides the loops 122 at both ends of the fabric. As can be seen in FIG. 6, in the preferred weaving arrangement, the upper weft yarn passes 3 , 4 and 7 , 8 will be joined at the loop end of the woven fabric 110 as represented at 150 . To facilitate opening of the fabric 110 , these weft yarns are cut at 150 . It will be understood that various other weaving patterns can be used which will leave these ends separate, thereby eliminating the need for cutting of the upper weft layer yarns.
As can be seen in FIG. 9, the upper layer MD yarns 118 substantially increase the number of entanglement points on the upper surface of the base fabric 110 . The increase in entanglement points allows greater adherence of the batt material 112 to the base fabric 110 . | A papermaker's fabric having a system of primary machine direction yarns which form seaming loops at each end of the fabric and a system of secondary machine direction yarns. A system of cross-machine direction yarns are interwoven with the primary and secondary systems of machine direction yarns in a weave pattern that provides adjacent balancing yarns that maintain the seam loops in substantially vertical alignment. | 3 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of Invention
[0002] The invention relates to an automatic detecting device for signals of land pre-pits on digital video/audio optical disks, utilizing gain adjustment of push-pull signals to raise the signal to noise ratio of the land pre-pits signal to the wobble signal. Digital logic computation is also utilized to recognize the practical position of the land pre-pits. The level automatic detection of the RC circuit and the fixed slice level compose an automatic slice level, which is the basis for detecting the land pre-pits.
[0003] 2. Related Art
[0004] A current write-once DVD (DVD-R) or re-writable DVD (DVD-RW) has the same structure, where records relative data, such as laser wavelength, write power, write strategy, manufactures, or track positions. FIG. 1A illustrates the schematic diagram of the data tracks of a DVD. The land pre-pits 15 of a DVD-R or a DVD-RW are formed in the grooves 17 relative to the peak of the wobbles. The grooves 11 and the lands 17 interlace with each other. After data are recorded in the grooves 11 of the disk, a mark 12 is written in the pre-pits area 15 of the land 17 , as shown in FIG. 1B . The un-continuity of the lands 17 in each land pre-pits area 15 results in edge effect of heat diffusion. The mark 12 in the grooves 11 diffuses to the pre-pits area 15 . The LPP signal is thus influenced. The amplitude of LPP signals relative to the wobble signal decreases after data are written onto the disk. This leads to decrease of the signal to noise ratio.
[0005] FIG. 2A shows the waveform of land pre-pits (LPP) signals not being affected by written data before writing a DVD. A constant LPP slice level, as denoted by dot lines in the figure, is adopted to obtain correct digital LPP signals through comparators. FIG. 2B shows the waveforms after the DVD is written. The LPP signal is usually generated by push-pull approach and constant LPP slice level. The LPP signal is illustrated as waveform A. After data are written on the disk, the amplitude of the LPP signals relative to the wobble signals recesses, which is illustrated as waveform B in the figure. In this situation, adoption of the constant LPP signal slice level brings low accuracy of the LPP signal. The accuracy is still low, even after being protected through Error Correcting Code (ECC). The phenomenon affects access of the lead-in information of the disk drive and access of the address during track jump. The characteristic of the LPP signal of the inner circle and that of the outer circle is not in unanimity during tracking following on the same disk. Furthermore, the influence of written data, the difference between different disks, and writing times lead to accuracy decrease of the LPP signals. Therefore, an automatic level adjusting mechanism is necessary to obtain correct LPP signals under all circumstances.
[0006] FIG. 3 describes the circuit for generating LPP signals of the prior art. The circuit involves comparing the fixed LPP slice level V 1 and the LPP signal V 2 in the comparator 31 to obtain the LPP slice signal V 12 . The LPP slice signal V 12 is synchronized with the wobble clock V 3 through the noise gate 33 in the circuit to eliminate unnecessary glitches. The filtered LPP slice signal V 4 is delivered to a LPP decoder 35 . Under the influence of high frequency RF signals, the amplitude of LPP signals relative to the wobble signal decrease after data are written onto the disk. Therefore, the credibility of the LPP slice signal before writing data onto the DVD is better than that after writing data onto the DVD.
[0007] FIG. 4 illustrates the block diagram of the circuit of the prior art for amending the slice level of land pre-pits. The circuit improves the method of the constant slice level of land pre-pits. The land pre-pits signal V 2 is delivered to a level limiter 41 and filtered by a band pass filter 43 , thereby amending the slice level. The filtered signal is then computed with the constant slice level V 1 and the computed signal is then sent to the comparator 31 to compare with the land pre-pits signal V 2 . The land pre-pits signal V 12 is thus obtained. In order to eliminate the unnecessary pulse interference, the land pre-pits signal V 12 is synchronized with the wobble clock V 3 through the noise gate circuit 33 . The protected land pre-pits signal V 4 is then generated and delivered to the land pre-pits decoding circuit 35 . However, the affection of the adjacent land pre-pits causes the insufficient amendment in the slice level and erroneous judgment of land pre-pits. The accuracy rate of the LPP signals is not improved too much.
[0008] The invention employs automatic detection to detect the variation of the wobble signals to overcome the technical difficulties of prior art, and improves the accuracy rate of the LPP signals in coordination with digital logic computation.
SUMMARY OF THE INVENTION
[0009] The main object of the invention is to provide an automatic detecting device for land pre-pits signals. The LPP auto slice level technology overcomes the heat diffusion affection of the LPP signal on the land when writing data in grooves. The heat diffusion weakens the amplitude of the written LPP signal. Therefore, adopting a constant LPP slice level is not easy to obtain the LPP signal precisely. In order to raise the signal to the noise ratio of the LPP signal and wobble signal, the gain of the push-pull signal is adjusted. The practical position of land pre-pits is recognized by digital logical technology. Judgment of the land pre-pits is based on the automatic slice level, combined with the level automatic detection of the RC circuit and the fixed slice level. The method involves the influence of the written data to the wobble signal such that the possibility of slicing error digital LPP signals is greatly reduced. The drawback of not easily obtainable correct LPP signals from disks with recorded data through the constant LPP slice level technology of prior art is eliminated.
[0010] Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The present invention will become more fully understood from the detailed description given n the illustration below only, and is thus not limitative of the present invention, and wherein:
[0012] FIG. 1A is the schematic diagram of data tracks of a writable DVD of the prior art;
[0013] FIG. 1B is the schematic diagram showing writing data;
[0014] FIG. 2A is the waveform of the LPP signal of a writable DVD before writing;
[0015] FIG. 2B is the waveform of the LPP signal of a writable DVD after writing;
[0016] FIG. 3 is LPP signal generating circuit of the prior art;
[0017] FIG. 4 is the circuit for amending LPP slice level;
[0018] FIG. 5 is the schematic diagram the data tracks of a writable DVD;
[0019] FIG. 6 is the signal of LPP automatic detection slice level of the invention; and
[0020] FIG. 7 is the circuit of LPP signal automatic slice level detecting device of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0021] FIG. 5 illustrates the data tracks of a writable DVD. The figure shows the relationship of the wobble signals and land pre-pits (LPP). The land pre-pits 55 on the writable DVD are formed on the peak of the wobbles on the lands 57 . The grooves 51 and the lands 57 interlace with each other on the data tracks. The push-pull method is employed to obtain the LPP signals from the lands 57 . The gain of the puhs-pull signals is properly adjusted in order to raise the signal to the noise ratio of the grooves 51 to the wobble signals.
[0022] The invention discloses two methods to raise the accuracy rate of digital LPP signals. FIG. 6 describes the signals of the LPP signals automatic detecting the slice level of the embodiment of the invention. In view of digital signal processing, an optical pickup head retrieves a LPP signal, as shown in part A in the figure. In order to obtain the LPP position, a digital logic circuit is used to generate a wobble clock, as shown in part D in the figure. Two adjacent land pre-pits are separated by at least 8 wobble clocks according to the DVD specification. The LPP signal is divided into several portions according to the wobble signal. Each portion has eight wobble clocks. The previous three clocks may include LPP signals, while the latter five wobble signals do not have the LPP signals. A LPP window, as shown in part E in FIG. 6 , is generated for forecast in accordance to the wobble clock. The LPP window, which is open for three clocks and close for five clocks, is used as switching timing of RC impedance. The previous three clocks are for fast RC charge/discharge processing, while the latter five clocks are for slow RC charge/discharge processing, and a bottom hold signal is then generated accordingly, as shown in part F of FIG. 6 . A sample and hold signal in part G of FIG. 6 is used to retrieve the bottom hold signal to obtain the hold level signal as shown in part H of FIG. 6 . After obtaining the LPP-sliced signal, it needs to be synchronized with the wobble clocks in order to obtain the LPP-protect signal as shown in part C in FIG. 6 . The correct positions of LPP are consequently obtained, and the unnecessary glitches are eliminated. LPP Error Code Detection and Correction then proceeds to obtain precise LPP information.
[0023] In view of analog signal processing, the invention utilizes an automatic slice level. The sample and hold signal in FIG. 6 are used to sample and hold the LPP bottom signal in the area without land pre-pits. The level of the LPP bottom signal is recorded in the capacitor based on the RC charge/discharge principle. The RC circuit with larger resister value is used to sample and hold the LPP bottom signal to obtain a stable bottom signal level. In the area with land pre-pits, the sampled and held bottom signal and a fixed slice level are performed as analog computation to obtain a level-slicing signal. The digital LPP signals are obtained from a comparator processing the obtained level and the LPP signal. To avoid the stable bottom signal level in the RC circuit from being affected by the LPP signal, the resister value in the RC circuit becomes smaller when the LPP window is at high level such that quick change can prevent the bottom signal from being affected by the LPP signal. Therefore, the LPP bottom signal varies severely when the LPP window is at high level. The amplitude variation of the wobble signal caused by adjacent tracks and the influence after data writing can be eliminated through the proper slice level, generated by the LPP signal level automatic detecting device, to prevent the comparator from generating erroneous digital LPP signals and to raise the accurate rate.
[0024] FIG. 7 illustrates the circuit of the LPP signal level automatic detecting device. The circuit corresponding to the signals in FIG. 6 is described in details.
[0025] An optical pickup head 601 of an optical pickup circuit 600 in a writable DVD drive accesses the digital data on the disk. A second signal 62 is delivered to a gain balancer 605 to obtain a fourth signal 64 , whose amplitude is the same as the first signal 61 . A third signal 63 is generated by the first signal 61 and the fourth signal 64 through a push-pull method. The third signal 63 is then transmitted to a spin motor controller 603 through the wobble phase lock loop (PLL) 602 , thereby controlling the spin motor 604 in the drive. The control signal can be implemented by prior art.
[0026] The fourth signal 64 is delivered to a gain weightier 606 to generate the fifth signal 65 such that the signal to noise ratio of the LPP signal and the wobble signal is raised through adjusting the first signal 61 and the fifth signal 65 . The fifth signal 65 and the first signal 61 are added to obtain the LPP signal A, which is delivered to a comparator 607 and a bottom signal generator 609 respectively. The bottom signal generator 609 produces the LPP bottom signal F, which is shown in FIG. 6 , through the LPP signal A and the LPP window E from the digital processor 60 . The sample signal generator 610 receives the LPP bottom signal F and the sample signal from the digital processor 60 to obtain a level hold signal H. The level hold signal H and a constant LPP slice signal V 1 generated by a fixed voltage are transmitted to an analog computer 608 , thereby producing the LPP sliced level signal I.
[0027] The comparator 607 receives the LPP signal A, which is processed by the gain balancer 605 and the gain weightier 606 , and the LPP sliced level signal I. The two signals are compared to obtain the LPP signal B as shown in FIG. 6 .
[0028] The bottom signal generator 609 and the sample signal generator 610 receive the LPP window E and the sample signal G from the digital processor 60 to obtain the sliced level signal H.
[0029] The digital processor 60 includes a synchronous signal corrector 611 , a LPP window generator 612 , and a LPP decoder 613 . The synchronous signal corrector 611 receives the LPP sliced signal B from the comparator 607 and the wobble clock D from the PLL 602 for synchronous correction. The LPP window generator 612 receives the fixed wobble clock generated from PLL 602 , thereby generating a signal that is open for three pulses and closed for five pulses, which signal is shown in FIG. 6 . The LPP window E and the LPP signal from the synchronous signal corrector 611 are proceeded AND logic computation to generate the protected LPP signal C. The LPP decoder 613 receives the protected LPP signal C for decoding the land pre-pits to obtain the land pre-pits information.
[0030] The automatic adjusting slice level of the land pre-pits is obtained by the slice level, which is generated by the bottom signal generator 609 and the sample signal generator 610 , through the analog computer 608 . Then the LPP position signal C is obtained through the comparator 607 , the synchronous corrector 611 and the LPP window generator 612 . Finally, the precise LPP information is obtained from the LPP decoder 613 .
[0031] The LPP signal level automatic detecting device of the invention utilizes a LPP signal level automatic detection technology to detect the variation of the wobble signal, to overcome the drawback of the conventional technology. The accuracy of the LPP signal is improved by digital logic computation, and the unnecessary glitches are eliminates. The error rate of decoding LPP signals due to the LPP signals error reduces substantially.
[0032] Reading 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. | An automatic detecting device of land pre-pits signal is disclosed. The device adjusts gain of push-pull signals to raise the signal to noise ratio of the land pre-pits signal to the wobble signal. Digital logic computation is also utilized to recognize the practical position of the land pre-pits. The level automatic detection of the RC circuit and the fixed slice level compose an automatic slice level, which is the basis for detecting the land pre-pits. The disclosed device eliminates the drawback of not easy to obtain correct land pre-pits signal from written disks by the conventional of fixed land pre-pits slice level technology. | 6 |
FIELD OF THE INVENTION
This invention relates in general to sheet feeding technology and, more particularly, to interchanging separator rollers and feed rollers in a sheet feeder.
BACKGROUND OF THE INVENTION
A sheet feeder retrieves a single sheet from a stack of sheets and provides the single sheet to a device. Examples of devices that utilize sheet feeders include printers, copiers, scanners, facsimile machines, and multifunction devices.
One example of a conventional sheet feeder includes three rollers that cooperate to carry out the function of the sheet feeder. The three rollers are often referred to as pick, feed, and separator rollers. The pick roller contacts one of the sheets in a stack of sheets and rotates to urge the contacted sheet between the feed and separator rollers. Occasionally, the contacted sheet adheres to an adjacent sheet and both sheets move towards the feed and separator rollers.
The feed roller rotates to advance the contacted sheet. The separator roller rotates in a direction opposite the feed roller to help prevent an adhering sheet from being advanced with the contacted sheet. The contacted sheet advances against the rotation of the separator roller until the torque reaches a threshold. Then, the separator roller reverses direction. This action causes the separator roller to wear at a greater rate than the pick and feed rollers. Consequently, the separator roller must be replaced more frequently than the pick and feed rollers.
SUMMARY OF THE INVENTION
According to principles of the present invention, a sheet feeding system has a pick roller, a separator roller, and a feed roller. The ends of the separator and feed rollers are coupled together. The pick roller acquires, or picks, a sheet from a stack of sheets and passes the sheet to the separator and feeder roller. The separator roller discourages unintended sheets passed with the sheet picked from the stack. The feed roller advances the sheet. A logic processor evaluates interchange conditions and activates a drive mechanism when the interchange conditions meet interchange criteria. The drive mechanism interchanges the separator roller and the feed roller so that the separator roller becomes the feed roller and the feed roller becomes the separator roller.
According to further principles of the present invention, the drive mechanism includes either a rotatable shaft axially parallel to the first and second rollers and coupled to one of the first and second ends and a shaft driver configured to rotate the shaft or a toothed wheel gear coupled to one of the first and second ends and a gear driver configured to drive the gear, rotating the system.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is diagrammatical, partially cut away, front elevation representing one embodiment of the feed and separator rollers of the present invention.
FIG. 2 is diagrammatical side elevation representing one embodiment of a sheet feeding system of the present invention with the feed and separator rollers of FIG. 1 .
FIG. 3 is diagrammatical, front elevation representing one embodiment of the drive mechanism of FIG. 1 .
FIG. 4 is diagrammatical side elevation representing the drive mechanism of FIG. 3 .
FIG. 5 is diagrammatical, front elevation representing an alternate embodiment of the drive mechanism of FIG. 1 .
FIG. 6 is diagrammatical side elevation representing the drive mechanism of FIG. 5 .
FIG. 7 is diagrammatical, front elevation representing another alternate embodiment of the drive mechanism of FIG. 1 .
FIG. 8 is diagrammatical side elevation representing the drive mechanism of FIG. 7 .
FIG. 9 is a flow chart illustrating one embodiment of the method of the present invention for preserving a feed and separator roller combination.
DETAILED DESCRIPTION OF THE INVENTION
Illustrated in FIGS. 1 and 2 is one embodiment of a sheet feeding system 2 of the present invention. Sheet feeding system 2 includes combination 4 and pick roller 6 . Combination 4 includes feed roller 8 , separator roller 10 , roller driver 12 , coupling 16 , drive mechanism 18 , and optionally, coupling 14 , logic processor 20 and pivot shaft 22 .
Pick roller 6 is any one or more rotatable, generally cylindrically shaped rolling objects configured to frictionally contact one sheet 24 from a stack of sheets 26 and, by rolling, urge sheet 24 towards feed roller 8 and separator roller 10 . For clarity, contacting sheet 24 and urging sheet 24 towards feed roller 8 and separator roller 10 will be referred to as picking. In one embodiment, stack of sheets 26 reside in a sheet bin, cartridge, or tray 28 until picked by pick roller 6 .
Feed roller 8 is any one or more rotatable, generally cylindrically shaped, rolling objects configured to receive and frictionally contact sheet 24 and, by rolling, advance sheet 24 between feed roller 8 and separator roller 10 to a device or system (not shown). Examples of devices or systems to which feed roller 8 advances sheet 24 include printers, copiers, scanners, facsimile machines, and multifunction devices.
Feed roller 8 includes a rolling surface 30 and an inner core 32 . Rolling surface 30 may be of the same or a different material than inner core 32 . Rolling surface 30 and inner core 32 may be unitary or separate.
Separator roller 10 is any one or more rotatable, generally cylindrically shaped, rolling objects configured to receive and frictionally contact sheet 24 and, by rolling, discourage any of the sheets of stack 26 from advancing with sheet 24 to the device or system. Separator roller 10 is substantially parallel to feed roller 8 . Separator roller 10 rolls or rotates in a direction opposite feed roller 8 .
Separator roller 10 includes a rolling surface 34 and an inner core 36 . Rolling surface 34 may be of the same or a different material than inner core 36 . Rolling surface 34 and inner core 36 may be unitary or separate. Rolling surface 34 is adjacent rolling surface 30 .
In one embodiment, feed roller 8 and separator roller 10 extend only a portion of the way across a sheet pathway and are unsupported at one end. In this embodiment, coupling 14 and pivot shaft 22 are not present. In an alternate embodiment, feed roller 8 and separator roller 10 extend entirely across the sheet pathway and are supported at both ends. In this embodiment, coupling 14 and pivot shaft 22 are present.
Roller driver 12 is any apparatus or system for rotating feed roller 8 and separator roller 10 . In one embodiment, roller driver 12 includes two toothed wheel gears 38 . One gear 38 is affixed to feed roller 8 and the other gear 38 is affixed to separator roller 10 .
Couplings 14 , 16 are any mechanism connecting an end of feed roller 8 to an end of separator roller 10 . Each coupling 14 , 16 connects one set of ends of feed roller 8 and separator roller 10 .
Drive mechanism 18 is any apparatus or system configured to rotate combination 4 and interchange, in position, feed roller 8 and separator roller 10 . Once interchanged, feed roller 8 becomes separator roller 10 and separator roller 10 becomes feed roller 8 . In one embodiment, drive mechanism 18 is controlled by logic processor 20 . Drive mechanism 18 may be on the same ends of feed roller 8 and separator roller 10 as roller driver 12 or on opposite ends of feed roller 8 and separator roller 10 as roller driver 12 .
In one embodiment, drive mechanism 18 and couplings 14 , 16 are sized and shaped so that feed roller 8 and separation roller 10 are centered within a sheet path. In alternate embodiments, drive mechanism 18 and couplings 14 , 16 are sized and shaped so that feed roller 8 and separation roller 10 are located in any position across a sheet path.
Logic processor 20 is any apparatus or system configured to evaluate interchange conditions and to control drive mechanism 18 . Interchange conditions are any conditions useful for determining whether to interchange feed roller 8 and separator roller 10 . Examples of interchange conditions include number of sheets advanced by feed roller 8 and number of print jobs during which feed roller 8 advances sheets. In one embodiment, logic processor 20 is further configured to vary the interchange criteria that must be met by the interchange conditions before activating drive mechanism 18 .
Pivot shaft 22 extends from one of the couplings 14 , 16 opposite drive mechanism 18 . Pivot shaft 22 is rotatably mounted in a position to provide a point of rotation for combination 4 to interchange feed roller 8 and separator roller 10 .
Illustrated in FIGS. 3 and 4 are one embodiment of drive mechanism 18 . Drive mechanism 18 includes shaft 40 and shaft driver 44 . Shaft driver 44 extends from or is attached to one of couplings 14 , 16 . Shaft driver 44 rotates shaft 40 that rotates combination 4 and interchanges, in position, feed roller 8 and separator roller 10 .
Illustrated in FIGS. 5 and 6 are an alternate embodiment of drive mechanism 18 . Drive mechanism 18 includes toothed wheel gear 46 and gear driver 48 . Toothed wheel gear 46 extends from or is attached to one of couplings 14 , 16 . Gear driver 48 rotates gear 46 that rotates combination 4 and interchanges, in position, feed roller 8 and separator roller 10 .
Illustrated in FIGS. 7 and 8 are another alternate embodiment of drive mechanism 18 . Drive mechanism 18 includes pulley wheel 50 , belt 52 , and belt driver 54 . Pulley wheel 50 extends from or is attached to one of couplings 14 , 16 . Belt 52 interconnects pulley wheel 50 and belt driver 54 . Belt driver 54 rotates pulley wheel 50 that rotates combination 4 and interchanges, in position, feed roller 8 and separator roller 10 .
FIG. 9 is a flow chart representing steps of one embodiment of the present invention. Although the steps represented in FIG. 9 are presented in a specific order, the present invention encompasses variations in the order of steps. Furthermore, additional steps may be executed between the steps illustrated in FIG. 9 without departing from the scope of the present invention.
Feed roller 8 and separator roller 10 are interchangeable. Since feed roller 8 and separator roller 10 are interchangeable, they are alternatively referred to as first roller and second roller. Either feed roller 8 or separator roller 10 may be referred to as first roller and either may be referred to as second roller.
Sheet 24 is picked 56 and urged 58 between first and second rollers. One of the first and second rollers rotates to advance 60 sheet 24 while the other of the first and second rollers rotates to discourage additional sheets from stack 26 from advancing with sheet 24 .
Criteria for interchanging first and second rollers are evaluated 62 . In one embodiment, evaluating 62 criteria for interchanging includes counting the pages advanced 60 by the first and second rollers. In an alternate embodiment, evaluating 62 criteria for interchanging includes measuring the sheet slippage of sheet 24 as sheet 24 is advanced 60 and comparing the sheet slippage to a slippage threshold.
If the evaluated criteria for interchanging indicate no interchange of first and second rollers is desirable, the process repeats until an interchange of first and second rollers is desirable. If the evaluated interchange conditions indicates an interchange of first and second rollers is desirable, second roller is interchanged 64 for first roller and first roller is interchanged 64 for second roller. An interchange of first and second rollers may be desirable upon any desired condition. Examples of desired conditions include after a desired number of print jobs, after a desired number of pages, and after an equal number of pages have been advance since a previous interchange.
In one embodiment, interchanging 64 the rollers includes activating shaft driver 44 to rotate shaft 42 and shaft 42 rotating combination 4 to interchange the first and second rollers.
In an alternate embodiment, interchanging 64 the rollers includes activating gear driver 48 to rotate gear 46 and gear 46 rotating combination 4 to interchange the first and second rollers.
In another alternate embodiment, interchanging 64 the rollers includes activating belt driver 54 to rotate pulley 50 and pulley 50 rotating combination 4 to interchange the first and second rollers.
The process may be repeated as many times as desired. In one embodiment, the process is repeated until rolling surface 30 or rolling surface 34 has worn so that it no longer functions properly.
The foregoing description is only illustrative of the invention. Various alternatives and modifications can be devised by those skilled in the art without departing from the invention. Accordingly, the present invention embraces all such alternatives, modifications, and variances that fall within the scope of the appended claims. | A sheet feeding system has a pick roller, a first roller, and a second roller. The ends of the first and second rollers are coupled together. The pick roller acquires, or picks, a sheet from a stack of sheets and passes the sheet to the first and second rollers. One of the first and second rollers discourages unintended sheets passed with the sheet picked from the stack. The other of the first and second rollers advances the sheet. A logic processor evaluates interchange conditions and activates a drive mechanism when the evaluated interchange conditions reaches a threshold value. The drive mechanism interchanges the first and second rollers so that the second roller becomes the first roller and the first roller becomes the second roller. | 1 |
FIELD OF THE INVENTION
[0001] This invention relates generally to the regeneration of hydrocarbon conversion catalysts in the presence of a halogen-containing material.
BACKGROUND OF THE INVENTION
[0002] Numerous hydrocarbon conversion processes are widely used to alter the structure or properties of hydrocarbon streams. Such processes include isomerization from straight chain paraffinic or olefinic hydrocarbons to more highly branched hydrocarbons, dehydrogenation for producing olefinic or aromatic compounds, reforming to produce aromatics and motor fuels, alkylation to produce commodity chemicals and motor fuels, transalkylation, and others.
[0003] Many such processes use catalysts to promote hydrocarbon conversion reactions. These catalysts tend to deactivate for a variety of reasons, including the deposition of carbonaceous material or coke upon the catalyst, sintering or agglomeration or poisoning of catalytic metals on the catalyst, and/or loss of catalytic metal promoters such as halogens. Consequently, these catalysts are typically reactivated in a process called regeneration.
[0004] Reactivation can include, for example, removing coke from the catalyst by burning, redispersing catalytic metals such as platinum on the catalyst, oxidizing such catalytic metals, reducing such catalytic metals, replenishing catalytic promoters such as chloride on the catalyst, and drying the catalyst. For example, U.S. Pat. No. 6,153,091 discloses a method for regenerating spent catalyst.
[0005] In a some regeneration processes, a catalyst is passed from a reaction zone to a regeneration zone which may include a burn zone, a catalyst heating zone, a chlorination zone, a catalyst drying zone, and a catalyst cooling zone, and wherein the catalyst includes coke; burning off the coke from the catalyst in the burn zone; increasing a temperature of the catalyst in the catalyst heating zone; dispersing the a metal on the catalyst in the chlorination zone, replacing a chloride on the catalyst or both; drying the catalyst in the catalyst drying zone; cooling the catalyst in the catalyst cooling zone.
[0006] However, some regeneration processes/systems may require a higher temperature to achieve an optimal desired temperature in the chlorination zone. Therefore, it would be desirable to provide a process which allows for a desired temperature (or range) in the chlorination zone to be achieved.
[0007] Additionally, some regeneration processes may require a higher temperature to achieve an optimal drying zone temperature. Therefore, it would be desirable to provide a process which allows for desired temperature in the drying zone to be achieved.
[0008] Furthermore, some regeneration processes/systems rely on electric heaters for oxygen supplied to the system. Therefore, it would be desirable to provide a process which allows for the regeneration process to be run with a wider range of catalyst coke values.
[0009] Additionally, it would be desirable to provide a process which allows for the proper amount of chlorine to be introduced to disperse the metals on the catalyst, without increasing the amount of chloride on the regenerated catalyst. In other words, it would be desirable to have a process in which the chloride level of the catalyst is decoupled from the chorine used for dispersion so that the process can operate at a lower level of chloride while achieving a sufficient metal dispersion.
[0010] Furthermore, some current designs may not allow metal to be dispersed in the chlorination zone or drying zone during some modes of operation. More specifically, in a “black burn” mode the catalyst has high levels of coke and only nitrogen is injected into these two zones. Additionally, no chloride is injected into the regenerator. This operation condition prohibits metal (including platinum) dispersion during the black burn mode resulting in decline in catalyst performance, loss of C 5 + yield, hydrogen product yield and low activity.
[0011] Furthermore, during other operation modes, coke slippage or slightly higher coked catalyst passing into the chlorination zone, may result in poor metal dispersion, catalyst damage, catalyst fines generation, and equipment fouling. These can shorten the process turnaround interval leading to potential of a unit shutdown resulting in loss of production in the reforming unit. Therefore, it would be desirable for a process in which metal dispersion occurs during various operation modes. It would also be desirable to provide a system which also increases the coke burn to avoid coked catalyst from burning in the chlorination zone.
[0012] Therefore, there remains a need for effective and efficient processes for regenerating catalyst.
SUMMARY OF THE INVENTION
[0013] The present invention is directed to providing effective and efficient processes for regenerating catalyst.
[0014] Accordingly, in one aspect of the present invention, the present invention provides a process for the continuous regeneration of a catalyst in which a catalyst is passed from a reaction zone to a regeneration zone, wherein the regeneration zone includes at least a burn zone to remove coke from the catalyst, the catalyst is recycled from the regeneration zone back to the reaction zone, and wherein the catalyst is cooled in a catalyst cooling zone after the catalyst exits the burn zone while the catalyst passes through a chloride, and, a metal is dispersed on the catalyst with chloride in a chlorination zone after the catalyst has left the catalyst cooling zone.
[0015] It is contemplated that the chlorination zone is disposed below the burn zone so that chloride in the chlorination zone flows upwards towards the burn zone.
[0016] It is also contemplated that in some embodiments the cooling zone the catalyst is cooled to a temperature at least 100° C. lower than a temperature of the catalyst as the catalyst enters the chlorination zone. Additionally or alternatively, in the cooling zone the catalyst is cooled to a temperature between approximately 350° C. to 70° C.
[0017] In some embodiments, a chloride content on catalyst exiting the cooling zone is higher than a chloride content on catalyst entering the cooling zone.
[0018] In another aspect of the present invention, a process for the continuous regeneration of a catalyst is provided which includes: passing a catalyst from a reaction zone to a regeneration zone, wherein the regeneration zone includes at least a burn zone to remove coke from the catalyst; recycling the catalyst from the regeneration zone back to the reaction zone; dispersing a metal on the catalyst in a chlorination zone of the regeneration zone; drying the catalyst in a catalyst drying zone of the regeneration zone, wherein catalyst drying zone receives a heated ambient oxygen; removing a portion of the heated ambient oxygen from the catalyst drying zone; passing the removed portion of the heated ambient oxygen to an oxygen heating zone; heating the removed portion of the heated ambient oxygen in the oxygen heating zone to provide a reheated ambient oxygen; and, passing the reheated ambient oxygen into the chlorination zone, and wherein a flow rate of the heated ambient oxygen is capable of being maintained while a flow rate of the reheated ambient oxygen is decreased.
[0019] In some embodiments, chloride is mixed with the reheated ambient oxygen and the mixture of chloride and the reheated ambient oxygen is passed into the chlorination zone.
[0020] In some embodiments, an operating parameter of the oxygen heating zone is controlled based upon the temperature of the chlorination zone. The operating parameter may be a temperature or a flow rate.
[0021] In still other embodiments of the present invention, process utilizing this aspect of the present invention may also include: cooling the catalyst in a catalyst cooling zone of the regeneration zone, wherein the catalyst cooling zone receives an ambient oxygen from outside of the regeneration zone; removing a portion of the ambient oxygen from the catalyst cooling zone; passing the removed portion of the ambient oxygen to a second oxygen heating zone; and, heating the removed portion in the second oxygen heating zone to provide the heated ambient oxygen which is passed to the catalyst drying zone.
[0022] In further embodiments of the present invention, the processes may include: passing a portion of the reheated ambient oxygen to a compression zone to provide a compressed ambient oxygen; mixing the compressed ambient oxygen with an additional ambient oxygen from outside of the regeneration zone; and, passing a mixture of the compressed ambient oxygen and the additional ambient oxygen to the catalyst cooling zone.
[0023] In another aspect of the present invention, another process is provided for the regeneration of a catalyst which includes: passing a catalyst from a reaction zone to a regeneration zone, wherein the regeneration zone includes at least a burn zone to remove coke from the catalyst; recycling the catalyst from the regeneration zone back to the reaction zone; heating the catalyst in a catalyst heating zone so that a temperature of the catalyst has increased at least after the catalyst has flowed out of the burn zone; and, passing a heated ambient oxygen to the catalyst heating zone to increase the temperature in the catalyst heating zone so that the temperature of the catalyst increases.
[0024] In some embodiments, a flow of the heated ambient oxygen is directed into the catalyst heating zone with an air flow direction device. The air flow direction device may be a baffle. Additionally, the air flow direction device may direct the split portion of the ambient oxygen in a direction generally parallel to a flow of the catalyst through the catalyst heating zone.
[0025] In some embodiments, a chloride is mixed with the heated ambient oxygen and the mixture of chloride and the heated ambient oxygen is passed into the catalyst heating zone. Additionally, nitrogen may be passed into the regeneration zone below the catalyst heating zone.
[0026] In still another aspect of the present invention, a process for the continuous regeneration of a catalyst includes: passing a catalyst from a reaction zone to a regeneration zone, wherein the regeneration zone includes at least a burn zone to remove coke from the catalyst; recycling the catalyst from the regeneration zone back to the reaction zone; removing a regeneration gas from the regeneration zone; recovering a chloride from the regeneration gas; and, recycling the recovered chloride back to the regeneration zone.
[0027] In some embodiments an amount of recovered chloride may be selectively controlled independently of a flow of the catalyst.
[0028] In at least one embodiment, the recovered chloride is recycled back to the burn zone of the regeneration zone. In some embodiments, the recovered chloride is recycled back to at least one of the following zones in the regeneration zone: the burn zone; a chlorination zone; and, a catalyst drying zone. Any amounts of recovered chloride may be selectively controlled.
[0029] In yet another aspect of the present invention, a regeneration zone includes at least two, at least three, or all of the above described aspects of the present invention.
[0030] Additional objects, embodiments, and details of the invention are set forth in the following detailed description of the invention.
DETAILED DESCRIPTION OF THE DRAWING
[0031] The drawings are simplified process flow diagrams in which:
[0032] FIG. 1 shows a process according to one or more aspects of the present invention for the regeneration of a catalyst;
[0033] FIG. 2 shows another process according to one or more aspects of the present invention for the regeneration of a catalyst;
[0034] FIG. 3 shows yet another process according to one or more aspects of the present invention for the regeneration of a catalyst; and,
[0035] FIG. 4 shows still another process according to one or more aspects of the present invention for the regeneration of a catalyst.
DETAILED DESCRIPTION OF THE INVENTION
[0036] One or more processes have been developed for the regeneration of a catalyst used in a catalytic reforming reaction.
[0037] A catalytic reforming reaction is normally effected in the presence of catalyst particles comprised of one or more Group VIII noble metals (e.g., platinum, iridium, rhodium, palladium) and a halogen combined with a porous carrier, such as a refractory inorganic oxide. The halogen is normally chloride. Alumina is a commonly used carrier. The preferred alumina materials are known as the gamma, eta and theta alumina with gamma and eta alumina giving the best results. An important property related to the performance of the catalyst is the surface area of the carrier.
[0038] Catalyst particles are usually cylindrical or spheroidal, having a diameter of from about 1/16 th to about 1/8 th inch (1.5-3.1 mm), though they may be as large as 1/4 th inch (6.35 mm). When cylindrical, the catalyst particles have a length of from about 1/8 th to about 1/4 th inch (3.1-6.35 mm) In a particular catalyst bed, however, it is desirable to use catalyst particles which fall in a relatively narrow size range. A preferred catalyst particle diameter is 1/16 th inch (3.1 mm) During the course of a reforming reaction, catalyst particles become deactivated as a result of mechanisms such as the deposition of coke on the particles; that is, after a period of time in use, the ability of catalyst particles to promote reforming reactions decreases to the point that the catalyst is no longer useful. The catalyst must be regenerated before it can be reused in a reforming process.
[0039] Accordingly, in the various aspects of the present invention a catalyst having coke is passed via a line from a reaction zone to a regeneration zone. As will be discussed in more detail below, the regeneration zone may include a tower which may includes, one or more of: a burn zone; a catalyst heating zone; a chlorination zone; a catalyst drying zone; a catalyst cooling zone; or any combination of these zones. The catalyst can be recovered from the cooling zone, subjected to a reduction or other known processing steps, and then recycled back to the reaction zone as regenerated catalyst and reused.
[0040] Returning to the regeneration zone, the burn zone comprises a portion of the regeneration zone in which coke combustion takes place. Coke which could have accumulated on surfaces of the catalyst because of the reforming reactions can be removed by combustion. Coke is comprised primarily of carbon but is also comprised of a relatively small quantity of hydrogen, generally from 0.5 to 10 wt-% of the coke. The mechanism of coke removal includes oxidation to carbon monoxide, carbon dioxide, and water. The coke content of spent catalyst may be as much as 20% by weight of the catalyst weight, but 5-7% is a more typical amount. Coke is usually oxidized at temperatures approximately in the range of 400° C. to 700° C. As a result of the high temperature, catalyst chloride is quite readily removed from the catalyst during coke combustion.
[0041] In order to increase the temperature of the catalyst for processing in further zones, the catalyst passes out of the burn zone and may be passed into a catalyst heating zone. In the catalyst heating zone, the catalyst is heated by the gases rising form the lower portions of the regeneration zone (discussed in more detail below).
[0042] The catalyst may pass from the catalyst heating zone to a chlorination zone. In the chlorination zone, the catalyst metal is dispersed. The dispersion typically involves chlorine or another chloro-species that can be converted in the regeneration zone to chlorine. The chlorine or chloro-species is generally introduced in a small stream of carrier gas that is added to the chlorination zone. Although the actual mechanism by which chlorine disperses catalyst metal is the subject of a variety of theories, it is generally recognized that the metal may be dispersed without increasing the catalyst chloride content. In other words, although the presence of chlorine is a requirement for metal dispersion to occur, once the metal has been dispersed it is not necessary that the catalyst chloride content be maintained above that of the catalyst prior to dispersion. Thus, the agglomerated catalyst can be dispersed without a net increase in the overall chloride content of the catalyst. Notwithstanding same, in the chlorination zone the gas may also replace chloride on the catalyst.
[0043] After the chlorination zone, the catalyst may pass to a catalyst drying zone in which the catalyst is dried to remove water, and then to a catalyst cooling zone in which the catalyst is cooled to a temperature that is safe for handling and further processing.
[0044] After cooling, the catalyst may be subjected to subsequent processing such as reduction, and then may be re-used as a catalyst in the reaction zone.
[0045] Turning to FIG. 1 , as shown in this aspect of the present invention, a process is directed to the regeneration of catalyst used in a reaction zone 10 . The catalyst is passed, via traditional transportation devices and means, to a regeneration zone 20 which may include one or more regeneration towers 22 .
[0046] The regeneration zone 20 includes, at least, a burn zone 24 , a top cooling zone 26 , and a chlorination zone 28 . In the burn zone 24 , coke present on the catalyst is burned off, as discussed above.
[0047] After the catalyst exits the burn zone 24 , it passes into a top cooling zone 26 . In the top cooling zone 26 , chloride, contained in gases flowing upward, contacts the catalyst (which is typically moving in the opposite direction). In this manner, the chloride content on the catalyst as it exits the top cooling zone 26 is higher than the chloride content on the catalyst as it enters the top cooling zone 26 .
[0048] It is contemplated that in the top cool zone 26 the catalyst cools to a temperature between 350° C. to 70° C. It is also contemplated that in the top cool zone 26 the catalyst cools to a temperature that is at least 100° C. lower than a temperature of the catalyst as the catalyst enters the chlorination zone 28 .
[0049] In the chlorination zone 28 , the catalyst contacts chloride which acts to re-disperse the metal on the catalyst.
[0050] Additional zones may also be present in the regeneration zone 20 , including, one or more zones discussed elsewhere in this application, for example, a catalyst reheat zone may disposed after the top cool zone 26 and before the chlorination zone 28 .
[0051] The catalyst may be recycled back to the reaction zone 10 and re-used in the process.
[0052] The inclusion of the top cooling zone 26 allows for the chloride content of the catalyst as it passes into the chlorination zone 28 to be increased, at least 0.1% higher, without increasing the overall chloride content in the regeneration zone 20 . More specifically, as the catalyst passes into the top cooling zone 26 , the cooling of the catalyst will result in chloride, from the gas moving upward, depositing on the catalyst. Thus, the amount of chloride on the catalyst as it enters the chlorination zone 28 will be higher. Additionally, chloride will be released by the catalyst as the catalyst is heated in the chlorination zone 28 . This will allow the chloride content of the chlorination zone 28 to be higher without increasing the chloride content of the burn zone 24 or chloride delivery to the regeneration zone 20 . Additionally, the top cool zone 26 will maintain the chloride in the regeneration tower 22 , at least until the concentration of the chloride is high enough that it can pass out of the regeneration zone 20 .
[0053] In order to cool the catalyst after it leaves the burn zone 24 , the top cooling zone 26 may include direct heat exchanges, indirect heat exchanges with the catalyst moving through cooled tubes, or both.
[0054] It is also contemplated that this aspect of the invention is combined with, at least one additional aspect of the present invention described herein.
[0055] As shown in FIG. 2 , in this aspect of the present invention, another process is directed to the regeneration of catalyst used in a reaction zone 200 . The catalyst is passed, via traditional transportation devices and means, to a regeneration zone 202 which may include one or more regeneration towers 204 .
[0056] The regeneration zone 202 includes, at least, a burn zone 206 , a chlorination zone 208 , a catalyst drying zone 210 , a catalyst cooling zone 212 . Again, in the burn zone 206 , as discussed above, coke is burned off of the catalyst. In the chlorination zone 208 , chloride re-disperses the metal on the catalyst, chloride content of the catalyst is increased, or both. Finally, in the catalyst drying zone 210 , the catalyst is dried. In the catalyst cooling zone 212 , the catalyst is cooled so that it can be handled by other process devices to transport same.
[0057] In order to cool the catalyst, ambient oxygen is passed to the regeneration zone 202 , typically to the catalyst cool zone 212 . Since the ambient oxygen will absorb heat from the catalyst (to cool it) it will travel upward. A portion may be removed, for example with a baffle 214 . The removed portion may be passed, via a line 216 , to an oxygen heating zone. The oxygen heating zone 218 may include, for example, an electric heater 220 . The oxygen heating zone 218 heats the ambient oxygen which may be passed to the catalyst drying zone 210 .
[0058] The heated ambient oxygen will dry the catalyst and continue to travel upwards. Again it may be removed with a baffle 222 , or other devices. Once again the removed portion may be passed, via a line 224 , to another oxygen heating zone 226 . Again this may include an electric heater 228 . This oxygen heating zone 226 reheats the ambient oxygen which may be passed into the chlorination zone 208 .
[0059] Chloride may be injected into one of the zones in the regeneration zone 202 , and preferably, it may be mixed with the gases entering the various zones discussed above.
[0060] In at least this aspect of the present invention, a flow rate of the heated ambient oxygen in the catalyst drying zone 210 is capable of being maintained (or adjusted) while a flow rate of the reheated ambient oxygen in the chlorination zone 208 is decreased. This may be accomplished, for example, by splitting a portion of the reheated ambient oxygen and recycling same to the catalyst cooling zone 212 . The split portion preferably passes though a compression zone 230 having, for example, a compressor 232 . It may also be cooled prior to being reintroduced into the catalyst drying zone 212 .
[0061] Accordingly, the flow of oxygen used to cool and dry the catalyst can be operated in a independently from the amount of gas heating the chlorination zone 208 . Thus, the same amount of the ambient oxygen can be used to cool the catalyst and dry the catalyst while the flow of reheated ambient oxygen is lowered. This would be desirable if, for example, there is low coke amount on the catalyst; yet, the same temperature in the chlorination zone 208 is desired.
[0062] It is also contemplated to measure the temperature of the chlorination zone 208 and control at least one operating parameter of the oxygen reheating zone 226 based upon the temperature. Such a parameter may be flow, operating temperature, both, or another parameter.
[0063] Additional zones may also be present in the regeneration zone 202 , including, one or more zones discussed elsewhere herein.
[0064] The catalyst may be recycled back to the reaction zone 200 and re-used in the process.
[0065] Again, it is also contemplated that this aspect of the invention is combined with, at least, one additional aspect of the present invention described herein.
[0066] Turning to FIG. 3 , as shown in this aspect of the present invention, a process is also directed to the regeneration of catalyst used in a reaction zone 300 . The catalyst is once again passed, via traditional transportation devices and means, to a regeneration zone 302 which may include one or more regeneration towers 304 .
[0067] The regeneration zone 302 includes, at least, a burn zone 306 , a catalyst heating zone 308 , and chlorination zone 310 . Again, in the burn zone 306 coke present on the catalyst is removed via combustion. While this temperature is sufficiently high to burn most of the catalyst off, it is possible that some heavily coked catalyst may pass from the burn zone 306 to the catalyst heating zone 308 .
[0068] In the catalyst heating zone 308 , the catalyst typically reaches a temperature so that it may pass to additional zones such as a chlorination zone 310 with a temperature around 400° C. to 600° C. Typically the oxygen content in the catalyst heating zone is approximately 0.7 (mol %).
[0069] As discussed above, any coke that enters this zone will combust, damaging the catalyst. Accordingly, a regeneration zone may operate in “black burn” mode when the coke level on the catalyst is high and nitrogen may be introduced into the bottom of the tower 304 . However, no chloride will be introduced into the regeneration zone 302 , meaning that catalyst chloride level on the regenerated catalyst will be lower than a desired amount. Additionally, metal dispersion on the regenerated catalyst will be less than ideal. Both of these factors will lower that catalyst efficiency and thus, negatively impact the reaction zone 300 products.
[0070] Accordingly, for either “black burn” mode or normal (“white burn”) mode, heated ambient oxygen maybe passed into the catalyst heat zone 308 . A heater 312 or other temperature increasing device can be used.
[0071] In “white burn” operations, the oxygen content in the catalyst heating zone 308 may be increased by approximately 1% (mol) (total 1.7%). Additionally, in “black burn” the oxygen content can be increased to a range between 2 to 10% (mol). The amount of heated ambient oxygen can be selectively controlled by, for example, flow control devices within lines, valves, or other devices.
[0072] In a preferred embodiment, the flow of the heated ambient oxygen into the catalyst heating zone 308 is directed with an air flow direction device 314 , such as a baffle 316 . It is preferred that the flow direction device 314 directs the flow of the heated ambient oxygen, at least initially, in a direction that is parallel (but opposite) to the flow of catalyst through the regeneration zone 302 . The use of flow direction device 319 , as opposed to, for example, a simple introduction of gaseous flow, allows for a smaller sized (circumference) regeneration zone 308 because it will more evenly disperse the oxygen into the catalyst heating zone 308 . Typically reheat zone 308 is 15% of regeneration zone 306 by size, but it could range from 5% to 25%.
[0073] Additionally, it is contemplated that in some instances it may be desirable to introduce chloride into the burn zone 306 . Accordingly, a line 318 may be used to combine chloride with the heated ambient oxygen and the mixture may be introduced into the catalyst heating zone 308 . In this manner, if the regeneration zone 302 is operated in “black burn” mode, chloride will still be introduced into the regeneration zone 302 to increase the chloride content of the catalyst and re-disperse the metal on the catalyst.
[0074] Additional zones may also be present in the regeneration zone 302 , including, one or more zones discussed herein.
[0075] The catalyst may be recycled back to the reaction zone 300 and re-used in the process.
[0076] While this and other aspects of the invention may be described with respect to black burn mode, it is also contemplated to utilize same in white burn, or normal operation.
[0077] Again, it is also contemplated that this aspect of the invention is combined with, at least, one additional aspect of the present invention described herein.
[0078] Turning to FIG. 4 , as shown in this aspect of the present invention, another process is shown which is also directed to the regeneration of catalyst used in a reaction zone 400 . The catalyst is once again passed, via traditional transportation devices and means, to a regeneration zone 402 which may include one or more regeneration towers 404 .
[0079] The regeneration zone 402 includes, at least, a burn zone 406 , a chlorination zone 408 , and a catalyst drying zone 410 . As previously discussed, in the burn zone 406 coke is burned off the catalyst.
[0080] As discussed herein, chloride may introduced in one or more zones to increase the chloride content on the catalyst, re-disperse the metal on the catalyst, or both. Typically, this will result in the gas at the top of the regeneration tower 404 containing chloride. Some processes pass the catalyst through this gas in an attempt to recover some chloride. While other known processes remove all of the gas and scrub all of the gas to remove the chloride, it was discovered that a recovery process could be utilized to recover and recycle the chloride back to the regeneration zone 402 .
[0081] Accordingly, at least a portion of the regeneration gas may be taken or removed from the regeneration zone 402 , preferably at the top of regeneration tower 404 , and passed to a chloride recovery zone 412 . A second portion of regeneration gas may be recycled back to the burn zone 406 , for example.
[0082] In the chloride recovery zone 412 , chloride is recovered from the regeneration gas. The recovered chloride may be recycled back to the regeneration zone 402 , and more specifically may be passed to the burn zone 406 , the chlorination zone 408 , the catalyst drying zone 410 , or any other zone. It is contemplated that any amount of recycled chloride is selectively controlled, for example, with a valve. Such a chloride recovery allows for recovery independent of catalyst flow. Known processes for the recovery of chloride include those described in U.S. Pat. Nos. 6,117,809 and 6,153,091, the entirety of which is incorporated herein by reference.
[0083] Additional zones may also be present in the regeneration zone 302 , including, one or more zones discussed elsewhere herein.
[0084] The catalyst may be recycled back to the reaction zone 400 and re-used in the process.
[0085] Such a process may lower the amount of new chlorine species added to the regeneration zone as well as reduce the chloride species from the regeneration gas.
[0086] Once again, it is also contemplated that this aspect of the invention is combined with, at least, one additional aspect of the present invention described herein.
[0087] A process including at least one of the above aspects is beneficial and desirable for the reasons described herein.
[0088] It should be appreciated and understood by those of ordinary skill in the art that various other components such as valves, pumps, filters, coolers, etc. were not shown in the drawings as it is believed that the specifics of same are well within the knowledge of those of ordinary skill in the art and a description of same is not necessary for practicing or understating the embodiments of the present invention.
[0089] While at least one exemplary embodiment has been presented in the foregoing detailed description of the invention, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the invention, it being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended claims and their legal equivalents. | A process for regenerating a catalyst used in a reaction zone. In a regeneration zone, the catalyst may be cooled before passing into a chloride rich zone. The regeneration zone may also receive a heated ambient oxygen in a catalyst heating zone. The regeneration zone may also receive recovered chloride from a chloride recovering zone which removes and recovers chloride from regeneration gas taken from the regeneration zone. Heated ambient oxygen may also be introduced into a chlorination zone. | 2 |
FIELD OF THE DISCLOSURE
[0001] The present disclosure relates generally to signal processing techniques, and more specifically to a method and apparatus for filtering signals.
BACKGROUND
[0002] Audio circuits often suffer from a problem where the output signal is fed back into an input channel due to poor isolation. This feedback can be caused by any number of sources such as for example a leakage or crosstalk path in the audio circuit, audio loop back, an echo, and so on.
[0003] A need therefore arises for a method and apparatus for filtering signals.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] FIG. 1 depicts an exemplary embodiment of a communication system;
[0005] FIG. 2 depicts an exemplary embodiment of a processor operating in the communication system;
[0006] FIG. 3 depicts an exemplary method operating in the processor; and
[0007] FIGS. 4-8 depict exemplary embodiments of the method operating in the processor.
DETAILED DESCRIPTION
[0008] FIG. 1 depicts an exemplary embodiment of a communication system 100 . The communication system 100 can comprise a number of processors 102 wirelessly coupled to a network 101 for communicating with a server 104 . The speech processors 102 can utilize common wireless access technologies such as Bluetooth™, Wireless Fidelity (WiFi), Worldwide Interoperability for Microwave Access (WiMAX), Ultra Wide Band (UWB), software defined radio (SDR), Zigbee, or cellular for accessing the network 101 . The network 101 can comprise a number of dispersed wireless access points that supply the speech processors 102 wireless communication services in an expansive geographic area according to any of the aforementioned wireless protocols. The server 104 can comprise a scalable computing device for performing the operations depicted in the present disclosure. The communication system 100 can have many applications including among others a means for task processing in a medical services environment, or managing logistics of a commercial enterprise such as inventory management, shipping, distribution, and so on.
[0009] FIG. 2 depicts an exemplary embodiment of the speech processor 102 . The speech processor 102 can comprise a wireless transceiver 202 , a user interface (UI) 204 , a headset 205 , a power supply 214 , and a controller 206 for managing operations of the foregoing components. The wireless transceiver 202 can utilize common communication technologies to support singly or in combination any number of wireless access technologies of the network 101 including without limitation Bluetooth™, WiFi, WiMax, Zigbee, UWB, SDR, and cellular access technologies such as CDMA-1X, W-CDMA/HSDPA, GSM/GPRS, TDMA/EDGE, and EVDO. SDR can be utilized for accessing public and private communication spectrum with any number of communication protocols that can be dynamically downloaded over-the-air to the speech processor 102 . Next generation wireless access technologies can also be applied to the present disclosure.
[0010] The UI 204 can include a keypad 208 with depressible or touch sensitive keys, a touch sensitive screen, and/or a navigation disk for manipulating operations of the speech processor 102 . The UI 204 can further include a display 210 such as monochrome or color LCD (Liquid Crystal Display) for conveying images to the end user of the speech processor 102 , and an audio system 212 for conveying audible signals to the end user and for intercepting audible signals from the end user by way of a tethered or wireless headset 205 .
[0011] The power supply 214 can utilize common power management technologies such as rechargeable and/or replaceable batteries, supply regulation technologies, and charging system technologies for supplying energy to the components of the speech processor 102 and to facilitate portable applications. The controller 206 can utilize computing technologies such as a microprocessor and/or digital signal processor (DSP) with associated storage memory such a Flash, ROM, RAM, SRAM, DRAM or other like technologies for controlling operations of the speech processor 102 .
[0012] FIG. 3 depicts an exemplary method 300 operating in the speech processor 102 . Method 300 can operate in a portion of the speech processor 102 as software, hardware, or combinations thereof. FIGS. 4-8 depict exemplary embodiments of portions of method 300 .
[0013] With this in mind, method 300 begins with step 302 in which a first audio signal is transmitted to an end user of the speech processor 102 . The audio signal can be, for example, a “low battery” chirp or a voice message (such as a logistics command, medical directive, or status) transmitted by way of a speaker or audio transducer circuit of the audio system 212 . In applications where the speech processor 102 is configured for full duplex communications, a second audio signal can be received in step 304 by the audio system 212 while the first audio signal is transmitted. The second audio signal can include voice signals of the end user such as a command, or speech responsive to the first audio signal, as well as other ambient sounds.
[0014] Because both input and output channels are concurrently active in the audio system 212 , leakages, crosstalk, reflections, audio loopback, echoes or any number of other distortions from the first audio signal can be inadvertently injected electrically or electro-magnetically into the second audio signal by, for example, a tethered headset 205 that couples to the audio system 212 with a common ground shared between the speaker and microphone elements of the headset 205 . Steps 306 - 308 can be applied to the speech processor 102 for removing this distortion. In step 306 , the audio system 212 can be designed or programmed to generate delayed samples of the first audio signal according to a delay estimated between the first and second audio signals. In step 308 , the audio system 212 can be designed to remove a portion of the first audio signal from the second audio signal by using the delayed samples of the first audio signal, the second audio signal, and a filtered received signal generated thereby.
[0015] FIG. 4 depicts an exemplary embodiment of steps 306 - 308 . In this embodiment, the controller 206 is coupled to the audio system 212 by way of a digital interface. The audio system 212 comprises a codec 402 , a delay estimation module 404 and a filtration module 406 . The codec 402 includes a common digital to analog converter (DAC) for transforming digital samples of a first audio signal generated by the controller 206 into a first analog signal. The first analog signal is coupled to a common speaker circuit (not shown) of the audio system 212 for conveying audible signals to the end user.
[0016] The codec 402 further includes a common analog to digital converter (ADC) for transforming a second analog signal intercepted by a common microphone (not shown) of the audio system 212 into digital samples representing a second audio signal. The first audio signal can be supplied to the delay estimation module 404 from a feedback path located prior to the codec 402 , or from a digital feedback path (FB) within the codec 402 .
[0017] FIG. 5 depicts an exemplary embodiment of the delay estimation module 404 . The delay estimation module 404 can comprise a delay estimator 502 and associated delay element 504 for generating as discussed in step 306 delayed samples of the first audio signal according to an estimated delay between the first and second audio signals. The delay estimator 502 can utilize a common correlator for estimating the delay between the first and second audio signals. The delay element 504 utilizes common technology for delaying digital samples of the first audio signal according to the delay estimated by the delay estimator 502 . The delay estimator 404 time-aligns the signals that are received by the filtration module 406 with each other. It estimates and accounts for the difference in time between the first audio signal and the portion of the first audio signal received in the second audio signal. This difference can be due, for example, to asynchronous buffering (depicted by the letter “B” in FIGS. 4 and 7 ) at the interfaces of the codec 402 . In an alternative embodiment, the first audio signal can be constructed by the controller 206 with a marker signal which the delay estimation module 404 can utilize for assessing delay.
[0018] The filtration module 406 can comprise an adaptive filter such as, for example, a recursive least squares filter. FIG. 6 depicts an exemplary embodiment of the adaptive filter which comprises a filter estimator 602 and corresponding filter 604 coupled to a difference element 606 . The filter 604 can be instantiated as a finite impulse response (FIR) filter (herein referred to as FIR filter 604 ). The filter estimator 602 can comprise a recursive least squares estimator for adjusting the filter coefficients of the FIR filter 604 . The FIR filter 604 generates according to the delayed samples of the first audio signal and the coefficients determined by the filter estimator 602 a signal that approximates the portion of the first audio signal embedded in the second audio signal. Accordingly, the difference element 606 removes in whole or in part the portion of the first audio signal embedded in the second audio signal thereby generating the filtered signal which is in large part free of the distortions introduced by the first audio signal.
[0019] FIG.7 provides an alternative embodiment to the embodiment of FIG. 4 . In this embodiment, the first audio signal is fed back in analog form through the codec or by way of an external input channel thereby incurring the same or similar delay as the portion of the first audio signal that exists in the second audio signal. With a predictable delay applied to the first audio signal by way of the loopback internal or external to the codec 402 , the delay estimator can be removed and the filtration module 406 can operate as described earlier. This approach can be utilized when the two audio input channels (i.e., the second audio signal and the looped back first audio signal ) are synchronized. The second audio signal and the looped back first audio signal can be synchronized much like left and right stereo input channel signals are commonly synchronized in time.
[0020] FIG. 8 provides yet another alternative embodiment for steps 306 - 308 in which a common gain element 802 included in the codec 402 feeds back an adjusted first audio signal into a difference element 804 which removes in whole or in part a portion of the first audio signal embedded in the second signal thereby generating the filtered signal. This difference operation can be performed on either analog or digital signals. In this embodiment, the controller 206 can be programmed to perform signal processing on the filtered signal similar in operation to the filter estimator 602 and thereby adjust the gain element 802 to remove the embedded first audio signal in the incoming second audio signal.
[0021] Once the second audio signal has been filtered as described by the foregoing embodiments of FIGS. 4-8 , voice signals of the end user can be processed by the controller 206 in step 310 of FIG. 3 according to common voice processing techniques (e.g., speech recognition, speaker identification, speaker verification, and so on). According to the voice signal supplied by the end user, the controller 206 can be programmed in step 312 to transmit the processed voice signal to the server 104 of FIG. 1 (as text or unadulterated speech), or it can respond to said voice signals with a third audio signal. In a logistics or medical services application, for example, the end user's voice signals can represent commands or responses to commands emanating from the server 104 , or locally within the speech processor 102 .
[0022] It would be evident to an artisan with ordinary skill in the art that the aforementioned embodiments of method 300 for removing distortion associated with the first audio signal embedded in the second audio signal can be modified, reduced, or enhanced without departing from the scope and spirit of the claims described below. For example, all or a portion of the delay estimation module 404 and filtration module 406 can be embedded in the codec 402 or the controller 206 . Additionally, a portion of the controller 206 can be embedded in the codec 402 also. System 400 can be utilized as a single chip solution embodied in a computing device or audio headset. Similarly, all or a portion of the delay estimation module 404 and filtration module 406 can be implemented in software, hardware or firmware. These are but a few examples of modifications that can be applied to the present disclosure. Accordingly, the reader is directed to the claims below for a fuller understanding of the breadth and scope of the present disclosure.
[0023] The illustrations of embodiments described herein are intended to provide a general understanding of the structure of various embodiments, and they are not intended to serve as a complete description of all the elements and features of apparatus and systems that might make use of the structures described herein. Many other embodiments will be apparent to those of skill in the art upon reviewing the above description. Other embodiments may be utilized and derived therefrom, such that structural and logical substitutions and changes may be made without departing from the scope of this disclosure. Figures are also merely representational and may not be drawn to scale. Certain proportions thereof may be exaggerated, while others may be minimized. Accordingly, the specification and drawings are to be regarded in an illustrative rather than a restrictive sense.
[0024] Such embodiments of the inventive subject matter may be referred to herein, individually and/or collectively, by the term “invention” merely for convenience and without intending to voluntarily limit the scope of this application to any single invention or inventive concept if more than one is in fact disclosed. Thus, although specific embodiments have been illustrated and described herein, it should be appreciated that any arrangement calculated to achieve the same purpose may be substituted for the specific embodiments shown. This disclosure is intended to cover any and all adaptations or variations of various embodiments. Combinations of the above embodiments, and other embodiments not specifically described herein, will be apparent to those of skill in the art upon reviewing the above description.
[0025] The Abstract of the Disclosure is provided to comply with 37 C.F.R. §1.72(b), requiring an abstract that will allow the reader to quickly ascertain the nature of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. In addition, in the foregoing Detailed Description, it can be seen that various features are grouped together in a single embodiment for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed embodiments require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive subject matter lies in less than all features of a single disclosed embodiment. Thus the following claims are hereby incorporated into the Detailed Description, with each claim standing on its own as a separately claimed subject matter. | A system ( 100 ) and method ( 300 ) are disclosed for filtering signals. A system that incorporates teachings of the present disclosure may include, for example, a speech processor ( 102 ) having an audio system ( 212 ) for audibly transmitting a rendition of a message, and for removing a portion of the rendered message embedded in a received signal as a result of at least one among electrical and electrical-magnetic interference between the rendered message and the received signal, thereby generating a filtered received signal. The audio system can capture the received signal while audibly transmitting the rendered message. Additional embodiments are disclosed. | 7 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to the field of pumps and more particularly to a pump with an enhanced high-pressure seal.
[0003] 2. Description of the Related Art
[0004] High pressure pumps are used in many applications including hydraulic systems, pressure washers and presses. A high-pressure pump is described in U.S. Pat. No. 6,092,370 to Tremoulet, Jr. et al., issued on Jul. 25, 2000 and is hereby incorporated by reference in its entirety.
[0005] Often, high pressure pumps are used in applications where leaks are a problem. For example, a leaking pump in an airplane may cause the loss of hydraulic fluid. Furthermore, the lost fluid may create an environmental issue or, at least, may create a stain or a slippery area that may contribute to falling or slipping danger.
[0006] One problem area in high pressure pumps is the high pressure seal which helps keep pressurize fluids inside the pump. At high pressures, some exceeding 100,000 psi, high pressure seals often fail. It is believed that leaking of the high pressure seal may be the most common problems in high pressure pumps. The failure usually begins with a slow leak, wherein the pump is fully functional and only a small amount of fluid is lost. Furthermore, beyond a slight loss in output pressure, leaks from the high pressure seal can also impact other parts of the pump through loss of lubrication, fatigue and corrosion.
[0007] This problem is known in the industry and has been addressed by many solutions including placing a higher, more even force on the seal. For example, US Publication 2005/0074350A1 to Raghavan, et al., published Apr. 7, 2005, describes a “Device and Method for Maintaining a Static Seal of a High Pressure Pump,” and is hereby incorporated by reference. A pump is described in U.S. Pat. No. 3,966,360 to Greene, issued Jun. 29, 1976. This pump has an outer casing forming a reservoir. Such solutions may improve the performance of such seals, but they do not prevent the problem and, when a seal leaks, the loss of fluid or the resulting spill may cause problems.
[0008] What is needed is a pump with a high pressure seal in which any leaking in the high pressure seal feed back into the input chamber of the pump.
SUMMARY OF THE INVENTION
[0009] In one embodiment, a pump is disclosed including a cylinder in which a fluid is compressed, an inlet for accepting a fluid into the pump, an inlet area connected to the inlet for transporting the fluid across the pump and a feed tube for transporting the fluid from the inlet area to the cylinder. A check valve is provided to allow the fluid to flow from the feed tube and into the cylinder while blocking the flow of the fluid from the cylinder back into the feed tube. A piston is configured within the cylinder for compressing the fluid and a piston rod is coupled to the piston for exerting force on the piston. The piston is held within the cylinder by a high pressure seal. A high-pressure output port is connected to the cylinder for outputting the fluid under pressure. The high pressure seal interfaces with the inlet area so that any leakage of the fluid through the high pressure seal leaks back into the inlet area.
[0010] In another embodiment, a method of reducing leakage in a pump is disclosed including providing a fluid into an inlet of a pump, the fluid flowing through an inlet area and flowing through a feed tube and flowing through a check valve and into a cylinder; then applying force to the piston within the cylinder to pressurize the fluid. The check valve prevents the fluid from leaving the cylinder back into the feed tube. The piston and cylinder are sealed using a high pressure seal and potential leakage is captured from the high pressure seal by interfacing the high pressure seal with the inlet area.
[0011] In another embodiment, a pump is disclosed including a cylinder having a bore in which a fluid may be compressed with an inlet for accepting the fluid into the pump and an inlet area connected to the inlet for conducting fluid across the pump. A feed tube for transports the fluid from the inlet area to a first end of the cylinder and a check valve allows the fluid to flow in one direction into the first end of the cylinder from the feed tube. A piston within the cylinder compresses the fluid whereby a piston rod coupled to the piston exerts force on the piston. A high pressure seal is provided for retaining the piston within the cylinder while retarding the fluid from leaking from the cylinder under pressure and a high-pressure output port is connected to a second end of the cylinder for outputting the fluid under pressure. The high pressure seal interfaces with the inlet area such that any leakage of the fluid through the high pressure seal feeds back into the inlet area.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The invention can be best understood by those having ordinary skill in the art by reference to the following detailed description when considered in conjunction with the accompanying drawings in which:
[0013] FIG. 1 illustrates a pictorial view of a pump of a first embodiment of the present invention.
[0014] FIG. 2 shows a cross section along line 2 - 2 of FIG. 1 .
[0015] FIG. 3 shows a cross section along line 2 - 2 of FIG. 1 .
[0016] FIG. 4 shows a cross section along line 2 - 2 of FIG. 1 .
DETAILED DESCRIPTION OF THE INVENTION
[0017] Reference will now be made in detail to the presently preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings. Throughout the following detailed description, the same reference numerals refer to the same elements in all figures.
[0018] Referring to FIG. 1 , a pictorial view of a pump present invention is shown. Shown is the pump 10 with inlet 11 providing a source of fluids to the pump. A mounting plate 34 is provided with mounting bolts 32 . Tie rods 24 are provided to maintain pressure on the seals. A piston rod adapter 24 provides reciprocating motion to a piston within the pump 10 , pressurizing the fluid.
[0019] Referring now to FIG. 2 , the components of the pump 10 will be described. A mounting plate 34 has mounting bolts 32 for mounting the pump 10 to other equipment. A piston rod 25 couples the piston rod adapter 24 to the piston 26 so that reciprocating motion applied to the piston rod adapter 24 causes the piston 26 to move in and out of the cylinder 27 formed by cylinder walls 29 . An inlet 11 is provided for allowing fluid to enter the pump 10 through the inlet area 13 , where it flows through to a feed tube 24 and enters the cylinder 27 through a first check valve 16 which restricts the direction of flow of the fluid in a direction into the cylinder. In some embodiments, the check valve 16 is a ball 16 made of a hard material such as steel. In some embodiments, the ball 16 prevents a reverse flow of fluids by seating against a seat 19 when reverse pressure is applied. In some embodiments, gravity or fluid pressure seats the ball 16 . In some embodiments, a spring 17 maintains pressure on the ball 16 to reduce back pressure.
[0020] In some embodiments, a second check valve 18 is adapted within the piston 26 , restricting the direction of flow of fluid, allowing flow from within the cylinder 27 below the piston 26 into the cylinder 27 above the piston 26 . A high pressure seal 14 helps prevent fluid under a high pressure from leaking while a low-pressure seal 12 helps prevent low pressure fluid from leaking. A guide bushing 9 keeps the low pressure seal 12 in place. To prevent external leakage of fluid, the high pressure seal 14 is interfaced and enclosed by the fluid inlet area 13 such that leakage through the high pressure seal 14 will seep into the fluid inlet area 13 and re-circulate through the pump 10 instead of exiting the pump 10 .
[0021] Referring now to FIGS. 3 and 4 , the operation of the pump will be described. FIG. 3 describes the operation of the pump during an up stroke of the piston rod 25 . During this, as the piston 26 moves up within the cylinder 27 , the space vacated by the piston 26 is replaced by fluid entering through the check valve 16 from the feed tube 24 , which receives fluid through an inlet 11 , passing through inlet area 13 . During this movement, fluid from a previous stroke 31 in the cylinder above the piston 26 is prevented from flowing back below the piston 26 by a second check valve 18 , thereby forcing the fluid under high pressure to exit the outlet 29 . FIG. 4 describes the operation of the pump during a down stroke of the piston rod 25 . During this, the piston 26 moves down within the cylinder 27 , placing a pressure on the fluid already within the cylinder 27 . The check valve 16 prevents the fluid from exiting through the feed tube 24 . Being that the volume of the lower part of the cylinder 27 is greater than the volume of the cylinder above 31 the piston 26 , the fluid is forced through the second check valve 18 and into the upper portion of the cylinder and out the outlet 29 under pressure.
[0022] Being that the fluid is under a very high pressure, a high pressure seal 14 helps prevent the high pressure liquid from leaking out of the pump. A low pressure seal 12 is provided to help keep low pressure fluids from leaking out of the pump 10 . A guide bushing 9 keeps the low pressure seal 12 in place. Being that the high pressure seal interfaces with the fluid inlet area 13 , any fluid leaking through the high pressure seal 14 will re-circulate through the inlet area 13 and mix with low pressure fluid, flowing back through the feed tube 24 into the pump 10 instead of exiting the pump.
[0023] Equivalent elements can be substituted for the ones set forth above such that they perform in substantially the same manner in substantially the same way for achieving substantially the same result. Although the above description describes a double acting pump, in that a symmetrical pressure is created on both the up stroke and the down stroke, the same high-pressure seal and fluid inlet area interface can be equally applied to a single action pump without veering from the present invention.
[0024] It is believed that the system and method of the present invention and many of its attendant advantages will be understood by the foregoing description. It is also believed that 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 exemplary and explanatory embodiment thereof. It is the intention of the following claims to encompass and include such changes. | The invention concerns a fluid pump with a cylinder, piston and check valve for compressing the fluid having a high-pressure seal for precluding leakage of pressurized fluid. Any leakage from the high-pressure seal feeds back into an inlet area of the pump and recycles through the pump instead of leaking externally. | 5 |
RELATED APPLICATIONS
This patent application is a continuation of U.S. patent application Ser. No. 13/937,512, filed Jul. 9, 2013, which is a continuation of U.S. patent application Ser. No. 13/441,783, filed Apr. 6, 2012, now U.S. Pat. No. 8,632,760, issued Jan. 21, 2014, which is a continuation of U.S. patent application Ser. No. 13/356,284, filed Jan. 23, 2012, now U.S. Pat. No. 8,263,054, issued Sep. 11, 2011, which is a continuation of U.S. patent application Ser. No. 12/425,933, filed Apr. 17, 2009, now U.S. Pat. No. 8,298,518, issued Oct. 30, 2012, which is a continuation of U.S. patent application Ser. No. 11/943,714, filed Nov. 21, 2007, now U.S. Pat. No. 8,038,988, issued Oct. 18, 2011, which is a continuation of U.S. patent application Ser. No. 11/805,122, filed May 22, 2007, now U.S. Pat. No. 8,101,161, issued Jan. 24, 2012, which is a continuation of U.S. patent application Ser. No. 10/345,788, which was filed on Jan. 15, 2003, now U.S. Pat. No. 7,351,404, issued Apr. 1, 2008, which claims the benefit of U.S. Provisional Application No. 60/354,425, filed on Feb. 4, 2002, all of which are hereby incorporated by reference herein.
FIELD OF THE INVENTION
This invention relates to a method for stimulating the growth of mammalian hair comprising the application to mammalian skin of a cyclopentane heptanoic acid, 2-cycloalkyl or arylalkyl derivative or a pharmacologically acceptable acid addition salt thereof, alone, or in association with a topical pharmaceutical carrier.
BACKGROUND OF THE INVENTION
Dermatologists recognize many different types of hair loss, the most common by far being “alopecia” wherein human males begin losing scalp hair at the temples and on the crown of the head as they get older. While this type of hair loss is largely confined to males, hence its common name “male pattern baldness,” it is not unknown in women. No known cure has yet been found despite continuing attempts to discover one.
A good deal is known about various types of human hair and its growth patterns on various parts of the body.
For purposes of the present invention, it is necessary to consider various types of hair, including, terminal hairs and vellus hairs and modified terminal hairs, such as seen in eye lashes and eye brows. Terminal hairs are coarse, pigmented, long hairs in which the bulb of the hair follicle is seated deep in the dermis. Vellus hairs, on the other hand, are fine, thin, non-pigmented short hairs in which the hair bulb is located superficially in the dermis. As alopecia progresses, a transition takes place in the area of approaching baldness wherein the hairs themselves are changing from the terminal to the vellus type.
Another factor that contributes to the end result is a change in the cycle of hair growth. All hair, both human and animal, passes through a life cycle that includes three phases, namely, the anagen phase, the catagen phase and the telogen phase. The anagen phase is the period of active hair growth and, insofar as scalp hair is concerned, this generally lasts from 3-5 years. The catagen phase is a short transitional phase between the anagen and telogen phases which, in the case of scalp hair, lasts only 1-2 weeks. The final phase is the telogen phase which, for all practical purposes, can be denominated a “resting phase” where all growth ceases and the hair eventually is shed preparatory to the follicle commencing to grow a new one. Scalp hair in the telogen phase is also relatively short-lived, some 3-4 months elapsing before the hair is shed and a new one begins to grow.
Under normal hair growth conditions on the scalp, approximately 88% of the hairs are in the anagen phase, only 1% in catagen and the remainder in telogen. With the onset of male pattern baldness, a successively greater proportion of the hairs are in the telogen phase with correspondingly fewer in the active growth anagen phase.
Alopecia is associated with the severe diminution of hair follicles. A bald human subject will average only about 306 follicles per square centimeter, whereas, a non-bald human in the same age group will have an average of 460 follicles per square centimeter. This amounts to a one-third reduction in hair follicles which, when added to the increased proportion of vellus hair follicles and the increased number of hair follicles in the telogen phase, is both significant and noticeable. Approximately 50% of the hairs must be shed to produce visible thinning of scalp hair. It is thus a combination of these factors: transition of hairs from terminal to vellus, increased number of telogen hairs—some of which have been shed, and loss of hair follicles that produces “baldness”.
While a good deal is known about the results of male pattern baldness, very little is known about its cause. The cause is generally believed to be genetic and hormonal in origin although, the known prior art attempts to control it through hormone adjustment have been singularly unsuccessful.
One known treatment for male pattern alopecia is hair transplantation. Plugs of skin containing hair are transplanted from areas of the scalp where hair is growing to bald areas with reasonable success; however, the procedure is a costly one in addition to being time-consuming and quite painful. Furthermore, the solution is inadequate from the standpoint that it becomes a practical, if not an economic, impossibility to replace but a tiny fraction of the hair present in a normal healthy head of hair.
Other non-drug related approaches to the problem include such things as ultra-violet radiation, massage, psychiatric treatment and exercise therapy. None of these, however, has been generally accepted as being effective. Even such things as revascularization surgery and acupuncture have shown little, if any, promise.
By far, the most common approach to the problem of discovering a remedy for hair loss and male pattern alopecia has been one of drug therapy. Many types of drugs ranging from vitamins to hormones have been tried and only recently has there been any indication whatsoever of even moderate success. For instance, it was felt for a long time that since an androgenic hormone was necessary for the development of male pattern baldness, that either systemic or topical application of an antiandrogenic hormone would provide the necessary inhibiting action to keep the baldness from occurring. The theory was promising but the results were uniformly disappointing.
The androgenic hormone testosterone was known, for example, to stimulate hair growth when applied topically to the deltoid area as well as when injected into the beard and pubic regions. Even oral administration was found to result in an increased hair growth in the beard and pubic areas as well as upon the trunk and extremities. While topical application to the arm causes increased hair growth, it is ineffective on the scalp and some thinning may even result. Heavy doses of testosterone have even been known to cause male pattern alopecia.
Certain therapeutic agents have been known to induce hair growth in extensive areas of the trunk, limbs and even occasionally on the face. Such hair is of intermediate status in that it is coarser than vellus but not as coarse as terminal hair. The hair is generally quite short with a length of 3 cm. being about maximum. Once the patient ceases taking the drug, the hair reverts to whatever is normal for the particular site after six months to a year has elapsed. An example of such a drug is diphenylhydantoin which is an anticonvulsant drug widely used to control epileptic seizures. Hypertrichosis is frequently observed in epileptic children some two or three months after starting the drug and first becomes noticeable on the extensor aspects of the limbs and later on the trunk and face. (The same pattern of hypertrichosis is sometimes caused by injury to the head.) As for the hair, it is often shed when the drug is discontinued but may, in some circumstances, remain.
Streptomycin is another drug that has been found to produce hypertrichosis, in much the same way as diphenylhydantoin, when administered to children suffering from tuberculous meningitis. About the same effects were observed and the onset and reversal of the hypertrichosis in relation to the period of treatment with the antibiotic leave little question but that it was the causative agent.
Two treatments have been demonstrated as showing some promise in reversing male pattern alopecia. These treatments include the use of a microemulsion cream containing both estradiol and oxandrolone as its active ingredients and the use of organic silicon.
In addition to the foregoing, it has been reported in U.S. Pat. Nos. 4,139,619 and 4,968,812 that the compound minoxidil is useful for the treatment of male pattern baldness. That compound, among others, has proven to have considerable therapeutic value in the treatment of severe hypertension. It is a so-called “vasodilator” which, as the name implies, functions to dilate the peripheral vascular system. Dermatologists and others have recognized that prolonged vasodilation of certain areas of the human body other than the scalp sometimes result in increased hair growth even in the absence of any vasodilating therapeutic agent. For instance, increased hair growth around surgical scars is not uncommon. Similarly, arteriovenous fistula have been known to result in increased vascularity accompanied by enhanced hair growth. Externally-induced vasodilation of the skin, such as, for example, by repeated biting of the limbs by the mentally retarded and localized stimulation of the shoulders by water carries has been known to bring on hypertrichosis in the affected areas. Be that as it may, similar techniques such as continued periodic massage of the scalp have been found to be totally ineffective as a means for restoring lost hair growth to the scalp. Scar tissue on the scalp inhibits rather than promotes hair growth.
U.S. Pat. No. 6,262,105 to Johnstone suggests that prostaglandins and derivatives thereof are useful in a method of enhancing hair growth.
Bimatoprost, which is sold by Allergan, Inc. of Irvine, Calif., U.S.A. as Lumigan® ophthalmic solution, for treating glaucoma now has been found as being effective to increase the growth of eyelashes when applied in the FDA approved manner.
It is, therefore, a principal object of the present invention to provide a novel and effective treatment for the stimulation of hair growth and the treatment of male pattern baldness.
Another object of the invention is to provide a method of stimulating hair growth in humans and non-human animals that is compatible with various types of therapeutic agents or carriers and, therefore, would appear to be combinable with those which, by themselves, demonstrate some therapeutic activity such as, for example, microemulsion creams or topical compositions containing estradiol and oxandrolone, minoxidil or agents that block the conversion of testosterone to dihydrotesterone (Procipia).
Still another objective is the provision of a treatment for the stimulation of hair growth which, while effective for its intended purpose, is apparently non-toxic and relatively free of unwanted side effects.
An additional object of the invention herein disclosed and claimed is to provide a method for treating hair loss in men or women which can be applied by the patient under medical supervision no more stringent than that demanded for other topically-administered therapeutic agents.
Other objects of the invention are to provide a treatment for male pattern alopecia which is safe, simple, painless, cosmetic in the sense of being invisible, easy to apply and quite inexpensive when compared with hair transplants and the like.
SUMMARY OF THE INVENTION
This invention provides pharmaceutical compositions for topical application to enhance hair growth comprising an effective amount of a cyclopentane heptanoic acid, 2-cycloalkyl or arylalkyl compound represented by the formula I
wherein the dashed bonds represent a single or double bond which can be in the cis or trans configuration, A is an alkylene or alkenylene radical having from two to six carbon atoms, which radical may be interrupted by one or more oxa radicals and substituted with one or more hydroxy, oxo, alkyloxy or alkylcarboxy groups wherein said alkyl radical comprises from one to six carbon atoms; B is a cycloalkyl radical having from three to seven carbon atoms, or an aryl radical, selected from the group consisting of hydrocarbyl aryl and heteroaryl radicals having from four to ten carbon atoms wherein the heteroatom is selected from the group consisting of nitrogen, oxygen and sulfur atoms; X is —N(R 4 ) 2 wherein R 4 is selected from the group consisting of hydrogen, a lower alkyl radical having from one to six carbon atoms,
wherein R 5 is a lower alkyl radical having from one to six carbon atoms; Z is ═O; one of R 1 and R 2 is ═O, —OH or a —O(CO)R 6 group, and the other one is —OH or —O(CO)R 6 , or R 1 is ═O and R 2 is H, wherein R 6 is a saturated or unsaturated acyclic hydrocarbon group having from 1 to about 20 carbon atoms, or —(CH 2 )mR 7 wherein m is 0 or an integer of from 1 to 10, and R 7 is cycloalkyl radical, having from three to seven carbon atoms, or a hydrocarbyl aryl or heteroaryl radical, as defined above in free form or a pharmaceutically acceptable salt thereof, in association with a pharmaceutical carrier adapted for topical application to mammalian skin.
Preferably, the compound is a cyclopentane heptanoic acid, 2-(phenyl alkyl or phenyloxyalkyl) represented by the formula II
wherein y is 0 or 1, x is 0 or 1 and x and y are not both 1, Y is a radical selected from the group consisting of alkyl, halo, e.g. fluoro, chloro, etc., nitro, amino, thiol, hydroxy, alkyloxy, alkylcarboxy, halo substituted alkyl wherein said alkyl radical comprises from one to six carbon atoms, etc. and n is 0 or an integer of from 1 to 3 and R 3 is ═O, —OH or —O(CO)R 6 wherein R 6 is as defined above or a pharmaceutically acceptable salt thereof.
More preferably the compound is a compound of formula III.
wherein hatched lines indicate α configuration, solid triangles are used to indicate β configuration.
More preferably y is 1 and x is O and R 1 , R 2 and R 3 are hydroxy.
Most preferably the compound is cyclopentane N-ethyl heptanamide-5-cis-2-(3α-hydroxy-5-phenyl-1-trans-pentenyl)-3,5-dihydroxy, [1 α ,2 α ,3 α ,5 α ], also known as bimatoprost.
Another aspect of the invention provides methods for stimulating the rate of hair growth and for stimulating the conversion of vellus hair or intermediate hair to growth as terminal hair in a human or non-human animal by administering to the skin of the animal an effective amount of a compound wherein the compound has the formula:
wherein the dashed bonds represent a single or double bond which can be in the cis or trans configuration, A is an alkylene or alkenylene radical having from two to six carbon atoms, which radical may be interrupted by one or more oxa radicals and substituted with one or more hydroxy, oxo, alkyloxy or alkylcarboxy groups wherein said alkyl radical comprises from one to six carbon atoms; B is a cycloalkyl radical having from three to seven carbon atoms, or an aryl radical, selected from the group consisting of hydrocarbyl aryl and heteroaryl radicals having from four to ten carbon atoms wherein the heteroatom is selected from the group consisting of nitrogen, oxygen and sulfur atoms; X is —N(R 4 ) 2 wherein R 4 is selected from the group consisting of hydrogen, a lower alkyl radical having from one to six carbon atoms,
wherein R 5 is a lower alkyl radical having from one to six carbon atoms; Z is ═O; one of R 1 and R 2 is ═O, —OH or a —O(CO)R 6 group, and the other one is —OH or —O(CO)R 6 , or R 1 is ═O and R 2 is H, wherein R 6 is a saturated or unsaturated acyclic hydrocarbon group having from 1 to about 20 carbon atoms, or —(CH 2 )mR 7 wherein m is 0 or an integer of from 1 to 10, and R 7 is cycloalkyl radical, having from three to seven carbon atoms, or a hydrocarbyl aryl or heteroaryl radical, as defined above in free form or a pharmaceutically acceptable salt thereof.
These and other aspects of the invention will become apparent from the description of the invention which follows below.
BRIEF DESCRIPTION OF THE DRAWING FIGURE
The FIGURE shows the effect on the eyelashes of one patient treated for glaucoma with Lumigan® bimatoprost for six months.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Alopecia (baldness) a deficiency of either normal or abnormal hair, is primarily a cosmetic problem in humans. It is a deficiency of terminal hair, the broad diameter, colored hair that is readily seen. However, in the so-called bald person although there is a noticeable absence of terminal hair, the skin does contain vellus hair which is a fine colorless hair which may require microscopic examination to determine its presence. This vellus hair is a precursor to terminal hair. In accordance with the invention as described herein, compounds represented by
wherein R 1 , R 2 , A, B, Z and X are defined above, can be used to stimulate, such as stimulating the conversion of vellus hair to growth as terminal hair as well as increasing the rate of growth of terminal hair.
The present invention was discovered as follows:
In the course of treating patients having glaucoma, treatment may only be appropriate in one eye. Within the course of daily practice it was discovered that a patient who been treated with bimatoprost has lashes that were longer, thicker and fuller in the treated eye than in the non-treated eye. On examination the difference was found to be very striking. The lashes were longer and had a more full dense appearance in the treated eye. The lash appearance on the lids of the treated eye would have appeared quite attractive if it represented a bilateral phenomenon. Because of its asymmetric nature, the long lashes on one side could be construed as disturbing from a cosmetic standpoint. Because of the very unusual appearance a systematic examination of other patients who were taking bimatoprost in only one eye was made. It soon became apparent that this altered appearance was not an isolated finding. Comparison of the lids of patients who were taking bimatoprost in only one eye revealed subtle changes in the lashes and adjacent hairs of the bimatoprost-treated side in several patients. Definite differences could be identified to varying degrees in the lashes and adjacent hairs of all patients who were taking the drug on a unilateral basis for longer than 6 months.
These findings were totally unexpected and surprising. Minoxidil is thought to stimulate hair growth by its ability to cause vasodilation suggesting that agents with such a capability may be uniquely effective in stimulating hair growth. The finding that bimatoprost, which, as explained below, is not a prostaglandin derivative, such as latanoprost stimulates hair growth is especially surprising and unexpected.
The changes in the lashes were apparent on gross inspection in several patients once attention was focused on the issue. In those with light colored hair and lashes, the differences were only seen easily with the aid of the high magnification and lighting capabilities of the slit lamp biomicroscope. In the course of a glaucoma follow up examination, attention is generally immediately focused on the eye itself. Because of the high power magnification needed only one eye is seen at a time and the eye is seen at a high enough power that the lashes are not in focus. At these higher powers, any lash asymmetry between the two eyes is not likely to be noticed except by careful systematic comparison of the lashes and adjacent hairs of the eyelids of the two eyes.
Observed parameters leading to the conclusion that more robust hair growth occurred in the treated area following administration of bimatroprost were multiple. They included increased length of lashes, increased numbers of lashes along the normal lash line, increased thickness and luster of lashes, increased auxiliary lash-like terminal hair in transitional areas adjacent to areas of normal lash growth, increased lash-like terminal hairs at the medial and lateral canthal area, increased pigmentation of the lashes, increased numbers, increased length, as well as increased luster, and thickness of fine hair on the skin of the adjacent lid, and finally increased perpendicular angulation of lashes and lash-like terminal hairs. The conclusion that hair growth is stimulated by bimatoprost is thus supported not by evidence of a difference in a single parameter but is based on multiple parameters of hair appearance in treated vs. control areas in many subjects. This finding is entirely unexpected and represents a previously unrecognized effect of bimatoprost on stimulation of hair follicles. The modified hairs of the lashes normally turn over slowly and are in their resting phase longer than hair on, for example, the scalp. The ability to cause differences in appearance of lashes, the ability to stimulate conversion of vellus or intermediate hair to terminal hairs in transitional areas and the ability to stimulate growth of vellus hair on the skin indicates that bimatoprost is a diversely effective and efficacious agent for the stimulation of hair growth. Thus, the present invention provides a treatment by bimatoprost of hair of the scalp, eyebrows, beard and other areas that contain hair that results in increased hair growth in the corresponding areas.
Patients that are treated in or around the eye with compounds of the invention, such as bimatoprost, regularly develop hypertrichosis including altered differentiation, numbers, length, thickness, curvature and pigmentation in the region of treatment.
Some examples of representative compounds useful in the practice of the present invention include the compounds shown in Table 1:
TABLE 1
cyclopentane heptenamide-5-cis-2-(3α-hydroxy-5-phenyl-
1-trans-pentenyl)-3,5-dihydroxy, [1 α , 2 β , 3 α , 5 6 α]
cyclopentane N,N-dimethylheptenamide-5-cis-2-(3α-hydroxy-5-phenyl-
1-trans-pentenyl)-3,5-dihydroxy, [1 α , 2 β , 3 α , 5 α ]
cyclopentane heptenylamide-5-cis-2-(3α-hydroxy-4-meta-chlorophenoxy-
1-trans-pentenyl)-3,5-dihydroxy, [1 α , 2 β , 3 α , 5 α ]
cyclopentane heptenylamide-5-cis-2-(3α-hydroxy-4-trifluoromethyl-
phenoxy-1-trans-pentenyl)-3,5-dihydroxy, [1 α , 2 β , 3 α , 5 α ]
cyclopentane N-isopropyl heptenamide-5-cis-2-(3α-hydroxy-5-phenyl-
1-trans-pentenyl)-3,5-dihydroxy, [1 α , 2 β , 3 α , 5 α ]
cyclopentane N-ethyl heptenamide-5-cis-2-(3α-hydroxy-5-phenyl-
1-trans-pentenyl)-3,5 dihydroxy, [1 α , 2 β , 3 α , 5 α ]
cyclopentane N-methyl heptenamide-5-cis-2-(3α-hydroxy-5-phenyl-
1-trans-pentenyl)-3,5-dihydroxy, [1 α , 2 β , 3 α , 5 α ]
cyclopentane heptenamide-5-cis-2-(3α-hydroxy-4-meta-chlorophenoxy-
1-trans-butenyl)-3,5-dihydroxy, [1 α , 2 β , 3 α , 5 α ]
One presently preferred compound for use in the practice of the present invention is cyclopentane N-ethyl heptanamide-5-cis-2-(3α-hydroxy-5-phenyl-1-trans-pentenyl)-3,5-dihydroxy, [1 α ,2 α ,3 α ,5 α ], also known as bimatoprost and sold under the name of Lumigan® by Allergan, Inc., California, USA. This compound has the following structure:
The synthesis of the above compounds described above has been disclosed in U.S. Pat. No. 5,607,978. This patent also shows, particularly in Examples 1, 2, 5 and 7 that these compounds are not prostaglandins, in that they do not behave as prostaglandins in art-recognized assays for prostaglandin activity. The invention thus relates to the use of the above compounds, or prodrugs of the active compounds, for treatment for the stimulation of hair growth. As used herein, hair growth includes hair associated with the scalp, eyebrows, eyelids, beard, and other areas of the skin of animals.
In accordance with one aspect of the invention, the compound is mixed with a dermatologically compatible vehicle or carrier. The vehicle which may be employed for preparing compositions of this invention may comprise, for example, aqueous solutions such as e.g., physiological salines, oil solutions or ointments. The vehicle furthermore may contain dermatologically compatible preservatives such as e.g., benzalkonium chloride, surfactants like e.g., polysorbate 80, liposomes or polymers, for example, methyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone and hyaluronic acid; these may be used for increasing the viscosity. Furthermore, it is also possible to use soluble or insoluble drug inserts when the drug is to be administered.
The invention is also related to dermatological compositions for topical treatment for the stimulation of hair growth which comprise an effective hair growth stimulating amount of one or more compounds as defined above and a dermatologically compatible carrier. Effective amounts of the active compounds may be determined by one of ordinary skill in the art but will vary depending on the compound employed, frequency of application and desired result, and the compound will generally range from about 0.0000001 to about 50%, by weight, of the dermatological composition, preferably. from about 0.001 to about 50%, by weight, of total dermatological composition, more preferably from about 0.1 to about 30%, by weight of the composition.
The present invention finds application in all mammalian species, including both humans and animals. In humans, the compounds of the subject invention can be applied for example, to the scalp, face, beard, head, pubic area, upper lip, eyebrows, and eyelids. In animals raised for their pelts, e.g., mink, the compounds can be applied over the entire surface of the body to improve the overall pelt for commercial reasons. The process can also be used for cosmetic reasons in animals, e.g., applied to the skin of dogs and cats having bald patches due to mange or other diseases causing a degree of alopecia.
The pharmaceutical compositions contemplated by this invention include pharmaceutical compositions suited for topical and local action.
The term “topical” as employed herein relates to the use of a compound, as described herein, incorporated in a suitable pharmaceutical carrier, and applied at the site of thinning hair or baldness for exertion of local action. Accordingly, such topical compositions include those pharmaceutical forms in which the compound is applied externally by direct contact with the skin surface to be treated. Conventional pharmaceutical forms for this purpose include ointments, liniments, creams, shampoos, lotions, pastes, jellies, sprays, aerosols, and the like, and may be applied in patches or impregnated dressings depending on the part of the body to be treated. The term “ointment” embraces formulations (including creams) having oleaginous, water-soluble and emulsion-type bases, e.g., petrolatum, lanolin, polyethylene glycols, as well as mixtures of these.
Typically, the compounds are applied repeatedly for a sustained period of time topically on the part of the body to be treated, for example, the eyelids, eyebrows, skin or scalp. The preferred dosage regimen will generally involve regular, such as daily, administration for a period of treatment of at least one month, more preferably at least three months, and most preferably at least six months.
For topical use on the eyelids or eyebrows, the active compounds can be formulated in aqueous solutions, creams, ointments or oils exhibiting physiologically acceptable osmolarity by addition of pharmacologically acceptable buffers and salts. Such formulations may or may not, depending on the dispenser, contain preservatives such as benzalkonium chloride, chlorhexidine, chlorobutanol, parahydroxybenzoic acids and phenylmercuric salts such as nitrate, chloride, acetate, and borate, or antioxidants, as well as additives like EDTA, sorbitol, boric acid etc. as additives. Furthermore, particularly aqueous solutions may contain viscosity increasing agents such as polysaccharides, e.g., methylcellulose, mucopolysaccharides, e.g., hyaluronic acid and chondroitin sulfate, or polyalcohol, e.g., polyvinylalcohol. Various slow releasing gels and matrices may also be employed as well as soluble and insoluble ocular inserts, for instance, based on substances forming in-situ gels. Depending on the actual formulation and compound to be used, various amounts of the drug and different dose regimens may be employed. Typically, the daily amount of compound for treatment of the eyelid may be about 0.1 ng to about 100 mg per eyelid.
For topical use on the skin and the scalp, the compound can be advantageously formulated using ointments, creams, liniments or patches as a carrier of the active ingredient. Also, these formulations may or may not contain preservatives, depending on the dispenser and nature of use. Such preservatives include those mentioned above, and methyl-, propyl-, or butyl-parahydroxybenzoic acid, betain, chlorhexidine, benzalkonium chloride, and the like. Various matrices for slow release delivery may also be used. Typically, the dose to be applied on the scalp is in the range of about 0.1 ng to about 100 mg per day, more preferably about 1 ng to about 10 mg per day, and most preferably about 10 ng to about 1 mg per day depending on the compound and the formulation. To achieve the daily amount of medication depending on the formulation, the compound may be administered once or several times daily with or without antioxidants.
The invention is further illustrated by the following non-limiting examples:
Example 1
In Vivo Treatment
A study is initiated to systematically evaluate the appearance of lashes and hair around the eyes of patients who are administering bimatoprost in only one eye. The study involves 10 subjects, 5 male, 5 female, average age 70 years, (ranging from 50-94 years). All patients have glaucoma. Each subject is treated daily by the topical application of one drop of bimatoprost at a dosage of 1.5.mu.g/ml/eye/day (0.03%, by weight, ophthalmic solution, sold under the name Lumigan® by Allergan, Irvine, Calif., U.S.A.) to the region of one eye by instilling the drop onto the surface of the eye. The region of the fellow control eye is not treated with bimatoprost and served as a control.
In the course of treatment with eye drops, there is typically spontaneous tearing, and excess fluid from the drops and associated tears gathers at the lid margins. In the course of wiping the drug containing fluid from the lid margins and adjacent lid, a thin film of the fluid is routinely spread to contact the adjacent skin of the lid area. This widespread exposure of the skin around the lid to the effect of drops is regularly demonstrated in patients who develop a contact dermatitis. Typically the entire area of the upper and lower lid are involved with induration, erythema and edema demonstrating the regular extensive exposure of the ocular adnexa to the influence of topically applied drugs.
The study is limited to subjects who have administered bimatoprost to one eye for more than 3 months. The mean duration of exposure to bimatoprost prior to assessing the parameter of lash growth between the control and study eye is 129 days (range 90-254 days). Observations are made under high magnification at the slit lamp biomicroscope. Documentation of differences between the control and treatment areas is accomplished using a camera specially adapted for use with the slit lamp biomicroscope.
The results of the observations are as follows:
Length of lashes: Increased length of eyelashes is regularly observed on the side treated with bimatoprost. The difference in length varies from approximately 10% to as much as 30%.
Number of lashes: Increased numbers of lashes are observed in the treated eye of each patient. In areas where there are a large number of lashes in the control eye, the increased number of lashes in the bimatoprost-treated eye gave the lashes on the treated side a more thickly matted overall appearance.
Auxiliary lash-like hair growth: Several patients have an apparent increase in lash-like hair in transitional areas adjacent to areas of normal lash distribution. These prominent robust appear lash-like hairs appeared to be of comparable length to the actual lashes. These long, thick lash-like hairs were present in the central portion of the lids of several patients in a linear arrangement just above the lash line. Hairs are present at similar locations in the control eyes but are by contrast thinner or more fine in appearance, have less luster and pigment and are more flat against the skin of the lid typical of vellus or intermediate hairs. In several patients, lash-like terminal hairs grow luxuriantly in the medial canthal area in the treated eye. In the corresponding control eye, vellus hairs are seen at the same location. Lash-like hairs are also present in the lateral canthal area of the treated eye but not the control eye in several subjects. Large lashes are not normally present at the lateral canthus and the area is generally free of all but a few occasional very fine lashes or vellus hairs.
Increased growth of vellus hair on lids: Fine microscopic vellus hair is present on the skin of the lids and is easily seen with the slit lamp biomicroscope. This vellus hair is typically denser adjacent to and below the lateral portion of the lower lids. While remaining microscopic, vellus hairs are increased in number, appear more robust and are much longer and thicker in treated than in control eyes in the areas below and lateral to the lower lid.
Perpendicular angulation of hairs: In areas where there are lash-like hairs above the lash line and in the medial and lateral canthal areas, the hairs are much longer, thicker and heavier. They also leave the surface of the skin at a more acute angle, as though they are stiffer or held in a more erect position by more robust follicles. This greater incline, pitch, rise or perpendicular angulation from the skin surface gives the appearance of greater density of the hairs.
The foregoing observations clearly establish that bimatoprost can be used to increase the growth of hair in man. This conclusion is based on the regular and consistent finding of manifestations of increased hair growth in treated vs. control areas in human subjects. The conclusion that the drug bimatoprost is capable of inducing increased robust growth of hair is based not on a single parameter, i.e., length, but is based on multiple lines of evidence as described in the results. Detailed examination and description of multiple parameters of differences in hair is greatly facilitated by the ability to examine the hairs at high magnification under stable conditions of fixed focal length and subject position utilizing the capabilities of the slitlamp biomicroscope.
The FIGURE shows the actual results on the eyelashes of a patient treated for glaucoma with Lumigan® bimatoprost for 6 months.
Example 2
Topical Cream
A topical cream is prepared as follows: Tegacid and spermaceti are melted together at a temperature of 70-80° C. Methylparaben is dissolved in about 500 gm of water and propylene glycol, polysorbate 80, and bimatoprost are added in turn, maintaining a temperature of 75-80° C. The methylparaben mixture is added slowly to the Tegacid and spermaceti melt, with constant stirring. The addition is continued for at least 30 minutes with additional stirring until the temperature has dropped to 40-45° C. Finally, sufficient water is added to bring the final weight to 1000 gm and the preparation stirred to maintain homogeneity until cooled and congealed.
Example 3
Topical Cream
A topical cream is prepared as follows: Tegacid and spermaceti are melted together at a temperature of 70-80° C. Methylparaben is dissolved in water and propylene glycol, polysorbate 80, and bimatoprost are added in turn, maintaining a temperature of 75-80° C. The methylparaben mixture is added slowly to the Tegacid and spermaceti melt, with constant stirring. The addition is continued for at least 30 minutes with additional stirring until the temperature has dropped to 40-45° C. Finally, sufficient water is added to bring the final weight to 1000 gm and the preparation stirred to maintain homogeneity until cooled and congealed.
The composition is applied to bald human scalp once daily to stimulate the growth of hair.
Example 4
Topical Ointment
An ointment containing 2% by weight bimatoprost is prepared as follows:
White petrolatum and wool fat are melted, strained and liquid petrolatum is added thereto. The bimatoprost, zinc oxide, and calamine are added to the remaining liquid petrolatum and the mixture milled until the powders are finely divided and uniformly dispersed. The mixture is stirred into the white petrolatum, melted and cooled with stirring until the ointment congeals.
The foregoing ointment can be applied topically to mammalian skin for increased rate of hair growth, and can be prepared by omitting the zinc oxide and calamine.
Example 5
Ointment
A dermatological ophthalmic ointment containing 10% by weight bimatoprost is prepared by adding the active compound to light liquid petrolatum. White petrolatum is melted together with wool fat, strained, and the temperature adjusted to 45-50° C. The liquid petrolatum slurry is added and the ointment stirred until congealed. Suitably the ointment is packaged in 30 gm tubes.
The foregoing ointment can be applied to the eyelid to enhance the growth of eyelashes. Similarly the composition can be applied to the brow for eyebrow growth.
Example 6
Solution
An aqueous solution containing 5%, by weight, bimatoprost is prepared as follows. Bimatoprost is dissolved in water and the resulting solution is sterilized by filtration. The solution is aseptically filled into sterile containers.
The composition so prepared can be used in the topical treatment of baldness by application to the scalp daily.
Example 7
Lotion
A sample of bimatoprost is dissolved in the vehicle of N-methylpyrrolidone and propylene glycol. The composition can be used for application to dogs or cats having hair loss due to mange or alopecia of other causes.
Example 8
Aerosol
An aerosol containing approximately 0.1% by weight bimatoprost is prepared by dissolving the bimatoprost in absolute alcohol. The resulting solution filtered to remove particles and lint. This solution is chilled to about minus 30° C. To the solution is added a chilled mixture of dichlorodifluoromethane and dichlorotetrafluoroethane.
Thirteen ml plastic-coated amber bottles are cold filled with 11.5 gm each of the resulting solution and capped.
The composition can be sprayed on the scalp daily to stimulate the growth of hair.
Example 9
Dusting Powder
A powder of the compound bimatoprost is prepared by mixing in dry form with talcum powder at a weight/weight ratio of 1:10. The powdered mixture is dusted on the fur of minks or other commercially valuable fur bearing animals and show animals for increased rate of hair growth.
Example 10
Related Compounds
Following the procedure of the preceding Examples, compositions are similarly prepared substituting an equimolar amount of a compound of Table 1 for the bimatoprost disclosed in the preceding Examples. Similar results are obtained.
While the preferred embodiment of the invention has been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows: | Methods and compositions for stimulating the growth of hair are disclosed wherein said compositions include a cyclopentane heptanoic acid, 2-cycloalkyl or arylalkyl compound represented by the formula I
wherein the dashed bonds represent a single or double bond which can be in the cis or trans configuration, A, B, Z, X, R 1 and R 2 are as defined in the specification. Such compositions are used in treating the skin or scalp of a human or non-human animal. Bimatoprost is preferred for this treatment. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of PCT/CN2015/095549, filed on Nov. 25, 2015. The contents of PCT/CN2015/095549 are all hereby incorporated by reference. PCT/CN2015/095549 claims priority of Chinese application No. 201410770984.1, filed on Dec. 12, 2014.
BACKGROUND
Technical Field
[0002] The present disclosure relates to an electronic skin and a manufacturing method therefor.
Related Arts
[0003] An electronic skin is prepared by embedding various flexible thin film transistors (TFTs) and various sensors into a soft plastic thin film, and can satisfy large-area requirements of a human body because the electronic skin is soft and thin like a skin and is also an electronic device attached on a skin. The electronic skin not only can sense pressure and temperatures, but also can sense light, humidity, tension, ultrasonic waves, and the like, and can provide feedback in time to human body health data changes by means of real-time monitoring of human body health physiological indexes such as pulses, heartbeats, body temperatures, and muscle group vibrations, and even implement prophase prevention and diagnosis of diseases. Meanwhile, the electronic skin may further be equipped with a memory, and may also have the functions of wireless power supply and wireless data transmission, so that the electronic skin can be carried around, and perform continuous medical signal monitoring for a long time. Therefore, the technology opens a door leading to a micro mobile health monitor. It is necessary to provide a highly-sensitive and durable electronic skin with a simple structure.
SUMMARY
[0004] To resolve the foregoing technical problems, the present disclosure provides an electronic skin and a manufacturing method therefor. The electronic skin may simultaneously measure pressure and temperatures, and has a simple structure, a low working voltage, small power consumption, high sensitivity, and small interference between sensor signals.
[0005] To achieve the foregoing objectives, the present disclosure uses the following technical solutions:
[0006] The present disclosure discloses an electronic skin, where an oxide TFT, a pressure sensor, and a temperature sensor are disposed on a flexible substrate, the pressure sensor and the temperature sensor are respectively located on two sides of the flexible substrate, the oxide TFT includes a first TFT and a second TFT, the pressure sensor is configured to drive the first TFT, and the temperature sensor is configured to drive the second TFT.
[0007] Preferably, a material of the flexible substrate is polyimide having a thickness of 10 μm to 50 μm.
[0008] Preferably, the first TFT and the second TFT use a same top gate structure, and each of the pressure sensor and the temperature sensor is provided with a corresponding storage capacitor.
[0009] Preferably, each of the first TFT and the second TFT includes a drain, a source, a gate, an active layer, a first gate insulation layer, and a second gate insulation layer, and
[0010] the drain and the source are located on a same layer, the active layer is located on the layer where the corresponding drain and source are located and partially overlaps with the corresponding drain and source, the first insulation layer covers the corresponding active layer, the second insulation layer covers the corresponding drain and source and the first insulation layer, and the gate is located on the corresponding second insulation layer; and the source of the first TFT is connected to the pressure sensor, and the source of the second TFT is connected to the temperature sensor through a through hole of the flexible substrate.
[0011] Preferably, the drain, the source, and the gate of each of the first TFT and the second TFT use a metal electrode, a transparent conductive electrode, or a carbon nano-tube, the active layer of each of the first TFT and the second TFT uses a metal oxide semiconductor, the first insulation layer of each of the first TFT and the second TFT uses SiOx, and the second insulation layer of each of the first TFT and the second TFT uses SiNx.
[0012] In addition, the present disclosure further discloses a method for preparing an electronic skin, where a first TFT, a second TFT, a pressure sensor, and a temperature sensor are formed, by means of etching and deposition, on a flexible substrate whose double sides are covered with conductive materials, and the pressure sensor and the temperature sensor are respectively formed on two sides of the flexible substrate.
[0013] Preferably, the manufacturing method specifically comprises the following steps:
[0014] S 1 : etching a pattern A on one side of the flexible substrate whose double sides are covered with conductive materials, where the pattern A includes a source and a drain of the first TFT and a source and a drain of the second thin film transistor;
[0015] S 2 : etching a pattern B on the other side of the flexible substrate, where the pattern B includes an electrode of the temperature sensor;
[0016] S 3 : drilling a hole at a corresponding position, connected to the pattern B, of the flexible substrate, and electroplating the drilling position, so that the pattern B is electrically connected to the pattern A;
[0017] S 4 : forming a semiconductor layer on the pattern A, then depositing an insulation layer on the semiconductor layer, separately etching active layers of the first TFT and the second TFT on the semiconductor layer, separately etching first insulation layers of the first TFT and the second TFT on the insulation layer, and then depositing second insulation layers on the first insulation layers of the first TFT and the second TFT; and
[0018] S 5 : forming a conductive layer on the second insulation layers, and etching gates of the first TFT and the second TFT and the pressure sensor.
[0019] Preferably, step S 4 specifically includes:
[0020] S 41 : forming a metal oxide semiconductor layer on the pattern A by using a magnetron sputtering method, and then forming an SiOx layer on the metal oxide semiconductor layer by using an ALD method;
[0021] S 42 : respectively etching the first insulation layers of the first TFT and the second TFT on the SiOx layer by using a dry etching process, and respectively etching the active layers of the first TFT and the second TFT on the metal oxide semiconductor layer by using a wet etching process; and
[0022] S 43 : forming the second insulation layers of the first TFT and the second TFT on the first insulation layers of the first TFT and the second TFT by using a plasma enhanced chemical vapor deposition method (PECVD), and forming, by using a dry etching method, through holes at corresponding positions where the second insulation layers are connected to the sources.
[0023] Preferably, step S 5 specifically includes:
[0024] S 51 : forming the conductive layer on the second insulation layers of the first TFT and the second TFT by using a magnetron sputtering method, and etching the gates of the first TFT and the second TFT and lower electrodes of the pressure sensor and the temperature sensor;
[0025] S 52 : forming a passivation layer by using a PECVD method; and
[0026] S 53 : etching a sensitive area of the pressure sensor by using a dry etching process, forming a sensitive layer of the pressure sensor by using a printing method or an ink jet printing method, and then forming an upper electrode of the pressure sensor on the sensitive layer.
[0027] Preferably, a distance between the source and the drain of the first TFT is 2 μm to 20 μm and a distance between the source and the drain of the second TFT is 2 μm to 20 μm.
[0028] Compared with the prior art, beneficial effects of the present disclosure are that: in the electronic skin provided in the present disclosure, the pressure sensor and the temperature sensor are disposed on two sides of the flexible substrate, so that pressure and temperatures may be simultaneously measured; the electronic skin is flexible, and has a simple structure, a low working voltage, small power consumption, high sensitivity, and small interference between sensor signals.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] The present disclosure will become more fully understood from the detailed description given herein below for illustration only, and thus are not limitative of the present disclosure, and wherein:
[0030] FIG. 1 is a schematic sectional view of an electronic skin according to a preferable embodiment of the present disclosure;
[0031] FIG. 2 is an equivalent circuit diagram of a sensor unit;
[0032] FIG. 3 is a driving pulse diagram of the sensor unit;
[0033] FIG. 4 is a schematic diagram 1 of manufacturing of an electronic skin according to a preferable embodiment of the present disclosure;
[0034] FIG. 5 is a schematic diagram 2 of manufacturing of an electronic skin according to a preferable embodiment of the present disclosure;
[0035] FIG. 6 is a top view in a manufacturing process of an electronic skin according to a preferable embodiment of the present disclosure; and
[0036] FIG. 7 is a schematic diagram of a connection of a temperature sensor of an electronic skin according to a preferable embodiment of the present disclosure.
DETAILED DESCRIPTION
[0037] The present disclosure is described in further detail below with reference to embodiments and the accompanying drawings.
[0038] FIG. 1 is a schematic sectional view of an electronic skin according to a preferable embodiment of the present disclosure. The electronic skin includes a flexible substrate 50 . A first TFT, a second TFT, a pressure sensor, and a temperature sensor are disposed on the flexible substrate 50 . The pressure sensor and the temperature sensor are respectively located on two sides of the flexible substrate. The first TFT is configured to drive the pressure sensor, and the second TFT is configured to drive the temperature sensor. The first TFT includes a drain 11 , a source 12 , a gate 13 , an active layer 14 , a first insulation layer 15 , and a second insulation layer 16 . The second TFT includes a drain 21 , a source 22 , a gate 23 , an active layer 24 , a first insulation layer 25 , and a second insulation layer 26 . The drain 11 , the source 12 , the drain 21 , and the source 22 are located on a same layer. The active layer 14 is located on the layer where the drain 11 and the source 12 are located, and partially overlaps with the drain 11 and the source 12 . The active layer 24 is located on the layer where the drain 21 and the source 22 are located and partially overlaps with the drain 21 and the source 22 . The first insulation layer 15 covers the active layer 14 . The first insulation layer 25 covers the active layer 24 . The second insulation layer 16 covers the drain 11 , the source 12 , and the first insulation layer 15 . The second insulation layer 26 covers the drain 21 , the source 22 , and the first insulation layer 25 . The gate 13 is located on the second insulation layer 16 . The gate 23 is located on the second insulation layer 26 . The pressure sensor includes a lower electrode 31 , an upper electrode 32 , a pressure sensitive area 33 , and an electrode 34 . The lower electrode 31 of the pressure sensor is connected to the source 12 of the first TFT through a through hole 70 . The lower electrode 31 , the second insulation layer 16 , and the electrode 34 form a storage capacitor of the pressure sensor. Active areas of the pressure sensitive area 33 and the upper electrode 32 are limited by a passivation layer 60 . The temperature sensor includes a lower electrode 41 , an electrode 42 , a through hole 43 , and an electrode 44 . The electrode 42 of the temperature sensor is connected to the source 22 of the second TFT through a through hole 80 and the through hole 43 . The electrode 44 , the second insulation layer 26 , and the lower electrode 41 form a storage capacitor of the temperature sensor. Preferably, a material of the flexible substrate is polyimide having a thickness of 10 μm to 50 μm. The drain 11 , the source 12 , the gate 13 , the drain 21 , the source 22 , the gate 23 , the lower electrode 31 , the upper electrode 32 , the electrode 34 , the lower electrode 41 , the electrode 42 , the electrode 44 , and interconnected conductive layers may use a metal electrode, a transparent conductive electrode, conductive nano silver, a carbon nano-tube, and the like. The active layers 14 and 24 may use a metal oxide semiconductor, such as zinc tin oxide (ZTO) or indium gallium zinc oxide (IGZO). The first insulation layers 15 and 25 may use SiOx. The second insulation layers 16 and 26 may use SiNx. The pressure sensitive layer 33 may use a QTC material, a piezoelectric material, a piezoresistive material, or the like. The passivation layer 60 uses SiNx.
[0039] A sensor unit of the electronic skin may read, by means of scanning and addressing, electrical signals generated by means of pressure and temperature changes. An equivalent circuit of the sensor unit is shown in FIG. 2 , and a corresponding driving pulse is shown in FIG. 3 . A row electrode 110 is connected to the gate of the first TFT T 1 ; a signal of a row driver 130 provides a scan pulse Vgate to the first TFT T 1 to select a row electrode; the source of the first TFT T 1 and the source of the second TFT T 2 are connected to a column electrode 120 . Equivalently, a pressure sensing unit may be a variable resistor R 1 . When there is a touch, the size of resistance is relevant to the size of pressure; when there is no touch, the resistance is great, and signals are stored in a capacitor C 1 . Equivalently, a temperature sensing unit is a variable resistor R 2 that changes with temperatures, and signals are stored in a capacitor C 2 .
[0040] With reference to FIG. 2 and FIG. 3 , when Vgate is low, the first TFT T 1 and the second TFT T 2 are cut off, and the pressure sensor and the temperature sensor are both in a signal integration phase. When there is a touch action or when the temperature changes, resistance of the pressure sensing unit or the temperature sensing unit changes, and the corresponding storage capacitor discharges by using the corresponding sensing unit, and a voltage of a node A 1 or node A 2 changes; when Vgate is high, the first TFT T 1 and the second TFT T 2 are conducted, and the pressure sensor and the temperature sensor are both in a signal reading phase, and the column electrode 120 charges the capacitor C 1 and the capacitor C 2 respectively by using the first TFT T 1 and the second TFT T 2 , and charging signals are read by a column amplifier 140 .
[0041] A method for manufacturing an electronic skin according to a preferable embodiment of the present disclosure includes the following steps.
[0042] As shown in FIG. 4 , a flexible substrate 50 whose double sides are covered with conductive materials is first selected. Preferably, the thickness of the flexible substrate is 10 μm to 50 μm. In this embodiment, a polyimide material whose double sides are covered with copper and thickness is 25 μm is selected. A pattern 100 is etched on copper on one side of the flexible substrate 50 , and the pattern 100 represents a source and a drain of a TFT, an electrode of a capacitor, a row electrode (data line), a column electrode (scanning line), interconnected conductive wires, and the like of. A pattern 200 is etched on copper on the other side of the flexible substrate 50 , and the pattern 200 represents an electrode and the like of a temperature sensor.
[0043] As shown in FIG. 5 , then the pattern 200 is protected by using an adhesive 300 . A hole is drilled at a corresponding position, connected to the pattern 200 , of the flexible substrate 50 . The aperture is preferably 10 μm to 50 μm. Then electroplating is performed to form a through hole 43 , and the adhesive 300 is removed.
[0044] FIG. 6 is a top view of the flexible substrate 50 including a first TFT and a second TFT. It is seen from FIG. 6 that copper on the flexible substrate 50 is etched to form: a source 12 and a drain 11 of the first TFT, a source 22 and a drain 21 of the second TFT, a row electrode (data line) 120 connected to both the drains 11 and 21 , an electrode 34 of a storage capacitor C 1 and an electrode 44 of a storage capacitor C 2 , and the through hole 43 formed by electroplating. The width of a channel between the source 12 and the drain 11 of the first TFT is 2 μm to 20 μm, and is preferably 10 μm, so as to satisfy the feature of flexibility of the electronic skin.
[0045] With reference to FIG. 1 , FIG. 5 , and FIG. 6 , a semiconductor layer, such as ZTO and IGZO, is formed on the etched pattern 100 by using a magnetron sputtering method. Preferably, the thickness is 40 to 60 nm. An SiOx layer is deposited by using an ALD method. Preferably, the thickness is 20 nm. Then a first insulation layer 15 of the first TFT and a second insulation layer 25 of the second TFT are formed by using a dry etching process; and an active layer 14 of the first TFT and an active layer 24 of the second TFT are formed by using a wet etching process. An SiNx layer is deposited on the first insulation layer 15 of the first TFT and on the first insulation layer 25 of the second TFT by using a PECVD method. Preferably, the thickness is 80 nm to 200 nm, that is, a second insulation layer 16 of the first TFT and a second insulation layer 26 of the second TFT are simultaneously formed. A through hole 70 and a through hole 80 are formed by using a dry etching process. Then a conductive layer is formed by using a magnetron sputtering method. The formed conductive layer is etched to form: a gate 13 of the first TFT, a gate 23 of the second TFT, a column electrode (scanning line) 120 connected to the gates 13 and 23 , a lower electrode 31 of the pressure sensor, and a lower electrode 41 of the temperature sensor. The lower electrode 31 of the pressure sensor is connected to the source 12 of the first TFT through the through hole 70 . The lower electrode 31 of the pressure sensor and the electrode 34 form the storage capacitor C 1 . The lower electrode 41 of the temperature sensor is connected to the source 22 of the second TFT through the through hole 80 , and is also connected to the temperature sensor below the flexible substrate 50 through the through hole 43 . The lower electrode 41 of the temperature sensor and the electrode 44 form a storage capacitor C 2 .
[0046] Finally, a passivation layer 60 is formed by using a PECVD method. A sensitive area of the pressure sensor is formed by using a dry etching method. A pressure sensitive layer 33 is formed by using a printing method and an ink jet printing method, and then an upper electrode 32 of the pressure sensor is formed by using a magnetron sputtering method.
[0047] The temperature sensor may use a stacking method. However, flexibility of the manner is relatively poor. Therefore, a temperature sensor shown in FIG. 7 is used in this preferable embodiment of the present disclosure. Electrodes 421 and 422 are both connection wires of the temperature sensor, that is, both correspond to the electrode 42 of the temperature sensor shown in FIG. 1 . The electrode 421 is connected to the source of the second TFT. There may be multiple choices for the temperature sensor. A thermistor 45 is used in this preferable embodiment of the present disclosure, and the thermistor 45 is connected to the electrodes 421 and 422 within a plane.
[0048] The electronic skin provided in the present disclosure is an electronic skin based on an oxide TFT. The electronic skin includes a flexible substrate, an oxide TFT, a pressure sensor, and a temperature sensor. The oxide TFT includes a first TFT and a second TFT. The first TFT and the second TFT use a same top gate structure, and are formed at a time in process. A source of the first TFT is connected to the pressure sensor; the first TFT becomes a signal reading mechanism of the pressure sensor; pressure signals are stored in a corresponding storage capacitor; a source of the second TFT is connected to the temperature sensor through a through hole on the flexible substrate; the second TFT becomes a signal reading mechanism of the temperature sensor, and temperature change signals are stored in a corresponding storage capacitor. In addition, the pressure sensor and the temperature sensor are located in a same TFT array, and the pressure change signals and the temperature change signals are read by using a row electrode (data line) by using a same scanning reading pulse.
[0049] The electronic skin prepared by using the manufacturing method of the present disclosure implements the function of simultaneously measuring pressure and temperatures, may be used in detection of human pulses, heartbeats, intraocular pressure, muscular movement, and the like, and may also be used in detection of body temperatures or environmental temperatures.
[0050] Although the present disclosure is described above in further detail with reference to specific preferable implementation manners, it should not be considered that the present disclosure is merely limited to the specific implementation manners. Several equivalent replacements or obvious variations with the same performance or purpose may be further made without departing from the spirit of the present disclosure by a person skilled in the art to which the present disclosure belongs shall fall within the protection scope of the present disclosure. | An electronic skin is manufactured by disposing an oxide thin film transistor (TFT), a pressure sensor, and a temperature sensor on a flexible substrate. The pressure sensor and the temperature sensor are respectively located on two sides of the flexible substrate. The oxide TFT includes a first TFT and a second TFT. The pressure sensor is configured to drive the first TFT, and the temperature sensor is configured to drive the second TFT. The method for preparing the electronic skin is to form an oxide TFT, a pressure sensor, and a temperature sensor by means of etching and deposition on a flexible substrate whose double sides are covered with conductive materials. The electronic skin provided in the present invention may simultaneously measure pressure and temperatures, and has a simple structure, a low working voltage, small power consumption, high sensitivity, and small interference between sensor signals. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
The application claims the benefit of provisional application 60/432,083, filed Dec. 11, 2002.
BACKGROUND OF THE INVENTION
The invention relates to the processing of waste materials or contaminated materials.
SUMMARY OF THE INVENTION
The present invention provides a digester for handling waste or contaminated materials. A process and an apparatus for processing are disclosed. A Dry Cycle Anaerobic Digester (DCAD) uses tanks to perform aerobic and anaerobic digestion to eliminate the waste, while producing little or no sludge.
The present invention is versatile, dependable and can be tuned for variable operation. Optimum operation could be maximum reduction and degradation of a waste stream with only carbon dioxide, soluble nutrients and water emissions; alternatively the maximum production of methane gas may be the most desirable operating environment. The system design allows for the selection of the microbial environment that provides the best operating conditions, as determined by the user. The system is designed to mimic Mother Nature and the Earths natural systems that deal with nutrient cycling. The system consists of alternating aerobic and anaerobic digestion cycles.
Maximizing time intervals for substrate introduction increases the aerobic time cycle and encourages high rates of digestion. This introduces a large amount of carbon dioxide into the microbial environment. Substantial heat production occurs during this phase and the high temperature during this stage of operation aids in the degradation or digestion of the material through simple hydrolysis. Enzymes from a wide array of microorganisms also play an important part in this digestion stage. Soluble organics and carbon dioxide rich water travel to the second digester and undergo anaerobic digestion where considerable methane production occurs.
Decreasing the time between wetting intervals increases the methane production and is the beginning of the anaerobic cycle. This cycle has lower efficiency for digesting a wide variety of material. The methanogens utilize fatty acids and in the process co-metabolize carbon dioxide into methane. However, total organic processing capability would decrease. This can lead to a larger size unit for the same nutrient load. However, a sufficiently oversized reactor can be a significant methane producer that will produce good quality gas for use in a boiler, gas turbine engine or modified diesel generator.
Tuning the DCAD unit is simple. The primary decision is whether the farm operation requires the removal of the largest amount of waste possible by the DCAD or the production of methane gas. If the primary goal is to digest the farm waste organic material into carbon dioxide and water then you want your unit tuned to provide maximum aerobic cycle times. This means that introduction of solid waste material my be possible providing that water introduction is timed at wide intervals, resulting in a reactor that is running with a high oxidation rate. This system operation will degrade organic farm waste very efficiently and is similar to the green hay phenomenon that has burned down many barns. Unlike the barn example, when the digester pile has reached a predetermined temperature the pile is wetted and the digester swings into anaerobic digestion mode. Bacteria that were dormant rapidly swing into action and utilize the fatty acid production that has built up from the rapidly degrading organic pile.
This action is very similar to the rain event and drying cycles that occur everyday on Earth. Life is dynamic and has evolved to deal with change. Change is ubiquitous in the environment. Bacteria that are active after a wetting event are utilizing simple sugars and water-soluble proteins and carboxylic acids. While utilizing these compounds for life support they produce an exogenous material that works on the more complex structure in the organic farm waste. As the pile begins to dry the environment becomes micro aerophylic and bacteria begin to utilize some of the early degradation compounds. These bacteria also emit exogenous material that act as enzymes and begin to further degrade the reacting pile. The temperature of the pile begins to elevate and the pile loses more water. Now the environment is shifting to aerobic and the result is rapidly rising temperature and very efficient biological degradation. These microbes are releasing their exogenous compounds and further adding to the degradation of the most complex proteins, cellulose and lignin. At this point the bacteria population has reached the senescence phase of their population growth and would begin to decline naturally, leading to a lower level of activity associated with the stagnant environment. In this system a wetting event occurs at a selected parameter and the whole cycle begins over. Each cycle and interval in the cycle produces some desired effect with respect to the digesting pile and the cycle will continue as long as water and an energy supply is available.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic drawing of a digester system according to an embodiment of the invention.
FIG. 2A is a top view of a digester tank that may be used in embodiments of the invention.
FIG. 2B is a section view of the digester tank in FIG. 2A .
FIG. 3A is a top view of a digester tank that may be used in embodiments of the invention.
FIG. 3B is a section view of the digester tank in FIG. 3A .
FIG. 4 is a schematic drawing of a digester system according to an embodiment of the invention.
FIG. 5 is a schematic drawing of a digester system according to an embodiment of the invention.
FIG. 6 is a flow diagram of a method of digesting materials according to an embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The process is a multiple environment biological process. The natural model of microbial succession is paramount in the operation of the process. In the natural environment, there are rain events and drying events. This causes a natural biological succession where different microbes that are favored by the particular environmental conditions at that time grow and proliferate rapidly. As these microbes begin to flourish and their populations climb they begin to ameliorate their immediate environment, changing the ecological conditions to favor another group of microbes that in turn grow and ameliorate their environment to produce condition favoring the next group of microbes. This produces in a cyclical environment that favors a large diversity of microbes able to perform different tasks in the degradation of organic material. Therefore, all organic material is eventually degraded into carbon dioxide, methane, and water.
With reference to FIGS. 5 and 6 , the procedure for system ( 100 ) start up is that all of the tanks ( 2 , 4 , 6 & 8 ) are filled with the waste water at S 100 . This is done by closing valve ( 9 ) and allowing tank ( 8 ) to fill until it reaches the point where the level indicator ( 34 ) is actuated. This stops the inflow into tank ( 8 ) by closing valve ( 7 ) and begins to fill tank ( 6 ). This tank ( 6 ) again fills until the level indicator ( 33 ) is actuated and closes valve ( 5 ) stopping the flow into tank ( 6 ) and begins to fill tank ( 4 ). Tank ( 4 ) fills until it reaches the point where the level indicator ( 32 ) is actuated and closes valve ( 3 ) causing tank ( 2 ) to begin to fill. Tank ( 2 ) again fills until it reaches the point where the level indicator ( 31 ) is actuated and close valve ( 1 ).
At this point the system is full and held like this for a specified time at S 105 as determined by the operator to begin the bacterial growth phase. Once the allotted time has passed tank ( 8 ) is emptied at S 110 and held in this drying condition for a specified time as selected by the operator at S 115 . When the allotted time has passed valve ( 7 ) is opened by the time and tank ( 6 ) is drained into tank ( 8 ) at S 120 until the level indicator in tank ( 8 ) is actuated and closes valve ( 7 ). Now tank ( 8 ) is again full and tank ( 6 ) is empty. Tank ( 6 ) is held in this drying condition for an allotted amount of time as determined by the operator at S 125 . After the specified time has passed the timer actuates valve ( 5 ) and begins to fill tank ( 6 ) and empty tank ( 4 ) at S 130 . Tank ( 4 ) is again held empty for a specified time for its drying event at S 135 and then the timer will actuate valve ( 3 ) and begin to fill tank ( 4 ) again and empty tank ( 2 ) at S 140 . Tank ( 2 ) is held empty for a specified time as determined by the operator at S 145 . When the allotted time has passed the timer will actuate valve ( 1 ) and allow untreated grey water from the fat floatation system to flow into tank ( 2 ) at S 150 . This system of sequencing the filling and emptying of the tanks ( 2 , 4 , 6 , & 8 ) continue indefinitely. The times for the drying events are dependent upon the water analysis of the water leaving the system at valve ( 10 ). Valve 10 is normally open during operation and only closed if purging the tanks becomes necessary. Once the appropriate time has been determined the system will continue in this cycle for as long as desired.
One final purge system has been added to this process for the purpose of cleaning the tanks if necessary. This system consists of a pump and valves. These valves are manually set by the operator to provide for flushing the tanks ( 2 , 4 , 6 , & 8 ) by pump if and when needed. They can be energized in any sequence that will allow for back flushing the required tank and then switching the valve so the pump can then empty the tank this will allow the removal of mineral sediment and the transfer of this sediment to a lagoon or marsh land area. These valves can also be switched so that they allow the water from the bottom of any one of the tanks ( 2 , 4 , 6 , & 8 ) by pump and then pumped to the top of any one of the tanks ( 2 , 4 , 6 ,& 8 ). This will allow for the water to be trickled through the tank that is desired and increase the microbial activity and contact with the surface area of the filter medium.
This system has 3 optional systems. The first option is that atmospheric air can be drawn in through a check valve if found to be required under normal activity. This would only be needed if the flow of air into the system was not sufficiently supplied by the vent stack or that the fumes coming out of the system were not desirable. Normally any vent air should have no odor or minimal odor associated with it due to the aerobic activity in the digester system. However, if this does become a problem the vent stack would be closed and the air would be drawn in through the check valve and leave through another valve and travel to the lagoon and be exited the system under water to filter out unwanted odor. This normally will not be a problem, but is included in the design for situations that may require this to be done.
The last optional system is one to provide the microbial community nutrients if they require it. Some material such as fat may require the addition of small amounts of limiting nutrient to provide for the effective degradation of the fat. If this becomes a problem, a tank, and pump will be added to supply liquid nutrients to the process system. | The present invention provides a digester for handling waste or contaminated materials. A process and an apparatus for processing are disclosed. A Dry Cycle Anaerobic Digester (DCAD) uses tanks to perform aerobic and anaerobic digestion to eliminate the waste, while producing little or no sludge. | 2 |
FIELD OF INVENTION
[0001] The invention relates to synthetic molecules that spontaneously and stably incorporate into lipid bi-layers, including cell membranes. Particularly, although not exclusively, the invention relates to the use of these molecules as synthetic membrane anchors or synthetic molecule constructs to effect qualitative and quantitative changes in the expression of cell surface antigens.
BACKGROUND
[0002] Cell surface antigens mediate a range of interactions between cells and their environment. These interactions include cell-cell interactions, cell-surface interactions and cell-solute interactions. Cell surface antigens also mediate intra-cellular signalling.
[0003] Cells are characterised by qualitative and quantitative differences in the cell surface antigens expressed. Qualitative and quantitative changes in the cell surface antigens expressed alter both cell function (mode of action) and cell functionality (action served).
[0004] Being able to effect qualitative and/or quantitative changes in the surface antigens expressed by a cell has diagnostic and therapeutic value. Transgenic and non-transgenic methods of effecting qualitative and/or quantitative changes in the surface antigens expressed by a cell are known.
[0005] Protein painting is a non-transgenic method for effecting qualitative and/or quantitative changes in the surface antigens expressed by a cell. The method exploits the ability of GPI linked proteins to spontaneously anchor to the cell membrane via their lipid tails. The method described in the specification accompanying international application no. PCT/US98/15124 (WO 99/05255) includes the step of inserting a GPI linked protein isolated from a biological source into a membrane. Isolated GPI-anchored proteins are stated as having an unusual capacity to reintegrate with a cell-surface membrane.
[0006] Cells exist in an aqueous environment. The cell membrane is a lipid bilayer that serves as a semi-permeable barrier between the cytoplasm of the cell and this aqueous environment. Localising antigens to the cell surface may also be achieved by the use of glycolipids as membrane anchors.
[0007] The method described in the specification accompanying international application no. PCT/NZ02/00214 (WO 03/034074) includes the step of inserting a controlled amount of glycolipid into a membrane. The amount of glycolipid inserted is controlled to provide cells with a desired level of antigen expression.
[0008] The method described in the specification accompanying international application no. PCT/NZ03/00059 (WO 03/087346) includes the step of inserting a modified glycolipid into a membrane as a “membrane anchor”. The modified glycolipid provides for the localisation of antigens to the surface of the cell or multicellular structure. New characteristics may thereby be imparted on the cell or multicellular structure.
[0009] These methods typically include the isolation of a glycolipid or glycolipid-linked antigen from a biological source. The isolation of glycolipids or glycolipid-linked antigens from biological sources is costly, variable and isolatable amounts are often limited. Obtaining reagents from zoological sources for therapeutic use is particularly problematic, especially where the reagent or its derivative products are to be administered to a human subject.
[0010] Synthetic molecules for which the risk of contamination with zoo-pathogenic agents can be excluded are preferred. Synthetic counterparts for naturally occurring glycolipids and synthetic neo-glycolipids have been reported. However, for a synthetic glycolipid to be of use as a membrane anchor it must be able to spontaneously and stably incorporate into a lipid bi-layer from an aqueous environment. The utility of synthetic glycolipids in diagnostic or therapeutic applications is further limited to those synthetic glycolipids that will form a solution in saline.
[0011] Organic solvents and/or detergents used to facilitate the solubilization of glycolipids in saline must be biocompatible. Solvents and detergents must often be excluded or quickly removed as they can be damaging to some cell membranes. The removal of solvents or detergents from such preparations can be problematic.
[0012] Damage to cell membranes is to be avoided especially where the supply of cells or multicellular structures is limited, e.g. embryos, or the cells are particularly sensitive to perturbation, e.g. hepatocytes.
[0013] There exists a need for water soluble synthetic molecules that are functionally equivalent to naturally occurring glycolipids and glycolipid-linked antigens in respect of their ability to spontaneously and stably incorporate into lipid bi-layers, including cell membranes.
[0014] Providing such synthetic molecules would obviate the limitations of glycolipids and glycolipid-linked antigens isolated from biological sources and facilitate being able to effect qualitative and/or quantitative changes in the surface antigens expressed by a cell.
[0015] It is an object of this invention to provide such synthetic molecules and a method for their preparation. It is a further object of this invention to provide synthetic molecules for use in diagnostic and therapeutic applications. The preceding objects are to be read disjunctively with the object to at least provide the public with a useful choice.
STATEMENTS OF INVENTION
[0016] In a first aspect the invention consists in a synthetic membrane anchor or synthetic molecule construct of the structure F—S 1 —S 2 -L where:
F is selected from the group consisting of carbohydrates; S 1 —S 2 is a spacer linking F to L; and L is a lipid selected from the group consisting of diacyl- and dialkyl-glycerolipids, including glycerophospholipids, and sphingosine derived diacyl- and dialkyl-lipids, including ceramide.
[0020] Preferably L is a lipid selected from the group consisting of diacyl- and dialkyl-glycerolipids, including glycerophospholipids. More preferably L is selected from the group consisting of: diacylglycerolipids, phosphatidate, phosphatidyl choline, phosphatidyl ethanolamine, phosphatidyl serine, phosphatidyl inositol, phosphatidyl glycerol, and diphosphatidyl glycerol derived from one or more of trans-3-hexadecenoic acid, cis-5-hexadecenoic acid, cis-7-hexadecenoic acid, cis-9-hexadecenoic acid, cis-6-octadecenoic acid, cis-9-octadecenoic acid, trans-9-octadecenoic acid, trans-11-octadecenoic acid, cis-11-octadecenoic acid, cis-11-eicosenoic acid or cis-13-docsenoic acid. More preferably the lipid is derived from one or more cis-destaurated fatty acids. Most preferably L is selected from the group consisting of: 1,2-O-dioleoyl-sn-glycero-3-phosphatidylethanolamine (DOPE), 1,2-O-distearyl-sn-glycero-3-phosphatidylethanolamine (DSPE) and rac-1,2-dioleoylglycerol (DOG).
[0021] Preferably L is a glycerophospholipid and the molecule includes the substructure:
[0000]
[0000] where n=3 to 5, X is H or C, and * is other than H. Preferably n is 3.
[0022] Preferably the molecule is water soluble.
[0023] Preferably the molecule spontaneously incorporates into a lipid bi-layer when a solution of the molecule is contacted with the lipid bi-layer. More preferably the molecule stably incorporates into the lipid bilayer.
[0024] Preferably F, S 1 , S 2 and L are covalently linked.
[0025] Preferably F is selected from the group consisting of naturally occurring or synthetic glycotopes.
[0026] S 1 —S 2 is selected to provide a water soluble synthetic membrane anchor or synthetic molecule construct.
[0027] In a first embodiment F is a naturally occurring or synthetic glycotope. Preferably F is a naturally occurring or synthetic glycotope consisting of three (trisaccharide) or more sugar units. More preferably F is a glycotope selected from the group consisting of lacto-neo-tetraosyl, lactotetraosyl, lacto-nor-hexaosyl, lacto-iso-octaosyl, globoteraosyl, globo-neo-tetraosyl, globopentaosyl, gangliotetraosyl, gangliotriaosyl, gangliopentaosyl, isoglobotriaosyl, isoglobotetraosyl, mucotriaosyl and mucotetraosyl series of oligosaccharides. Most preferably F is selected from the group of glycotopes comprising the terminal sugars GalNAcα1-3(Fucα1-2)Galβ; Galα1-3Galβ; Galβ; Galα1-3(Fucα1-2)Galβ; NeuAcα2-3Galβ; NeuAcα2-6Galβ; Fucα1-2Galβ; Galβ1-4GlcNAcβ1-6(Galβ1-4GlcNAcβ1-3)Galβ; Fucα1-2Galβ1-4GlcNAcβ1-6(Fucα1-2Galβ1-4GlcNAcβ1-3)Galβ; Fucα1-2Galβ1-4GlcNAcβ1-6(NeuAcα2-3Galβ1-4GlcNAcβ1-3)Galβ; NeuAcα2-3Galβ1-4GlcNAcβ1-6(NeuAcα2-3Galβ1-4GlcNAcβ1-3)Galβ; Galα1-4Galβ1-4Glc; GalNAcβ1-3Galα1-4Galβ1-4Glc; GalNAcα1-3GalNAcβ1-3Galα1-4Galβ1-4Glc; or GalNAcβ1-3GalNAcβ1-3Galα1-4Galβ1-4Glc.
[0028] When F is a glycotope, L is a glycerophospholipid and S 2 is selected from the group including: —CO(CH 2 ) 3 CO—, —CO(CH 2 ) 4 CO— (adipate), —CO(CH 2 ) 5 CO— and —CO(CH 2 ) 5 NHCO(CH 2 ) 5 CO—, preferably S 1 is a C 3-5 -aminoalkyl selected from the group consisting of: 3-aminopropyl, 4-aminobutyl, or 5-aminopentyl. More preferably S 1 is 3-aminopropyl.
[0029] In a second embodiment F is a molecule that mediates a cell-cell or cell-surface interaction. Preferably F is a carbohydrate with an affinity for a component expressed on a targeted cell or surface. More preferably F has an affinity for a component expressed on epithelial cells or extra-cellular matrices. Yet more preferably F has an affinity for a component expressed on the epithelial cells or the extra-cellular matrix of the endometrium. Most preferably the component expressed on the epithelial cells or the extra-cellular matrix of the endometrium can be a naturally expressed component or an exogenously incorporated component.
[0030] In a third embodiment F is a molecule that mediates a cell-solute interaction. Preferably F is a ligand for a binding molecule where the presence of the binding molecule is diagnostic for a pathological condition. More preferably F is a ligand for an antibody (immunoglobulin).
[0031] In specific embodiments the water soluble synthetic membrane anchor or synthetic molecule construct has the structure:
[0000]
[0000] designated A tri -sp-Ad-DOPE (I); the structure:
[0000]
[0000] designated A tri -spsp 1 -Ad-DOPE (II); the structure:
[0000]
[0000] designated A tri -sp-Ad-DSPE (III); the structure
[0000]
[0000] designated B tri -sp-Ad-DOPE (VI); the structure:
[0000]
[0000] designated H tri -sp-Ad-DOPE (VII); the structure:
[0000]
[0000] designated H di -sp-Ad-DOPE (VIII); the structure:
[0000]
[0000] designated Galβ i -sp-Ad-DOPE (IX); the structure:
[0000]
[0000] designated Fucα1-2Galβ1-3GlcNAcβ1-3Galβ1-4GlcNAc-sp-Ad-DOPE (XII); or the structure:
[0000]
[0000] designated Fucα1-2Galβ1-3(Fucα1-4)GlcNAc-sp-Ad-DOPE (XIII).
[0032] M is typically H, but may be replaced by another monovalent cation such as Na + , K + or NH 4 + .
[0033] In a second aspect the invention consists in a method of preparing a synthetic membrane anchor or synthetic molecule construct of the structure F—S 1 —S 2 -L including the steps:
1. Reacting an activator (A) with a lipid (L) to provide an activated lipid (A-L); 2. Derivatising an antigen (F) to provide a derivatised antigen (F—S 1 ); and 3. Condensing A-L with F—S 1 to provide the molecule;
where:
A is an activator selected from the group including: bis(N-hydroxysuccinimidyl), bis(4-nitrophenyl), bis(pentafluorophenyl), bis(pentachlorophenyl) esters of carbodioic acids (C 3 to C 7 ); L is a lipid selected from the group consisting of diacyl- and dialkyl-glycerolipids, including glycerophospholipids, and sphingosine derived diacyl- and dialkyl-lipids, including ceramide. F is selected from the group consisting of carbohydrates; and S 1 —S 2 is a spacer linking F to L where S 1 is selected from the group including: primary aminoalkyl, secondary aliphatic aminoalkyl or primary aromatic amine; and S 2 is absent or selected from the group including: —CO(CH 2 ) 3 CO—, —CO(CH 2 ) 4 CO— (adipate), and —CO(CH 2 ) 5 CO—.
[0041] Preferably the molecule is water soluble.
[0042] Preferably the molecule spontaneously incorporates into a lipid bi-layer when a solution of the molecule is contacted with the lipid bi-layer. More preferably the molecule stably incorporates into the lipid bilayer.
[0043] Preferably F, S 1 , S 2 and L are covalently linked.
[0044] Preferably F is selected from the group consisting of naturally occurring or synthetic glycotopes.
[0045] Preferably L is a lipid selected from the group consisting of diacyl- and dialkyl-glycerolipids, including glycerophospholipids. More preferably L is selected from the group consisting of: diacylglycerolipids, phosphatidate, phosphatidyl choline, phosphatidyl ethanolamine, phosphatidyl serine, phosphatidyl inositol, phosphatidyl glycerol, and diphosphatidyl glycerol derived from one or more of trans-3-hexadecenoic acid, cis-5-hexadecenoic acid, cis-7-hexadecenoic acid, cis-9-hexadecenoic acid, cis-6-octadecenoic acid, cis-9-octadecenoic acid, trans-9-octadecenoic acid, trans-11-octadecenoic acid, cis-11-octadecenoic acid, cis-11-eicosenoic acid or cis-13-docsenoic acid. More preferably the lipid is derived from one or more cis-destaurated fatty acids. Most preferably L is selected from the group consisting of: 1,2-O-dioleoyl-sn-glycero-3-phosphatidylethanolamine (DOPE), 1,2-O-distearyl-sn-glycero-3-phosphatidylethanolamine (DSPE) and rac-1,2-dioleoylglycerol (DOG).
[0046] Preferably L is a glycerophospholipid and the molecule includes the substructure:
[0000]
[0000] where n=3 to 5, X is H or C, and * is other than H. Preferably n is 3.
[0047] Preferably A (R—S 2 ) and S 1 are selected to provide a water soluble synthetic molecule construct.
[0048] In a first embodiment F is a naturally occurring or synthetic glycotope. Preferably F is a naturally occurring or synthetic glycotope consisting of three (trisaccharide) or more sugar units. More preferably F is a glycotope selected from the group consisting of lacto-neo-tetraosyl, lactotetraosyl, lacto-nor-hexaosyl, lacto-iso-octaosyl, globoteraosyl, globo-neo-tetraosyl, globopentaosyl, gangliotetraosyl, gangliotriaosyl, gangliopentaosyl, isoglobotriaosyl, isoglobotetraosyl, mucotriaosyl and mucotetraosyl series of oligosaccharides. Most preferably F is selected from the group of glycotopes comprising the terminal sugars GalNAcα1-3(Fucα1-2)Galβ; Galα1-3Galβ; Galβ; Galα1-3(Fucα1-2)Galβ; NeuAcα2-3Galβ; NeuAcα2-6Galβ; Fucα1-2Galβ; Galβ1-4GlcNAcβ1-6(Galβ1-4GlcNAcβ1-3)Galβ; Fucα1-2Galβ1-4GlcNAcβ1-6(Fucα1-2Galβ1-4GlcNAcβ1-3)Galβ; Fucα1-2Galβ1-4GlcNAcβ1-6(NeuAcα2-3Galβ1-4GlcNAcβ1-3)Galβ; NeuAcα2-3Galβ1-4GlcNAcβ1-6(NeuAcα2-3Galβ1-4GlcNAcβ1-3)Galβ; Galα1-4Galβ1-4Glc; GalNAcβ1-3Galα1-4Galβ1-4Glc; GalNAcα1-3GalNAcβ1-3Galα1-4Galβ1-4Glc; or GalNAcβ1-3GalNAcβ1-3Galα1-4Galβ1-4Glc.
[0049] When F is a glycotope, L is a glycerophospholipid and S 2 is selected from the group including: —CO(CH 2 ) 3 CO—, —CO(CH 2 ) 4 CO— (adipate), —CO(CH 2 ) 5 CO— and —CO(CH 2 ) 5 NHCO(CH 2 ) 5 CO—, preferably S 1 is a C 3-5 -aminoalkyl selected from the group consisting of: 3-aminopropyl, 4-aminobutyl, or 5-aminopentyl. More preferably S 1 is 3-aminopropyl.
[0050] In a second embodiment F is a molecule that mediates a cell-cell or cell-surface interaction. Preferably F is carbohydrate with an affinity for a component expressed on a targeted cell or surface. More preferably F has an affinity for a component expressed on epithelial cells or extra-cellular matrices. Yet more preferably F has an affinity for a component expressed on the epithelial cells or the extra-cellular matrix of the endometrium. Most preferably the component expressed on the epithelial cells or the extra-cellular matrix of the endometrium can be a naturally expressed component or an exogenously incorporated component.
[0051] In a third embodiment F is a molecule that mediates a cell-solute interaction. Preferably F is a ligand for a binding molecule where the presence of the binding molecule is diagnostic for a pathological condition. More preferably F is a ligand for an antibody (immunoglobulin).
[0052] In specific embodiments the water soluble synthetic molecule construct has the structure:
[0000]
[0000] designated A tri -sp-Ad-DOPE (I); the structure:
[0000]
[0000] designated A tri -spsp 1 -Ad-DOPE (II); the structure:
[0000]
[0000] designated A tri -sp-Ad-DSPE (III); the structure
[0000]
[0000] designated B tri -sp-Ad-DOPE (VI); the structure:
[0000]
[0000] designated H tri -sp-Ad-DOPE (VII); the structure:
[0000]
[0000] designated H di -sp-Ad-DOPE (VIII); the structure:
[0000]
[0000] designated Galβ i -sp-Ad-DOPE (IX); the structure:
[0000]
[0000] designated Fucα1-2Galβ1-3GlcNAcβ1-3Galβ1-4GlcNAc-sp-Ad-DOPE (XII); or the structure:
[0000]
[0000] designated Fucα1-2Galβ1-3(Fucα1-4)GlcNAc-sp-Ad-DOPE (XIII).
[0053] M is typically H, but may be replaced by another monovalent cation such as Na + , K + or NH 4 + .
[0054] In a third aspect the invention consists in a water soluble synthetic membrane anchor or synthetic molecule construct prepared by a method according to the second aspect of the invention.
[0055] In a fourth aspect the invention consists in a method of effecting qualitative and/or quantitative changes in the surface antigens expressed by a cell or multi-cellular structure including the step:
1. Contacting a suspension of the cell or multi-cellular structure with a synthetic membrane anchor or synthetic molecule construct according to the first aspect or third aspect of the invention for a time and at a temperature sufficient to effect the qualitative and/or quantitative change in the surface antigens expressed by the cell or multi-cellular structure.
[0057] Preferably the cell or multi-cellular structure is of human or murine origin.
[0058] Preferably the concentration of the water soluble synthetic membrane anchor or synthetic molecule construct in the suspension is in the range 0.1 to 10 mg/mL.
[0059] Preferably the temperature is in the range 2 to 37° C. More preferably the temperature is in the range 2 to 25° C. Most preferably the temperature is in the range 2 to 4° C.
[0060] In a first embodiment the cell is a red blood cell.
[0061] In this embodiment preferably F is selected from the group of glycotopes comprising the terminal sugars GalNAcα1-3(Fucα1-2)Galβ; Galα1-3Galβ; Galβ; Galα1-3(Fucα1-2)Galβ; NeuAcα2-3Galβ; NeuAcα2-6Galβ; Fucα1-2Galβ; Galβ1-4GlcNAcβ1-6(Galβ1-4GlcNAcβ1-3)Galβ; Fucα1-2Galβ1-4GlcNAcβ1-6(Fucα1-2Galβ1-4GlcNAcβ1-3)Galβ; Fucα1-2Galβ1-4GlcNAcβ1-6(NeuAcα2-3Galβ1-4GlcNAcβ1-3)Galβ; NeuAcα2-3Galβ1-4GlcNAcβ1-6(NeuAcα2-3Galβ1-4GlcNAcβ1-3)Galβ; Galα1-4Galβ1-4Glc; GalNAcβ1-3Galα1-4Galβ1-4Glc; GalNAcα1-3GalNAcβ1-3Galα1-4Galβ1-4Glc; or GalNAcβ1-3GalNAcβ1-3Galα1-4Galβ1-4Glc. More preferably F is selected from the group of glycotopes consisting of the oligosaccharides GalNAcα1-3(Fucα1-2)Galβ and Galα1-3(Fucα1-2)Galβ.
[0062] Preferably the synthetic molecule construct is selected from the group including: A tri -sp-Ad-DOPE (I); A tri -spsp 1 -Ad-DOPE (II); A tri -sp-Ad-DSPE (III); B tri -sp-Ad-DOPE (VI); H tri -sp-Ad-DOPE (VII); H di -sp-Ad-DOPE (VIII); Galβ i -sp-Ad-DOPE (IX); Fucα1-2Galβ1-3GlcNAcβ1-3Galβ1-4GlcNAc-sp-Ad-DOPE (XII); and Fucα1-2Galβ1-3(Fucα1-4)GlcNAc-sp-Ad-DOPE (XIII).
[0063] In a second embodiment the multi-cellular structure is an embryo.
[0064] In this embodiment preferably F is an attachment molecule where the attachment molecule has an affinity for a component expressed on the epithelial cells or the extra-cellular matrix of the endometrium.
[0065] The component expressed on the epithelial cells or the extra-cellular matrix of the endometrium can be a naturally expressed component or an exogenously incorporated component.
[0066] Preferably the synthetic membrane anchor or synthetic molecule construct is selected from the group including: A tri -sp-Ad-DOPE (I); A tri -spsp 1 -Ad-DOPE (II); A tri -sp-Ad-DSPE (III); B tri -sp-Ad-DOPE (VI); H tri -sp-Ad-DOPE (VII); H di -sp-Ad-DOPE (VIII); Galβ i -sp-Ad-DOPE (IX); Fucα1-2Galβ1-3GlcNAcβ1-3Galβ1-4GlcNAc-sp-Ad-DOPE (XII); and Fucα1-2Galβ1-3(Fucα1-4)GlcNAc-sp-Ad-DOPE (XIII).
[0067] In a third embodiment the cell is red blood cell.
[0068] In this embodiment preferably F is a ligand for a binding molecule where the presence of the binding molecule is diagnostic for a pathological condition. More preferably F is a ligand for an antibody (immunoglobulin).
[0069] In a fifth aspect the invention consists in a cell or multi-cellular structure incorporating a water soluble synthetic membrane anchor or synthetic molecule construct according to the first or third aspect of the invention.
[0070] Preferably the cell or multi-cellular structure is of human or murine origin.
[0071] In a first embodiment the cell is a red blood cell incorporating a water soluble synthetic membrane anchor or synthetic molecule construct selected from the group including: A tri -sp-Ad-DOPE (I); A tri -spsp 1 -Ad-DOPE (II); A tri -sp-Ad-DSPE (III); B tri -sp-Ad-DOPE (VI); H tri -sp-Ad-DOPE (VII); H di -sp-Ad-DOPE (VIII); Galβ-sp-Ad-DOPE (IX); Fucα1-2Galβ1-3GlcNAcβ1-3Galβ1-4GlcNAc-sp-Ad-DOPE (XII); and Fucα1-2Galβ1-3(Fucα1-4)GlcNAc-sp-Ad-DOPE (XIII).
[0072] In a second embodiment the multi-cellular structure is an embryo incorporating a water soluble synthetic membrane anchor or synthetic molecule construct selected from the group consisting of: A tri -sp-Ad-DOPE (I); A tri -spsp 1 -Ad-DOPE (II); A tri -sp-Ad-DSPE (III); B tri -sp-Ad-DOPE (VI); H tri -sp-Ad-DOPE (VII); H di -sp-Ad-DOPE (VIII); Galβ-sp-Ad-DOPE (IX); Fucα1-2Galβ1-3GlcNAcβ1-3Galβ1-4GlcNAc-sp-Ad-DOPE (XII); and Fucα1-2Galβ1-3(Fucα1-4)GlcNAc-sp-Ad-DOPE (XIII).
[0073] In a sixth aspect the invention consists in a kit comprising a dried preparation or solution of a water soluble synthetic membrane anchor or synthetic molecule construct according to the first or third aspect of the invention.
[0074] Preferably the synthetic membrane anchor or water soluble synthetic molecule construct according to the first or third aspect of the invention is selected from the group consisting of: A tri -sp-Ad-DOPE (I); A tri -spsp 1 -Ad-DOPE (II); A tri -sp-Ad-DSPE (III); B tri -sp-Ad-DOPE (VI); H tri -sp-Ad-DOPE (VII); H di -sp-Ad-DOPE (VIII); Galβ-sp-Ad-DOPE (IX); Fucα1-2Galβ1-3GlcNAcβ1-3Galβ1-4GlcNAc-sp-Ad-DOPE (XII); and Fucα1-2Galβ1-3(Fucα1-4)GlcNAc-sp-Ad-DOPE (XIII).
[0075] In an seventh aspect the invention consists in a kit comprising a suspension in a suspending solution of cells or multi-cellular structures according to the fifth aspect of the invention.
[0076] Preferably the suspending solution is substantially free of lipid.
[0077] Preferably the cell or multi-cellular structure is of human or murine origin.
[0078] Preferably the cells are red blood cells that do not naturally express A- or B-antigen and incorporate a water soluble synthetic membrane anchor or synthetic molecule construct selected from the group consisting of: A tri -sp-Ad-DOPE (I); A tri -spsp 1 -Ad-DOPE (II); A tri -sp-Ad-DSPE (III); B tri -sp-Ad-DOPE (VI); H tri -sp-Ad-DOPE (VII); H di -sp-Ad-DOPE (VIII); Galβ-sp-Ad-DOPE (IX); Fucα1-2Galβ1-3GlcNAcβ1-3Galβ1-4GlcNAc-sp-Ad-DOPE (XII); and Fucα1-2Galβ1-3(Fucα1-4)GlcNAc-sp-Ad-DOPE (XIII). More preferably the cells are sensitivity controls.
[0079] In a eighth aspect the invention consists in a pharmaceutical preparation comprising a dried preparation or solution of a water soluble synthetic membrane anchor or synthetic molecule construct according to the first or fourth aspect of the invention.
[0080] Preferably the pharmaceutical preparation is in a form for administration by inhalation.
[0081] Preferably the pharmaceutical preparation is in a form for administration by injection.
[0082] In an ninth aspect the invention consists in a pharmaceutical preparation comprising cells or multi-cellular structures according to the fifth aspect of the invention.
[0083] Preferably the cells or multi-cellular structures are of human or murine origin.
[0084] Preferably the pharmaceutical preparation is in a form for administration by inhalation.
[0085] Preferably the pharmaceutical preparation is in a form for administration by injection.
DETAILED DESCRIPTION
[0086] The synthetic molecule constructs of the invention spontaneously and stably incorporate into a lipid bi-layer, such as a membrane, when a solution of the molecule is contacted with the lipid bi-layer. Whilst not wishing to be bound by theory it is believed that the insertion into the membrane of the lipid tails of the lipid (L) is thermodynamically favoured. Subsequent disassociation of the synthetic molecule construct from the lipid membrane is believed to be thermodynamically unfavoured. Surprisingly, the synthetic molecule constructs identified herein have also been found to be water soluble.
[0087] The synthetic molecule constructs of the invention are used to transform cells resulting in qualitative and/or quantitative changes in the surface antigens expressed. It will be recognised that the transformation of cells in accordance with the invention is distinguished from transformation of cells by genetic engineering. The invention provides for phenotypic transformation of cells without genetic transformation.
[0088] In the context of this description the term “transformation” in reference to cells is used to refer to the insertion or incorporation into the cell membrane of exogenously prepared synthetic molecule constructs thereby effecting qualitative and quantitative changes in the cell surface antigens expressed by the cell.
[0089] The synthetic molecule constructs of the invention comprise an antigen (F) linked to a lipid portion (or moiety) (L) via a spacer (S 1 —S 2 ). The synthetic molecule constructs can be prepared by the condensation of a primary aminoalkyl, secondary aliphatic aminoalkyl or primary aromatic amine derivative of the antigen with an activated lipid. Methods of preparing neoglycoconjugates have been reviewed (Bovin, N. Biochem. Soc. Symp., 69, 143-160).
[0090] A desired phenotypic transformation may be achieved using the synthetic molecule constructs of the invention in a one step method or a two step method. In the one step method the water soluble synthetic molecule construct (F—S 1 —S 2 -L) comprises the surface antigen as F.
[0091] In the two step method the synthetic molecule construct (F—S 1 —S 2 -L) comprises an antigen (F) that serves as a functional group to which a surface antigen can be linked following insertion of the synthetic molecule construct into the membrane. The functional group can be a group such as a lectin, avidin or biotin. When used in the two step method the synthetic molecule construct is acting as a synthetic membrane anchor.
[0092] In accordance with the invention the primary aminoalkyl, secondary aliphatic aminoalkyl or primary aromatic amine and the activator of the lipid are selected to provide a synthetic molecule construct that is water soluble and will spontaneously and stably incorporate into a lipid bi-layer when a solution of the synthetic molecule construct is contacted with the lipid bi-layer.
[0093] In the context of this description the phrase “water soluble” means a stable, single phase system is formed when the synthetic molecule construct is contacted with water or saline (such as PBS) in the absence of organic solvents or detergents, and the term “solution” has a corresponding meaning.
[0094] In the context of this description the phrase “stably incorporate” means that the synthetic molecule constructs incorporate into the lipid bi-layer or membrane with minimal subsequent exchange between the lipid bi-layer or membrane and the external aqueous environment of the lipid bi-layer or membrane.
[0095] The selection of the primary aminoalkyl, secondary aliphatic aminoalkyl or primary aromatic amine and the activator depends on the physico-chemical properties of the antigen (F) to be linked to the lipid (L).
[0096] It will be understood by those skilled in the art that for a non-specific interaction, such as the interaction between a diacyl- or dialkyl-glycerolipid and a membrane, structural and stereo-isomers of naturally occurring lipids can be functionally equivalent. For example, it is contemplated by the inventors that diacylglycerol 2-phosphate could be substituted for phosphatidate (diacylglycerol 3-phosphate). Furthermore it is contemplated by the inventors that the absolute configuration of phosphatidate can be either R or S.
[0097] The inventors have determined that to prepare synthetic molecule constructs of the invention where the antigen (F) is an oligosaccharide selected from the group of glycotopes for A-, B- and H-antigens of the ABO blood groups, the primary aminoalkyl, secondary aliphatic aminoalkyl or primary aromatic amine, and the activator should be selected to provide a spacer (S 1 —S 2 ) with a structure according to one of those presented here:
[0000]
Alternative structures of S 1 -S 2 for a water soluble synthetic molecule
construct (F-S 1 -S 2 -L) where F is a carbohydrate (or other antigen)
with similar physico-chemical properties to the carbohydrate portion
of the A-, B- or H-antigens of the ABO blood groups and L is a
glycerophospholipid (n, m independently = 2 to 5)
S 1 is selected from:
S 2 is selected from:
—O(CH 2 )nNH—
—CO(CH 2 ) n CO—
or
—CO(CH 2 ) m NHCO(CH 2 ) n CO—
[0098] It will be understood by one skilled in the art that once the structure of the spacer (S 1 —S 2 ) has been determined for a given class of antigens, the same structure of the spacer can be adopted to prepare synthetic molecule constructs of other classes of antigen with similar physico-chemical properties.
[0099] For example, the structure of the spacer for synthetic molecule constructs (F—S 1 —S 2 -L) where F is a glycotope of the A-, B- and H-antigens of the ABO blood groups, may be the structure of the spacer selected to prepare synthetic molecule constructs of other antigens with physico-chemical properties similar to the glycotopes of the A-, B- and H-antigens of the ABO blood groups.
[0100] In principle the glycotope of a broad range of blood group related glycolipids or glycoproteins could be the antigen (F) of the synthetic molecule construct F—S 1 —S 2 -L where S 1 —S 2 -L is identical or equivalent to the corresponding portion of the synthetic molecule constructs designated A tri -sp-Ad-DOPE (I), A tri -spsp 1 -Ad-DOPE (II), A tri -sp-Ad-DSPE (III), B tri -sp-Ad-DOPE (VI), H tri -sp-Ad-DOPE (VII), H di -sp-Ad-DOPE (VIII), Galβ-sp-Ad-DOPE (IX), Fucα1-2Galβ1-3GlcNAcβ1-3Galβ1-4GlcNAc-sp-Ad-DOPE (XII), and Fucα1-2Galβ1-3(Fucα1-4)GlcNAc-sp-Ad-DOPE (XIII).
[0101] The structures of known blood group-related glycolipids and glycoproteins (see references) are provided in the following list:
Glucolipids*
[0102] (*In general, for almost all examples of A-antigens the terminal A sugar GalNAc can be replaced with the B sugar Gal. Additionally, the lack of either the A or B determinant creates the equivalent H determinant.)
[0000]
O-Linked Glycoproteins
[0103]
N-Linked Glycoproteins
[0104]
[0105] It will be understood by those skilled in the art that the synthetic molecule constructs (F—S 1 —S 2 -L) of the invention where F is an oligosaccharide may be used as “synthetic glycolipids” and substituted for glycolipids obtained from biological (botanical or zoological) sources.
[0106] In the context of this description of the invention the term “glycolipid” means a lipid containing carbohydrate of amphipathic character including: glycosylated glycerolipids, such as glycosylated phosphoglycerides and glycosylglycerides; glycosylated sphingolipids (neutral glycolipids) such as glycosylceramides or cerebrosides; and gangliosides (acidic glycolipids).
[0107] In the context of this description of the invention the phrase “glycolipid-linked antigen” means a lipid containing carbohydrate in which an antigen (e.g. a protein) is linked to the glycolipid via the carbohydrate portion of the molecule. Examples of glycolipid-linked antigens include GPI-linked proteins.
[0108] It will be understood by those skilled in the art that a glycolipid is itself an antigen. The term and phrase “glycolipid” and “glycolipid-linked antigen” are used to distinguish between naturally occurring molecules where the antigen is the glycolipid and naturally occurring molecules where the antigen is linked to the glycolipid via the carbohydrate portion of the glycolipid. By analogy the synthetic molecule constructs of the invention could be described as both “synthetic glycolipids” and synthetic membrane anchors to the extent that the antigen may be the synthetic glycolipid per se or attached to the synthetic glycolipid.
[0109] It will be understood by those skilled in the art that the carbohydrate portion of a glycolipid may be modified and linked to other antigens by the methods described in the specification accompanying the international application no. PCT/NZ2003/00059 (published as WO03087346).
[0110] In the context of this description of the invention the term “glycotope” is used to refer to the antigenic determinant located on the carbohydrate portion of a glycolipid. The classification of glycolipid antigens in blood group serology is based on the structure of the carbohydrate portion of the glycolipid.
[0111] In blood group serology it is known that the terminal sugars of the glycotopes of A-antigens are GalNAcα1-3(Fucα1-2)Galβ, and the terminal sugars of the glycotopes of the B-antigens are Galα1-3(Fucα1-2)Galβ. Incorporation into the membrane of RBCs of water soluble synthetic molecule constructs of the invention where F is GalNAcα1-3(Fucα1-2)Galβ or Galα1-3(Fucα1-2)Galβ provides RBCs that are serologically equivalent to A-antigen or B-antigen expressing RBCs, respectively.
[0112] The terminal three sugars of the carbohydrate portion of the naturally occurring A- or B-antigen are the determinant of the A and B blood groupings. The terminal four or five sugars of the carbohydrate portion of the naturally occurring A-antigen are the determinant of the A blood sub-groupings A type 1, A type 2, etc. Accordingly the RBCs incorporating the synthetic molecule constructs of the invention can be used to characterise and discriminate between blood typing reagents (antibodies) of differing specificity.
[0113] Water soluble synthetic molecule constructs of the invention that exclude a carbohydrate portion are contemplated by the inventors. Antigens other than carbohydrates or oligosaccharides, but with similar physico-chemical properties, may be substituted for F in the “synthetic glycolipids” described.
[0114] Synthetic molecule constructs of the invention that comprise an antigen (F) with differing physico-chemical properties to those of carbohydrates or oligosaccharides are also contemplated by the inventors. Water soluble synthetic molecule constructs comprising these antigens may be prepared by selecting different spacers.
[0115] The advantages provided by the synthetic molecule constructs of this invention will accrue when used in the practice of the inventions described in the specifications for the international application nos. PCT/N02/00212 (published as WO03/034074) and PCT/NZ03/00059 (published as WO03087346). The specifications accompanying these applications are incorporated herein by reference.
[0116] The synthetic molecule constructs overcome many of the limitations of using natural glycolipids in the practice of these inventions. A particular advantage of the synthetic molecule constructs is their superior performance and ability to be used in the transformation of cells at reduced temperatures, e.g. 4° C.
[0117] As described herein not all structures of the spacer (S 1 —S 2 ) will provide a synthetic molecule construct (F—S 1 —S 2 -L) that is water soluble and spontaneously and stably incorporate in to a lipid bilayer such as a cell membrane. The synthetic molecule constructs designated A tri -sp-lipid (IV) and Atri-PAA-DOPE (V) were determined not to be water soluble and/or unable to spontaneously and stably incorporate in to a lipid bilayer such as a cell membrane.
[0000]
[0118] The invention will now be illustrated by reference to the following non-limiting Examples and Figures of the accompanying drawings in which:
[0119] FIG. 1 shows Diamed results of Cellstab™ stored cells transformed by natural A glycolipid transformation solution at (L to R) 10 mg/mL, 5 mg/mL, 2 mg/mL, 2 mg/mL* and 1 mg/mL. Antisera used are Albaclone (top) and Bioclone (bottom). (*-transformation solution (containing glycolipids) was not washed out after the incubation, it was left in over night and washed out the next day (day 2).)
[0120] FIG. 2 shows Diamed results of Cellstab™ stored cells transformed by natural B glycolipid transformation solution at (L to R) 10 mg/mL, 5 mg/mL, 2 mg/mL, 2 mg/mL* and 1 mg/mL. Antisera used are Albaclone (top) and Bioclone (bottom). (*-transformation solution (containing glycolipids) was not washed out after the incubation, it was left in over night and washed out the next day (day 2)).
[0121] FIG. 3 shows FACS analysis following in vitro transformation of human Le(a-b-) red cells with natural Le b -6 glycolipid over time at three transformation temperatures, 37° C. (top), 22° C. (middle) and 4° C. (bottom).
[0122] FIG. 4 shows Diamed results of cells transformed at 4° C. by A tri -sp-Ad-DOPE (I) transformation solution at (L to R): washed 0.08 mg/mL; unwashed 0.08 mg/mL; washed 0.05 mg/mL; unwashed 0.05 mg/mL; washed 0.03 mg/mL; and unwashed 0.03 mg/mL. The antisera used was Bioclone anti-A.
[0123] FIG. 5 shows cells that were no longer washed prior to testing. Diamed results of cells transformed at 4° C. by A tri -sp-Ad-DOPE (I) transformation solution at (L to R): 0.08 mg/mL, 0.05 mg/mL and 0.03 mg/mL. The antisera used was Bioclone anti-A.
[0124] FIG. 6 shows in the left column Diamed results of cells transformed at 4° C. by B tri -sp-Ad-DOPE (VI) transformation solution at (L to R): washed 0.6 mg/mL; unwashed 0.6 mg/mL; washed 0.3 mg/mL; unwashed 0.3 mg/mL; washed 0.15 mg/mL; and unwashed 0.15 mg/mL; and in the right column Diamed results of cells transformed at 4° C. by B tri -sp-Ad-DOPE (VI) transformation solution at (L to R): washed 0.08 mg/mL; unwashed 0.08 mg/mL; washed 0.05 mg/mL; unwashed 0.05 mg/mL; washed 0.03 mg/mL; and unwashed 0.03 mg/mL. The antisera used was Bioclone anti-B.
[0125] FIG. 7 shows cells that were no longer washed prior to testing. Diamed results of cells transformed at 4° C. by B tri -sp-Ad-DOPE (VI) transformation solution at (L to R): 0.6 mg/mL, 0.3 mg/mL and 0.15 mg/mL.
[0126] FIG. 8 shows Diamed results of cells transformed at 4° C. by parallel transformation with A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI). Wells 1 and 2 (L to R) contain washed A 0.07+B 0.3 mg/mL against anti-A and anti-B. Wells 3 and 4 contain unwashed A 0.07+B 0.3 mg/mL against anti-A and anti-B.
[0127] FIG. 9 shows cells that were no longer washed prior to testing. Diamed results of cells transformed at 4° C. by parallel transformation with A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI). Wells 1 and 2 (L to R) contain unwashed A 0.07+B 0.3 mg/mL against anti-A and anti-B.
[0128] FIG. 10 shows Diamed results of cells transformed at 4° C. by parallel transformation with A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI). Wells 1 and 2 (L to R) contain washed A 0.07+B 0.2 mg/mL against anti-A and anti-B. Wells 3 and 4 contain unwashed A 0.07+B 0.2 mg/mL against anti-A and anti-B.
[0129] FIG. 11 shows cells that were no longer washed prior to testing. Diamed results of cells transformed at 4° C. by parallel transformation with A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI). Wells 1 and 2 (L to R) contain unwashed A 0.07+B 0.2 mg/mL against anti-A and anti-B.
[0130] FIG. 12 shows Diamed results of cells transformed at 4° C. by parallel transformation with A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI). Wells 1 and 2 (L to R) contain washed A 0.06+B 0.3 mg/mL against anti-A and anti-B. Wells 3 and 4 contain unwashed A 0.06+B 0.3 mg/mL against anti-A and anti-B.
[0131] FIG. 13 shows cells that were no longer washed prior to testing. Diamed results of cells transformed at 4° C. by parallel transformation with A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI). Wells 1 and 2 (L to R) contain unwashed A 0.06+B 0.3 mg/mL against anti-A and anti-B.
[0132] FIG. 14 shows Diamed results of cells transformed at 4° C. by parallel transformation with A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI). Wells 1 and 2 (L to R) contain washed A 0.06+B 0.2 mg/mL against anti-A and anti-B. Wells 3 and 4 contain unwashed A 0.06+B 0.2 mg/mL against anti-A and anti-B.
[0133] FIG. 15 shows cells that were no longer washed prior to testing. Diamed results of cells transformed at 4° C. by parallel transformation with A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI). Wells 1 and 2 (L to R) contain unwashed A 0.06+B 0.2 mg/mL against anti-A and anti-B.
[0134] FIG. 16 shows Diamed results of cells transformed at 4° C. by parallel transformation with A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI). Wells 1 and 2 (L to R) contain washed A 0.05+B 0.3 mg/mL against anti-A and anti-B. Wells 3 and 4 contain unwashed A 0.05+B 0.3 mg/mL against anti-A and anti-B.
[0135] FIG. 17 shows cells that were no longer washed prior to testing. Diamed results of cells transformed at 4° C. by parallel transformation with A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI). Wells 1 and 2 (L to R) contain unwashed A 0.05+B 0.3 mg/mL against anti-A and anti-B.
[0136] FIG. 18 shows Diamed results of cells transformed at 4° C. by parallel transformation with A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI). Wells 1 and 2 (L to R) contain washed A 0.05+B 0.2 mg/mL against anti-A and anti-B. Wells 3 and 4 contain unwashed A 0.05+B 0.2 mg/mL against anti-A and anti-B.
[0137] FIG. 19 shows cells that were no longer washed prior to testing. Diamed results of cells transformed at 4° C. by parallel transformation with A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI). Wells 1 and 2 (L to R) contain unwashed A 0.05+B 0.2 mg/mL against anti-A and anti-B.
COMPARATIVE EXAMPLES
[0138] The Comparative Examples do not form part of the invention claimed. The Comparative Examples describe red blood cell transformation with natural glycolipids.
Comparative Example 1
Preparation of Natural Glycolipids
Purification by HPLC
[0139] In the first stage, columns were packed with dry silica (15-25 μm) before each run. Relatively dirty samples could be used in HPLC because the silica could be discarded along with the theoretically high level of irreversibly bound contaminants.
[0140] Glycolipids were separated on silica gel with a mobile phase of increasing polarity. The program was a linear gradient beginning with 100% chloroform-methanol-water 80:20:1 (v/v) and ending with 100% chloroform-methanol-water 40:40:12 (v/v).
[0141] The HPLC equipment used was a Shimadzu system capable of pumping and mixing four separate solvents at programmed ratios. As chloroform, methanol and water evaporate at different rates, a program was developed whereby the solvent components were not mixed prior to entering the HPLC.
[0142] The Shimadzu HPLC mixes four different liquids by taking a “shot” from each of four bottles in turn. “Shots” of chloroform and water directly next to each other in the lines may cause miscibility problems. Methanol was sandwiched in between these two immiscible components. Additionally, the water was pre-mixed with methanol in a 1:1 ratio to further prevent problems with miscibility.
Comparative Example 2
Transformation of Red Blood Cell Transformation with Natural Glycolipids
Agglutination
[0143] Transformation of red blood cells was assessed by agglutination using the Diamed-ID Micro Typing System in addition to using conventional tube serology. Diamed ABO typing cards were not used. The cards used were NaCl, Enzyme test and cold agglutinin cards, which were not pre-loaded with any antisera or other reagents. This allowed the use of specific antisera with both methodologies.
[0000]
TABLE 1
Gel-cards.
Manufacturer
Catalogue ref
Diamed
NaCl, Enzyme test and cold agglutinin cards
[0144] A comparative trial was carried out between tube serology and the Diamed system to establish the performance of the two systems. Cells were transformed at 25° C. for 4 hours. Seraclone and Alba-clone anti-A sera were used to gauge equivalency. The results are shown in Table 3 below.
[0000]
TABLE 2
Antisera used in comparison of tube
serology with the Diamed system.
Manufacturer
Catalogue ref
Lot
Expiry
Albaclone, SNBTS
Anti-A.
Z0010770
12 Dec. 2004
Seraclone, Biotest
801320100
1310401
12 Apr. 2003
[0000]
TABLE 3
Agglutination results comparing tube
serology with the Diamed system.
A glycolipid (mg/mL)
10
5
2
1
0
Tube
Albaclone
3+
2+
0
0
0
Seraclone
3+
2+
0
0
0
Diamed
Albaclone
2+
2+
0
0
0
Seraclone
3+
2+
1+
w+
0
[0145] In this experiment, the Diamed system proved to be more sensitive to the weaker reactions than tube serology with the Seraclone anti-A, but not with Albaclone. These reagents are formulated differently, and are thus not expected to perform identically. However, the fact that the Seraclone anti-A tube serology combination did not detect positivity is probably due to operator interpretation. The weaker reactions are notoriously difficult to accurately score, and the difference between 1+ and 0 can be difficult to discern in tubes.
Optimisation
[0146] The variables of glycolipid concentration, incubation temperature, incubation duration, diluent and storage solution were examined for their effect on cell health. Efficiency and stability of transformation was assessed by agglutination with the relevant antibody.
[0000]
TABLE 4
Tube serology agglutination of natural glycolipid A transformed
cells over different times and temperatures.
A
10
5
2
1
0.1
0.01
0.001
0.0001
0
Seraclone
3+
2+
0
0
0
(37° C. for
1.5 hours)
Seraclone
4+
3+
2+
1+
w+
0
0
0
0
(25° C. for
4 hours)
Glycolipid Concentration
[0147] Initial transformation experiments were carried out with a highly purified (HPLC) Le b glycolipid sample and a less pure blood group A glycolipid sample. Transformation was performed at 37° C. for 1.5 hours
[0148] The A glycolipid sample contained other lipid impurities and thus comparatively less blood group A molecules by weight than the Le b glycolipid sample of equivalent concentration (w/v). This seems to be borne out by the fact that higher concentrations of the A glycolipid than the Le b glycolipid were required to produce equivalent agglutination scores (see Table 6).
[0149] The level of impurity in the A glycolipid sample may also have contributed to the lower stability over the 62 day period—the A-transformed cells ‘died’ at the highest concentration (having received the largest dose of impurity).
[0000]
TABLE 5
Anti-A and anti-Le b used in initial testing
of natural glycolipid transformation.
Manufacturer
Catalogue ref
Batch number
Expiry
Anti-A
Seraclone, Biotest
801320100
1310401
12 Apr. 2003
Anti-Le b
CSL
12801
[0000]
TABLE 6
Stability of RBCs transformed with natural A and Le b glycolipid as
assessed by tube serology agglutination over the period of 62 days.
Glycolipid
Le b
A
(mg/mL)
Day 1
Day 25
Day 62
Day 1
Day 25
Day 62
10
4+
2-3+
3+
2+
?
5
4+
2-3+
2+
2+
w+
2
3+
1-2+
0
1+
0
1
4+
2+
0
1+
0
0.1
3+
2+
0
0
0.01
2+
2+
0
0
0.001
2+
2+
0
0
0.0001
2+
0
0
0
0
0
0
0
0
0
0
[0150] The above cells were also rated for haemolysis and these results are shown in Table 7 below.
[0000]
TABLE 7
Haemolysis as assessed visually.
Glycolipid
Haemolysis
concentration
Le b
A
(mg/mL)
Day 1
Day 25
Day 62
Day 1
Day 25
Day 62
10
h
0
h
h
h
dead
5
hh
0
hhh
w
0
hh
2
w
0
hhh
w
0
hhhhh
1
w
0
hhh
h
0
hhhh
0.1
h
hhh
0.01
hh
0.001
h
0.0001
h
Control
h
0
h
h
h
Day 1—in the supernatant of the first wash after transformation; Days 25 and 62—in the cell preservative solution before the cells are resuspended after storage. Scoring scale is analogous to the 4+ to 0 agglutination scale: hhhh—severely haemolysed, hhh—very haemolysed, hh—moderately haemolysed, h—mildly haemolysed, w—faintly haemolysed and 0—no haemolysis seen.
[0151] These results show that cell haemolysis can be shown to be associated with transformation with high concentrations of glycolipid. It is unclear whether the mechanism underlying this is disruption of the plasma membrane by large amounts of glycolipid being inserted, the rate of that insertion, or is possibly due to the quantity of associated impurity. However, the results for Le b at day 62 seem to support the first explanation.
[0152] The Le b sample was highly purified—before being dissolved, it was a powder of pure white colour, and thus it is unlikely that the haemolysis was due to the deleterious effect of impurities. It is clear to see that at 62 days, the amount of haemolysis occurring diminishes in line with the decrease in the glycolipid concentration.
Incubation Temperature
[0153] Experiments were carried out to investigate other possible mechanisms for the reduction of haemolysis of RBCs during the insertion step. Previous experiments had shown that haemolysis was worse at higher glycolipid concentrations than at lower concentrations, and it is thought that haemolysis may also be related to the rate of glycolipid insertion. Since temperature is believed to affect the rate of insertion, experiments were conducted comparing transformation at 37° C. with transformation at room temperature (RT; 25° C.).
[0154] Since the rate was expected to slow down as temperature decreased, the incubation period for the RT experiment was 4 hrs. Haemolysis was assessed visually and scored following insertion. Serology tests were also performed on the cells. The results are shown in Table 8.
[0000]
TABLE 8
The effect of incubation temperature on haemolysis and agglutination
during insertion of glycolipids into RBC membranes. Haemolysis
was scored visually at each of the three washes.
Haemolysis
RT
37° C.
Glycolipid
wash
wash
wash
wash
wash
wash
Serology
(mg/mL)
1
2
3
1
2
3
RT
37° C.
10
w
0
0
hh
w
0
2+
2+
1
w
0
0
hh
h
vw
1+
w+
Incubation Duration
[0155] Incubation at 37° C. was carried out for 1 and 2 hours and its effect on cell health and transformation assessed by agglutination with the relevant antibody.
[0000]
TABLE 9
Antisera used in the duration of incubation trial.
Manufacturer
Catalogue ref
Batch number
Expiry date
Albaclone, SNBTS
Anti-A.
Z0010770
12 Dec. 2004
Bioclone, OCD
Anti-A,
DEV01102
—
experimental
reagent
Albaclone, SNBTS
Anti-B
Z0110670
01 Jul. 2005
Bioclone, OCD
Anti-B,
DEV01103
—
experimental
reagent
[0000]
TABLE 10
Effect of incubation time on agglutination of
cells transformed with natural glycolipids.
Concentration
Albaclone
BioClone
Glycolipid
(mg/mL)
1 hour
2 hours
1 hour
2 hours
A
10
4+
4+
4+
4+
5
4+
4+
4+
2+
2
4+
3+
3+
2+
1
3+
2+
2+
2+
0.5
2+
2+
1+
w+
B
10
3+
2+
4+
1+
5
3+
2+
3+
2+
2
2+
2+
2+
1+
1
1+
w+
1+
w+
0.5
1+
w+
w+
w+
[0156] These results indicate that increasing the duration of incubation during natural glycolipid insertion does not enhance agglutination. In fact, the agglutination scores are reduced after the two hour incubation. This may be due to the destabilisation of the membrane or exchange of the glycolipids back into solution.
Diluent
[0157] Experiments were also carried out to determine if changing the glycolipid diluent solution could reduce haemolysis. Working strength PBS was compared with 2×PBS and 2% Bovine Serum Albumin (BSA) in working strength PBS. Cells were incubated at 37° C. for 1.5 hours. The results are shown in Table 11.
[0000]
TABLE 11
Study on the effect on haemolysis of changing the glycolipid diluent
solutions during insertion of glycolipids into RBC membranes.
Glycolipid
concentration
Glycolipid Diluent Solution
(mg/mL)
PBS
2 × PBS
2% BSA in PBS
40
Hhh
hhh
hhh
30
Hhh
hhh
hhh
20
Hhh
hhh
hhh
10
Hhh
hhh
hhh
0
0
0
0
Stability
[0158] Once A and B blood group glycolipids had been HPLC purified to an acceptable level, an experiment to find the appropriate concentrations for stability trials was carried out.
[0000]
TABLE 12
Early stability trial of cells transformed with natural A glycolipid.
A
Expt
Day
10
5
2
1
0.1
0.01
0.001
0.0001
0
1
7
4+
3-4+
1+
0
0
0
0
0
0
2
43
3+
w+
0
0
0
0
0
0
0
3
50
1+
0
0
0
4
60
3+
1+
0
5
67
w+
vw
vw
6
74
2+
0
0
7
81
2+
1+
0
[0000]
TABLE 13
Antisera used in stability trials (Table 14 and Table 15).
Manufacturer
Catalogue ref
Batch number
Expiry date
Albaclone, SNBTS
Anti-A.
Z0010770
12 Dec. 2004
Bioclone, OCD
Anti-A,
DEV01102
—
experimental
reagent
Albaclone, SNBTS
Anti-B
Z0110670
01 Jul. 2005
Bioclone, OCD
Anti-B,
DEV01103
—
experimental
reagent
[0000]
TABLE 14
Tube serology of O RBCs transformed with A glycolipid in order
to establish appropriate concentrations for stability trials.
A glycolipid (mg/mL)
Anti-A
Expt
10
5
2
1
0.5
0.1
0.01
0.001
0
Alba
1
3+
2+
1+
0
0
0
0
0
2
4+
4+
3+
2+
w+
Bio
1
3+
2+
1+
0
0
0
0
0
2
4+
4+
3+
2+
w+
1 & 2 Transformation at 25° C. for 4 hours
[0000]
TABLE 15
Tube serology of O RBCS transformed with B glycolipid in order
to establish appropriate concentrations for stability trials.
B glycolipid (mg/mL)
Anti-B
Expt
10
5
2
1
0.5
0.1
0.01
0.001
0
Alba
1
2+
1+
w+
0
0
0
0
0
2
1+
1+
w+
0
w+
Bio
1
3+
2+
w+
0
0
0
0
0
2
1+
1+
w+
0
w+
1 & 2 Transformation at 25° C. for 4 hours
[0159] Two sets of cells were transformed with different concentrations of natural A glycolipid. Transformation was performed at 25° C. One set of cells was tested long term, and one set of cells was tested weekly for agglutination. The agglutination results from tube serology and Diamed are shown in Table 16 below. All cells were stored in Cellstab™ in bottles with flat bases. The cells showed minimal to no haemolysis at any time.
[0000]
TABLE 16
Agglutination results for cells transformed with
different concentrations of natural A glycolipid.
Results were obtained using Albaclone anti-A.
A glycolipid (mg/mL)
10
5
2
1
0.1
control
Long term testing
Day 1
Tube
4+
3+
2+
1+
+w
0
Diamed
3+
3+
+w
0
0
0
Day 17
Tube
3+
2+
0
0
0
Diamed
3+
2+
1+
0
0
Weekly testing
Day 1
Tube
3+
2+
0
0
Diamed
3+
0
0
0
Day 8
Tube
1+
0
0
0
Diamed
3+
0
0
0
Day 15
Tube
1+
0
0
0
Diamed
3+
2+
0
0
Day 22
Tube
3+
0
0
0
Diamed
3+
0
0
0
Day 29
Tube
*+w
*0
*0
*0
Diamed
*3+
*0
*0
*0
Day 36
Tube
*
*
*
*0
Diamed
*3+
*0
*0
*0
Day 43
Tube
*
*
*
*0
Diamed
*
*
*
*0
*Albaclone, while all others used Seraclone anti-A.
Storage Solution
[0160] Comparison of the two cell storage solutions, Celpresol™ (CSL) and Cellstab™ (Diamed) was carried out to test their relative abilities to support modified RBCs.
[0161] The stability of RBCs transformed with blood group A and B antigen solutions of varying concentrations when stored in two different cell preservative solutions—Cellstab™ and Alsevers™—was trialed.
[0162] A and B antisera from two different sources were used in serology testing.
[0163] All cells were tested using the standard tube serology platform up to 42 days, at which time the cell agglutination reactions had become too difficult to score manually (see Table 17 for A results and Table 18 for B results).
[0164] Diamed gel-card testing was carried out to day 56 for the Alsevers stored cells, and discontinued at day 63 due to fungal contamination (although still returning positive scores).
[0165] The Cellstab™ stored cells continued to be tested up to day 70, and were still viable at this point (see FIG. 1 for A results and FIG. 2 for B results).
[0166] The reagents used in the stability trial are shown in Table 13.
[0000]
TABLE 17
Tube serology results of stability trial of cells transformed with varying
concentrations of A glycolipid and stored in either Cellstab ™ or Alsevers ™
Albaclone Anti-A
Bioclone Anti-A
Cell
(SNBTS) Transformation
(OCD - Developmental
storage
Solution (mg/mL)
reagent)
Day
solution
10
5
2
2*
1
10
5
2
2*
1
2
Alsevers
4+
3+
2+
1+
w+
3+
3+
1+
1+
0
Cellstab ™
4+
4+
3+
1+
1+
3+
3+
2+
1+
0
8
Alsevers
4+
4+
2+
1+
1+
2+
2+
1+
1+
0
Cellstab ™
4+
4+
3+
2+
1+
3+
3+
2+
w+
0
14
Alsevers
4+
3+
2+
2+
w+
2+
1+
w+
vw
0
Cellstab ™
4+
3+
3+
2+
w+
3+
2+
w+
vw
0
21
Alsevers
3+
2+
2+
2+
1+
2+
2+
2+
1+
0
Cellstab ™
3+
3+
2+
+
‡
2+
‡
‡
‡
0
28
Alsevers
2+
2+
1+
1+
0
2+
2+
1+
1+
0
Cellstab ™
2+ ‡
2+ ‡
‡
‡
0
1+
w+
0
0
0
36
Alsevers
3+
2+
2+
2+
1+
3+
3+
2+
1+
1+
Cellstab ™
3+ ‡
2+ ‡
‡
‡
‡
3+ ‡
‡
‡
‡
‡
42
Alsevers
3+
3+
1+
w+
0
2+
2+
2+
1+
1+
Cellstab ™
4+ ‡
4+ ‡
‡
‡
‡
‡
‡
‡
‡
0
*transformation solution (containing glycolipids) was not washed out after the incubation, it was left in over night and washed out the next day.
‡ positive cell button, but cells fall off as negative (score assignment impossible).
[0000]
TABLE 18
Tube serology results of stability trial of cells transformed
with varying concentrations of B glycolipid and stored
in either Cellstab ™ or Alsevers ™.
Albaclone Anti-B
Bioclone Anti-B
Cell
(SNBTS) Transformation
(OCD - Developmental
storage
Solution (mg/mL)
reagent)
Day
solution
10
5
2
2*
1
10
5
2
2*
1
2
Alsevers
3+
3+
1+
1+
1+
2+
1+
1+
1+
0
Cellstab ™
3+
3+
2+
2+
1+
2+
2+
2+
1+
w+
8
Alsevers
1+
1+
w+
0
0
0
0
0
0
0
Cellstab ™
2+
1+
w+
0
1+
1+
w+
0
0
14
Alsevers
2+
2+
0
w+
0
0
1+
1+
2+
0
Cellstab ™
1+
w+
0
0
0
2+
2+
w+
1+
1+
21
Alsevers
‡
‡
‡
‡
‡
1
1
‡
‡
‡
Cellstab ™
‡
‡
‡
‡
‡
+
+
+
‡
‡
28
Alsevers
2+
1+
w+
0
0
2+
1+
2+
0
0
Cellstab ™
‡
‡
‡
0
0
‡
0
‡
‡
0
36
Alsevers
2+
2+
2+
1+
1+
2+
2+
2+
1+
1+
Cellstab ™
‡
‡
‡
‡
‡
‡
‡
‡
‡
‡
42
Alsevers
2+
2+
2+
2+
w+
2+
2+
1+
w+
w+
Cellstab ™
‡
‡
‡
‡
‡
‡
‡
‡
‡
‡
*transformation solution (containing glycolipids) was not washed out after the incubation, it was left in over night and washed out the next day.
‡ positive cell button, but cells fall off as negative (score assignment impossible).
FACS Analysis of Glycolipid Insertion
[0167] Transformation of human Le(a-b-) red cells with natural Le b -6 glycolipid over time at three transformation temperatures (37° C., 22° C. and 4° C.) was performed ( FIG. 3 ). Natural Le b -6 glycolipid was dissolved in plasma and used to transform RBCs at a final concentration of 2 mg/mL and a final suspension of 10%.
[0168] Reactivity was determined by FACS analysis using a Gamma anti-Leb. (The serological detection level is around 10 2 molecules. The insertion of natural glycolipids at 4° C. for 8 hours was not detectable by agglutination with antibodies.) Projection of the rate of insertion curve from FACS analysis did not indicate that the rate of insertion at 4° C. would have reached agglutination detection levels within 24 hours.
Low Incubation Temperature
[0169] Transformation of RBCs with natural A or B glycolipid was perfomed at 37° C. for 1 hour and 2° C. for varying intervals. Cells were agglutinated with Bioclone anti-A or Bioclone anti-B. The results are provided in Tables 19 and 20.
[0000]
TABLE 19
Diamed results of comparison of natural A glycolipid transformation at
37° C. for 1 hour and 2° C. for varying intervals.
Time
Nat A (mg/mL)
Temp
(hours)
10
5
2
1
0
37° C.
1
3+
3+
2-3+
2+
0
2° C.
1
0
0
0
0
0
4
0
0
0
0
0
8
1-2+
0
0
0
0
24
2-3+
2+
1-2+
0
0
48
3+
2-3+
2-3+
0
0
72
3-4+
3+
2+
0
0
[0000]
TABLE 20
Diamed results of comparison of natural B glycolipid transformation at
37° C. for 1 hour and 2° C. for varying intervals.
Time
Nat B (mg/mL)
Temp
(hours)
10
5
2
1
0
37° C.
1
3+
2-3+
2+
0
0
2° C.
1
0
0
0
0
0
4
0
0
0
0
0
8
0
0
0
0
0
24
1+
0
0
0
0
48
2+
1-2+
0
0
0
72
2+
1+
0
0
0
[0170] The rate of transformation is slow for both natural A glycolipid and natural B glycolipid as demonstrated by the negative agglutination scores after 1 hour at 2° C. Considerable insertion at 37° C. for this time interval has been demonstrated.
[0171] Natural A glycolipid insertion at 2° C. required 48 hours to reach the same level of insertion obtainable by transformation at 37° C. After this time further insertion was not observed. Likewise, natural B glycolipid insertion at 2° C. was not as rapid as transformation at 37° C. The agglutination scores did not improve upon continued incubation and thus seemed to have reached maximal insertion at this time point for these concentrations.
EXAMPLES
[0172] The Examples describe red blood cell transformation with the synthetic molecule constructs of the invention. In the context of these examples the term “synthetic glycolipids” is used to refer to these constructs.
Example 1
Preparation of Synthetic Glycolipids
Materials and Methods
[0173] TLC analysis was performed on silica gel 60 F 254 plates (Merck), the compounds were detected by staining with 8% of phosphoric acid in water followed by heating at over 200° C. Column chromatography was carried out on silica gel 60 (0.2-0.063 mm, Merck) or Sephadex LH-20 (Amersham). 1 H NMR spectra were acquired on a Bruker DRX-500 spectrometer. Chemical shifts are given in ppm (δ) relative to CD 3 OD.
Synthesis of activated 1,2-O-dioleoyl-sn-glycero-3-phosphatidylethanolamine (DOPE) and 1,2-O-distereoyl-sn-glycero-3-phosphatidylethanolamine (DSPE)(glycerophospholipids)
[0174] To a solution of bis(N-hydroxysuccinimidyl) adipate (A) (70 mg, 205 μmol) in dry N,N-dimethylformamide (1.5 ml) were added DOPE or DSPE (L) (40 μmol) in chloroform (1.5 ml) followed by triethylamine (7 μl). The mixture was kept for 2 h at room temperature, then neutralized with acetic acid and partially concentrated in vacuo.
[0175] Column chromatography (Sephadex LH-20, 1:1 chloroform-methanol, 0.2% acetic acid) of the residue yielded the activated lipid (A-L) (37 mg, 95%) as a colorless syrup; TLC (chloroform-methanol-water, 6:3:0.5): R f =0.5 (DOPE-A), R f =0.55 (DSPE-A).
[0176] 1 H NMR (CDCl 3 /CD 3 OD, 2:1), δ:
[0177] DOPE-A—5.5 (m, 4H, 2×(—C H ═C H —), 5.39 (m, 1H, —OCH 2 —C H O—CH 2 O—), 4.58 (dd, 1H, J=3.67, J=11.98, —CCOOHC H —CHO—CH 2 O—), 4.34 (dd, 1H, J=6.61, J=11.98, —CCOO H CH—CHO—CH 2 O—), 4.26 (m, 2H, PO—C H 2 —CH 2 —NH 2 ), 4.18 (m, 2H, —C H 2 —OP), 3.62 (m, 2H, PO—CH 2 —C H 2 —NH 2 ), 3.00 (s, 4H, ONSuc), 2.8 (m, 2H, —C H 2 —CO (Ad), 2.50 (m, 4H, 2×(—C H 2 —CO), 2.42 (m, 2H, —C H 2 —CO (Ad), 2.17 (m, 8H, 2×(—C H 2 —CH═CH—C H 2 —), 1.93 (m, 4H, COCH 2 C H 2 C H 2 CH 2 CO), 1.78 (m, 4H, 2×(COCH 2 C H 2 —), 1.43, 1.47 (2 bs, 40H, 20 CH 2 ), 1.04 (m, 6H, 2 CH 3 ).
[0178] DSPE-A—5.39 (m, 1H, —OCH 2 —C H O—CH 2 O—), 4.53 (dd, 1H, J=3.42, J=11.98, —CCOOHC H —CHO—CH 2 O—), 4.33 (dd, 1H, J=6.87, J=11.98, —CCOO H CH—CHO—CH 2 O—), 4.23 (m, 2H, PO—C H 2 —CH 2 —NH 2 ), 4.15 (m, 2H, —C H 2 —OP), 3.61 (m, 2H, PO—CH 2 —C H 2 —NH 2 ), 3.00 (s, 4H, ONSuc), 2.81 (m, 2H, —C H 2 —CO (Ad), 2.48 (m, 4H, 2×(—C H 2 —CO), 2.42 (m, 2H, —C H 2 —CO (Ad), 1.93 (m, 4H, COCH 2 C H 2 C H 2 CH 2 CO), 1.78 (m, 4H, 2×(COCH 2 C H 2 —), 1.43, 1.47 (2 bs, 40H, 20 CH 2 ), 1.04 (m, 6H, 2 CH 3 ).
[0000] Condensing Activated DOPE (or DSPE) with Aminopropylglycoside.
[0179] To a solution of activated DOPE (or DSPE) (A-L) (33 μmol) in N,N-dimethylformamide (1 ml) 30 μmol of Sug-S 1 —NH 2 (F—S 1 —NH 2 ) and 5 μl of triethylamine were added. For example, the Sug may be either the aminopropyl glycoside (F—S 1 —NH 2 ) of either GalNAcα1-3(Fucα1-2)Galβ trisaccharide (A-glycotope) (F) or Galα1-3(Fucα1-2)Galβtrisaccharide (B-glycotope) (F).
[0180] The mixture was stirred for 2 h at room temperature. Column chromatography (Sephadex LH-20 in 1:1 chloroform-methanol followed by silica gel in ethyl acetate-isopropanol-water, 4:3:1 (v/v/v) of the mixture typically yielded 85-90% of the synthetic molecule construct, for example, A tri -sp-Ad-DOPE (I) or B tri -sp-Ad-DOPE (VI).
[0181] 1 H NMR (CDCl 3 /CD 3 OD, 1:1), δ:
[0182] A tri -sp-Ad-DOPE (I)—5.5 (m, 4H, 2×(—C H ═C H —), 5.43-5.37 (m, 2H, H−1 (GalNHAc) and —OCH 2 —C H O—CH 2 O—), 5.32 (d, 1H, H−1, J=3.5H−1 Fuc), 2.50 (m, 4H, 2×(—C H 2 —CO), 2.40 (m, 4H, COC H 2 CH 2 CH 2 C H 2 CO), 2.20 (m, 8H, 2×(—C H 2 —CH═CH—C H 2 —), 2.1 (s, 3H, NHAc), 1.92 (m, 2H, O—CH 2 C H 2 CH 2 —NH), 1.8 (m, 8H, COCH 2 C H 2 C H 2 CH 2 CO and 2×(COCH 2 C H 2 —), 1.43, 1.47 (2 bs, 40H, 20 CH 2 ), 1.40 (d, 3H, J=6.6, CH 3 Fuc), 1.05 (m, 6H, 2 CH 3 ).
[0183] A tri -spsp 1 -Ad-DOPE (II)—5.5 (m, 4H, 2×(—C H ═C H —), 5.43-5.37 [m, 2H, H−1 (GalNHAc) and —OCH 2 —C H O—CH 2 O—], 5.32 (d, 1H, H−1, J=3.6H−1 Fuc), 2.50 (m, 4H, 2×(—C H 2 —CO), 2.40-2.32 (m, 6H, COC H 2 CH 2 CH 2 C H 2 CO and COC H 2 — (sp 1 ), 2.18 [m, 8H, 2×(—C H 2 —CH═CH—C H 2 —)], 2.1 (s, 3H, NHAc), 1.95 (m, 2H, O—CH 2 C H 2 CH 2 —NH), 1.8 [m, 10H, COCH 2 C H 2 C H 2 CH 2 CO, 2×(COCH 2 C H 2 — . . . ), —COCH 2 CH 2 (CH 2 ) 3 NH—], 1.68 (m, 2H, CO(CH 2 ) 3 C H 2 CH 2 NH—), 1.43, 1.47 (2 bs, 42H, 22 CH 2 ), 1.37 (d, 3H, J=5.6, CH 3 Fuc), 1.05 (m, 6H, 2 CH 3 ).
[0184] A tri -sp-Ad-DSPE (III)—5.42-5.38 (m, 2H, H−1 (GalNHAc) and —OCH 2 —C H O—CH 2 O—), 5.31 (d, 1H, H−1, J=3.5H−1 Fuc), 2.48 [m, 4H, 2×(—C H 2 —CO)], 2.42 (m, 4H, COC H 2 CH 2 CH 2 C H 2 CO), 2.18 (s, 3H, NHAc), 1.95 (m, 2H, O—CH 2 C H 2 CH 2 —NH), 1.8 [m, 8H, COCH 2 C H 2 C H 2 CH 2 CO and 2×(COCH 2 C H 2 —)], 1.43, 1.47 (2 bs, 56H, 28 CH 2 ), 1.38 (d, 3H, J=6.6, CH 3 Fuc), 1.05 (m, 6H, 2 CH 3 ).
[0185] B tri -sp-Ad-DOPE (VI)—5.5 (m, 4H, 2×(—C H ═C H —), 5.42-5.38 [m, 2H, H−1 (Gal) and —OCH 2 —C H O—CH 2 O—], 5.31 (d, 1H, H−1, J=3.7, H−1 Fuc), 2.48 [m, 4H, 2×(—C H 2 —CO)], 2.39 (m, 4H, COC H 2 CH 2 CH 2 C H 2 CO), 2.18 [m, 8H, 2×(—C H 2 —CH═CH—C H 2 —)], 1.93 (m, 2H, O—CH 2 C H 2 CH 2 —NH), 1.8 [m, 8H, COCH 2 C H 2 C H 2 CH 2 CO and 2×(COCH 2 C H 2 —)], 1.43, 1.47 (2 bs, 40H, 20 CH 2 ), 1.36 (d, 3H, J=6.6, CH 3 Fuc), 1.05 (m, 6H, 2 CH 3 ).
[0186] H tri -sp-Ad-DOPE (VII)—5.5 [m, 4H, 2×(—C H ═C H —)], 5.4 (m, 1H, —OCH 2 —C H O—CH 2 O—), 5.35 (d, 1H, H−1, J=3.2, H−1 Fuc), 4.65, 4.54 (2 d, J=7.4, J=8.6, H−1 Gal, H−1 GlcNHAc), 4.46 (dd, 1H J=3.18, J=12, —CCOO H CH—CHO—CH 2 O—), 4.38-4.28 (m, 2H, H-5 Fuc, CCOOHC H —CHO—CH 2 O—), 2.48 [m, 4H, 2×(—C H 2 —CO)], 2.40 (m, 4H, COC H 2 CH 2 CH 2 C H 2 CO), 2.18 [m, 8H, 2×(—C H 2 —CH═CH—C H 2 —)], 2.08 (s, 3H, NHAc), 1.92 (m, 2H, O—CH 2 C H 2 CH 2 —NH), 1.82-1.72 [m, 8H, COCH 2 C H 2 C H 2 CH 2 CO and 2×(COCH 2 C H 2 —)], 1.48, 1.45 (2 bs, 40H, 20 CH 2 ), 1.39 (d, 3H, J=6.5, CH 3 Fuc), 1.05 (m, 6H, 2 CH 3 ).
[0187] H di -sp-Ad-DOPE (VIII)—5.49 (m, 4H, 2×(—C H ═C H —), 5.37 (m, 1H, —OCH 2 —C H O—CH 2 O—), 5.24 (d, 1H, H−1, J=2.95, H−1 Fuc), 4.46 (d, J=7.34, H−1 Gal), 2.48 [m, 4H, 2×(—C H 2 —CO)], 2.42-2.35 (m, 4H, COC H 2 CH 2 CH 2 C H 2 CO), 2.17 [m, 8H, 2×(—C H 2 —CH═CH—C H 2 —)], 1.95 (m, 2H, O—CH 2 C H 2 CH 2 —NH), 1.81-1.74 [m, 8H, COCH 2 C H 2 C H 2 CH 2 CO and 2×(COCH 2 C H 2 —)], 1.45, 1.41 (2 bs, 40H, 20 CH 2 ), 1.39 (d, 3H, J=6.5, CH 3 Fuc), 1.03 (m, 6H, 2 CH 3 ).
[0188] Galβ-sp-Ad-DOPE (IX)—5.51 [m, 4H, 2×(—C H ═C H —)], 5.4 (m, 1H, —OCH 2 —C H O—CH 2 O—), 4.61 (dd, 1H J=3.18, J=12, —CCOO H CH—CHO—CH 2 O—), 4.41 (d, J=7.8, H−1 Gal), 4.37 (dd, 1H, J=6.6, J=12, —CCOOHC H —CHO—CH 2 O—), 2.50 [m, 4H, 2×(—C H 2 —CO)], 2.40 (m, 4H, COC H 2 CH 2 CH 2 C H 2 CO), 2.20 [m, 8H, 2×(—C H 2 —CH═CH—C H 2 —)], 1.97 (m, 2H, O—CH 2 C H 2 CH 2 —NH), 1.82-1.72 [m, 8H, COCH 2 C H 2 C H 2 CH 2 CO and 2×(COCH 2 C H 2 —)], 1.48, 1.45 (2 bs, 40H, 20 CH 2 ), 1.05 (m, 6H, 2 CH 3 ).
Example 2
Solubility of Synthetic Glycolipids
[0189] For use in the transformation of cells the first criterion that synthetic glycolipids must satisfy is that they are soluble in aqueous solvents, e.g. phosphate buffered saline. A number of techniques, including heat and/or sonication, were employed initially in order to maximise the solubility of the synthetic glycolipids tested (Table 21).
[0190] The synthetic glycolipid must also be able to insert into the membrane and be recognisable to the appropriate antibody for transformation to be detected by agglutination. Initial tests on the molecules were to establish solubility and thus eliminate those molecules that were unsuitable for use in the transformation of cells.
[0191] The results of these initial tests are provided in Table 22.
[0000]
TABLE 21
The range of synthetic glycolipid molecules tested.
DOPE Lipid Tails:
B tri -sp-Ad-DOPE (VI)
A tri -sp-Ad-DOPE (I)
Galβ-sp-Ad-DOPE (IX)
H di -sp-Ad-DOPE (VIII)
H tri -sp-Ad-DOPE (VII)
A tri -spsp 1 -Ad-DOPE (II)
B tri -PAA-DOPE (V)
Different Lipid Tails:
A tri -sp-lipid (IV)
A tri -sp-Ad-DSPE (III)
[0000]
TABLE 22
Solubility of synthetic glycolipids in
hot PBS and transformation ability.
Detectable transformation
Synthetic
Water solubility
ability
A tri -sp-lipid (IV)
No
No
B tri -PAA-DOPE (V)
No
No
B tri -sp-Ad-DOPE (VI)
Yes
Yes
A tri -sp-Ad-DOPE (I)
Yes
Yes
Galβ-sp-Ad-DOPE (IX)
Yes
No
H di -sp-Ad-DOPE (VIII)
Yes
No
H tri -sp-Ad-DOPE (VII)
Yes
Yes
A tri -spsp 1 -Ad-DOPE (II)
Yes
Yes
A tri -sp-Ad-DSPE (III)
Yes
Yes
[0192] The lack of detectable transformation for Galβ-sp-Ad-DOPE (IX) and H di -sp-Ad-DOPE (VIII) was thought to be due to the inability of the antibody to recognise the glycotope of these synthetic molecules. A tri -sp-lipid (IV) has a single rather than a diacyl tail and it was proposed that there was no insertion of this synthetic molecule into the membrane bilayer.
Example 3
Low Temperature Transformation of RBCs by A Tri -Sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI) Synthetic Glycolipids
[0193] RBCs are healthier when stored at 4° C., and likewise are believed to be healthier when transformed at 4° C. It was not thought that a significant rate of insertion of the synthetic glycolipids would occur at 4° C. due to our previous studies (see Comparative Examples) and studies by others (Schwarzmann, 2000). These studies were performed with natural glycolipids. Surprisingly these studies did not predict the behaviour of the synthetic glycolipids of the invention.
[0194] Whilst not wishing to be bound by theory, in the studies of Schwarzmann the low rate of insertion of the natural glycolipids may be due to the physicochemical properties of the natural glycolipid tail; a sphingolipid and a fatty acid.
[0195] The diacyl tail of the glycolipid may be important in determining the rate of insertion. Certain diacyl tails may retain greater fluidity at lower temperatures. Alternatively, the domain of the plasma membrane into which the diacyl tail of these glycolipids inserts may retain this greater fluidity.
[0196] It is known that the sphingolipid tails of natural glycolipids congregate in rigid domains and these domains may not allow further incorporation of glycolipid at low temperatures. Synthetic glycolipids with cis-desaturated diacyl tails may be favoured for use.
[0197] Transformation of RBCs with synthetic glycolipids with different lipid tails was first evaluated (Tables 22 and 24).
[0000]
TABLE 23
Antisera used to obtain results presented in Tables 24 to 27.
Manufacturer
Catalogue ref
Batch number
Expiry date
Anti-A
Albaclone, SNBTS
Z0010770
12 Dec. 2004
BioClone, OCD
Experimental
01102
—
reagent
Anti-B
Albaclone, SNBTS
Z0110600
27 Apr. 2003
BioClone, OCD
Experimental
01103
—
reagent
[0000]
TABLE 24
Evaluation of insertion of different lipid tails by agglutination with the relevant antisera.
Anti-
Transformation solution (μg/mL)
Molecule
sera
1000
500
250
125
100
60
50
40
30
20
10
A tri -sp-Ad-
Alba
w+
w+
0
0
0
DOPE (I)
Bio
2+
1+
w+
0
0
Alba
4+
3+
2-3+
2+
Bio
4+*
4+*
3+*
3+
DBA
0
B tri -sp-Ad-
Alba
3+
DOPE (VI)
Bio
3+
Alba
2+
2+
1+
0
0
Bio
3+
2+
1+
0
0
A tri -spsp 1 -Ad-
Alba
0
0
0
0
0
DOPE (III)
Bio
0
0
0
0
0
Alba
4+
3+
2+
2+
Bio
4+*
3-4+*
3+*
2+
DBA
0
A tri -sp-lipid
Alba
0
(IV)
Bio
0
A tri -sp-Ad-
Alba
0
0
0
0
0
DSPE (III)
Bio
0
0
0
0
0
Alba
2-3+
2-3+
2+
2+
Bio
3+
2-3+
2+
2+
DBA
0
*splatter.
[0198] Transformation of RBCs with synthetic glycolipids A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI) at 4° C. was then evaluated (Tables 25 to 28). These transformations were directed towards the preparation of cells expressing low levels of A, B or A and B glycotopes (“weak A, B and AB cells”).
[0199] For the preparation of weak A and B cells transformation solutions (20 μL, A tri -sp-Ad-DOPE (I) at 0.08, 0.05 and 0.03 mg/mL, and B tri -sp-Ad-DOPE (VI) at 0.6, 0.3, 0.15, 0.08, 0.05 and 0.03 mg/mL) in 1×PBS were mixed with washed, packed group O RBCs (60 μL).
[0200] For the preparation of weak AB cells transformation solutions (20 μL, A tri -sp-Ad-DOPE (I) at 0.07, 0.06 and 0.05 mg/mL, and B tri -sp-Ad-DOPE (VI) at 0.3, and 0.2 mg/mL) in 1×PBS were combined in block titre with washed, packed group O RBCs (60 μL). The combinations were: A tri -sp-Ad-DOPE (I) at 0.07 mg/mL+B tri -sp-Ad-DOPE (VI) at 0.3 mg/mL; A tri -sp-Ad-DOPE (I) at 0.07 mg/mL+B tri -sp-Ad-DOPE (VI) at 0.2 mg/mL; A tri -sp-Ad-DOPE (I) at 0.06 mg/mL+B tri -sp-Ad-DOPE (VI) at 0.3 mg/mL; A tri -sp-Ad-DOPE (I) at 0.06 mg/mL+B tri -sp-Ad-DOPE (VI) at 0.2 mg/mL; A tri -sp-Ad-DOPE (I) at 0.05 mg/mL+B tri -sp-Ad-DOPE (VI) at 0.3 mg/mL; and A tri -sp-Ad-DOPE (I) 0.05+B tri -sp-Ad-DOPE (VI) 0.2 mg/mL.
[0201] Cells and transformation solutions were placed in a 4° C. fridge. Pipette mixing was performed at intervals. Cells were removed for testing at intervals against the relevant antisera and were tested in both washed and unwashed states (i.e. washed samples had the transformation solution removed).
[0202] After 48 hours Celpresol™ was added to the cells so that the final cells:non-cells ratio was 3:5 (v/v). The cells continued to be tested at intervals. Testing was discontinued after 10 days because cells turned brown.
[0203] This discolouration could be attributed to a number of factors including: cells were already 21 days old when transformed; 48 hour transformation was in PBS not Celpresol™ so cells stressed for this time; and cells may have been mishandled in transit between the transforming and testing laboratories. This may be mitigated by transformation of the cells in Celpresol™ as opposed to PBS.
[0000]
TABLE 25
Diamed results of weak A RBCs transformed
at 4° C. against anti-A.
A tri -sp-Ad-DOPE (I) (mg/mL)
Washed
unwashed
Time
0.08
0.05
0.03
0.08
0.05
0.03
2
hrs
0
0
0
0
0
0
4
hrs
1+
0
0
2+
0
0
6
hrs
2+
0
0
2+
0
0
8
hrs
2+
0
0
2-3+
0
0
12
hrs
2-3+
0
0
3+
1+
0
24
hrs
3-4+
1+
0
3-4+
2+
0
30.5
hr
3-4+
1+
0
3-4+
2+
0
48
hrs
4+
2+
0
4+
2+
0
72
hrs
4+
2+
0
4+
2-3+
0
96
hrs
4+
2-3+
0
4+
2-3+
0
Day
7
3-4+
2+
0
Day
10
3-4+
2+
0
[0000]
TABLE 26
Diamed results of weak B RBCs transformed
at 4° C. against anti-B.
B tri -sp-Ad-DOPE (VI) (mg/mL)
washed
unwashed
Time
0.6
0.3
0.15
0.6
0.3
0.15
2
hrs
0
0
0
0
0
0
4
hrs
0
0
0
1+
0
0
6
hrs
w+
0
0
1+
0
0
8
hrs
2+
0
0
2+
w+
0
12
hrs
2+
w+
0
2-3+
2+
0
24
hrs
4+
3+
2+
4+
3+
2+
30.5
hr
4+
2-3+
0
4+
2-3+
w+
48
hrs
4+
3+
1+
4+
3+
2+
72
hrs
4+
4+
2+
4+
4+
2+
96
hrs
4+
3-4+
2-3+
4+
3-4+
2-3+
Day
7
4+
2-3+
0
Day
10
4+
2+
0
[0000]
TABLE 27
Diamed results of weak AB RBCs transformed
at 4° C. in block titre against anti-A.
B tri -sp-Ad-
A tri -sp-Ad-DOPE (I) (mg/mL)
DOPE (VI)
washed
unwashed
Day
(mg/mL)
0.07
0.06
0.05
0.07
0.06
0.05
1
0.3
2+
1-2+
w+
2-3+
2+
1+
0.2
2+
1-2+
0
2-3+
2+
1+
5
0.3
2+
1-2+
1+
2-3+
2+
1-2+
0.2
2+
1-2+
w+
2-3+
2+
1-2+
8
0.3
2-3+
2+
2+
0.2
2-3+
2+
1-2+
[0000]
TABLE 28
Diamed results of weak AB RBCs transformed
at 4° C. in block titre against anti-B.
B tri -sp-Ad-
A tri -sp-Ad-DOPE (I) (mg/mL)
DOPE (VI)
washed
unwashed
Day
(mg/mL)
0.07
0.06
0.05
0.07
0.06
0.05
1
0.3
3+
3+
2+
3+
3+
2-3+
0.2
1+
1-2+
0
2+
2+
1-2+
5
0.3
2+
2+
1+
2+
2+
2+
0.2
0
w+
vw
1+
w+
vw
8
0.3
2+
2+
2+
0.2
1+
1+
0
Example 4
Insertion Efficiency of Transformation of RBCs by A tri -sp-Ad-DOPE (I) and B tri -sp-Ad-DOPE (VI) Synthetic Glycolipids
[0204] The post-transformation supernatant solutions (from A tri -sp-Ad-DOPE (I) at 0.08 mg/mL, 0.05 mg/mL and 0.03 mg/mL, and B tri -sp-Ad-DOPE (VI) at 0.6 mg/mL, 20 pt) were added neat and in a 1:2 dilution to washed, packed RBCs (60 μL). The tubes were incubated in a 37° C. waterbath for one hour, with mixing taking place every 15 minutes.
[0205] The transformed RBCs were washed 3× with PBS and then suspended in Cellstab™ at the appropriate concentration for serology testing.
[0000]
TABLE 29
Tube serology
Pre-trans conc (mg/mL)
Score
A tri -sp-Ad-DOPE (I) at 0.08
0
1:2 ofA tri -sp-Ad-DOPE (I) at 0.08
0
A tri -sp-Ad-DOPE (I) at 0.05
0
1:2 of A tri -sp-Ad-DOPE (I) at 0.05
0
A tri -sp-Ad-DOPE (I) at 0.03
0
1:2 of A tri -sp-Ad-DOPE (I) at 0.03
0
B tri -sp-Ad-DOPE (VI) at 0.60
vw+
1:2 of B tri -sp-Ad-DOPE (VI) at 0.60
0
[0206] The score given by the post-transformation supernatant solution (from the 0.08 mg/mL pre-transformation solution) is not even that of the 0.03 mg/mL transformation solution in the first pass (w+). These results indicate that >75% of the molecules are inserted into the RBC membrane on the first pass.
[0207] In addition, the post-transformation solutions were concentrated 20× and compared in parallel with the transformation solutions of known concentration. Only the post-transformation solutions derived from the 0.08 mg/mL A tri -sp-Ad-DOPE (I) and 0.6 mg/mL B tri -sp-Ad-DOPE (VI) solutions were tested.
[0208] Post-transformation solutions (20 μL) were dialysed (pore size 500 Da) against de-ionised water for 2 days. The samples were left to dry in a fumehood for 10 days. At the end of this time they were transferred into a rotavapor flask and set on the rotavapor to rotate under vacuum with no heat overnight.
[0209] Samples were dried in a water bath at 40° C. and washed over into smaller vessels with chloroform-methanol 2:1 leaving significant amounts of dried cellular material. The chloroform-methanol 2:1 washings were dried down, washed over again into test-tubes with chloroform-methanol 2:1 and dried down. These samples were redissolved in 1 mL of 1×PBS and used for transformation experiments. The cellular material in the bottom of the flasks was washed out with water into another set of tubes.
[0210] The post-transformation solutions (from A tri -sp-Ad-DOPE (I) at 0.08 mg/mL and B tri -sp-Ad-DOPE (VI) at 0.6 mg/mL, 20 μL) were added to washed, packed RBCs (60 μL). In parallel, the transformation solutions (A tri -sp-Ad-DOPE (I) at 0.08 mg/mL, 0.05 mg/mL and 0.03 mg/mL, and B tri -sp-Ad-DOPE (VI) at 0.6 mg/mL, 20 μL) were added to washed, packed RBCs (60 μL).
[0211] The tubes were incubated in a 37° C. waterbath for one hour, with mixing taking place every 15 minutes. The transformed RBCs were washed 3× with PBS and then suspended in Cellstab™ at the appropriate concentration for serology testing.
[0000]
TABLE 30
Diamed serology
conc (mg/mL)
Score
A tri -sp-Ad-DOPE (I) at 0.08
3+
A tri -sp-Ad-DOPE (I) at 0.05
2+
A tri -sp-Ad-DOPE (I) at 0.03
1+
From A tri -sp-Ad-DOPE (I) at 0.08
0
B tri -sp-Ad-DOPE (VI) at 0.60
4+
From B tri -sp-Ad-DOPE (VI) at 0.60
0
[0212] These results suggest that there are not enough molecules in the post-transformation solution, even when concentrated 20×, to be detected by serology.
Example 5
Transformation of Murine RBCs by H tri -sp-Ad-DOPE (VII) Synthetic Glycolipid
[0213] Mouse cells were transformed at 37° C. for 1 hour.
[0000]
TABLE 31
Anti-H reagents used for results in Tables 32 and 33.
Antisera
Manufacturer
Batch
Anti-H IgM
Japanese Red Cross
HIRO-75
UEA
Lorne Laboratories
11549E D.O.E. 06.2004
Bio-UEA
EY Labs
201105-2
[0000]
TABLE 32
Tube Serology.
H Antisera
UEA
Cells
IgM
T = 0
T = 20
Bio-UEA
Mouse RBCs (−control)
0
0
0
Mouse RBCs + 0.01 mg/mL
0
H tri -sp-Ad-DOPE (VII)
Mouse RBCs + 0.05 mg/mL
1+
H tri -sp-Ad-DOPE (VII)
Mouse RBCs + 0.1 mg/mL
3+
H tri -sp-Ad-DOPE (VII)
Mouse RBCs + 0.25 mg/mL
4+
1+
H tri -sp-Ad-DOPE (VII)
Mouse RBCs + 1 mg/mL
2+
2+
H tri -sp-Ad-DOPE (VII)
Human O RBCs (+control)
4+
1+
2/3+
4+
[0000]
TABLE 33
Diamed
Cells
Score
Mouse RBCs + 0.01 mg/mL H tri -sp-Ad-DOPE
0
(VII)
Mouse RBCs + 0.05 mg/mL H tri -sp-Ad-DOPE
0
(VII)
Mouse RBCs + 0.1 mg/mL H tri -sp-Ad-DOPE
2+
(VII)
Mouse RBCs + 0.25 mg/mL H tri -sp-Ad-DOPE
3+
(VII)
Example 6
Transformation of RBCs by Filtered A tri -sp-Ad-DOPE (I) Synthetic Glycolipid
[0214] Some A tri -sp-Ad-DOPE (I) had been sterile-filtered through a 0.2 μm filter. To investigate whether transformation would be the same with this product a comparative trial was done.
[0000]
TABLE 34
Anti-A used for results presented in Table 35.
Manufacturer
Catalogue ref
Batch number
Expiry date
BioClone, OCD
Experimental reagent
01102
—
[0000]
TABLE 35
Column agglutination of A RBCs transformed
with varying concentrations of sterile-filtered vs
unfiltered A tri -sp-Ad-DOPE (I).
Concentration
Sterile-filtered
Unfiltered
(mg/mL)
A tri -sp-Ad-DOPE (I)
A tri -sp-Ad-DOPE (I)
0.2
4+
4+
0.1
4+
3-4+
0.05
2-3+
2-3+
0.01
0
0
Control 37° C.
0
Control 25° C.
0
[0215] These results show no significant difference between the two preparations of A tri -sp-Ad-DOPE (I) and suggests that filtration through a 0.2 μM filter did not remove molecules or change the composition or properties of the fluid to the point that transformation was affected.
Example 7
Storage of Transformed Cells
[0216] To investigate whether storage at 4° C. or 37° C. changed the agglutination results of A tri -sp-Ad-DOPE (I) and natural A glycolipid transformed O RBCs, identified as “Syn-A” and “Nat-A” cells respectively, were divided in two and suspended to 5% in Cellstab™
[0217] One set of cells was stored at 4° C. and the other set of cells was stored at 37° C. in a waterbath. Agglutination of the stored transformed cells was assessed (Table 36).
[0000]
TABLE 36
Syn-A
A tri -sp-Ad-
Nat-A
Time
Plat-
Temp
DOPE (I) at
At
At
(hours)
form
(° C.)
0.1 mg/mL
1 mg/mL
10 mg/mL
Control
0
Tube
3+
0
1-2+
0
20
Column
4
4+
0
3+
0
37
4+
0
3+
0
44
Column
4
4+
3+
0
37
4+
3+
0
Example 8
RBC Transformation with A- and B-Antigen Synthetic Glycolipids with Different Non-Carbohydrate Structures
[0218] The water soluble synthetic glycolipids designated A tri -sp-Ad-DOPE (I), A tri -sp 1 sp 2 -Ad-DOPE (II), A tri -sp-Ad-DSPE (III), and B tri -sp-Ad-DOPE (VI) were prepared according to the method described in Example 1 with necessary modifications.
[0219] Washed packed group O red blood cells (RBCs) (3 parts by volume) and the synthetic glycolipid solution (1 part by volume, varying concentrations) were added to an eppendorf tube. The tube was incubated in a 37° C. waterbath for one hour, mixing every 15 minutes. The transformed RBCs were washed 3× with PBS and then suspended in Cellstab™ at the appropriate concentration for serology testing.
[0220] Tube serology and Diamed gel-card results for RBCs transformed with the different synthetic molecule constructs are provided in Table 38. Results for the stability of the RBCs transformed with the different synthetic glycolipids at different concentrations are provided in Tables 39 to 44.
[0000]
TABLE 37
Antisera used for results presented in Tables 38 to 44.
Antisera
Manufacturer
Batch
Albaclone anti-A
SNBTS
Z0010770 - D.O.E 12.12.04
Bioclone anti-A
Ortho Diagnostics
01102 - D.O.M 16.05.02
Albaclone anti-B
SNBTS
Z0110670 - D.O.E 12.12.04
Bioclone anti-B
Ortho Diagnostics
01103 - D.O.M 16.05.02
[0000]
TABLE 38
Comparison of transformation of RBCs using A-antigen
synthetic glycolipids at different concentrations.
A Antisera
Conc
Albaclone anti-A
Bioclone anti-A
Synthetic
mg/mL
Tube
Diamed
Tube
Diamed
A tri -sp-Ad-DOPE
0.25
n.d.
4+
n.d.
4+
(I)
0.1
n.d.
4+/3+
n.d.
4+/3+
0.05
w+
2+
2+
2+
0.04
w+
n.d.
1+
n.d.
0.03
0
n.d.
w+
n.d.
0.02
0
n.d.
0
n.d.
0.01
0
0
0
0
A tri -sp-Ad-DSPE
0.25
n.d.
0
n.d.
0
(III)
0.1
n.d.
0
n.d.
0
0.05
0
0
0
0
0.04
0
n.d.
0
n.d.
0.03
0
n.d.
0
n.d.
0.02
0
n.d.
0
n.d.
0.01
0
0
0
0
A tri -sp 1 sp 2 -Ad-DOPE
0.25
n.d.
4+
n.d.
4+
(II)
0.1
n.d.
4+
n.d.
4+/3+
0.05
0
3+
0
3+
0.04
0
n.d.
0
n.d.
0.03
0
n.d.
0
n.d.
0.02
0
n.d.
0
n.d.
0.01
0
0
0
0
Incubated control
—
0
n.d.
0
n.d.
Bench control
—
0
n.d.
0
n.d.
Abbreviations: n.d. Not determined
[0000]
TABLE 39
Stability trial of RBCs transformed with A tri -sp-Ad-DOPE
(I) at high concentrations (1 mg/mL, 0.5 mg/mL and 0.25
mg/mL). Agglutination by manual tube serology.
Cell
Albaclone anti-A
Bioclone anti-A
storage
Concentration of Transformation Solution (mg/mL)
Day
solution
1
0.5
0.25
1
0.5
0.25
2
Alsevers
4+
4+
4+
4+ o
4+ o
4+ o
Cellstab ™
4+
4+
3+
4+ o
4+ o
4+ o
10
Alsevers
3+
2+
2+
4+ o
4+ o
3+
Cellstab ™
4+ o
3+ o
2+
4+ o
4+ o
4+ o
17
Alsevers
4+
4+
4+
4+ o
4+ o
4+ o
Cellstab ™
4+
4+
4+
4+ o
4+ o
4+ o
24
Alsevers
4+
4+
4+
4+
4+
4+
Cellstab ™
4+
4+
4+
4+ o
4+
4+
Abbreviations: o splatter
[0000]
TABLE 40
Stability trial of RBCs transformed with A tri -sp-Ad-DOPE
(I) at low concentrations (0.1 mg/mL, 0.05 mg/mL and 0.025
mg/mL). Agglutination by manual tube serology.
Cell
Albaclone anti-A
Bioclone anti-A
storage
Concentration of Transformation Solution (mg/mL)
Day
solution
0.1
0.05
0.025
0.1
0.05
0.025
2
Alsevers
3+/2+
1+
1+/w+
2+
2+/1+
1+
Cellstab ™
3+/2+
2+
1+
3+/2+
3+/2+
2+
8
Alsevers
2+
1+
w+
3+/2+
2+
2+
Cellstab ™
2+
1+/w+
vw
3+ o
2+
1+
15
Alsevers
2+
1+
0
3+
2+
Vw
Cellstab ™
4+
w+
0
4+
4+
1+
22
Alsevers
2+
2+
0
3+
2+
w+
Cellstab ™
4+
4+
1+
4+
4+
1+
44
Alsevers
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
Cellstab ™
4+
2+
w+
4+
2+
w+
Abbreviations: n.d. Not determined
o splatter
[0000]
TABLE 41
Stability trial of RBCs transformed with A tri -sp-Ad-DOPE
(I) at high concentrations (1 mg/mL, 0.5 mg/mL and
0.25 mg/mL). Agglutination in Diamed gel-cards.
Cell
Albaclone anti-A
Bioclone anti-A
storage
Concentration of Transformation Solution (mg/mL)
Day
solution
1
0.5
0.25
1
0.5
0.25
2
Alsevers
4+
4+
4+
4+
4+
4+
Cellstab ™
4+
4+
4+
4+
4+
4+
10
Alsevers
4+
4+
4+
4+
4+
4+
Cellstab ™
4+
4+
4+
4+
4+
4+
17
Alsevers
4+
4+
4+
4+
4+
4+
Cellstab ™
4+
4+
4+
4+
4+
4+
24
Alsevers
4+
4+
4+
4+
4+
4+
Cellstab ™
4+
4+
4+
4+
4+
4+
45
Alsevers
4+
4+
4+
4+
4+
4+
Cellstab ™
4+
4+
4+
4+
4+
4+
59
Alsevers
4+
4+
4+
4+
Cellstab ™
4+
4+
4+
4+
4+
4+
73
Alsevers
Cellstab ™
4+
4+
4+
4+
4+
4+
88
Alsevers
Cellstab ™
4+
4+
4+
4+
4+
4+
Where there were insufficient cells for testing, blank spaces have been left.
[0000]
TABLE 42
Stability trial of RBCs transformed with A tri -sp-Ad-DOPE
(I) at low concentrations (0.1 mg/mL, 0.05 mg/mL and
0.025 mg/mL). Agglutination in Diamed gel-cards.
Cell
Albaclone anti-A
Bioclone anti-A
storage
Concentration of Transformation Solution (mg/mL)
Day
solution
0.1
0.05
0.025
0.1
0.05
0.025
2
Alsevers
4+
2+
0
4+
3+
1+
Cellstab ™
4+
2+
0
4+
3+
1+
8
Alsevers
4+
3+
0
4+
4+
1+
Cellstab ™
4+
3+
0
4+
4+
1+
15
Alsevers
4+
2+
0
4+
3+/2+
1+
Cellstab ™
4+
4+
0
4+
4+
1+
22
Alsevers
4+
3+/2+
0
4+
3+
w+
Cellstab ™
4+
4+
0
4+
4+
1+
29
Alsevers
4+
2+
0
4+
3+
w+
Cellstab ™
4+
3+
0
4+
4+
2+
43
Alsevers
4+
3+
w+
4+
4+
2+
Cellstab ™
4+
4+/3+
0
4+
4+
1+
50
Alsevers
4+
3+
w+
4+
4+
2+
Cellstab ™
4+
3+
0
4+
4+
1+
57
Alsevers
4+
3+/2+
4+
4+
Cellstab ™
4+
3+
0
4+
3+
w+
63
Alsevers
Cellstab ™
4+/3+
2+
0
4+
3+
0
71
Alsevers
Cellstab ™
4+/3+
2+
0
4+
3+
0
86
Alsevers
Cellstab ™
4+/3+
2+
0
4+
3+
0
Where there were insufficient cells for testing, blank spaces have been left.
[0000]
TABLE 43
Stability trial of RBCs transformed with B tri -sp-Ad-DOPE
(VI) at high concentrations (1 mg/mL, 0.5 mg/mL and 0.25
mg/mL). Agglutination by manual tube serology.
Cell
Albaclone anti-B
Bioclone anti-B
storage
Concentration of Transformation Solution (mg/mL)
Day
solution
1
0.5
0.25
1
0.5
0.25
2
Alsevers
3+
3+
2+
2+
1+
1+
Cellstab ™
3+
2+
2+
2+
2+
1+
9
Alsevers
4+
4+
2+
4+
3+
2+
Cellstab ™
4+
4+
3+
4+
4+
2+
16
Alsevers
4+
4+
3+
4+
4+
2+
Cellstab ™
4+
4+
2+
4+
4+
2+
23
Alsevers
4+
4+
3+
4+
4+
3+
Cellstab ™
4+
4+
3+
4+
4+
3+
30
Alsevers
3+
3+
2+
2+
2+
2+
Cellstab ™
4+
3+
2+
3+ o
3+ o
2+
37
Alsevers
3+
2+
1+
3+
2+
1+
Cellstab ™
3+
3+
2+/1+
4+ o
3+
1+
44
Alsevers
4+
3+
1+
3+
3+
w+
Cellstab ™
4+
4+
n.d.
4+
4+
‡
51
Alsevers
3+
3+
2+
4+
3+
2+
Cellstab ™
4+
4+
n.d.
4+
4+
2+
Abbreviations: o splatter
[0000]
TABLE 44
Stability trial of RBCs transformed with B tri -sp-Ad-DOPE
(VI) at high concentrations (1 mg/mL, 0.5 mg/mL and
0.25 mg/mL). Agglutination in Diamed gel-cards.
Cell
Albaclone anti-B
Bioclone anti-B
storage
Concentration of Transformation Solution (mg/mL)
Day
solution
1
0.5
0.25
1
0.5
0.25
2
Alsevers
4+
4+
2+
4+
4+
2+
Cellstab ™
4+
4+
2+
4+
4+
2+
9
Alsevers
4+
4+
2+
4+
4+
2+
Cellstab ™
4+
4+
3+
4+
4+
3+
16
Alsevers
4+
4+
2+
4+
4+
1+
Cellstab ™
4+
4+
3+
4+
4+
3+
23
Alsevers
4+
4+
3+
4+
4+
3+
Cellstab ™
4+
4+
3+
4+
4+
3+
30
Alsevers
4+
4+
3+
4+
4+
3+
Cellstab ™
4+
4+
3+
4+
4+
3+
37
Alsevers
4+
4+
3+
4+
4+
3+
Cellstab ™
4+
4+
3+
4+
4+
3+
44
Alsevers
4+
4+
2+
4+
4+
3+
Cellstab ™
4+
4+
3+
4+
4+
4+/3+
51
Alsevers
4+
4+
2+
4+
4+
3+
Cellstab ™
4+
4+
3+
4+
4+
3+
58
Alsevers
4+
1+
4+
2+
Cellstab ™
4+
4+
2+
4+
4+
2+
72
Alsevers
4+
2+
4+
3+
Cellstab ™
4+
4+
3+/2+
4+
4+
3+
87
Alsevers
Cellstab ™
4+
4+/3+
1+
4+
4+/3+
2+/1+
116
Alsevers
Cellstab ™
4+
3+
0
4+
4+/3+
1+
Where there were insufficient cells for testing, blank spaces have been left.
Example 9
Red Blood Cell Transformation with H-Antigen Synthetic Glycolipids
[0221] The water soluble synthetic glycolipids designated H tri -sp-Ad-DOPE (VII), H di -sp-Ad-DOPE (VIII) and Galβ-sp-Ad-DOPE (IX) were prepared according to the method described in Example 1 with necessary modifications.
[0222] Washed packed mouse RBCs (3 parts by volume) and the synthetic glycolipid solutions (1 part by volume of varying concentrations) were added to an eppendorf tube. The tube was incubated in a 37° C. waterbath for one hour, mixing every 15 minutes. The transformed RBCs were washed 3× with PBS and then suspended in Cellstab™ at the appropriate concentration for serology testing.
[0223] Tube serology and Diamed gel-card results for RBCs transformed with the different synthetic glycolipids are presented in Table 46. The results show that three sugars (H tri ) are required for detection by anti-H IgM, at least by the reagent used.
[0000]
TABLE 45
Antisera used for results presented in Table 46.
Antisera
Manufacturer
Batch
Anti-H IgM
Japanese Red Cross
HIRO-75
UEA
Lorne Laboratories
11549E D.O.E. 06.2004
Bio-UEA
EY Labs
201105-2
[0000]
TABLE 46
Comparison of transformation of RBCs using H-
antigen synthetic glycolipids with different
glycotopes made to different concentrations.
H Antisera
UEA
Conc
IgM
Tube
Tube
Bio-UEA
Synthetic
mg/mL
Tube
Diamed
T0
T20
Tube
H tri -sp-
1
n.d.
n.d.
2+
n.d.
2+
Ad-DOPE
0.25
4+
3+
n.d.
n.d.
1+
(VII)
0.1
3+
2+
n.d.
n.d.
n.d.
0.05
1+
0
n.d.
n.d.
n.d.
0.01
0
0
n.d.
n.d.
n.d.
H di -sp-
0.25
0
n.d.
n.d.
n.d.
n.d.
Ad-DOPE
0.1
0
n.d.
n.d.
n.d.
n.d.
(VIII)
0.05
0
n.d.
n.d.
n.d.
n.d.
0.01
0
n.d.
n.d.
n.d.
n.d.
Galβ-sp-
0.25
0
n.d.
n.d.
n.d.
n.d.
Ad-DOPE
0.1
0
n.d.
n.d.
n.d.
n.d.
(IX)
0.05
0
n.d.
n.d.
n.d.
n.d.
0.01
0
n.d.
n.d.
n.d.
n.d.
Human O
—
4+
n.d.
1+
2/3+
4+
cells
Incubated
—
0
n.d.
0
0
n.d.
control
Bench
—
0
n.d.
n.d.
n.d.
n.d.
control
Abbreviations: n.d. Not determined
Example 10
Insertion of H di -sp-Ad-DOPE (VIII) and Galβ-sp-Ad-DOPE (IX) Synthetic Glycolipids into Murine Red Blood Cells
[0224] The water soluble synthetic glycolipids designated H di -sp-Ad-DOPE (VIII) and Galβ-sp-Ad-DOPE (IX) were prepared according to the method described in Example 1 with necessary modifications.
[0225] Murine RBCs were washed 3× in 1×PBS. 30 μl of packed RBCs were combined with 30 μl of H di -sp-Ad-DOPE (VIII), and 30 μl of packed RBCs were combined with 30 μl Galβ-sp-Ad-DOPE (IX), respectively. Both synthetic molecule constructs were at a concentration of 1.0 mg/ml. 30 μl of 1×PBS was added to 30 μl of packed RBCs to act as the control group. Cells were incubated for 90 minutes in a 37° C. shaking water-bath. RBCs were washed 3× in 1×PBS.
[0226] Three groups of packed RBCs were incubated with an equal volume of lectin UEA-1 for 30 minutes at room temperature. The lectin was prepared in 1×PBS at a concentration of 0.1 mg/ml. 50 μl of a 3% cell suspension was spun for 15 seconds in an Immunofuge at low speed. Results were read by tube serology. The results are presented in Table 48. The results show that neither anti-H IgM nor UEA-1 detects two sugars (H di ).
[0000]
TABLE 47
Antisera used for results presented in Table 48.
Antisera
Manufacturer
Batch
Biotest anti-H
Biotest AG
UEA
EY Labs
201105-2
[0000]
TABLE 48
Murine RBCs transformed with Galβ-sp-Ad-DOPE
or H di -sp-Ad-DOPE, assessed by agglutination.
Cell Type
Inserted Molecule
UEA-1
Mouse IgM H
Murine RBC
Galβ (1 mg/ml)
0
n.d.
Murine RBC
H di (1 mg/ml)
0
0
Murine RBC
Control (PBS)
0
0
Human RBC
Control(PBS)
4+
3+
Abbreviations: n.d. Not determined
Example 11
Preparation of Sensitivity Controls
[0227] The synthetic glycolipids of the invention may be used in the preparation of “sensitivity controls” (also referred to as “quality control cells”, “serology controls”, or “process controls”) as described in the specification accompanying international application no. PCT/NZ02/00214 (WO 03/034074). The synthetic glycolipids provide the advantage that the transformation of the RBCs may be achieved at reduced temperatures.
RBC Transformation Solutions
[0228] Two stock solutions are used:
Solution 1:1 mg/mL A tri -sp-Ad-DOPE (I) suspended in Celpresol™ solution. Solution 2: 5 mg/mL B tri -sp-Ad-DOPE (VI) suspended in Celpresol™ solution.
[0231] Glycolipids are manufactured in a white dry powder. Glycolipids in this form (enclosed in a sealed container under a controlled temperature) are stable for an indefinite period of time. The glycolipids are suspended in solution (e.g. Celpresol™) by weight in order to formulate the transformation solutions.
[0232] Once the transformation solutions are received at CSL, they are filtered (through a MILLEX®-GV 0.22μ filter unit) under aseptic conditions.
Processing of RBCs
[0233] RBC donations are processed using a continuous flow centrifuge washer under aseptic conditions. RBC donations are washed in buffered saline followed by Celpresol™ solution. The PCV of the RBC donations is measured on a Beckman Coulter AcT Diff analyser. The donations are then adjusted to a packed cell volume (PCV) of 50% with the addition of Celpresol™.
Transformation of RBCs to Provide “Weak AB Cells”
[0234] RBCs are washed in buffered saline and Celpresol™. The cells are suspended in Celpresol™ solution to a PCV of >50%. The PCV of red cells is measured using a Beckman Coulter AcT Diff. The mass of the red cell solution is weighed.
[0235] The amount of A tri -sp-Ad-DOPE (I), B tri -sp-Ad-DOPE (VI) and Celpresol™ for transformation is calculated using the following equations:
[0000]
a
=
P
×
F
S
b
=
P
×
F
S
c
=
P
-
(
1
-
P
)
-
a
-
b
[0000] where
a=amount of A tri -sp-Ad-DOPE (I) to be added per 1 mL of red cells (mL) b=amount of B tri -sp-Ad-DOPE (VI) to be added per 1 mL of red cells (mL) c=amount of Celpresol™ to be added per 1 mL of red cells (mL) to dilute cells to 50% PCV P=PCV of red cell solution F=Final desired concentration of glycolipid S=Concentration of stock glycolipid solution
[0242] To determine the amount of glycolipid and Celpresol™ to add to a bulk sample of red cells, multiply each of a, b and c by the red cell volume. Add A tri -sp-Ad-DOPE (I), B tri -sp-Ad-DOPE (VI) and Celpresol™ to the red cell bulk sample aseptically.
[0243] Incubate the sample for 3 hours at 20° C. under controlled temperature conditions and constant gentle agitation. At the end of the 3 hour period, aseptically remove a sample of red cells and test the sample to confirm transformation of the RBCs. Perform blood grouping using tube, tile and column agglutination technology (CAT) techniques.
[0244] Incubate the red cell sample for 3 hours at 2-8° C. under controlled temperature conditions and constant gentle agitation for 18 hours. At the end of the 3 hour period, aseptically remove a sample of red cells and test the sample to confirm transformation of the red cells. Perform blood grouping using tube, tile and CAT techniques.
[0245] Wash the transformed red cells using a continuous flow centrifuge method, under aseptic conditions using Celpresol™ solution. Measure the PCV of the washed red cells and adjust to 50% PCV by the addition of Celpresol™ solution.
Formulation and Dispensing
[0246] Aseptically combine a volume of the transformed RBCs with a volume of simulated plasma diluent (SPD). The plasma may contain monoclonal and polyclonal antibodies. Antibodies are selected according to the desired characteristics of the sensitivity controls. The plasma may additionally contain tartrazine and bovine serum albumin.
[0247] Blood grouping and antibody screening is performed on the bulk samples using tube, tile and CAT techniques. The transformed RBC-SPD blend is then aseptically dispensed into BD Vacutainer tubes and the tubes labelled accordingly.
Validation Testing
[0248] Weak AB cells produced by the use of synthetic glycolipids (designated A w B w in Tables 51 to 53) were used to validate a range of testing platforms in parallel with naturally occurring weak A, weak B and weak AB cells.
[0000]
TABLE 49
Reagents and cards used in validation testing.
Method Reagent
Tube Epiclone
Tile Epiclone
Ref
Manufacturer and type
Batch
Expiry
CAT 1
OCD BioVue ABD/Rev
ABR528A
16 Jun. 2005
CAT 2
OCD BioVue ABD/Rev
ABR521A
06 May 2006
CAT 3
OCD BioVue ABD/ABD
ACC255A
24 May 2005
CAT 4
Diamed ID-MTS
50092.10.02
April 2005
CAT 5
Diamed ID-MTS Donor typing
51051.05.04
March 2005
CAT 6
Diamed ID-MTS Recipient typing
50053.07.02
April 2005
CAT 7
Diamed ID-MTS Cord typing
50961.08.03
July 2005
[0000]
TABLE 50
Testing platform methodology for validation testing.
Tile
1 drop 3% cells, 2 drops reagent, 15 min @ RT
in moist chamber.
Tube
2 drops @ RT, 10 min.
ID-MTS
As per manufacturers instructions using Dil-2.
BioVue
As per manufacturers instructions using 0.8% RCD.
[0000]
TABLE 51
Validation results across all methods against anti-A.
Testing platform
Cell
Type
Tube
Tile
CAT 1
CAT 2
CAT 3
CAT 4
CAT 5
CAT 6
CAT 7
1
A x
w+
0
2+
1+
0
0
0
0
2
A x
w+
0
2+
2+
0
0
0
0
3
A 1 B
4+
4+
4+
4+
4+
4+
4+
4+
4+
4
A x
w+
0
2+
2+
0
0
0
0
5
A 2 B
3+
3+
4+
3+
3+
1+
2+
3+
6
A x
w+
0
2+
2+
0
0
0
0
7
A x
1+
0
2+
2+
0
0
0
0
8
A x
w+
0
2+
2+
0
0
0
0
9
A x
0
0
1+
1+
0
0
0
0
10
A x
w+
0
2+
2+
0
0
0
0
11
A 3
4+
4+
4+
3+
3+
1+
1+
3+
12
A 3 B
3+
3+
3+
3+
2+
w+
w+
2+
13
B 3
0
0
0
0
0
0
0
0
0
14
B 3
0
0
0
0
0
0
0
0
0
15
A w B w
2+
2+
2+
2+
2+
0
0
0
0
[0000]
TABLE 52
Validation results across all methods against anti-B.
Testing platform
Cell
Type
Tube
Tile
CAT 1
CAT 2
CAT 3
CAT 4
CAT 5
CAT 6
CAT 7
1
A x
0
0
0
0
0
0
0
0
2
A x
0
0
0
0
0
0
0
0
3
A 1 B
4+
4+
4+
4+
4+
4+
3+
3+
4+
4
A x
0
0
0
0
0
0
0
0
5
A 2 B
4+
4+
4+
4+
4+
3+
3+
4+
6
A x
0
0
0
0
0
0
0
0
7
A x
0
0
0
0
0
0
0
0
8
A x
0
0
0
0
0
0
0
0
9
A x
0
0
0
0
0
0
0
0
10
A x
0
0
0
0
0
0
0
0
11
A 3
0
0
0
0
0
0
0
0
12
A 3 B
4+
4+
4+
4+
4+
4+
4+
4+
13
B 3
2+
2+
3+
2+
2+
2+
2+
2+
2+
14
B 3
2+
2+
2+
2+
2+
2+
1+
1+
2+
15
A w B w
3+
3+
1+
1+
1+
0
0
0
0
[0000]
TABLE 53
Validation results across all methods against anti-AB.
Testing platform
Cell
Type
Tube
Tile
CAT 1
CAT 2
CAT 3
CAT 4
CAT 5
CAT 6
CAT 7
1
A x
3+
2+
2+
2
A x
4+
2+
3+
3
A 1 B
4+
4+
4+
4
A x
3+
2+
3+
5
A 2 B
4+
4+
4+
6
A x
4+
4+
3+
7
A x
4+
4+
3+
8
A x
3+
4+
3+
9
A x
4+
2+
2+
10
A x
3+
4+
3+
11
A 3
4+
4+
4+
12
A 3 B
4+
4+
4+
13
B 3
2+
2+
2+
14
B 3
2+
2+
2+
15
A w B w
3+
3+
3+
Example 12
Attachment of Modified Embryos to Transformed Endometrial Cells
[0249] The ability to effect qualitative and quantitative differences in the cell surface antigens expressed by cell types other than RBCs was investigated. The ability to enhance the adhesion of embryos to endometrial cells was adopted as a model system.
[0250] The synthetic molecules may be used as synthetic membrane anchors and/or synthetic molecule constructs. Therefore, they may also be employed in the method of enhancing embryo implantation as described in international patent application no PCT/NZ2003/000059 (published as WO 03/087346) which is incorporated by reference.
Endometrial Cell Transformation
Insertion of Water Soluble Synthetic Molecule Construct
[0252] A single cell suspension of endometrial epithelial cells was prepared. The endometrial cells were washed 3× by resuspending in CMF HBSS and centrifuging at 2000 rpm for 3 minutes. The washed cell preparation was resuspended in 50 μl of M2.
[0253] Micro-centrifuge tubes each containing a 50 μl solution of 5M/ml endometrial cells were prepared. To separate tubes of endometrial cells 50 μl of synthetic glycolipids A tri -sp-Ad-DOPE (I) or B tri -sp-Ad-DOPE A (VI), or 50 μl M2 were added to the control cells. The cells were incubated for 90 minutes at 37° C. on a mixer. The endometrial cells were washed 3× by resuspending in CMF HBSS media and centrifuging at 2000 rpm for 3 minutes. The washed cell preparation was resuspended in 50 μl of M2.
Test for Insertion Using Fluorescent Probe:
[0254] 50 μl of corresponding primary murine monoclonal antibody was added to each tube. Each tube was incubated at room temperature for 10 minutes. Cells were washed 3× in M2 media. 10 μl of mouse anti-IgG FITC was added to each tube. Tubes were incubated at room temperature in dark conditions for 10 minutes. Endometrial cells were mounted on glass slides and viewed under a fluorescence microscope.
Test for Direct Agglutination:
[0255] 5 μl of each group of cells was placed onto separate microscope slides. To each 5 μl drop of cells 5 μl of a corresponding antibody was added. The cells were gently mixed on the slide for 2 minutes. Agglutination was visualised under the microscope. The results are presented in Table 55.
[0000]
TABLE 54
Antisera used for results presented in Table 55.
Antisera
Manufacturer
Bioclone anti-A
Ortho Diagnostics
01102 D.O.M. 16.05.02
Bioclone anti-B
Ortho Diagnostics
Developmental reagent
[0000]
TABLE 55
Endometrial cells transformed with A tri -sp-Ad-DOPE (I) or
B tri -sp-Ad-DOPE A (VI), as visualised using fluorescence.
Agglutination
Fluorescence score
reaction by
after incubation with
microscopic
Cell Type
Inserted Antigen
1° antibody
IgFITC Probe
visualisation
Endometrial
A tri -sp-Ad-DOPE
Anti-A Bioclone
4+
4+
cells
(I) (1 mg/ml)
Endometrial
B tri -sp-Ad-DOPE
Anti-B Bioclone
1+
3+
cells
(VI) (1 mg/ml)
Endometrial
Control (M2
Anti-A Bioclone
0
0
cells
media)
Embryo Modification
Insertion of Water Soluble Synthetic Molecule Construct:
[0257] The embryo zona pellucida was removed by treating embryos with 0.5% pronase in a 37° C. oven for 6 minutes or until all zonas were removed. Micro-drops were prepared by adding 5 μl of synthetic glycolipid A tri -sp-Ad-DOPE (I) or B tri -sp-Ad-DOPE (VI), at a concentration of 1 mg/mL to a 45 μl drop of M2 media overlaid with mineral oil. All embryo groups were incubated in the 50 μl micro-drops for 1 hour at 37° C. Embryos from experimental and control groups were washed 3× with M2 media.
Test for Insertion:
[0258] Embryos from experimental and control groups were placed into a micro-drop of corresponding antibody and incubated for 30 min at 37° C. Embryos from experimental and control groups were washed 3× with M2 media.
[0259] Embryos from all experimental and control groups were placed into micro-drops of anti-mouse Ig FITC (1:50 dilution anti-mouse Ig FITC in M2) and incubated for 30 min at 37° C. Embryos from experimental and control groups were washed 3× with M2 media. Embryos were mounted on microscope slides in a 5 μl drop of M2 and the drops overlaid with oil.
[0260] The slides were viewed under a fluorescence microscope. Results are presented in Tables 56 and 57. The negative result for transformation with B tri -sp-Ad-DOPE (VI) is attributed to a lack of 1° antibody sensitivity.
[0000]
TABLE 56
Embryos transformed with A tri -sp-Ad-DOPE (I) as visualised using fluorescence.
Fluorescence score
Embryo
after incubation with
Morphology 24 hr
Cell Type
Inserted Antigen
1° antibody
IgFITC Probe
post insertion
Embryos
A tri -sp-Ad-DOPE (I)
Anti-A Bioclone
2+/1+
Appeared viable
Embryos
Control
Anti-A Bioclone
0
Appeared viable
[0000] TABLE 57 Embryos transformed with A tri -sp-Ad-DOPE (I) or B tri -sp-Ad-DOPE (VI), as visualised using fluorescence. Fluorescence score Embryo after incubation with Morphology 24 hr Cell Type Inserted Antigen 1° antibody IgFITC Probe post insertion Embryos A tri -sp-Ad-DOPE Anti-A Bioclone 2+ n.d. (I) Embryos B tri -sp-Ad-DOPE Anti-B Bioclone 0 n.d. (VI) Embryos Control (M2 Anti-A Bioclone 0 n.d. media) Abbreviations: n.d. Not determined
Enhanced Attachment Transformed Endometrial Cells to Modified Embryos Modified embryos (BioG-Avidin-BiolgG B and BioG-Avidin-BiolgM A ) were prepared in accordance with the methods described in the specification accompanying the international application no. PCT/NZ03/00059 (published as WO03/087346).
[0261] Two concave glass slides were prepared, one with two wells of synthetic glycolipid A tri -sp-Ad-DOPE (I) inserted endometrial cells and the other with two wells of synthetic glycolipid B tri -sp-Ad-DOPE (VI) inserted endometrial cells.
[0262] The two groups of embryos were transferred to each of the concave glass slides:
Slide 1 A tri /IgG B embryos
A tri /IgM A embryos
Slide 2 B tri /IgG B embryos
B tri /IgM A embryos
[0267] The embryos were surrounded with endometrial cells. The wells were covered with mineral oil and incubated for 15 minutes at 37° C. Using a wide bore handling pipette each group of embryos were carefully transferred to a fresh drop of M2 media. The embryos were gently washed. The embryos were gently transferred into 2 μL of M2 media on a marked microscope slide. Each drop was overlaid with mineral oil
[0268] Under a central plane of focus on an Olympus microscope the number of endometrial cells adhered to the embryos in each group was assessed. The number of cells adhered to each embryo was recorded. Results are presented in Table 58.
[0000]
TABLE 58
Endometrial cells transformed with A tri -sp-Ad-DOPE (I) or B tri -sp-Ad-DOPE (VI),
and embryos modified with BioG-Avidin-BioIgG B or BioG-Avidin-BioIgM A .
Assessment by attachment of endometrial cells to embryos.
Transformed
Average number of
endometrial
endometrial cells attached
Cell Type
cells
Modified embryos
to modified embryos
Endometrial
A tri -sp-Ad-DOPE
BioG-Avidin-BioIgG B
2.3
cells
(I)
BioG-Avidin-BioIgM A
7.25
Endometrial
B tri -sp-Ad-DOPE
BioG-Avidin-BioIgG B
6.7
cells
(VI)
BioG-Avidin-BioIgM A
3.4
[0269] Where in the foregoing description reference has been made to integers or components having known equivalents then such equivalents are herein incorporated as if individually set forth.
[0270] Although the invention has been described by way of example and with reference to possible embodiments thereof it is to be appreciated that improvements and/or modification may be made thereto without departing from the scope or spirit of the invention.
REFERENCES
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Fukuda M N, Dell A, Oates J E, Wu P, Klock J C & Fukuda M. (1985) Structures of glycosphingolipids isolated from human granulocytes. The presence of a series of linear poly-N-acetyllactosaminylceramide and its significance in glycolipids of whole blood cells. J. Biol. Chem. 260: 1067-1082.
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Hakomori S I, Nudelman E, Levery S B & Kannagi R. (1984) Novel fucolipids accumulating in human adenocarcinoma. I. Glycilipids with di- or trifucosylated type 2 chain. J. Biol. Chem. 259: 4672-4680
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BACKGROUND
[0001] Field of the Invention
[0002] The present invention relates to a control line pusher arm for use in positioning control lines to be secured to two parallel tubular strings being run into a dual completion well.
[0003] Background of the Related Art
[0004] In a dual well completion, a single wellbore has a plurality of tubular strings in addition to related packers and other tools to enable production from two different and isolated geologic zones. Generally, two tubing strings are used to provide the necessary level of control, safety and segregation between fluids from the two different subsurface geological zones penetrated by a single, dual-completion wellbore.
[0005] A control line pusher arm is used on a rig for positioning an elongate control line, also called an umbilical, so that it can be secured to a tubular string as the tubular string is made up and run into a wellbore. A conventional control line pusher arm moves between a retracted position, distal to the tubular string, and an engaged position, proximal to the tubular string, to move an adjacent portion of a control line proximal to the tubular string so that a clamp or other securing member can be applied to secure the portion of the control line to the adjacent portion of the tubular string.
[0006] What is needed is a control line pusher arm that can be used to position a plurality of control lines for being secured to a plurality of tubular strings being run into a single wellbore.
BRIEF SUMMARY
[0007] One embodiment of the present invention provides a control line pusher arm for use in positioning two control lines for securing one of the control lines to a first tubular string and for securing the other of the control lines to a second tubular string wherein the first tubular string and the second tubular string are together being run into a dual-completion wellbore.
[0008] A first embodiment of the apparatus of the present invention comprises a base supportable on a rig floor, a carrier coupled to the base and movable relative to the base between a first position and a second position, a pusher arm pivotally coupled at a lower end to the carrier and pivotable between a retracted position and an engaged position to position a control line head coupled to a second end of the pusher arm, a first motive member coupled intermediate the carrier and the pusher arm to pivot the pusher arm between the retracted position and the engaged position, and a second motive member coupled intermediate the carrier and the base to move the carrier between the first position and the second position. The apparatus may further comprise a worm gear coupled to the base to rotate about an axis by operation of the second motive member, wherein the carrier includes a plurality of teeth engaged by the worm gear. In one embodiment of the apparatus comprising a worm gear coupled to the base to rotate by operation of the second motive member, the second motive member is a hydraulic motor. Alternately, in another embodiment of the apparatus that comprises a worm gear, the worm gear is coupled to the carrier to rotate about an axis by operation of the second motive member, and the base includes a plurality of teeth engaged by the worm gear. In one embodiment of the apparatus comprising a worm gear coupled to the carrier to rotate by operation of the second motive member, the second motive member is a hydraulic motor.
[0009] In one embodiment of the apparatus, the first motive member of the apparatus that moves the pusher arm to pivot between the retracted position and the engaged position may comprise a fluid cylinder coupled at a first end to the carrier and coupled at a second end to the pusher arm and operable to pivot the pusher arm between the retracted position and the engaged position.
[0010] In one embodiment of the apparatus, the second motive member of the apparatus that moves the carrier between the first position and the second position comprises a fluid cylinder.
[0011] In one embodiment of the apparatus, the second motive member of the apparatus that moves the carrier between the first position and the second position comprises a worm gear disposed intermediate the carrier and the base.
[0012] In one embodiment of the apparatus, the carrier is slidably coupled to the base.
[0013] In one embodiment of the apparatus, the carrier is translatably moved between the first position and the second position on the base.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0014] FIG. 1 is a perspective view of an embodiment of an apparatus of the present invention with a pivotal pusher arm in a first position that is proximal to a first tubular string in a dual completion well and with the pusher arm in the retracted position.
[0015] FIG. 2 is the perspective view of the embodiment of the apparatus of FIG. 1 after the pusher arm is pivoted from the retracted position illustrated in FIG. 1 to an engaged position to position a portion of a first control line proximal to the first tubular string in a dual completion well to enable the application of a clamp to secure the portion of the first control line to the first tubular string.
[0016] FIG. 3 is the perspective view of the embodiment of the apparatus of FIG. 2 after the pusher arm is retracted away from the first tubular string (to the position illustrated in FIG. 1 ), the pusher arm is translated laterally to a second position that is proximal to a second tubular string adjacent to the first tubular string in the dual completion well, and the pusher arm is pivoted from the retracted position to the engaged position to position a portion of a control line proximal to a second tubular string to enable the application of a clamp to secure the portion of a second control line to the second tubular string.
[0017] FIG. 4 is a plan view of the base and the carrier of the embodiment of the apparatus of FIGS. 1-3 , and of the motor and threaded shaft arrangement for moving the carrier on the base and between the first position and the second position.
[0018] FIG. 5 is an elevation view of a portion of the apparatus showing the interaction between the pivotal pusher arm and a pivotal first motive member, between the carrier and the base of the apparatus, and between the carrier and the threaded shaft that is driven to rotate about an axis by a second motive member (not shown in FIG. 5 —see FIG. 4 ) to move the carrier on the base.
[0019] FIG. 6 is the plan view of FIG. 4 after the carrier is moved by operation of the second motive member from the first position (see FIG. 4 ) to the second position.
[0020] FIG. 7 is a flowchart illustrating the logic followed by a safety lockout system that protects the carriage from being moved between the first position and the second position while the pusher arm is engaged with a control line.
[0021] FIG. 8 illustrates an alternate second motive member that is secured to the carriage and operable to engage a rack including a row of teeth along an edge of the base.
[0022] FIG. 9 is an enlarged view of the motive member, the carriage on which it moves and the rack engaged by the motive member through the gear disposed on the motive member.
DETAILED DESCRIPTION
[0023] One embodiment of the apparatus of the present invention is illustrated in FIG. 1 . FIG. 1 is a perspective view of an embodiment of the apparatus 10 supported on a rig floor 13 . FIG. 1 shows a first tubular string 40 and a second tubular string 42 extending generally vertically into a dual completion well (not shown). The apparatus 10 comprises a pusher arm 30 pivotally coupled at a lower end 37 to a carriage 14 . The pusher arm 30 is pivotally coupled to the carriage 14 and movable relative to the carriage 14 between an arm-retracted position, illustrated in FIG. 1 , to an arm-engaged position, as illustrated in FIG. 2 and discussed below. The carrier 14 translates on a base 12 of the apparatus 10 between a carriage first position, proximal to the first tubular string 40 and illustrated in FIG. 1 , to a carriage second position.
[0024] FIG. 2 is the perspective view of FIG. 1 after the pusher arm 30 pivots from the arm-retracted position, illustrated in FIG. 1 , to the arm-engaged position to position a portion of the control line 80 proximal to the first tubular string 40 . The first motive member 32 , a fluid cylinder, is illustrated as being coupled intermediate the pusher arm 30 and the carriage 14 . The first motive member is coupled to the carriage 14 at a location that is spaced-apart from the location where the pusher arm 30 is pivotally coupled to impart on the pusher arm 30 a force having a component that will cause the pusher arm 30 to rotate from the pusher arm-retracted position, illustrated in FIG. 1 , towards the first tubular string 40 and to the pusher arm-engaged position, illustrated in FIG. 2 . The movement of the pusher arm 30 to the pusher arm-engaged position moves the control line 80 to a position enabling the application of the clamp 60 to secure the control line 80 to the first tubular string 40 .
[0025] FIG. 3 is the perspective view of FIG. 2 after the pusher arm 30 is retracted away from the first tubular string 40 (to return to the pusher arm-retracted position illustrated in FIG. 1 ), translated laterally to a second position that is proximal to a second tubular string 42 that is adjacent to the first tubular string 40 , and then again pivoted from the pusher-arm retracted position to the pusher arm engaged position to position a portion of a second control line 82 proximal to the second tubular string 42 to enable the application of a clamp (not shown) similar to the clamp 60 shown in FIG. 3 as securing the first control line 80 to the first tubular string 40 .
[0026] FIG. 4 is a plan view of the base 12 and the carrier 14 of the apparatus 10 of FIGS. 1-3 , and of a motor 25 on the base 12 that, when activated, drives a threaded shaft 19 to rotate. FIG. 4 further reveals a proximal end 16 of the carriage, a distal end 18 of the carriage 14 , and an internally-threaded nut 17 secured within a well 15 on the carriage 14 between the proximal end 16 and the distal end 18 of the carriage 14 . The shaft 19 is threadably engaged with the internally-threaded nut 17 secured within the well 15 on the carriage 14 intermediate the proximal end 16 and the distal end 18 . Upon activation of the motor 25 by one of an electrical current and a hydraulic circuit (meaning hydraulic pressure on one side, and relatively less hydraulic pressure on the other) through one of electrical and hydraulic conduits 26 and 27 , respectively, the shaft 19 rotates to move the carrier 14 on the base 12 between the carriage first position, illustrated in FIG. 1 , and the carriage second position illustrated in FIG. 3 . It will be understood that the carriage 14 could be moved between the carriage first position, illustrated in FIG. 1 , and the carriage second position illustrated in FIG. 3 , using other motive members such as, for example, a double-acting fluid cylinder disposed intermediate the base 12 and the carriage 14 , an electromagnet on one of the base 12 and the carriage 14 and a magnet disposed on the other of the base 12 and the carriage 14 , and a worm gear coupled intermediate the base 12 and the carriage 14 .
[0027] FIG. 5 is an elevation view of a portion of the apparatus 10 showing the interaction between the pusher arm 30 and the first motive member 32 , and also between the carrier 14 and the threaded shaft 19 driven by the second motive member (not shown in FIG. 5 —see FIG. 4 ). FIG. 5 shows a proximal end 16 of the carriage 14 and a distal end 18 of the carriage, and the carriage 14 slidably seated within the base 12 . The threaded shaft 19 is threadably received within the internally threaded nut 17 of the carriage 14 . The first motive member 32 is a fluid cylinder that is pivotally coupled to an ear 38 on the carriage 14 . It will be understood that the extension of the first motive member 32 pivots the pusher arm 30 in the clockwise direction about the proximal ear 36 and retraction of the first motive member 32 pivots the pusher arm 30 in the counterclockwise direction about the proximal ear 36 .
[0028] FIG. 6 is the plan view of FIG. 4 after the carriage 14 is moved on the base 12 from the first position (see FIGS. 1, 2 and 4 ), with the carriage 14 proximal to the first tubular string 40 (not shown in FIG. 6 —see FIG. 1 ), to the second position (see FIG. 3 ), with the carriage 14 proximal to the second tubular string 42 .
[0029] FIG. 7 is a high-level flowchart illustrating steps for automatically protecting the apparatus 10 and the tubular strings 40 and 42 against damage that may be caused by inadvertently operating the second motive member 25 of the apparatus 10 when the pusher arm 30 is engaged with the first control line 80 or the second control line 82 . The flowchart of FIG. 7 illustrates the steps performed by a processor and beginning at step 101 . In step 102 , the signal to actuate the second motive member 25 is received. In step 103 , the position of the pusher arm 30 is determined and, if the pusher arm is in the retracted position so that it can be moved along with the carriage between the pusher arm first position and the pusher arm second position then, in step 105 , the position of the carriage 14 on the base 12 is determined. If the carriage 14 is determined to be in one of the carriage first position and the carriage second position, corresponding to a position proximal to the first tubular string 40 and a position proximal to the second tubular string 42 then, in step 107 , the circuit is activated and the second motive member 25 is energized so that the carriage 14 is moved from the carriage first position to the carriage second position, or vice versa.
[0030] In the event that it is determined in step 103 that the pusher arm is not in the retracted position then, in step 104 , an error message is displayed to alert rig personnel that not all of the conditions for energizing the second motive member 25 exist. In the event that it is determined in step 105 that the carriage is not in the first position or the carriage second position then, in step 106 , an error message is displayed to alert rig personnel that not all of the conditions for energizing the second motive member 25 exist. It will be understood that the apparatus 10 may comprise switches and sensors that generate a signal when, for example, the pusher arm 30 is in the pusher arm retracted position or when, for example, the carriage 14 is in the carriage first position and/or in the carriage second position. It will be understood that such switches and sensors are easily and conveniently secured to the base, the carriage, the first motive member and/or the pusher arm of the apparatus.
[0031] It will be understood that the second motive member 25 can, in one embodiment, be an electrically powered motor, and the conduits 26 and 27 in FIG. 4 are electrical conductors such as, for example, a pair of wires. In another embodiment, the second motive member 25 can be a hydraulically powered motor, and the conduits 26 and 27 in FIG. 4 are hydraulic conduits such as, for example, metal tubing. In a preferred embodiment, the second motive member 25 is a pneumatically powered motor, and the conduits 26 and 27 in FIG. 4 are pneumatic conduits such as, for example, metal tubing.
[0032] It will be understood that the second motive member 25 can provide for movement between the base 12 and the carriage 14 in other ways other than through the use of the threaded shaft 19 coupled to the base 12 and the internally-threaded nut 17 on the carriage 14 , as illustrated in FIG. 4 . For example, but not by way of limitation, FIG. 8 illustrates an alternate second motive member 52 that is secured to the carriage 14 and operable to engage a rack 54 including a row of teeth along an edge of the base 12 . The alternate second motive member 52 rotates a gear 53 that engages the rack 54 and, depending on the rotational direction of the gear 53 , the carriage 14 will move along the base 12 in response to the rotation of the gear 53 by the alternate second motive member 52 . It should be noted that, in the embodiment of the apparatus 10 illustrated in FIGS. 8 and 9 , the alternate second motive member 52 moves with the carriage 14 . To provide continuous power to the alternate second motive member 52 , a coiled power delivery conduit 58 can be used. It will be understood that, in FIG. 8 for example, if the alternate second motive member 52 is operated to move the carriage 14 on the base 12 from left to right in FIG. 8 , the conduit 58 will extend so that continuous power is delivered through the conduit 58 to the alternate second motive member 52 on the carriage 14 as it moves. It will be further understood that the alternate second motive member in FIGS. 8 and 9 may be, in one embodiment, an electric motor and the conduit 58 can be a pair of conductive wires or, in another embodiment, the alternate second motive member 52 can be a hydraulic or pneumatic motor and the conduit can be one of a pair of hydraulic hoses or a pneumatic hose.
[0033] 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, components and/or groups, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The terms “preferably,” “preferred,” “prefer,” “optionally,” “may,” and similar terms are used to indicate that an item, condition or step being referred to is an optional (not required) feature of the invention.
[0034] The corresponding structures, materials, acts, and equivalents of all means or steps plus function elements in the claims below are intended to include any structure, material, or act for performing the function in combination with other claimed elements as specifically claimed. The description of the present invention has been presented for purposes of illustration and description, but it is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated. | An umbilical manipulator arm for positioning control lines for being secured to a plurality of tubular strings being made up and run into a dual completion wellbore includes a carriage movable on a base that is securable to a rig floor adjacent to two tubular strings. An umbilical manipulator arm is coupled to the carriage and movable relative to the carriage between a pusher arm retracted position distal to a tubular string and a pusher arm engaged position proximal to a tubular string. The carriage is movable between a carriage first position proximal to a first tubular string and a carriage second position proximal to a second tubular string. The umbilical manipulator arm can be used to position control lines for being secured to the plurality of tubular strings as they are being made up and run into the wellbore. | 4 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This non-provisional application claims priority under 35 U.S.C. §119(a) on Patent Application No. 2006-209587 filed in Japan on Aug. 1, 2006, the entire contents of which are hereby incorporated by reference.
TECHNICAL FIELD
[0002] This invention relates to a hydraulic composition such as plastering and tile mortar including lightweight mortar and repair mortar. More specifically, this invention relates to a hydraulic composition which exhibits an improved workability in its coating with a trowel, and hence, an improved working efficiently in the coating.
BACKGROUND ART
[0003] Workability in the coating with a trowel of a hydraulic composition such as plastering material has been realized by adding a natural seaweed glue such as the one prepared form Chondrus ocellatus. Since the development of methylcellulose (a semi-synthetic resin), it has been commonly used for providing the workability.
[0004] The properties required for the hydraulic composition include good workability (ease of coating and finishing), high water retention (prevention of curing failure caused, for example, by drying out), and resistance to sagging (moving) (prevention of the coated mortal from deformation by its own weight and prevention of adhered tile from moving), and even severer requirements are imposed with the recent streamlining of the workplace.
[0005] JP-A 11-349367 (Patent Document 1) discloses a method for use in the field of concretes, and this method uses a combination of AE (air entraining) agent which is an anionic surfactant and a shrinkage reducing agent such as a polyoxyalkylene copolymer. When the content disclosed in the JP-A 11-349367 for the concretes is used in the present invention, the excessively high content results in the significant loss of workability as well as inferior properties of the cured product, and the object of the present invention is never realized.
DISCLOSURE OF THE INVENTION
[0006] The present invention has been completed in view of the situation as described above, and an object of the present invention is to provide a hydraulic composition which exhibits an improved workability in its coating with a trowel, and hence, an improved working efficiency with no adverse effects on its physical properties.
[0007] In order to realize such object, the inventors of the present invention made an intensive study and found that workability in the coating of the hydraulic composition with a trowel is markedly improved by the combination of a foaming anionic surfactant with an antifoaming agent which is a nonionic surfactant. The present invention has been completed on the basis of such finding.
[0008] Accordingly, the present invention provides a hydraulic composition comprising at least one surfactant selected from anionic surfactants having foaming ability (group A); at least one surfactant selected from surfactants which are nonionic antifoaming agents (group B); and a water-soluble cellulose ether. In this composition, the surfactant of group A and the surfactant of group B are respectively added at 0.000005 to 0.004% by weight (solid content) in relation to the entire powder ingredients of the hydraulic composition, and the water-soluble cellulose ether is added at 0.02 to 1.2% by weight of the hydraulic composition.
EFFECTS OF THE INVENTION
[0009] The present invention is capable of remarkably improving workability in its coating with a trowel without adversely affecting water retention or strength properties of the hydraulic composition.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0010] Next, the present invention is described in detail.
[0011] The present invention relates to a hydraulic composition which contains an anionic surfactants having foaming ability (a group A surfactant) and a surfactants which is a nonionic antifoaming agent (a group B surfactant). When the surfactant having foaming ability is added to a hydraulic composition, weight per unit volume of the resulting hydraulic composition is normally reduced, and workability in its coating with a trowel will be improved with sacrifice in water retention and strength of the hydraulic composition itself. On the other hand, when the surfactant which is an antifoaming agent is solely added, the resulting hydraulic composition will have an increased weight per unit volume, and workability in its coating with a trowel will be greatly reduced.
[0012] The mechanism involved in the present invention is not yet fully resolved. However, it is unlikely that the workability is improved solely by simple control of the amount of air trapped in the composition by the combination of the foaming agent and the antifoaming agent, and improvement in the surface property of the powder ingredients by the adsorption of the surfactants to the inorganic powder is more likely to be closely involved.
[0013] Examples of the anionic surfactant having foaming ability (group A surfactant) used in the hydraulic composition of the present invention include fatty acid soap surfactants, amide ether sulfate surfactants, dodecyl benzenesulfonate surfactants, lauryl acid surfactants, lauryl sulfate surfactants, lauroyl sarcosinate surfactants, sulfosuccinic acid surfactants, alkyl sulfate surfactants, and alkyl ether sulfate surfactants, which are typically added at an amount in solid content of 0.000005 to 0.004% by weight, preferably 0.00001 to 0.0035% by weight, and more preferably 0.00005 to 0.003% by weight in relation to the powder ingredients. When the content of the anionic surfactant having foaming ability is less than 0.000005% by weight, improvement of the workability is not recognized, and incorporation in excess of 0.004% by weight invites excessive inclusion of the air in the hydraulic composition resulting in the loss of strength.
[0014] Examples of the surfactant which is a nonionic antifoaming agent (group B surfactant) include polyether surfactants, silicone surfactants, alcohol surfactants, mineral oil surfactants, and vegetable oil surfactants, which are typically added at an amount of 0.000005 to 0.004% by weight, preferably 0.00001 to 0.0035% by weight, and more preferably 0.00005 to 0.003% by weight in solid content in the powder ingredients. When the content the surfactant which is a nonionic antifoaming agent is less than 0.000005% by weight, improvement of the workability is not recognized, and incorporation in excess of 0.004% by weight invites excessively reduced inclusion of the air in the hydraulic composition resulting in the loss of workability.
[0015] The surfactant which is a nonionic antifoaming agent (the group A surfactant) and the surfactant which is a nonionic antifoaming agent (the group B surfactant) are added at a weight ratio (solid content) of A/B of 10/90 to 90/10, preferably at 20/80 to 80/20, and more preferably at 30/70 to 70/30. When these surfactants are incorporated at a ratio outside the range as described above, namely, at a ratio outside the range of 10/90 to 90/10, strength of the hydraulic composition will be lost by the excessive amount of bubbles generated by the group A surfactant, or workability will be greatly reduced by the failure of the entrainment of the air which should have been included in the hydraulic composition, since the content of the group B surfactant becomes too much.
[0016] Since the surfactants are incorporated at an extremely minute amount, the surfactants of groups A and B may be incorporated by impregnating in an inorganic support such as a silica based fine powder or an organic support such as a cellulose ether. Exemplary silica based fine powders used for the support of the surfactant include amorphous silicon dioxide such as white carbon, porous silicon dioxide such as diatomaceous earth, and porous silicic acid calcium. Examples of the cellulose ether used for the support of the surfactant include water-soluble alkylcellulose, water-soluble hydroxyalkylcellulose, and the water-soluble hydroxyalkylalkylcellulose as will be described below.
[0017] In this case, the surfactant and the organic or inorganic support are preferably used at a weight ratio (solid content) of 30/70 to 5/95.
[0018] The hydraulic composition of the present invention also contains a water-soluble cellulose ether which imparts water retention property and plasticity with the composition. Exemplary water-soluble cellulose ethers include water-soluble alkylcelluloses such as methylcellulose, hydroxypropyl methylcellulose, and hydroxyethylmethylcellulose; water-soluble hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose; and water-soluble hydroxyalkylalkylcellulose such as hydroxyethylethylcellulose. The water-soluble cellulose ether may be added at an amount of 0.02 to 1.2% by weight, preferably 0.03 to 0.7% by weight, and more preferably 0.04 to 0.55% by weight of the entire composition. When the water-soluble cellulose ether is added at an amount less than 0.02% by weight, water retention of the resulting composition will be insufficient, and due to the resulting drying out and insufficient plasticity, the composition will suffer from insufficient adhesion to the underlying substrate, and after the curing, from peeling of the coated composition from the underlying substrate. On the contrary, addition at an amount in excess of 1.2% by weight will invite unduly increased viscosity which results in the failure of improving the workability as well as economical disadvantage.
[0019] The water-soluble cellulose ether preferably has a viscosity as measured at 20° C. for 1% by weight aqueous solution by a model B or Brookfield viscometer at 20 rpm of 5 to 30,000 mPa·s, more preferably 10 to 10,000 mPa·s, and more preferably 15 to 7,000 mPa·s. When the viscosity is less than 5 mPa·s, water retention of the hydraulic composition may be insufficient, and when the viscosity is in excess of 30,000 mPa·s, the hydraulic composition will have an excessively high viscosity, and improvement of the workability can not be expected.
[0020] The hydraulic composition of the present invention may also contain a cement, gypsum, fine aggregates, an inorganic extender, an organic extender, water, and the like in addition to the components as described above.
[0021] Exemplary cements used include normal Portland cement, high early strength Portland cement, moderate heat Portland cement, blast furnace cement, silica cement, fly ash cement, alumina cement, and jet cement, and the cement may be partly or entirely replaced with gypsum such as gypsum hemihydrate. If necessary, anhydrous gypsum or dehydrate gypsum may be added for adjusting coagulation. The cement or the gypsum may be added at 15 to 85 parts by weight, preferably at 20 to 80 parts by weight, and more preferably 25 to 75 parts by weight. (The amount indicated in parts by weight in relation to 100 parts by weight of the total of the cement, the gypsum, the fine aggregates, and the extender. For other additives, the amount is indicated in % by weight in relation to 100 parts by weight of the total amount as described above). When the amount is less than 15 parts by weight, the curing may be significantly retarded or absent. When the amount is in excess of 85 parts by weight, shrinking upon drying or self-shrinkage may take place, and cracks may be formed on the surface after curing.
[0022] Exemplary preferable fine aggregates include river sand, mountain sand, sea sand, and ground sand, or fine aggregates for plastering. These fine aggregates may have a particle size of up to 5 mm, preferably up to 2 mm, and more preferably up to 1 mm. The fine aggregates are preferably added at 85 to 15 parts by weight, preferably at 80 to 20 parts by weight, and more preferably at 75 to 25 parts by weight. The fine aggregates may be partly replaced with an inorganic or organic extender, and exemplary such inorganic extenders include fly ash, blast furnace slug, talc, calcium carbonate, marble dust (lime stone powder), pearlite, and shirasu balloons, and the inorganic extender typically has a particle size of up to 5 mm. Exemplary organic extenders include styrene foam beads, and pulverized ethylene vinyl alcohol foam, and the organic extender typically has a particle size of up to 10 mm.
[0023] The hydraulic composition may also contain a synthetic polymer such as polyvinyl alcohol, polyethylene oxide, polyethylene glycol, or polyacrylamide, a natural polymer such as pectin, gelatin, casein, welan gum, gellan gum, locust bean gum, guar gum, or a starch derivative, and other reinforcements which has the effect of preventing the composition from sagging and moving, as a content that does not adversely affect the physical properties of the hydraulic composition.
[0024] The hydraulic composition of the present invention is used by adding water to the composition, and kneading the mixture by the method commonly used in the art. The water is added at an amount that does not adversely affect strength and physical properties of the hydraulic composition.
EXAMPLES
[0025] Next, the present invention is described in further detail by referring to the Examples which by no means limit the scope of the present invention.
[Materials Used]
[0000]
Cement: Normal Portland cement
(manufactured by Taiheiyo Materials Corporation)
Gypsum hemihydrate:
Reagent (manufactured by Wako Pure Chemical Industries, Ltd.)
Mikawa silica sand:
Nos. 5 and 6 (manufactured by Mikawa Silica Sand)
Fly ash: Commercially available product (manufactured by Joban Fly Ash)
Calcium carbonate:
Reagent (manufactured by Wako Pure Chemical Industries, Ltd.)
Styrene foam beads:
Particle size, 1 mm or less
Redispersible powder resin:
LDM7100P (manufactured by Nichigo Mowinyl Co., Ltd.)
Anionic foaming agent (surfactant): shown in Table 1
Nonionic antifoaming agent (surfactant): shown in Table 2
Water-soluble cellulose ether: shown in Table 3
[0000]
TABLE 1
Reagent No.
Type
Composition
Manufacturer
A-1
Lipon
Alkylaryl sulfate
Lion Corporation
A-2
Emal
Alkyl sulfate
Kao Corporation
A-3
Sunamide
Amide ether sulfate
NOF Corporation
A-4
Persoft
Alkylether sulfate
NOF Corporation
A-5
Nonsoul
Fatty acid soap
NOF Corporation
[0000]
TABLE 2
Reagent No.
Type
Composition
Manufacturer
B-1
Nopco PD-1
Mineral oil base
San Nopco
B-2
Pluronic L61
Polyoxyalkylene glycol
Adeca
Corporation
B-3
KM73
Modified silicone
Shin-Etsu
Chemical
Co., Ltd.
[0042] The surfactants shown in Tables 1 and 2 were used after impregnating in a silica fine powder (the surfactant/silica (weight ratio of the solid content), 50/50).
[0000]
TABLE 3
Degree of
Viscosity of
substitution
1 wt % aqueous
Reagent
OMe
OHP
OHE
solution
No.
Composition
(DS)
(MS)
(MS)
(mPa · s)
Manufacturer
C-1
MC
1.8
—
—
6.2
Shin-Etsu Chemical Co., Ltd.
C-2
HPMC
1.4
0.20
—
29,000
Shin-Etsu Chemical Co., Ltd.
C-3
HPMC
1.4
0.20
—
310
Shin-Etsu Chemical Co., Ltd.
C-4
HEC
—
—
2.20
9,580
SE Tylose
C-5
HPMC
1.4
0.20
—
2,300
Shin-Etsu Chemical Co., Ltd.
C-6
HEMC
1.5
—
0.30
5,200
Shin-Etsu Chemical Co., Ltd.
HPMC: hydroxypropylmethylcellulose (a hydroxyalkylalkylcellulose)
HEMC: hydroxyethylmethylcellulose (a hydroxyalkylalkylcellulose)
HEC: hydroxyethylcellulose (a hydroxyalkylcellulose)
MC: methylcellulose (an alkylcellulose)
Examples 1 to 10 and Comparative Examples 1 to 5
[0043] The materials as described above were mixed at the proportion shown in Tables 4 to 8 to produce a hydraulic composition. Experiments were conducted by using the thus prepared composition to evaluate table flow, workability, water retention, and flexural strength. The results are shown in Tables 4 to 8.
[0044] In the Tables 4 to 8 as described below, amount of the reagents A, B, and C is the amount of the solid content of the reagent in relation to the powder ingredients (for example, water and ingredients other than the reagents A to C), and amount of the water added is the amount in solid content of the water in relation to the ingredients other than the reagents A to C. It is to be noted that the ratio of the reagent A/the reagent B is measured in terms of the solid content.
[0000]
TABLE 4
Example
Experiment No.
1
2
3
4
5
Composition
Cement (g)
1,000
1,000
1,000
1,000
1,000
Silica sand (g)
1,000
1,000
1,000
1,000
1,000
Type of reagent A
A-1
A-2
A-3
A-4
A-5
Amount of reagent A
0.004
0.0035
0.00022
0.003
0.00006
(% by weight)
Type of reagent B
B-3
B-1
B-2
B-1
B-2
Amount of reagent B
0.00049
0.00093
0.00022
0.0013
0.00013
(% by weight)
Reagent A/Reagent B
89/11
79/21
50/50
69/31
31/69
Type of reagent C
C-1
C-2
C-3
C-4
C-5
Amount of reagent C
0.45
0.10
0.22
0.20
0.20
(% by weight)
Water (% by weight)
23.2
20.3
21.0
21.8
20.4
Experimental
Table flow (mm)
162
166
165
166
169
results
Workability (coating ability)
5
5
5
5
5
Water retention (%)
94.6
92.4
93.5
91.2
94.8
Flexural strength (N/mm 2 )
6.5
6.8
6.7
6.2
6.5
[0000]
TABLE 5
Example
Experiment No.
6
7
8
Composition
Cement (g)
1,000
1,000
600
Silica sand (g)
1,000
1,000
—
Calcium carbonate (g)
—
—
50
Fly ash (g)
—
—
260
Styrene foam beads (L)
—
—
5.5
Redispersible powder resin (g)
—
—
2.0
Type of reagent A
A-5
A-3
A-3
Amount of reagent A (% by weight)
0.000049
0.000006
0.002
Type of reagent B
B-3
B-2
B-2
Amount of reagent B (% by weight)
0.000013
0.000049
0.002
Reagent A/Reagent B
79/21
11/89
50/50
Type of reagent C
C-6
C-3
C-5
Amount of reagent C (% by weight)
0.15
0.15
1.0
Water (% by weight)
20.6
20.6
21.0
Experimental
Table flow (mm)
168
168
165
results
Workability (coating ability)
4
3
5
Water retention (%)
92.1
93.1
98.0
Flexural strength (N/mm 2 )
6.6
6.6
0.6
[0000]
TABLE 6
Example
Experiment No.
9
10
Composition
Cement (g)
800
—
Hemihydrate gypsum (g)
200
1,500
Silica sand (g)
1,000
—
Calcium carbonate (g)
—
500
Type of reagent A
A-1
A-4
Amount of reagent A
0.004
0.003
(% by weight)
Type of reagent B
B-3
B-1
Amount of reagent B
0.00049
0.0013
(% by weight)
Reagent A/Reagent B
89/11
69/31
Type of reagent C
C-1
C-4
Amount of reagent C
0.45
0.20
(% by weight)
Water (% by weight)
25.0
44.0
Experimental
Table flow (mm)
160
140
results
Workability (coating ability)
5
5
Water retention (%)
95.6
67.5
Flexural strength (N/mm 2 )
5.3
3.0
[0000]
TABLE 7
Comparative Example
Experiment No.
1
2
3
Composition
Cement (g)
1,000
1,000
1,000
Silica sand (g)
1,000
1,000
1,000
Type of reagent A
—
A-1
—
Amount of reagent A (% by weight)
—
0.03
—
Type of reagent B
—
—
B-2
Amount of reagent B (% by weight)
—
—
0.2
Type of reagent C
C-3
C-3
C-3
Amount of reagent C (% by weight)
0.22
0.22
0.22
Water (% by weight)
21.0
20.4
21.5
Experimental
Table flow (mm)
162
164
163
results
Workability (coating ability)
3
4
1
Water retention (%)
94.0
84.1
80.2
Flexural strength (N/mm 2 )
6.2
3.8
7.3
[0000]
TABLE 8
Comparative
Example
Experiment No.
4
5
Composition
Cement (g)
600
—
Hemihydrate gypsum (g)
—
1,500
Silica sand (g)
—
—
Calcium carbonate (g)
50
500
Fly ash (g)
260
—
Styrene foam beads (L)
5.5
—
Redispersible powder resin (g)
2.0
—
Type of reagent A
—
—
Amount of reagent A (% by weight)
—
—
Type of reagent B
B-2
B-4
Amount of reagent B (% by weight)
0.2
0.2
Type of reagent C
C-1
C-4
Amount of reagent C (% by weight)
1.0
0.20
Water (% by weight)
21.0
43.0
Experimental
Table flow (mm)
160
140
results
Workability (coating ability)
2
3
Water retention (%)
92.2
65.2
Flexural strength (N/mm 2 )
0.7
3.1
(Evaluation Method)
[0045] The ingredients other than the water (i.e. the powders) were preliminarily mixed, and after introducing the powder mixture in a 5 liter mortar mixer, predetermined amount of water was added to the mixture with stirring and the kneading was continued for 3 minutes. The measurements as described below were thereafter conducted.
[Measurement]
[0000]
(1) Table flow test
[0047] Table flow was measured according to JIS R 5201.
(2) Trowel workability
[0049] Sensory test: Average of the evaluation by a panel of three people are indicated. Normal workability was evaluated “3” while “5” indicates that the sample was easiest to coat, and “1” indicates that the sample was hardest to coat.
(3) Water retention
[0051] Water retention was measured according to JIS A 6916.
(4) flexural strength
[0053] The sample was prepared according to JIS R 5201, and cured according to JIS A 1171.
[0054] Japanese Patent Application No. 2006-209587 is incorporated herein by reference.
[0055] Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims. | A hydraulic composition is provided. This composition exhibits an improved workability in its coating with a trowel, and accordingly, an improved working efficiency with no adverse effects on its physical properties. The hydraulic composition comprises at least one surfactant selected from anionic surfactants having foaming ability (group A), at least one surfactant selected from surfactants which are nonionic antifoaming agents (group B), and a water-soluble cellulose ether. The surfactants of group A and group B are respectively added at 0.000005 to 0.004% by weight (solid content) in relation to the powder ingredients in the hydraulic composition, and the water-soluble cellulose ether is added at 0.02 to 1.2% by weight of the hydraulic composition. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to nickel electroforms.
2. Description of Prior Art
Nickel electrodeposition processes are well-known and pulse currents with rectangular waveforms, instead of direct current, are commonly used to enhance deposition quality. The quality and repeatability of surface finishes provided by this process, especially to meet the requirements of modern micro-device products, has generated many proposals that are generally focussed on using different rectangular waveforms. It has however been proposed to use other types of waveforms in a Paper published in Surface Coatings & Technology 115 (1999) 132-139 entitled ‘A study of surface finishing in pulse current electroforming of nickel by utilising different shaped waveforms’. However, repeatable extremely high quality surface finishes have not yet been attained.
SUMMARY OF THE INVENTION
It is an object of the invention to overcome or at least reduce this problem.
According to the invention there is provided a nickel electrodisposition process for creating electroforms having extremely high quality surface finishes, the process comprising applying pulses of direct current in which each pulse has a waveform with a ramp-down spike.
Each waveform may have a ramp-down spike in a rectangular waveform, in a triangular waveform, or, preferably, in a ramp down waveform.
BRIEF DESCRIPTION OF THE DRAWINGS
Processes according to the invention will now be described by way of example with reference to the accompanying drawings in which:
FIG. 1 is a schematic layout of apparatus for carrying out the processes;
FIG. 2 is a current time graph showing a first waveform of pulses applied during electroforming;
FIG. 3 is a current time graph showing a second waveform of pulses applied during electroforming;
FIG. 4 is a current time graph showing a third waveform of pulses applied during electroforming;
FIG. 5 illustrates the surface of an electroform after applying pulses of the first waveform;
FIG. 6 illustrates the surface of an electroform after applying pulses of the second waveform;
FIG. 7 illustrates the surface of an electroform after applying pulses of the third waveform;
FIG. 8 shows comparative illustrations of surface finishes provided by prior art processes and processes according to the invention; and
FIG. 9 is Table 1 showing comparisons of surface finishes using the described methods.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings, in FIG. 1 a conventional electroforming bath 10 has a magnetic stirrer 11 and two electrodes 12 and 13 . The cathode 12 and anode 13 are supplied with pulsed current of different shaped waveforms from a pulse waveform generator 14 in a manner explained below.
The bath solution was nickel sulphamate 330 g/l, nickel chloride 15 g/l, boric acid 30 g/l and sodium dodecyl sulphate 0.2 g/l. The temperature was kept at 50±1°C. The initial pH of the electrolyte was 4.2, which is typical for electroforming. The cathode mandrel electrode was made of polished stainless steel and had dimensions of 100×3×1 mm. Electroforming processes were carried out using different shaped current pulses, as explained below.
The current pulses were each provided with repetitive ramp down spikes, which is a characteristic of embodiments of this invention. The preferred forms of each of the waveforms is shown in FIGS. 2 to 4 . In the Figures, i c is the cathodic peak current density, t a is the pause time, and t c is the cathodic time. Typically in the Figures, the maximum i c is 500 mA/cm 2 , and t c and t a are equal to Sins. The waveforms represent the applied conditions in each case.
FIGS. 5, 6 and 7 show the surface of the electroform generated using the waveforms of FIGS. 2, 3 and 4 respectively; the condition used was a fixed deposition thickness condition. The thickness of the electroforms produced for the different waveforms is about 15 μm.
In FIG. 8, the illustrations provide comparisons, in pairs, between the electroform surfaces deposited when ramp down spikes are not applied (see FIGS. 8 ( a ), 8 ( b ) and 8 ( c )) and when ramp down spikes are applied, see FIGS. 8 ( d ), 8 ( e ) and 8 ( f ). Thus, the refinement in grain structure is clearly illustrated by comparing FIGS. 8 ( a ) and 8 ( d ), 8 ( b ) and 8 ( e ), and 8 ( c ) and 8 ( f ). FIGS. 8 ( d ), 8 ( e ) and 8 ( f ) correspond to FIGS. 5, 6 , and 7 respectively. The improvements in surface finishing are clearly shown in Table 1. | It is known to apply a pulse current during electrodeposition of nickel. In the invention, pulse current waveforms have ramp-down spikes leading to improvements in surface finishes of electroforms created by the process. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Application No. 60/921,967, filed on Apr. 5, 2007, entitled “DOUBLE GYROID STRUCTURE NANOPOROUS FILMS AND NANOWIRE NETWORKS,” the entire contents of which are incorporated herein by reference.
This invention was made in part with government support from CAREER Award No. 0134255-CTS awarded by the National Science Foundation (“NSF”). The Government has or may have certain rights in the invention.
TECHNICAL FIELD
The present invention generally relates to porous films where the pore sizes are controlled by a process of self-assembly. The pores are on the nanometer length scale, and the films are referred to as nanoporous or mesoporous. In particular, the invention relates to nanoporous films and their use in forming nanowires that are interconnected in three dimensions to yield a periodic network that is derived from a double-gyroid topology.
BACKGROUND OF THE INVENTION
Highly ordered nanoporous films that provide accessibility to an underlying substrate are a key cornerstone of nanofabrication. Bottom-up fabrication technologies based on both anodic oxidation of aluminum and orienting assembled block copolymers have advanced rapidly and are now widely used to generate films with controlled pore sizes below 50 nm that directly access the substrate. However, for pores in the 1-10 nm range, similar milestones have not been reached, and there are no bottom-up technologies that provide well-defined periodic access to a substrate at this length scale without also yielding cracks or access through larger openings. 1-10 nm is an important size range though since the surface area increases dramatically as pore size decreases (at constant void fraction) and many quantum size effects are only observed when the length scale is less than the thermal de Broglie wavelength (which is typically less than 10 nm). As a result developing nanoporous films with smaller pores that access the substrate are important for the development of high sensitivity sensors, high surface area electrodes for fuel cells or photoelectrochemical devices, and nanostructured thermoelectrics or photovoltaics.
Nanofabrication by electrochemical deposition in an ordered porous template can be used to generate new materials for the devices above. However, this technique requires that solution phase species are able to access the substrate and transfer electrons. One way to generate this access is to self-assemble a 3D nanostructure based on a low interfacial curvature phase. One such nanostructure is the phase based on the gyroid minimum surface. This zero mean curvature surface divides space into two continuous, non-intersecting domains. When a wall replaces the gyroid surface, a tricontinuous structure results (one wall and two pore systems). Tricontinuous gyroid structures are actually quite common in block copolymer systems and typically occur between the lamellar and cylindrical phases on the spectrum of interfacial curvature. (It should be noted that there may some microporosity in the wall that connects the two pore systems. Regardless of this, the films are still referred to as “tricontinuous”). However, the synthesis of nanoporous gyroid structures in thin film morphology with small pore sizes has proven very challenging.
BRIEF SUMMARY OF THE INVENTION
The present teachings are directed to highly ordered nanoporous films with a structure based on the gyroid minimum surface and the use of these films to template other materials. The nanoporous films are formed by self-assembly of inorganic species and surfactant molecules using a new approach that yields coating solutions that are stable for months and may be used over a broad range of temperature and relative humidity (spanning normal laboratory conditions) from commercially available surfactants. This new approach differs from previous art in many ways including the use of aging (prior to coating) to control the phase that self-assembles. After self-assembly and consolidation of the inorganic material, the surfactant molecules are removed by calcination, solvent extraction, ozone treatment, or plasma treatment to yield nanoporous films. These nanoporous films are then used as a template by filling the pore system with another material. The structures may be used as is, or the original inorganic material may be removed to yield a new nanoporous film. In exemplary embodiments, the tricontinuous films synthesized on conducting electrodes are composed of one continuous dense silica wall approximately 4.6 nm thick and two continuous but non-intersecting pore systems with characteristic pore diameter of approximately 4.3 nm. Moreover, the void fraction and surface area are approximately 0.48 and 477 m 2 /g, respectively. Electrochemical impedance spectroscopy is used to quantitatively determine the diffusion coefficient in the film and the percentage of the substrate that is accessible to electrochemical probe molecules when the walls are at their isoelectric point. The values for accessibility obtained electrochemically (31%±3%) matches well the value obtained from the model of the nanoporous film reconstructed from GISAXS, FESEM and TEM data (31%). Additionally, the liquid phase diffusion coefficient of a molecule in the water filled film is measured to be 0.44 times the diffusion coefficient in bulk liquid. This shows the dramatic difference in accessibility and mass transport when compared to other nanoporous films.
According to one exemplary illustration, highly ordered and oriented nanoporous silica films based on 3D face-centered cubic or 2D hexagonal nanostructures are measured by the same method to have accessible areas less than 0.02% and diffusion coefficients less than 0.01 time the diffusion coefficient in bulk liquid. Platinum nanowire films are then fabricated by electrochemical deposition to fill the two pore systems followed by an etching step to remove the silica. The local and long-range order of the nanowire network is retained from the silica template and results in replication of the nanopore network with high fidelity. These new nanoporous silica film coated electrodes and platinum nanowire electrodes should be of immediate interest for electrochemical sensors, fuel cell electrodes, and photoelectrochemical devices. In addition, these films open up a general route for nanofabrication of ordered structures on the sub-10 nm length scale yielding a route to nanostructured thermoelectrics and photovoltaics that utilize quantum confinement.
The present teachings involve a convenient and reproducible, room temperature synthesis of tricontinuous silica films from commercially available templates that yield an accessible area of the substrate through the well-defined mesopores. In certain exemplary embodiments, the pore network comprises two mesopore networks separated by a microporous inorganic wall. In one exemplary embodiment at least about 25% of the substrate is accessible through the mesopores. In further exemplary embodiments, at least about 30% of the substrate is available through the mesopores. In yet further exemplary embodiments, at least about 31% of the substrate is available through the mesopores. In still further exemplary embodiments, at least about 50% of the substrate is available through the mesopores. It is believed that this is the first room temperature synthesis of gyroid-based silica films with pores less than about 10 nm and the first quantitative and accurate measurement of substrate accessibility for self-assembled silica films. This facile accessibility is exploited to electrodeposit platinum in the pore structure to yield highly ordered platinum nanowire networks. According to one exemplary embodiment, the rate of filling the pore network is at least about 30% as fast as electrodepositing onto a substrate as if no silica film were present. According to another exemplary embodiment, the rate of filling the pore network is at least about 50% as fast as electrodepositing onto a substrate as if no silica film were present. In additional exemplary embodiments, the rate of filling the pore network is at least about 70% as fast as electrodepositing onto a substrate as if no silica film were present. In still further exemplary embodiments, the rate of filling the pore network is at least about 90% as fast as electrodepositing onto a substrate as if no silica film were present. While this is the first report of electrodeposition in a gyroid-based structure, it is also the first report of any sub-10 nm diameter nanowire network with long-range order.
In one example, the present invention provides a method of forming a nanoporous film. The method comprises forming a coating solution including inorganic clusters, surfactant molecules, and a solvent and then aging the coating solution for a predetermined time period to control the phase that will self-assemble under a given set of environmental conditions. The method further comprises applying the coating solution on a substrate and evaporating the solvent from the coating solution. The method further comprises removing the surfactant molecules to yield the nanoporous film. In certain exemplary illustrations according to this embodiment, the coating solution is aged for a time period (prior to the coating process) that is selected to correspond to a desired interfacial curvature of the nanoporous film. In specific exemplary embodiments, the inorganic clusters are comprised of silicon and oxygen to yield silica nanoporous films. In further specific exemplary embodiments, the inorganic clusters are formed from the hydrolysis of a silicon alkoxide, such as tetraethylorthosilicate. In further specific exemplary embodiments, the clusters are organic-inorganic species consisting formed from the hydrolysis of a silicon alkoxide, such as tetraethylorthosilicate.
In another example, the present invention provides a nanoporous structure. The nanoporous structure comprises a substrate and a nanoporous film deposited on the substrate. The film defines a pore network having pores with an average size of less than about 10 nm, wherein at least about 25% of the substrate is accessible through the pore network at the substrate-film interface.
In further exemplary embodiments according to the present teachings, the pore network is comprised of pores with an average size of less than about 5 nm.
BRIEF DESCRIPTION OF THE DRAWINGS
The above-mentioned aspects of the present teachings and the manner of obtaining them will become more apparent and the teachings will be better understood by reference to the following description of the embodiments taken in conjunction with the accompanying drawings, wherein:
FIGS. 1 a - c depict GISAXS patterns of nanostructured tricontinuous films before and after copolymer removal with overlays of predicted positions of diffraction spots calculated under the DWBA using NANOCELL;
FIGS. 2 a - h depict experimental and simulated TEM images of nanoporous films;
FIGS. 3 a - d depict three dimensional rendering of contracted tricontinuous nanoporous films reconstructed from GISAXS, TEM, and FESEM;
FIG. 4 a depicts measured electrochemical impedance data showing that the tricontinuous double-gyroid films yield facile access to the substrate for molecules in solution;
FIG. 4 b illustrates how measured electrochemical impedance data relates to the Randles equivalent circuit fit for bare FTO;
FIG. 4 c depicts measured electrochemical impedance data of a modified Randles circuit fit for a tricontinuous silica film on FTO;
FIGS. 5 a - g depict electron microscopy of platinum nanowire structures after the removal of silica;
FIG. 6 a depicts a measured GISAXS pattern of a platinum nanostructure after silica removal;
FIG. 6 b depicts a simulated GISAXS pattern of a platinum nanostructure after silica removal;
FIGS. 7( a ) and 7 ( c ) depict transmission optical micrographs of nanoporous films before electrochemical deposition
FIG. 7( b ) and ( d ) depict transmission optical micrographs of films after electrodeposition of cobalt in the pores to form an array of cobalt nanowires
FIG. 8( a )-( b ) depict GISAXS patterns of silica films; and
FIG. 9 depicts a cyclic voltammogram of bare FTO and tricontinuous film on FTO.
FIG. 10( a ) depicts a photograph of a nanoporous film that has been electrochemically filled with PbSe. The PbSe nanowires have the same structure as the platinum wires in FIG. 5 .
FIG. 10( b ) depicts the reflectance spectra of the PbSe nanowires and shows oscillations due to quantum confinement.
FIG. 10( c ) depicts reflectivity data showing oscillations due to quantum confinement.
Corresponding reference characters indicate corresponding parts throughout the several views.
DETAILED DESCRIPTION OF THE INVENTION
The embodiments of the present teachings described below are not intended to be exhaustive or to limit the teachings to the precise forms disclosed in the following detailed description. Rather, the embodiments are chosen and described so that others skilled in the art may appreciate and understand the principles and practices of the present teachings.
Robust Synthesis of Tricontinuous-Phase NanoDorous Films
In the evaporation induced self-assembly (EISA) synthesis of nanoporous films discussed here, the coating solution contains an inorganic or inorganic-organic precursor species that may undergo hydrolysis, condensation, and/or protonation/deprotonation reactions. As a result, the precursor molecules exist as single molecules or as clusters that evolve with aging time prior to coating. In one exemplary embodiment, the precursor is the silicon alkoxide species called tetraethylorthosilicate (TEOS). In this example the clusters are built from a silicon atom with any mixture of the following groups attached: —OH, —OH2 + , —O − , —OCH2CH3, —O—Si≡. In another exemplary embodiment, the precursor is an organosilica bridge silesquioxane species called 1,2-bis(triethoxysilyl)ethane (BTESE). In this example, the clusters are built from a core of ≡Si—C—C—Si≡ with any of the following groups attached: —OH, —OH2 + , —O − , —OCH2CH3, ≡Si—C—C—Si≡). As a result changes in coating solution with aging time, there is typically a window of time over which EISA yields an ordered nanostructure that depends on the coating solution composition (for example the pH and hydrolysis ratio). The coating solutions are then applied by dip-coating or spin-coating to form a thin liquid film on a substrate. Other liquid coating techniques such as spray-coating, roll coating, or knife coating may be used as well. After coating, the vapor-phase composition (humidity and the presence of other solvents) plays a key role in determining the interfacial curvature of the nanostructure. For CTAB templated silica films aging time primarily affects the degree of ordering. However, as shown by the present teachings, for films templated by surfactants containing poly(ethylene oxide) as the hydrophilic component, aging of the coating solution provides a means to precisely and subtly control interfacial curvature.
In one exemplary embodiment this approach is used to synthesize nanoporous films with the double gyroid structure from an alkane-modified poly(ethylene oxide)-poly(propylene oxide) surfactant that displays a region of cubic phase stability in its aqueous phase diagram at compositions between the 2D hexagonal and lamellar phases (about 62-66 wt % copolymer for EO 17 -PO 12 -C 14 at room temperature). After mixing the coating solution, films formed by EISA show a systematic progression from high to low curvature silica nanostructures with increasing aging time of the coating solution (3D packing of spherical silica/micelle structures→2D packing of cylindrical silica/micelle structures→tricontinuous (double gyroid) structure→lamellar). After 10 days of aging at room temperature, high-quality pure tricontinuous-phase nanostructured films self-assemble when dip-coated. The time window where good quality films may be dip-coated extends up to about 30 days when the coating solution is stored at room temperature. However, if the coating solution is refrigerated after about 10 days of aging at room temperature, consistently high-quality nanoporous silica films with the tricontinuous structure are obtained even after 3 months of storage and even when dip-coated over a broad range of relative humidity (between about 25% and 75%). If the amount of water added to make the coating solution changes, the optimum aging time changes. Also, if the temperature at which the solution is aged changes, the optimum aging time also changes. The optimum aging time can be shift to times shorter than 6 hours as well as times exceeding about 30 days.
In another exemplary embodiment Pluronic P84 was used as the templating surfactant molecule (instead of the EO 17 -PO 12 -C 14 ). P84 has a formula of approximately EO 19 -PO 43 -EO 19 . The same phenomena with aging are observed
Film Structure, Order, and Orientation
In one exemplary illustration according to the present teachings, grazing-angle-of-incidence small-angle x-ray scattering (GISAXS) is used to assess the symmetry and order in the films. The GISAXS patterns are interpreted using the Distorted Wave Born Approximation (DWBA) to calculate the positions of the Bragg diffraction spots, including the effects of refraction and reflection ( FIG. 1 ). According to this exemplary illustration, the Bragg spots of the as-synthesized film can be accurately described by a gyroid cubic structure that is highly oriented with its 211 planes parallel to the substrate and has undergone a 7% contraction perpendicular to the substrate. The (211) oriented domains span the thickness of the film and extend laterally several microns. Despite the fact cubic symmetry is broken, the systematic absences are still explained by the gyroid extinction conditions (space group Ia-3d) since the distribution of electron density still possesses this symmetry. After copolymer removal by calcination, the extent of unidirectional contraction increases to about 40%. The main features of the GISAXS pattern are still well-described by the systematic absences of the double gyroid structure ( FIG. 1 b ). However, smaller intensity peaks do appear and can be used to identify which symmetry elements are broken. These broken symmetries are b and c glide planes parallel to the (100) of the uncontracted cubic structure; the c and a glide planes parallel to the (010); the d glide planes parallel to the (1-10) and (110); and the d glide planes parallel to the (−101) and (101). These relax the extinction conditions 0kl (for k,l=2n); h0l (for h,l=2n); hhl and h−hl (for 2 h+l=4n); and hkh and −hkh (for 2h+k=4n), respectively. Here it should be noted that in bicontinuous gyroid structures where one of the two enantiomeric continuous regions is filled and the other continuous region is empty (the pore system), the structure has l4 1 32 symmetry which would yield additional peaks not observed here. This suggests that the nanoporous silica films have a tricontinuous structure—two individually continuous pore systems separated by a non-porous inorganic wall, such as a continuous silica wall that is based on a uniaxially contracted gyroid minimum surface.
The structure and topology were examined by FESEM and TEM ( FIG. 2 ). Experimental TEM images were compared with projections of electron density calculated from several possible structures that are based on the gyroid minimum surface. An excellent match was found between the observed TEM images and those simulated from a tricontinuous structure where the gyroid minimal surface runs down the center of a silica wall separating the two pore systems. The uncontracted cubic structure was generated by assuming a constant wall thickness (t) and placing electron density in regions of space defined by a constant level of the periodic nodal surface given in terms of wall thickness by:
sin ( 2 π x a ) cos ( 2 π y a ) + sin ( 2 π y a ) cos ( 2 π z a ) + sin ( 2 π z a ) cos ( 2 π x a ) ≤ 3 2 sin 2 π t 3 a
where a is the lattice constant of the uncontracted cubic structure (determined from GISAXS of planes perpendicular to the substrate to be 17.9 nm). This structure was then oriented such that the (211) planes were parallel to the substrate and then uniaxially contracted towards the substrate by applying rotation and deformation matrices. Due to the contraction, the wall thickness of the contracted structure is not constant, and varies systematically from about 3.4 nm to about 5.7 nm, with an average of about 4.6 nm (commensurate with FESEM data). The projected electron densities along any given [hkl] direction were then calculated by integration. A Gaussian blur was applied to the projected density to account for aberration in the imaging process.
Determination of the lattice constants and orientation from GISAXS, the topology from TEM imaging and simulation, and the wall thickness from FESEM imaging allows the reconstruction of a low resolution 3D model of the structure ( FIG. 3 ). The volume void fraction and mesopore surface area were calculated numerically from the 3D reconstruction of the film to be about 0.48 cm 3 pore /cm 3 film and about 5.82×10 6 cm 2 surface /cm 3 film . Also, the critical angle for x-ray scattering for the calcined nanoporous film was measured by GISAXS to be about 0.165°. The average electron density of the calcined film is then calculated from the critical angle to be about 347 electrons/nm 3 . The density of the silica wall may then be calculated from the electron density and void fraction and is found to be about 2.24 g/cm 3 . This corresponds closely to the value of dense amorphous silica and suggests that there is little microporosity in the wall (however, this should be confirmed by a higher resolution technique). From these parameters, the internal mesopore surface area and mesopore volume of the contracted film are calculated to be about 477 m 2 /g and about 0.56 cm 3 /g. For comparison, a 2D hexagonal silica phase with the same minimum wall thickness and pore diameter (about 3.4 nm and about 4.3 nm) has an internal mesopore surface area and mesopore volume of about 81 m 2 /g and about 0.17 cm 3 /g, respectively. It was recently suggested on the basis of HRTEM and electron crystallography that the two continuous pore systems (for gyroid structure nanoporous silica powders) may be interconnected by a small pore through the silica wall at the 16a site. However, the resolution of the reconstruction reported here is too low to determine if similar structural phenomena occur in the film morphology.
The planar void fraction for any slice of the tricontinuous nanostructure may also be calculated from the reconstructed model. Both the minimum and maximum planar void fractions occur for slices parallel to the (211) planes, ranging from about 0.31 to about 0.63. The slice with the lowest planar void fraction (highest fraction of silica) should be the most hydrophilic while the highest planar void fraction should be the most hydrophobic. This explains why the films are (211) oriented. Further, it is hypothesized that the slice parallel to the (211) with the highest planar density of silica will be the slice in contact with the substrate (since the substrate is hydrophilic), and will thus determine the footprint the film leaves on the electrode and determine the fraction of accessible substrate area. The footprint that results from this slice is shown in FIG. 3 b.
Electrochemically Accessible Substrate Area
The accessibility of the pore volume in nanoporous powders is typically determined using nitrogen adsorption. However, this technique is not capable of giving any direct indication of accessibility to the substrate underlying a nanoporous film. Also, due to solvation and surface charge effects, the accessibility of the substrate to a solution phase species can be vastly different from the accessibility of a gas phase species. Electrochemical techniques may be used to address this question, but care must be taken to calculate accurate values of the accessible area. There have been only a few electrochemical studies that involve self-assembled continuous nanoporous film coated electrodes. However, only one reports a quantitative measure of the accessible substrate area. It is believed that about 70% of the substrate is electrochemically accessible by comparing the peak currents from cyclic voltammetry (CV) of coated and bare electrodes. However, this method is accurate only when the diffusion layer thickness (δ) is much smaller than the length scale of active regions of the electrode (d a ). When δ is on the order of d a but smaller than the distance of separation between active patches (d s ), it yields values of accessible area that are artificially high, due to the increased current from 3D diffusion at the edges of the active regions. However, when δ>>d a and δ>>d s , as is the case for surfactant templated nanoporous films, this method may over estimate of the accessible surface area. Under these conditions the area that contributes to the peak current in CV is the geometric area, and increasing the fraction of the electrode surface that is blocked will only decrease the apparent rate constant, which will ultimately cause peak separation in the CV. For this same reason, as long as the standard rate constant is reasonably large, CV from highly blocked electrodes (with δ>>d a and δ>>d s ) can look identical to CV from a bare electrode. When the rate constant is lower, the CV becomes quasireversible, and the peak current decreases slightly.
In general, CV and chronoamperometry present difficulties in determining the accessible substrate area due to their dependence on diffusion. However, methods based on measuring the apparent rate constant can yield accurate values. Electrochemical impedance spectroscopy (EIS) can be used to separate the interfacial kinetics from diffusion, solution resistance, and double layer charging currents that may cause inaccuracy. This method has been used to great advantage to examine the fractional surface coverage of self-assembled monolayers. In this method, a small magnitude sinusoidal voltage, V(ω), is superimposed on the applied DC potential, set to the formal potential of the redox couple. The current response, I(ω), is measured and the complex impedance is calculated via Z(ω)=V(ω)/I(ω) over a broad range of frequencies. If the impedance data can be fit to simple, physically reasonable, equivalent circuits, then the accessible area of a bare or monolayer coated substrate may be accurately determined from the charge transfer resistance. For an electrode coated with a nanoporous film, only the product of the accessible area (A) and the partition coefficient (P) may be determined unambiguously. In the absence of a specific interaction between the redox couple and the silica wall and for pores much larger than the redox couple, P will approach unity. At about pH 2 (where all EIS data were collected in this study), the silica wall is neutral and decorated with hydroxyl groups. As such the partition coefficient is expected to be very close to unity. Further, at about pH=2 hydrolytic degradation of the silica film is negligible, as EIS experiments on the same film immersed for days in the solution yield the same value of the measured accessible area.
The EIS data of ferrocene dimethanol on a bare fluorine-doped tin oxide (FTO) electrode fit a Randles equivalent circuit. The charge transfer resistance yielded a value of the standard rate constant of 0.0045 cm/s (using the geometric area of the bare FTO). The measured real and imaginary components of the electrochemical impedance and fitted equivalent circuit models are shown in FIG. 4 as parametric plots as a function of frequency. FTO electrodes coated with crack-free nanoporous silica films show a slightly depressed semicircle in their impedance spectra. This is due to the fact that the double layer at the electrode surface is not a simple planar surface, but extends slightly into the wall structure of the film. Replacing the double layer capacitance (C dl ) with a constant phase element (CPE) allows one to model this deviation from planarity. The impedance due to a CPE is given by Z CPE =1/T(jω) p . The fractional exponent p characterizes the width of the relaxation time distribution due to the inhomogeneity, with p=1 representing a single pure capacitor. The behavior of the diffusion impedance in the mass transfer controlled regime (low frequency) deviates slightly from that expected from Fickian 1D diffusion (an infinite length Warburg element or a CPE with p=0.5). A CPE is used to model this data and yielded a value of p=0.59. However, this element does not affect the value of R ct which is dictated by the higher frequency data where the diffusion impedance is very small.
EIS data were collected from many typical nanoporous films and reveal that highly ordered and oriented contracted 2D hexagonal films and contracted 3D cubic films (rhombohedral space group R-3m) have extremely low accessible substrate areas (less than 0.02%), for the ˜6 Å diameter ferrocene dimethanol probe molecule. However, the new tricontinuous films synthesized here have accessible areas of 31%±3%, compared to a bare substrate. The low accessibility in 2D hexagonal films is expected since the mesopores are aligned parallel to the substrate. However, low accessibility in rhombohedral films is surprising, as these films show large nanopore openings in top-view FESEM and are expected to have intercage connections similar to those observed in cubic phase nanoporous silica powders, particularly Fm-3m structures. This lack of accessibility in highly ordered rhombohedral films could be due to the lack of intercage openings or due to the presence of a thin but dense silica layer beneath the nanoporous film. The accessibility increases for hexagonal and rhombohedral films as they become less ordered and less oriented (as the redox couple is able to move through defects and irregular mesopore connections). However, this type of accessibility is qualitatively different for the tricontinuous films reported here, as the accessibility is determined by the regular mesopore structure. This accessible area of the substrate matches amazingly well with footprint the tricontinuous films leaves of the substrate (about 31%) as determined from the structural model derived from GISAXS and TEM ( FIG. 3 b ).
Platinum Nanowire Films with the Double-Gyroid Structure
There are previous reports of electrochemical deposition within nanoporous silica films. However, these were either in contracted 2D hexagonal films with pores parallel to the substrate (meaning the deposition occurred though film defects, regions of nanostructure disorder, or microporosity) or in cage-like cubic structures with irregular pore openings. As a result, none of these electrodeposited structures retain good order after silica removal by etching. The first electrochemical deposition of metals into a true double gyroid-based nanoporous silica film is reported here. The metal fills each of the two continuous pore systems, and due to the pore connectivity and the high pore filling, the nanowire networks are stable to removal of the silica and retain the local and long-range order imposed by the nanopores system of the film. FESEM and TEM micrographs of a platinum nanowire film after removal of the silica by etching in HF are shown in FIG. 5 . TEM images were simulated as discussed above, except they were based on a structure where platinum fills the both pore systems and the original silica wall is absent ( FIG. 3 d ). The observed TEM images compare very well with the simulated electron density projections for the [111], [211], and [311] directions.
GISAXS patterns were also collected from the Pt films after silica removal ( FIG. 6 ) and show that long-range order and orientation of the Pt is retained. The observed GISAXS spot pattern and relative intensities match nearly identically to that for the nanoporous silica film (as would be expected by the Babinet Principle). Further, we carried out simulation of the full GISAXS pattern (under the Born Approximation) by taking the discrete Fourier Transform of the Pt nanostructure with the form shown in FIG. 3 d . An apodization function (Hanning window) was applied to the data to minimize aliasing effects, and reciprocal space was integrated radially about the [211] axis. The resulting pattern is shown in FIG. 6 b . Comparison of the relative peak intensities and peak positions between measured and simulated GISAXS patterns shows that the Pt nanowire network maintains the structure shown in FIG. 3 d over large length scales. This also shows that the two continuous nanowire systems (blue and green in FIG. 3 d ) do not shift relative to one another in contrast to that observed in carbon materials templated by MCM-48. This may be due to the fact that each nanowire network is independently (and regularly) connected to the substrate or perhaps the presence of interconnections such as those observed by Sakamoto.
PbSe Quantum Wire Films with the Double-Gyroid Structure
Following the same procedure as above described for platinum nanowires, wires of other materials may also be grown by electrodeposition in these nanoporous film templates. We have demonstrated this for Pt, Co, Cu, Bi, Bi2Te2, CuInSe2, CdSe, CdTe, PbTe, and PbSe. In FIG. 10 , results for PbSe are shown. FIG. 10( a ) shows a photograph of a nanoporous silica film that has been filled with PbSe by electrochemical deposition. The photograph shows the macroscopic uniformity of the films and the high fill fraction of PbSe. The films shown in FIG. 10( a ) is composed of about 4 nm wires of PbSe. For this material, these are not just uniform nanowires (which are wires of uniform diameter less than about 100 nm), but they are quantum wires. The small diameter of the wires and the uniform structure provided by the double-gyroid topology results in quantum confinement of electrons in the PbSe. The is shown in reflectivity data shown in FIG. 10( b ). The oscillations in the reflectivity are due to spikes in the density of states due to quantum confinement. This is a key discovery since it is believed that quantum confinement is a key and necessary feature for enhanced efficiency photovoltaics devices and thermoelectric devices. In our studies we have been able to make sub 5 nm wires from any metal or semiconductor we have tried. These results prove the general utility of the present teachings for making small diameter nanowire or quantum wire arrays.
Methods
Synthesis of NanoDorous Silica Films
For tricontinuous silica films from TEOS and EO 17 -PO 12 -C 14 , tetraethyl orthosilicate (TEOS) was prehydrolyzed at room temperature. About 6.35 g of about a pH 1.76 solution of HCl in water was added to about 12.86 g of ethanol in an HDPE bottle. About 12.2 g of TEOS was then added quickly. The bottle was immediately sealed and stirred for about 20 minutes at about 21° C. The prehydrolysis solution had a molar ratio of 1 TEOS: 0.0019HCl: 6.0 H 2 O: 4.8 EtOH. Immediately after prehydrolysis, about 13.9 g of about 37 wt % EO 17 -PO 12 -C 14 in ethanol was added to form the coating solution. The coating solution was then aged for different times at about 21° C. The final molar composition of the coating solution was 1 TEOS: 0.054 EO 17 -PO 12 -C 14 : 0.0019HCl: 6.0 H 2 O: 8.0 EtOH. Before coating, fluorine-doped SnO 2 (FTO) substrates were cleaned by immersion in about 1 wt % Alconox at about 65° C. for about 30 seconds followed by rinsing with copious quantities of RO water and air dried. Films were dip-coated on FTO using this solution at a withdrawal speed of 1 mm/sec. High quality films were formed after dip-coating at about 40% relative humidity (RH) after about 10 days of aging of the coating solution. After coating, films were left at the same RH for about 12 hrs and then calcined in air at about 400° C. for about 4 hours (with about 1° C./min ramps). Contracted 2D hexagonal films (plane group c2 mm) were synthesized as published by Cagnol, and contracted face-centered cubic films (rhombohedral space group R-3m) were synthesized as published previously.
For tricontinuous silica films from TEOS and EO 19 -PO 43 -EO 19 , the EO 19 -PO 43 -EO 19 (P84) surfactant was received as a gift from BASF and was used as-received. The nominal molecular weight of Pluronic-P84 is 4200 and its EO content is approximately 40%. Tetraethyl orthosilicate (TEOS, 98% w/w, Aldrich) was used as the silica precursor. Concentrated (37% w/w) hydrochloric acid was purchased from Aldrich and ethyl alcohol (>99.5%) from EMD Chemicals. All chemicals were ACS reagent grade and were used as-received. The coating solution is prepared by mixing a pre-hydrolyzed silicate solution with an ethanolic surfactant solution. Specifically, about 5.49 g of Pluronic-P84 was dissolved in about 14 g of ethyl alcohol and was allowed to equilibrate overnight at about 21° C. with vigorous stirring. TEOS was pre-hydrolyzed at room temperature (about 21° C.). About 6.35 g of about 0.017 M hydrochloric (pH ˜1.8) was mixed with about 12.9 g of ethyl alcohol in an HDPE bottle. To this solution, about 12.19 g of TEOS was added and the bottle was sealed. The solution was stirred vigorously at about 21° C. for about 20 min. The molar composition of the pre-hydrolysis solution was: TEOS:HCl:H 2 O:EtOH=1:0.0019:6.0:4.8. After the pre-hydrolysis step, the surfactant solution was mixed with the pre-hydrolyzed silicate solution and stirred vigorously at room temperature for about 10 min. This mixed solution, termed as ‘coating solution’, was afterwards allowed to age at room temperature without stirring. The molar composition of the coating solution was: TEOS:P84:HCl:H 2 O:EtOH=1:0.02229:0.0019:6.0:10. Periodically, thin films were prepared from the coating solution by a dip-coating process at different aging times. The substrates, fluorine-doped tin oxide (FTO) slides with sheet resistance of 8 Ω/sq, were cleaned by immersing in a boiling, about 2% (w/w) solution of Alconox laboratory detergent for about 5 min, followed by rinsing in RO water to remove traces of detergent. Then they were immersed in a solution consisting of about 70% (w/w) nitric acid and 37% (w/w) hydrochloric acid in 1:3 weight ratio (‘aqua-regia’) for 20 min at 21° C., followed by a rinse in RO water. The FTO substrates were then dried in a stream of clean, dry air and were used immediately for dip-coating. Silica films were dip-coated on the substrates at a withdrawal speed of about 1 mm/sec under controlled relative humidity of about 40% at room temperature (about 21° C.). These are the same coating conditions we used previously with EO 17 -PO 12 -C 14 /silica system. The films were left at the same relative humidity overnight, before being calcined at about 450° C. for about 4 hours in air with a ramp of about 2° C./min. Double-gyroid silica films are obtained this solution after aging for only about 6 hours and can be made beyond about 3 days of aging.
Determination of Accessible Area of the Substrate
A standard three-electrode cell was used for all experiments with the calcined nanoporous film coated FTO as the working electrode (about 1.5 cm 2 geometric area submersed), a platinum counter electrode with about 20 cm 2 , and a Ag/AgCl reference electrode. The electrolyte contained 1 mM 1,1′-ferrocenedimethanol redox couple, 1M KCl supporting electrolyte, and 0.01 M HCl such that the pH≈2. The formal potential was determined by cyclic voltammetry using a PAR 283 potentiostat to be 0.21 V vs Ag/AgCl. Electrochemical impedance spectroscopy data were then collected using a Solartron 1260 with a DC bias set to the measured formal potential with an AC bias of magnitude 10 mV (rms). These data were collected over a frequency range from about 0.1 Hz to 0.1 MHz. The data were fit by complex non-linear least squares to either a Randles equivalent circuit or a modified Randles circuit with constant phase elements substituted for the double layer capacitance or the Warburg element. The accessible area was then calculated from the charge transfer resistance for the one-electron reaction given by: R ct =RT/F 2 kAPC, where k is the standard rate constant, A the accessible substrate area, P the partition coefficient of the redox couple in the film, C the bulk concentration of the redox couple, and F is the Faraday constant. k was determined by EIS on a bare electrode under identical conditions.
Electrodeposition of Nanowire Networks in Nanoporous Silica Films
The same three electrode cell as above was used for potentiostatic depositions. The working electrode (nanoporous film coated FTO) was immersed into a deoxygenated electrolyte solution for ten minutes prior to deposition. For platinum nanowires the electrolyte was about 0.022M hexachloroplatinic acid (H 2 PtCl 6 ) in RO water (pH=1.5), and the depositions were carried out at a constant potential of −0.3V vs. Ag/AgCl at about 21° C. until the current integrated to 1.5 C/cm 2 . The silica was then removed by etching the film in about a 2 wt % HF solution for about 4 hours at about 21° C. For PbSe quantum wire films the electrodeposition bath contained about 0.1 M Pb(NO 3 ) 2 and 0.001 M SeO 2 dissolved in about a 0.1 M HNO 3 aqueous solution. Prior to electrodeposition, nitrogen or argon gas was bubbled through the solution for 10 min. The electrochemical cell contained a double-gyroid silica coated FTO as working electrode, a Pt wire as counter electrode and an Ag/AgCl in about 4 M KCl reference electrode. Stoichiometric PbSe films could be deposited from this bath under potentiostatic conditions over a potential range of about −0.20 V to −0.40 V versus the Ag/AgCl electrode. Unless otherwise stated, all films reported in this work were deposited at about −0.30V versus the Ag/AgCl electrode. The thickness of deposited PbSe could be controlled by controlling the amount of charge passed. ˜300 nm thick PbSe/silica nanocomposite film was created by passing a charge of about 0.27 C/cm 2 of substrate area. The films were rinsed in RO water after deposition and allowed to dry in air. While as deposited PbSe films were crystalline, a thermal treatment in flowing nitrogen at about 500° C. was done to improve structural strength of the PbSe nanowire network embedded in silica. The silica template was then removed by etching in freshly prepared 1 M KOH for about 30 min.
Reflectivity Measurements
The Reflectivity measurements were done on bulk and double-gyroid PbSe films using Analytical Spectral Devices, Inc. FieldSpec® 3 portable spectroradiometer. The spectral range for this instrument is 350 nm-2500 nm, corresponding to an energy range from about 3.54 eV-0.50 eV. The probe was mounted directly on the thin film to measure the reflectance from the film. The film was artificially illuminated by an external broadband direct current light source with reflectance measured on 2151 channels. Prior to doing measurements on actual films, the instrument was calibrated using Labsphere Spectralon® white reflectance material. The instrument was set to measure the reflectance from the PbSe film (not radiance, which would include contributions from the source lamp).
Further description of the present invention may be found in “Nanofabrication of Double-Gyroid Thin Films,” Journal of the American Chemical Society, Vol. 19, No. 4, pp 768-777 (2007), Vikrant N. Urade et al., see Appendix A; “Controlling Interfacial Curvature in Nanoporous Silica Films Formed by Evaporation-Induced Self-Assembly from Nonionic Surfactants. I. Evolution of Nanoscale Structure in Coating Solutions,” Journal of the American Chemical Society, Vol. 23, No. 8, pp 4257-4267 (2007), Luis Bollmann et al., see Appendix B; “Controlling Interfacial Curvature in Nanoporous Silica Films Formed by Evaporation-Induced Self-Assembly from Nonionic Surfactants. II. Effect of Processing Parameters on Film Structure,” Journal of the American Chemical Society, Vol. 23, No. 8, pp 4268-4278 (2007), Vikrant N. Urade et al., see Appendix C; and “Mass Transport and Electrode Accessibility Through Periodic Self-Assembled Nanoporous Silica Thin Films,” Journal of the American Chemical Society, Vol. 23, No. 10, pp 5689-5699 (2007), Ta-Chen Wei et al., see Appendix D, the entire contents of each are incorporated herein by reference.
While an exemplary embodiment incorporating the principles of the present invention has been disclosed hereinabove, the present invention is not limited to the disclosed embodiments. Instead, this application is intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims. | A method of forming a nanoporous film is disclosed. The method comprises forming a coating solution including clusters, surfactant molecules, a solvent, and one of an acid catalyst and a base catalyst. The clusters comprise inorganic groups. The method further comprises aging the coating solution for a time period to select a predetermined phase that will self-assemble and applying the coating solution on a substrate. The method further comprises evaporating the solvent from the coating solution and removing the surfactant molecules to yield the nanoporous film. | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of Korean Patent Application No. P2008-0116735, filed on Nov. 24, 2008, which is hereby incorporated by reference as if fully set forth herein.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a method for transmitting an uplink signal in a multiple antenna scheme, and more particularly, to a method for acquiring precoding information efficiently and transmitting an uplink signal using the precoding information in a multiple antenna scheme.
[0004] 2. Discussion of the Related Art
[0005] The present invention relates to a method for transmitting MIMO is short for Multiple Input Multiple Output. Beyond conventional schemes using a single Transmit (Tx) antenna and a single Receive (Rx) antenna, MIMO uses a plurality of Tx antennas and a plurality of Rx antennas to thereby increase the transmission and reception efficiency of data. With the use of multiple antennas at a transmitter or a receiver, MIMO seeks to increase capacity or improve performance in a wireless communication system. The term “MIMO” is interchangeable with “multiple antenna”.
[0006] The MIMO technology does not depend on a single antenna path to receive an entire message. Rather, it completes the message by combining data fragments received through a plurality of antennas. Because MIMO may increase data rate within a certain area or extend system coverage at a given data rate, it is considered as a promising future-generation mobile communication technology that may find its use in a wide range including mobile terminals, relays, etc. With the growth of data communication, MIMO is attracting attention as a future-generation technology that may overcome a limit on transmission capacity that is almost reached due to the increased data communication.
[0007] FIG. 1 illustrates the configuration of a typical MIMO communication system. Referring to FIG. 1 , a simultaneous increase in Tx antennas of a transmitter to N T and in Rx antennas of a receiver to N R increases a theoretical transmission capacity in proportion to the number of antennas, compared to use of a plurality of antennas at only one of the transmitter and the receiver. Therefore, transmission rate is increased and frequency efficiency is remarkably increased. Given a maximum transmission rate R o that may be achieved in case of a single antenna, the increase of channel capacity may increase the transmission rate, in theory, to the product of R o and R i in case of multiple antennas. R i is a transmission rate increase rate.
[0008] For instance, a MIMO communication system with four Tx antennas and four Rx antennas may achieve a four-fold increase in transmission rate theoretically, relative to a single-antenna system. Since the theoretical capacity increase of the MIMO system was proved in the middle 1990 's, many techniques have been actively studied to increase data rate in real implementation. Some of the techniques have already been reflected in various wireless communication standards for 3 rd Generation (3G) mobile communications, future-generation Wireless Local Area Network (WLAN), etc.
[0009] Concerning the research trend of MIMO, active studies are underway in many respects of MIMO, inclusive of studies of information theory related to calculation of multi-antenna communication capacity in diverse channel environments and multiple access environments, studies of measuring MIMO radio channels and MIMO modeling, studies of time-space signal processing techniques to increase transmission reliability and transmission rate, etc.
[0010] There are two types of MIMO schemes: spatial diversity and spatial multiplexing. Spatial diversity increases transmission reliability using symbols that have passed in multiple channel paths, whereas spatial multiplexing increases transmission rate by transmitting a plurality of data symbols simultaneously through a plurality of Tx antennas. Taking advantages of these two schemes by using them in an appropriate combination is a recent active study area.
[0011] To describe a communication scheme in a MIMO system in detail, the following mathematical model may be used.
[0012] It is assumed that there are N T Tx antennas and N R Rx antennas as illustrated in FIG. 1 . Regarding a transmission signal, up to N T pieces of information can be transmitted through the N T Tx antennas, as expressed as the following vector.
[0000] s=[s 1 ,s 2 , . . . ,s N T ] T [Equation 1]
[0013] A different transmit power may be applied to each piece of transmission information s 1 , s 2 , . . . , s N T . Let the transmit power levels of the transmission information be denoted by P 1 , P 2 , . . . , P N T , respectively. Then the power-controlled transmission information ŝ may be given as [Equation 2].
[0000] ŝ=[ŝ 1 ,ŝ 2 , . . . ,ŝ N T ] T =[P 1 s 1 ,P 2 s 2 , . . . ,P N T s N T ] T [Equation 2]
[0014] ŝ may be expressed as a diagonal matrix P of transmit power.
[0000]
s
^
=
[
P
1
0
P
2
⋱
0
P
N
T
]
[
s
1
s
2
⋮
s
N
T
]
=
Ps
[
Equation
3
]
[0015] Meanwhile, actual N T transmitted signals x 1 , x 2 , . . . , x N T may be configure by applying a weight matrix W to the power-controlled information vector ŝ. The weight matrix W functions to appropriately distribute the transmission information to the Tx antennas according to transmission channel statuses, etc. These transmitted signals x 1 , x 2 , . . . , x N T are represented as a vector x, which may be determined as
[0000]
x
=
[
x
1
x
2
⋮
x
i
⋮
x
N
T
]
=
[
w
11
w
12
…
w
1
N
T
w
21
w
22
…
w
2
N
T
⋮
⋱
w
i
1
w
i
2
…
w
iN
T
⋮
⋱
w
N
T
1
w
N
T
2
…
w
N
T
N
T
]
[
s
^
1
s
^
2
⋮
s
^
j
⋮
s
^
N
T
]
=
W
s
^
=
WPs
[
Equation
4
]
[0016] w ij denotes a weight for a j th piece of information ŝ j transmitted through an i th Tx antenna and the weights are expressed as the matrix W. W is referred to as a weight matrix or a precoding matrix.
[0017] The afore-mentioned transmitted signal x may be considered in two cases: spatial diversity and spatial multiplexing.
[0018] In spatial multiplexing, different signals are multiplexed prior to transmission. Accordingly, the elements of the information vector s have different values. In contrast, the same signal is transmitted in a plurality of channel paths in spatial diversity. As a result, the elements of the information vector s have the same value.
[0019] Spatial multiplexing and spatial diversity may be used in combination. For example, the same signal may be transmitted through three Tx antennas in spatial diversity, while different signals may be transmitted through the other Tx antennas in spatial multiplexing.
[0020] Given N R Rx antennas, signals received at the Rx antennas, y 1 , y 2 , . . . , y N R may be represented as the following vector.
[0000] y=[y 1 ,y 2 , . . . ,y N R ] T [Equation 5]
[0021] When channels are modeled in the MIMO communication system, they may be distinguished according to the indexes of Tx and Rx antennas and the channel between a j th Tx antenna and an i th Rx antenna may be represented as h ij . It is to be noted herein that the index of the Rx antenna precedes that of the Tx antenna in h ij .
[0022] The channels may be represented as vectors and a matrix by grouping them. The vector representation of channels may be carried out in the following manner.
[0023] FIG. 2 illustrates channels from N T Tx antennas to an i th Rx antenna.
[0024] Referring to FIG. 2 , the channels from the N T Tx antennas to the i th Rx antenna may be expressed as [Equation 6].
[0000] h i T =[h i1 ,k i2 , . . . ,h iN T ] [Equation 6]
[0025] Also, all channels from N T Tx antennas to N R Rx antennas may be expressed as the following matrix.
[0000]
H
=
[
h
1
T
h
2
T
⋮
h
i
T
⋮
h
N
R
T
]
=
[
h
11
h
12
…
h
1
N
T
h
21
h
22
…
h
2
N
T
⋮
⋱
h
i
1
h
i
2
…
h
iN
T
⋮
⋱
h
N
R
1
h
N
R
2
…
h
N
R
N
T
]
[
Equation
7
]
[0026] Actual channels experience the above channel matrix H and then are added with Additive White Gaussian Noise (AWGN). The AWGN n 1 , n 2 , . . . , n N R added to the N R Rx antennas is given as the following vector.
[0000] n=[n 1 ,n 2 , . . . ,n N R ] T [Equation 8]
[0027] From the above modeled equations, the received signal is given as
[0000]
y
=
[
y
1
y
2
⋮
y
i
⋮
y
N
R
]
=
[
h
11
h
12
…
h
1
N
T
h
21
h
22
…
h
2
N
T
⋮
⋱
h
i
1
h
i
2
…
h
iN
T
⋮
⋱
h
N
R
1
h
N
R
2
…
h
N
R
N
T
]
[
x
1
x
2
⋮
x
j
⋮
x
N
T
]
+
[
n
1
n
2
⋮
n
i
⋮
n
N
R
]
=
Hx
+
n
[
Equation
9
]
[0028] In a 3GPP LTE system attracting attention as a future-generation mobile communication technology, the above-described MIMO operation applies only to downlink signal transmission from a Base Station (BS) to a User Equipment (UE). As efforts are continuous to increase transmission rate and achieve diversity gain also from uplink signal transmission, there exists a need for specifying this uplink MIMO technology in upcoming standards.
SUMMARY OF THE INVENTION
[0029] Accordingly, the present invention is directed to a method for selecting a Precoding Matrix Index (PMI) for a non-adaptive Hybrid Automatic Repeat reQuest (HARM) operation in a Multiple Input Multiple Output (MIMO) wireless communication system that substantially obviates one or more problems due to limitations and disadvantages of the related art.
[0030] An object of the present invention is to provide to provide a method for efficiently applying a MIMO scheme to uplink signal transmission.
[0031] Another object of the present invention is to provide a method for acquiring precoding information efficiently and transmitting an uplink signal using the precoding information in a MIMO scheme.
[0032] Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
[0033] To achieve these objects and other advantages and in accordance with the purpose of the invention, as embodied and broadly described herein, a method for transmitting an uplink signal in a UE in a wireless communication system includes receiving from a BS a scheduling grant signal including precoding matrix information to be used for an uplink signal transmission from the UE, precoding an uplink signal using the precoding matrix information included in the received scheduling grant signal, transmitting the precoded uplink signal initially to the BS, and retransmitting the uplink signal at least one time, if the BS fails to receive the initially transmitted uplink signal. If a scheduling grant signal is not received for the retransmission from the BS, the uplink signal is precoded and retransmitted using precoding matrix information included in a latest scheduling grant signal received for transmission of an uplink signal having an HARQ process number equal to an HARQ process number of the uplink signal to be retransmitted.
[0034] If the scheduling grant signal is not received for the retransmission from the BS and there is not the latest received precoding matrix information for an uplink signal having the same HARQ process number of the uplink signal to be retransmitted, the uplink signal may be precoded and retransmitted using precoding matrix information included in a latest scheduling grant signal received for transmission of an uplink signal having the same rank and/or frequency band as a rank and/or frequency band of the uplink signal to be retransmitted. When a different precoding matrix is used according to a frequency band allocated to the UE, a precoding matrix for an uplink signal having the same rank and frequency band as the rank and frequency band of the uplink signal to be retransmitted may be used as a precoding matrix for the uplink signal to be retransmitted. If a precoding matrix applies to a total system band, only a rank may be considered.
[0035] If the scheduling grant signal is not received for the retransmission from the BS and there is not the latest received precoding matrix information for an uplink signal having the same rank and/or frequency band as the rank and/or frequency band of the uplink signal to be transmitted, the uplink signal may be precoded and retransmitted using the precoding matrix information included in the scheduling grant signal received for the initial transmission.
[0036] In another aspect of the present invention, a method for transmitting an uplink signal in a UE in a wireless communication system includes receiving from a BS a scheduling grant signal including precoding matrix information to be used for an uplink signal transmission from the UE, precoding an uplink signal using the precoding matrix information included in the received scheduling grant signal and transmitting the precoded uplink signal initially to the BS, and retransmitting the uplink signal at least one time, if the BS fails to receive the initially transmitted uplink signal. If a scheduling grant signal is not received for the retransmission from the BS, the uplink signal is precoded and retransmitted using a precoding matrix of a precoding matrix group preset between the UE and the BS in a sequential order, the precoding matrix group including one or more precoding matrices.
[0037] The wireless communication system may be a synchronous HARQ system and the UE may transmit the uplink signal using multiple antennas.
[0038] It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0039] The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principle of the invention. In the drawings:
[0040] FIG. 1 illustrates the configuration of a typical Multiple Input Multiple Output (MIMO) communication system.
[0041] FIG. 2 illustrates channels from N T Transmission (Tx) antennas to an i th Reception (Rx) antenna.
[0042] FIGS. 3( a ) and 3 ( b ) illustrate methods for transmitting an uplink signal in a MIMO scheme in a User Equipment (UE) according to exemplary embodiments of the present invention.
[0043] FIG. 4 is a flowchart illustrating a method for acquiring precoding matrix information for a retransmission in a UE, when the UE fails to receive a scheduling grant signal from a Node B according to an exemplary embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0044] Reference will now be made in detail to the preferred embodiments of the present invention with reference to the accompanying drawings. The detailed description, which will be given below with reference to the accompanying drawings, is intended to explain exemplary embodiments of the present invention, rather than to show the only embodiments that can be implemented according to the invention.
[0045] The following detailed description includes specific details in order to provide a thorough understanding of the present invention. However, it will be apparent to those skilled in the art that the present invention may be practiced without such specific details. In some instances, known structures and devices are omitted or are shown in block diagram form, focusing on important features of the structures and devices, so as not to obscure the concept of the present invention. The same reference numbers will be used throughout this specification to refer to the same or like parts.
[0046] A User Equipment (UE) needs to efficiently acquire precoding information to transmit an uplink signal in a Multiple Input Multiple output (MIMO) scheme. Sets of available precoding vectors or precoding matrices are preset in the form of a codebook between a transmitter and a receiver, and a Precoding Matrix Index (PMI) is transmitted as precoding information between the transmitter and the receiver. The precoding matrices of the codebook may be grouped into different subsets according to channel ranks. To help the understanding of such precoding matrix information, a codeword as a transmission unit, a rank, and a stream will first be described in brief.
[0047] In a typical communication system, the transmitter encodes transmission information using a Forward Error Correction (FEC) code prior to transmission so that the receiver may correct channel errors in the received information. The receiver recovers the transmitted information by demodulating the received signal and then FEC-decoding the demodulated signal. During the decoding, the receiver corrects the channel errors in the received signal.
[0048] Every error correction code has its maximum limit in channel error correction. If a received signal has errors beyond the limit of an error correction code, the receiver cannot decode the received signal to error-free information. Accordingly, the receiver needs a criterion by which it determines whether the decoded information has errors or not. Aside from the error correction, a special coding process is required for error detection. In general, a Cyclic Redundancy Check (CRC) is used as an error detection code.
[0049] CRC is one of coding methods for error detection, not for error correction. Typically, the transmitter encodes transmission information with a CRC and then encodes the CRC-coded information with an FER code. The resulting one coded unit is referred to as “codeword”.
[0050] In the mean time, the numbers of rows and columns in a channel matrix H representing channel statuses are determined according to the numbers of Transmission (Tx) and Reception (Rx) antennas. The number of rows is identical to that of Rx antennas, N R and the number of columns is identical to that of Tx antennas, N T . Thus, the channel matrix H is of size N R *N T .
[0051] In general, the rank of a matrix is defined as the minimum of the numbers of independent rows or columns. Accordingly, the rank of the matrix is not larger than the number of rows or columns. For example, the rank of the matrix H, rank(H) is limited as follows.
[0000] rank( H )≦min( N T ,N R ) [Equation 10]
[0052] If the matrix is eigenvalue-decomposed, its rank may be defined as the number of non-zero eigenvalues. Similarly, in case of Singular Value Decomposition (SVD), the rank may be defined as the number of non-zero singular values. Therefore, the rank of a channel matrix physically means the maximum number of different pieces of information that can be transmitted on given channels.
[0053] A different piece of information transmitted in MIMO is referred to as ‘transmission stream’ or shortly ‘stream’. The ‘stream’ may be called ‘layer’. It is thus concluded that the number of transmission streams is not larger than the rank of channels, i.e. the maximum number of different pieces of transmittable information.
[0054] The channel matrix H is determined by
[0000] # of streams≦rank( H )≦min( N T ,N R ) [Equation 11]
[0055] # of streams denotes the number of streams. One thing to be noted herein is that one stream may be transmitted through one or more antennas.
[0056] As stated before, it is assumed that available precoding matrices are preset in the form of a codebook between the transmitter and the receiver. It is also assumed that available subsets of precoding matrices are predetermined according to channel ranks.
[0057] If a subset of precoding matrices with of a specific rank in the codebook includes a subset of precoding matrices with a rank lower than the specific rank, it is said that the codebook satisfies a nested property. Therefore, precoding matrix information for a specific rank may be derived from a subset of precoding matrices with a higher or lower rank.
[0058] Exemplary embodiments of the present invention are based on the assumption that a UE transmits an uplink signal in MIMO in an HARQ system.
[0059] HARQ is a hybrid technology of channel coding and Automatic Repeat reQuest (ARQ) in combination to improve decoding performance by retransmitting an erroneous data block and combining the initial transmission data block with the retransmission data block. HARQ schemes may be categorized according to the regularity of retransmission timings: asynchronous HARQ and synchronous HARQ. The asynchronous HARQ is characterized by a variable retransmission timing, whereas the synchronous HARQ by a preset retransmission timing. Meanwhile, the HARQ schemes are classified into Chase Combining (CC) and Incremental Redundancy (IR) depending on the types of Redundancy Versions (RVs) used for retransmission. In CC, a retransmission data block is identical to a previously transmitted data block, thus resulting in a Signal-to-Noise Ratio (SNR) gain. In contrast, IR achieves a coding gain by retransmitting a data block including data of a different RV from a previous transmission data block.
[0060] The following description is made with the appreciation that an HARQ process unit is referred to as an “HARQ process block”, or simply an “HARQ process” unless it causes obscurity. An Identifier (ID) that identifies an HARQ process is referred to as an HARQ process number.
[0061] Now a detailed description will be made of a method for applying MIMO to uplink signal transmission of a UE according to an exemplary embodiment of the present invention.
[0062] In accordance with the exemplary embodiment of the present invention, it is assumed that the UE acquires precoding information from a scheduling grant signal received from a Node B, for use in uplink signal transmission. In other words, the Node B transmits PMI information and MIMO signal transmission information by a scheduling grant signal to the UE, for use in uplink signal transmission.
[0063] In an asynchronous HARQ system characterized by a variable retransmission timing, the UE needs to receive a scheduling grant signal from the Node B, for every uplink signal transmission. In this case, the UE may acquire precoding matrix information from the scheduling grant signal and precodes an uplink signal based on the precoding matrix information, prior to transmission to the Node B in accordance with the exemplary embodiment of the present invention.
[0064] Meanwhile, a synchronous HARQ system that presets a retransmission timing does not require the UE to receive a scheduling grant signal from the Node B, for each uplink retransmission. Accordingly, there exists a need for a method for efficiently acquiring precoding matrix information that will apply to a particular retransmission HARQ process block, taking into account the feature of the synchronous HARQ system in the UE, which will be described below in detail.
[0065] Further, when the system employs semi-persistent scheduling (SPS), such as the system providing services for VoIP (Voice over Internet Protocol), the BS sets transmission parameters such as RB allocation and MCS semi-statically. In SPS operation, a BS does not transmit scheduling grant signal for initial uplink transmission and may transmit scheduling grant for a retransmission if necessary. Accordingly, there exists a need for a method for efficiently acquiring precoding matrix information that will apply to a particular retransmission HARQ process block, taking into account the feature of the SPS system in the UE, which also will be described below in detail.
[0066] FIG. 3 illustrates methods for transmitting an uplink signal in a MIMO scheme in a UE according to exemplary embodiments of the present invention.
[0067] FIG. 3( a ) illustrates a case of receiving a scheduling grant signal from a Node B, for every uplink transmission in a UE, as in the asynchronous HARQ system, and FIG. 3( b ) illustrates a case of not receiving a scheduling grant signal from a Node B, for an uplink retransmission in a UE, as in the synchronous HARQ system.
[0068] Referring to FIG. 3( a ), the UE may receive a scheduling grant signal from the Node B, for an uplink signal transmission, in step S 301 a . The received scheduling grant signal may include precoding matrix information (e.g. PMI 1 ) for an upcoming uplink signal transmission of the UE. In step S 302 a , the UE may transmit an uplink signal to the Node B using an acquired precoding matrix (e.g. PMI 1 ).
[0069] If the Node B fails to receive the uplink signal in step S 302 a , it may transmit a Negative ACKnowledgment (NACK) to the UE in step S 303 a . At the same time, the Node B may transmit a scheduling grant signal including precoding matrix information (e.g. PMI 2 ) to the UE, for a retransmission of the HARQ process in step S 303 a . Upon receipt of the scheduling grant signal, the UE may retransmit the HARQ process using a precoding matrix (e.g. PMI 2 ) indicated by the scheduling grant signal in step S 304 a.
[0070] The system operating in the manner described in FIG. 3( a ) may be an asynchronous HARQ system. Notably, when a synchronous HARQ system is configured so as to transmit a scheduling grant signal from the Node B to the UE for every uplink retransmission, it may operate in the manner described in FIG. 3( a ) in an exemplary embodiment of the present invention.
[0071] However, when the Node B does not transmit a scheduling grant signal to the UE for every uplink retransmission in the synchronous HARQ system, the following problem may occur.
[0072] Referring to FIG. 3( b ), the UE receives a scheduling grant signal for an initial uplink signal transmission from the Node B in step S 301 b . The scheduling grant signal includes precoding matrix information (e.g. PMI 1 ) for use in the initial uplink signal transmission. As in the asynchronous HARQ system, the UE always receives a scheduling grant signal from the Node B, for an initial uplink transmission in the synchronous HARQ system. Subsequently, the UE may transmit an uplink signal using a precoding matrix (e.g. PMI 1 ) indicated by the scheduling grant signal in step S 302 b.
[0073] If the Node B fails to receive the uplink signal in step S 302 b , it may transmit a NACK to the UE in step S 303 b . The Node B may not transmit a scheduling grant signal to the UE, for retransmission of the HARQ process. Then the UE needs a method for determining precoding matrix information for use in one or more subsequent retransmissions in step S 304 b.
[0074] According to another embodiment of the present invention for the system employing SPS, the Node B does not transmit scheduling grant signal to the UE for initial transmission and may transmit scheduling grant signal to the UE for retransmission signal if necessary. Thus, the UE needs a method for determining precoding matrix information for use in one or more retransmissions, similar to FIG. 3( b ).
[0075] FIG. 4 is a flowchart illustrating a method for acquiring precoding matrix information in a UE, when the UE fails to receive a scheduling grant signal from a Node B according to an exemplary embodiment of the present invention.
[0076] Referring to FIG. 4 , the UE determines whether a scheduling grant signal has been received and a retransmission PMI has been acquired from the scheduling grant signal, for an uplink retransmission in step S 401 . If the Node B transmits a PMI (e.g. PMI 1 ) by a scheduling grant signal for every uplink retransmission even in the synchronous HARQ system as in the foregoing exemplary embodiment of the present invention, the UE may retransmit data using PMI 1 successfully.
[0077] However, if the UE does not receive PMI information for the retransmission from the Node B, it determines whether there is a latest scheduling grant signal including a PMI (e.g. PMI 2 ) for an HARQ process with the same number as a current HARQ process to be retransmitted in step S 402 . In general, a retransmission using a latest received PMI for the same HARQ process may be carried out successfully in MIMO without much performance degradation.
[0078] However, it may occur that there is not a latest received PMI for the same HARQ process. That is, the UE may initiate a new transmission in a different HARQ process during the time period between the initial transmission and the retransmission. Then the UE needs to consider the followings to select a PMI for the retransmission. The PMI selection may vary depending on an algorithm that the Node B uses to calculate a PMI in transmission of a scheduling grant signal.
[0079] First of all, it is assumed that the Node B calculates the same PMI for a total system band (Wide band PMI). In this case, the PMI may not be changed according to the size or position of resources allocated by a Node B scheduler. Thus, the retransmission may be carried out without performance degradation by use of a PMI set in a latest scheduling grant signal indicating a rank identical to the rank of a current retransmission signal.
[0080] Specifically, the UE may determine whether there is a PMI indicated by a latest scheduling grant signal received for a signal of the same rank as a current HARQ process to be retransmitted in step S 403 . If the PMI exists and it equally applies to the total system band, the UE may perform the retransmission using the PMI (e.g. PMI 3 ).
[0081] Meanwhile, the Node B may calculate the same PMI only for a frequency band to be used for the receiver, not for the system band. The PMI is not viable if the size or position of resources indicated by a current scheduling grant signal is changed from that indicated by a previous scheduling grant signal. Even though the size or position of resources is not changed, the same PMI is not available when a rank is different. Thus the UE may use a PMI indicated by a latest scheduling grant signal that allocates the same size or position of resources and/or the same rank.
[0082] Therefore, if a latest received PMI exists for the same-rank signal but the PMI does not apply uniformly to the total system band in step S 403 , the UE additionally determines whether the PMI is for a signal identical to the uplink signal to be retransmitted in the size and position of resources (e.g. frequency band) in step S 404 . If the PMI is for a signal having resources of the same size and position, the UE may perform the retransmission using the PMI (e.g. PMI 3 ). On the other hand, in the absence of the PMI, the UE may perform the retransmission using a PMI (e.g. PMI 4 ) indicated by a scheduling grant signal received for an initial uplink transmission in the exemplary embodiment of the present invention.
[0083] For the most part, a MIMO system performs best when a channel does not change rapidly. If the UE does not receive a scheduling grant signal for a retransmission, it uses the same frequency resources as used for an initial uplink transmission in the exemplary embodiment of the present invention. Therefore, unless a channel changes fast, the use of the PMI used in the initial transmission for a retransmission does not affect performance much.
[0084] Meanwhile, if there is no latest received PMI for an HARQ process of the same rank in step S 403 , the UE uses the PMI (e.g. PMI 4 ) indicated by the scheduling grant signal received for the initial uplink transmission, as illustrated in FIG. 4 . Notably, if a precoding codebook satisfies the nested property, the UE may also use a precoding matrix of the same index under a higher or lower rank. The nested property means that a precoding matrix of a specific rank includes a precoding matrix of a lower rank. When the codebook satisfies the nested property, the UE may use a PMI indicated by a latest scheduling grant signal despite a different rank.
[0085] It may be further contemplated as another exemplary embodiment of the present invention that when a UE does not receive a scheduling grant signal for a retransmission, it uses a PMI preset between the transmitter and the receiver. The PMI may be preset in many ways.
[0086] For example, a predetermined precoding matrix may be selected from a set of precoding matrices of an intended rank. One or more precoding matrices may be selected. In case of selecting a plurality of precoding matrices, the UE uses the PMIs indicating the precoding matrices cyclically in a predetermined order. For instance, the order may be defined as a function of fixed timing such as system timing.
[0087] On the other hand, another embodiment of the present invention, regarding the system using SPS, permits the UE to use the PMI information received via RRC (Radio Resource Configuration) signaling. Node B in the system using SPS does not transmit scheduling grant signal to the UE even for the initial transmission. In this case, the UE cannot acquire the latest PMI information or the like. Thus, the UE according to the present embodiment use PMI information received via RRC signaling, and transmit uplink signal (e.g. VoIP packet) using this information. Additionally, in SPS operation, if UE receives a scheduling grant in a retransmission, UE retransmits using the parameters in the scheduling grant. After receiving a scheduling grant, the method to determine PMI for the subsequent retransmission is the same as the previously explained method.
[0088] As is apparent from the above description, when a UE transmits an uplink signal in MIMO, the UE can efficiently acquire precoding information and transmit the uplink signal based on the precoding information.
[0089] The foregoing exemplary embodiments of the present invention are applicable to a variety of future-generation wireless communication systems using MIMO for uplink signal transmission.
[0090] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. | A method for transmitting an uplink signal at a User Equipment (UE) in a wireless communication system includes receiving, from a Base Station (BS), an uplink scheduling grant for multi-antenna transmission; transmitting the uplink signal precoded using precoding information included in the received uplink scheduling grant to the BS; and retransmitting the uplink signal to the BS according to Acknowledgment/Negative Acknowledgment (ACK/NACK) corresponding to the transmitted uplink signal. The retransmitted uplink signal is precoded using precoding information included in a most recent uplink scheduling grant or a predetermined precoding matrix if an uplink scheduling grant for the retransmission is not received from the BS. | 7 |
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part application of copending application Ser. No. 145,974, filed May 2, 1980, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the water-tight connection of pipes, and, more particularly, to the connection of pipes for low-pressure water systems.
2. Description of the Prior Art
Low pressure water systems, such as used in evaporative coolers, include various types of connections in the water system. For example, evaporative coolers include a reservoir usually connected to a standard water supply. Within the reservoir there is a standpipe to limit the height of the water within the reservoir. The standpipe is connected to the reservoir in a fluid-tight connection. There are many other types of systems which must be connected to a water supply through some type of water-tight connection. There are many other types of systems which must be connected to a water supply through some type of water-tight connection. Most apparatus requiring fluid-tight couplings include threaded fittings, or connections.
Threaded connections for water-tight conduits are typically made of brass, with machined threads externally and internally. A gasket is needed to insure that the threaded connection remains water-tight. Relatively expensive tooling, etc., is required.
Threaded connections may also be made of various types of plastic or polymer materials. External threads may be cut into molds and accordingly machining is not required. However, internal threads are difficult and relatively expensive to make.
A typical use application for a fluid-tight connection is found in evaporative cooler standpipes. The use of galvanized pipe is, or has, given away to the use of plastic pipe for such applications.
Evaporative coolers include a water reservoir and a pump in the reservoir that supplies water to soak cooler pads. The pumped water flows downwardly through the pads by gravity and the excess water returns to the reservoir. To maintain a predetermined amount of water in the reservoir, a source of water is connected to the reservoir. The height of the water in the reservoir is typically controlled by a float valve connected to the input source. However, the float valve may sometimes malfunction, and in such case, the input water keeps flowing into the reservoir, and an overflow pipe is used to drain away the excess water. When the water level reaches the top of the standpipe or overflow pipe, the excess flows into the overflow pipe, and into a hose generally connected to the pipe, which drains away the excess water.
The simplest form of the prior art comprises a vertically extending pipe secured to the bottom pan of an evaporative cooler. The pipe is of a predetermined length, and is simply threaded into some type of bushing or pipe fitting which is in turn connected to a hose. The hose allows the water flowing into the standpipe or overflow pipe to drain away from the evaporative cooler. The vertical height of the pipe is preferably fixed, but it is difficult to consistently provide for the same overflow level due to the threaded engagement of the pipe. Due primarily to the electrical components in the cooler, a predetermined and consistent maximum height or level of the water is highly desirable.
The problem of sealing the standpipes and of adjusting or determining the vertical height of the standpipes are problems which are very real. The threaded engagement of the mating pipes comprises the seal in the prior art. That is, the seal is dependent upon the threads of the pipe fittings.
Another problem is the economics of metal pipe versus plastic pipe. The cost of metal (galvanized steel) pipe, which resists the attack of the corrosive salts in the water, is greater than the cost of plastic pipe, which also is corrosion resistant. However, fabrication of internal threads in plastic pipe is an expensive process.
While plastic pipe has a general cost advantage over galvanized steel pipe, the cost involved in fabricating internal threads within the plastic pipe substantially decreases the attractiveness of plastic pipe as an alternative to galvanized steel pipe.
Another problem of the prior art is the inability to adapt overflow pipes to flat or shallow sloped roofs. If a hose is coupled directly to a pipe, there is a likelihood of kinking which prevents water from running through the hose, and thus blocks the overflow pipe.
The apparatus of the present invention is adaptable to rooofs of varying slopes, and solves the prior art problems of seals and threads, all with plastic material. Moreover, a substantially uniform height of the overflow pipe is consistently obtained.
Of primary importance in evaporative cooler standpipes is a water tight connection of the standpipe and any train line connected to it and a water tight connection with the evaporative cooler housing floor. A threaded connection is used to connect the several components together. In the apparatus of the present invention, both a tapered connection and an internal thread having less than a complete, helical thread length of less than three hundred sixty degrees are used. The parts or elements are made of a plastic or polymer material, amenable to molding techniques.
Threaded connections of various types, involving either a tapered connection or a thread of very few turns, or both, are shown in U.S. Pat. Nos. 2,454,465; 3,281,869; 3,404,540; 3,540,757; 3,749,424; 3,876,234; and 4,212,335.
SUMMARY OF THE INVENTION
The invention described and claimed herein comprises a pipe connection for an overflow pipe and a bushing into which the pipe fits and which includes tapered sections on both of the elements which fit together to effect a seal, and a lock nut having a shutoff type thread which comprises an internal helix of less than three hundred sixty degrees, and a street ell which is secured to the bushing.
Among the objects of the present invention are the following:
To provide new and useful overflow pipe apparatus;
To provide new and useful overflow pipe apparatus for an evaporative cooler system;
To provide new and useful standpipe apparatus having a street ell secured thereto;
To provide new and useful bushing having an internal thread of less than three hundred sixty degrees which mates with external threads;
To provide new and useful adjustable height standpipe apparatus;
To provide a new and useful pipe connection;
To provide a new and useful pipe connection having a pair of tapered surfaces;
To provide a new and useful internally threaded bushing; and
To provide a new and useful threaded connection.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a perspective view of the apparatus of the present invention.
FIG. 2 is a perspective view of the apparatus of the present invention with the elements or components spaced apart from each other.
FIG. 3 is a view in partial section of the apparatus of FIG. 1, taken generally along line 3--3 of FIG. 1.
FIG. 4 is a top view of a portion of the apparatus of the present invention.
FIG. 5 is a view in partial section of the apparatus of FIG. 4, taken generally along line 5--5 of FIG. 4.
FIG. 6 is a fragmentary view in partial section of an alternate embodiment of a portion of the apparatus of the present invention.
FIG. 7 is a view in partial section of a pipe and a bushing spaced apart.
FIG. 8 is a view in partial section of an alternate embodiment of a bushing.
FIG. 9 is a view in partial section of the apparatus of FIG. 1, taken generally along line 9--9 of FIG. 8.
FIG. 10 comprises a perspective view, with a portion broken away, of the apparatus of FIGS. 8 and 9.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 comprises a perspective view of overflow pipe apparatus 10 secured to a bottom or floor 2 of an evaporative cooler. FIG. 2 comprises an exploded perspective view of the overflow pipe apparatus 10 of FIG. 1, and FIG. 3 comprises a view in partial section of the overflow apparatus 10 of FIG. 1, taken generally along line 3--3 of FIG. 1. Included as a component of the overflow pipe apparatus 10 is a nut 70. FIG. 4 comprises a top view of the nut 70, and FIG. 5 is a view in partial section of the nut 70 taken generally along line 5--5 of FIG. 4. For the following general discussion, reference will be made to FIGS. 1, 2, and 3. For discussion of the nut 70, reference will be made to FIGS. 4 and 5 in addition to FIGS. 1, 2, and 3.
Included in the standpipe or overflow pipe apparatus 10 is an overflow pipe or tube 20 which is secured to and within a bushing 40. The bushing 40 is in turn secured to an aperture or hole in the floor 2 by a nut 70. Also secured to the bushing 40, but at the lower portion of the bushing, remote from the overflow pipe 20, and below the floor 2, is an ell 90. The ell is shown only in FIGS. 1 and 3, while the other components of the overflow pipe apparatus 10 are shown in FIGS. 2, 4, and 5 in addition to FIGS. 1 and 3.
The overflow pipe 20 has a hexagonal outer configuration 22, which comprises six vertically extending flats or panels, as best shown in FIGS. 1 and 2. The purpose of the hexagonal outer configuration of the overflow pipe 20 is to allow a wrench, or other appropriate tool, to maintain a hold or grip on the overflow pipe while the apparatus is being secured to the bushing 40.
At the upper portion of the overflow pipe 20 is a top shoulder 24. Extending above the top shoulder 24 is a cylindrical boss 20. The top shoulder 24 comprises a transition between the cylindrical boss 26 and the hexagonal outer portion 22. While the top shoulder 24 extends inwardly from the hexagonal portion 22 to the cylindrical boss 26, a lower shoulder 30 extends outwardly from the lower part of the hexagonal outer portion 22. The top shoulder 24 and the lower shoulder 30 are substantially parallel to each other, but spaced apart by the outer hexagonal portion 22.
An inwardly tapering portion 32, which is of a generally conical configuration, intersects the lower shoulder 30 and extends inwardly and downwardly therefrom. The conical tapered portion 32 extends inwardly and downwardly and terminates in an externally threaded portion 34. The external threads 34 in turn terminate at a bottom 36, best shown in FIG. 3. An interior cylindrical bore 28 extends the full length of the overflow pipe 20.
The bushing 40 includes an upper nut portion 42 and a lower threaded portion 60. The nut portion 42 includes six flats 44 which are connected to each other to define a hexagonal outer portion.
Extending downwardly from a top surface 48 of the nut portion 42 are a plurality of castellated grooves 46. The grooves 46 extend radially with respect to the nut portion of the bushing 40, and intersect the center portion of each of the flats 44, as best shown in FIGS. 1 and 2. The purpose of the castellations or grooves is to help drain the water through the bushing from the reservoir. The pan or floor 2 comprises the bottom of the reservoir, and the top 27 of the pipe 20 comprises the maximum water level of the reservoir. By removing the pipe 20 from the bushing 40, the reservoir may be drained. The castellations allow maximum drainage without removing the bushing 40 and nut 70. As indicated above, the hexagonal outer configuration of the pipe 20 allows the pipe to be conveniently held by a wrench, and likewise the bushing 40, for assembling and disassembling the pipe and bushing.
Parallel to the top surface 48 of the nut portion 42 is a bottom surface 56. An O-ring protrusion 58 extends outwardly (downwardly) from the bottom surface 56. The O-ring protrusion 58 is a circular protrusion which provides a seal against the top surface of a gasket 8, such as a washer or O-ring, disposed on the floor 2, as best shown in FIG. 3.
A tapered bore 50 extends downwardly and inwardly from the top surface 48 of the nut portion 42. The tapered bore 50 is of a generally conical configuration, and its taper is above twelve degrees. It receives and mates with the exterior conically tapered portion 32 of the overflow pipe 20, whose taper is about ten degrees. The interior conical portion 50 intersects with a central cylindrical bore 52. The cylindrical bore 52 is disposed primarily in the lower threaded portion 60. The unequal tapers intersect and seal just above the exterior threads 34 of the pipe 20.
The cylindrical bore 52 includes, at its upper portion, spaced apart slightly downwardly from, but adjacent to, the conically tapered portion 50, a lock thread 54. The lock thread 54 comprises a helically extending ridge on the interior bore 52 which receives the exterior threads 34 of the overflow pipe 20. The lock thread 54 comprises an interior thread which extends arcuately on the interior of the bore 52 slightly less than 360°. The lock thread 54 is thus free of axial overlap and is substantially similar to a lock thread 80 of the nut 70, which will be discussed in detail below, and which is illustrated in detail in FIGS. 4 and 5.
The lower threaded portion 60, and also the cylindrical interior bore 52, terminate in a bottom or lower end 62. It will be noted that the threads 60 extend from the bottom surface 56 of the nut portion 42 to the bottom or lower end 62.
As best shown in FIGS. 1 and 3, the overflow pipe 20 mates with the bushing 40. The lower threaded portion 34 of the overflow pipe 20, which threaded portion defines external threads, extends through the conically tapered bore 50 of the bushing 40 and into the cylindrical bore 52 of the bushing 40. The exterior threads 34 matingly engage the lock thread 54, which comprises the interior thread of the bushing 40. The bushing and the overflow pipe are then threaded together until the exterior conical portion 32 is secured against the interior conical bore 50 of the bushing 40. The mating engagement of the two conically tapered portions provides a positive seal between the overflow pipe 20 and the bushing 40.
In addition to the positive seal between the two elements, the taper lock defined by the juncture of the two conically tapered portions automatically establishes the same height of the overflow pipe, and thus obviates the necessity of a measurement to arrive at substantially the same height each time a unit is assembled. or each time a unit is disassembled, cleaned, and reassembled. Thus, the height of the overflow pipe 20 above the cooler pan floor 2 may be predetermined with substantial accuracy and without the necessity of measuring each time the overflow pipe apparatus 10 is assembled to an evaporative cooler, or to any other type of apparatus which requires a predetermined, relatively constant height for an overflow pipe.
The bushing 40, with the overflow pipe 20 secured thereto, is held in place in an aperture or hole 6 which extends through the floor 2 by a nut 70. The hole 6 is located in a dimple 4 which extends downwardly from the general plane of the pan or floor 2. The purpose of the dimple or recess is to expedite and/or simplify the draining of the water reservoir. As best shown in FIGS. 4 and 5, the nut 70 includes six exterior flats 72. The flats 72 comprise a hexagonal outer portion similar to the hexagonal outer configuration of the nut portion 42 of the bushing 40 and also of the outer configuration 22 of the overflow pipe 20. The hexagonal flats are the typical configuration used for nuts and bolts for convenience of use with an appropriate wrench. The size of the two hexagonal portions of the nut 70 and the nut portion 42 of the bushing 40 are substantially the same, thus allowing for the use of the same size wrench for securing the two elements together.
Above the flats 72 is a top surface 74, and at the bottom of the hex flats 72 is a lower or bottom surface 82. The top surface 74 and the bottom surface 82 are substantially parallel to each other. An O-ring protrusion 76 extends upwardly (outwardly) from the top surface 74 and an O-ring protrusion 84 extends outwardly (downwardly) from the bottom surface 82. The O-ring protrusions 76 and 84 are substantially identical to the O-ring protrusion 56, discussed above in conjunction with the bushing 40. The reason for having the two O-ring protrusions 76 and 84 on the nut 70 is simply for convenience in using the nut. With an O-ring protrusion extending outwardly from both top and bottom surfaces of the nut 70, the nut is substantially vertically symmetrical and accordingly can be used without requiring a particular orientation. The O-ring protrusions 58 and 76 are shown in FIG. 3 disposed against a pair of gaskets 8, making positive seals therewith, or with any similar appropriate flexible seal.
Within the nut 70 is an internal bore 78. The bore 78 is cylindrical and is accordingly substantially perpendicular to both the top and bottom surfaces 74 and 82, respectively. Extending inwardly with respect to the bore 78 is a helically extending lock thread 80. The lock thread 80 comprises an inwardly extending helical ridge which extends about the cylindrical bore 78 a total arcuate distance or length of slightly less than 360°. There accordingly is an arcuate space S between the respective ends of the lock thread 80, as may be seen in FIGS. 2, 4, and 5. The lock thread 80 is thus free of axial overlap.
The thread 80, which comprises an internal thread for the nut 70, engages the external threads 60 of the bushing 40 to secure the bushing to the pan 2. As best shown in FIGS. 1 and 3, the nut 70 is snugged against the bottom surface of the pan 2 to secure the bushing 40 and the overflow pipe 20 securely in place.
It will be noted that the use of the internal lock threads 54 and 80, which are less than 360° of arc in their respective bores, permits the internal threads to be conveniently molded integrally with their respective elements and without the necessity of spiral windings, and the like, which characterized internal threads on molded plastics of the prior art. Moreover, it will also be noted that the employment of the taper lock of the pipe and bushing eliminates the reliance or burden on the threads as a seal. Rather, the seal is effected by the mating engagement of the conically tapered portions of the overflow pipe and the bushing, as discussed above.
For adapting a water cooler to roofs of various slopes or pitches, and particularly with flat roofs or with roofs of a very shallow pitch, the street ell 90 is shown secured to the bottom of the bushing 40. The ell 90 includes a vertical cylindrical portion 92 which extends into the lower part of the interior cylindrical bore 52 of the bushing 40. A shoulder 94 is defined between the cylindrical portion 92 and an elbow 96. The elbow 96 comprises a 90° juncture between the cylindrical portion 92 and a horizontal cylindrical portion 98, best shown in FIG. 1. With the ell 90 is an interior bore 100. The bore 100 is continuous from the vertical cylindrical portion 92 through the elbow 96 and through the horizontal cylindrical portion 98, as best shown in FIG. 3.
It will be noted that the exterior configuration of the cylindrical portion 92 is smooth, and its exterior diameter is substantially the same as the interior diameter of the bore 52. Accordingly, a relatively tight fit occurs between the ell 90 and the bushing 40. Typically, the ell 90 may be cemented to the bushing 40.
As shown in FIG. 3, the interior bore 52 of the bushing 40 includes an interior protrusion 64. The protrusion or ridge 64 comprises a stop to limit the vertical height or distance within the bore 52 that the vertical cylinder 92 of the ell may extend. It will be noted that the ridge 64 has no effect on the mating engagement of the external and internal conical portions 32 and 50, respectively.
As shown in FIG. 1, another ell 110 may be secured to the street ell 90, for connection to a pipe, hose, or the like, to conduct away the water which flows into the overflow pipe 20 from the cooler pan 2 on which the overflow pipe apparatus 10 is secured.
As is well known and understood in the art, an evaporative cooler includes a reservoir of water on the bottom pan and a circulating pump which pumps the water upwardly. The water that is pumped vertically then falls by gravity through pads and the excess water is returned to the reservoir. The reservoir is in turn connected to a water source and the water source flows through a float controlled valve. The valve and float arrangement maintains the water level within the reservoir at a predetermined height. However, in case of a malfunction of the valve, or the like, an overflow pipe is connected to the reservoir to allow the excess water to flow out of the cooler reservoir. The overflow pipe apparatus extends through a hole in the bottom of the reservoir and accordingly must be sealed to prevent water from leaking away from the reservoir. In actuality, two seals are involved, one seal between the cooler and the overflow pipe, and a second seal internally of the overflow pipe.
With the apparatus of the prior art, seals depend primarily on the threads connecting the overflow pipe apparatus together. When the overflow pipe apparatus is to be made of plastic material, the integrity of the threaded seal is questionable. With the apparatus of the present invention, no dependency is made on a threaded seal. Rather, the threads are simply used to secure the various elements of the standpipe apparatus 10 together.
The seal between the elements comprises the mating and sealing engagement of the tapered portions 32 and 50, which is a positive seal held together by the threads. This also obviates the use of an O-ring or gasket between the elements (the pipe and the bushing) of the present invention.
With respect to the seal effected between the standpipe apparatus 10 and the cooler pan 2, a pair of washers 8, as shown in FIG. 3, or other appropriate flexible seal, may be used, as desired. The washers are disposed on opposite sides of the hole or aperture 6 of the pan 2, and about both the pipe 20 and bushing 40. Actually, the lower portion of the bushing 40, below the nut portion 42 and comprising the external threads 60, extends through both washers. The pipe 20 is in turn secured to the bushing 40. A positive contact with the seal is effected by the protrusions on both the bushing 40 and the nut 70. The protrusions make positive contact with the flexible seals throughout a full 360° by putting a positive pressure on them.
For insuring the integrity of the seal between the tapered bore 50 of the bushing 40 and the tapered portion 32 of the pipe 20, it may be desirable to provide an integral peripherally extending sealing element 38 on the tapered portion 32 of the pipe 20. The sealing element 38 is shown in FIG. 6, which comprises a fragmentary view in partial section of a portion of the pipe 20. The sealing element 38 comprises a ridge which extends outwardly and circumferentially or circularly about or on the periphery of the taper 32. The sealing element 38 is preferably disposed or located toward the lower end of the tapered portion 32, spaced slightly above the juncture of the threads 34 and the tapered portion 32.
The sealing element 38 acts as an integral O-ring with respect to the sealing engagement between the mating tapers 32 and 50. The sealing element 38 need not extend or protrude outwardly very far from the conically configured tapered portion 32 in order to effectively perform the function of sealing the bushing and the pipe together at their tapered portions. Rather, it need only extend outwardly a relatively slight distance. Accordingly, it is preferably simply an outwardly extending protrusion which extends circumferentially about the tapered portion 32.
An advantage to having an integral sealing element such as the sealing element 38, rather than a groove and a separate O-ring, is the reduction in parts. Moreover, an integral sealing element does not require the extra step of inserting an O-ring into a groove. Furthermore, the inherent characteristics of the material out of which the standpipe is made lends itself very well to the use of an integral sealing element extending outwardly, as does the element 38, and thereby makes a sealing engagement when the bushing and the pipe are mated together. The pressure of the nut on the external threads of the standpipe provides sufficient force to maintain the sealing engagement between the bushing and the integral seal of the pipe. However, a peripheral groove and an O-ring inserted into the groove may be used as a sealing element, if desired.
While the sealing element 38 is shown in FIG. 6 as being generally rounded, the particular configuration of the element is not critical. The cross-sectional configuration accordingly may be rounded convexly as shown in FIG. 6, or it may be triangular in cross-sectional configuration, or it may have any other appropriate configuration.
FIG. 7 comprises a view in partial section of a pipe 20 and a bushing 120. The bushing and the pipe are spaced apart from each other, as if in preparation for securing the two elements together. The pipe 20 is disposed above the bushing 120, in preparation for its threaded portion 34 to mate with the bushing 120.
The pipe 20 is substantially as described above, particularly in conjunction with FIG. 6, which illustrates the external seal 38. The seal 38 comprises an integral O-ring disposed on the conically tapered portion 32 of the pipe 20. The O-ring 38 is integral with the tapered portion 32 and thus extends outwardly therefrom. When the threads 34 of the pipe 20 are secured to internal threads within the bushing 120, the integral O-ring 38 helps to insure a water-tight seal between the pipe 20 and the bushing 120.
The bushing 120 may be similar to the bushing 40, described above in conjunction with FIGS. 1-3. However, it may be simply a bushing for connecting two lengths of tubing (or pipe) together, with or without external threads. For purposes of FIG. 7, external threads have been omitted from the bushing 120.
The bushing 120 includes an upper, hexagonal nut portion 122 and a lower, stem portion 130. The hexagonal nut portion 122 is generally wider than the lower, stem portion 130. The external configuration of the upper portion 142 is substantially as shown and described above, particularly as shown and discussed in conjunction with FIG. 2, except that the nut portion 122 need not include the castellated groove 46 for purposes of using the bushing 120 as a connector.
A tapered bore 126 extends downwardly and inwardly from an upper surface 124 of the upper, hex nut portion 122 of the bushing 120. The bore 126 extends downwardly and inwardly to join an internal bore 132 which extends through the stem 130 of the bushing 120. The bore 132 is generally cylindrical in configuration. An internal thread 134 extends outwardly into the bore 132. The internal thread 134 is a lock thread, substantially identical to the lock threads 54 and 80 discussed above in conjunction with the embodiments of FIGS. 1-5. The thread 134 extends helically with respect to the bore 132 and is less, circumferentially, than 360°, thus defining a gap or space 136 between the opposite ends of the helical thread 134. It will be noted that the space 136 is offset axially due to the helical nature of the thread 134. The thread 134 is substantially the same as the thread 54 of the bushing 40 and as the thread 80 of the nut 70 of FIGS. 4 and 5.
For joining the pipe 20 and the bushing 120, the external threads 34 at the lower end of the tapering, conical portion 32 of the bushing 20 is inserted through the tapered portion 134 of the bushing 120 and into the bore 132. A mating engagement between the internal thread 134 and the external threads 34 is accomplished in a normal, well-known manner.
The angular extent or external taper of the conical portion 32 is not the same as the angular extent or taper of the bore 126. Measuring upwardly from the horizontal, the angle of the taper of the conical portion 32 is greater than that of the bore 126. Measuring from the vertical, the tapered portion 126 is at a greater angle than the tapered portion 32. The tapered portion 32 accordingly will be drawn downwardly deeper into the bushing 120 to cause an even tighter seal as relative rotation between the pipe 20 and the bushing 120 is effected. It will be noted, as discussed above, that the hexagonal outer configuration 22 of the pipe 20 and the hexagonal configuration of the upper portion 122 of the bushing 120 lend themselves well to the use of appropriate wrenches for securing the pipe 20 and the bushing 120 together.
As the pipe 20 is threaded into the bushing 120, the seal 38 is drawn into a tight, sealing engagement with the tapered bore 126 of the bushing 120 as the tapers 126 and 32 are drawn together. A fluid-tight connection between the pipe and the bushing results.
FIG. 8 is a view in partial section of an alternate embodiment 140 of the bushing 120. A bushing 140 is shown in partial section in FIG. 8 with substantially the same outer configuration as the bushing 120. The bushing 140 includes an upper portion 142 which is preferably of a hexagonal outer configuration to accommodate an appropriate wrench for securing the bushing 140 to a pipe or stem, such as to the pipe 20. The upper, hexagonally configured portion 142 includes an upper surface 144 and an inwardly and downwardly extending conically tapered portion 146.
Beneath the upper portion 142 is a stem 150. The stem 150 includes a cylindrical bore 152 which is connected to the conical portion 146 and extends downwardly therefrom. Within the cylindrical bore 152 is a plurality of thread portions 154. The thread portions 154 extend in a discontinuous manner along the bore 152. The thread portions 154, while discontinuous, are helically arranged and aligned with each other to produce the effect of a continuous thread of greater than 360°. However, the thread portions 154 are spaced apart vertically and angularly to provide a discontinuity within the bore 152 the thread portions 152 and 154 are also free of axial overlap. The discontinuity is shown best in FIG. 9, which comprises a view in partial section of the stem 150 of the bushing 140, taken generally along line 9--9 of FIG. 8. FIG. 10 comprises a perspective view of the bushing 140, in partial section, with a portion broken away, illustrating a discontinuity of the thread portions 154 in the bore 152.
The thread segments 154 extend inwardly with respect to the bore 152, and are spaced apart from each other circumferentially so that there is a slight gap between each segment, as viewed from the top or the bottom of the bushing 140, with respect to the bore 152. This is best shown in FIG. 9. The overall helical extent of the thread 154 may provide the effect of several continuous threads, such as two or three threads, depending on the linear extent of each thread segment or element and the desired spacing between the elements.
The effect of the discontinuity with respect to the thread elements 154 produces substantially the same overall result for the embodiment of FIGS. 8 and 9 as is produced by the continuous lock thread 134 of FIG. 7 and the continuous lock threads 54 and 80 of FIGS. 1-5, as discussed above. However, the advantage of the embodiment of the apparatus of FIG. 9 over that of FIG. 7, and of the other, continuous thread elements, is that less than a single helical thread is produced by the apparatus shown in FIGS. 1-5 and 7, while the effect of more than one, or two or three, threads, axially, is produced by the bushing of FIGS. 8 and 9. However, the internal thread of the bushing or nut is amenable to molding techniques for mass production purposes, which is generally not possible with internal threads of the prior art.
It will be noted that in FIGS. 8 and 9 a bushing 140 is illustrated. However, the same type of discontinuous internal thread portions 154 are applicable to the nut, such as illustrated in FIGS. 4 and 5, as compared with the single, continuous thread 80 illustrated therein. The overall effect of the lock thread of less than a single, 360° extent is still applicable, whether the internal thread be in a nut or in a bushing.
Referring again to FIGS. 2, 3, 6, and 7, it will be noted that the threads 34 on the lower stem of the pipe 20 begin at the lower portion of, and adjacent to, the exterior conical portion of the pipe. Depending on the placement of the interior thread on the bore of the bushing or nut to which the pipe is to be secured, the longitudinal extent of the exterior threads on the lower stem of the pipe may or may not be of substantial importance. For example, it will be noted that in the bushings illustrated in FIGS. 2, 3, 7, and 8, and in the nut illustrated in FIGS. 4 and 5, the interior thread is disposed within the cylindrical bores downwardly from the top of the bore. In the case of the bushings, the thread is spaced downwardly from the internal conical portion. With respect to the nut of FIGS. 4 and 5, the internal thread is about centered in the bore of the nut.
With respect to the bushings, if the internal thread were located closer to the juncture of the internal conical portion in the cylindrical bore, the extent of the exterior threads on the mating pipe stem would be of more importance, even to the extent of becoming of prime importance with respect to the securing of the pipe and the bushing together. Since in each case, as illustrated in the Figures, the internal thread extends for a total circumferential distance of less than 360°, the entire thread, or all of the thread segments or elements, as in the embodiment of FIGS. 8 and 9, must preferably be engaged with the exterior threads of the mating pipe. The exterior threads on the mating pipe should extend a sufficient axial length to fully engage the interior thread segments for properly securing the two mating elements together.
While the principles of the invention have been made clear in illustrative embodiments, there will be immediately obvious to those skilled in the art many modifications of structure, arrangement, proportions, the elements, materials, and components used in the practice of the invention, and otherwise, which are particularly adapted for specific environments and operative requirements without departing from those principles. The appended claims are intended to cover and embrace any and all such modifications, within the limits only of the true spirit and scope of the invention. This specification and the appended claims have been prepared in accordance with the applicable patent laws and the rules promulgated under the authority thereof. | Two pipes for low pressure water systems include a pair of tapering surfaces secured together by a threaded engagement in which the thread of one member extends helically for less than three hundred sixty degrees. | 5 |
FIELD OF THE INVENTION
[0001] The invention relates to a membrane for an electroacoustic transducer having a first area, a second area, which is arranged for translatory movement in relation to said first area, and a third area, which connects said first area and said second area. The invention furthermore relates to a transducer comprising an inventive membrane and a device comprising an inventive transducer.
BACKGROUND OF THE INVENTION
[0002] The ever decreasing size and increased complexity of current devices lead to certain consequences for an inbuilt transducer. To optimize the ratio between space needed inside the device and sound-emanating area, speakers are more and more rectangular or oval instead of circular for example. Whereas circular speakers are fully symmetrical, rectangular and ovals speakers comprise some asymmetries which in turn lead to poor sound quality, which is to improved.
[0003] FIGS. 1 a and 1 b show a first (left half) and a second (right half) embodiment of a rectangular prior art speaker 1 with rounded corners, FIG. 1 a in top view, FIG. 1 b in a cross-sectional view. Speaker 1 comprises a membrane 2 , a coil 3 attached to said membrane 2 , a magnet system 4 interacting with coil 3 and a housing 5 for carrying aforesaid parts. The membrane 2 of the second embodiment additionally comprises corrugations 6 .
[0004] The membrane 2 is divided into a first area A 1 , a second area A 2 , which is arranged for translatory movement in relation to said first area A 1 , and a third area A 3 , which connects said first A 1 and said second area A 2 . Furthermore, a closed line L is shown, which is arranged within said third area A 3 and encompasses said second area A 2 . As said line L is parallel to the outer border of the rectangular speaker 1 with rounded corners or the identically shaped membrane 2 respectively, it comprises four straight sections a with four curved sections b in-between. Furthermore, two directions are shown in FIGS. 1 a and 1 b . First, a direction of translatory movement DM, which is parallel to the axis of the speaker 1 and which indicates the direction of movement of said second area A 2 . Second, a direction DL of said line L, which is obvious for the straight sections a and which is the tangent to said line L in the curved sections b. Line direction DL and translatory movement direction DM are perpendicular to each other in each point of said line L. FIGS. 1 a and 1 b only show 2 examples of such pairs, one situated in a straight section a and one in a curved section b (not shown in FIG. 1 b ).
[0005] The first area A 1 in the present example is the border of the membrane 2 , which is connected to the housing 5 and therefore immovable with respect to the housing 5 . Said second area A 2 is the area inside the outer border of coil 3 in the present example. Second area A 2 therefore covers the joint face between coil 3 and membrane 2 as well as the so-called dome. Said second area A 2 may translatorily move in relation to first area A 1 . Other movements, which occur in a real and thus non-ideal speaker, such as rocking, bending and a certain side movement are disregarded for the further considerations. Second area A 2 is therefore considered to move as a whole, which means that it does not change its shape.
[0006] Third area A 3 now connects said first A 1 and said second area A 2 . Since said second area A 2 moves in relation to said first area A 1 , said third area A 3 changes its shape. In the straight sections a there is a simple rolling movement, which means that there are no movements in line direction DL inside the membrane 2 . A completely different situation exists in the curved sections b. Here a movement of the membrane 2 in translatory movement direction DM causes a relative movement in line direction DL inside the membrane 2 . This relative movement is caused by a change of radius of the curved sections b which in turn is caused by the translatory movement of second area A 2 .
[0007] The problem addressed is well known in the prior art, why usually corrugations 6 as the second embodiment of speaker 1 has are put in the curved sections b so as to allow aforesaid relative movement in line direction DL. The exact physical explanation is, that the planar spring constant psc, which is in line direction DL, has decreased. So normally the planar spring constant psc in a curved section b is lower than in a straight section a. However, it has been found out that simply putting corrugations 6 into curved sections b is not sufficient for a satisfying function of a speaker, which is explained in more detail in the following section.
[0008] Reference is therefore made to FIG. 2 a , which shows a graph of the planar spring constant psc and the translatory spring constant tsc of aforesaid prior art membranes 2 along a quarter of said line L, hence sweeping half of a straight section a of the long side of membrane 2 , a curved section b, and half of a straight section a of the small side of the membrane 2 . The planar spring constant psc is in line direction DL and the translatory spring constant tsc is in translatory movement direction DM as mentioned before.
[0009] The solid lines show parameters for the first embodiment of the prior art membrane 2 with no corrugations. Here the planar spring constant psc is more or less constant provided that the membrane 2 is homogeneous. As a result, the translatory spring constant tsc is dramatically increased in the corners of the membrane 2 or in the curved sections b respectively which in turn leads to some unwanted consequences:
warping of membrane 2 , which in turn leads to distorted sound reproduction as well as to increased local loads on the coil 3 . This might damage the coil 3 , in particular in case of a so-called self supporting coil; decreased stroke of membrane 2 , which in turn leads to reduced volume or poor efficiency respectively; local peak loads within membrane 2 , which in turn leads to buckling or breaking of membrane 2 .
[0013] The dashed lines now show parameters for the membrane 2 having corrugations 6 in the curved sections b. Thus the planar spring constant psc shows a step down in the curved section b. The corrugations 6 are well designed, so that the translatory spring constant tsc in the middle of the curved section b has the same value as in the straight sections a. So one could believe that the problem is solved therewith, which was obviously a doctrine in speaker design. However, there is an unpredictable rise and drop in the graph of the translatory spring constant tsc at the border between the straight sections a and curved sections b, which again leads to the addressed consequences. This is because of the interaction between the straight sections a and curved sections b. If the third area A 3 is theoretically split into separate straight sections a and curved sections b, the associated deformations will be different when the second area A 2 moves. But because the straight sections a and the curved sections b are interconnected at their edges, said interaction and in turn an influence of the translatory spring constant tsc occur. More recent investigations have revealed this unwanted effect.
[0014] It should be noted that there are some further embodiments of prior art membranes comprising complex structures of bulges and corrugations in different embodiments, which are difficult to manufacture and which do not sufficiently solve the objects addressed above either.
OBJECT AND SUMMARY OF THE INVENTION
[0015] It is an object of the invention to provide a membrane of the type mentioned in the first paragraph and a transducer of the type mentioned in the first paragraph, and a device of the type mentioned in the first paragraph which obviate the drawbacks described hereinbefore.
[0016] To achieve the object described above, a membrane for a transducer as characterized in the opening paragraph is disclosed, wherein local, planar spring constants along a closed line, which is arranged within said third area encompassing said second area, each in the direction of said line are determined in such a way that local, translatory spring constants along said line each in a direction of said translatory movement are substantially constant or exclusively have substantially flat, mutual changes.
[0017] The object of the invention is further achieved by a transducer comprising an inventive membrane and by a device comprising an inventive transducer.
[0018] In this way the performance of a membrane is dramatically increased. Since there are no or no substantial changes of the translatory spring constant along aforesaid line, the warping of the membrane is decreased, the stroke of the membrane is improved, and local peak loads on the membrane are avoided which results in improved sound reproduction, improved efficiency and improved lifetime.
[0019] More recent investigations have surprisingly shown, that simply putting corrugations in the curved sections of a membrane only is not sufficient for a satisfactory quality of a transducer. With various experiments and computer simulations it has been found, that there are unexpected differences of the translatory spring constants, even when the membrane comprises corrugations in its curved sections. This is even the case when said corrugations would provide satisfactory performance for a circular membrane, meaning that cutting a circular membrane with a perfect arrangement of corrugations in four quarters and putting them in the corners of a rectangular membrane with rounded corners does not lead to a perfect rectangular membrane.
[0020] It is advantageous, when said local, planar spring constants along each closed line, which is arranged within said third area encompassing said second area, each in the direction of said line are determined in such a way that local, translatory spring constants along said line each in a direction of said translatory movement are substantially constant or exclusively have substantially flat, mutual changes. Here the inventive characteristics are applied to the whole third area, meaning that the translatory spring constants are equalized over the whole third area. Hence the performance of the membrane is further improved.
[0021] An advantageous embodiment of the membrane is achieved, when the ratio between the highest translatory spring constant and the lowest translatory spring constant does not exceed 1.5. A further advantageous limit for said ratio is 1.3. Finally, it is very advantageous, when said ratio does not exceed 1.1. In this way the translatory spring constants are held within a certain bandwidth, thus allowing certain variations around a constant value. Therefore the design of a membrane is simplified, since the requirements are less strict.
[0022] A further advantageous embodiment of the membrane is achieved when a relative translatory spring constant is defined as the ratio between a translatory spring constant and the lowest translatory spring constant, wherein the relative length is defined as the ratio between a length and the total length of said line, and wherein a differential slope of said relative translatory spring constant over said relative length does not exceed 100. A further advantageous limit for said differential slope is 50. Finally, it is very advantageous, when said differential slope does not exceed 20 in any point of said line. In this way the difference between adjacent translatory spring constants is held within a certain bandwidth, thus allowing only slow changes. Therefore, steps or fast changes of the translatory spring constants along said line are avoided, which results in reduced peak loads within the membrane and in turn to a longer life time. It should be noted at this point that the aforesaid limits are related to the macroscopic graph of the translatory spring constant. A possibility to generate a “macroscopic graph” is to take discrete values of translatory spring constant, for instance in the middle of each corrugation, that is to say, at its highest point and to interpolate values in between. But it is also imaginable to determine the differential slope by means of two adjacent discrete values.
[0023] It is of advantage, when said line is substantially parallel to the border of said third area. Therefore, a simple definition of the location of the line is given and a homogeneous load on the coil (when considering the border with the second area) and/or on the housing (when considering the border with the first area) is achieved at the same time.
[0024] It is further advantageous, when said third area is ring-shaped and said line is the centerline of said third area. This is an additional simple definition of the line, also achieving homogeneous loads on the coil as well as on the housing.
[0025] A very advantageous embodiment of an inventive membrane is achieved, when said planar spring constants are determined by variation of a thickness of said membrane. This is an easy measure to achieve equalized translatory spring constants, as a rectangular membrane for example usually has to be softer in the corners and as a membrane more or less automatically gets thinner in the corners during the ironing process. But also besides this particular example of controlling the thickness is an advantageous parameter to achieve the inventive object, in particular when a membrane is die cast.
[0026] A very advantageous embodiment of an inventive membrane is further achieved when said membrane comprises corrugations, wherein said planar spring constants are determined by variation of shape of said corrugations. Corrugations are quite common means for allowing elongation and compression of the membrane in curved sections. Therefore, it is comparably easy to adapt the well known corrugations to the inventive object. In most cases corrugations alone are sufficient to achieve equalized translatory spring constants, so that additional structures such as bulges may be avoided, which significantly simplifies the manufacturing of a membrane, in particular the manufacturing of a corresponding mold.
[0027] Yet another very advantageous embodiment is achieved when said planar spring constants are determined by variation of depth, density, length, radius, and/or width of said corrugations. These are advantageous parameters of a corrugation to influence the planar spring constant of a membrane or its compliance respectively. The deeper, the longer, and the denser corrugations are the more compliant a membrane is, meaning that its planar spring constant is reduced. In contrast, a membrane is stiffer, meaning that its planar spring constant is increased, the wider a corrugation or the greater the radius at the bends of a corrugation is.
[0028] Finally, it is of particular advantage when said line comprises straight sections and curved sections and wherein said variation of said corrugations or of said membrane is situated in said curved sections as well as at least partly in said straight sections. It has been found out that it is not sufficient for a satisfactory quality of a membrane to put corrugations only in the curved sections or to make the membrane thinner therein. These measures rather have to extend into the straight sections, which is very surprising, because in the straight sections there is a simple rolling movement, which means that there is no relative movement in line direction within the membrane, as already stated above. Hence prior art transducers do not comprise corrugations in the straight sections since this is not necessary due to kinematic reasons and since corrugations in straight section rather hinder the rolling movement. Contrary to the known doctrine it has been found out that corrugations advantageously extend into straight sections due to mechanical reasons.
[0029] These and other aspects of the invention are apparent from and will be elucidated with reference to the embodiments described hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] The invention will be described in greater detail hereinafter, by way of non-limiting example, with reference to the embodiments shown in the drawings.
[0031] FIGS. 1 a and 1 b show two embodiments of rectangular prior art speakers;
[0032] FIG. 2 a shows a graph of the planar and the translatory spring constant of prior art membranes;
[0033] FIG. 2 b shows the correlation between membrane parameters, the planar and the translatory spring constant for an inventive membrane;
[0034] FIG. 2 c is a diagram similar to FIG. 2 b for another inventive membrane;
[0035] FIG. 3 shows how a differential slope of a relative translatory spring constant over a relative length may be calculated;
[0036] FIG. 4 shows the planar and the translatory spring constant along a line joining first area and second area;
[0037] FIG. 5 a shows four embodiments of an inventive membrane;
[0038] FIG. 5 b shows another four embodiments of an inventive membrane;
[0039] FIGS. 6 a to 6 f show variations of corrugations.
[0040] The Figures are schematically drawn and not true to scale, and the identical reference numerals in different figures refer to corresponding elements. It will be clear for those skilled in the art that alternative but equivalent embodiments of the invention are possible without deviating from the true inventive concept, and that the scope of the invention will be limited by the claims only.
DESCRIPTION OF EMBODIMENTS
[0041] FIG. 5 a shows a first set of four possible embodiments of an inventive membrane 2 ′ comprising corrugations 6 , each embodiment in one of four quadrants I to IV. In a first quadrant I the length of corrugations 6 is varied, wherein all corrugations 6 start at the inner border of third area A 3 . In a second quarter II again the length of corrugations 6 is varied, but in contrast to the first embodiment the corrugations 6 are arranged in the middle of third area A 3 . In a third quadrant III the density of identical corrugations 6 is varied. Finally, the width of equally spaced corrugations 6 is varied in a fourth quadrant IV. It should be noted that the corrugations 6 are not arranged in the curved section b only, but also extend into the straight sections a.
[0042] FIG. 5 b shows another set of four possible embodiments of an inventive membrane 2 ′ comprising corrugations 6 , each embodiment again in one of four quadrants I to IV. Here the kind of corrugations 6 is the same for all four quadrants I-IV. This Figure is to show that the invention does not only apply to rectangular speakers 1 with rectangular coils 3 , but also to rectangular speakers 1 with cylindrical coils 3 (first quadrant I), to elliptical speakers 1 with cylindrical coils 3 (second quadrant II), to elliptical speakers 1 with elliptical coils 3 (third quadrant III), and finally, to rectangular speakers 1 with elliptical coils 3 (fourth quadrant IV).
[0043] Further variations of corrugations 6 are shown in FIGS. 6 a to 6 f , all showing an unrolling of a cross section along line L, sweeping a part of a straight section a, a curved section b, and a part of a straight section a. All FIGS. 6 a to 6 f show an arrangement of corrugations 6 that decrease the planar spring constant psc in and around the curved section b.
[0044] FIG. 6 a simply shows that a membrane 2 ′ may continuously be made thinner in the curved section b. FIG. 6 b shows that the width wid of equally spaced corrugations 6 is varied. The smaller the width wid, the smoother the membrane 2 ′, meaning that its planar spring constant psc is decreased. Yet another embodiment is shown in FIG. 6 c . Here the depth dep of equally spaced corrugations 6 is varied for the same reason. FIG. 6 d furthermore shows that the density den of corrugations may be varied so as to decrease the planar spring constant psc in the curved sections b. Here the space (reciprocal value of density den) between identical corrugations is different. Yet another possibility is shown in FIG. 6 e , where the shape, in particular the radius rad of each corrugation 6 , is varied. The smaller the radius rad, the lower the planar spring constant psc. FIG. 6 f finally, shows a combination of all previous embodiments. Here the thickness of the membrane 2 ′, the width wid, the depth dep, the density den as well as the radius rad of corrugations 6 is varied, so as to end in a further decrease of the planar spring constant psc in the curved section b.
[0045] It should be noted that the invention is not restricted to a single embodiment ( FIG. 6 a - FIG. 6 e ) or to the combination shown ( FIG. 6 f ), but rather any combination of aforesaid embodiments is possible in principle. It is also imaginable that two opposed embodiments are combined. As an example a membrane 2 ′ is mentioned, which is very thin in the corners or curved sections b after the ironing process. It is assumed that it is so thin that at least some translatory spring constants tsc in the curved sections b are smaller than in the straight sections a thus reversing the inventive object. In this special case the planar spring constants psc have to be increased in those areas. So taking the length len of corrugations 6 as an example and assuming that the minimum of the translatory spring constants tsc is situated in the middle of said curved sections b, the length len of the corrugations 6 is decreased around said middle, contrary to the arrangements shown in FIGS. 3 a and 3 b.
[0046] To explain the consequences of such an arrangement of corrugations 6 shown in FIGS. 5 a - 5 b and 6 a - 6 f , reference is now made to FIG. 2 b , which shows certain parameters of membranes 2 ′ along a quarter of said line L similar to the diagram shown in FIG. 2 a . Hence again half a straight section a of the long side of membrane 2 ′, a curved section b, and half a straight section a of the small side of the membrane 2 ′ is swept. FIG. 2 b shows planar spring constant psc, which is in line direction DL, and the translatory spring constant tsc, which is in translatory movement direction DM.
[0047] To obtain a constant translatory spring constant tsc along line L as it is shown in FIG. 2 b , the planar spring constant psc should have the graph shown, having a smooth depression in and around the curved section b. This means that the membrane 2 ′ should be softer in the corners or curved sections b respectively. The exact graph has to be calculated by means of computer simulation using the finite elements method. Consequently, the density den, the depth dep, or the length len of corrugations 6 has to be increased in and around the curved section b. Alternatively, the width wid, the radius rad of corrugations 6 as well as the thickness of the membrane 2 ′ has to be decreased in and around the curved section b. It should be noted that the diagram is simplified for the sake of brevity, meaning that of course the graphs for the depth dep and the length len for example might be different for obtaining the same graph for the planar spring constant psc. So the diagram shows general principles (e.g. the lower the depth dep is, the lower the planar spring constant psc is) but no exact values.
[0048] The solid thin lines show the optimum graph for a certain characteristic of a corrugation 6 or the membrane 2 ′ respectively. Obviously the graph for the density den for example cannot continuously change as a corrugation 6 has a finite size. In other words: Only a certain finite number of corrugations 6 fit onto a membrane 2 ′ so that only a certain finite number of changes of the planar spring constant psc may be achieved. As a first approximation, steps are shown in the graphs (solid bold lines). The only exception is the thickness of the membrane 2 ′. Of course it may continuously change. As a further consequence, also the translatory spring constant tsc does not have the same value in every single point of the line L. The graph rather shows small bumps, caused by the finite number of corrugations 6 . So the translatory spring constants tsc along said line L are constant in the inventive sense, when they are macroscopically constant, meaning that bumps cannot be avoided on the grounds addressed above. Concluding the translatory spring constants tsc has to stay between a certain lowest translatory spring constant ltsc and a certain highest translatory spring constant htsc.
[0049] FIG. 2 c now shows another diagram similar to that shown in FIG. 2 b . Here the desired graph for the planar spring constant psc which would be necessary for obtaining a constant translatory spring constant tsc shows a dramatic depression in the curved section b (solid line). It is now assumed, that even a combination of every possibility to decrease the planar spring constant psc is not sufficient to obtain the desired graph. Hence at least flat slopes for the graph of the translatory spring constant tsc are aimed at. The result can be seen in FIG. 2 c . Indeed the translatory spring constants tsc (solid line) are not constant but the changes are far smoother than those of a prior art speaker as shown in FIG. 2 a.
[0050] FIG. 2 c furthermore shows the case of a membrane 2 ′, which is too thin in the corners due to the ironing process as addressed above, where it is assumed that the minimum of the translatory spring constants tsc is situated in the middle of said curved sections b. The desired graph for the planar spring constant psc (dashed line) shows two depressions around one elevation. Hence the length len of corrugations 6 (dashed line) slowly increases coming from the straight sections a but decreases again in the middle of the curved section b. As a result the translatory spring constants tsc (dashed line) are constant along the line L. It should be noted that in FIG. 2 c as well as in FIG. 2 a any steps, caused by the finite number of corrugations 6 , are omitted for the sake of brevity. However, in reality finite corrugations 6 cause a ripple in the graph of the translatory spring constants tsc also in these examples.
[0051] FIG. 3 now shows how a differential slope of a relative translatory spring constant tscrel over said relative length lrel may be calculated. First, a relative translatory spring constant tscrel is defined as the ratio between a translatory spring constant tsc and the lowest translatory spring constant ltsc. Therefore, the x-axis crosses the y-axis at 100% which means that this is the lowest value of a translatory spring constant tsc along a line L. It is further assumed that the bump shown is the highest along said line. So also the ratio between highest translatory spring constant htsc and lowest translatory spring constant ltsc, here 120%, is shown in FIG. 3 . Second, a relative length lrel of said line L is defined as the ratio of a length and the total length of said line L. FIG. 3 only shows a small cutout of about 2.5% of the overall length of said line L. Now the differential slope of said relative translatory spring constant tscrel over said relative length lrel may be calculated. Therefore the difference of two relative translatory spring constants Δtscrel and the difference of two relative length Δlrel is taken to calculate the differential slope
[0000]
Δ
tscrel
Δ
lrel
=
tsc
2
1
tsc
-
tsc
1
1
tsc
l
2
1
tot
-
l
1
1
tot
=
tsc
2
-
tsc
1
l
2
-
l
1
·
1
tot
1
tsc
[0000] wherein tsc 1 and tsc 2 are two (absolute) values of the translatory spring constant tsc, ltsc is the lowest translatory spring constant ltsc as mentioned before, l 1 and l 2 are two (absolute) values of a length and ltot is the total length of said line L. In the example shown the differential slope is about
[0000]
Δ
tscrel
Δ
lrel
=
4
%
0.2
%
=
20
[0000] It should be noted at this point that the graph of FIG. 3 is a macroscopic view of the relative translatory spring constant tscrel, which means that variations within a corrugation 6 are not shown. For example discrete values each in the middle of a corrugation 6 are taken and interpolated in between, thus resulting in a graph shown in FIG. 3 . Similarly, discrete values at the highest or lowest elevation of each corrugation 6 may be taken.
[0052] FIG. 4 finally, shows a diagram for the planar spring constant psc and the translatory spring constant tsc along a joining line, joining first area A 1 and second area A 2 . In the following example it is assumed that said joining line is perpendicular to the line L, which encompasses the second area A 2 . The first area A 1 is the mounting portion of the membrane 2 ′, where the membrane 2 ′ is joined to a housing 5 and the second area A 2 is the portion of the membrane 2 ′, where the membrane 2 ′ is joined to a coil 3 . As the housing 5 and the coil 3 are assumed to be quite stiff, at least compared to the membrane 2 ′, the planar spring constant is nearly infinite at the border area between first A 1 and third area A 3 or second A 2 and third area A 3 respectively. In between it is softer and has a certain value, which is highly influenced by the measures taken as described before (see FIGS. 5 a - 5 b , 6 a - 6 f ). The translatory spring constant tsc is infinite as well at the border between first A 1 and third area A 3 as the third area A 3 may not move in relation to the first area A 1 at the border. Over the joining line the value for the translatory spring constant tsc decreases and reaches a certain value at the border between second A 2 and third area A 3 . This value is relevant for designing the coil 3 , as a current through said coil within the magnet system 4 causes a force to occur which in turn causes a movement to occur of the second area A 2 according to said value of the translatory spring constant tsc. Accordingly, the translatory spring constants tsc which are aimed to be constant or to have substantially flat, mutual changes may be at the border between second A 2 and third area A 3 and not necessarily on a line L, where the planar spring constant psc is varied.
[0053] It should be noted that—although reference is mostly made to speakers—the invention similarly relates to microphones. The only difference it the way of action and reaction. Whereas a current causes sound waves in the case of a speaker, a sound wave causes a current in the case of a microphone. But the kinematic and mechanic principles are the same for both devices.
[0054] It finally, should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be capable of designing many alternative embodiments without departing from the scope of the invention as defined by the appended claims. In the claims, any reference signs placed in parentheses shall not be construed as limiting the claims. The word “comprising” and “comprises”, and the like, does not exclude the presence of elements or steps other than those listed in any claim or the specification as a whole. The singular reference of an element does not exclude the plural reference of such elements and vice-versa. In a device claim enumerating several means, several of these means may be embodied by one and the same item of hardware. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. | A membrane ( 2′ ) for an electroacoustic transducer ( 1 ) is disclosed having a first area (A 1 ), a second area (A 2 ), which is arranged for translatory movement in relation to said first area (A 1 ), and a third area (A 3 ), which connects said first (A 1 ) and said second area (A 2 ), wherein local, planar spring constants (psc) along a closed line (L) within said third area (A 3 ) encompassing said second area (A 2 ), are determined in such a way that local, translatory spring constants (tsc) along said line (L) in a direction (DM) of said translatory movement are substantially constant or exclusively have substantially flat, mutual changes. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention concerns an arrangement for mounting a parallel-guiding device in a force measuring apparatus, particularly in a balance. A load receiver formed by a first leg of the parallelogram in the parallel-guiding device and serving to receive the load to be measured is guided in parallel motion relative to a second leg of the parallelogram by two mutually parallel guide links that are rigid in their lengthwise direction but elastically flexible to bend in the plane of the parallelogram. The second leg of the parallelogram has a fastening area serving to mount it on a supporting part of the force-measuring apparatus, and it also has a portion that projects into the space inside the parallel-guiding device that is delimited by the two guide links. In the direction transverse to the plane of the parallelogram, the parallel-guiding device is delimited by two lateral boundary surfaces that are parallel to the plane of the parallelogram, with the legs of the parallelogram and the guide links extending between them.
2. Description of the Related Art
In mounting arrangements of this kind, the fastening area of the stationary second leg of the parallelogram has to take up the entire moment generated by the force that is to be measured and that acts on the first leg of the parallelogram. This can cause deformations of the parallel-guiding device. In addition, the mounting attachment of the second leg of the parallelogram at its fastening area can introduce stresses into the parallel-guiding device and into parts connected to it. The deformations as well as the mounting stresses can be detrimental to the measuring accuracy.
In a known arrangement of the kind named at the beginning (DE 43 05 425 A1), the stationary as well as the movable leg of the parallelogram have the shape of a hollow profile whose cross-section in the plane of the parallelogram is triangular. The respective sides of the triangle of the stationary and of the movable leg of the parallelogram that extend in the lengthwise direction of the guide links toward the outside of the parallel-guiding device serve as mounting surface to a base plate of the balance and as fastening support for a weighing pan, respectively. Through this sturdy design of the two legs of the parallelogram in the shape of hollow profiles and through the associated mounting geometry, it is possible, admittedly, to alleviate the problems of stress introduction and deformation. However, this design configuration is space-consuming and requires a relatively large amount of material.
Also known (EP 0 573 806 A1) is a design where, in order to reduce unwanted stresses, the block-shaped measuring cell of a force-measuring apparatus is arranged between the two legs of a stiff U-profile that extend parallel to the main planes of the block. By one of its lateral surfaces extending between the main planes of the block, the measuring cell is attached to the bottom portion of the U that connects the two legs. But here, too, the U-profile represents a relatively expensive component. Also, exacting requirements need to be imposed on the lateral surface of the measuring cell that serves for the mounting attachment and on the inside of the U-profile that is in contact with it.
SUMMARY OF THE INVENTION
Therefore, the object of the present invention is to provide a mounting arrangement of the kind named at the beginning that, on the one hand, is simple and inexpensive to manufacture and, on the other hand, deteriorates the measuring accuracy as little as possible.
According to the invention, the problem is solved by arranging the fastening area on that portion of the second leg of the parallelogram that projects into the space inside the parallelogram.
The inventive mounting arrangement conserves space. Also, it does not require expensive work operations on the second leg of the parallelogram that comprises the fastening area. Likewise, no expensive profile component is needed for mounting the parallel-guiding device. Finally, the location chosen for the fastening area in the inventive fastening arrangement is advantageous with regard to the moment generated by the force to be measured, as well as with regard to limiting the undesirable stress introduction.
As a preferred embodiment of the invention, the fastening area is located on a portion projecting between the lateral boundary surfaces into the space inside the parallelogram in a surface part that faces one of the guide links. The guide link next to that surface part has an opening opposite the fastening area through which passes that portion of the supporting part that has an area where it is connectively engaged to the fastening area.
Because the guide links extending between the lateral boundary surfaces parallel to the plane of the parallelogram are opposite the transverse surface areas (relative to the plane of the parallelogram) of the portion that projects into the interior space, the mounting attachment provided in this embodiment traverses one of the guide links. Therefore, the respective guide link is equipped with an opening that allows the passage of the portion of the supporting part that serves for the mounting attachment. Although this opening weakens the guide link to a certain extent, this drawback is offset by the advantages that the mounting arrangement is exceptionally space-saving, that the place on the parallel-guiding device where the mounting portion of the supporting part is joined to the transverse surface area (relative to the plane of the parallelogram) of the portion that projects into the interior space can be kept small, and that it does not require a special operation in the manufacturing process.
In this context, as a further practical refinement of the design, the fastening area and the portion of the supporting part that is joined to it are clamped together with at least one threaded bolt that is engaged in a tapped hole of the portion of the second leg and extends parallel to the plane of the parallelogram. In this configuration, the parallel-guiding device has enough space between its two guide links in the axial direction of the threaded bolt to allow the threaded bolt to be securely anchored in the portion that projects into the interior space.
Deviating from this design, the fastening area and the portion of the supporting part that is joined to it are clamped together with at least one threaded bolt that is engaged in a tapped hole of the supporting part and extends parallel to the plane of the parallelogram. The head of the bolt is arranged in a recess of the portion that projects into the interior space, and the shaft of the bolt passes through a part of the portion that extends from the recess to the transverse surface area. In this configuration, the tapped hole is in the supporting part rather than in the portion of the parallel-guiding device that projects into the interior space. This kind of attachment reduces the mounting stresses in the parallel-guiding device.
In an alternative embodiment, the fastening area is located on one of the lateral boundary surfaces of the portion of the second leg of the parallelogram that projects into the interior of the parallel-guiding device, and the supporting part is provided with a portion that extends along the lateral boundary surface at the location of the fastening area and has an area where it is joined to the fastening area.
Because the lateral boundary surfaces of the portion of the second leg of the parallelogram that projects into the interior of the parallel-guiding device are open on both sides of the parallel-guiding device, the place for the fastening area is freely selectable in accordance with applicable requirements within the entire available surface area of the lateral boundary surfaces of the portion that projects into the interior. In contrast to the attachment on a transverse surface area—opposite one of the guide links—of the portion that projects into the interior, which requires a certain minimum dimension of that portion transverse to the plane of the parallelogram, this alternative embodiment has the great advantage that the dimension of the parallel-guiding device transverse to the plane of the parallelogram can be as small as desired, which can bring considerable material and cost savings.
Similar advantages are achieved with an embodiment wherein the fastening area is arranged on the portion of the second leg of the parallelogram that projects into the interior of the parallelogram-guiding device in places that are across from each other in the direction perpendicular to the plane of the parallelogram. Further in this embodiment, the supporting part is provided with two portions, each of which extends along and has an area where it is joined to one of the places that are across from each other. While in the embodiment of the preceding paragraph the attachment to the supporting part takes place on only one of the two lateral boundary surfaces, the embodiment of the present paragraph provides for the supporting part to be joined to both lateral boundary surfaces of the portion projecting into the interior of the parallel-guiding device. Added to the advantages of the previously described attachment on only one of the lateral boundary surfaces, this bilateral mode of attachment enhances the rigidity.
With both the one-sided as well as the double-sided attachment of the foregoing description, it is practical if the fastening area and the matching area or areas of the supporting part are bolted together by a screw bolt that extends transverse to the plane of the parallelogram. With either mode of attachment, a secure connection between the parallel-guiding device and the supporting part is accomplished.
Within the scope of the invention, it is further of practical advantage that the supporting part has the form of a mounting plate that extends transverse to the plane of the parallelogram and can be anchored on a chassis base of the force-measuring apparatus. The portion of the supporting part that has an area where it joins the fastening area extends perpendicular to the mounting plate.
In the embodiment of the inventive arrangement that is based on the concept of a mounting plate, the parallel-guiding device is not directly connected to the chassis base of the force-measuring apparatus, but rather by means of the mounting plate which, in turn, is anchored to the chassis base. This has the effect of delaying the propagation of temperature changes, and it facilitates work operations in manufacturing as well as in servicing the force-measuring apparatus. The mounting plate also has the advantage that it can be adapted to different existing chassis bases or enclosures if it is equipped with different corresponding mounting holes.
The inventive arrangement is particularly advantageous in embodiments where the parallel-guiding device comprises a force-transmitting lever whose fulcrum is supported by the portion of the second leg of the parallelogram that projects into the interior of the parallel-guiding device.
The force-transmitting lever serves to transmit the force that is to be measured from the first leg of the parallelogram, which functions as force receiver, to a measuring system of the force-measuring apparatus, such as a magnetic force compensation system. Because on the one hand the force-transmitting lever bearing the force to be measured is supported by the portion that projects into the interior and on the other hand the fastening area of the parallel-guiding device, too, is located on this portion, the force taken up by the fulcrum support of the force-transmitting lever is transferred to the fastening area in a very direct manner.
As a practical design of all embodiments, the parallel-guiding device can be formed out of a single, essentially brick-shaped material block. In this, the individual portions of the parallel-guiding device, such as the two legs of the parallelogram, the guide links and the portion projecting into the interior, may be separated from each other by only narrow linear cuts of the kind that can, e.g., be made by spark erosion. The inventive arrangement of the fastening area on that portion of the second leg of the parallelogram that projects into the interior of the parallel-guiding device has the purpose of utilizing the advantages that are gained from this kind of a space- and labor-saving design of the parallel-guiding device.
Other characteristic features, details, and advantages of the invention will be presented in the following description and in the drawing that also has the express purpose of disclosing all details essential to the invention that are not mentioned in the text.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 represents a side view of an embodiment of a parallel-guiding device seen in a direction perpendicular to the plane of the parallelogram.
FIG. 2 represents the parallel-guiding device of FIG. 1 mounted in a force-measuring apparatus, shown in a cross-sectional view parallel to the plane of the parallelogram.
FIG. 3 represents a view from above of the mounted parallel-guiding device, perpendicular to the viewing direction of FIG. 2, wherein the line A—A indicates the plane of the section of FIG. 2 .
FIG. 4 represents a view from above of the mounting plate used in the embodiment of FIGS. 1 to 3 .
FIG. 5 represents a side view, perpendicular to the plane of the parallelogram, of another embodiment of a parallel-guiding device mounted in a force-measuring apparatus.
FIG. 6 represents the mounted parallel-guiding device of FIG. 5 as seen from the right, viewing in a direction parallel to the plane of the drawing of FIG. 5 .
FIG. 7 represents a partially cut-away perspective view of an embodiment that is analogous to the embodiment of FIGS. 1 to 4 but incorporates a variation in the mounting connection.
DETAILED DESCRIPTION OF THE INVENTION
As shown in FIG. 1, in a brick-shaped material block whose main surface lies in the plane of the drawing and is facing the viewer and whose thickness, perpendicular to the plane of the drawing, is markedly less than its dimensions along the plane of the drawing, thin linear cuts are formed, e.g., by spark erosion, that are cutting through the material block in the direction of its thickness. One of these thin linear cuts, shown in FIG. 1 as linear cut 2 which runs parallel to and near the bottom edge 1 of the material block, delimits a lower guide link 3 on the side of the link that faces the interior of the material block, while a linear cut 5 that runs parallel to and near the top edge 4 of the material block delimits an upper guide link 6 on the side of the link that faces the interior of the material block. The sides of the guide links 3 and 6 that face away from the interior are formed by portions of the side surfaces of the material block that are perpendicular to the plane of the drawing.
The two linear cuts 2 , 5 have curved end portions that are convex toward the outside of the material block. Opposite the curved end portions of the cuts and shaped like their mirror images are depressions in the bottom edge 1 and top edge 4 of the material block. As a result, the ends of the guide links 3 , 6 are shaped as thinned-down portions 7 , 8 , 9 , 10 from which the guide links, while maintaining their rigidity lengthwise, receive elastic flexibility to bend in a direction transverse to their longitudinal axis and parallel to the plane of the drawing.
In this mode of displacement, the thinned-down portions 7 , 8 , 9 , 10 , defining the pivot lines of the guide links 3 , 6 , lie at the corners of a parallelogram in the drawing plane of FIG. 1. A first leg 11 of this parallel-guiding device is formed by the portion of the material block shown to the left of the two thinned-down portions 7 , 10 on the left in FIG. 1 . Opposite the first leg 11 that connects the two guide links 3 , 6 at their left thinned-down portions 7 , 10 in FIG. 1, the second parallelogram leg 12 that connects the guide links 3 , 6 beyond the two thinned-down portions 8 , 9 on the right in FIG. 1 is formed by the portion 12 of the material block. The second parallelogram leg 12 , delimited on its outward-facing side 13 by lateral surface portions of the material block that are perpendicular to the drawing plane of FIG. 1, has a portion 14 projecting into the interior space of the parallel-guiding device that is enclosed by the two legs 11 , 12 of the parallelogram and the two guide links 3 , 6 .
The portion 14 is separated from the lower guide link 3 by the linear cut 2 . Where the latter changes from a straight line to the curve that defines the lower left thinned-down portion 7 , another linear cut 15 branches off extending in the direction from the lower guide link 3 toward the upper guide link 6 and separating the portion 14 , in FIG. 1 to the right of the linear cut 15 , from a coupling member 16 located to the left of the linear cut. In the area of the two end portions of the coupling member 16 , which are located on an imaginary connecting line 17 between and at a distance from the two thinned-down portions 7 , 10 , the linear cut 15 has sections that are convex-curved to the left. In combination with a linear cut 18 forming the mirror image of cut 15 relative to the imaginary connecting line 17 , the curved sections define thinned-down portions 19 , 20 of the coupling member 16 centered on the connecting line 17 . From the thinned-down portion 20 of the coupling member 16 next to the thinned-down portion 10 of the upper guide link 6 , the linear cut 18 runs into the cut 5 that defines the upper guide link 6 . The linear cut 15 demarcates the portion 14 along the section that starts from linear cut 2 to the place where it enters into the curve that defines the thinned-down portion 20 of the coupling member 16 near the thinned-down portion 10 of the upper guide link. At this point, a linear cut 21 branches off forming the continuing border of the portion 14 and ending in a curve whose convex side faces an imaginary line 22 that runs transverse to the upper guide link 4 . Another linear cut 23 starts with a convex curve that mirrors the cut 21 relative to the imaginary line 22 , then extends essentially in the longitudinal direction of the upper guide link 6 to a bore hole 24 , continues from there for a short distance to another bore hole 25 that connects to the linear cut 5 that delimits the upper guide link 6 . Through this design, the portion 14 projecting from the second parallelogram leg 12 is delimited entirely by the lower linear cut 2 , the linear cut 15 that branches off from cut 2 , the linear cut 21 branching off from cut 15 , the further cut 23 and, connected to the latter, a part of the linear cut 5 that delimits the upper guide link 4 .
At the same time, the curves of the linear cuts 21 and 23 that mirror each other across the imaginary line 22 define between themselves a standing flexure fulcrum 26 for a force-transmitting lever 27 that is separated from the portion 14 by the linear cuts 21 and 23 and from the upper guide link 6 by the part of cut 5 that lies opposite the further cut 23 . The arm of the force-transmitting lever which in FIG. 1 lies to the left of the standing flexure fulcrum 26 and whose left end is separated from the first parallelogram leg 11 by the part of cut 18 running toward the thinned-down portion 10 is connected to the thinned-down portion 20 of the coupling member 16 whose opposite thinned-down portion 19 is, in turn, connected to the first parallelogram leg 11 .
The parallel-guiding device shown in FIG. 1 is mounted in a manner illustrated in FIGS. 2 through 4 in a force-measuring apparatus, e.g., in a balance. An essentially flat mounting plate 28 , shown by itself in FIG. 4 and in the assembled state in FIGS. 2 and 3, serves as supporting part. It has different configurations of attachment holes 29 for anchoring it with screws on chassis frames of force measuring apparatuses of different designs, e.g., on the enclosure bottom parts of balances. A raised portion 30 projects from the plane of the mounting plate 28 , which in the assembled state is transverse to the plane of the parallelogram. The dimensions of the raised portion transverse to the plane of the parallelogram are smaller than the respective dimensions of the lower guide link 3 . In accordance with FIG. 2, in the assembled state the raised portion 30 passes with clearance through an opening 31 in the lower guide 3 . At its free end 32 , which extends transverse to the plane of the parallelogram, the raised portion 30 engages a surface portion 33 of the portion 14 of the second parallelogram leg 12 that projects into the interior of the parallel-guiding device, the surface portion 33 being transverse to the plane of the parallelogram, facing the lower guide link 3 and serving as fastening area.
At the location of the opening 31 , the portion 14 of the second parallelogram leg 12 that projects into the interior of the parallel-guiding device has two tapped holes 34 whose axial direction is transverse to the lengthwise direction of the lower guide link 3 as well as parallel to the plane of the parallelogram. Matching the two tapped holes 34 , the mounting plate 28 has two through holes 35 in the portion 30 that serves for the mounting connection. Passing through the through holes 35 are two screw bolts 36 whose threaded shafts engage the tapped holes 34 and whose heads bear against the side of the mounting plate 28 that faces away from the parallel-guiding device. Thereby, the mounting plate 28 and the parallel-guiding device are firmly clamped together.
FIGS. 2 and 3 show additional components of the balance that are fastened to the parallel-guiding device for which the latter is equipped with mounting holes shown in FIG. 1 . At the detail level, the portion 14 of the second parallelogram leg 12 that projects into the interior of the parallel-guiding device has in its lower part, adjacent to the lower guide link, two clear mounting holes 37 , whose axial direction is transverse to the plane of the parallelogram. By means of screw bolts passing through the mounting holes 37 and spacers 38 , two lateral holders 40 are connected to the parallel-guiding device with clearance space to the two lateral boundary surfaces 39 that are parallel to the plane of the parallelogram. The lateral holders 40 extend along both sides of the parallel-guiding device parallel to the lengthwise direction of the guide links 3 , 6 toward the second parallelogram leg 12 and beyond. In the space beyond the second parallelogram leg 12 , the lateral holders 40 form a support platform 41 for a permanent magnet of a magnetic force compensation system 42 . Within this concept, the two lateral holders 40 may be parts of an integral single-piece unit.
Further, the force-transmitting lever 27 has two mounting holes 43 transverse to the plane of the parallelogram that are to receive screw bolts 44 by which lever extensions 45 are attached to the force-transmitting lever 27 on both sides of the parallel-guiding device with spacers 38 providing clearance. The lever extensions 45 extend at a distance from the lateral boundary surfaces 39 toward the magnetic compensation system 42 where they form a holding frame for a compensation coil that is immersed in the magnetic field of the permanent magnet of the force compensation system.
The first parallelogram leg 11 has an upper rim surface 46 parallel to the top edge 4 of the upper guide link 6 , on which a weighing pan carrier 47 extending toward the second parallelogram leg 12 about as far as the center of the upper guide link 6 is attached by means of two screw bolts 48 that extend parallel to the plane of the parallelogram and transverse to the lengthwise direction of the guide links 3 , 6 and engage in tapped holes 49 of the first parallelogram leg 11 . At the opposite end of the weighing pan carrier 47 , relative to the first parallelogram leg 11 , a weighing pan support cone 50 is resiliently supported by means of a helix spring 51 . The helix spring 51 is guided along the outer circumference of a tube-shaped part that rises from the topside (which faces away from the upper guide link 6 ) of the weighing pan carrier 47 . A guide bolt 53 , attached to the weighing pan support cone 50 , is movably guided inside the tube-shaped part.
The tube-shaped part 52 and the guide bolt 53 held inside it project beyond the bottom surface of the weighing pan carrier 47 that faces the upper guide link 6 and extend with clearance into an opening 54 that is formed in the upper guide link 6 and in the adjacent area of the portion 14 . The opening 54 lies opposite the opening 31 of the lower guide link.
The weighing pan carrier 47 that extends above the upper guide link 6 essentially transverse to the plane of the parallelogram has angled-down side portions 55 at a distance from, as well as parallel to, the lateral boundary surfaces 39 of the parallel-guiding device. The side portions 55 extend in the direction toward the lower guide link 3 about as far as the center of the parallel-guiding device. A part of the side portions 55 that projects beyond the front surface 56 of the first parallelogram leg 11 extending between the two guide links 3 , 6 is equipped with a holder 57 onto which a reference weight may be placed for the purpose of calibrating the apparatus.
In a partially cut-away perspective view FIG. 7 shows an embodiment that largely coincides with the embodiment of FIGS. 1 through 4. The corresponding parts are identified by the same reference numbers, and the description of FIGS. 1 through 4 also applies to them. As a first dissimilarity, the mounting plate 28 in FIG. 7 is shaped somewhat differently, distinguished particularly by a perforated, latticed design. Apart from this, however, the essential difference is that the fastening portion 30 of the mounting plate 28 has tapped holes instead of the through holes 35 of the embodiment of FIGS. 1 through 4. Instead of the screw bolts 36 of the embodiment of FIGS. 1 through 4, the embodiment of FIG. 7 has two screw bolts 136 extending from the portion 14 that projects into the interior of the parallel-guiding device into the tapped holes of the mounting plate 28 and are firmly engaged in these tapped holes. As seen in FIG. 7, in the part that is cut away to the central plane of the parallel-guiding device, the portion 14 has an opening 138 , also extending through the upper guide link 6 , which runs parallel to the lateral boundary surfaces that delimit the parallel-guiding device and extends in the direction toward the surface portion 33 of the portion 14 that faces the lower guide link 3 . The end of the opening 138 closest to the surface portion 33 is parallel to the surface portion 33 and serves as shoulder area for the bolt heads 137 of the screw bolts 136 , whereby the parallel-guiding device by means of screw bolts 136 is clamped firmly against the free end 32 of portion 30 of the mounting plate 28 .
An embodiment illustrated in FIGS. 5 and 6 essentially corresponds to the embodiment of FIGS. 1 through 4 except for the mounting attachment of the parallel-guiding device. Therefore, the corresponding parts were given the same reference numbers, and the description of FIGS. 1 through 4 also applies to them. Only the somewhat different design of the side portions 55 of the weighing pan carrier 47 needs to be pointed out. To indicate the difference in shape, the reference number 55 ′ for these side portions in FIGS. 5 and 6 is differentiated by the prime symbol.
Deviating from the embodiment shown in FIGS. 1 through 4, the fastening area of the parallel-guiding device in the embodiment of FIGS. 5 and 6 is located on the lateral boundary surface 39 —facing the viewer in FIG. 5 and located to the left in FIG. 6 —of the portion 14 of the second parallelogram leg 12 projecting into the interior of the parallel-guiding device. For this purpose, the mounting plate 28 ′ that is otherwise essentially identical with the mounting plate 28 of FIG. 4, instead of the pedestal-shaped portion 30 shown in FIG. 4, has a plate-shaped portion 30 ′ that stands out perpendicularly from the main plane of the mounting plate 28 ′ and parallel to the plane of the parallelogram. The portion 30 ′, through one of its two surfaces that are parallel to the plane of the parallelogram, is joined to the lateral boundary surface 39 of the parallel-guiding device. Two screw bolts 59 extending transverse to the plane of the parallelogram clamp the portion 30 ′ of the mounting plate 28 ′ to the portion 14 of the second parallelogram leg 12 that projects into the interior of the parallel-guiding device.
The principle on which the mounting attachment in FIGS. 5 and 6 is based could also be realized in such a manner that also the lateral boundary surface 39 facing away from the plate-shaped portion 30 ′ is in contact with a portion corresponding to the portion 30 ′ and standing out from the main plane of the mounting plate 28 ′ where the two portions are clamped together with the parallel-guiding device by means of the screw bolts 59 (FIG. 5 ). Particularly in FIG. 1 there are additional through holes and tapped holes without reference numbers. These are irrelevant for the mounting of the parallel-guiding device or for the attachment of the other parts of the balance and are therefore not covered in detail in this description. In part, they serve to hold the material block in the process of producing the linear cuts through electrical discharge erosion or for inserting the erosion wire or also for other purposes. In addition, the FIGS. 3 and 6 show in a generalized manner a circuit board 60 complete with electronic components. This circuit board 60 performs the electronic processing of the measuring signal generated by the magnetic force compensation. The measuring signal occurs when a load is placed on a weighing pan (not shown) held by the weighing pan support cone 50 whereby the first parallelogram leg 11 , being connected to the weighing pan carrier 47 , is being displaced by a small amount relative to the second parallelogram leg 12 . This displacement is transferred from the first parallelogram leg 11 through the flexibly connected coupling member 16 to the likewise flexibly connected force-transmitting lever 27 . As a result, the compensation coil attached to the lever extensions 45 is displaced inside the electromagnetic force compensation system by a corresponding amount in proportion to the lever ratio. The electromagnetic force compensation system controls and adjusts the compensating current in the force compensation coil in such a manner that the displacement is cancelled. The measuring signal is derived from the compensation current required to restore the state of equilibrium.
LIST OF REFERENCE NUMBERS
1 bottom edge
2 linear cut
3 lower guide link
4 top edge
5 linear cut
6 upper guide link
7 thinned-down portion
8 thinned-down portion
9 thinned-down portion
10 thinned-down portion
11 first leg of the parallelogram
12 second leg of the parallelogram
13 outward-facing side of 12
14 portion of 12
15 linear cut
16 coupling member
17 imaginary connecting line
18 linear cut
19 thinned-down portion
20 thinned-down portion
21 linear cut
22 imaginary line
23 additional linear cut
24 bore hole
25 bore hole
26 standing flexure fulcrum
27 force-transmitting lever
28 , 28 ′ mounting plate
29 attachment holes
30 , 30 ′ portion of 28 , 28 ′
31 opening
32 free end of 30
33 surface portion of 14
34 tapped holes
35 through holes
36 screw bolt
37 mounting holes
38 spacer
39 lateral boundary surfaces
40 lateral holders
41 support platform
42 magnetic force-compensation system
43 mounting holes
44 screw bolt
45 lever extensions
46 upper rim surface of 11
47 weighing pan carrier
48 screw bolt
49 tapped hole
50 pan support cone
51 helix spring
52 tube-shaped part
53 guide bolt
54 opening
55 , 55 ′ side portions of 47
56 front surface of 11
57 holder for reference weight
59 screw bolt
60 circuit board
136 screw bolt
137 bolt head
138 opening
139 part of 14 | To counteract the adverse effects associated with mounting a parallel-guiding device on a supporting part of a balance, the attachment area ( 30 ) is located on a portion ( 14 ) of the stationary leg ( 12 ) of the parallel-guiding device. Portion 14 projects into the space between the two guide links 3 and 6 by which the load-receiving movable leg ( 11 ) of the parallelogram is guided in parallel motion relative to the stationary leg ( 12 ). | 6 |
GOVERNMENT FUNDING
This application was funded, at least in part, by a grant from the United States Government, which may have certain rights therein.
This application is a continuation-in-part of U.S. application Ser. No. 08/813,514 filed Mar. 7, 1997, all aspects of which that do not conflict with this application are incorporated herein in their entirety.
BACKGROUND OF THE INVENTION
It was recently discovered that arisugacin, a natural product isolated from a culture of Penicillium, is an inhibitor of acetylcholinesterase (AChE), and on this basis arisugacin has been predicted to be effective in the treatment of Alzheimer's disease. Related compounds also showed inhibitory activity. Omura, S., et al. (1995), "Arisugacin, a Novel and Selective Inhibitor of Acetylcholinesterase from Penicillium sp. FO-4259," J. Antibiotics 48:745-746. Arisugacin and the related compounds are tetracyclic pyrones (having four fused rings). Other tetracyclic pyrones, certain pyripyropenes, have been shown to be inhibitors of cholesterol acyltransferase (ACAT), and therefore have been predicted to be effective in the treatment of atherosclerosis and hypercholesterolemia. Omura, S., et al. (1993), "Pyripyropenes, Highly Potent Inhibitors of Acyl-CoA; Cholesterol Acyltransferase Produced by Aspergillus fumigatus," J. Antibiotics 46:1168-1169; and "Kim, Y. K. et al. (1994), "Pyripyropenes, Novel Inhibitors of Acyl-CoA:Cholesterol Acyltransferase Produced by Aspergillus fumigatus," J. Antibiotics 47:154-162. Pyripyropene A, one such inhibitor, is further characterized in Tomoda, H., et al. (1994), "Relative and Absolute Stereochemistry of Pyripyropene A, A Potent, Bioavailable Inhibitor of Acyl-CoA:Cholesterol Acyltransferase (ACAT)," J. Am. Chem. Soc. 116:12097-12098.
A number of multicyclic pyrones are known to the art and described in Chemical Abstracts; however, tricyclic and tetracycic pyrones as disclosed and claimed herein, appear not to have been previously described.
There is a need for simpler inhibitors of AchE and ACAT that are useful as treatments for Alzheimer's disease, atherosclerosis and hypercholesterolemia.
SUMMARY OF THE INVENTION
The tricyclic and tetracyclic pyrones of this invention are useful as inhibitors of AChE and ACAT, and can be used in the treatment of Alzheimer's disease, atherosclerosis and hypercholesterolemia. The tricyclic compounds are also potent inhibitors of cancer cell growth and macromolecule synthesis (e.g., DNA, RNA and protein synthesis) and can be used in the treatment of various forms of cancers including leukemia, ascites, and solid tumors. Further, their short-term inhibition of macromolecule synthesis is reversible following removal, but their long-term inhibition of tumor cell growth is not. Importantly, the tricyclic compounds are also powerful inhibitors of tubulin polymerization and may be useful as cell cycle-specific anticancer drugs. As hereinafter described, certain of these pyrones are useful intermediates in the synthesis of other pyrones of this invention. The tricyclic compounds are cytostatic but not overly cytotoxic.
The tricyclic pyrones of this invention include compounds selected from the group of compounds of the formula: ##STR1## wherein: T is independently CH, N, S or O;
X is independently O, NH or S;
Y is independently O, NH or S;
Z is independently CH, N, S or O;
R 1 is independently Formula I; or
R 1 and R 3 and R 4 and R 5 are, independently, H, OH, alkyl, alkenyl, alkynyl, an aromatic ring system, ##STR2## wherein R and M are independently H, alkyl, alkenyl or alkynyl, an aromatic ring system amino, amido, sulfhydryl, or sulfonyl, W is Cl, F, Br or OCl, and A is an aromatic ring system.
R 2 and R 9 are independently H or R where R is as defined above.
As used herein, the term "aromatic ring system" includes five and six-membered rings, fused rings, heterocyclic rings having oxygen, sulfur or nitrogen as a ring member, OR-substituted and R-substituted aromatic rings where R is defined as above. Preferably the substituents have one to five carbons. As used herein, the terms "alkyl," "alkenyl," an "alkynyl" include C1-C6 straight or branched chains. Unless otherwise specified, a general formula includes all stereoisomers.
Compounds of this invention also include compounds of the formula: ##STR3## wherein: X, Y and R 2 -R 3 are as set forth for Formula I;
R 1 is independently Formula II or as set forth for Formula I;
R 15 is independently NH 2 , OH, or OCOR where R is H, or alkyl;
R 16 is independently OH or H; and
R 15 and R 16 taken together are O;
compounds of the formula: ##STR4## wherein: X, Y, T, Z and R 2 and R 3 are as set forth for Formula I;
R 1 is independently Formula III or as set forth for Formula I; and
R 6 is H when R 7 is OH, or R 6 is OH when R 7 is H, or R 6 and R 7 taken together are ═O;
compounds of the formula: ##STR5## wherein R 1 is independently Formula IV or as set forth for Formula I, and R 3 is as set forth for Formula I above; and R 2 , R 4 and R 5 are defined as R 3 for Formula I above; and compounds of the formula: ##STR6## wherein R 1 is Formula V or independently is as set forth for Formula I above.
The tetracyclic pyrones of this invention include compounds selected from the group of compounds of the formula: ##STR7## wherein: R 1 and R 2 are independently as defined as R 3 as set forth for Formula I above;
R 10 and R 11 and R 13 and R 14 are independently defined as R 3 as set forth for Formula I above; and
R 12 is H, alkyl, alkenyl or alkynyl, an aromatic ring system, amino, amido, sulfhydryl, or sulfonyl.
A preferable class of compounds of this invention useful as macromolecule synthesis inhibitors in cancer cells are compounds selected from compounds of the formula: ##STR8## wherein: R 1 is independently selected from the group consisting of H, R, 3-pyridyl, R-substituted 3-pyridyl, phenyl, R-substituted, di-substituted and tri-substituted phenyl, O--R-substituted, di-substituted and tri-substituted phenyl where R is as defined above; and preferably comprises an aromatic ring;
R 2 and R 9 are independently selected from the group consisting of H and R, where R is as defined above;
R 3 , R 4 and R 5 are independently selected from the group H, R, OH, OCHO, and OR where R is as defined above; and
T and Z are independently selected from the group consisting of CH, N, S or O.
Most preferably, the compounds are selected from the group consisting of compounds of Formula 1 wherein:
R 1 is independently selected from the group consisting of alkyl, 3-pyridyl and 3,4-dimethoxyphenyl; preferably 3-pyridyl or 3,4-dimethoxyphenyl;
R 2 is independently selected from the group consisting of H and CH 3 ;
R 3 is independently selected from the group of H, OH, and OCHO;
R 4 and R 5 are independently H;
R 9 is independently selected from the group of H and isopropenyl; and
T and Z are independently CH.
Throughout the specification hereof, chemical structures are depicted and numerically labelled. The names of the numbered structures are set forth in Table 1 and indicated in boldface in the text.
TABLE 1______________________________________Names of Structures______________________________________1A 3-methyl-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran1B cis-3-5a-dimethyl-6-hydroxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran1C trans-3-5a-dimethyl-6-hydroxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran1D cis-3-5a-dimethyl-6-formyloxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran1E trans-3-5a-dimethyl-6-formyloxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran2A 3-(3-pyridyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran2B cis-3-(3-pyridyl)-5a-methyl-6-hydroxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran2C trans-3-(3-pyridyl)-5a-methyl-6-hydroxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran2D cis-3-(3-pyridyl)-5a-methyl-6-formyloxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran2E trans-3-(3-pyridyl)-5a-methyl-6-formyloxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran3A 3-(3,4-dimethoxyphenyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran3B cis-3-(3,4-dimethoxyphenyl)-5a-methyl-6-hydroxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran3C trans-3-(3,4-dimethoxyphenyl)-5a-methyl-6-hydroxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran3D cis-3-(3,4-Dimethoxyphenyl)-6-formyloxy-5a-methyl-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran3E trans-3-(3,4-Dimethoxyphenyl)-6-formyloxy-5a-methyl-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran4A cyclohexenecarboxaldehyde4B 3-hydroxy-2-methyl-1-cyclohexen-1-carboxaldehyde4C 3-formyloxy-2-methyl-1-cyclohexen-1-carboxaldehyde5A 4-hydroxy-6-methyl-2-pyrone5B 4-hydroxy-6-(3-pyridyl)-2-pyrone5C 4-hydroxy-6-(3,4-dimethoxyphenyl)-2-pyrone 6 3-5a-dimethyl-6-oxo-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran 7 2-methylcyclohexan-1-one 8 2-methyl-2-cyclohexen-1-one 9 1,3-dithiane10 1- 2-(1,3-dithianyl)!-2-methyl-2-cyclohexen-1-ol11 3- 2-(1,3-dithianyl)!-2-methyl-2-cyclohexen-1-ol12A ethyl nicotinate12B ethyl 3,4-dimethoxybenzoate13A ethyl 5-(3-pyridyl)-3,5-dioxopentanoate13B methyl 5-(3,4-dimethoxyphenyl)-3,5-dioxopentanoate14A 3-methyl-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!quinoline14B cis-3-5a-dimethyl-6-formyloxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!quinoline14C cis-3-5a-dimethyl-6-formyloxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzothiin18 4-bromo-6-methyl-2-pyrone19 4-azido-6-methyl-2-pyrone20 4-amino-6-methyl-2-pyrone21 4-mercapto-6-methyl-2-pyrone22 tri(deacetyl)pyripyropene A23 20(S)-camptothecin (CPT)24 1H-6,7,8,9-tetrahydro-1-oxopyrano 4,3-b!quinoline26 1H-7,8,9,10-tetrahydro-1-oxopyrano 4,3-c!isoquinoline27 (S)-(-)-perillaldehyde28 (5aS, 7S)-7-Isopropenyl-3-methyl-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1! benzopyran29 (5aS, 7S)-7-Isopropenyl-3-(3-pyridyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran30 (5aS, 7S)-7-Isopropenyl-3-(3,4-dimethoxyphenyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1! benzopyran31 3-(Methoxycarbonylmethyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran32 3-(Carboxymethyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1! benzopyran33 1,8-Di-{3- 1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1! benzopyranyl!}-2,7-octanedione34 (5aS, 7S)-7- 2-(1-hydroxypropyl)!-3-methyl-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1! benzopyran35 (5aS, 7S)-7- 1-(Formyl)ethyl!-3-methyl-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1! benzopyran36 (5aS, 7S)-7- 2-(1-Hydroxypropyl)!-10-hydroxy-3-(3,4-dimethoxyphenyl)-1H-5a,6,7,8,9,9a,10-heptahydro-1-oxopyrano 4,3-b! 1! benzopyran37 (5aS, 7S)-7- 2-(1-Pentanoyloxypropyl)!-10-hydroxy-3-(3,4-dimethoxyphenyl)-1H-5a,6,7,8,9,9a,10-heptahydro-1-oxopyrano 4,3-b! 1! benzopyran38A (5aS*, 9aS*, 10S*)-9a,10-Epoxy-3-(3-pyridyl)-1H-5a,6,7,8,9,9a,10-heptahydro-1-oxopyrano 4,3-b! 1! benzopyran38B (5aS*, 9aR*, 10R*)-9a,10-Dihydroxy-3-(3-pyridyl)-1H-5a,6,7,8,9,9a,10-heptahydro-1-oxopyrano 4,3-b! 1! benzopyran39 (R)-(-)-carvone40 cis-1-iodo-3-(methanesulfonyloxy)-1-propene41 (5R,6S)-2,6-Dimethyl-6-(cis-3-iodo-2-propenyl)-5-isopropenyl-2-cyclohexen-1-one42 (4aS,5R,8aS)-Methyl-(1H)-1-Oxo-4,4a,5,8,8a-pentahydro-2,5,8a-trimethylnaphthalene-5-acetate43 (4aS,5R,8aS)-(1H)-1-Oxo-4,4a,5,8,8a-pentahydro-2,5,8a-trimethylnaphthalene-5-acetic acid44 (1S,4aS,8aS)-(1H)-1- 2-(1,3-dithianyl)!-1-hydroxy-4,4a,5,8,8a-pentahydro-2,5,8a-trimethylnaphthalene-5-acetic acid45 (4aS,5R,8aS)-(1H)-1-carboxaldehyde-3-formyloxy-4,4a,5,8,8a-pentahydro-2,5,8a-trimethylnaphthalene-5-acetic acid46 (4R,4aS,6aS,12bS)-1H,11H-4,4a,5,6,6a,12b-Hexahydro-6-formyloxy-11-oxo-9-(3-pyridyl)-4,6a,12b-trimethylnaphtho 2,1-b!pyrano 3,4-e!pyran-4-acetic acid47 (4aS,5S,8aS)-Methyl-(1H)-1-Oxo-4,4a,5,8,8a-pentahydro-2,5,8a-trimethylnaphthalene-5-acetate______________________________________
Preferred compounds of this invention are shown in below in Scheme 1 and include compounds selected from the group consisting of: 3-(3-pyridyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 2A!; 3-(3 ,4-dimethoxyphenyl)-1H-5a, 6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 3A!; cis- and trans-3-(3 ,4-dimethoxyphenyl)-5a-methyl-6-formyloxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 3D and 3E!; cis- and trans-3-(3-pyridyl)-5a-methyl-6-formyloxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3b!benzopyran 2D and 2E!; cis- and trans-3-(3,4-dimethoxyphenyl)-5a-methyl-6-hydroxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 3B and 3C!; 3-methyl-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 1A!; cis- and trans-3-5a-dimethyl-6-formyloxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 1D and 1E!; and cis- and trans-3-(3-pyridyl)-5a-methyl-6-hydroxy-1H-5a, 6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 2B and 2C!.
A more preferred class of compounds of this invention includes compounds selected from the group consisting of 3-(3-pyridyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 2A!; 3-(3 ,4-dimethoxyphenyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 3A!; cis- and trans-3-(3,4-dimethoxyphenyl)-5a-methyl-6-formyloxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 3D and 3E!; cis- and trans-3-(3-pyridyl)-5a-methyl-6-formyloxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 2D and 2E!; cis- and trans-3-(3,4-dimethoxyphenyl)-5a-methyl-6-hydroxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 3B and 3C!; and cis- and trans-3-(3,4-dimethoxyphenyl)-5a-methyl-6-hydroxy-1H-5a, 6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 3B and 3C!; 1H-6,7,8,9-tetrahydro-1-oxopyrano 4,3-b!quinoline 24!; 1H-7,8,9,10-tetrahydro-1-oxopyrano 4,3-c!isoquinoline 26!; (5aS*, 9aR*, 10R*)-9a,10-Dihydroxy-3-(3-pyridyl)-1H-5a,6,7,8,9,9a,10-heptahydro-1-oxopyrano 4,3-b! 1!benzopyran 38B!; (5aS, 7S)-7- 2-(1-Pentanoyloxypropyl)!-10-hydroxy-3-(3,4-dimethoxyphenyl)-1H-5a,6,7,8,9,9a,10-heptahydro-1-oxopyrano 4,3-b! 1!benzopyran 37!; (5aS, 7S)-7-Isopropenyl-3-(3,4-dimethoxyphenyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran 30!; (5aS, 7S)-7-Isopropenyl-3-(3-pyridyl)-1 H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran 29!; (5aS, 7S)-7-Isopropenyl-3-methyl-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran 28!; and 3-(Carboxymethyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! l! benzopyran 32!.
A most preferred class of compounds of this invention includes compounds selected from the group consisting of 3-(3-pyridyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 2A!; 3-(3,4-dimethoxyphenyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 3A!; cis- and trans-3-(3,4-dimethoxyphenyl)-5a-methyl-6-formyloxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 3D and 3E!; and cis- and trans-3-(3,4-dimethoxyphenyl)-5a-methyl-6-hydroxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!benzopyran 3B and 3C!; and 1,8-Di-{3- 1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyranyl!}-2,7-octanedione 33!.
This invention also provides methods as illustrated in Schemes 1, 2, 6, 7, 8 and 9 below for making the above compounds via condensation reactions between an aldehyde of a cyclohexene having R 2 and R 3 substituents as defined above, and an ortho-oxy-substituted heterocyclic ring having as a para-substituent a reactive group capable of reacting with the β carbon of the enal function (carbon containing R 2 ) to form the tricyclic product. These anticancer drugs are easy to prepare in large quantities using few steps.
The method comprises contacting:
(a) a compound of the formula: ##STR9## wherein X is as defined for Formula I; wherein R 1 is defined as R 3 as set forth in Formula I above; and
Z is a reactive group comprising Y (as defined in Formula I above, i.e. O, S or N);
with
(b) a compound having an aldehyde substituent of the formula: ##STR10## wherein: R 2 and R 3 are as defined above for Formula I, R 6 is defined as R 3 for Formula I above, and
R 4 and R 5 are as defined above for Formula I; and T and Z are independently CH, N, S or O under reaction conditions whereby a condensation reaction takes place between said compounds of paragraphs (a) and (b) whereby reactive groups R 3 and Z react with said substituted ene aldehyde to form a compound as defined in the Formula I above.
Compounds of Formula I and Formula 1 where X≠Y may be made by means known to the art by methods analogous to those disclosed herein. Further, compounds of Formula I and Formula 1 where T÷#CH, Z÷CH, R 4 ÷H, or R 5 ÷H may be made by means known to the art by methods analogous to those disclosed herein.
More preferably, the method comprises making a compound of Formula 1 comprising contacting:
(a) a compound of the formula: ##STR11## wherein R 2 and R 3 are as defined for Formula 1 above, with (b) a compound of the formula: ##STR12## wherein: R 1 is defined as R 3 as set forth for Formula 1 above.
Methods are also provided for making compounds of Formula IV above comprising reacting (a) compounds of the formula: ##STR13## wherein R 1 is defined as R 3 as set forth above for Formula I; with
(b) compounds of the formula: ##STR14## wherein R 2 and R 3 are as defined above for Formula I.
Methods are provided for making compounds of Formula VI above comprising reacting (a) compounds of the formula: ##STR15## wherein:
R 17 and R 18 are independently defined as R 3 as set forth for Formula I above;
R 9 is CH 2 R, wherein R is as defined as R 3 as set forth for Formula I above; with
(b) compounds of the formula: ##STR16## wherein R 1 is defined as R 3 as set forth for Formula I above.
Methods are also provided for making a compound of Formula E above comprising reacting:
(a) a compound of the formula: ##STR17## wherein R 1 is defined as R 3 as set forth for Formula I above; with
(b) a compound of the formula: ##STR18## wherein X is I, Br, or Cl, and Ms is methanesulfonyl.
A method is also provided for inhibiting an enzyme selected from the group consisting of acetylcholinesterase and cholesterol acyltransferase in a patient comprising administering to the patient an effective amount of a compound of this invention. An effective amount is an amount capable of effecting measurable inhibition, preferably an amount capable of effecting inhibition equivalent or greater than that of known AChE inhibitor Tacrine or known ACAT inhibitor CP-113,818 (see Examples hereof). As is known to the art, dosage can be adjusted depending on the bioactivity of the particular compound chosen. The compound may be administered in combination with a suitable pharmaceutical carrier such as DMSO, ethyl alcohol, or other carriers known to the art.
Patients include humans, large mammals, livestock animals, pets, and laboratory animals.
A method is also provided for inhibiting macromolecule (e.g., DNA, RNA and protein) synthesis and growth of cancer cells in a patient comprising administering to the patient an effective amount of a compound of this invention. Suitable pharmaceutical carriers may be used for administration of the compound. An effective amount to inhibit macromolecule synthesis or cell growth is an amount sufficient to inhibit macromolecule production or cell growth at least as well as 20(S)-camptothecin (CPT) as measured in standard assays as described in the Examples hereof.
A method is also provided for inhibiting tubulin polymerization in a patient comprising administering to the patient an effective amount of a compound of this invention. Suitable pharmaceutical carriers may be used for administration of the compound. An effective amount is an amount capable of effecting measurable inhibition, preferably an amount capable of effecting inhibition equivalent to known tubulin polymerization inhibitor colchicine.
Methods are also provided herein for prevention of tubulin polymerization, tumor development, inhibiting the rate of tumor growth, and inducing regression of pre-existing tumors comprising administering to a patient an effective amount of a compound of this invention. An effective dosage for each purpose may be readily calculated by those of skill in the art based on effective dosages for inhibition of macromolecule synthesis, optimized and adjusted as required for individual patients.
Interestingly, Tau, which is a major component of the abnormal intracellular tangles of filaments found in the brain of Alzheimer patients, is a non-energy transducing microtubule-associated protein. If tricyclic pyrones bind to tubulin and disrupt microtubule dynamics, they should also decrease or prevent the interactions of Tau and other microtubule-associated proteins with microtubules that are involved in Alzheimer's disease.
The mechanism of action by which the compounds inhibit cancer cells is unknown; however, a possible mechanism is that the compounds bind selectively and strongly with one of the oxidative enzymes which undergoes oxidation at the C 3 -C 4 double bond to form the corresponding C 3 -C 4 epoxide and this epoxide then subsequently undergoes a ring opening reaction with a nucleophile of DNA, RNA, or enzymes in the cancer cell.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a comparison of the effects of four new tricyclic pyrone derivatives and CPT on DNA synthesis in L1210 cells in vitro. About 2.53×10 6 cells suspended in 0.5 ml of RPMI 1640 medium were incubated at 37° C. for 90 minutes in the presence or absence (control) of the indicated concentrations of drugs. The cells were then pulse-labeled for an additional 30 minutes to determine the rate of 3 H-thymidine incorporation into DNA. DNA synthesis in vehicle-treated control cells was 43,956±4,569 cpm (100±11%). The blank value (1,241±99 cpm) for cells pulse-labeled for 0 minutes with 1 μCi of 3 H-thymidine has been subtracted from the results. Bars: means±SD (n=3). a P<0.1, significantly smaller than control; b not significantly different from control; c not different from CPT (20 μM).
FIG. 2 shows a comparison of the effects of 10 new tricyclic pyrone derivatives and CPT on DNA synthesis in L1210 cells in vitro. The protocol of the experiment was identical to that of FIG. 1, except that the cell density was 2.64×10 6 cells/0.5 ml. DNA synthesis in vehicle-treated control cells was 60,998±4,636 cpm (100±8%). The blank value (1,297±182 cpm) for cells pulse-labeled for 0 minutes with 1 μCi of 3 H-thymidine has been subtracted from the results. Bars: means±SD (n=3). a P<0.025, significantly smaller than 3B & 3C; b not significantly different from control; c not different from CPT (20 μM); d P<0.025, smaller than 2B & 2C; e not different from 1A; f P<0.025, smaller than 1D & 1E; g P<0.025, smaller than control.
FIG. 3 illustrates the concentration-dependent inhibition of DNA synthesis by the new tricyclic pyrone analog 3A () and CPT (∘) in L1210 cells in vitro. The protocol of the experiment was identical to that of FIG. 1, except that the cell density was 2.07×10 6 cells/0.5 ml. DNA synthesis in vehicle-treated control cells was 29,813±1,282 cpm (100±4%; striped area). The blank value (954±238 cpm) for cells pulse-labeled for 0 minutes with 1 μCi of 3 H-thymidine has been subtracted from the results. The concentrations of drugs are plotted on a logarithmic scale. Bars: means±SD (n=3). a P<0.005, significantly smaller than control; b not significantly different from control.
FIG. 4 shows the concentration-dependent inhibition of DNA synthesis by the new tricyclic pyrone analog 2A () in L1210 cells in vitro. The protocol of the experiment was identical to that of FIG. 1, except that the cell density was 2.83×10 6 cells/0.5 ml. DNA synthesis in vehicle-treated control cells was 94,547±7,564 cpm (100±8%; striped area). The blank value (1,580±92 cpm) for cells pulse-labeled for 0 minutes with 1 μCi of 3 H-thymidine has been subtracted from the results. The concentrations of drugs are plotted on a logarithmic scale. Bars: means±SD (n=3). a P<0.025, significantly smaller than control.
FIG. 5 shows a comparison of the effects of six new tricyclic pyrone analogs and CPT on the growth of L1210 cells in vitro. Cells were plated at an initial density of 1×10 4 cells/0.5 ml/well in RPMI 1640 medium, containing 7.5% fortified bovine calf serum, and grown at 37° C. for 4 days in a humidified incubator in 5% CO 2 in air. Cells were incubated in the presence or absence (.sup., control) of 50 μM 3A (▪), 2D & 2E (□), 3D & 3E (▴), 2B & 2C (Δ) 2A (♦), 3B & 3C (⋄), or 10 μM CPT (∘) and their density was monitored in triplicate every 24 h using a Coulter counter. Cells numbers are plotted on a logarithmic scale.
In FIG. 6, the abilities of the drugs tested in FIG. 5 to inhibit the growth of L1210 cells in vitro are compared at days 3 (open) and 4 (striped). The results are expressed as % of the numbers of vehicle-treated control cells after 3 (396,200±38,431 cells/ml; 100±10%; open) and 4 days in culture (991,907±129,245 cells/ml; 100±13% striped). Bars: means±SD (n=3). a P<0.05, significantly smaller than control; b not significantly different from control; c not different from control or 2D & 2E.
FIG. 7 shows the concentration-dependent inhibition of the growth of L1210 cells in vitro by the new tricyclic pyrone analogs 3A and 3D & 3E. The protocol of the experiment was identical to that of FIG. 5. Cells were incubated in the presence or absence (.sup., control) of 3.12 μM 3A (▪), 3D & 3E (□) and CPT (◯), 12.5 μM 3A (▴) and 3D & 3E (Δ), or 50 μM 3A (♦) and 3D & 3E (⋄), and their density was monitored in triplicate every 24 hours. Cell numbers are plotted on a logarithmic scale.
In FIG. 8 the abilities of the concentrations of 3A tested in FIG. 7 to inhibit the growth of L1210 cells in vitro are compared at days 1 (□), 2 (▪), 3 (◯) and 4 (). The results are expressed as % of the numbers of vehicle-treated control cells after 1 (15,387±1,723 cells/ml), 2 (54,880±6,256 cells/ml), 3 (458,280±52,244 cells/ml), and 4 (1,185,000±125,610 cells/ml) days in culture (100±11 %; striped area). The concentrations of 3A are plotted on a logarithmic scale. Bars: means±SD (n=3). a Not significantly different from control; b P<0.025 and c P<0.05, significantly smaller than control.
In FIG. 9, the abilities of the concentrations of 3D & 3E tested in FIG. 7 to inhibit the growth of L1210 cells in vitro are compared at days 1 (□), 2 (▪), 3 (◯) and 4 (). The determination of the results was identical to that of FIG. 8. The concentrations of 3D & 3E are plotted on a logarithmic scale. Bars: means±SD (n=3). a Not significantly different from control; b P<0.05, significantly smaller than control.
FIG. 10 shows the concentration-dependent inhibition of the growth of L1210 cells in vitro by the new tricyclic pyrone analog 2A. The protocol of the experiment was identical to that of FIG. 5. Cells were incubated in the presence or absence (.sup., control) of 1.56 (▪), 3.12 (□), 6.25 (▴), 12.5 (Δ), 25 (♦) and 50 μM 2A (⋄) or 1.56 μM CPT (◯), and their density was monitored in triplicate every 24 hours. Cell numbers are plotted on a logarithmic scale.
In FIG. 11, the abilities of the concentrations of 2A tested in FIG. 10 to inhibit the growth of L1210 cells in vitro are compared at days 1 (□), 2 (▪), 3 (◯) and 4 (). The results are expressed as % of the numbers of vehicle-treated control cells after 1 (46,480±4,462 cells/ml), 2 (135,880±13,004 cells/mil), 3 (495,440±51,823 cells/ml), and 4 (1,009,520±103,476 cells/ml) days in culture (100±10%; striped area). The concentrations of 2A are plotted on a logarithmic scale. Bars: means±SD (n=3). a Not significantly different from control; b P<0.025 and c P<0.005, significantly smaller than control.
FIG. 12 shows the concentration-dependent inhibition of the growth of L1210 cells in vitro by the new tricyclic pyrone analog 2A. The protocol of the experiment was identical to that of FIG. 5. Cells were incubated in the presence or absence (.sup., control) of 0.19 (▪), 0.39 (□), 0.78 (▴), 1.56 (Δ) 3.12 (♦), 6.25 (⋄) and 12.5 μM 2A (▾) or 0.78 μM CPT (∘), and their density was monitored in triplicate every 24 hours. Cell numbers are plotted on a logarithmic scale.
In FIG. 13, the abilities of the concentrations of 2A tested in FIG. 12 to inhibit the growth of L1210 cells in vitro are compared at days 1 (□), 2 (▪), 3 (◯) and 4 (). The results are expressed as % of the numbers of vehicle-treated control cells after 1 (50,560±2,730 cells/ml), 2 (198,987±9,452 cells/ml), 3 (862,707±39,253 cells/ml) and 4 (1,655,240±86,900 cells/ml) days in culture (100±5%; striped area). The concentrations of 2A are plotted on a logarithmic scale. Bars: means±SD (n=3). a Not significantly different from control; b P<0.05 and c P<0.005, significantly smaller than control.
FIG. 14 shows the ability of the new tricyclic pyrone analog 2A to completely inhibit polymerization of pure tubulin in a cell-free system in vitro. In a final volume of 200 μl, a solution of 2.5 mg/ml tubulin protein from bovine brain, 80 mM PIPES buffer, pH 6.8, 1 mM MgCl 2 , 1 mM EGTA, 1 mM GTP, and 10% glycerol was incubated at 35° C. for 20 minutes in the presence or absence (control) of 25 μM of compound 2A. The absorbance of the solution at OD 340 nm was measured to determine the rate of tubulin polymerization.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Tricyclic pyrones of this invention were tested for their ability to prevent L1210 leukemic cells from synthesizing macromolecules and growing in vitro. The term macromolecules, as used herein, refers to DNA, RNA and proteins. The compounds tested are listed with structures) in Table 2.
TABLE 2______________________________________Compounds Tested for Antitumor Activity______________________________________1 #STR19##222 #STR20##1A3 #STR21##1D & 1E: R = CHO4 #STR22##3A5 #STR23##3B & 3C: R = H3D & 3E: R = CHO6 #STR24##2A7 #STR25##2B & 2C: R = H2D & 2E: R = CHO8 #STR26##5B9 #STR27##23______________________________________
Compound 23, 20(S)-camptothecin (CPT), a known anticancer drug, which inhibits topoisomerase I activity and exhibits a broad spectrum of antitumor activity, was also tested for purposes of comparison, as was compound 22, tri(deacetyl)pyripyropene A (Tomoda, H., et al. (1994), "Relative and Absolute Stereochemistry of Pyripyropene A, A Potent, Bioavailable Inhibitor of Acyl-CoA:Cholesterol Acyltransferase (ACAT),"J. Am. Chem. Soc. 116:12097-12098), Obata, R. et al. (1996), "Chemical modification and structure-activity relationships of pyripyropenes. 1. Modification at the four hydroxyl group,"J. Antibiotics 49:1133-1148, a tetracyclic pyrone, and compound 5B (4-hydroxy-6-(3-pyridyl)-2-pyrone), a monocyclic pyrone. The most preferred compounds of this invention were more effective than compounds 22 and 5B in inhibiting DNA synthesis and tumor cell growth, and were somewhat less effective than CPT at the concentrations tested.
This invention also provides a new chemical reaction as shown in Scheme 1 involving the condensation of pyrones with cyclohexenecarboxaldehydes to synthesize the cancer-active tricyclic pyranes of this invention. For example, equivalent molar amounts of the aldehyde and pyrone in solution, e.g., in ethyl acetate and 0.5 equivalents of L-proline, are stirred together under argon for three days, increasing the temperature from about 25° C. the first day to about 60° C. the last day, followed by dilution, washing, drying and concentrating.
More specifically, a simple synthesis of tricyclic pyrones with the general structure as depicted in Formula 1 (Scheme 1) is provided using a coupling reaction of 1-cyclohexenecarboxaldehydes (4) and 6-substituted 4-hydroxy-2-pyrones (5). For example, treatment of 1-cyclohexenecarboxaldehyde (4A) with one equivalent of 4-hydroxy-6-methyl-2-pyrone (5A) and 0.5 equivalent of L-proline in ethyl acetate at 70° C under argon for 12 hours provided an 80% yield (based on reacted pyrone 5A) of 1A (Scheme 2). The structure of 1A was determined by 1 H and 13C NMR, mass spectrometry, IR, elemental analysis, and single-crystal X-ray analysis. ##STR28##
Similarly, Pyrone 5A also condensed with carboxaldehydes 4B and 4C separately in the presence of 0.5 equivalent of L-proline or catalytic amount of piperidine and acetic acid in ethyl acetate at 60-80° C. to give a 72% yield of a mixture of 1B and 1C (in a ratio of 1.6:1; determined by 1H NMR spectrum) and a 62% yield of a mixture of 1D and 1E (in a ratio of 3:1), respectively (Scheme 2). Compounds 1B and 1C were not separated; however, oxidation of this mixture with 1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one 1 in CH 2 Cl 2 at room temperature gave the corresponding C-6 ketone 6. Reduction of ketone 6 with diisobutylaluminum hydride in THF provided pure cis-alcohol 1B. Pyranobenzopyrans 1D and 1E were separated by column chromatography and the structure of the cis-isomer, 1D, was unequivocally determined by a single-crystal X-ray analysis. Basic hydrolysis of pure 1D with K 2 C0 3 in MeOH at room temperature gave pure alcohol 1B (Scheme 3). ##STR29##
Aldehydes 4B and 4C were synthesized by a modification of the procedure reported by Corey and Erickson (Corey, E. J. and Erickson, B. W. (1971) "Oxidative hydrolysis of 1,3-dithiane derivatives to carbonyl compounds using N-halosuccimide reagent," J. Org. Chem. 36(3):553-560) which is depicted in Scheme 4. Bromination of 2-methylcyclohexanone (7) with 1 equivalent of N-bromosuccinimide (Rinne, W. W. et al., "New methods of preparation of 2-methylcyclohexen-1-one," J. Am. Chem. Soc. (1950) 72:5759-5760) in refluxing CCl 4 for 12 hours gave quantitative yield of 2-bromo-2-methylcyclohexanone. Dehydrobromination of this bromide with three equivalents of Li 2 CO 3 and three equivalents of LiBr in N,N-dimethylformamide (DMF) (Stotter, P. L. and Hill, K. A., "α Halocarbonyl Compounds. E. A Position-Specific Preparation of α-Bromo Ketones by Bromination of Lithium Enolates. A Position-Specific Introduction of α, β-Unsaturation into Unsymmetrical Ketones,"J. Org. Chem. (1973) 38:2576-2578) at 130° C. for 3 h provided a 72% yield of 2-methyl-2-cyclohexen-1-one (8). A 1,2-addition reaction of 8 with 1.5 equivalents of lithiated 1,3-dithiane generated from 1,3-dithiane (9) with n-BuLi in THF! in THF at -10° C. to give a 96% yield of the 1,2-adduct 10. Rearrangement of 10 with 1 % sulfuric acid in p-dioxane (52% yield) followed by removal of the dithiane protecting group of the resulting alcohol, 11, with N-chlorosuccinimide (NCS) and silver nitrate in acetonitrile-water gave aldehyde 4B (50% yield). Alcohol 4B is not a stable compound and decomposes upon standing at room temperature in a few days. A more stable material, 4C, was synthesized in a better yield from the rearrangement reaction of 10 in formic acid-THF in the presence of catalytic amount of p-toluenesulfonic acid (70% yield) followed by removal of the dithiane moiety with NCS-AgNO 3 (59% yield) (Scheme 4). In the formic acid rearrangement reaction, besides the desired product, 1- 2-(1,3-dithianyl)!-3-formyloxy-2-methyl-1-cyclohexene, 9% yield of 3- 2-(1,3-dithianyl)!-2-methyl-2-cyclohexen-1-ol (11) was also isolated.
To demonstrate the generality of the newly-developed condensation reaction (i.e., Scheme 2), other pyrones such as 5B and 5C were also prepared and used in the condensation reaction. Scheme 5 outlines the preparation of 5B and 5C by following a small modification of the reported procedure (only 5B was reported)(Narasimhan, N. S. and Ammanamanchi, R., "Mechanism of acylation of dilithium salts of β-ketoesters: an efficient synthesis of anibine,"J. Org. Chem (1983) 48:3945-3947). Treatment of ethyl acetoacetate in diethyl ether with 2.5 equivalents of lithium diisopropylamide (LDA) at 0° C. for 1 h followed by 1 equivalent of ethyl nicotinate (12A) gave an 87% yield of triketone 13A (Scheme 5). Cyclization of 13A at 150° C. under 3 mm Hg reduced pressure for 0.5 h gave an 89% yield (based on 10.9% of recovered starting triketone) of pyrone 5B. Similarly, pyrone 5C was synthesized from ethyl 3,4-dimethoxybenzoate (12B). However, during the work-up procedure of coupling reaction of ethyl acetoacetate and 12B, the corresponding carboxylic acid of 13B was isolated, which upon methylation with diazomethane in methylene chloride and diethyl ether afforded a 56% yield of methyl ester 13B. Intramolecular cyclization of 13B gave a 70.5% yield (based on 60% recovery of starting triketone 13B) of 5C. ##STR30##
Condensation of aldehyde 4A with pyrones 5B and 5C separately in the presence of 0.5 equivalent of L-proline in ethyl acetate at 70° C. generated pyranobenzopyrans 2A and 3A in 73% and 62% yield, respectively (Scheme 6). In the condensation of formyloxy aldehyde 4C, some of the formyloxy group was hydrolyzed to produce the corresponding alcohol. Hence, treatment of aldehyde 4C with pyrone 5B and 0.5 equivalent of L-proline in ethyl acetate at 70° C. afforded 39% yield of formates 2D and 2E (in a ratio of 2:1) and 11% yield of alcohols 2B and 2C (ratio of 2:1). ##STR31## Similarly condensation of 4C and 5C gave a 48% yield of 3D and 3E (2:1) and a 24% yield of 3B and 3C (2:1). In general, these cis and trans isomers (such as 3D and 3E, etc.) are separable by silica gel column chromatography (see Experimental Section). Condensation of alcohol 4B with pyrone 5C also provides a mixture of 2:1 ratio of the cis and trans adducts 3B and 3C.
This condensation reaction apparently is a general reaction and therefore can be applied to nitrogen and sulfur analogs. Hence, general structures, 14 (Scheme 7), can be synthesized from this reaction and subsequent chemical conversion of compounds 1-3 and 14 will provide a large number of derivatives, some of which are outlined in Scheme 7, such as 15 and 16. In Scheme 7, the synthesis of nitrogen analogs, 14A and 14B, and a sulfur analog, 14C, are demonstrated. The precursor pyrone 20 is a known compound (Cervera, M. et al., "R-4-Amino-6-methyl-2H-pyran-2-one, Preparation and Reactions with Aromatic Aldehydes," Tetrahedron (1990) 46:7885-7892). We have already prepared this compound and the reactions are depicted in Scheme 7.
Additionally, a simple synthesis of nitrogen-containing tricyclic pyrones with general structure as depicted in Formulas IV and V is provided using a coupling reaction of 4-amino-pyrones and 1-cyclohexenecarboxaldehydes. Syntheses for the 5-nitrogen analogs 24 and 26 are shown in Scheme 8. It should be noted that nitrogen analog 14A was expected to be found from the reaction of 20 and 4A. However, 14A undergoes dehydrogenation under the reaction conditions to give compound 24. The synthesis of the 5-nitrogen analogs 24 and 26 were accomplished by heating 4-aminopyrone 20 with aldehyde 4A in the presence of a catalytic amount of (S)-(+)-10-camphorsulfonic acid in toluene at 85° C. to give 19% yield (based on unrecovered starting material) and 48% yield of the isomer 26 (Scheme 8b). The NMR spectra alone cannot determine the structures of 24 and 26. Single crystals of 24 and 26 were obtained (separately) and their structures were firmly established by single-crystal X-ray analyses. ##STR32##
A remarkable asymmetric induction was also observed for the newly-developed condensation reaction from a C-4 stereogenic center in the carboxaldehyde, such as (S)-(-)-perillaldehyde (27). Treatment of (S)-27 with pyrone 5A, 5B, and 5C separately gave single diastereomers 28 (78% yield), 29 (65% yield), and 30 (63% yield), respectively (Scheme 9). The structure of 28 was firmly established by single-crystal X-ray analysis and the data from 1 H NMR spectra also agrees with the same stereochemical assignment: 5aS and 7S: the C-5a proton (for example, in 28) resonates at δ 5.15 ppm as a doublet of a doublet with J=11.2 Hz and 5.2 Hz (axial-axial and axial-equatorial couplings), indicative of an axial hydrogen (at C-5a). ##STR33##
To demonstrate the possibility of preparing various substituted derivatives, several chemical manipulations were also performed on the newly-developed tricyclic pyrones. Scheme 10 summarizes these manipulations. Deprotonation of 1A with lithium diisopropylamide (LDA) in THF at -78° C. followed by methyl chloroformate gave a 72% yield of methyl ester 31. Basic hydrolysis of 31 with KOH in THF and H 2 O provided a good yield of the acid 32. The lithiated anion derived from 1A and LDA also reacted with 0.5 equivalent of dielectrophile, adipoyl chloride, to produce diketone 33 (which exists as the enol form). The isopropenyl group of C-7 substituted tricyclic pyrones such as 28 can be hydroxylated with 1 equivalent of borane-THF followed by NaOH-30% H 2 O 2 to give primary alcohols 34 (69% yield; two inseparable diastereomers at C-12). Oxidation of alcohols 34 with 1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one in methylene chloride gave an 87% yield of aldehydes 35.
When a greater than 1 equivalent of borane was used, both C-11 and C-9a double bonds can be oxidized to afford a mixture of diols such as 36 (2 diastereomers at C-11). Hence, hydroboration of pyrone 30 with excess of borane in THF followed by NaOH-30% H 2 O 2 gave diol 36 as a 1:1 mixture of two diastereomers at C-11. Acylation of 36 with pyridine and valeryl chloride in methylene chloride gave good yield of ester 37. C-9a double bond of 2A was epoxidized with 1 equiv of HCl (to protonate the pyridine nitrogen) followed by 1 equiv of m-chloroperbenzoic acid (MCPBA) to give a 1:4.1 ratio of 38A and 38B. ##STR34##
In addition to tricyclic pyrones, this invention provides a facile synthesis of tetracyclic pyrones (such as 46, Scheme 11). Treatment of (R)-carvone (39) with lithium diisopropylamide (LDA) in THF at -40° C. and MeI (-30° C.) gave an excellent yield of the corresponding C-6-monomethylated product. The regiospecific alkylation of carvone at C-6 is a known reaction (Gesson, J-P et al., "A New Annulation of Carvone to Chiral Trans and Cis Fused Bicyclic Ketones," Tetrahedron (1986) 27:4461-4464). Subsequently, alkylation of this methylated product with LDA in THF at 0° C., followed by I equivalent of hexamethyl-phosphoramide (HMPA), and cis-1-iodo-3-(methanesulfonyloxy)-1-propene (40) at 0° C. then room temperature gave a 73% yield of iodide 41 as a single diastereomer and 14% recovery of 6-monomnethylated carvone (Scheme 11). No other stereoisomer was detected. Cyclization of iodide 41 with palladium acetate, triphenylphosphine, silver carbonate, CO, and MeOH in DMF at 32° C. gave a 50% yield (isolated) of ester 42. Ester 42 was converted into its carboxylic acid 43 in 96% yield by the treatment with KOH in MeOH and water at 25° C. As far as we know, this is the shortest route for the synthesis of optically pure trans-decalinone derivatives, such as 42; in this synthesis, no protecting group is needed. Addition reaction of acid 43 with the lithiated anion of 9 in THF gave adduct 44 which can be converted into aldehyde 45. Condensation of 45 with pyrone 5B will give tetracyclic pyrone 46 (a new compound).
A 23% yield of the correspnding β-isomer, compound 47, was also isolated from the above palladiun-cyclization reaction. The stereochemistry of these compounds, 42 and 47, were firmly established by 2D NOESY spectroscopy and the results are depicted in structure 47 (Scheme 12). For example, in the 2D NOESY spectrum of the minor product, 47, NOE appears between C4a-H and C-10-methyl; and C-11-CH 2 and C-13-CH 2 . The NMR signals of C-13 and C-10 methyls of 42 are close to each other, hence it is difficult to determine their NOE. ##STR35##
Clearly, as will be appreciated by one skilled in the art, many other chemical manipulations can be carried out on the tricyclic and tetracyclic pyrones to produce various useful biologically active drugs. Additionally, the reactions illustrated in Schemes 1-11 can be modified to produce similar compounds, as will be appreciated by those skilled in the art.
The following examples illustrate the invention:
EXAMPLES
Compound Syntheses
General Methods. Nuclear magnetic resonance spectra were obtained at 400 MHz for 1 H and 100 MHz for 13 C in deuteriochloro-form, unless otherwise indicated. Infrared spectra are reported in wavenumbers (cm -1 ). Mass spectra were taken from a Hewlett Packard 5890 Series II, GC-HPLC-MS. FAB spectra were taken by using Xe beam (8 KV) and m-nitrobenzyl alcohol as matrix. Davisil silica gel, grade 643 (200-425 mesh), was used for the flash column chromatographic separation. THF and diethyl ether were distilled over sodium and benzophenone before use. Methylene chloride was distilled over CaH 2 and toluene and benzene were distilled over LiAlH 4 . Ethyl acetate was dried over CaCl 2 and filtered and distilled under argon atmosphere.
General Procedure for the Condensation of Pyrone and Enal
The following reaction procedures are representative of the condensation reactions of this invention.
cis- and trans-3,5a-Dimethyl-6-formyloxy-1H-5a,6,7,8 9-pentahydro-1-oxopyranol 4,3-b! 1!benzopyran (1D and 1E)
A solution of 0.147 g (0.88 mmol) of aldehyde 4C, 0.11 g (0.88 mmol) of pyrone 5A, and 0.05 g (0.4 mmol) of L-proline in 10 mL of ethyl acetate was stirred under argon at 25° C. for 1 day, 40° C. (bath temperature) for 3 days, and 60° C. for 1 day. The mixture was diluted with 120 mL of methylene chloride, washed with 50 mL of saturated aqueous NaHCO 3 , and then with 50 mL of brine, dried (MgSO 4 ), concentrated, and column chromatographed on silica gel using a gradient mixture of hexane and diethyl ether as eluant to give 0.1133 g (46.5% yield) of 1D and 0.0378 g (15.5% yield) of 1E. Compound 1D: mp 138-140° C. IR (Nujol) v 2980, 1720, 1690, 1630, 1550, 1110; 1 H NMR δ 8.14 (d, J=1 Hz, 1 H, CHO), 6.18 (d, J=2.2 Hz, 1 H, C10 H), 5.73 (s, 1 H, C4 H), 5.31 (dd, J=11.6 Hz, 4.4 Hz, 1 H, C6 H, axial H), 2.39-2.33 (m, 1 H), 2.292.23 (m, 1 H), 2.19 (d, J=0.44 Hz, 3 H, Me), 2.12-2.05 (m, 1 H), 1.88-1.8 (m, 1 H), 1.7-1.5 (m, 2 H), 1.54 (s, 3 H, Me); 13 C NMR δ 162.4 (s, C=O), 162.32 (s), 160.36 (s, 2C), 132.74 (s, C10a), 112.51 (d, C10), 100.08 (d, C4), 97.7 (s, C9a), 84.4 (s, C5a), 76.46 (d, C6), 31.3 (t), 29.26 (t), 23.12 (t), 20.31 (q, Me), 18.88 (q, Me); MS.FAB, m/z 277 (M+1, 100%), 230, 139, 91. Analysis calc for C 15 ,H 16 O 5 : C, 65.21; H, 5.84. Found: C, 65.47; H, 5.61. Single crystals were obtained from the recrystallization in ether and the structure was unequivocally determined by an X-ray analysis.
Compound 1E: 1 H NMR δ 8.11 (d, J=0.92 Hz, 1 H, CHO), 6.23 (d, J=1.6 Hz, 1 H, C10 H), 5.72 (s, 1 H, C4 H), 2.44-2.28 (m, 2 H), 2.19 (d, J=0.6 Hz, 3 H, Me), 2.1-2.0 (m, 1 H), 1.9-1.64 (a series of m, 3 H), 1.57 (s, 3 H, Me); MS.FAB, m/z 277 (M+1, 100%). Basic hydrolysis of 1E with K 2 CO 3 in MeOH gave the corresponding C6 alcohol having exact same NMR as the trans-alcohol obtained from the condensation of pyrone 5A and alcohol 4B.
3-Methyl-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran (1A).
A solution of 0.1 g (0.91 mmol) of cyclohexenecarboxaldehyde (4A), 0.115 g (0.91 mmol) of 4-hydroxy-6-methyl-2-pyrone (5A), and 0.052 g (0.455 mmol) of L-proline in 5 mL of ethyl acetate was heated at 70° C. under argon atmosphere for 24 h. The mixture was cooled to room temperature, diluted with 100 mL of methylene chloride, washed with saturated aqueous NaHCO 3 solution twice (30 mL each), with water (60 mL), and then with brine (60 mL), dried (MgSO 4 ), filtered, and concentrated to give 0.20 g of crude product. Column chromatography on silica gel of the crude product using a gradient mixture of hexane:ether as eluant gave 0.15 g (80% yield based on recovered starting pyrone) of 1A and 0.006 g (5% recovery) of 5A. Compound 1A: mp 110-112° C.; X-ray analysis was carried out on a single crystal obtained from the recrystallization from ether-hexane and the structure was solved. IR (Nujol) v 1710 (s, C═O), 1630 (C═C), 1560. 1 H NMR δ6.07 (s, 1 H C10H), 5.7 (s, 1 H, C4H), 5.02 (dd, J=11, 5 Hz, 1H, C5aH), 2.41 (m, 1H, C9H), 2.18 (s, 3H, Me), 2.13 (m, 1H, C5aH), 2.02-1.88 (m, 2 H), 1.8-1.7 (m, 2H), 1.5-1.4 (m, 2H); 13 C NMR δ 174 (s, C═O), 163.24 (s, C3), 161.38 (s, C4a), 133.06 (s, C10a), 109.17 (d, C10), 99.76 (d, C4), 97.33 (s, C9a), 79.69 (s, C5a), 35.15 (t, C9), 33.14 (t, C6), 26.89 (t, C7), 24.52 (t, C8), 20.06 (q, Me); MS (CI) m/z 219 (M+1). Analysis Calculated for C 13 H 14 O 3 : C 71.54; H 6.47. Found: C, 71.39; H, 6.53.
Preparation of 2-methyl-2-cyclohexen-1-one (8)
A solution of 15 g (0.134 mol) of 2-methyl-1-cyclohexanone (7) and 23.84 g (0.134 mol) of N-bromosuccinimide in 150 mL of carbon tetrachloride was stirred and heated to reflux for 12 h under argon. The mixture was cooled to room temperature, filtered through Celite to remove succinimide and the filter cake was washed with 150 mL of ether. The filtrate was concentrated to give 25.6 g (100% yield) of 2-bromo-2-methyl-1-cyclohexanone. 1 H NMR δ 3.21 (td, J=16 Hz, 8 Hz, 1 H, CH--CO), 2.36 (m, 2 H), 2.06 (m, 2 H), 1.82 (s, 3 H, Me), 1.77 (m, 2 H), 1.62 (m, 1 H).
A mixture of 25.6 g (0.134 mol) of the above 2-bromo-2-methylcyclohexanone, 29.7 (0.4 mol) of Li 2 CO 3 and 34.9 g (0.4 mol) of LiBr in 300 mL of DMF was heated at 130° C. under argon for 3 h. The reaction mixture was cooled to room temperature, diluted with 400 mL of water, and extracted three times with ether (300 mL×2 and 200 mL). The combined extract was dried (MgSO 4 ), concentrated on a rotary evaporator to give 12.96 g of crude product which was subjected to vacuum distillation to give 10.6 g (72% yield) of 8, bp. 90-95° C./45 mm Hg; Lit. (Rinne, W. W. et al., "New Methods of Preparation of 2-methylcyclohexen-1-one," J. Am. Chem. Soc (1950) 72:5759-5760) 93-97° C./25 mm Hg; 1 H NMR δ 6.75 (broad s, 1 H, ═CH), 2.42 (dd, J=5.6 Hz, 5 Hz, 2 H), 2.33 (m, 2H), 1.95 (pent, J=8 Hz, 2 H), 1.78 (q, J=2 Hz, 3 H, Me); 13 C NMR δ 199.88 (s, C═O), 145.61 (d, ═CH), 135.65 (s, ═C), 38.33 (t), 26.04 (t), 23.32 (t), 15.97 (t).
1- 2-(1,3-Dithianyl)!-2-methyl-2-cyclohexen-1-ol (10)
To a cold (-10° C.) solution of 6.71 g (55.9 mmol) of 1,3-dithiane (9; commercially available) in 50 mL of THF under argon was added 24.6 mL (55.9 mmol; from a 2.27 M solution in hexane) of n-BuLi dropwise via syringe over 35 minutes and the resulting solution was stirred for 2 hours. In a separate flask, a solution of 4.10 g (37.7 mmol) of 8 in 25 mL of THF was prepared and this solution was added via cannula into the above dithiane anion solution. The solution was stirred at -10C. for 1 h and kept in the refrigerator for 18 h, diluted with 100 mL of water, stirred for 10 minutes, and extracted three times with diethyl ether (100, 75, and 50 mL). The combined extract was washed twice with brine (2×100 mL), dried (MgSO 4 ), filtered, concentrated to give 13.147 g of crude product. Column chromatographic separation on silica gel using a gradient mixture of hexane:ether as eluant gave 8.208 g (96% yield) of 10 as an oil. 1 H NMR δ 5.74 (t, J=4 Hz, 1 H, ═CH), 4.42 (s, 1 H, CH--S), 3.0-2.8 (m, 4 H CH 2 --S), 2.28 (s, 1 H, OH), 2.16-1.6 (series of m, 8 H), 1.82 (broad s, 3 H, Me); 13 C NMR δ 133.81 (s, ═C), 130.25 (d, ═CH), 74.04(s, CO), 59.13 (d, CH--S), 33.88 (t, CH 2 S), 31.78 (t, CH 2 S), 31.33 (t, CH 2 ), 26.37 (t, CH 2 ), 25.61 (t, CH 2 ), 18.73 (t, CH 2 ), 17.75 (q, Me); MS (EI) m/z 230 (M + ).
3- 2-(1,3-Dithianyl)!-2-methyl-2-cyclohexen-1-ol (11)
A solution of 1.031 g (4.48 mmol) of alcohol 10 in 50 mL of p-dioxane and 75 mL of 1% aqueous solution of H 2 SO 4 was stirred at 25° C. for 5.5 h, and then extracted three times with diethyl ether (100 mL each). The combined extract was washed with 80 mL of saturated aqueous NaHCO 3 , twice with water (80 mL each) and 80 mL of brine, dried (MgSO 4 ), concentrated, and column chromatographed on silica gel using a gradient mixture of hexane and diethyl ether as solvent to give 0.533 g (58% yield based on recovered starting material 10) of 11 as an oil and 0.11 g (11% recovery) of 10. Compound 11: 1 H NMR δ 5.09 (s, 1 H, CHS), 3.97 (broad s, 1 H, CHO), 3.04-2.95 (m, 2 H, CH 2 S), 2.87-2.81 (m, 2 H, CH 2 S), 2.32-2.24 (m, 1 H), 2.16-2.07 (m, 2 H), 1.91 (t, J=4 Hz, 3 H, Me), 1.89-1.58 (a series of m, 5 H); 13C NMR δ 132.89 (s, C═), 131.85 (s, ═C), 69.6 (d, CO), 51.11 (d, CHS), 31.81 (t), 31.36 (2 C, t, CH 2 S), 26.6 (t), 25.45 (t), 18.48 (t), 16.41 (q, Me); MS (EI) m/z 230 (M+). Analysis Calc. for C 11 H 18 OS 2 : C, 57.35; H, 7.87. Found: C, 57.56; H, 8.10.
3-Hydroxy-2-methyl-1-cyclohexen-1-carboxaldehyde (4B)
To a flask containing a stirring bar, 0.197 g of AgNO 3 (1.16 mmol) and 0.139 g (1.04 mmol) were added and the content was dried under vacuum, maintained under argon atmosphere, and 6 mL of CH 3 CN and 2.5 mL of H 2 O were added. The flask was stirred and cooled over ice-water bath, and a solution of 0.059 g (0.26 mmol) of 11 in 5 mL of acetonitrile was added dropwise via cannula. The solution was stirred at 0° C. for 45 min, and 1 mL each of saturated aqueous Na 2 SO 3 and Na 2 CO 3 were added at 1 min interval, and then 20 mL of a 1:1 mixture of CH 2 Cl 2 and petroleum ether was also added. The resulting mixture was filtered through Celite and the solid carefully washed with 120 mL of 1:1 mixture of CH 2 Cl 2 and petroleum ether. The filtrate was transferred into a separatory funnel and the water layer was removed. The organic layer was washed with 10 mL of saturated aqueous NAHCO 3 , dried (MgSO 4 ), concentrated to give 31.5 mg of the crude aldehyde 4B. The 1 H NMR spectrum of the crude product indicated 18 mg (50% yield) of the desired aldehyde and 13 mg of succinimide. This material can be used directly in the next reaction without further purification. In a separated reaction, the mixture was separated on silica gel flash column chromatography and provided 18 mg (50% yield) of pure 4B. Aldehyde 4B is not a stable compound and elemental analysis was not performed. 1 H NMR δ 10.18 (s, 1 H, CHO), 4.16 (broad s, 1 H, CH--O), 2.27 (s, 3 H, Me), 2.31-1.6 (a series of m, 6 H); 13 C NMR δ 192.37 (s, C═O), 154.24 (s, C═), 134.96 (s, C═), 70.32 (d, C-O), 31.79 (t), 22.7 (t), 17.91 (t), 14.85 (q, Me); MS, FAB m/z 141 (M+1, 100%), 140 (M+).
3-Formyloxy-2-methyl-1-cyclohexen-1-carboxaldehyde (4C)
A solution of 0.494 g (2.15 mmol) of alcohol 10 and three crystals of p-toluenesulfonic acid (anhydrous) in 2.43 mL of formic acid and 15 mL of THF was stirred under argon at 25° C. for 16 h. The solution was diluted with 100 mL of diethyl ether, washed with 40 mL of saturated aqueous NaHCO 3 , and 50 mL of brine, dried (MgSO 4 ), concentrated, and column chromatographed on silica gel using a gradient mixture of hexane and diethyl ether as eluant to give 0.388 g (70% yield) of 1- 2-(1,3-dithianyl)!-3-formyloxy-2-methyl-1-cyclohexene and 0.048 g (9% yield) of alcohol 11. 1- 2-(1,3-dithianyl)!-3-formyloxy-2-methyl-1-cyclohexene: 1 H NMR δ 8.12 (s, 1 H, CHO), 5.36 (broad s, 1 CHO), 5.1 (s, 1 H, CHS), 3.05-2.95 (m, 2 H, CH 2 S), 2.9-2.8 (m, 2 H, CH 2 S), 2.4-2.3 (m, 1 H), 2.2-2.05 (m, 2 H), 1.94-1.6 (m, 5 H), 1.78 (s, 3 H, Me); 13 C NMR δ 160.97 (s, C═O), 135.18 (s, C═), 128.43 (s, C═), 71.68 (d, C--)), 50.95 (d, CS), 31.34 (t, 2 C, CS), 28.7 (t), 26.43 (t), 25.42 (t), 18.55 (t), 16.31 (q, Me); MS, FAB m/z 259 (M+1), 258 (M+).
To a dried 100 mL-round-bottomed flask 1.19 g (7 mmol) of AgNO 3 , 0.828 g (6.2 mmol) of N-chlorosuccinimide, 40 mL of CH 3 CN and 16 mL of H 2 O were added under argon, and the solution was stirred and cooled over ice-water bath. To it, a solution of 0.4 g (1.55 mmol) of 1- 2-(1,3-dithanyl)!-3-formyloxy-2-methyl-1-cyclohexene in 10 mL of CH 3 CN was added dropwise over 30 min. To the reaction solution, 2 mL saturated aqueous solution of Na 2 SO 3 , 2 mL of saturated aqueous NaCl solution, and 20 mL of a 1:1 mixture of CH 2 Cl 2 :petroleum ether were added sequentially at 1 minute intervals. The whole mixture was then filtered through Celite, washed with 100 mL of CH 2 Cl 2 and petroleum ether. The filtrate was transferred into a separatory funnel, the water layer was separated and extracted with 40 mL of CH 2 Cl 2 . The combined organic layers were dried (MgSO 4 ), filtered, concentrated, and column chromatographed on silica gel using a gradient mixture of hexane and diethyl ether as eluant to give 0.154 g (59% yield) of pure 4C; IR (neat) ν 2750, 1720, 1680 (C═O); 1 H NMR δ 10.2 (s, 1 H, CHO), 8.18 (d, J=0.8 Hz, 1 H, formyloxy CH), 5.53 (t, J=4.8 Hz, 1 H, CH--O), 2.39-2.3 (m, 1 H), 2.14 (s, 3 H, Me), 2.17-2.08 (m, 1 H), 1.94-1.6 (a series of m, 4 H); 13 C NMR δ 191.59 (s, C═O aldehyde), 160.66 (s, C═O of formyloxy), 148.69 (s, C═), 137.36 (s, C═), 71.72 (d, CH--O), 28.57 (t), 22.48 (t), 17.89 (t), 14.76 (q, Me); MS, FAB m/z 169 (M+1), 168 (M+).
Ethyl 5-(3-pyridyl)-3,5-dioxopentanoate (13A)
To a cold (-10° C.) solution of 13.45 mL (96.2 mmol) of diisopropylamine in 150 mL of diethyl ether under argon was added 42.36 mL (96.2 mmol; 2.27 M solution in hexanes) of n-BuLi via syringe and the solution was stirred for 1 h. In a separated flask, 5 g (38.5 mmol) of freshly distilled ethyl acetoacetate and 60 mL of diethyl ether were added and the solution was cooled to -78° C. To it, the above LDA solution was added via cannula, then 5.8 mL (38.5 mmol) of N,N,N',N'-tetramethylethylenediamine (TMEDA) (distilled from LiAlH 4 ) was added via syringe, and the solution was stirred at 0° C. for 3 h. To this dianion solution, a solution of 5.81 g (38.5 mmol) of ethyl nicotinate (freshly distilled) in 60 mL of diethyl ether was added via cannula and the reaction solution was warmed to room temperature and stirred for 30 h. To the solution, 5.5 mL of acetic acid was added and stirred for 10 min, filtered through fritted funnel, and the solid (desired product; exists as a protonated salt) was washed with 200 mL of diethyl ether. The filtrate was concentrated to give 1.691 g of material and the NMR spectrum indicated that it is a mixture of starting material and some unidentified components. The solid was transferred into a beaker and dissolved in 160 mL of distilled water and 60 mL of 1 N HCl, and extracted three times with methylene chloride (120 mL each). The combined extract was washed with 100 mL of brine, dried (MgSO 4 ), concentrated to give 7.921 g (87.5% yield) of the desired product 13A. 1 H NMR spectrum of this material indicated it is sufficiently pure and can be used in the next reaction without purification. Mp 38.5-39° C.; 1 H NMR δ 9.07 (s, 1 H, C-2' H, pyr.), 8.74 (d, J=4.6 Hz, 1H, C6'H, pyr.), 8.16 (d, J=8 Hz, C4'H), 7.41 (dd, J=8 Hz, 4.6 Hz, C5'H), 6.32 (s, 1 H, ═CH of enol; the compound completely exists as enol form at C4), 4.22 (q, J=7.2 Hz, 2 H, OCH 2 ), 3.5 (s, 2 H, CH 2 --C═O), 1.3 (t, J=7.2 Hz, 3 H, Me); 13 C NMR δ 189.93 (s, C═O, C3), 179.97 (s, O--C=, C5), 167.11 (s, C═O ester), 152.74 (d, C2'), 148.13 (d, C6'), 134.3 (d, C4'), 129.7 (s, C3'), 123.41 (d, C5'), 97.18 (d, ═CH, C4), 61.39 (t, OCH 2 ), 45.66 (t, CH 2 ), 13.93 (q, Me); MS.FAB, m/z 236 (M+1), 235 (M+).
4-Hydroxy-6-(3-pyridyl)-2-pyrone-(5B)
To a flask equipped with an adaptor connecting to a manifold, 0.594 g (2.53 mmol) of ester 13A was added while the flask was maintained under argon. The flask was then connected to a vacuum set at 3 mm Hg pressure and heated over an oil bath at 150° C. The flask was kept at this temperature for 0.5 h and then cooled to room temperature. Diethyl ether was added to the crude product and filtered, washed with diethyl ether. The solid after drying under vacuum gave 0.38 g (89% yield based on recovered starting ester 13A) of 5B. The filtrate was concentrated and column chromatographed to give 0.065 g (10.9% recovery) of starting ester 13A. Compound 5B: mp 187-189° C.; Lit. (Narashimhan, N. S. and Ammanamanchi, R., "Mechanism of acylation of dilithium salts of β-ketoesters: an efficient synthesis of anibine," J. Org. Chem. (1983) 48:3945-3947) 254-255° C.; 1 H NMR(CDCl 3 and DMSO-d6) δ 9.03 (s, 1 H, C2'H), 8.67 (d, J=5.2 Hz, 1 H, C6'H) pyr ring), 8.13 (d, J=8 Hz, 1 H, C4'H), 7.41 (dd, J=8 Hz, 5.2 Hz, 1 H, C5'H), 6.56 (d, J=1.6 Hz, 1 H, C3 H), 5.62 (d, J=1.6 Hz, 1 H, C5 H); MS.FAB, m/z 190 (M+1), 189 (M+).
Methyl 5-(3,4-dimethoxyphenyl)-3,5-dioxopentanoate (13B)
To a cold (-20° C.) solution of 8.9 mL (63.7 mmol) of diisopropylamine in 100 mL of diethyl ether under argon was added 28.1 mL (63.7 mmol; 2.27 M solution in hexanes) of n-BuLi via syringe and the solution was stirred at 0° C. for 45 min. In a separated flask, 3.315 g (25.5 mmol) of freshly distilled ethyl acetoacetate and 50 mL of diethyl ether were added and the solution was cooled to -78° C. To it, the above LDA solution was added via cannula, then 3.84 mL (25.5 mmol) of N,N,N',N'-tetramethylethylenediamine (TMEDA) (distilled from LiAlH 4 ) was added via syringe, and the solution was stirred at 0° C. for 3 h. To this dianion solution, a solution of 5.0 g (25.5 mmol) of methyl 3,4-dimethoxybenzoate in 50 mL of diethyl ether was added via cannula and the reaction solution was warmed to room temperature and stirred for 40 h. The reaction mixture was filtered through fritted funnel, and the solid (desired product) was saved. The organic filtrate from the above filtration was washed with a solution of 50 mL of 1N HCl and 50 mL of distilled water, and then with 80 mL of brine, dried (MgSO 4 ), and concentrated to give the desired product, 5-(3,4-dimethoxyphenyl)-3,5-dioxopentanoic acid. The solid obtained above was dissolved in 80 mL of distilled water and 10 mL of 1N HCl solution, and washed twice with methylene chloride (100 mL each). The water layer was further acidified with 100 mL of 1N HCl, extracted twice with methylene chloride (50 mL each). The combined methylene chloride extract was washed with 80 mL of brine, dried (MgSO 4 ), concentrated to give the desired carboxylic acid 5-(3,4-dimethoxyphenyl)-3,5-dioxopentanoic acid!. This acid and the above acid from the filtrate were combined and dissolved in 50 mL of CH 2 Cl 2 , cooled over ice-water bath, and a solution of diazomethane in diethyl ether was added dropwise until the carboxylic acid was no longer present. The solution was concentrated on a rotary evaporator and dried under vacuum, and column chromatographed on silica gel using a gradient mixture of hexane and ethyl acetate as eluant to give 3.798 g (56% yield) of pure 13B. 1 H NMR δ 7.51 (dd, J=8.5 Hz, 2 Hz, 1 H, C5' H, Ar), 7.45 (d, J=2 Hz, 1 H, C2' H), 6.9 (d, J=8.5 Hz, 1 H, C6' H), 6.24 (s, 1 H, ═CH of enol at C4& 5), 3.95 (s, 6 H, 2 OMe on Ar ring), 3.77 (s, 3 H, MeO), 3.47 (s, 2 H, CH 2 ); 13 C NMR δ 186.18 (s, C3 C═O), 184.05 (s, C5═C--O), 168.21 (s, C═O ester), 153.16 (s, C4' Ar), 149.07 (s, C3' Ar), 127.04 (s, Cl' Ar), 121.49 (d, C2'), 110.56 (d, C5'), 109.66 (d, C6'), 96.17 (d, C4 ═CH), 56.06 (q, OMe), 56.0 (q, OMe), 52.32 (q, OMe of ester), 44.89 (t, CH 2 ); MS.FAB, m/z 281 (M+1), 280 (M+).
4-Hydroxy-6-(3,4-dimethoxyphenyl)-2-pyrone (5C)
A flask containing the methyl ester 13B (2.2 g; 7.86 mmol) was connected into a vacuum system to provide -3 mmHg pressure and heated over an oil bath to 160° C. over a one hour period. The reaction was kept at this temperature for another one hour, cooled to room temperature, diluted with a small amount of ether and filtered to collect the yellow solids, washed with ether, and the solids were dried under vacuum to give 1.04 g (70.5% yield based on recovered starting material 13B) of pyrone 5C and 0.534 g (24% recovery) of starting ester 13B. Compound 5C: mp 210-212° C., 1 H NMR δ 7.40 (dd, J=8.3 Hz, 2 Hz, 1 H, C6' of the phenyl ring), 7.33 (d, J=2 Hz, 1 H, C2' of Ph ring), 6.91 (d, J=8.3 Hz, 1 H, C5'), 6.40 (s, C3 H), 5.55 (s, 1 H, C5 H), 3.95 (s, 3 H, OMe), 3.94 (s, 3 H, OMe); MS.FAB, m/z 249 (M+1), 248 (M+).
cis- and trans-3,5a-Dimethyl-6-hydroxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b!1!-benzopyran (1B and 1C)
From 0.024 g (0.188 mmol) of aldehyde 4B and 23.7 mg (0.188 mmol) of pyrone 5A, heating with 3 mL of ethyl acetate and 3 drops (˜15 mg) of piperidine and 3 drops of acetic acid at 80° C. for 18 h, 0.033 g (72% yield) of a mixture of 1B and 1C in a ratio of 1.6:1 (obtained from 1 H NMR spectrum) was obtained. Compound 1B: 1 H NMR δ 6.13 (d, J=2 Hz, 1 H, C10 H), 5.77 (s, 1 H, C4 H), 4.07 (dd, J=8.4 Hz, 3.4 Hz, 1 H, C5a H), 2.36-2.16 (a series of m, 2 H), 2.21 (s, 3 H, C3 Me), 2.14 (broad s, 1 H, OH), 1.98-2.04 (m, 1 H), 1.83-1.76 (m, 1 H), 1.56-1.42 (m, 2 H), 1.47 (s, 3 H, C5a Me); 13 C NMR δ 162.42 (s, C1), 162.08 (s, C4a), 158 (s, C3), 134.17 (s, C10a), 111.67 (d, C10), 100.13 (d, C4), 98.08 (s, C9a), 87.07 (s, C5a), 76.16 (d, C6),31.59 (t), 30.94 (t), 23.20 (t), 20.36 (q, Me), 17.52 (q, Me); MS.FAB, m/z 249 (M+1), 248 (M+). Compound IC: 1 H NMR δ 6.23 (d, J=3 Hz, 1 H, C10 H), 5.80 (s, 1 H, C4 H), 3.87 (t, J=1 Hz, 1 H, CSa H), 2.21 (s, 3 H, C3 Me), 1.44 (s, 3 H, C5a Me), 2.4-1.5 (a series of m, 6 H); MS.FAB, m/z 249 (M+1), 248 (M+).
3-(3-Pyridyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran (2A)
From 0.344 g (1.82 mmol) of pyrone 5B and 0.2 g (1.82 mmnol) of aldehyde 4A, 0.373 g (73% yield) of 2A was obtained after column chromatographic separation. IR (Nujol) ν3070, 1690, 1620, 1540, 1200, 1060, 1020. 1 H NMR δ 8.99 (d, J=2 Hz, 1 H, Pyr.), 8.65 (dd, J=4.9 Hz, 2 Hz, 1 H, C6'H), 8.1 (dt, J=8 Hz, 2 Hz, 1 H, C4'H), 7.38 (dd, J=8 Hz, 4.9 Hz, 1 H, C5'H), 6.44 (s, 1 H, C10H), 6.14 (s, 1 H, C4 H), 5.14 (dd, J=11 Hz, 5 Hz, 1 H, C5a H), 2.47 (m, 1H, C9 H), 2.19 (m, 1 H, C9 H), 2.03 (m, 1 H), 1.94 (m, 1 H), 1.86-1.76 (m, 2 H), 1.5 (dt, J=13 Hz, 3.4 Hz, 1 H), 1.37 (dt, J=13 Hz, 3.4 Hz, 1 H); 13 C NMR δ 162.63 (s, C1), 161.44 (s, C4a), 156.51 (s, C3), 151.22 (d, C2'), 146.73 (d, C6'), 134.94 (s, C3'), 132.84 (d, C4'), 127.56 (s, C10a), 123.73 (d, C5'), 109.22 (d, C10), 99.84 (s, C9a), 98.57 (d, C4), 80.08 (d, C5a), 35.34 (t, C9), 33.38 (t, C6), 27.01 (t, C7), 24.62 (t, C8); MS.FAB, m/z 282 (M+1, 100%), 281 (M+), 252, 202, 148, 136, 106. Anal. Calc. for C 17 H 15 NO 3 : C, 72.58; H, 5.37. Found: C, 72.33; H, 5.42.
3-(3,4-Dimethoxyphenyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3b!- 1!benzopyran (3A)
From 0.2 g (0. 81 mmol) of 5C and 0.135 g (0.81 mmol) of aldehyde 4A, 0.20 g (62% yield) of 3A was obtained after column chroinatographic separation. Mp. 137-138° C.; IR (Nujol) ν 3010, 3050, 1700, 1650, 1630, 1560, 1520, 1280, 1240, 1150; 1 H NMR δ 7.37 (dd, J=8.5 Hz, 2 Hz, 1 H, C6'H, Ph ring), 7.28 (d, J=2 Hz, 1 H, C2'H), 6.9 (d, J=8.5 Hz, 1 H, C5'H), 6.29 (s, 1 H, C10 H), 6.14 (s, 1 H, C4 H), 5.07 (dd, J=11.4 Hz, 5.2 Hz, 1 H, C5a H), 3.94 (s, 3 H, OMe), 3.93 (s, 3 H, OMe), 2.45 (d, J=14 Hz, 1 H, C9 H), 2.18 (m, 1 H), 2.02 (m, 1 H), 1.92(m, 1H), 1.78 (m, 2 H), 1.54-1.34 (m, 2 H); 13 C NMR δ 163.44 (s, C1), 161.95 (s, C4a), 159.28(s, C3), 151.3 (s, C4', Ph ring), 149.16 (s, C3'), 133.61 (s, C1'), 124.13 (s, C10a), 118.89 (d, C2'), 111.05 (d, CS'), 109.38 (d, C10), 108.12 (d, C6'), 98.05 (s, C9a), 96.1 (d, C4), 79.75 (d, C5a), 56.12 (q, OMe), 56.04 (q, OMe), 35.25 (t, C9), 33.25 (t, C6), 26.95 (t, C7), 24.58 (t, C8); MS.FAB, m/z 341 (M+1, 100%), 340 (M+), 307, 289, 261, 235, 219. Anal. Calc. for C 20 H 20 O 5 : C,70.58; H, 5.92. Found: C,70.31; H, 6.11.
cis- and trans-3-(3-Pyridyl)-5a-methyl-6-hydroxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!-benzopyran (2B and 2C) and cis- and trans-3-(3-pyridyl)-5a-methyl-6-formyloxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!-benzopyran (2D and 2E):
Condensation of 0.073 g (0.39 mmol) of pyrone 5 B and 0.065 g (0.39 mmol) of aldehyde 4C in the presence of 0.023 g (0.19 ininol) of L-proline in 5 mL of ethyl acetate under argon at 70° C. was carried out for 3 days and then 3 mL of N,N-dimethylformamide (DMF) was added and the reaction mixture was heated at the same temperature for another 3 days. After aqueous work-up as described in the general procedure, 0.131 g of crude product was obtained. Column chromatographic separation of this material afforded 39% yield of formates 2D and 2E (in a ratio of 2:1) and 11% yield of alcohols 2B and 2C (ratio of 2:1). Compounds 2D and 2E, and 2B and 2C are separable by a careful silica-gel column chromatography to give 34 mg (26% yield) of 2D, 17 mg (13% yield) of 2E, 9 mg (7.3% yield) of 2B, and 4 mg (3.7% yield) of 2C. Compounds 2B and 2C were probably formed from the hydrolytic reaction with trace amount of H 2 O contained in DMF.
Compound 2D: Mp. 160-161° C.; 1 H NMR δ 9.0 (d, J=2 Hz, 1 H, C2' H, pyr.), 8.66 (dd, J=5 Hz, 2 Hz, 1 H, C6'H), 8.18 (s, 1 H, CHO), 8.09 (dt, J=8 Hz, 2 Hz, 1 H, C4'H), 7.39 (dd, J=8 Hz, 5 Hz, 1 H, C5'H), 6.46 (s, 1 H, C10H), 6.26 (s, 1 H, C4H), 5.38 (dd, J=12 Hz, 5 Hz, 1 H, C6H), 2.42 (m, 1 H, C9H), 2.3 (m, 1 H, C9H), 2.12 (m, 1 H), 1.88 (m, 1 H), 1.7-1.52 (m, 2 H), 1.60 (s, 3 H, Me); 13 C NMR δ 161.5 (s, C1), 160.14 (d, s, 2 C, CHO & C4a), 157.12 (s, C3), 151.33 (d, C2', pyr.), 146.72 (d, C4'), 134.2 (d, C3'), 132.8 (d, C4'), 127.31 (s, C10a), 123.6 (d, C5'), 112.25 (d, C10), 99.82 (s, C9a), 98.5 (d, C4), 84.61 (s, C5a), 76.18 (d, C6), 31.25 (t, C9), 29.07 (t, C7), 22.85 (t, C8), 18.85 (q, Me); MS.FAB, m/z 340 (M+1, 100%), 293, 278, 266, 240, 202, 173. Anal. Calc. for C 19 H 17 NO 5 : C, 67.25; H, 5.05. Found: C, 67.07; H, 5.29.
Compound 2E: 1 H NMR δ 9.0 (d, J=2 Hz, 1 H, C2'H, pyr.), 8.66 (dd, J=5 Hz, 2 Hz, 1 H, C6'H), 8.14 (s, 1 H, CHO), 8.10 (dt, J=8 Hz, 2 Hz, 1 H, C4'H), 7.39 (dd, J=8 Hz, 5 Hz, 1 H, C5'H), 6.45 (s, 1 H, C10H), 6.31 (s, 1 H, C4H), 5.28 (broad s, 1 H, C6H), 2.46-1.5 (a series of m, 6 H), 1.64 (s, 3 H, Me); MS.FAB, m/z 340 (M+1, 100%).
Compound 2B: 1 H NMR δ 9.0 (d, J=2 Hz, 1 H, C2'H, pyr.), 8.66 (d, J=4 Hz, 1 H, C6'H), 8.10 (dt, J=8 Hz, 2 Hz, 1 H, C4'H), 7.39 (dd, J=8 Hz, 4 Hz, 1 H, C5'H), 6.51 (s, 1 H, C10H), 6.20 (d, J=2 Hz, 1 H, C4H), 4.14 (dd, J=12 Hz, 4.4 Hz, 1 H, C6H), 2.42-1.4 (a series of m, 6 H), 1.54 (s, 3 H, Me); Anal. Calc. for C 18 H 17 NO 4 : C, 69.44; H, 5.50. Found: C, 69.17; H, 5.21.
Compound 2C: 1 H NMR δ 9.0 (d, J=2 Hz, 1 H, C2'H, pyr.), 8.66 (d, J=4 Hz, 1 H, C6'H), 8.10 (dt, J=8 Hz, 2 Hz, 1 H, C4'H), 7.39 (dd, J=8 Hz, 4 Hz, 1 H, C5'H), 6.32 (s, 1 H, C10H), 6.20 (d, J=2 Hz, 1 H, C4H), 3.94 (broad s, 1 H, C6H), 2.42-1.4 (a series of m, 6 H), 1.51 (s, 3 H, Me); MS.FAB, m/z 312 (M+1, 100%).
cis- and trans-3-(3,4-Dimethoxyphenyl)-5a-methyl-6-hydroxy-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3b! 1!-benzopyran (3B and 3C)
Condensation of 0.103 g (0.41 mmol) of pyrone SC and 0.058 g (0.41 mmol) of hydroxy aldehyde 4B gave 3B and 3C in a ratio of 2:1. Column chromnatographic separation gave pure 3B and 3C.
Compound 3B: 1 H NMR δ 7.39 (dd, J=8 Hz, 2 Hz, 1 H, C6', Ph), 7.29 (d, J=2 Hz, C2'H), 6.9 (d, J=8 Hz, 1 H, C5'H), 6.37 (s, 1 H, C10H), 6.2 (d, J=2 Hz, 1 H, C4H), 4.12 (dd, J=12 Hz, 5 Hz, 1 H, C6H), 3.94 (s, 3 H, OMe), 3.93 (s, 3 H, OMe), 2.36 (m, 1 H), 2.26 (m, 1 H), 2.04 (m, 1 H), 1.82 (I, 1 H), 1.6-1.46 (m, 2 H), 1.51 (s, 3 H, Me); MS.FAB, m/z 371 (M+1, 100%), 370 (M+), 355, 325, 307, 261, 219, 207. Anal. Calc. for C 12 H 22 O 6 : C, 68.10; H, 5.99. Found: C, 67.89; H, 5.73.
Compound 3C: 1 H NMR δ 7.38 (dd, J=8 Hz, 2 Hz, 1 H, C6', Ph), 7.29 (d, J=2 Hz, C2'H), 6.9 (d, J=8 Hz, 1 H, C5'H), 6.37 (s, 1 H, C1OH), 6.31 (d, J=2 Hz, 1 H, C4H), 3.92 (m, 1 H, C6H), 3.94 (s, 3 H, OMe), 3.93 (s, 3 H, OMe), 2.53 (broad s, 1 H, OH), 2.42 (1 H), 2.3 (m, 1 H), 2.08 (m, 1 H), 1.88 (m, 1 H), 1.77 (m, 1 H), 1.58 (m, 1 H), 1.49 (s, 3 H, Me); 13 C NMR δ 162.29(s, Cl), 161.6 (s, C4a), 159.52 (s, C3), 151.4 (C4', Ph), 149.19 (s, C3'), 133.87 (s, C1'), 124.01(s, C10a), 118.9 (d, C2'), 112.65 (d, C5'), 111.04 (d, C10), 108.17 (d, C6'), 99.07 (s, C9a), 96.18 (d, C4), 85.62 (s, C5a), 73.07 (d, C6), 56.10 (q, OMe), 55.99 (q, OMe), 31.21 (t, C9), 29.03 (t, C7), 22.62 (t, C8), 19.56 (q, Me); MS.FAB, m/z 371 (M+1, 100%), 370 (M+).
cis- and trans-3-(3,4-Dimethoxyphenyl)-6-formyloxy-5a-methyl-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!-benzopyran (3D and 3E)
From 0.062 g (0.25 mmol) of pyrone 5C and 0.042 g (0.25 mmol) of aldehyde 4C, 48 mg (48% yield) of a 2:1 mixture of formyloxy derivatives 3D and 3E, and 22 mg (24% yield) of a 2:1 mixture of alcohol 3B and 3C were obtained after column chromatographic separation.
Compound 3D: IR (Nujol) ν 3080, 1690 (s, C=O), 1640, 1610, 1595, 1535, 1485, 1310, 1255, 1170, 1130, 1010, 970, 955, 845, 790; 1 H NMR δ 8.20 (s, 1H, CHO), 7.40 (dd, J=8 Hz, 2 Hz, 1 H, C6'H,Ph), 7.27 (d, J=2 Hz, 1 H, C2'H), 6.90 (d, J=8 Hz, 1 H, C5'H), 6.32 (s, 1 H, C10H), 6.24 (d, J=2 Hz, 1 H, C4H), 5.34 (dd, J=12 Hz, 4.6 Hz, 1 H, C6H), 3.94 (s, 3 H, OMe), 3.92 (s, 3 H, OMe), 2.4-1.5 (a series of m, 6 H), 1.58 (q, Me); 13 C NMR δ from a 2:1 ratio of a mixture of 3D (c) and 3E (t)! 162.28 (Cl, t), 162.08 (C1,c), 161.33 (C4a, t), 161.23 (C4a, c), 160.09 (CHO, c), 159.98 (CHO, t), 159.65 (C3, c), 159.40 (C3, t), 151.19 (C4', c), 151.14 (C4', t), 148.88 (C3', c & t), 132.72 (C1', c), 131.79 (C1', t), 123.65 (C10a, c & t), 118.80 (C2', c), 118.73 (C2', t), 112.24 (C5', c), 112.12 (C5', t), 110.77 (C10, c & t), 107.84 (C6', c), 107.77 (C6', t), 97.87 (C9a, c), 97.45 (C9a, t), 95.85 (C4, c), 95.69 (C4, t), 83.98 (C5a, c), 82.67 (C5a, t), 76.23 (C6, c), 73.97 (C6, t), 56.83 (OMe, c & t), 55.74 (OMe, c & t), 30.91 (C9, c), 30.81 (C9, t), 28.82 (C7, c), 27.67 (C7, t), 22.65 (C8, c), 20.36 (C8, t), 18.46 (Me, c & t); MS.FAB, m/z 399 (M+1, 80%), 398 (M+), 352 (90%), 261, 165 (100%), 136.
Compound 3E (pure): 1 H NMR δ 8.15 (s, 1 H, CHO), 7.40 (dd, J=8 Hz, 2 Hz, 1 H, C6'H, Ph), 7.27 (d, J=2 Hz, 1 H, C2'H), 6.90 (d, J=8 Hz, 1 H, C5'H), 6.32 (s, 1 H, C1OH), 6.29 (s, 1 H, C4H), 5.28 (s, 1 H, C6H), 3.94 (s, 3 H, OMe), 3.92 (s, 3 H, OMe), 2.4-1.5 (a series of m, 6 H), 1.62(q, Me); MS.FAB, m/z 399 (M+1, 80%), 398 M+).
Synthesis of 1H-6,7,8,9-tetrahydro-1-oxopyrano 4,3-b!quinoline (24) and 1H-7,8,9,10-tetrahydro-1-oxopyrano 4,3-c!isoguinoline (26) by Scheme 8.
A mixture of 0.190 g (1.52 mmol) of pyrone 20, 250 mg (2.28 mmol) of aldehyde 4A, and 35 mg (0.15 mmol) of (S)-(+)-10-cainphorsulfonic acid in 12 mL of toluene was heated at 85° C. for 3 days under argon atmosphere. The mixture was cooled to room temperature, filtered, and washed with 20 mL of ethyl acetate. The filtrate was diluted with 100 mL of methylene chloride, washed with 50 mL of water, and 50 mL of brine, dried (MgSO 4 ), concentrated, and column chromatographed on silica gel using ethyl acetate:hexane (2:1) as eluant to give 13.3 mg (19% yield; based on unrecovered starting material) of 24, 33 mg (48% yield) of 26, and 150 mg (79% recovery) of pyrone 20. Pyrone 20 can be reused under similar reaction conditions to provide more materials of 24 and 26.
Compound 24: white solids, mp 71-72° C.; 'H NMR (CDCl 3 ) δ 8.15 (s, 1 H, CO H), 6.44 (s, 1 H, C4 H), 3.01 (t, J=7 Hz, 2 H, CH 2 ), 2.88 (t, J=7 Hz, 2 H, CH 2 ), 2.31 (s, 3 H, Me), 1.95 (m, 2 H, CH 2 ), 1.86 (m, 2 H, CH 2 ); 13 C NMR (CDCl 3 ) δ 168 (s, Cl), 165.71 (s, C5 a), 157.69 (s, C4a), 152.22 (s, C3), 137.2 (d, C10), 132.34 (s, C10a), 114.0 (s, C9a), 105.48 (d, C4), 33.34 (t, CH 2 ), 28.69 (t, CH 2 ), 22.59 (t, CH 2 ), 22.32 (t, CH 2 ), 19.89 (q, Me); MS (FAB) 216 (M+1). The structure was unequivocally determined by a single-crystal X-ray analysis.
Compound 26: white solids, mp 73-74° C.; 1 H NMR (CDCl 3 ) δ 8.50 (s, 1 H, C10 H), 6.43 (s, 1 H, C4 H), 3.35 (t, J=6 Hz, 2 H, CH 2 ), 2.82 (t, J=6 Hz, 2 H, CH 2 ), 2.29 (s, 3 H, Me), 1.90-1.80 (m, 4 H, CH 2 ); 13 C NMR (CDCl 3 ) δ 162.5 (s, Cl), 157.4 (s), 156.4 (d, C6), 154.4 (s), 151.4 (s), 132.7 (s), 114.6 (s), 106.5 (d, C4), 28.6 (t, CH 2 ), 27.6 (t, CH2), 22.6 (t, CH 2 ), 21.7 (t, CH 2 ), 19.8 (q, Me); MS (FAB) 216 (M+1), 215, 188, 154, 136. The structure was unequivocally determined by a single-crystal X-ray analysis.
(5aS, 7S)-7-Isopropenyl-3-methyl-1H-5a,6,7,8,9-pentahydyro-1-oxopyrano 4,3-b! 1!benzopyran (28)
From 1.000 g (7.93 mmol) of 5A and 1.191 g (7.93 mmol) of aldehyde (S)-27, 1.596 g (78% yield) of 28 was obtained after column chromatographic separation; yellow solids, mp 140-141° C. α! D 22 =+31.9° (c 0.75, CHCl 3 ); 1 H NMR δ 6.1 (s, 1 H, C10H), 5.72 (s, 1 H, C4 H), 5.1 (dd, J=11 Hz, 5 Hz, 1 H, C5a H), 4.75 (m, 1 H, ═CH), 4.73 (m, 1 H, ═CH), 2.48 (ddd, J=14 Hz, 4 Hz, 2.4 Hz, 1 H), 2.22-2.02 (series of m, 3 H), 2.19 (s, 3 H, C4-Me), 1.88-1.72 (series of m, 2 H), 1.74 (s, 3 H, Me--C═), 1.31 (ddd, J=25 Hz, 12.8 Hz, 4 Hz, 1 H); 13 C NMR δ 163.4 (s, C=O), 162.6 (s, C3), 161.7 (s, C4a), 147.9 (s, C10a), 132.3 (s, ═C), 109.8 (d, C10), 109.6 (t, ═CH 2 ), 99.9 (d, C4), 97.5 (s, C9a), 79.4 (s, C5a), 43.6 (d, C7), 40.0 (t), 32.5 (t), 32.1 (t), 20.9 (q, Me), 20.3 (q, Me); MS. FAB, m/z 259 (M+1; 70%), 258, 257, 215, 189, 139 (100%); Anal. Calc. for C 16 H 18 O 3 : C, 74.40; H, 7.02. Found: C, 74.17; H, 7.33.
(5aS,7S)-7-Isopropenyl-3-(3-pyridyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopvran (29).
From 0.200 g (1.06 mmol) of 5B and 0.160 g (1.06 mmol) of aldehyde (S)-27, 0.221 g (65% yield) of 29 was obtained after column chromatographic separation; yellow solids, mp 99-100° C. α! D 22 =+100.6° (c 0.77, CH 2 Cl 2 ); 1 H NMR δ 8.98 (d, J=2 Hz, 1 H, C2' H, Pyr.), 8.65 (dd, J=4.8 Hz, 2 Hz, 1 H, C6'H), 8.07 (dt, J=8 Hz, 2 Hz, 1 H, C4'H), 7.38 (dd, J=8 Hz, 4.8 Hz, 1 H, C5'H), 6.44 (s, 1H, C10 H), 6.15 (s, 1 H, C4 H), 5.17 (dd, J=11.6 Hz, 5.2 Hz, 1 H, C5a H), 4.74 (In, 2 H, ═CH 2 ), 2.52 (m, 1 H), 2.26-1.75 (a series of m, 5 H), 1.75 (s, 3 H, Me), 1.3 (m, 1 H); 13 C NMR δ 162.5 (s, C1), 161.3 (s, C4a), 156.6 (s, C3), 151.2 (d, C2'), 147.6 (d, C6'), 146.7 (s, C═), 133.9 (s, C3'), 132.7 (d, C4'), 127.4 (s, C10a), 123.7 (d, C5'), 109.9 (d, C10), 109.4 (t, ═CH 2 ), 99.8 (s, C9a), 98.4 (d, C4), 79.6 (d, C5a), 43.4 (d, C7), 39.9 (t), 32.5 (t), 31.9 (t), 20.8 (q, Me); MS. FAB, m/z 322 (M+1, 100%), 278 (M+), 252, 202, 148, 106. Anal. Calc. for C 20 H 19 NO 3 : C, 74.75; H, 5.96. Found: C, 74.48; H, 6.12.
(5aS,7S)-7-Isopropenyl-3-(3,4-dimethoxyphenyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3b! 1!benzopyran (30)
From 0.200 g (0.81 mmol) of 5C and 0.121 g (0.81 mmol) of aldehyde (S)-27, 0.193 g (63% yield) of 30 was obtained after colulmn chromatographic separation; yellow solids, mp 119-120° C. α! D 22 =+90.4° (c 0.76, CHCl 3 ); 1 H NMR δ 7.37 (dd, J=8.8 Hz, 2.4 Hz, 1 H, C6' H, Ph ring), 7.28 (d, J=2.4 Hz, 1 H, C2' H), 6.89 (d, J=8.8 Hz, 1 H, C5' H), 6.29 (s, 1 H, C10 H), 6.17 (s, 1 H, C4 H), 5.15 (dd, J=11 Hz, 5Hz, 1 H, C5a H), 4.75 (m, 2H, ═CH 2 ), 3.94 (s, 3 H, OMe), 3.92 (s, 3 H, OMe), 2.52 (ddd, J=13 Hz, 6 Hz, 3.6 Hz, 1 H), 2.26-2.24 (a series of in, 3 H), 1.88-1.76 (m, 2 H), 1.75 (s, 3 H, Me), 1.34 (m, 1 H); 13 C NMR δ 163.6 (s, Cl), 162.1 (s, C4a), 159.7 (s, C3), 151.6 (s, C4'), 149.4 (s, C3'), 148.0 (s, ═C), 132.8 (s, Cl'), 124.3 (s, C10a), 119.1 (d, C2'), 111.3 (d, C5'), 109.9 (d, =CH 2 ), 109.9 (d, C10), 108.4 (d, C6'), 98.3 (s, C9a), 96.2 (d, C4), 79.5 (d, C5a), 56.3 (q, OMe), 56.2 (q, OMe), 43.6 (d, C7), 40.1 (t), 32.6 (t), 32.1 (t), 20.9 (q, Me); MS. FAB, m/z 381 (M+1, 100%), 380 (M+). Anal. Calc. for C 23 H 24 O 5 : C, 72.61; H, 6.36. Found: C, 72.43; H, 6.17.
3-(Methoxycarbonylmethyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran (31)
To a cold (-78° C.) solution of 0.4 g (1.83 mmol) of pyrone 1A in 10 mL of THF under argon was added a cold (0° C.) solution of LDA freshly prepared from 0.31 mL (2.2 mmol) of diisopropylanine and 1.4 mL (2.2 mmol; 1.6 M in hexane) of n-BuLi in 10 mL of ether under argon at -10° C. for 1 h!. To the reaction solution, 0.32 mL (1.83 mmol) of HMPA (hexamethylphosphoramide) was added, the resulting solution was stirred at -78° C. for 3 h, and then 0.14 mL (1.83 mmol) of methyl chloroformate was added. After the solution was stirred at room temperature for 16 h, it was diluted with 20 mL of water, and extracted with 50 mL of methylene chloride. The methylene chloride extract was dried (MgSO 4 ), concentrated, and column chromatographed on silica gel using a gradient mixture of hexane and ether as eluant to give 0.215 g (72% yield; based on recovered starting material) of 31 and 0.165 g (41% recovery) of pyrone 1A. Compound 31: 1 H NMR δ 6.1 (s, 1 H, C4 H), 6.06 (s, 1 H, C10 H), 5.06 (dd, J=11, 5 Hz, 1 H, C5a H), 3.81 (s, 2 H, CH 2 ), 3.80 (s, 3 H, OMe), 2.43 (m, 1 H), 1.98-1.74 (m, 5 H), 1.54-1.3 (m, 2 H); 13 C NMR δ 165.2 (s, C═O), 162.3 (s, C═O), 161.4 (s, C3), 153.8 (s, C4a), 134.7 (s, C10a), 108.9 (d, C10), 102.6 (d, C4), 99.5 (s, C9a), 80.1 (s, C5a), 56.0 (q, OMe), 53.6 (t, CH 2 ), 35.3 (t), 33.3 (t), 27.0 (t), 24.5 (t).
3-(Carboxylmethyl)-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran (32)
A solution of 0.08 g (0.29 mmol) of ester 31 and 0.033 g (0.58 mmol) of KOH in 4 mL of THF-H 2 O (1:3) was stirred at 40° C. for 30 h, cooled to room temperature, diluted with 30 mL of distilled water, and extracted with 40 mL of diethyl ether and then with 40 mL of methylene chloride. The combined extracts were washed with 30 mL of water, and with 30 mL of brine, dried (MgSO 4 ), concentrated to give 20.5 mg (26% recovery) of starting material 31. The combined aqueous layers were acidified with 1N HCl, and extracted three times with 50 mL-portion of methylene chloride. The combined extract was washed twice with water (40 mL each), with 40 mL of brine, dried (MgSO 4 ), concentrated to give 32.5 mg OH (58% yield; based on recovered starting material) of 32. 1 H NMR δ 6.8 (broad s, 1 H, OH), 6.04 (s, 1 H, C10H), 5.96 (s, 1 H, C4 H), 5.07 (dd, J=11, 5 Hz, 1 H, C5a H), 3.51 (s, 2 H, CH 2 ), 2.42 (dd, J=14 Hz, 2 Hz, 1 H), 2.2-1.7 (m, 5H), 1.5-1.2 (m, 2 H).
1,8-Di-{3- 1H-5a,6,7,8,9-pentahydro-1-oxopyrano4,3-b! 1!benzopyranyl!}-2,7-octanedione (33)
The reaction conditions are simiIar to those of the preparation of 31. From 0.40 g (1.83 mmol) of pyrone 1A, 2.2 mmol of LDA, 1.83 mmol of HMPA, and 0.13 mL (0.5 equiv.; 0.9 mmol) of adipoyl chloride in 10 mL of THF and 10 mL of ether gave 0.091 g (38% yield; based on recovered starting material) of 33 and 0.18 g (45% recovery) of starting material 1A after column chromatography. Compound 33: Mp. 161-162° C.; 1 H NMR δ 6.39 (s, 2 H, ═CH of enol of the side chain), 6.07 (s, 2 H, C10H), 5.64 (s, 2 H, C4 H), 5.04 (dd, J=11, 5 Hz, 2 H, C5a H), 2.6-1.3 (m, 24 H); 13 C NMR δ 170.4 (s, C--O of enol), 162.9 (s, C═O), 161.6 (s, C3), 156.1 (d, ═CH of enol), 154.7 (s, C4a), 134.6 (s, C10a), 109.3 an 109.2 (d, C10), 102.3 (d, C4), 99.4 (s, C9a), 79.8 (s, C5a), 35.3 (t), 34.6 (t), 33.3 (t), 28.9 (t), 27.0 (t), 24.6 (t), 22.8 (t).
(5aS,7S)-7- 2-(1-Hydroxypropyl)!-3-methyl-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran (34)
To a cold (-20° C.) solution of 0.10 g (0.39 mmol) of pyrone 28 in 3 mL of THF under argon was added a solution of 0.39 mL (0.39 mmol) of BH 3 .THF (1.0M in THF). After the solution was stirred at -20° C. for 1 h, and -15° C. for 1 h, 2 mL of 1% aqueous NaOH and 1.5 mL of 30% H 2 O 2 were added, and resulting solution was stirred at 25° C. for 3 h. The reaction mixture was diluted with 20 mL of distilled water, extracted three times with methylene chloride (40, 30, and 20 mL), and the combined extracts were washed with 30 mL of brine, dried (MgSO 4 ), concentrated, and column chromatographed on silica gel using a gradient mixture of hexane and ether as eluant to give 0.074 g (69% yield) of alcohols 34 as a 1:1 mixture of two diastereomers at C-12: 1 H NMR δ 6.05 (s, 1 H, C10 H), 5.72 (s, 1 H, C4 H), 5.07 (m, 1 H, C5a H), 3.58 (ddd, J=11 Hz, 6 Hz, 3 Hz, 1 H, CHO), 3.54 (dd, J=11 Hz, 6 Hz, 1 H, CHO), 2.46 (d, J=12 Hz, 1 H), 2.19 (s, 3 H, Me), 2.18-1.3 (series of m, 7 H), 0.906 (d, J=6.8 Hz, 3 H, Me), 0.902 (d, J=6.8 Hz, 3 H, Me); 13 C NMR δ 163.5 (s, C═O), 162.8 (s, C3), 161.6 (s, C4a), 133.0 (s, C10a), 109.1 (d, C10), 100.0 (d, C4), 97.5 (s, C9a), 79.8 and 79.7 (s, C5a; 2 isomers), 65.71 and 65.69 (t, CH 2 O, 2 isomers), 40.1 and 39.4 (t), 37.4, 37.3, 37.0, 32.5, 32.4, 31.2, 28.6, 20.2 (q, Me), 13.3 and 13.2 (q, Me).
(5aS,7S)-7- 1-(Formyl)ethyl)!-3-methyl-1H-5a,6,7,8,9-pentahydro-1-oxopyrano 4,3-b! 1!benzopyran (35)
A solution of 0.07 g (0.25 mmol) of alcohols 34 and 0.16 g (0.38 mmol) of 1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1 H)-one in 4 mL of methylene chloride was stirred at 25° C. under argon for 48 h. The mixture was filtered through Celite, washed with 50 mL of methylene chloride, and the filtrate was concentrated and column chromatographed on silica gel using a gradient mixture of hexane and ether as eluant to give 0.060 g (87% yield) of the desired aldehyde 35 as a mixture of two diastereomers; 1:1 (indicated by proton and carbon NMR spectra). 1 H NMR δ 9.68 (d, J=0.8 Hz, 1 H, CHO), 6.09 (s, 1 H, C10 H), 5.71 (s, 1 H, C4 H), 5.1 (m, 1 H, C5a H), 2.47 (d, J=12 Hz, 1 H), 2.35 (m, 1 H, C12 H), 2.19 (s, 3 H, Me), 2.18-1.2 (series of m, 6 H), 1.10 (d, J=6.8 Hz, 3 H, Me); 13 C NMR δ 204.14 and 204.1 (d, CHO), 163.29 and 163.27 (s, C═O), 162.5 (s, C3), 161.8 (s, C4a), 141.7 (s, C10a), 109.9 (d, C10), 99.8 (d, C4), 97.4 (s, C9a), 79.03 and 78.9 (s, C5a; 2 isomers), 50.79 and 50.73, 39.2 (t), 37.3, 36.3 and 36.2, 32.2 and 32.1, 31.2, 29.2, 20.2 (q, Me), 10.2 and 10.1 (q, Me).
(5aS,7S,10S)-7- 2-(1-Hydroxypropyl)!-10-hydroxy-3-(3,4-dimethoxyphenyl)-1H-5a,6,7,8,9,9a,10-heptahydro-1-oxopyrano 4,3-b! 1!benzopyran (36)
To a cold (-20° C.) solution of 0.120 g (0.31 mmol) of pyrone 30 in 5 mL of THF under argon was added 1 mL (1 mol) of BH 3 .THF (1 M in THF). After the solution was stirred at -20° C. for 30 min., 0° C. for 2 h, and 25° C. for 12, h, 2 mL of 1% NaOH and 2 mL of 30% H 2 O 2 were added, and the resulting solution was stirred at room temperature for 3 h. The reaction solution was diluted with 20 mL of distilled water, extracted three times with methylene chloride (40, 30 and 20 mL), and the combined extract was washed with 40 mL of brine, dried (MgSO 4 ), concentrated, and column chromatographed on silica gel using hexane, ether, and ethyl acetate as eluants to give 0.021 g (16% yield) of diol 36 as a 1:1 mixture of two diastereomers at C11: α! D 22 =-7.4° (c=0.68, CHCl 3 ); 1 H NMR δ 7.39 (dd, J=8.8 Hz, 2.4 Hz, 1 H, C6'H, Ph ring), 7.28 (d, J=2.4 Hz, 1 H, C2'H), 6.91 (d, J=8.8 Hz, 1 H, C5' H), 6.33 and 6.328 (two s, 1 H, C10 H; 2 isomers), 4.73 (dd, J=9 Hz, 3.3 Hz, 1 H, C5a H), 4.5 (m, 1 H, C10 H), 4.34 (broad s, 1 H, OH), 3.95 (s, 3 H, OMe), 3.93 (s, 3 H, OMe), 3.6 (m, 2H, CH 2 O), 2.3-2.17 (m, 2 H), 1.85-1.3 (a series of m, 7 H), 0.92 and 0.91 (2 d, J=7 Hz, 3 H, Me; 2 diastereomers); 13 C NMR δ 165.0 (s, C1), 164.5 (s, C4a), 151.8 (s, C3), 149.5 (s, C4'), 142 (s, C3'), 124.0 (s, C1'), 119.3 (s, C10a), 111.3 (d, C2'), 108.5 (d, C5'), 100.3 (d, C6'), 97.1 (d, C4), 66.1, 66.1, 56.4 (q, OMe), 56.3 (q, OMe), 39.7, 38.3, 38.2, 31.9, 24.6, 13.8 (q, Me).
(5aS,7S,10S)-7- 2-(1-Pentanoyloxypropyl)!-10-hydroxy-3-(3,4-dimethoxyphenyl)-1H-5a,6,7,8,9,9a, 10-heptahydro-1-oxopyrano 4,3-b! 1!benzopyran (37)
A solution of 0.014 g (0.034 mmol) of alcohol 36, 4 mg (0.034 mmol) of valeryl chloride, and 0.03 mL (0.34 mmol) of pyridine in 1 mL of methylene chloride was stirred under argon at room temperature for 14 h. A solution of 7 mg of valeryl chloride in 0.2 mL of methylene chloride was added and the solution was stirred at 50° C. for 20 h. The progress of the reaction was monitored by TLC, and 0.015 g of veleryl chloride was added. After 10 min of stirring, the reaction was quenched by adding 20 mL of methylene chloride, washed with 15 mL of saturated aqueous NaHCO 3 . The aqueous layer was extracted twice with methylene chloride (15 and 10 mL). The combined extracts were washed with 20 mL of brine, dried (MgSO 4 ), concentrated and column chromatographed on silica gel using a gradient mixture of hexane and ether as eluant to give 9 mg (53% yield) of ester 37 as a 1:1 mixture of 2 diastereomers at C11 (A & B); 1 H NMR δ 7.44 (dd, J=8.4 Hz, 2 Hz, 1 H, C6' H, Ph ring; isomer A), 7.41 (dd, J=8.4 Hz, 2 Hz, 1 H, C6' H, Ph ring; isomer B), 7.32 (d, J=8.4 Hz, 1 H, C5' H), 6.39 and 6.27 (two s, 1 H, C10 H; 2 isomers), 5.84 (broad s, 1 H, OH of A), 5.75 (broad s, 1 H, OH of B), 4.45 (m, 1 H, C5a H), 4.32 (m, 1 H, C10 H), 4.06-3.99 (m, 2 H, CH 2 O), 3.96 (s, 3 H, OMe of A), 3.95 (s, 3 H, OMe of B), 3.94 (s, 6 H, 2 OMe of A & B), 2.4-1.0 (a series of m, 15 H), 0.96-0.90 (t & d, 6 H, 2 Me; 2 diastereomers).
(5aS*,9aS*,10S*)-9a, 10-Epoxy-3-(3-pyridyl)-1H-5a.6,7,8,9,9a, 10-heptahydro-1-oxopyrano 4,3-b! 1!benzopyran (38A) and (5aS*,9aR*,10R*)-9a,10-Dihydroxy-3-(3-pyridyl)-1H-5a,6,7,8.9,9a, 10-heptahydro-1-oxopyrano 4,3-b! 1!benzopyran (38B)
To a cold (0° C.) solution of 90 mg (0.3 mmol) of pyrone 2A in 5 mL of methylene chloride under argon was added 0.3 mL (0.3 mmol) of a solution of HCI in ether (1 M). The solution was stirred for 10 min., warmed to room temperature and 0.102 g (0.32 mmol) of m-chloroperbenzoic acid (MCPBA; 55% pure) was added. After two hours of stirring, the mixture was neutralized with 1 M aqueous NaOH, and extracted with 20 mL of CH 2 Cl 2 . The extract was dried (MgSO 4 ), concentrated and column chromatographed on silica gel using ether as eluant to give 7 mg (7% yield) of epoxide 38A and 29 mg (30% yield) of dihydroxide 38B.
Compound 38A: 1 H NMR δ 9.03 (s, 1 H, C2'H, Pyr.), 8.7 (s, 1 H, C6' H), 8.13 (dt, J=8 Hz, 2 Hz, 1 H, C4' H), 7.42 (dd, J=8 Hz, 4.9 Hz, 1 H, C5' H), 6.51 (s, 1 H, C4 H), 5.11 (s, 1 H, C10 H), 4.52 (dd, J=12 Hz, 5 Hz, 1 H, C5a H), 2.43 (m, 1 H), 2.15-1.4 (a series of m, 7 H).
Compound 38B: 1 H NMR δ 9.03 (s, 1 H, C2' H, Pyr.), 8.72 (s, 1 H, C6' H), 8.14 (dt, J=8 Hz, 2 Hz, 1 H, C4' H), 7.42 (dd, J=8 Hz, 4.9 Hz, 1 H, C5' H), 6.51 (s, 1 H, C4 H), 5.04 (s, 1 H, C10 H), 4.81 (s, 1 H, C5a H), 2.3-1.2 (a series of m, 8 H). MS (FAB) m/z: 316 (M+1).
(5R,6S)-2,6-dimethyl-6-(cis-3-iodo-2-propenyl)-5-isopropenyl-2-cyclohexen-1-one (41)
To a cold (-40° C.) solution of 46 mL (21 mmol) of LDA (prepared as mentioned above from 2.9 mL of diisopropylamine and 13 mL of n-BuLi in 30 mL of THF) under argon was added a solution of 1.69 g (10.3 mmol) of (5R,6S)-2,6-dimethyl-5-isopropenyl-2-cyclohexen-1-one in 30 mL of ether was added via cannula, an the resulting solution was stirred at 0° C. for 45 min. To it, 1.8 mL (10 mmol) of HMPA was added, stirred at the same temperature for 4 hours, and a solution of 5.68 g (22 mmol) of (cis-3-iodo-2-propenyl) methanesulfonate (40) 2 in 30 mL of ether was added. After stirring at room temperature for 12 hours, the reaction mixture was poured into an aqueous solution of NaHCO 3 , extracted three times with ether, and the combined extracts were washed with brine, dried (MgSO 4 ), and concentrated. The residue was column chromatographed on silica gel using a hexane:methylene chloride (3:2) as eluant to give 2.48 g (73% yield) of 41 and 0.237 g (14% recovery) of the starting material.
Compound 41: α! D 22 =-31.9° (c=1.5, CHCl 3 ); 1 H NMR δ 6.63 (m, 1 H, C3 H), 6.3 (dt, J=8 Hz, 1.6 Hz, 1 H, ═CH--I), 6.12 (dt, J=8 Hz, 6.4 Hz, 1 H, ═CH), 4.83 (s, 1 H, ═CH 2 ), 4.74 (s, 1 H, ═CH 2 ), 2.7-2.3 (a series of m, 5 H), 1.79 (s, 3 H, =C-Me), 1.65 (s, 3 H, ═C--Me), 1.09 (s, 3 H, Me); 13 C NMR δ 203.4 (s, C1), 145.8 (s, ═C), 142.4 (d, ═CH), 137.7 (d, ═CH), 134.2 (s, ═C), 114.8 (t, ═CH 2 ), 84.9 (d, CH-I), 50.5 (d, C5), 48.0 (s, C6), 42.8 (t), 29.2 (t), 22.5 (q, Me), 19.3 (q, Me), 16.6 (q, Me).
(4aS,5R,8aS)-Methyl-(1 H)-1-Oxo-4,4a,5,8,8a-pentahydro-2,5,8a-trimethylnaphthalene-5-acetate (42) and (4aS,5S,8aS)-Methyl-(1H)-1-Oxo-4,4a5,8,8a-pentahydro-2,5,8a-trimethylnaphthalene-5-acetate (47)
A mixture of 0.387 g (1.72 mmol) of Pd(OAc) 2 and 0.904 g (3.44 mmol of Ph 3 P in 10 mL of DMF under argon was stirred at room temperature for one hour. To it, a solution of 0.569 g (1.72 mmol) of iodide 41 in 10 mL of DMF was added via cannula, and the mixture was stirred at 32° C. for 30 min. After 10 mL of MeOH was added, the mixture was maintained under 1 atmosphere of CO (a CO balloon was used), and 0.476 g (1.72 mmol) for Ag 2 CO 3 was added. After stirring at 32° C. for 15 hours, the mixture was cooled to room temperature, filtered, washed the solids with methylene chloride, and the filtrate was concentrated. The residue was dissolved in either and washed with brined, dried (MsSO 4 ), concentrated, and column chromatographed on silica gel using a hexane:ether (10:1) as eluant to give 0.332 g (73% yield) of a mixture of 2.2:1 of 42 and 47.
Pure compound 47: 1 H NMR δ 6.77 (m, 1 H, C3 H), 5.68 (ddd, J=10 Hz, 5.6 Hz, 2 Hz, 1 H, C7 H), 5.56 (dd, J=10 Hz, 2 Hz, 1 H, C6 H), 3.67 (s, 3 H, OMe), 2.62 (d, J=13 Hz, 1 H, CH 2 CO 2 ), 2.36 (m, 1 H), 2.31 (d, J=13 Hz, 1 H, CH 2 CO 2 ), 2.28 (m, 2 H), 2.14 (d, J=18 Hz, 1 H, C8 H), 2.02 (dd, J=11 Hz, 5 Hz, 1 H, C4a H), 1.77 (s, 3H, ═C--Me), 1.21 (s, 3 H, C5--Me), 1.10 (s, 3 H, C8a--Me).
Compound 42 from a mixture of 42 (major) and 47 (minor)!: 1 H NMR δ 6.77 (m, 1 H, C3 H), 5.68 (m, 1 H, C7 H), 5.53 (dd, J=10 Hz, 2 Hz, 1 H, C6 H), 3.62 (s, 3 H, OMe), 2.62 (d, J=13 Hz, 1 H, CH 2 CO 2 ), 238-2.26 (a series of m, 4 H), 2.12 (d, J=18 Hz, 1 H, C8 H), 2.01 (dd, J=11 Hz, 5 Hz, 1 H, C4a H), 1.77 (s, 3 H, ═C--Me), 1.12 (s, 3 H, C5--Me), 1.07 (s, 3 H, C8a--Me); 13 C NMR δ a mixture of 42 (designated as A) and 47 (designated as B) 204.5 (s, C1, A), 204.47 (s, C1, B), 172.5 (s, C2, A), 171.8 (s, C2, B), 143.7 (d), 134.8 (s), 133.8 (s), 133.7 (s), 133.4 (d, A), 132.5 (d, B), 123.7 (d, A), 123.5 (d, B), 51.5, 51.45, 48.0, 47.2, 46.9, 44.3, 44.1, 43.6, 41.7, 38.1, 36.7, 33.7, 33.1, 28.4, 24.3, 23.9, 23.8, 18.0, 17.99, 16.43 (q, A), 16.41 (q, B).
(4aS,8aS)-(1H)-1-Oxo-4,4a,5,8,8a-pentahydro-2,5,8a-trimethylnaphthalene-5-acetic acid (43); a mixture of 2.2:1 of 5R and 5S)
A solution of 0.127 g (0.48 mmol) of methyl esters 42 and 47 (2.2: 1) and 90 mg (1.6 mmol) of KOH in 0.5 mL of water and 2 mL of MeOH was stirred at room temperature for 22 hours. The solution was acidified with 1N aqueous HCl, extrated three times with CH 2 Cl 2 , and the combined extract was washed with brine, dried (MgSO 4 ), concentrated, and column chromatographed on silica gel using hexane:ether (1:1) as eluant to give 0.116 g (96% yield) of the acids 43 as a mixture of 2 isomers at C5.
Compounds 43: 1 H NMR δ 6.79 (m, 1 H, C3 H), 5.74-5.6 (m, 1 H, C7 H), 5.57 (dd, J=10 Hz, 2 Hz, 1 H, C6 H), 2.64 (d, J=13 Hz, 1 H, CH 2 CO 2 ), 2.42-2.2 (a series of m, 4 H), 2.16 (d, J=18 Hz, 1 H, C8 H), 2.05 (dd, J=11 Hz, 5 Hz, 1 H, C4a H), 1.77 (s, 3 H, ═C--Me), 1.24 (s, 3 H, C5--Me of minor isomer), 1.15 (s, 3 H, C5--Me of major isomer), 1.11 (s, 3 H, C8a--Me of minor isomer), 1.08 (s, 3 H, C8a--Me of major isomer); 13 C NMR δ a mixture of the α-isomer (major) (designated as A) and β-isomer (minor) (designated as B) 204.75 (s, C1, A), 204.55 (s, C1, B), 178.4 (s, C2, B), 177.5 (s, C2, A), 143.9 (d, A), 143.84 (d, B), 133.9 (B), 133.8 (A), 133.0 (A), 132.2 (B), 124.2 (A), 123.9 (B), 48.1, 46.8, 44.4, 44.2, 43.6, 41.8, 38.2, 36.6, 33.8, 33.1, 28.4, 24.4, 24.0, 23.9, 18.1, 16.51 (q, A), 16.49 (q, B).
(1S,4aS,8aS)-(1H)-1- 2-(1,3-dithianyl)!-1-hydroxy-4,4a,5,8,8a-pentahydro-2,5,8a-trimethylnaphthalene-5-acetic acid (44)
To a cold (0° C.) solution of 0.116 g of 1,3-dithiane (9) in 4 mL of THF under argon was added 0.6 mL (0.97 mmol) of n-BuLi (1.6M in hexane). After the solution was stirred at -10° C. for two hours, a solution of 0.080 g (0.32 mmol) of enone 43 in 1 mL of THF was added via cannula. The solution was stirred at room temperature for 16 hours, diluted with 20 mL of water and 5 mL of 6N HCl, and extracted three times with 40 mL portion of methylene chloride. The combined extract was washed with 30 mL of water, and 30 mL of brined, dried (MgSO 4 ), concentrated and column chromatographed on silica gel using a gradient mixture of hexane and diethyl ether as eluant to give a good yield of 44. 1 H NMR (CDCl 3 ) δ 5.75 (m, 1 H, C7 H), 5.6 (broad s, 1 H, C3 H), 5.58 (dd, J=10 Hz, 2 Hz, 1 H, C6 H), 4.57 (s, 1 H, CH--S), 2.9-2.6 (m, 4 H, CH 2 S), 2.41 (d, J=14 Hz, 1 H, CH 2 CO 2 H), 2.25 (d, J=14 Hz, 1 H, CH 2 CO 2 H), 2.3-1.2 (a series of m, 7 H), 1.83 (s, 3 H, ═CCH 3 ), 1.08 (s, 3 H, Me), 1.01 (s, 3 H, Me).
Biological Studies
Acetylcholinesterase Assay and Inhibition Kinetics: Tricyclic pyrones of this invention were tested for inhibition of AChE. The activities of electric eel acetylcholinesterase (EC 3.1.1.7, Sigma Chemical Co., St. Louis, Mo.), and fetal bovine serum acetylcholinesterase (Ralston, J. S. et al. (1985), "Acetylcholinesterase from Fetal Bovine Serum," J. Biol. Chem. 260:4312-4318) were determined colorimetrically by the method of Ellman (Ellman, G. L. et al. (1961), "A new and rapid colorimetric determination of acetylcholinesterase activity," Biochem. Pharmacol. 7:88-95) as described by Main et al. (Main, A. R. et al. (1974), "Purification of cholinesterase from horse serum," Biochem. J. (1974) 143:733-744). Reactions were carried out at 30° C. in 0.1M sodium phosphate buffer at pH 8.0 in the presence of 10 -3 acetylthiocholine and 3.3×10 -4 M 3-carboxy-4-nitrophenyl disulfide. Aliquots of incubating mixtures containing enzyme alone, or enzyme in the presence of each carbamate, were withdrawn at selected time intervals and assayed for enzyme activity in order to obtain kinetic data. From the kinetic data, inhibition and bimolecular rate constants were calculated by the equation: ##EQU1## in which k app is the pseudo-first-order rate constant. The bimolecular rate constant (k 3 ') is equal to k 3 /K T . All the tricyclic pyrones are inactive against butyrylcholinesterase (BChE). BChE does not affect the formation of Aβ. The AChE inhibitory data of various tricyclic pyrones are summarized in Table 3. The inhibition of Ki of the tricyclic pyrones are in the μM range; while tacrine, an art-known AChE inhibitor, is in the nM range.
TABLE 3______________________________________The AChE inhibition constant Ki of various tricyclic pyronesTricyclic Pyrones Ki(μM) ± std. error______________________________________1A 7 ± 1.21B 20 ± 5.81D 5 ± 1.72B 8 ± 2.32D 26 ± 2.33A 23 ± 3.53B 4 ± 0.63D 15 ± 5.8tacrine 1 nM______________________________________
Inhibition of liver and intestinal microsomal ACAT activity: Several synthesized tricyclic pyrones were tested for their inhibition of liver and intestinal microsomal ACAT along with pyripyropene A and CP-113,818 (as control) (Marzetta, C. A. et al. (1994), "Pharmacological properties of a novel ACAT inhibitor (CP-113,818) in cholesterol-fed rats, hamsters, rabbits, and monkeys," J. Lipid Res. 35:1829-1838). Microsomes were prepared from liver and intestinal mucosal scrapings by sequential centrifugation and in vitro ACAT activity assays were done according to the method of Billheimer (Billheimer, J. T. (1985), "Cholesterol acyltransferase," In Methods in Enzymology 111:286-293). Briefly, 100 μg microsomal protein, 22 μg BSA, and 52 nmol cholesterol and the synthesized drug in 5 μL DMSO were preincubated for 30 minutes at 37° C. in a phosphate buffer (200 μL total volume). After 30 minutes, 1 nmol 14 C!oleoyl-CoA was added as substrate and incubated for an additional 20 minutes. The reaction was stopped with the addition of 1 mL ethanol and lipids were extracted with hexane. Cholesteryl 14 C!oleate formation was quantified by thin-layer chromatography and data are expressed as percent inhibition of ACAT activity (pmol/μg protein per minute) compared to a control sample incubated with no drug. All samples were run in duplicate. Using the literature IC 50 value of pyripyropene of 58 nM as standard, it was found that IC 50 values for 2A, 3A, and 1D are 50 μM, 63 μM, and 52 μM, respectively.
TABLE 4______________________________________The Inhibition of ACAT by tricyclic pyrones and CP-113,818.Compound Concentration % Inhibition______________________________________24 100 μM 3.3 50 μM 1.926 100 μM 13.7 50 μM 2.738B 100 μM 11.4 50 μM 9.737 100 μM 52.4 50 μM 36.830 100 μM 21.9 50 μM 13.329 100 μM 39 50 μM 2128 100 μM 30 50 μM 1732 100 μM 7.9 50 μM 10.333 100 μM 76 50 μM 57CP-113,818 44 nM 42.5______________________________________
Inhibition of DNA Synthesis: Tricyclic pyrone derivatives of this invention were tested for their ability to prevent L1210 leukemic cells from synthesizing DNA and growing in vitro. At 50 μM, a pyripyropene analog, 22, has no effect, whereas four pentahydro-3-aryl-1-oxopyrano 4,3-b! 1!benzopyrans all inhibit DNA synthesis by 79-91% and tumor cell growth by 93-100%. These inhibitory effects are concentration-dependent with IC 50 around 8.5 μM for DNA synthesis at 2 h and 1.1 μM for tumor cell growth at 4 days. The aryl groups of the antitumor agents tested are either 3,4-dimethoxyphenyl or 3-pyridyl. Introduction of a methyl group at C5a and a formyloxy or hydroxy group at C6 does not alter the antitumor effects of the 3,4-dimethoxyphenyl benzopyrans but reduces those of the 3-pyridyl benzopyrans, which, at 50 μM inhibit DNA synthesis by only 32-49% and fail to alter tumor cell growth. The 4-hydroxy-6-(3-pyridyl)-2-pyrone (5B) has no effect and the tricyclic pyrones lacking aryl groups (e.g., 1A-1E) have less inhibitory effect on DNA synthesis, suggesting that a greater conjugation is required for the antitumor activity. The tricyclic pyrones also inhibit to a similar degree other macromolecule synthesis, e.g., RNA and protein synthesis. The 3,4-dimethoxyphenyl substituted tricyclic pyrone 3A being a more potent inhibitor of macromolecule synthesis than the 3-pyridyl substituted tricyclic pyrone 2A. Additionally, the tricyclic pyrones inhibit the growth of EMT6 mammary carcinoma cells and MCF-7 human breast cancer cells. However, in both these systems, tricyclic pyrone 2A has a greater inhibitory effect than tricyclic pyrone 3A. This lack of correlation between the ability of tricyclic pyrones to inhibit tumor cell growth and macromolecular synthesis suggests that other macromolecular targets may be involved in the antitumor action of these drugs.
Inhibition of Tubulin Polymerization
Tricyclic pyrone derivatives of this invention were tested for their ability to prevent tubulin polymerization. It was found that 2A completely inhibits tubulin polymerization and, therefore, works as a novel microtubule (MT) de-stabilizing drug. The ability of 2A to disrupt MT dynamics suggests that the anticancer activity of tricyclic pyrones may be cell cycle-specific. These anticancer drugs are therefore useful for arresting mammalian cells in mitosis. Tricyclic pyrones that can selectively disrupt MT dynamics and block the M-phase of the cell cycle have great therapeutic value.
Tubulin is a labile protein, which is unstable below 80 mM PIPES, should not be exposed to pH values less than 6.8 or greater than 7.0, and will not polymerize in the presence of Ca 2 +. GTP and Mg 2+ are necessary for tubulin nativity and glycerol stabilizes tubulin and lowers the initial concentration required to initiate polymerization.
The ability of 2A to alter the polymerization of pure tubulin in a cell-free system in vitro was analyzed using the assay kit purchased from Cytoskeleton (Denver, Co.). The polymerization reaction contained, in a final volume of 200 μl, tubulin protein from bovine brain (2.5 mg/ml), 80 mM PIPES buffer, pH 6.8, 1 mM MgCl 2 , 1 mM EGTA, 1 mM GTP and 10% glycerol. Compound 2A was added in 2 μl of DMSO:tubulin buffer (40:60) to obtain a final concentration of 25 μM. This vehicle did not affect the rate of tubulin polymerization in drug-untreated control reactions. Samples were incubated at 35° C. in quartz microcells and the rate of tubulin polymerization was followed over 20 min by measuring the increased absorbance of the solution at OD340 nm, using a Shimadzu UV-160 spectrophotometer equipped with dual-beam optics and a thermostatically-controlled cell holder.
FIGS. 14A-B show the three typical phases of MT polymerization normally occurring in vehicle-treated control samples. The lag phase I is necessary to create nucleation sites (small tubulin oligomers) from which longer MT polymers can form. The growth phase II reflects the rapid increase in the ratio of MT assembly: disassembly occurring under those experimental conditions. And the steady phase III is established when the residual concentration of free tubulin heterodimer becomes equal to the critical concentration required to initiate polymerization. One unit of tubulin is defined as 5 mg of purified protein. When tubulin at a concentration of 1 unit (5 mg)/ml is incubated at 35° C. for 30 min. in the presence of 80 mM PIPES, pH 6.8, 1 mM MgCl 2 , 1 mM EGTA, 1 mM GTP and 10% glycerol, the OD 340nm increases from 0.0 to 1.0, which indicates that about 97% of tubulin has polymerized to form a total MT polymer mass of 4.8 mg/ml. An increase in OD of 0.2 is roughly equal to a MT polymer mass of 1 mg/ml. The kinetics of MT polymerization in FIG. 14A, therefore, appear consistent with the initial concentration of 2.5 mg tubulin/ml used in our control assay. In contrast, no significant MT polymerization can be detected in the presence of 25 μM of 2A in FIG. 14B.
Materials and Methods
All solutions of tricyclic pyrone analogs were dissolved and diluted in 100% ethanol (ETOH), whereas CPT (Sigma Chemical Co., St. Louis, Mo.) solutions were prepared in 100% dimethyl sulfoxide (DMSO). Murine L1210 lymphoblastic leukemia cells, obtained from the American Type Culture Collection (Rockville, Md.), were maintained in continuous exponential growth by twice-a-week passage in RPMI 1640 medium supplemented with 7.5% fortified bovine calf serum (HyClone Laboratories, Inc., Logan, Utah). The cultures were incubated at 37° C. in a humidified atmosphere containing 5% CO 2 . All drugs were supplemented to the culture medium in 1- or 2 μl aliquots. The concentration of vehicle in the final incubation volume never exceeded 0.2-0.4%. Such low concentrations of EtOH or DMSO do not affect the rates of DNA synthesis and growth in L1210 cells. Control cells incubated in the absence of drugs were similarly treated with vehicle only and, in every experiment, all incubates received the same volume of solvent.
For DNA synthesis, L1210 cells were resuspended in fresh serum-free RPMI 1640 medium at a density of about 2.5×10 6 cells/0.5 ml. The cells were incubated at 37° C. for 90 min in the presence or absence of drugs and then pulse-labeled for an additional 30 min with 1 μCi of methyl- 3 H!thymidine (51 Ci/mmol; Amersham Corp., Arlington Heights, Ill.). The incubations were terminated by the addition of 0.5 ml of 10% trichloroacetic acid (TCA). After holding on ice for 15 min, the acid-insoluble material was recovered over Whatman GF/A glass microfibre filters and washed thrice with 2 ml of 5% TCA and twice with 2 ml of 100% EtOH. After drying the filters, the radioactivity bound to the acid-precipitable material was determined by liquid scintillation counting in 10 ml of Bio-Safe NA (Research Products International Corp., Mount Prospect, Ill.).
For tumor cell growth, L1210 cells were resuspended in fresh serum-containing RPMI 1640 medium, plated at an initial density of 1×10 4 cells/0.5 ml, and incubated in 48-well Costar cell culture plates (Costar, Cambridge, Mass.). Cells were grown for 4 days in the presence or absence of drugs and their density was monitored every 24 h using a Coulter counter (Coulter Electronics, Ltd., Luton Beds, England). Data of all in vitro experiments were analyzed using Student's t-test with the level of significance set at P<0.05.
The known anticancer drug CPT inhibits the incorporation of 1 H-thymidine into DNA in a concentration-dependent manner (FIG. 1). When tested at 25 μM, the new agent 3A inhibits DNA synthesis in L1210 cells by 62% but 22, 2D & 2E and 5B have no significant effects (FIG. 1). However, 2D & 2E can inhibit DNA synthesis by 49% at 50 μM (FIG. 2). In contrast, 22 and 5B remain ineffective even at this higher concentration (FIG. 2). Overall, four of the newly synthesized compounds can prevent leukemic cells from synthesizing DNA. Indeed, 50 μM 3A, 3D & 3E, 2A and 3B & 3C inhibit DNA synthesis in L1210 cells by 79-91%, an effect comparable to that of 20 μM CPT (FIG. 2). Besides 2D & 2E, which is a moderate inhibitor, the three remaining new compounds tested have very weak inhibitory in effects on DNA synthesis in L1210 cells. At 50 μM, 2B & 2C, 1A, and 1D & 1E inhibit this DNA response by only 17-32% (FIG. 2).
Although less potent than CPT, 3A and 2A both inhibit the DNA response of L1210 cells in the same concentration-dependent manner (FIGS. 3 and 4). In this L1210 system in vitro, the concentration of 3A or 2A that inhibits DNA synthesis by 50% (IC 50 ) is about 8.5 μM, whereas that of CPT is about 0.65 μM (FIGS. 3 and 4).
The ability of several of the new tricyclic pyrone analogs to inhibit the growth of L1210 cells in culture was assessed and compared to that of CPT (FIGS. 5 and 6). Over a 4-day period, there is a 50-fold increase in the number of control cells grown in the absence of drugs (FIG. 5). Since 22 and 5B fail to inhibit DNA synthesis (FIG. 2), their ability to alter L1210 cell growth has not been tested. It should be noted that 50 μM 2D and 2E and 2B and 2C, which inhibit the DNA response of L1210 cells by 31-49% (FIG. 2), cannot inhibit the growth of these leukemic cells over a 4-day period (FIG. 5). The effects of 1A and 1D and 1E on L1210 cell growth, therefore, are not worth testing. Since these compounds inhibit DNA synthesis to a lesser degree than 2D and 2E and 2B and 2C (FIG. 2), they are very unlikely to significantly decrease tumor cell growth in vitro. In contrast, the same four new compounds shown to inhibit DNA synthesis by 79% or more (FIG. 2) also dramatically block the growth of L1210 cells in vitro (FIG. 5). At 50 μM, 3A, 3D and 3E, 2A and 3B and 3C all mimic the inhibition of L1210 cell growth caused by 10 μM CPT (FIG. 5). The similar magnitude of these inhibitory effects is more evident on a non-logarithmic scale. Indeed, 50 μM 3A, 3D and 3E, 2A and 3B and 3C all reduce the increasing numbers of untreated L1210 cells observed in control wells after 3 and 4 days in culture by 91-100% (FIG. 6).
The ability of 3A and 3D and 3E to inhibit the growth of L1210 cells in vitro is clearly concentration-dependent between 3.12 and 50 μM (FIGS. 7-9). On an equal concentration basis, 3D and 3E are slightly more effective than 3A but 50 μM concentrations of these new agents are required to match the inhibitory effect of 3.12 μM CPT. When the inhibitory effects are expressed as % of the increasing numbers of untreated cells present each day in control culture wells, the magnitudes of inhibition for each concentration of 3A and 3D and 3E generally increase over a 4-day period (FIGS. 8 and 9). Because the drugs increasingly slow down or block the rate of tumor cell growth, the difference between the number of exponentially growing control cells and the reduced number of drug-treated cells keeps increasing with the number of days in culture. This effect is even more apparent with 2A (FIGS. 10 and 11).
The inhibition of tumor cell growth by 2A increases with the concentration tested (FIG. 10). And the effectiveness of each concentration increases with the time in culture (FIG. 11). But the shape of the concentration-response curve is similar at each time point tested. For instance, every day, the concentration-dependent inhibitory effect of 2A is maximal at 6.25 μM and plateaus thereafter (FIG. 11). However, the 6.25 μM concentration of 2A reduces the increasing numbers of untreated L1210 cells observed at 1, 2, 3 and 4 days in control wells by 28, 74, 90 and 94%, respectively (FIG. 11). These results, therefore, suggest that the effectiveness of 3A, 3D and 3E, 2A and 3B and 3C as inhibitors of tumor cell growth in vitro is a combination of drug concentration and duration of action. Obviously, concentrations of 2A much smaller than 1.56 μM should be tested since this level of drug has no effect after 24 h but inhibits tumor cell growth by 83% after 96 h (FIG. 11).
Concentrations of 2A up to 8 times lower than 1.56 μM, therefore, were tested in another experiment for their ability to inhibit the growth of L1210 cells in vitro (FIGS. 12 and 13). Again, the concentration-dependent inhibitory effects of 2A (FIG. 12) clearly increase with the number of days in culture (FIG. 13). As a result, the concentrations of 2A that reduce by 50% (lC 50 ) the increasing numbers of untreated cells in control wells at 1, 2, 3 and 4 days are 11.0, 2.0, 1.1 and 1.1 μM, respectively (FIG. 13). Similarly, 0.78 μM CPT reduces the increasing numbers of untreated L1210 cells observed at 1, 2, 3 and 4 days in control wells by 46, 85, 97 and 99%, respectively (FIG. 13). The magnitude of this effect over a 4-day period is mimicked by 6.25 μM 2A, suggesting that this new tricyclic pyrone analog is about 8 times less potent than the anticancer drug CPT at inhibiting leukemic cell growth in vitro, an observation which is consistent with the respective potencies of 2A and CPT on DNA synthesis in the same L1210 system. The apparent discrepancy between the effects of 1.56 μM 2A on DNA synthesis (FIG. 4) and tumor cell growth (FIGS. 11 and 13) may simply be due to the fact that the incorporation of 3 H-thymidine into DNA was determined after only 90 min of drug treatment. Longer periods of incubation prior to pulse labelling might be required to demonstrate the inhibitory effects of low concentrations of 3A, 3D & 3E, 2A and 3B & 3C on DNA synthesis.
This invention is described with reference to preferred embodiments; however, it will be apparent to those skilled in the art that additional equivalent procedures and compositions may be substituted in the practice of this invention for those disclosed herein within the scope and spirit of applicants' contribution to the art. The appended claims are to be interpreted to include all such modifications and equivalents. | This invention provides cancer-active tricyclic and tetracyclic oxypyrones and a method of synthesizing these compounds. Preferred compounds have aryl groups at the 3-position of the oxypyrone ring. The tricyclic oxyprone synthetic method is a simple condensation reaction of pyrones with cyclohexenecarboxaldehydes, providing high yields and using few steps. The tetracyclic oxypyrone synthetic method is a simple condensation reaction of carvones with pyrones. | 2 |
FIELD OF THE INVENTION:
The present invention relates to carriers for transporting workpieces along a conveyor from one workstation to the next in a series of workstations. More particularly, a workpiece carrier is provided that can be releasably mounted on a conveyor or other automation device to carry a workpiece along said series and present said workpiece to each said workstation in a desired positional orientation.
BACKGROUND OF THE INVENTION:
Work holders or tables for machining or other operations are known in the art. See, for example, U.S. Pat. No. 2,079,323 to Kokotiak for "Work Holder For Machining Operations"; U.S. Pat. No. 2,595,137 to Hagopian for "Work Holder"; U.S. Pat. No. 2,819,654 to Coy for "Machine Fixture"; and U.S. Pat. No. 3,143,791 to Lanahan et al. for "Work Positioning Table".
Positioning and holding a workpiece in a positional orientation relative to a workstation is well known. The prior art variously shows work holders for positioning a workpiece and holding it in any desired angular relation to a grinding wheel, drill, or other machining tool. Fixtures are shown for use with milling machines, jig bores, or the like.
It is also known in the art to use a conveyor to transport a workpiece from one workstation to another for presenting said workpiece for a series of operations, such as for example machining operations.
SUMMARY OF THE PRESENT INVENTION
In accordance with a preferred embodiment of the present invention, a device is provided for releasably mounting to a conveyor for carrying a workpiece to a series of workstations to present said workpiece in a number of positional orientations as required for each particular workstation. A number of these devices or workpiece carriers can be readily mounted in a series on a conveyor, with their respective workpieces mounted therein, for presenting a continuous series of workpieces to the workstations in seriatim. Preceding each workstation is an orientation station, and the conveyor is operated so that the workpiece carrier temporarily halts before the orientation station before proceeding to the associated workstation. The orientation station includes a plunger or other means that is extended to engage a camming surface on said carrier and cause repositioning of the workpiece for subsequent presentation to the workstation.
The device of the present invention comprises a base and a nesting receptacle mounted on the base. The receptacle holds the workpiece in a positional orientation with respect to the base, and the receptacle is movable relative to the base for changing the positional orientation. Means associated with at least one of the workstations, preferably a plunger operated at the orientation station, is provided for moving the receptacle from one position to at least one other position. Said moving means can be responsive to a protocol or perhaps computer control for establishing the proper positional orientation for each said associated workstation.
In accordance with a particularly preferred embodiment, the nesting receptacle is rotatably mounted in the base for receiving a workpiece, such as a part for being machined on two surfaces thereof, said surfaces being disposed at an angle to each other. The receptacle has two camming surfaces that are acted upon by plungers mounted at orientation stations preceding an associated workstation. The base carrying the receptacle is momentarily halted on the conveyor adjacent a first plunger at a first orientation station, which is aligned to engage a first camming surface and rotate the receptacle to a first position or angular orientation. The workpiece is then conveyed in the receptacle to the associated workstation for machining on one of the two surfaces.
After this first machining operation, the receptacle carries the workpiece to the second orientation workstation, where a second plunger is extended to engage a second camming surface and rotate the receptacle and the workpiece to a second position or angular orientation. The receptacle is thereafter conveyed to a subsequent workstation for machining on the second surface.
It is an object of the present invention to enable part positioning without the necessity for expensive part transfer devices and different fixtures for different orientations.
It is a further object of the present invention to provide a simple means of completely automatic part positioning.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a system using the multiple position, conveyor mountable workpiece carrier of the present invention;
FIG. 2 is a perspective view of a preferred embodiment of the workpiece carrier of the present invention, with a workpiece nested therein;
FIGS. 2A and 2B are side and top views respectively of a workpiece carried by the embodiment of FIG. 2;
FIG. 3 is a top view of the embodiment of FIG. 2 without the workpiece;
FIG. 4 is a side view of the embodiment of FIG. 3; and
FIGS. 5A, 5B, and 5C are top, bottom, and side views respectively of the nesting receptacle of the workpiece carrier of FIG. 2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference to FIG. 1, a system 10 is indicated generally wherein a series of workstations 12, 14, and 16 are disposed in alignment alongside a conveyor 18 defining a conveyor path 20. Three of the workpiece carriers 22 of the present invention are shown mounted onto conveyor 18 for conveying workpieces 24 from workstation to workstation in a preselected direction indicated by arrow 26. Located alongside conveyor 18 prior to each workstation are the orientation stations 28, 30, and 32 for changing the position of workpiece 24 in carrier 22 as described more fully in detail below. In the system of FIG. 1, orientation station 28 and its associated workstation 12 are alongside a first side of the conveyor 18, while orientation station 30 and its associated workstation 14 are alongside the opposite side. As explained below, this is to permit the two camming surfaces that are on opposite sides of the carrier 22 to be activated. Stations 32 and 16 are on the same side as stations 28 and 12. It is understood that the right-hand or left-hand positioning of the stations shown in FIG. 1 is by way of example only and is not intended to be limiting of the invention. Additionally, the orientation station and its associated workstation need not be on the same side, but can be on opposite sides depending upon the positional orientation of the workpiece that is desired. As further explained below, the two camming surfaces are on opposite sides and the orientation station and plunger can be placed on the left or right depending upon which camming surface is to be used.
Controller 11, which can be any suitable control means such as for example a programmable logic controller or computer system, directs the operation of workstations 12, 14, and 16 through lines 13, 15, and 17 respectively and the operation of orientation workstations 28, 30, and 32 through lines 29, 31, and 33 respectively. Motor 35, such as for example a servomotor, is also under direction of controller 11 through line 37 for indexing conveyor 18 to move workpieces 24 from workstation to workstation with stop-and-go motion as described more fully in detail below.
Workstations 12, 14, and 16 can be any desired routine machine for carrying out an operation of the desired kind on workpieces 24. These workstations can be, for example, machining stations, such as for grinding or polishing various surfaces of the workpieces.
For example, it can be appreciated by reference to FIGS. 2, 2A, and 2B that workpiece 24 is a swashplate, having an aperture 34, to be machined on first and second surfaces 36 and 38, which surfaces 36 and 38 lie in first and second planes 40 and 42 lying at an acute angle A with respect to each other. Corresponding surfaces 37 and 39 on the opposite side of part 24 may also be machined if part 24 is first flipped over.
Workstation 12 can, by way of example only, be adapted for machining surface 36, while workstation 14 can be adapted for machining surface 38. Workstation 16 may then be adapted for further machining surface 36 again in some fashion. That is, workstation 12 may include a grinding wheel 46 sized to machine surface 36. Wheel 46 is driven by motor 48 and is mounted on a shaft 50 which can be raised or lowered by threaded member 52, all of which can be accomplished under direction of controller 11. Wheel 46 is typically mounted for grinding in a plane parallel to conveyor surface 54; that is, a horizontal plane. Similarly, workstation 14 includes grinding wheel 53 sized for surface 38, wheel 53 having its own associated motor 58 and threaded member 60 controlled by controller 11. Wheel 53 would also conveniently be mounted for grinding in a horizontal plane, which can be accommodated because part 24 is tiltable in accordance with the present invention to present face 38 in the horizontal orientation required for wheel 53.
In accordance with the system of the present invention as explained in more detail below, the workpiece 24 rides in carrier 22 and is presented to the first orientation station 28, where carrier 22 is properly positioned or tilted if necessary for surface 36 to be presented to workstation 12 in a horizontal plane. After the desired operation, carrier 22 is moved to orientation station 30, where carrier 22 can be repositioned to tilt the workpiece 4 and present surface 38 to workstation 14 in a horizontal plane. The operation may be repeated, perhaps for a third workpiece surface or perhaps for surface 36 again, at a subsequent orientation station 32 with its associated workstation 16 and its motor 62, threaded member 64, and grinding wheel 66.
With reference now to FIGS. 2, 4, 5A, 5B, and 5C, the workpiece carrier 22 of the present invention includes a base 68 and a nesting receptacle 70 rotatably mounted on base 68 for holding workpiece 24.
Base 68 is preferably formed of a plastic material such as polyurethane, although other materials such as for example acetal, or other thermoplastic can be used as well. In the preferred embodiment, base 68 is a substantially planar member 72 with a bottom face 74 having apertures 76 and 78 for mating with protuberance pairs 80 and 82 on conveyor surface 54. Protuberance pairs 80 and 82 provide means for engaging base 68 to releasably mount base 68 and therefore nesting receptacle 70 onto conveyor 18. This releasable mounting feature provides the advantages of flexability of part orientation in an automatic mode. Protuberance pairs 80 and 82 also provide a convenient way of consistently aligning base 68 and therefore receptacle 70 from left to right and front to back on conveyor 18 for proper presentation to orientation stations 28, 30, and 32 and workstations 12, 14, and 16. Base 68 also has a perimeter 69 with flange 71 extending most of the way around perimeter 69 for the purpose of establishing a "false" thickness of the base without incurring unnecessary material cost.
Conveyor 18 is typically made up of chain links 19 joined to form an endless conveying surface. It is understood that not all chain links 19 need have protuberance pairs 80 and 82, which can be spaced as needed along conveyor 18. In this manner, a plurality of bases 68, 86, and 88 with corresponding nesting receptacles 70, 90, and 92 can be mounted in a series as shown in FIG. 1. It is understood that this series is not limited to three, but can be any reasonable number as determined by the size of the system.
Receptacle 70 is mounted on base 68 and comprises means for nesting the workpiece 24 in a positional orientation with respect to base 68. As seen in FIG. 4, in the preferred embodiment receptacle 70 can be repositioned from alignment generally parallel to base 68 to tilted at some angle A. Receptacle 70 is rotatably mounted on base 68 about a substantially horizontal axis 94. As shown in FIG. 4, receptacle 70 has a first position indicated at 96 characterized by a first angular displacement about axis 94, here forming an angle of substantially 0 with the horizontal. Receptacle 70 also has a second position indicated in phantom at 98 characterized by a second angular displacement A about axis 94. These two angular orientations can be designed to be different from the 0 and A. of the preferred embodiment by simply changing the length of the posts 100 and 102, which can be suitably lengthened or shortened to provide stops restricting the angle through which receptacle 70 can rotate, as described further in detail below.
Receptacle 70 has fitted flanges 104, 106, and 108 for abutting the sides of workpiece 24 to engage same in a relatively snug fit so that workpiece 24 is removably held or nested therein and can be gently pressed into or removed therefrom.
The receptacle 70 provides means for holding the workpiece 24 in a nesting plane 110 that defines the angular orientation of workpiece 24 nested therein, because workpiece 24 sits in and is held in position by the bottom 112 of receptacle 70, with surface 39 of workpiece 24 abutting bottom 112. Depending upon how receptacle 70 is rotatably adjusted about axis 94, plane 110 forms an orientation angle with the substantially horizontal plane of conveyor 18, with respect to which workstations 12, 14, and 16 are oriented. The angle A is adjustable under the influence of the repositioning and activating means as described more fully in detail below. Receptacle 70 is preferably formed of a plastic such as polyurethane, but can be any suitable material such as for example acetal.
Receptacle 70 is mounted between a pair of uprights 114 and 116 on opposing sides 118 and 120 of base 68. Uprights 114 and 116 are substantially perpendicular to planar member 72 comprising base 68. Journal means such as pins 122 and 124 mount receptacle 70 therebetween on corresponding bearing surfaces 126 and 128. Post 102 provides means for restricting the rotation of receptacle 70 in clockwise direction 130 about axis 94 past preselected clockwise angular displacement angle A, while post 100 provides means for restricting the rotation of receptacle 70 in a counterclockwise direction 132 about axis 94 past a preselected counterclockwise angular displacement, here the horizontal, or where A=0°.
Camming surfaces 134 and 136 formed in tabs 138 and 140 downwardly depending from receptacle 70 (see FIGS. 5A, 5B, and 5C) provide means for repositioning the angular orientation of receptacle 70 in response to the thrusting force of plungers 142, 144, and 146 (see FIG. 1), which are extendable from orientation stations 28, 30, and 32 respectively to exert a repositioning force F generally in directing transverse to path 26 and parallel to axis 94. If the orientation station is on the other side of the conveyor, the force is F' in an opposite direction. Such plungers provide means for activating the cam, or the repositioning means. Camming surfaces 134 and 136 cause receptacle 70 to rotate through an arc in response to forces F and F' applied thereto.
Camming surfaces 134 and 136 have curved contours, which contours are preferably the compliments of each other. That is, a plunger applied to camming surface 134 causes receptacle 70 to rotate about axis 94 in a first direction, while a plunger applied to camming surface 136 will cause receptacle 70 to rotate in the opposite direction. The exact shape of the camming surface contours are routinely determinable for relatively smooth motion.
The plungers such as 142 associated with station 28 as shown in FIG. 3 have a substantially spherically shaped end, such as a bullet nose, for pushing against the camming surfaces. Plungers 142, 144, and 146 can be operated by appropriate routine activators, such as solenoids, which can be suitably linked to a control system as desired. These plungers located in orientation stations bear a suitably spaced relationship to their associated workstations.
Uprights 114 and 116 have substantially cylindrical bores 148 and 150 for guiding the plungers into proper engagement with camming surfaces 134 and 136. The plungers are likewise substantially cylindrical along their operative lengths, the diameter of the bores and plungers being selected for slidable mating of the plungers 142, 144, and 146 with bores 148 and 150.
Tip 151 of screw 152 mounted in threaded bore 154 rides against the curved underside 156 of tab 138 and provides brake means for impeding the rotation of receptacle 70. Suitably shaped depressions 158 and 160 in curved underside 156 provide means for urging the retention of receptacle 70 at the two endpoints of its angular travel to provide stability for the workpiece during machining.
The device of the present invention can be used in a method of conveying a workpiece 24 along a series of workstations 12, 14, and 16 as shown in FIG. 1 under direction of controller 11, although it is understood that any series of workstations a, . . . , n, . . . , b can be used. The workpiece 24 is nested in receptacle 70, which is capable of assuming two angular orientations, one where A=0° and the other where A=K°, angle A being in this case an acute angle. It is understood, however, that receptacle 70 could also be made to assume not just two, but a variety of angular orientations by simply designing different camming surfaces and suitably controlling the action of plungers 142, 144, and 146, such that receptacle 70 might assume a plurality of positional orientations X, . . . , y.
While nested in receptacle 70, workpiece 24 is conveyed to a first orientation station 28 on conveyor 18 as operated by motor 35, which is temporarily halted with receptacle 70 aligned alongside orientation station 28 such that plunger 142 can be extended through bore 148 under direction of controller 11 to engage camming surface 136 and tilt receptacle 70 to the proper angular orientation. After this operation, conveyor 18 is indexed forward by motor 35 to an aligned position under grinding wheel 46 of workstation 12, where receptacle 70 is again temporarily halted for the first machining operation. It is understood that workstation 12 could also be designed to have the capacity to completely remove workpiece 24 from receptacle 70 for the necessary operation and then return workpiece 24 thereto.
After the machining operation at workstation 12, motor 35 indexes receptacle 70 forward and aligns the bore 150 on base 68 with plunger 144 of orientation station 30. Under controller 11's direction, plunger 144 is extended to engage camming surface 134 and reposition receptacle 70 by rotation about axis 94. The plunger 144 is then withdrawn, and receptacle 70 is conveyed to workstation 14. These steps are repeated for orientation station 32 and workstation 16, as well as for any other stations that may be positioned along path 26.
Although the invention herein has been described with respect to particular features and embodiments, and illustrated with reference to particular drawings, materials of construction and the like, it is to be understood that these are not considered to be limitations of the invention except as otherwise recited in the appended claims. | A device is provided for conveying a workpiece along a conveyor path having spaced therealong at least two workstations to present the workpiece in seriatim to the workstations in at least two positional orientations as required for each particular workstation. The device comprises a base for being transported along said path from a first workstation to a next successive workstation along the path, a member mounted on the base for nesting the workpiece in a positional orientation with respect to the base to present the workpiece to each of the workstations, and at least one device for repositioning the nesting member from one position to at least a second position. | 8 |
BACKGROUND
The present invention relates to automated laundry spreaders. In particular, a spreader for laying articles of laundry, such as towels or sheets, out flat is provided.
Many processes in laundries are automated. For example, machines in hotels spread out, iron and fold sheets without operator intervention. To begin the automated process, the operator identifies either corners or an edge of the sheet and places the corners or edge into the first machine. Since sheets have large dimensions with thin fabric, the sheets are often tangled together, necessitating either an automated separator machine or an operator for locating the edges or corners.
Since towels are smaller and thicker, towels may be less likely tangled after removal from a washing or drying machine. However, in typical towel processing, an operator still grabs individual towels and places them on folding machines. Where possible, automated processes may save money over a time.
Machines for automatically grabbing articles of laundry from a load of articles and spreading the articles have been attempted, but find little commercial success. Typically, these machines attempt to isolate diagonal corners and then opposite corners. Such isolation can be difficult and inconsistent when implemented with a machine.
BRIEF SUMMARY
By way of introduction, the preferred embodiments described below include apparatuses and methods for spreading an article of laundry from a load of articles of laundry. A first clamp moves along a run towards and away from the load to remove the article from the load. By changing an orientation of the run, articles may be removed from different locations, increasing the chance of grabbing an article when the number of articles in the load decreases. A second clamp rotates while holding the article until the article contacts a stop. The rotation generally flattens out the article. A third clamp grabs a portion of the article and further spreads the article for a fourth clamp to grab the article between the second and third clamps. This process may detangle or untwist the article. The untwisted article is dragged over a wheel or belt. The wheel or belt adjusts the amount of overhang on each side, making an edge of the article more horizontal. A plate lifts the edge up for clamping. The clamped article is dragged over a long roller. The roller moves into contact with a conveyor. The conveyor conveys the article to find a leading edge. The article is then conveyed in a spread position. Different features or components described above may be used separately or in combination.
In a first aspect, an apparatus is provided for spreading an article of laundry. The apparatus includes a first clamp connected with a frame. A rotatable and the first clamp are operable to move relative to each other such that the article of laundry held by the first clamp drapes over the rotatable support. A first drive is operable to rotate the rotatable support. The rotation alters the lengths of the article of laundry hanging from each side of the rotatable support.
In a second aspect, a method is provided for spreading an article of laundry. The article of laundry is clamped adjacent or at a corner. A first portion of the article of laundry spaced from the corner is clamped. A second portion is clamped between the corner and the first portion. The corner and the first portion are released. A first part of the article of laundry is dragged by the second portion over a rotatable support. A hanging of the article of laundry is rotatably adjusted with the rotatable support. An edge of the article of laundry is clamped.
In a third aspect, an apparatus is provided for separating a first article of laundry from a group of articles of laundry. A pick-up area has the group of articles of laundry. A first clamp connects with the frame and is operable to move towards and away from the pick-up area. A drive connects with the frame and is operable to alternatingly orient the first clamp to a first portion of the pick-up area and a second portion of the pick-up area. The first and second portions are at least horizontally spaced apart.
In a fourth aspect, an apparatus is provided for spreading an article of laundry. A first clamp is operable to clamp the article of laundry at or adjacent to a corner. A drive is operable to rotate the first clamp and the article of laundry clamped by the first clamp. A stop is positioned to contact the article of laundry during the rotation. A second clamp is operable to clamp a portion of the article of laundry spaced away from the corner and the first clamp. The second clamp clamps while the first clamp is clamped and the article of laundry is adjacent the stop.
In a fifth aspect, an apparatus is provided for spreading an article of laundry. A roller is adjacent a conveyor. A first drive is operable to position the roller against and spaced away from the conveyor. The article of laundry is deposited on the roller in the spaced away position. A sensor is operable to detect an edge of an article of laundry between the roller and the conveyor. A controller is operable to control the first drive to position the roller against the conveyor with the article of laundry in a nip between the roller and the conveyor, and convey the article of laundry such that the edge is adjacent the nip formed by the roller and the conveyor.
In a sixth aspect, a method is provided for spreading an article of laundry. The article of laundry is deposited on a roller. The roller is positioned against a conveyor. The article of laundry is conveyed so that an edge is adjacent a nip formed by the roller and conveyor. The article of laundry is conveyed away from the roller on the conveyor.
In a seventh aspect, an apparatus is provided for spreading an article of laundry from a group of articles of laundry. A pick-up area has the group of articles of laundry. A first clamp connects with the frame and is operable to move towards and away from the pick-up area. A first drive connects with the frame and is operable to alternatingly orient the first clamp to a first portion of the pick-up area and a second portion of the pick-up area. The first and second portions are at least horizontally spaced apart. A second clamp is operable to transfer the article of laundry from the fist clamp to a pair of first rollers forming a first nip. The pair of first rollers is operable to suspend the article of laundry from a first corner or adjacent edge. A third clamp is operable to clamp the article of laundry at or adjacent to the first corner. A second drive is operable to rotate the third clamp and the article of laundry clamped by the third clamp. A stop is positioned to contact the article of laundry during the rotation. A fourth clamp is operable to clamp a first portion of the article of laundry spaced away from the first corner and the third clamp. The fourth clamp clamps while the third clamp is clamped and the article of laundry is adjacent the stop. A fifth clamp is operable to clamp the article of laundry at a second portion between the third and fourth clamps. A rotatable support connects with the frame. The fifth clamp and rotatable support are operable to move relative to each other such that the article of laundry held by the fifth clamp drapes over the rotatable support. A third drive is operable to rotate the rotatable support where the rotation altering lengths of the article of laundry hanging from each side of the rotatable support. A second roller is adjacent the conveyor. A sixth clamp is operable to clamp a first edge of the article of laundry on the rotatable support and operable to deposit the article of laundry on the second roller. A fourth drive is operable to position the second roller against and spaced away from the conveyor. The article of laundry is deposited on the second roller in the spaced away position. A sensor is operable to detect a second edge of an article of laundry between the second roller and the conveyor. A controller is operable to control the fourth drive to position the second roller against the conveyor with the article of laundry in a second nip between the second roller and the conveyor, and convey the article of laundry such that the second edge is adjacent the second nip formed by the roller and the conveyor.
In an eighth aspect, a method is provided for spreading an article of laundry from group of articles of laundry. The article of laundry is clamped while in the group. A first location of the article of laundry is transferred to a rotatable clamp. The rotatable clamp rotates such that the article of laundry contacts a stop. A second location spaced from the first location is clamped. A third location between the first and second locations is clamped. The first and second locations are released. A first part of the article of laundry is dragged by the third location over a rotatable support. A hanging of the article of laundry is rotatably adjusted with the rotatable support. A first edge of the article of laundry is clamped. The article of laundry is deposited by the edge on a roller. The roller is positioned against a conveyor. The article of laundry is conveyed so that a second edge is adjacent a nip formed by the roller and conveyor. The article of laundry is conveyed away from the roller on the conveyor.
The present invention is defined by the following claims, and nothing in this section should be taken as a limitation on those claims. Further aspects and advantages of the invention are disclosed below in conjunction with the preferred embodiments.
BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS
The components and the figures are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention. Moreover, in the figures, like reference numerals designate corresponding parts throughout the different views.
FIG. 1 is a front view of initial stages of a linen spreader in one embodiment;
FIG. 2 is a side view of middle stages of the linen spreader in one embodiment;
FIG. 3 is a top view of part of the middle stages of FIG. 2 ;
FIG. 4 is a front view of one of the middle stages of FIGS. 2 and 3 ;
FIG. 5 is a back view of another one of the middle stages of FIG. 2 ; and
FIG. 6 is a top view of the middle stage of FIG. 5 and a final stage.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1-6 show various aspects of one embodiment. FIGS. 1-6 show an apparatus and represent the method for spreading an article of laundry. Various stages and aspects of the embodiment may be altered or changed based on now known or later developed devices and methods. Different stages or components may be used independently of other stages or components in alternative embodiments. Additional, different, or fewer components than described below may be used.
The spreader isolates a towel, sheet or other article of laundry from a load of articles of laundry and spreads the article out flat for subsequent processing. For example, a towel is output to an automated towel folder, such as disclosed in U.S. Pat. No. 5,300,007, the disclosure of which is incorporated herein by reference. Alternatively, the spread article is output to an operator or stacked for further use.
The linen spreader described herein is adapted for isolating and spreading rectangular or square towels, sheets, or other linens of various sizes, including bath towels, beach towels, and hand towels. For example, terry cloth bath towels of any size are processed. Larger towels or smaller towels may also be processed, such as square washcloths or cotton shop towels. Articles with thinner material, such as woven or knit pillowcases, pillow shams, or other laundry articles may also be processed. Other articles of laundry, such as sheets or blankets, may also be spread, in part or total, using one, more or all of the stages described herein.
FIGS. 1-6 show one apparatus positioned within a single frame structure. One example portion of the frame structure is represented at 21 for connecting with a drive 22 . The frame structure includes beams, plates, mounts, legs, covers, and/or other components. The clamps, drives, or other components described herein connect directly or indirectly with the frame. Bolts, welding, clamps, screws, pins, and/or other connectors may be used.
Different portions of the apparatus are shown in different views to illustrate the components and operation of various stages for spreading a linen. In one embodiment, the stages are built together within the framework in as small a space as possible while providing sufficient volume for spreading. Various plates for safety and preventing operators from entanglement within the spreader are included, but not shown. Electrical, hydraulic, and/or air pressure cables and hoses interconnect various components for controlling and operating spreading. These cables and hoses are configured and routed as is known in the art or later developed. One or more controllers, such as a processor, coordinate the movement and operation of the various components. These components are not shown to avoid complicating the Figures. Instead, the components operating on the article of laundry are shown and described.
The components include clamps and drives. Different clamps may have the same or different structures, such as a chuck, scissor clamp, two opposing plates, jaws, pinch roller, pinch plates, pinching belts, or other structure operable to hold a article of laundry. In one embodiment, the clamp includes two metal plates separated by a space for one jaw and an opposing metal jaw operable to move between the two plates of the other jaw. The article is clamped between the two jaws. In another embodiment, the clamp includes two prongs or plates operable to press together or one prong operable to press against another. In yet other embodiments, a cylinder or actuator extends against a plate or surface for clamping. One or more of the jaws may be toothed or coated in rough or gripping material.
The different clamps discussed below may be of one of the embodiments above or a different embodiment, such as a now known or later developed embodiment. One embodiment may be used below to describe a particular clamp, but other embodiments may be used.
The clamping motion, rotation, linear movement, or other movement of the clamps, rollers, runs, or other components are performed by drives. The drives include one or more pneumatic cylinder or cylinders, electric servos, air driven cylinders, hydraulic cylinders, pneumatic actuators, extending screw devices with an electric motor or other mechanism, combinations thereof, or other now known or later developed force applying device. The drives connect with the component being forced. For example, one or more jaws of a clamp are actuated by a pneumatic cylinder through a push/pull rod. Other drive structures may be provided, such as a pulley and motor with an endless belt or chain. For example, a timing belt with an inverter is used. As another example, a guide or run is provided for movement of a clamp between two locations. The drive includes an actuator long enough to extend to and retract from the two locations. Other now known or later developed drives and associated structures may be used.
The different drives and structures discussed below may be one of the embodiments above or a different embodiment, such as a now known or later developed embodiment. One embodiment may be used below to describe a particular drive or structure, but other embodiments may be used. Similarly, rotation or linear motion may be described below, but other motions may be provided.
The clamping and driving are controlled by a controller. The controller is a processor, computer, or other device for receiving inputs and generating outputs. In response to sensors, such as contact, infrared, light beam and detector, or other sensors, the controller causes the clamps to clamp, the drives to move, or other action. Any now known or later developed controller and sensors may be used. One embodiment may be used below to describe a particular controller and/or sensor, but other embodiments may be used.
Metal, plastic, wood, fabric, and/or other materials may be used for any component. The various components use materials now known or later developed, such as aluminum, steel, or other metal.
FIG. 1 shows a bin 12 for holding a load of articles 14 . The bin 12 is a pick-up area for holding a group of articles of laundry. The bin 12 is of various sizes or shapes. For example, the bin 12 is a wheeled laundry truck. The bin 12 has sides to contain the laundry, but may be a flat surface without walls, such as a conveyor or floor. In one embodiment, the bin 12 tapers towards one location at the bottom of the bin 12 . As articles are removed from the bin 12 , remaining articles migrate towards the location for clamping. In alternative embodiments, conveyors, vibration, tilting mechanisms, troughs, or other devices are provided for continually positioning articles near a clamping position. In other embodiments, no extra guidance is provided for the articles 14 in the bin 12 .
The bin 12 is fixed to the frame. Alternatively, the bin 12 is releasable from the frame, such as disclosed in U.S. Pat. No. 6,655,890, the disclosure of which is incorporated by reference. In another embodiment for use with a wheeled cart, a tapered plate 15 , rail, or other structure is provided to hold the bin 12 in place relative to the frame during operation. The bin 12 is wheeled over the plate 15 . The frame and plate 15 prevent the bin 12 from moving away from a clamp 18 .
For grabbing articles of laundry 16 from the bin 12 , the clamp 18 operates on a clamp run 20 . The clamp 18 is movable along the clamp run 20 . In one embodiment, the clamp 18 has two jaws coated or textured for gripping articles of laundry. The jaws are narrow plates that press together at the ends or along a portion of the plates. The clamp 18 is actuated by a pneumatic cylinder or other drive. One or both jaws of the clamp 18 connect with the pneumatic cylinder or a plurality of cylinders. The article 16 is clamped between the two jaws. For example, the clamp 18 is positioned on top of or in the load 14 . The article 16 of laundry is clamped while in the load 14 .
The clamp run 20 is a drive, guide, timing belt, toothed gear, chain, drive shaft, or other structure for moving the clamp 18 towards and away from the bin 12 . In one embodiment, the clamp run 20 is a pulley and motor with an endless belt or chain. For example, a timing belt with an inverter is used. The clamp 18 connects to the endless chain to clamp in a downward direction. The clamp run 20 may include a telescoping portion for further range of motion of the clamp 18 , such as the belt and pulley being on one portion operable to move relative to another portion.
The clamp run 20 mounts to the frame at a pivot point at any location. The clamp run 20 is moveable. In the embodiment shown, the clamp run 20 is generally vertical in one position, but may be rotated away from vertical as represented by the dashed lines. Alternatively, the clamp run 20 is fixed relative to the frame.
The clamp 18 is moved downward to a bottom of the clamp run 20 . A sensor, gravity, or interference by the load 14 may be used to determine where to stop the clamp 18 relative to the load 14 . The clamp 18 clamps one or more articles 16 . The clamp 18 is sized to most likely select a single article, such as by having jaws that extend only about one or a few inches. The clamped article 16 and clamp 18 are moved away from the load 14 , such as upwards. FIG. 1 shows the same clamp 18 at two different example locations. The clamp run 20 includes only a single clamp 18 , but may include multiple clamps.
The load 14 may be unevenly distributed or may not shift as articles or laundry are removed from a same location by the clamp 18 . By reorienting the clamp run 20 , the clamp 18 may be positioned into different horizontally spaced locations relative to the load 14 . Two or more different locations may be used.
The drive 22 connects with the frame 21 . The drive 22 includes a rod for extending and withdrawing. By operating the drive 22 , the clamp 18 and clamp run 20 are oriented at different locations or portions of the pick-up area. In the example shown, the clamp run 20 is vertical for clamping articles at a front of the bin 12 and at an angle from vertical for clamping articles at a back of the bin 12 . The angle results in the clamp run 20 being more horizontal than the vertical orientation. In alternative embodiments, the clamp run 20 and/or drive 22 operate to position the clamp 18 at different locations within the bin in other ways. For example, the clamp run 20 is always vertical, but the drive 22 moves the clamp run 20 relative to the bin 12 along a guide. As another example, the clamp run 20 is fixed relative to the frame, and the article of laundry 16 are moved under the clamp run 20 .
The clamp 18 repetitively clamps articles of laundry 16 from a same location. A sensor 19 detects whether an article is clamped during each attempt. Any sensors may be used, such as weight or light beam sensors. If an article is not clamped, the controller actuates the drive 22 to reorient the clamp 18 . In a next attempt, the clamp 18 will contact the load 14 at a different location. In alternative embodiments, the orientation of the clamp run 20 is changed for additional or alternative reasons than failure to clamp, such as changed periodically regardless of failure to clamp. The orientation may be changed due to failure to clamp or a number of attempts at one orientation.
The clamped articles of laundry 16 are positioned along the clamp run 20 near the top for clamping by the clamp 24 . In one embodiment, the clamp 24 is a pass-by scissors clamp with one serrated jaw passing between two serrated plates of the other jaw and a sensor for detecting clamping. The clamp 24 clamps near the pivot point so that clamping occurs at a same location regardless of the orientation of the clamp run 20 . Alternatively, the clamp 24 rotates about a pivot point to align with the orientation of the clamp run 20 . In another alternative, the clamp run 20 rotates to vertical for clamping by the clamp 24 . Combinations of these embodiments may be used.
In response to timing on a timing chain of the clamp run 20 and/or electric eyes indicating that the article 16 is positioned on the upper location, the clamp 24 is activated to move and/or rotate to the article of laundry. For example, the clamp 24 moves laterally and rotates to clamp. The clamp 24 clamps the article 16 of laundry just below the clamp 18 . In one embodiment, a sensor is provided to detect contact of the clamp 24 with the article 16 . In other embodiments, the clamp 24 is positioned to where a article 16 should be positioned. In response to the closing of clamp 24 , the clamp 18 releases the article 16 . The clamp 24 grabs the article 16 just below the clamp 18 or at another location anywhere on the article 16 .
The clamp 24 moves laterally to transfer the article 16 of laundry. The clamp 24 is shown in two different example positions in FIG. 1 . The two positions correspond generally to the extent of the lateral movement. One or more clamps 24 may be used. The clamp 24 moves the article of laundry from the clamp 18 to a pair of rollers 26 , 28 . Plates, guides, and/or brushes may be used to contact the article 16 of laundry during transfer to the rollers 26 , 28 . For example, a plate is provided at an angle (e.g., 45 degrees) to guide the article to the rollers 26 , 28 , reduce drag from the article 16 of laundry during operation of the rollers 26 , 28 , or guide discarded articles 16 back into the bin 12 . Brushes along the sides may assist in aligning the article of laundry to fall between the rollers 26 , 28 at a centered location.
The rollers 26 , 28 are clutch rollers, but other rollers may be used. Solid rollers, belts, conveyors, or other structures may be used for the rollers 26 , 28 . In one embodiment, the roller 28 is moveable to and away from the other roller 26 . Brackets supporting the roller 28 rotate to move the roller 28 . A drive positions the roller 28 spaced away from the roller 26 for receiving the article 16 of laundry. The clamp 24 releases the article 16 of laundry over the gap between the rollers 26 , 28 . Such a gap is shown in FIG. 1 .
Upon release by the clamp 24 , the roller 28 is rotated against or to contact the article 16 of laundry adjacent the roller 26 . A nip is formed between the rollers 26 , 28 . In alternative embodiments, the roller 26 moves or both rollers 26 , 28 move relative to each other.
The roller 28 is not a driven roller, but the roller 26 is driven. Both rollers 26 , 28 or the roller 28 may be driven. The roller 26 drives the article of laundry between the rollers 26 , 28 . For example, the article 16 of laundry is driven downwards as shown in FIG. 2 . The roller 26 continues rotating until a corner or last portion of the article 16 of laundry is between the rollers 26 , 28 . A sensor detects the trailing portion of the article 16 of laundry just above the nip formed by the rollers 26 , 28 . Once the trailing portion is between the rollers 26 , 28 , one or both of the rollers 26 , 28 are braked to hold the article 16 , such as suspended in FIG. 2 .
FIGS. 2 and 3 show further processing of the article 16 of laundry. The article 16 of laundry is transferred from the rollers 26 , 28 to a rotatable clamp 30 . FIG. 2 shows the rotatable clamp 30 in two positions from a side view, and FIG. 3 shows the rotatable clamp 30 in two positions from a top view. Only one rotatable clamp 30 is used, but multiple rotatable clamps 30 may be provided. In one embodiment, the rotatable clamp 30 is a pass-by scissors clamp with one serrated jaw passing between two serrated plates of the other jaw. The clamp 30 rotates in a horizontal plane, but may rotate vertically or out of the horizontal plane.
In one embodiment, the rotatable clamp 30 includes a drive for rotating about a pivot location 32 and a separate drive 34 for lateral movement. The clamp 30 may be on an arm or otherwise extend from the pivot location 32 to provide the desired range of motion and centrifugal force. The rotatable clamp 30 moves laterally while rotated to clamp the article 16 of laundry suspended from the rollers 26 , 28 . The article 16 of laundry is clamped adjacent to or just below the corner held by the rollers 26 , 28 , but other locations may be clamped. In one embodiment, a sensor is provided to detect contact of the clamp 30 with the article. In other embodiments, the clamp 30 is positioned to where an article should be positioned. In response to the closing of clamp 30 , the rollers 26 , 28 release the article.
Upon release, the clamp 30 and arm rotates. Any amount of rotation may be used, such as 180 degrees. The clamped article 16 of laundry is rotated with the clamp 30 . The rotation has sufficient force to cause part of the article of laundry to extend away from the clamped corner by centrifugal force. For example, the article 16 of laundry rotates sufficiently quickly that a corner extends outward relative to the clamped corner. The short edge is common to the clamped corner and the corner extending outward due to the rotation. Greater or less centrifugal force may be applied. Lateral movement of the clamp 30 during, before, or after rotation may or may not also be provided. Plates, rubber stoppers, other stoppers, pneumatic cylinders or other devices may be used for limiting the rotation. Alternatively, the operation of the drive is used to limit the rotation. In alternative embodiments, rotation is not provided or is slow enough to have little effect on spreading the article 16 of laundry.
The clamp 30 rotates and/or moves such that the article 16 of laundry contacts a stop 36 . The stop 36 is a bar, plate, or other structure at least partially interfering with movement of the article 16 of laundry. The stop 36 is smooth or textured, such as for limiting sliding of the article 16 . The stop 36 is positioned to contact the article 16 of laundry during the rotation in one embodiment. The stop 36 is sufficiently long to catch at least part or all of a width of the article 16 of laundry. By contacting just a portion of the width, the article of laundry may more likely spread out or be maintained spread out. The article 16 of laundry may extend from the clamp 30 to the end of the stop 36 with only one or no folds, such as a short edge or fold by the short edge extending from the stop 36 to the clamp 30 . The stop 36 is positioned at any level or height relative to the clamp 30 . In one embodiment, the top of the stop 36 is about ¼-½ the length of the article 16 below the clamp 30 .
In one embodiment, the stop 36 is fixed. For example, the clamp 40 drags the article 16 of laundry over the stop 36 . In other embodiments, the stop 36 rotates, slides, or otherwise moves. For example, the stop 36 blocks the article 16 of laundry during rotation or at the end of rotation, but moves to limit or avoid interfering with the article 16 of laundry while being moved by the clamp 40 . FIGS. 2 and 3 show the stop 36 able to rotate downwards to avoid interference and rotate upwards to horizontal to block. In one embodiment, the stop 36 rotates downward as or after the clamp 38 grabs the article 16 of laundry.
As shown in FIGS. 2-4 , a clamp 38 clamps the article 16 of laundry while the clamp 30 clamps but after rotation. The clamp 38 rotates downward and to the side to clamp a portion of the article 16 of laundry spaced away from the corner clamped by the rotatable clamp 30 . Due to the rotation, the clamp 38 likely clamps an edge or single fold of the article 16 , but spaced away from the corner portion clamped by the rotatable clamp 30 . For example, the clamp 38 clamps two-to-ten inches lower than the rotatable clamp 30 .
After clamping, the clamp 38 rotates away and upwards to spread the article 16 of laundry. FIG. 4 shows the article 16 of laundry with a portion spread apart between the clamp 38 and the rotatable clamp 30 . After or during spreading, the stop 36 may move away from the path of travel of the article 16 of laundry.
In an alternative embodiment for spreading sheets, an additional clamp, similar to clamp 38 but opposite clamp 38 relative to clamp 30 , operates in sequence with the clamp 38 . While held by the clamp 30 and clamp 38 , air is used to clean any wrinkles. The opposite clamp grabs the sheet and the clamp 38 releases the sheet. Clamp 30 continues to hold the sheet. The clamp 38 then grabs the sheet again for clamping by the clamp 40 . Other combinations of release and grabbing sequences may be used.
After spreading, the clamp 40 moves to clamp the article 16 of laundry. The clamp 40 has two plates for jaws to clamp an elongated region of the article 16 of laundry between the clamp 38 and the rotatable clamp 30 . The elongated region is wider than the portions clamped by the clamp 38 or rotatable clamp 30 , but may be the same or less. Multiple clamps or clamping a non-elongated region may be used.
The clamp 40 clamps between the clamp 38 and rotatable clamp 30 while held by both. The region may be on a similar level as the clamp 38 , the rotatable clamp 30 , and/or both, or a different level, such as a few inches below.
On the opposite side of the article 16 of laundry, an air jet 41 blows on the article 16 of laundry to more likely position the article 16 between the jaws of the clamp 40 . The air jet 41 rotates or moves into position. For example, the air jet 41 connects with the drive 34 or structure supporting the moveable clamp 30 . The rotatable clamp 30 rotates the article 16 of laundry around the air jet 41 , and the air jet 41 moves laterally with the rotatable clamp 30 . Alternatively, the air jet 41 is spaced away from the path of travel of the article 16 of laundry, but directed to jet air or other gas at the article 16 of laundry.
Once the clamp 40 clamps the article of laundry, the clamp 38 and rotatable clamp 30 release the article 16 of laundry. After release, the clamp 40 moves laterally with the article 16 of laundry. The clamp 40 drags the article 16 of laundry over a rotatable support 42 . The clamp 40 moves above the rotatable support 42 , dragging a part of the article 16 of laundry over the rotatable support 42 . Less than the entire article 16 of laundry is dragged past the rotatable support. For example, about ⅓-½ or other amount of the article length is dragged over the rotatable support 42 . Keeping the distance low for larger articles may allow articles of different sizes to be spread by the same apparatus. In alternative embodiments, the rotatable support 42 moves to drag the article 16 of laundry while the clamp 40 is stationary or also moving.
The rotatable support 42 is a wheel, roller, belt, or other device. In the embodiment shown, the rotatable support 42 includes a belt with two pulleys or wheels. In other embodiments, a single wheel or three or more wheels with or without a belt may be used.
The rotatable support 42 is positioned to provide rotation around an axis extending along the direction of relative movement of the clamp 40 and the rotatable support 42 . The rotatable support 42 is shown as being a generally vertical belt, but angled (see FIG. 2 ) to ease dragging (i.e., more vertical than horizontal). Other angles may be provided. The angle tensions the article 16 between the clamp 40 and the rotatable support 42 to avoid loss of traction and undesired sagging (too much vertical) and jamming (too much horizontal).
The rotation of the rotatable support 42 causes the article of laundry to have more or less material hanging on a given side of the rotatable support 42 . As shown in FIGS. 2 and 5 , the article 16 of laundry drapes over the rotatable support 42 while held by the clamp 40 . After dragging, the article 16 of laundry includes a portion near or at a short edge held above and to one side of the rotatable support 42 . The rotatable support 42 is at a middle or other region lengthwise, with a portion of the article hanging to each side and the remainder of the length hanging off that has not been dragged over the rotatable support 42 . Different amounts or a same amount of the width of the article 16 of laundry hang from each side. Depending on the draping and where the clamp 40 clamps the article 16 , the edges hanging from the sides of the rotatable support 42 may or may not be horizontal.
One or more sensors 45 detect an extent of the article 16 of laundry hanging from one or both sides of the rotatable support 42 . For example, a sensor 45 detects whether the article 16 of laundry hangs in front of the sensor about 6-24 inches down from the rotatable support 42 . The sensor 45 senses an edge of the article 16 of laundry. If blocked, the edge is below the sensor 45 . If not blocked, the edge is above the sensor 45 .
A drive rotates the rotatable support 42 . For example, an electric motor rotates a pulley, which rotates the belt. The direction of rotation depends on input from the sensor 45 . Alternatively, the direction of rotation is fixed. The rotatable support 42 is rotated to bring the edge up or down to the sensor 45 . Once the edge is detected, such as being no longer blocked or now being blocked, the rotation is stopped. The rotation may occur after dragging and/or during dragging. For example, the rotation occurs during dragging to prevent the article 16 of laundry from falling off the rotatable support 42 and occurs after dragging to align the article for further processing.
The rotation alters the lengths of the article of laundry hanging from each side of the rotatable support 42 . The hanging of the article 16 of laundry is rotatably adjusted such that an edge of the article 16 of laundry hanging from the rotatable support 42 is reoriented. For example, the edge may be shifted to be more horizontal. The rotation adjustment more likely results in a length of the article 16 on one side within a desired range.
In an alternative embodiment, two rotatable supports 42 face each other on opposite sides of the movable platform 44 . The two rotatable supports 42 create a v shape, but other relative orientations may be used. The clamp 40 may release the article 16 for rotation by both rotatable supports 42 . The wanted edge can be rolled evenly to within inches of the tops of each rotatable support 42 from either side, on clamps 48 side or the opposite side of rotatable supports 42 . The clamps 48 can retrieve the wanted edge at the top location.
A plate 46 , brush, or other structure may rotate towards and away from the moveable plate 44 . The plate 46 helps remove any improperly placed articles of laundry 16 to clear the move able plate 44 and the rotatable support 42 for subsequent articles of laundry 16 . The plate 46 moves to the position shown in FIG. 5 while the article 16 of laundry is dragged over the rotatable support 42 . Once the article 16 of laundry is being removed from the move able plate 44 , the plate 46 rotates one end away from the moveable plate 44 .
The moveable platform 44 is a plate, prongs, bars, and/or other structures. In one embodiment, the moveable platform includes two slots for clamping, such as providing three plates or two prongs and a center plate. The slot or slots extend into a portion of the plate 44 or along an entire length of the plate 44 (e.g., forming two or more separate plates separated by the slot(s)). The slots allow the clamps 48 move through, adjacent to, or into the slots to clamp the edge of the article 16 of laundry laying across the slots. The moveable plate 44 is metal, wood, plastic, fiberglass or other material. The movable plate 44 is sized to hold the edge spaced away from a center of the article 16 . The moveable plate 44 is square, rectangular, oblong, circular or other shape.
Pneumatic, chain, gear, air or other drive mechanisms may be provided to move the moveable plate 44 . For example, a hydraulic or electric actuator acts as a release. The actuator allows gravity to move the moveable plate 44 downwards. Alternatively, the actuator powers or drives the moveable plate 44 downwards. The actuator 44 is also operable to move the plate back to the substantially horizontal position.
The movable platform 44 is positioned adjacent the rotatable support 42 , such as extending generally along the axis of rotation of the rotatable support 42 or the direction of dragging. The move able platform 44 is between the rotatable support 42 and the clamp 40 . As the clamp 40 drags the article of laundry 42 over the rotatable support 42 , the article 16 of laundry is on or suspended over the moveable platform 44 .
The moveable plate 44 begins in a downward position, such as the vertical position shown in solid lines of FIGS. 2 and 5 . In response to the edge detection by the sensor 45 , the moveable plate 44 is rotated against the article 16 of laundry. After the edge is adjusted by the rotatable support 42 and before clamping by a clamp 48 , the edge is lifted. Part of the article 16 is lifted to a substantially horizontal position as shown in dashed lines in FIG. 5 . The movable plate 44 raises an edge of the article 16 of laundry hanging from one side of the rotatable support 42 .
A minor or major portion of the article 16 of laundry rests on the moveable plate 44 , including part of an edge. The edge is generally parallel with the axis of rotation of the moveable plate, but may be at a substantial angle. By lifting part of the article 16 of laundry from a vertical position hanging down from the rotatable support 42 and the clamp 40 to a horizontal position, the moveable plate 44 positions the article 16 of laundry for clamping by the clamps 48 .
Referring to FIGS. 5 and 6 , the clamps 48 are two clamps operating together and connected together. In one embodiment, the clamps 48 are metal cylinders extending from separate drives against plates. The clamps 48 are spaced apart by a same distance as slots in the moveable plate 44 , such as 4-20 inches. The clamps 48 are sized and spaced to clamp different locations on the edge of the article 16 of laundry. The clamps 48 may or may not spread apart to tension the article 16 between the clamps 48 after clamping. While two clamps 48 are shown, 1, 3, or other numbers of clamps may be used.
Both clamps 48 move laterally from the moveable plate 44 over a roller 50 and are shown in two locations in FIG. 6 . One or multiple groups of clamps 48 may be used. The clamps 48 are positioned against the article 16 of laundry as the article 16 of laundry rests on the moveable plate 44 . The clamps 48 are movable in a horizontal position towards and away from the article 16 of laundry and the moveable plate 44 . An electric eye or other detector may be used for determining when the clamps 48 are positioned against the article 16 of laundry. For example, the clamps 48 move towards the back of the moveable plate 44 until the article 16 of laundry is detected by sensors at both clamps 48 . Alternatively, the clamps 48 are positioned at a given location under the assumption that the article 16 of laundry is positioned at that location. The clamps 48 grab an edge of the article 16 of laundry. The edge is clamped in a middle portion of a long side, but may be clamped in other portions of the edge.
After the clamps 48 grab the edge of the article 16 of laundry, the clamps 48 are moved laterally to drag the article 16 of laundry over the roller 50 . The rotatable support 42 may rotate in the direction of movement to assist in dragging the article 16 off the rotatable support 42 . During the dragging, a smoothing beam 56 rests by gravity or is driven against the top of the article 16 of laundry. The smoothing beam 56 presses the article 16 of laundry against the roller 50 . In one embodiment, the smoothing beam 56 is plastic or fiber, but may be other materials. The smoothing beam 56 rotates to allow passing of the clamps 48 and positioning of the smoothing beam 56 on top of the article 16 of laundry while being dragged. The smoothing beam 56 is positioned to contact adjacent the end of the roller 50 closest to the moveable plate 44 .
The roller 50 is sufficiently long to be longer than the longest short edge of the type of articles of laundry to be processed, but a shorter roller may be used. The roller 50 is not driven or braked, but may be a clutch roller or driven roller in alternative embodiments. The ends of the roller 50 are supported by beams or other structure. The beams or structure include bearings, pins, or other devices allowing the roller to be rotated against and away from the conveyor 52 . In an alternative embodiment, the roller 50 is a conveyor, such as the transfer apparatus 67 described in U.S. Pat. No. 5,515,627, the disclosure of which is incorporated herein by reference. The clamps 48 deposit an edge into the transfer apparatus. The conveyor 52 is not provided.
A drive 53 connects with the beams supporting the roller 50 . The drive 53 is operable to position the roller 50 against and spaced away from the conveyor 52 . For depositing the article 16 of laundry from the clamps 48 , the roller 50 is spaced away from the conveyor 52 . The clamps 48 hold the article 16 of laundry on each side, but above, the roller 50 . A sensor detects a leading or trailing edge of the article 16 of laundry and/or a position of the clamps 48 to cause release of the article 16 of laundry by the clamps 48 onto the roller 50 .
Once deposited, the drive 53 positions the roller 50 adjacent the conveyor 52 . The roller 50 and one end of the conveyor 52 are at a same height, but may be at different heights, such as the conveyor 52 being slightly lower than the roller 50 when positioned against each other. The roller 50 and the conveyor 52 have a same or similar lateral extent, but one may be wider than the other.
The conveyor 52 includes one or more belts or straps tensioned over two or more rollers or pulleys. The conveyor 52 includes a platform beneath the straps in between the rollers in one embodiment, but embodiments may be provided without a platform. The conveyor 52 is driven by a gear, belt or chain connected from a motor to one or both of the rollers or pulleys. One of the rollers of the conveyor 52 is at the end for supporting the belts against the article 16 of laundry while being pressed by the roller 50 . The drive 53 uses sufficient force to allow transfer of rotation force from the conveyor 52 to the roller 50 .
The conveyor 52 rotates the upper run towards the roller 50 and article 16 of laundry. Since the article 16 of laundry contacts the conveyor 52 , the article 16 of laundry feeds downward through the nip formed by the roller 50 and the conveyor 52 .
A sensor 55 is positioned to detect an edge of the article 16 of laundry at or in the nip. The sensor 55 detects the edge. In response, the conveyor 52 reverses direction, preventing the article 16 of laundry from being discarded. Air jets 54 and/or force from conveying cause the detected edge to lay on the conveyor 52 as the article 16 of laundry is conveyed upward. For example, one or more air jet 54 blow the edge onto the conveyor 52 . The conveyor 52 continues conveying to provide the entire article 16 of laundry in a laid out and spread position for further processing.
The controller controls the drive 53 to position the roller 50 against the conveyor 52 with the article 16 of laundry in the nip between the roller 50 and the conveyor 52 . The controller controls the conveyor 52 based on the input from the sensor 55 to convey the article 16 of laundry such that the edge is adjacent the nip formed by the roller 50 and the conveyor 52 and to convey the article 16 of laundry away from the roller 50 on the conveyor 52 .
While the invention has been disclosed above by reference to various embodiments, it should be understood that many changes and modifications can be made without departing from the scope of the invention. For example, any number of additional stages may be provided. Different clamp, conveyor, sensor, actuator or drive structures may be used, including now known or later developed structures. As another example, clamps may release, components may rotate or move in opposite directions, or other actions may occur to remove a caught or misaligned article 16 of laundry. Blowers and/or sensors may be used to assist in control and/or transfer of the article between components.
It is therefore intended that the foregoing detailed description be understood as an illustration of the presently preferred embodiment of the invention, and not as a definition of the invention. It is only the following claims, including all equivalents that are intended to define the scope of this invention. | An article is selected and spread from a load of articles. A first clamp moves along a run to remove an article. By changing orientation of the run, articles may be removed from different locations. A second clamp rotates while holding the article. The rotation generally flattens out the article. A third clamp grabs a portion of the article and further spreads the article. This process may detangle or untwist the article. The untwisted article is dragged over a belt. The belt adjusts the amount of overhang on each side. A plate lifts a resulting edge. The article is clamped at that edge and dragged over a roller. The roller moves into contact with a conveyor. The conveyor conveys the article to find a leading edge. The article is then conveyed in a spread position. | 3 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of application Ser. No. 09/266,613, filed Mar. 9, 1999, and now U.S. Pat. No. 6,045,130, which is a continuation of application Ser. No. 08/967,850, filed Nov. 12, 1997, and now U.S. Pat. No. 5,913,726, which is a continuation of application Ser. No. 08/811,364, filed Mar. 6, 1997, and now U.S. Pat. No. 5,795,225, which is a continuation of application Ser. No. 08/337,661, filed Nov. 9, 1994, and now U.S. Pat. No. 5,626,341, which is a division of application Ser. No. 08/040,925, filed Mar. 31, 1993, and now U.S. Pat. No. 5,364,104, which is a division of application Ser. No. 07/800,631 filed Nov. 27, 1991 now U.S. Pat. No. 5,288,077; which is a continuation-in-part of application Ser. No. 07/361,276, filed Jun. 5, 1989 and now U.S. Pat. No. 5,078,405; which is a division of application Ser. No. 07/214,934, filed Jul. 5, 1988 and now U.S. Pat. No. 4,861,041; which is a continuation-in-part of application Ser. No. 07/182,374, filed Apr. 18, 1988 and now U.S. Pat. No. 4,836,553. The entire disclosures of each of the above-listed applications and patents are hereby incorporated by reference herein. The entire disclosure of copending application Ser. No. 07/814,712 filed Dec. 30, 1991 is also hereby incorporated by reference herein.
BACKGROUND OF THE INVENTION
The present invention generally relates to casino or cardroom gaming involving a progressive jackpot. More particularly, it relates to a progressive jackpot that is available to be played by participants in various casino or cardroom table games.
It has become common practice in gaming establishments to provide a progressive jackpot component in connection with electronic or mechanical gaming devices, such as slot machines, video poker machines or keno machines. Typically a plurality or “bank” of machines are electronically interconnected to a common progressive jackpot meter. As gaming tokens are fed into each machine, the amount shown on the jackpot meter progresses incrementally until some lucky player lines up the winning combination, such as three or four 7's on the same row of a slot machine. In video poker, a Royal Flush normally wins the jackpot, although in some variations, a player must achieve a Royal Flush in an exact order, such as A-K-Q-J-10 from left to right, or in a particular suit, such as Spades. In video keno, a player typically must match 15 out of 15 numbers to win the progressive jackpot.
It is an object of the present invention to provide a progressive jackpot component to typical casino or cardroom table games such as poker or Twenty-One.
It is a feature of the present invention to have each participant in the progressive jackpot component win all or part of the amount shown on the progressive jackpot meter if the participant achieves a particular predetermined playing hand.
It is an advantage of the present invention that when the progressive jackpot component is added to typical table games such as poker or Twenty-One that the players will enjoy these games more and that the amount of play will increase.
It is a further object of the present invention to provide apparatus useful in providing the progressive jackpot component to casino or cardroom table games such as poker or Twenty-One.
It is a further feature of the present invention to have a progressive jackpot meter electronically interconnected to one or more gaming tables to allow each player at his playing location to participate in the progressive jackpot component by wagering a gaming token which automatically activates an indicator showing the player's participation and also automatically increments the progressive jackpot meter.
It is an advantage of the present invention that the apparatus makes it easy for each player to participate in the progressive jackpot component of the game.
BRIEF SUMMARY OF THE INVENTION
The method of the present invention generally involves a typical casino or cardroom game modified to include a progressive jackpot component. During the play of a Twenty-One game, for example, in addition to his normal wager, a player will have the option of making an additional wager that becomes part of, and makes the player eligible to win, the progressive jackpot. If the player's Twenty-One hand comprises a particular, predetermined arrangement of cards, the player will win all, or part of, the amount showing on the progressive jackpot. This progressive jackpot feature is also adaptable to any other casino or cardroom game such as Draw Poker, Stud Poker, Lo-Ball Poker or Caribbean Stud™ Poker.
The apparatus used to practice the present invention comprises a gaming table, such as those used for Twenty-One or poker, modified with the addition of a coin acceptor that is electronically connected to a progressive jackpot meter. When a player drops a coin into the coin acceptor, a light is activated at the player's location indicating that he is participating in the progressive jackpot component of the game during that hand. At the same time, a signal from the coin acceptor is sent to the progressive meter to increment the amount shown on the progressive meter. At the conclusion of the play of each hand, the coin acceptor is reset for the next hand. When a player wins all or part of the progressive jackpot, the amount showing on the progressive jackpot meter is reduced by the amount won by the player. Any number of gaming tables can be connected to a single progressive jackpot meter.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the apparatus of the present invention using a casino gaming table with coin acceptors at each playing location electronically connected to a progressive jackpot meter.
FIG. 2 shows an alternate embodiment of the present invention using a cardroom gaming table with coin acceptors at each playing location electronically connected to a progressive jackpot meter.
FIG. 3 shows a block diagram of the operation of the present invention.
FIG. 4 shows a schematic diagram of the electronic circuitry of the present invention.
FIG. 5 shows a block diagram of a plurality of gaming tables connected to a single progressive jackpot meter.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As shown in FIG. 1, a casino gaming table 10 is provided having a plurality of playing locations 12 for players participating in the game being conducted, e.g., Twenty-One. A dealer is positioned at the dealer's location 14 adjacent a chip rack 16 . Adjacent to each player location 12 is a coin acceptor 20 . Each coin acceptor 20 is electronically connected to a main control board 40 to which is connected a number of odometer-type counters 42 corresponding to the number of playing locations 12 provided on the gaming table 10 . As shown in FIG. 1, seven playing locations 12 are preferably provided, although the number of playing locations can be more or less than seven. A reset switch 50 is located adjacent the dealer's location 14 and is electronically connected to the main control board 40 and provides a means whereby the dealer can reset the coin acceptors 20 prior to the beginning of the play of each hand. A lockout switch 55 , is also provided adjacent to the dealer's location 14 which is activated by the dealer to prevent later wagering as will be more fully explained herein.
A main control board 40 is electronically connected to a progressive jackpot control box 60 which receives the signals from each coin acceptor 20 and in response to those signals increments the progressive jackpot meter 70 , as will be more fully explained herein. Also electronically connected to the progressive control box 60 is the jackpot reset control 80 which provides means for resetting the amount shown on the progressive jackpot meter whenever a player wins all, or part of, the amount shown on the progressive jackpot meter 70 .
In operation, the present invention operates as follows. A conventional Twenty-One game is conducted on gaming table 10 . At the beginning of each hand, each player, in addition to making his usual wager for the play of the Twenty-One hand, may also make an additional wager to be eligible to participate in the progressive jackpot component of the game during that hand. To do so, a player places a gaming token into the coin acceptor 20 associated with that player's particular playing location 12 . As will be more fully explained herein, the coin acceptor 20 “recognizes” that a gaming token has been placed therein and an indicator signal 22 , preferably a light, adjacent to the coin acceptor 20 is activated showing that that particular player is participating in the progressive jackpot component of the game during the play of that hand.
Besides activating the indicator signal 22 , the coin acceptor 20 also sends an electronic signal to the main control board 40 . This signal is sent by the main control board 40 to the odometer-type counter 42 corresponding to the particular playing location 12 to keep a sequential count of the number of gaming tokens that are placed in the particular coin acceptor 20 .
The main control board 40 also activates the progressive jackpot control box 60 which in turn controls the progressive jackpot meter 70 . Each gaming token placed in a coin acceptor 20 results in the amount shown on the progressive jackpot meter being increased by a predetermined amount. If, for example, each gaming token has a value of one dollar, then the amount shown on the progressive jackpot meter would be increased by any amount up to one dollar for each gaming token placed into a coin acceptor 20 . In the preferred embodiment of the present invention, the progressive jackpot would be increased between 93% to 97% of the amount of each gaming token being wagered, the balance representing the house's share of the amount wagered for providing the progressive jackpot component of the game.
When each player has had a reasonable opportunity to make a progressive jackpot wager, the dealer activates lockout switch 55 which deactivates each coin acceptor 20 . Any tokens placed in a coin acceptor 20 after lockout switch 55 is activated will not register. This prevents late wagering after the cards are dealt.
The amount shown on the progressive jackpot meter will continue to increase for each gaming token wagered until a player achieves a winning hand. Preselected winning hands earn a player all or part of the amount shown on the progressive jackpot meter. In a preferred embodiment, the preselected wining hands and payoff amounts in Twenty-One game are as follows:
Winning Hand
Amount of Jackpot
Four 5's and an Ace
100%
Ace, two, three, four,
4%
five and six
Six, seven and eight
100 tokens
of same suit
Three 7's
50 tokens
The invention is not limited to these particular combinations of winning hands or payoffs; other winning hand combinations or payoff amounts can be utilized.
When a player achieves a winning hand, the jackpot reset control 80 is manually activated by pushing a button that corresponds to the type of hand that the player achieved. The amount won by the player is thus electronically deducted from the amount showing on the progressive jackpot meter.
When a particular hand is completed at gaming table 101 , the dealer presses the reset switch 50 , which deactivates the indicator signal 22 . Lockout switch 55 is also manually deactivated by the dealer. The coin acceptor 20 is thus readied to receive another gaming token for the next hand.
The progressive jackpot component of the present invention can also be used in connection with other types of casino games, e.g., Caribbean Stud™ Poker, which is the subject matter of U.S. patent application Ser. No. 182,374 filed Apr. 18, 1988, which is incorporated herein by reference thereto. Caribbean Stud™ Poker is a modification of conventional five-card stud poker. Each player makes an ante and a dealer deals five cards to each player and to himself. The player's cards are dealt face down and the dealer's cards are dealt four cards face down and one card face up. Each player views his hand and then decides whether to continue to play by making an additional bet or to fold or drop, in which case he loses his ante. The dealer then reveals his entire hand; if the dealer's hand does not have a poker value of at least Ace-King, then the dealer is not permitted to continue to play. In that case, the dealer pays even money on the remaining players' antes, and returns their bets to them. If the dealer's hand has a poker value of Ace-King or better, the dealer compares his hand to each player's hand, paying or collecting the bets as appropriate. The dealer also pays odds of more than even money on each winning player's hand of two pair or better according to a bonus payment schedule. This game can be played using the gaming table shown in FIG. 1 . Each player makes a progressive jackpot wager by placing a gaming token in the coin acceptor 20 which makes that player eligible to participate in the progressive jackpot amount shown on the meter 70 . The winning hands and amounts for Caribbean Stud Poker are preferably as follows:
Hand
Amount
Royal Flush
100%
Straight Flush
10%
Four of a Kind
1%
Full House
50 tokens
Flush
25 tokens
Again the invention is not limited to these particular combinations of hands or payoff amounts; other hand combinations or payoff amounts can be utilized.
The invention can also be adapted to other casino or cardroom poker games such as Stud Poker, Draw Poker or Lo-Ball Poker. The gaming table 100 used to play each of these games is modified as shown in FIG. 2 by the addition of coin acceptors 120 and indicator signals 122 at each player's location 112 . The electronics is the same as that shown in FIG. 1 and includes a main control board 140 , an odometer-type counter 142 , a progressive jackpot control box 160 , a progressive jackpot meter 170 and a jackpot reset control 100 . A reset switch 150 and a lockout switch 155 are located adjacent the dealer's location 114 next to the chip rack 116 .
The progressive jackpot meter 170 is incrementally increased in the same manner as that description in connection with FIG. 1 by each player placing a gaming token in the coin acceptor 120 .
The winning hands and payoff amounts are preselected as appropriate for the type of game being played. In the preferred embodiment, the winning hands and payoff amounts are as follows:
I. Five Card Draw Poker
Hand
Amount
Royal Flush
100%
Straight Flush
10%
Four of a Kind
100 tokens
Full House
25 tokens
II. Five Card Stud Poker
Hand
Amount
Royal Flush
100%
Straight Flush
10%
Four of a Kind
100 tokens
Full House
25 tokens
III. Seven Card Stud Poker
Hand
Amount
Royal Flush
100%
Straight Flush
10%
Four of a Kind
100 tokens
Full House
25 tokens
IV. Lo-Ball Poker
Hand
Amount
5-4-3-2-Ace
100%
6-4-3-2 Ace
5%
6-5-3-2-Ace
100 tokens
7-4-3-2-Ace
25 tokens
These winning hands and payoff amounts are merely preferred embodiments and the invention may be practiced using any appropriate combination of winning hands and payoff amounts.
As an alternative embodiment, progressive jackpot component of the game may be utilized as a consolation payoff for a player who otherwise loses during the play of the regular game. For example, assume the regular game being played is Five Card Stud. Players A and B are both eligible for the progressive jackpot amount because each has placed a gaming token in the coin acceptor prior to the beginning of the play of the hand. Player A holds a hand having Four of a Kind. Player B holds a Full House. Because Player A's hand is higher according to the customary poker hand ranking priority, Player A wins the pot wagered on the Five Card Stud game. As a consolation, however, Player B receives a payoff amount from the progressive jackpot for his Full House, e.g., 25 tokens. Player A does not receive a payoff from the progressive jackpot because he already has won the pot from the regular five Card Stud game. Thus, under this alternative embodiment, a player only receives a payoff from the progressive jackpot if the player both has a hand of the preselected type and loses to a higher hand in the game being played.
Another modification would have the two players sharing in the progressive jackpot amount; the player with the preselected type of hand receiving a percentage of the progressive jackpot amount and the player with the higher poker hand receiving the rest of the progressive jackpot amount. With reference to the example above, Player B would receive 80% of the progressive jackpot amount for a Full House and Player A would receive 20% of the progressive jackpot amount for a Full House.
FIG. 3 shows in block diagram form the operation of the present invention. Each playing location has a coin a acceptor 210 into which a player places a gaming token in order to be eligible for the progressive jackpot amount. When all players have had sufficient time to decide whether to participate in the progressive jackpot for that hand the dealer activates the lockout switch 220 which prevents late wagers. Each gaming token placed in a coin acceptor 210 energizes the progressive output control 230 which in turn activates three separate devices. An integrated circuit timer is energized which causes an indicator light 250 to be illuminated at the location on the coin acceptor in front of the player. This gives a visual indication to the dealer that that player is participating in the progressive jackpot during the play of that hand.
The signal from the progressive jackpot control 230 also activates an odometer-type counter 255 which increments by one unit for each gaming token wagered through the coin acceptor. This allows the gaming establishment to keep an accurate count of the number of wagers made on the progressive jackpot.
The third signal from the progressive jackpot control 230 goes directly to the progressive jackpot meter 270 . The progressive jackpot meter 270 shows the total amount available to be won by a player who obtains one of the preselected winning hands. The amount of the progressive jackpot meter 270 automatically increases a predetermined amount for each gaming token placed in a coin acceptor. The progressive jackpot meter 270 is programmed to increase a specified percentage of the amount wagered in the coin acceptor 210 . In the preferred embodiment, the progressive jackpot meter will be increased between about 93% to 97% of the amount wagered in the coin acceptor 210 .
The dealer then deals the cards to each player and the hand is played 280 . If a player has a preselected wining hand, the player is paid the amount corresponding to the type of winning hand that the player has. The jackpot reset control 290 is manually activated which results in the amount of the payoff being automatically deducted from the amount displayed on the progressive jackpot meter 270 .
After the winning players have been paid, the dealer activates the reset switch 295 which both turns off the integrated circuit timer 240 and turns off the indicator light 250 and the dealer deactivates the lockout switch 297 thereby activating the coin acceptor 210 for the next hand.
FIG. 4 in schematic form depicts the electronic circuitry to operate the apparatus of the present invention. The coin acceptor circuitry 300 is activated when a gaming token is dropped into the slot on the gaming table where the coin acceptor is mounted. The gaming token passes between an ultraviolet transmitter DS 1 and an optic receiver Q 1 (Model #MRD 300 transistor). This causes a pulse to be passed from the collector of Q 1 to the base of receiver Q 2 . Q 2 is a Model #2N3906 transistor and acts as an emitter follower and sends a pulse which is received by the integrated circuit 322 , 324 of the main control board 320 . The integrated circuit 322 , 324 is a Model #LM-556 Timer. The pulse from Q 2 is received at pin 325 of the lower portion 324 of the integrated circuit and this pulse causes pin 326 of the lower portion 324 to go high and turn on diode DS 2 (a Model P367 diode). This diode DS 2 is the indicator light 22 shown in FIG. 1 and this indicator light 22 stays on until the play of the hand is finished.
The pulse from Q 2 also is received by pin 323 on the upper portion 322 of the integrated circuit and this pulse creates a pulse at pin 327 of the upper portion 322 which causes transistor Q 3 (a Model #T1P120 transistor) to turn on, then off for the duration of the pulse created at pin 327 . The turning on and off of transistor Q 3 causes the odometer-type counter 42 shown in FIG. 1 to increment one digit. The odometer-type counter 330 is a six-digit non-resetable electronic 12 VDC, WICO Model #31-443400.
The pulse created at pin 327 of the upper portion 322 of the integrated circuit also goes to the opto isolator 340 (which is a Model #H11A16E Opto Isolator). The opto isolator 340 passes this pulse to the base of transistor Q 4 (a Model #2N3906 transistor) thereby turning on transistor Q 4 for the duration of the pulse. When transistor Q 4 is turned on, the pulse is passed to the progressive jackpot display meter 350 where the amount shown on the display meter 350 is increased by a predetermined percentage of the value of the gaming token placed in the coin acceptor 300 . The progressive jackpot display meter 350 can typically be a Game Technology Model having 3″ LED characters on a 44″ length single progressive display.
After all bets are made, the dealer manually presses a lockout switch 360 which will clamp the output of transistor Q 2 at a low level which ensures that there can be no late wagers made through the coin acceptor 300 . Once the output of transistor Q 2 is clamped at a low level, a gaming token placed in the coin acceptor 300 will not cause a pulse to flow through the rest of the circuitry.
The game is then played and once the game is completed, the dealer will manually press the reset switch 370 which creates a reset pulse that activates pin 320 which resets the lower portion 324 of the integrated circuit. This resetting causes pin 326 to go low which will extinguish diode DS 2 which turns off the indicator light 22 on the gaming table.
The dealer also manually presses the lockout switch 360 to open the circuit and remove the clamp on the emitter of transistor Q 2 which allows another hand to be played. The players commence the next hand by placing gaming tokens in the coin acceptor 300 and the process is repeated.
As will be apparent to those skilled in the art, various resistors and capacitors are provided to complete the circuitry. The specifications on the resistors and capacitors shown in FIG. 4 is as follows:
Resistors
Capacitors
R1-60 Ohm
C1-.1ufd/35v
R2-3 Kohm
R3-1 Kohm
C2-.01ufd/35v
R4-200 Ohm
R5-4.7 Kohm
C3-.1ufd/35v
R6-10 Kohm
R7-1 Mohm
C4-.1ufd/35v
R8-240 Ohm
R9-1 Kohm
R10-4.7 Kohm
R11-240 Ohm
R12-1 Kohm
As shown in FIG. 5, any number of gaming tables may be connected to a single progressive jackpot meter.
While the invention has been illustrated with respect to several specific embodiments thereof, these embodiments should be considered as illustrative rather than limiting. Various modifications and additions may be made and will be apparent to those skilled in the art. Accordingly, the invention should not be limited by the foregoing description, but rather should be defined only by the following claims. | A method for including a progressive jackpot component in a live casino table game. In addition to playing a live casino table game, each player makes an additional wager at the beginning of each hand that makes the player eligible to win all or part of a jackpot. If during the play of the hand a player is dealt a predetermined arrangement of cards, the player wins a preselected percentage of the jackpot amount. The jackpot is progressive in that unwon amounts of the jackpot carry over to the next hand. Apparatus is provided to receive each gaming token wagered for the jackpot component, to increment the jackpot meter whcih displays the jackpot amount, to decrement the jackpot meter whenever a winning hand is paid and to reset the apparatus for the next hand. | 6 |
This invention relates to a manually operated loom for the weaving of fabrics.
One object of the invention is to provide a loom of compact design and of relatively light weight, making it particularly suitable for use by the home craftsman and textile manufacturers involved in research and/or the production of fabrics of inovative texture and design.
A further object of the invention is to provide a loom for the conventional orthagonal two-thread weaving.
Still another object of the invention is to provide a loom for triweaving which is the intertwining of three threads producing a staple fabric having unusual bias strength and non-raveling characteristics.
A further object of the invention is to provide a loom for the combination of two and three thread weaving with or without discontinuous warp weaving to produce fabrics of various designs and characteristics.
A further object of the invention is to provide a loom requiring only hand motions for operation.
These and further objects of the invention will be apparent as the description proceeds in connection with the drawings in which:
IN THE DRAWINGS
FIG. 1 is a front elevation view of the loom in the weave tilt position as shown in side elevation views in FIGS. 3 and 4.
FIG. 2 is a top plan view of the loom in the warp transfer tilt position.
FIG. 3 is a side elevation view taken along the line 3--3 in the view shown in FIG. 1.
FIG. 4 is a side elevation view taken along the line 4--4 in FIG. 1.
FIG. 5 is a schematic illustration useful in explaining the construction and operation of the loom.
FIGS. 6A and 6B are top plan and side elevation views respectively of typical spacers used in arranging the warp arrays.
FIGS. 7-11 are schematic illustrations useful in explaining the operation of the main and control guides in forming a weave of desired configuration.
FIG. 12 is a fragmentary view illustrating an alternate means for carrying a weft thread back and forth between the warp threads when in a shed.
DETAILED DESCRIPTION
Referring to the drawings wherein like reference characters designate like or corresponding parts throughout the several views there is shown a base 2 having arms 4 in which are journaled the arms 4A of a rectangular frame 1 manually tiltable from a weave tilt position as shown in FIGS. 1, 3 and 4 to a warp transfer tilt position as shown in FIG. 2, identified as positions A and B respectively in FIG. 4. When in the weave tilt position the controls are exposed to an operator when facing the loom so that successive weaving operations may be performed. When in the warp transfer tilt position the warp arrays are in the line of vision of the operator facilitating circulation of the warp threads by indexing the warp arrays in one direction or the other and by transfer of a warp thread from one array to the other.
The entire operating mechanism of the loom, with the exception of a fabric roll 48, which is journaled in the arms 4, is supported by the frame 1. While the parts making up the mechanism are identified in FIGS. 1-4, reference should be made to FIG. 5 in the following the description, as this Fig. illustrates what may be termed a transverse schematic cross section of the loom mechanism, with some parts displaced from true position for clarity. In this Fig. conventional ground markings should be interpreted to mean the essential points of support of the mechanism in the frame 1.
Supported by the frame 1 are bearings 12 and 14 on which are slidably supported at one end a front cross member 16 and a rear cross member 18 which may be supported at their opposite ends by similar bearings mounted on the frame 1 or by other means such as rollers guided in suitable ways (not shown) in the frame 1.
The cross members 16 and 18 are simultaneously moved toward and away from each other to predetermine limits by rotation of a knob 20 operably connected to the cross members through a linkage shown diagrammatically in FIG. 5. Journaled in the frame 1 is a crank arm 22, secured to the knob 20. Pivotly connected to the crank arm 22 and a connecting rod 24 is a link 26. The connecting rod 24 is secured to the cross member 16 through an extension 16A and through a reversing link 28 to the extension 18A of cross member 18. Thus the cross members 16 and 18 will simultaneously be moved in opposite directions, that is to say, toward and away from each other, to preset limits by rotation of the knob 20 in one direction or the other. The cross members 16 and 18 are shown in mid position. Rotation of the knob 20 in a clockwise direction will cause cross members 16 and 18 to move away from each other to a limit set by a stop 29A, which, for reasons apparent as the description proceeds, is defined as the open shed position. Rotation of the knob 20 in a counterclockwise direction will cause members 16 and 18 to move toward each other to a limit set by a stop 29B and which is defined as the closed shed position.
Journaled in the front cross member 16 at both ends is a front warp translate screw 5A and a similar rear warp translate screw 5B journaled in the rear cross member 18 provided with knobs 6A and 6B (FIG. 2) respectively for rotating these screws in clockwise and counter clockwise directions. Carried by the screws 5A and 5B are one or more removable spacers 7, each having a pin 8 engaging a thread of a translate screw and a flat face engaging a way formed in one or the other of cross members 16, 18. Thus as a translate screw is rotated in one direction the spacer, or spacers, mounted thereon are moved to the left and when rotated in the opposite direction are moved to the right. When knobs 6A and 6B are rotated in opposite directions the spacers mounted on one translate screw will be axially positioned in opposite direction to the spacer, or spacers, mounted on the other translate screw.
Referring to FIG. 6A, each spacer 7 has a plurality of slots for supporting and locating the warp units to maintain a desired separation of and to assist in guiding the warp threads. As shown in FIG. 5, each warp unit 10 comprises a warp thread supply reel 11 rotatably mounted on a support plate 13 which is proveded with a thread tension control unit 34 and a finger 36 having a guide eye 38. The warp units are universal to allow their use as an upper or lower threading type, which when alternately utilized permit greater reel space to remove possible interference with adjacent warp units.
By way of example, and not as a limitation, each spacer 7 may be one inch long and provided with slots 9 for receiving seven warp units, thus a pair of opposed spacers will provide a total of fourteen warp threads per inch. The number of front and rear spacers and hence the number of warp threads employed in any particular case will be determined by the width of fabric to be woven. The pitch of the thread on the translate screws 5A and 5B may be such that a given number of revolutions of the knobs 6A or 6B, for example, two, indexes a warp unit one warp thread spacing. As will be evident as the description proceeds the axial indexing of the warp units provides a means for generating three thread weaving of the oscillating-warp type, or of the circulating warp type, wherein, in an open shed, the warp threads forming the front array are indexed in one direction and those forming the rear array are indexed in the opposite direction and circulation maintained by transferring the overhanging warp unit on the front array to the rear array and the overhanging warp unit on the rear array to the front array, and further, as required, transfering a spacer from the front to the rear translate screw and vice versa. Such circulation of the warp threads in conjunction with the transverse weft threads will produce a woven fabric similar to that shown in U.S. Pat. No. 1,368,215.
Journaled in the arms 4A of the frame 1 is a main guide 40, angularly positionable between limits by means of a hand operator 42 which is provided with semi-circular serrations or teeth 44 having a pitch equal to the spacing between adjacent warp units and subtending an angle less than one hundred eighty degrees to form a sharp lower lip for catching and positioning a weft thread at the appropriate point in each cycle of operation.
As shown in FIG. 5 the warp threads from each opposed pair of warp units 10, after passing through guide eyes 38 are carried through the same tooth on the main guide 40 to a temple roll 46, removably journaled in the arms 4A and thence on to the fabric roll 48. To maintain the desired tension on the warp threads during loom setup or the weaving operation, the fabric roll 48 may be rotated through a worm feed generally indicated at 50 comprising a gear 52 and a disengageable helical screw 54 rotatable by means of a knob 56, or by a direct feed knob 58 when the helical screw 54 is disengaged from the gear 52.
Weft threads may be inserted when the warp units, and consequently the warp threads, are in the open or closed shed position by means of a rapier 60 journaled in the frame 1 and propelled through the shed by means of a chain drive 62 operated by a knob 64. A weft thread supply spool 66 is carried on brackets 68 and the weft thread therefrom is guided along the rapier through a weft thread position guide 70, mounted on the rapier 60, and thence back adjacent to the rapier. In operation, assuming the warp threads form an open or closed shed, the rapier carries a weft thread from the right side of the loom as viewed in FIGS. 1 and 2 to the left side and thence back to the right side, forming looped weft ends at the right and left sides of the fabric as it is formed by the intertwining of the warp and weft threads upon the positioning of the warp threads to alternate sheds between insertion of the weft threads.
After a weft thread has been laid between the warp threads and the rapier 60 withdrawn from the loom, the weave is completed by means of an auxiliary control guide 72 pivotly connected to arms 74 loosely journaled coaxially with the main control guide 40. Conveniently, the left hand arm 74 is provided with an extension carrying a knob 75 for angular positioning of the arm and consequently of the auxiliary control guide 72. The control guide 72 is provided with semi-circular serrations or teeth 73 having the same pitch as the serrations on the main guide 40 and is spring urged to a transverse neutral position wherein the serrations or teeth are at one half tooth spacing relative to the teeth or serrations on the main guide 40. By means of suitable stops, the serrations or teeth on the control guide 72 are brought into alignment with those on the main guide 40 by transverse operation of the knob 75, the control guide serrations or teeth being restored to the neutral position upon release of the knob 75. The serrations or teeth on the control guide 72 also subtend an angle less than one hundred eighty degrees to form a sharp lower lip to position a weft thread over the periphery of the serrations in main guide 40 at the appropriate point in each cycle of operation. As shown, the control guide 72 is provided with a follower pin 78 riding upon a stationary cam 80 and hence follows a predetermined trajectory as the knob 75 is angularly positioned.
Having described the mechanical elements making up the essential mechanism of a loom incorporating the principle features of the invention, the functions of the main guide 40 and control guide 72 in generating a fabric will now be described.
FIG. 7 illustrates the weave control at rest with a weft thread 83 inserted at distance d 1 relative to the axis X--X and the opposed warp arrays as exemplified by a thread 82 carried by a finger 84 of a warp unit (not shown) and a warp thread 86 carried by a finger 88 of a warp unit (not shown) in open shed.
In FIG. 8 the shed is shown closed, the positions of threads 82 and 86 being exchanged to trap the weft thread 83 in the foldover of the warp threads.
In FIG. 9 the angle Alpha has been increased by clockwise positioning of control guide knob 75 and the angle Beta has been decreased by counterclockwise positioning of hand operator 42 of the main guide 40. The follower pin 78 has been positioned beyond the cam 80 and the control guide 72 rests upon the surface of the main guide 40. The control guide 72 thus assumes control of the transverse spacing of the warp threads; but the weft thread 83 remains essentially on the Z axis, trapped under the teeth of the control guide 72 above the main guide 40.
In FIG. 10 the angle Alpha has been increased due to further rotation of the control guide knob 75 in a clockwise direction and the angle Beta has decreased due to further rotation of the hand operator 42 in a counterclockwise direction. Weft thread 83 has been carried below main guide 40 but still remains essentially on the Z axis and control guide 72 continues to ride on main guide 40.
In FIG. 11 the angle Alpha has decreased due to counterclockwise rotation of control guide knob 75, whereas the angle Beta has remained unchanged. Weft thread 83, due to the tension of warp threads 82, 86 shifts to the left and is trapped under the main guide 40. Setting of the weft thread to form fabric is done by restoring the relationship of main guide 40 and control guide 72 as shown in FIG. 7. With the warp threads 82, 86 remaining in the closed shed position a weft thread may be passed through the shed and the operations illustrated in FIGS. 7-11 repeated. By repetitive operations with the shed alternately open and closed formation of the fabric proceeds.
As evident, by transverse movement of the guide 72 in one direction or the other an intertwining of the warp threads with the weft threads may be accomplished. Such intertwining in conjunction with circulation of the warp threads as heretofor described can be used to produce fabrics of a wide variety of weaves.
As evident from the foregoing description, during each weave cycle the rapier 60 is moved from its retracted position, shown as at the right side in FIGS. 1 and 2 to the opposite side and thence back to the retracted position. Two weft threads are therefor laid during each cycle. In FIG. 12 an alternate arrangement is shown whereby the loom can produce, for example, conventional orthagonal two-thread weaving. Shown is a shuttle, generally indicated at 30, comprising a bracket 31 which may be either detachably fastened to a rapier 60a by means of a hole 35 adapted to receive a pin 32, or to a bracket 71 mounted on the left side of the rectangular frams 1, by means of a hole 76 adapted to receive a pin 77. Rotatably mounted on the bracket 31 is a bobbin 33, carrying a supply of weft thread, replacing the weft supply spool 66 shown in FIG. 4. Secured to the lower end of bracket 31 is a thread position guide 70A.
In operation, assuming the rapier 60A to be in the retracted position and the shuttle 30 clipped thereto, with the warp threads in open shed, the rapier is extended to the left side of the loom, laying a weft thread along the vertex of the shed. Upon the rapier reaching the left side of the loom, the shuttle 30 is removed from the rapier 60A and clipped to the bracket 71. The rapier 60A is then withdrawn to the right side. The shed is then reversed and the weave operation completed by the cooperative movements of main guide 40 and control guide 72. The rapier 60A is then moved from the right side to the left side of the loom, the shuttle 30 transferred from the bracket to the rapier which is then returned to the right side, laying a weft thread as it traverses the shed. The shed is then reversed and the weave operation completed.
The bracket 31 may be provided with one or more guide eyes, such as shown at 81, through which the weft thread is threaded before leaving a weft guide eye 85, and a handle 79 for transfering the shuttle. | A manually operated loom for the weaving of two and/or three thread fabrics of various designs wherein the warp threads are individually detachably mounted and guided in opposed, axially movable arrays on parallel axes for circulation of the warp threads in clockwise or counterclockwise directions, each pair of opposed warp threads being held substantially parallel with adjacent pairs to the vertexes formed by serrations in an angularly positionable main guide running parallel to the axes of the arrays, means for reciprocating the arrays toward and away from each other to interchange the positions of the warp threads in each pair of opposed warp threads to form closed and open sheds respectively, means for passing a weft thread through a shed and an axially movable, angularly positionable control guide running parallel with the main guide for positioning a weft thread over the main guide to complete the weave and for shifting the warp threads of an array to adjacent serrations in the formation of three thread fabrics. | 3 |
[0001] This application claims priority under 35 USC 119(e) from provisional application No. 60/606,118 filed on Sep. 1, 2004, which is herein incorporated in its entirety by reference.
FIELD OF THE INVENTION
[0002] The present invention is directed to a cooking apparatus, and in particular, to an apparatus having a container and specially configured lids to allow for the use of a venting film during microwave cooking.
BACKGROUND ART
[0003] In the prior art, venting films and bags for microwave cooking are disclosed in U.S. Published Patent Application Nos. 2004/0069157, 2004/0103989, 2005/0003150, and 2005/0040161 to Lin, each of which are herein incorporated in its entirety by reference. For example, the film in 2004/0103989 is designed so that when a pressure differential exists, the film becomes air and vapor permeable. It is also very common to cook food in plastic containers such as Tupperware or disposable Gladware, and their use for leftovers and reheats is prevalent in peoples' lives.
[0004] One problem with disposable or other plastic containers during microwave cooking is that in order to avoid “splattering” inside the microwave oven, one must keep the lid on. This does not work well as pressure can build up in the container and the lid can blow off. The practicality of lifting the lid at one corner to relieve pressure does not assist in evenly heating the food product.
[0005] While vented films and bags provide a number of advantages over containers when microwave cooking, often times, it is not always practical to use the bags or film. In certain instances, containers are the preferred choice of cooking, particularly if the container is also used as part of the food preparation for cooking or for storage.
[0006] Accordingly, there is a need for improvements in the field of microwave cooking, particularly the utilization of the aforementioned venting material. The present invention responds to this need with an improved cooking apparatus that is particularly adapted for microwave cooking using venting films.
SUMMARY OF THE INVENTION
[0007] It is a first object of the present invention to provide an improved cooking apparatus.
[0008] Another object of the present invention is a method of microwave cooking using the inventive cooking apparatus.
[0009] Other objects and advantages of the present invention will become apparent as a description thereof proceeds.
[0010] In satisfaction of the foregoing objects and advantages, the present invention, in one mode, comprises a cooking apparatus having a container with an open top and a first lid adapted to attach to the container, the first lid having a first opening therein. A second lid is provided that is adapted to attach to the first lid, the second lid having a second opening therein, the first and/or second lid adapted to retain a venting film over the first opening. The first lid can attach to the container in any number of ways, including attaching to a periphery of the container. Similarly, the second lid can attach to the first lid in any fashion, one way being attachment to a periphery of the first opening in the first lid. The peripheral attachment of the first lid to the container, and the second lid to the first lid can employ lips on their respective peripheries.
[0011] The venting film can be any type that will allow for a release of pressure during cooking, but is preferably the type disclosed in the Lin publications mentioned above.
[0012] The invention also entails a method of preparing for microwave cooking comprising the steps of filling an open top container with food to be micro-waved and covering a portion of the open top of the container with a lid so as to leave a remaining opening. The remaining opening is covered with a venting film, with the venting film being retained over the remaining opening while still exposing at least a portion of the venting film to atmosphere so that pressure build up in the container can be released through the venting film. The covering step of the first container further comprises attaching a lid with an opening therein to the container.
[0013] The step of retaining the venting film can be achieved by attaching a second lid to the first lid, the second lid having an opening that exposes the venting film to atmosphere for pressure build up relief.
[0014] In yet another aspect of the invention, a cooking apparatus is provided that comprises a container having an open top and a first lid adapted to attach to the first container, the first lid having an opening therein. The apparatus also includes a venting film covering the first opening, the venting film functioning to vent the container as a result of an increase in pressure within the container. The venting film can be either integral with the first lid or removably attached thereto.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is a cross sectional view of a first embodiment of the invention;
[0016] FIG. 2 is a perspective view of one of the lids of the FIG. 1 embodiment;
[0017] FIG. 3 is a perspective view of the other lid of the FIG. 1 embodiment;
[0018] FIG. 4 is a partial cross sectional view of the apparatus showing a second embodiment of the invention;
[0019] FIG. 5 is a partial cross sectional view of the apparatus showing an alternative lid embodiment of the invention; and
[0020] FIG. 6 is a partial cross sectional view of the apparatus showing an additional lid configuration.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] The present invention offers significant improvements in microwave cooking using containers. The inventive cooking apparatus uses its lids to act as a support frame for the venting film, thus transforming a container with no venting capability into one with a breathable or pressure venting lid that allows pressure to build inside the container and then release as the venting film opens its pores to accommodate the pressure condition. The pores then close down as pressure normalizes. The venting film will continue in this breathing cycle until the food is cooked. The unique design of the inventive cooking apparatus employing the venting film or membrane has significant merit as it transforms a plastic container into a flexible pressure cooker.
[0022] Referring now to FIGS. 1-3 , one embodiment of the invention, in cross section, is designated by the reference numeral 10 , and is seen to include an open top container 1 , and first lid 3 , and a second lid 5 . The first lid attaches to the container 1 by engagement between the container lip 7 and first lid lip 9 .
[0023] The first lid 3 has an opening 11 , a periphery surrounding the opening 11 having a lip 13 . The second lid 5 has a lip 15 complementary to lip 13 so that the second lid 5 can be attached to the first lid 3 . Although the connection is not shown in FIG. 1 between the lids 3 and 5 , it would function similar to the connection between lips 7 and 9 . It should be understood that the mode of attachment between the container 1 and first lid 3 and between the first and second lids 3 and 5 can be any type known in the art that would provide a sealing engagement so that the venting film can function to provide pressure relief. The use of engaging lips as shown in FIG. 1 is but one example of such a sealing engagement. Clamps or other fasteners could be employed as well.
[0024] A venting film 17 , such as disclosed in the Lin publications, is arranged between the first lid 3 and second lid 5 , with the edges of the films designed to be sandwiched or held in place by the connection made between lips 13 and 15 . Of course, other means could be used to secure the film 17 to the lid 3 and/or 5 , just as long as the venting film 17 is secured in a way to seal the interior of the container 1 .
[0025] The second lid 5 has an opening 19 , which generally aligns with the opening 11 in the first lid, although the two openings can be offset from each other as well. The lid 5 in the embodiment of FIG. 2 assists in retaining the venting film 17 in a sealing position, while at the same time allowing the film 17 to function in its intended way during cooking.
[0026] In one exemplary use, food intended to be cooked is placed in the container. A piece of the venting film 17 is secured between the first and second lids 3 and 5 . This can be done before or after the first lid 3 is attached to the container 1 . The first lid 3 , with or without the second lid 5 , is attached to the container 1 . If the second lid 5 and venting film 17 were previously attached to the first lid 3 , the cooking apparatus 10 can be placed in the microwave for the intended time period. If the second lid 5 has not been attached, it is then attached to the first lid 3 , and the cooking apparatus is placed in the microwave oven for cooking. As noted above, the pores of the venting film open during cooking, allowing the interior of the container 1 to breathe or release pressure during the cooking cycle. Put another way, the method involves covering a portion of the open top of the container so as to leave an opening, and then covering a remaining opening with the venting film. The venting film is secured while leaving a portion exposed to atmosphere so that it can function in its intended way during cooking. Any type of cooking can be performed using the inventive apparatus, including pressure cooking, steaming, reheating, etc.
[0027] The cooking apparatus can also be used in food preparation by attaching the first lid and using the opening 11 to add to the container, or access the contents in the container for stirring or the like.
[0028] The container and lids can be made of any material that is appropriate for microwave cooking. Moreover, while the venting film disclosed in the Lin publications is a preferred venting film for use with the inventive cooking apparatus, other types of venting films suitable for microwave cooking that function in a similar manner could be employed.
[0029] The container and lids could have any configuration. As shown in FIG. 1 , the first lid 3 is configured to attach to a round container, but the opening 11 is oval in shape, thus defining the shape of the second lid 5 . While the opening in the first lid 3 is shown in general alignment with a center of the container, the opening 11 can be offset from the container center if so desired. Likewise, the opening in the second lid 5 could align generally with the opening in the first lid 3 , or it could be smaller in size if so desired, and also be offset from a center of the container.
[0030] While the venting film is used in combination with first and second lids, the venting film could be attached to the first lid alone, so that the second lid would not be needed. In this embodiment, the venting film could be removably attached over the opening in the first lid by any known means, e.g., held in place against a lip by an elastic band or the like. This embodiment is shown in FIG. 4 , wherein the venting film 17 is held on the lip 13 of the lid 3 by an elastic band 21 .
[0031] The venting film could also be made as an integral part of the lid, so that it would not be removable. This embodiment is shown in FIG. 5 , wherein a lid 3 ′ is shown with the venting film 17 made a part of thereof. The manner of integration of the film and lid 3 ′ can be any kind, e.g., an adhesive, molding or the like.
[0032] In another embodiment, the cooking apparatus can be used to seal the container for storage purposes or the like. Referring to FIG. 6 , a third lid 19 ′ can be provided that does not have an opening in it. The third lid is configured to attach to the first lid 3 to seal the interior of the container. In another alternative, the third lid could be made similar in shape to the first lid, but without the opening, whereby this third lid could attach directly to the container for sealing purposes. In yet another alternative, a non-venting film or other non-permeable material, e.g., a clear wrap like Saran wrap, could be employed between the first and second lids for sealing purposes.
[0033] As such, an invention has been disclosed in terms of preferred embodiments thereof, which fulfills each and every one of the objects of the present invention as set forth above and provides a new and improved cooking apparatus and method of use.
[0034] Of course, various changes, modifications and alterations from the teachings of the present invention may be contemplated by those skilled in the art without departing from the intended spirit and scope thereof. It is intended that the present invention only be limited by the terms of the appended claims. | A cooking apparatus combines an open top container, a lid adapted to attach to the container and an opening in the lid for placement of a venting film over the opening. The venting film and lid maintain the seal of the container, with the venting film allowing for pressure relief. The venting film can be retained over the opening using a second lid or other attachment device, or be part of the first lid. The apparatus can include additional lids to seal the container, or seal the opening in the first lid. | 1 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention is related to wire managers for managing the position of one or multiple electrical wires, and more specifically to a multi-branch current sensor array with optional voltage sensing.
[0003] 2. Description of Related Art
[0004] A need to measure power consumption in AC line powered systems is increasing due to a focus on energy efficiency for both commercial and residential locations. In order to measure power consumption of a circuit, the current drawn by the load must generally be measured, and for precise results, the characteristics of the load may also need to be known.
[0005] Adding current sensors to a power distribution system occupies space and adds complexity. If a large number of circuits must be measured, the installation difficulties are increased and the installation of the current sensor may cause disarray in the power distribution system.
[0006] It is also necessary to provide a safe environment for electrical workers and other personnel in the vicinity of the installations where power is being measured, because installation may be required in an electrical panel that is operational. Installation of current sensors in a live panel requires the use of insulating gloves that make it difficult to perform fine work with the fingers.
[0007] Therefore, it would be desirable to provide a current-sensing device that can provide isolated current draw information and optionally permit load characteristics to be taken into account, while providing safe and efficient installation with little additional space requirements within the power distribution system. It would further be desirable to provide such a device that is easy to operate while an installer is wearing insulating gloves.
BRIEF SUMMARY OF THE INVENTION
[0008] The invention is embodied in a current sensor for sensing currents passing through wires of multiple branch circuits and a method of operation.
[0009] The sensor has a first frame member and a second frame member in which are integrated corresponding portions of ferrite cylinders of the current sensors that, when the frame members are fastened together in a closed position, encircle the corresponding wire(s) of the branch circuit(s) associated with the individual sensors. The frame members may be separate, or may provide a sliding assembly that has an open and closed position for inserting and then retaining the wires, respectively. Measurement and communications electronics may be included in the first and/or second frame member to provide an efficient wireless or wired interconnect to other systems. Branch voltage sensing may be optionally integrated in the sensors, as well.
[0010] The foregoing and other objectives, features, and advantages of the invention will be apparent from the following, more particular, description of the preferred embodiment of the invention, as illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0011] The novel features believed characteristic of the invention are set forth in the appended claims. The invention itself, however, as well as a preferred mode of use, further objectives, and advantages thereof, will best be understood by reference to the following detailed description of the invention when read in conjunction with the accompanying Figures, wherein like reference numerals indicate like components, and:
[0012] FIG. 1A is an isometric view, and FIG. 1B is an exploded isometric view, of a multi-branch current-sensing device in accordance with an embodiment of the present invention.
[0013] FIGS. 2A-2B are illustrations showing details of current-sensing elements that can be used in the multi-branch current sensor of FIGS. 1A-1B .
[0014] FIG. 3A is an isometric view, and FIG. 3B is an exploded isometric view, of a multi-branch current-sensing device in accordance with another embodiment of the present invention.
[0015] FIGS. 4A-4B are illustrations showing details of current-sensing elements that can be used in the multi-branch current sensor of FIGS. 3A-3B .
[0016] FIG. 5 is a pictorial diagram showing current-sensing devices according to embodiments of the present invention installed in an electrical power distribution system.
[0017] FIG. 6 is a pictorial diagram showing wire managers 10 according to the present invention installed in an electrical power distribution system.
[0018] FIG. 7A is a top view of base portion 10 E and FIG. 7B is a side view of cover portion 10 D of wire managers 10 of FIG. 6 .
[0019] FIG. 8 is an electrical block diagram illustrating circuits that can be interfaced to, and optionally incorporated within, the multi-branch current sensors of FIGS. 1A-1B and FIGS. 3A-3B , according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0020] The present invention encompasses current sensors for multiple branch circuits, which optionally include voltage sensors and other features for providing input to power measurement systems. For example, the present invention can provide input to power monitoring equipment in computer server rooms, in which multiple branch circuits distribute power to various electronic chassis power supplies, and in which it is beneficial to provide power usage information for the various branch circuits to power monitoring and/or system control utilities within a computer operating environment. Other applications include power monitoring for commercial and/or residential energy management.
[0021] Referring now to FIG. 1A and FIG. 1B , a current-sensing device in accordance with an embodiment of the invention is shown. FIG. 1B shows an exploded view with details of current sensors formed by ferrite cylinder portions 14 A and 14 B integrated in respective frame members 10 A and 10 B. As illustrated in FIG. 1A , when frame members 10 A and 10 B are snapped together, they form a current-sensing and voltage-sensing device for measuring the current passing through, and the electrical potentials on, a plurality of wires that generally correspond to multiple branch circuits of a power distribution panel. For the purposes of measuring branch circuit current and voltage within a power distribution panel, the spacing of the current sensors formed by ferrite cylinder portions 14 A and 14 B is generally one inch, which is a standard circuit breaker terminal spacing. Alternatively, other spacings may be provided, such as one-half inch spacing for split breaker applications and two-inch spacing for high current/high voltage applications in which the breaker spacing is larger. Further, the above dimensions correspond to standardized U.S. breaker panels, and spacings may be adapted to accommodate standardized breaker spacings for the countries in which a particular design of the device is intended for use. Frame members 10 A, 10 B are generally non-conductive plastic materials, but may be made from alternative materials, depending on requirements.
[0022] The voltage-sensing elements mentioned above are provided by metal foils or metal layers 18 A and 18 B adhered to or deposited within the central cylindrical voids formed by ferrite cylinder portions 14 A and 14 B when frame members 10 A and 10 B are snapped together in the closed position as illustrated in FIG. 1A . The illustrated current-sensing devices are provided by semiconductor current sensors 17 disposed within a gap formed between ferrite cylinder portions 14 A and 14 B when frame members 10 A and 10 B are snapped together in the closed position. The high-permeability magnetic flux path around one of the branch circuit wires (not shown) inserted through the central void through a corresponding pair of ferrite cylinder portions 14 A and 14 B is interrupted by the gap and concentrates the field at the corresponding one of current sensors 17 for measurement. A retaining pin 13 or other clip feature on frame member 10 A mates with a mating recess 19 or other suitable feature on frame member 10 B, in order to secure frame members 10 A and 10 B together after installation. An integrated circuit assembly 20 receives electrical connections 15 from current sensors 17 and voltage-sensing elements 18 A and/or 18 B, and can provide a wireless interface to an external power monitoring system. Power for operating integrated circuit assembly 20 can be obtained from a battery integrated within integrated circuit assembly 20 . Alternatively, power can be obtained from a current-sensing winding that provides an alternative type of current sensor as described in further detail below, and which draws power from a branch circuit to which the current-sensing device is coupled.
[0023] Referring to FIG. 2A , an alternative form of current sensor is shown that can provide for a lower-profile form of frame member 10 B in FIGS. 1A-1B . In particular, when frame member 10 B is affixed to a power panel and thus acts as a base of the current-sensing device, having a thin structure facilitates the insertion of frame member 10 B behind existing branch circuit wires. To provide a thin structure, the ferrite cylinder halves providing ferrite cylinder portions 14 A, 14 B in FIGS. 1A-1B can be replaced by a flat ferrite piece 14 C integrated in base frame member 10 B and a U-shaped structure provided by ferrite cylinder portions 14 D. Current sensor 17 is embedded in frame member 10 A and wires 15 are also generally embedded in frame member 10 A and routed to integrated circuit assembly 20 . While FIG. 2A illustrates a current sensor formed from three ferrite portions, a current sensor can be formed by placing sensor 17 at one end of the U-shaped ferrite portion 14 D in a manner similar to that illustrated in FIG. 1B . Alternatively, U-shaped ferrite portion 14 D can be replaced by a half-cylinder with a sensor disposed at an end, such as ferrite cylinder portion 14 A illustrated in FIG. 1B .
[0024] Referring to FIG. 2B , another alternative form of current sensor is shown that can provide a lower-cost device and optionally provide power for operating integrated circuit assembly 20 . The current sensor of FIG. 2B uses a winding 16 disposed around ferrite cylinder portion 14 F rather than using a gap and semiconductor current sensor as illustrated above. The ends of winding 16 can be routed within frame member 10 A to integrated circuit assembly 20 . Another ferrite cylinder portion 14 E provides the remainder of the magnetic flux loop, which only requires such gaps as are made by the separate ferrite cylinder portions 14 E and 14 F, since a gap is not required for a semiconductor current sensor.
[0025] Referring to FIG. 3A and FIG. 3B , an alternative form of current-sensing device is shown that can provide for facile and temporary installation from the face of a power distribution panel without requiring insertion of a frame member behind the branch circuit wires. The current-sensing device of FIG. 3A and FIG. 3B is similar to the current-sensing device of FIGS. 1A-1B , so only differences between the current-sensing devices will be described below. The current-sensing device of FIG. 3A and FIG. 3B forms a unitary assembly with frame member 30 A inserted within frame member 30 B to provide a sliding action that, in an open position, provides gaps between the extensions of frame member 30 A and 30 B in which ferrite cylinder portions 14 C, 14 D and 14 E and current sensors 17 are integrated. A spring or other suitable restoring force element can be included within frame member 30 A to push the extensions of frame member 30 B against the extensions of frame member 30 A to bring ferrite cylinder portions 14 C, 14 D and 14 E into contact in the closed position around multiple branch circuit wires. In the open position, which can be maintained by using a finger or tool to move frame member 30 B with respect to frame member 30 A, or which alternatively may be maintained using a locking detent or other locking mechanism (not shown) between frame members 30 A and 30 B. The extensions of frame members 30 A and 30 B are separated to permit insertion of the current-sensing device over the multiple branch circuit wires. Voltage-sensing elements in the form of metal foils or layers 18 C and 18 D are also integrated within frame members 30 A and 30 B.
[0026] Referring now to FIG. 4A , an alternative current-sensing device similar to the current sensor of FIG. 2B is shown. Winding 16 is disposed around the extension of frame member 30 A and around ferrite cylinder portion 14 G, the connections of winding 16 are integrated within Frame member 30 A and routed to integrated circuit assembly 20 . FIG. 4B shows details of the current-sensing device including current sensor 17 as illustrated in FIGS. 3A-3B and as described above with reference to FIGS. 3A-3B .
[0027] Referring now to FIG. 5 , a power distribution system in accordance with an embodiment of the present invention is shown. A power distribution panel 8 receives service entrance wiring 5 and distributes power to branch circuit wires 3 via circuit breakers 9 . Branch circuit wires 3 are routed to supply power to loads via conduits or other raceways 7 . For the purposes of illustration, within power distribution panel 8 , current-sensing devices housed by frame members 10 A, 10 B as illustrated in FIGS. 1A and 1B are installed on the left side branch circuits, and current-sensing devices housed by frame members 30 A, 30 B as illustrated in FIGS. 3A and 3B are installed on the right side branch circuits.
[0028] Referring now to FIG. 6 , a wire manager in accordance with an embodiment of the present invention is shown installed in a power distribution system. A power distribution panel 8 receives service entrance wiring 5 and distributes power to branch circuit wires 3 via circuit breakers 9 . Branch circuit wires 3 are routed to supply power to loads via conduits or other raceways 7 . Within power distribution panel 8 , wire managers 10 , in accordance with an embodiment of the invention, are installed. Wire managers 10 include a cover portion 10 D and a base portion 10 E. Wire managers 10 control the position of branch circuit wires 3 and further include sensing elements 40 that are used to determine the current flowing through branch circuit wires 3 and optionally the magnitude and/or phase of the voltage on branch circuit wires 3 to provide for computation of the actual (complex) power delivered to the branch circuit loads. Sensing elements 40 have a split-core construction similar or identical to the sensors incorporated within the sensing device illustrated in FIG. 1A-1B , with the portion including current-sensing element 17 embedded within base portion 10 E and the other split cores that complete the magnetic paths with the bottom portion of sensors 40 integrated at a corresponding position on the bottom side of cover portion 10 D. Wire managers 10 also include an interface/processing unit 12 that provides a wired or wireless interface to an external processing system and generally provides for computation of power usage-related information prior to transmission to the external processing system, although raw current (and optionally voltage) sensor output information could alternatively be transmitted, with computation of power usage-related information performed in the external processing system. Interface/processing unit 12 may alternatively be placed in locations and be dimensioned other than as shown. For example, interface/processing unit 12 may be physically separate from wire manager 10 and be coupled to wire manager 10 by a wired, wireless, optical or other suitable interface.
[0029] Referring now to FIG. 7A , details of base portion 10 E of wire manager 10 of FIG. 6 are shown, in accordance with an embodiment of the invention. Base portion 10 E includes the ferrite cylinder portion 14 A, current-sensing element 17 and optional voltage-sensing element 18 A identical to those elements in FIGS. 1A-1B . Connections to current-sensing elements 17 are not shown for clarity, but are generally embedded within base portion 10 E and extend to measurement circuits within interface/processing unit 12 of FIG. 6 . Referring now to FIG. 7B , details of cover portion 10 D of wire manager 10 of FIG. 6 are shown, in accordance with an embodiment of the invention. Cover portion 10 D includes ferrite cylinder portion 14 B which completes the magnetic pathway around ferrite cylinder portion 14 A when cover portion 10 D is installed over base portion 10 E. Similarly, cover portion 10 D may include voltage-sensing element 18 B integrated within ferrite cylinder portion 14 B.
[0030] Referring now to FIG. 8 , details of integrated circuit assembly 20 as illustrated in FIG. 1B and FIG. 3B , and which are generally included in interface/processing unit 12 of FIG. 6 , is shown. A multiplexer 101 A receives signals from the individual current sensors 17 (or windings 16 ) and selects a sensor for measurement, providing input to a current measurement circuit 108 A, which is an analog circuit that appropriately scales and filters the current sensor output. The output of current measurement circuit 108 A is provided as an input to an analog-to-digital converter (ADC) 106 , which converts the current output waveform generated by current measurement circuit 108 A to sampled values provided to a central processing unit (CPU) 100 that performs power calculations in accordance with program instruction stored in a memory 104 coupled to CPU 100 . Alternatively, a separate current measurement circuit 108 A and multiplexer 101 A may not be necessary, and sensors 17 or windings 16 may be coupled directly to ADC 106 . The power usage by the branch circuit associated with a particular sensor can be determined by assuming that the branch circuit voltage is constant (e.g., 115 Vrms) and that the phase relationship between the voltage and current is aligned (i.e., in-phase). However, while the assumption of constant voltage is generally sufficient, as properly designed distribution systems do not let the line voltage sag more than a small amount, e.g., <3%, the phase relationship between voltage and current is dependent on the power factor of the load, and can vary widely and dynamically by load and over time. Therefore, it is generally desirable to at least know the phase relationship between the branch circuit voltage and current in order to accurately determine power usage by the branch circuit.
[0031] When voltage measurement is implemented, another multiplexer 101 B is provided to receive signals from the individual voltage-sensing elements, e.g., one of voltage-sensing elements 18 A, 18 B or 18 C, 18 D in the above-described current-sensing devices, if voltage-sensing is also implemented. Multiplexer 101 B receives signals from the individual voltage-sensing elements within the devices and selects a sensor for measurement, providing input to a voltage measurement circuit 108 B, which is an analog circuit that appropriately scales and filters the signal received from voltage-sensing elements 18 A, 18 B or 18 C, 18 D. A zero-crossing detector 109 may be used to provide phase-only information to a central processing unit 100 that performs power calculations, alternatively or in combination with providing an output of voltage measurement circuit to an input of ADC 106 . Alternatively, multiplexor 101 B may not be necessary and one or more voltage sensor outputs of sensors 17 (or windings 16 ) may be connected directly to ADC 106 . In particular, it may not be necessary to make voltage measurements at each of sensors 17 , for example, when sensing the phase of the voltage, a single measurement may suffice for providing a phase reference that is then used to determine the voltage-to-current phase difference for multiple branch circuits. Further, if multiple voltage measurements are taken, the voltage measurements may be used as an absolute voltage measurement, or the amplitude may be scaled to a known peak, r.m.s. or average value. An input/output (I/O) interface 102 provides either a wireless or wired connection to an external monitoring system 120 , such as a wireless local area network (WLAN) connection 122 A or wired Ethernet connection 122 B. When power factor is not taken into account, the instantaneous power used by each branch circuit can be approximated as:
[0000]
P
BRANCH
=V
rms
*I
meas
[0000] where V rms is a constant value, e.g. 115V and I meas is a measured rms current value. Power value P BRANCH may be integrated over time to yield the energy use. When the phase of the voltage is known, then the power may be computed more accurately as:
[0000] P BRANCH =V rms *I meas *cos(Φ)
[0000] where Φ is a difference in phase angle between the voltage and current waveforms. The output of zero-crossing detector 109 may be compared with the position of the zero crossings in the current waveform generated by current measurement circuit 108 A and the time ΔT between the zero crossings in the current and voltage used to generate phase difference Φ from the line frequency (assuming the line frequency is 60 Hz):
[0000] Φ=2Π*60 *ΔT
[0000] In general, the current waveform is not truly sinusoidal and the above approximation may not yield sufficiently accurate results. A more accurate method is to multiply current and voltage samples measured at a sampling rate much higher than the line frequency. The sampled values thus approximate instantaneous values of the current and voltage waveforms and the energy may be computed as:
[0000] Σ(V n *I n )
[0000] A variety of arithmetic methods may be used to determine power, energy and phase relationships from the sampled current and voltage measurements.
[0032] 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 the foregoing and other changes in form, and details may be made therein without departing from the spirit and scope of the invention. | A sensor array including multiple current sensors provides input for power measurement and management systems. The sensor array includes split ferrite cylinder portions connected by a frame, so that when the array is installed around multiple branch circuits in a power distribution panel or raceway, the ferrite cylinders are completed to surround the conductor(s) of the associated branch circuit. Voltage sensing may also be incorporated within the sensors by providing an electrically conductive plate, wire or other element that capacitively couples to the corresponding wire(s). | 6 |
BACKGROUND OF THE INVENTION
This invention relates to a method of drawing yarns in a draw zone which is equipped with a tempering device for influencing the temperature of the yarn, and an apparatus for drawing a yarn advancing through a draw zone with a tempering device for influencing the yarn temperature.
Such a method or such an apparatus are known, for example, from DE-OS 38 08 854, as well as from DE-PS 33 46 677, and DE-AS 22 04 535. In the known draw systems, the yarn is drawn by pulling it off the spinneret at very high withdrawal speeds and/or by the speed difference of two interposed draw rolls, and in each case it is heated in the draw zone. This invention is, however, not limited to such methods, but is suitable for all draw systems, which are equipped with tempering devices for influencing the yarn temperature.
In the art, there exists a factor of uncertainty in keeping the process parameters and the produced yarn properties constant in time, namely, in that the heat transfer between the yarn and the tempering device for influencing the yarn temperature, for example, a heated draw roll, heated tube, or cooling device (see, for example German Utility Model 9306510) does not remain constant, but changes in the course of time. Such unintended changes in the heat transfer cannot be detected, since in a continuous operation it is not possible to accurately measure the yarn temperature from the viewpoint of the measuring technology, whereas the temperature of the device for influencing the yarn temperature (hereafter described as tempering device or temperature modulating device) is controllable, though, but fails to be indicative of the actual heat exchange. Such variations in the exchange of heat, may originate, for example, from contaminations or wear or other operational, but unforeseen changes.
It is the object of this invention to describe a method and an apparatus, which allow the detect and eliminate unforeseen variations in the heat exchange between the tempering device and the yarn or their consequences.
SUMMARY OF THE INVENTION
The above and other objects and advantages of the present invention are achieved by the provision of a method and apparatus for processing an advancing yarn which includes the steps of advancing the yarn along a path of travel, applying a drawing force to the advancing yarn in a draw zone located along the path of travel and so as to draw the advancing yarn, and monitoring the tension of the advancing yarn at a location along the path of travel downstream of the draw zone and producing a control signal which is representative of the monitored tension. Further, the temperature of the advancing yarn is modulated so that the temperature of the yarn is controlled as a function of the control signal.
In accordance with the invention, the method of drawing yarns in a draw zone equipped with a tempering device for influencing the temperature of the yarn is characterized in that the yarn temperature influencing effect of the tempering device on the yarn is controlled as a function of a control signal, which is derived from the yarn tensile force (yarn tension) that is continuously measured at a measuring point within or downstream of the draw zone, the measuring point being selected such that the yarn speed remains substantially constant between the heating system and the measuring point. The formation of a difference between the actual value of the yarn tension and an predeterminable desired value is a further development, which has the advantage that from the viewpoint of process engineering an optimal input of the yarn tension is initially possible, and that only the variations from this input are detected and converted for adjusting the temperature of the tempering device, i.e., the heating or the cooling system.
The invention relates likewise to an apparatus for drawing a yarn advancing through a draw zone, which is provided with a tempering device for influencing the yarn temperature, and especially suitable for carrying out the method of the present invention. This apparatus comprises, in the draw zone or downstream thereof, a device for measuring continuously or at intervals the yarn tension, and an electronic evaluation unit for converting found variations of the tension into correcting signals, which is connected via a signal line with the device for measuring the yarn tension and, furthermore, with a temperature control of the tempering device.
The tempering device may be a heating device, with the device for measuring the yarn tension being connected via the signal line and the electronic evaluation unit with the device for controlling the temperature of the heating device. The preparation of measuring signals and the generation of correcting signals as a function of the variation of a measured actual value from a predetermined desired value may naturally be integrated already in the device for measuring the yarn tension with the further processing occurring then in the electronic evaluation unit.
In a draw system having a heated draw roll or godet and arrangements for influencing or controlling the godet temperature, the device for measuring the yarn tension is located, for example, downstream of the draw roll forming the end of the draw zone. It transmits the measured actual values or correcting values derived therefrom, via a signal line and an electronic evaluation unit for influencing the godet temperature, to a device for the control thereof.
For purposes of influencing, as a function of the yarn tension, the signals supplied by a central control unit for the godet heating, the actual value signals or signals derived therefrom may be supplied, for example, to one of the correcting value generators which follow the central control unit. In so doing, it has shown to be favorable for stabilizing the yarn tension, when the heated draw roll is preceded by a predraw godet. Advantageously, also the predraw godet is heated. In particular, with the use of an--unheated or heated--predraw godet, it is possible to arrange the device for measuring the yarn tension also between the two godets.
The method of the present invention may be employed in all draw systems, in which the temperature of the yarn advancing through the draw zone is influenced, aside from the aforesaid heated godet, by a heating device, such as, for example, a heating tube of any design, a hot plate, a heating chamber, or also by a cooling device.
Thus, in a special further development of the invention, the device for influencing the yarn temperature comprises, for example, a cooling tube as a cooling device with a controllable cooling effect, and with its wall being provided with air supply openings, which are associated with at least one adjustable throttle or shutter for controlling the air quantity and, thus, the cooling effect. The signals, which are in this embodiment supplied by the device for measuring the yarn tension arranged downstream of the cooling device, serve to adjust the throttle(s) or shutter(s).
The invention is based on the recognition, as has been verified by extensive tests, that the progression of the heat transfer influences the yarn tension very considerably, it being possible to measure the yarn tension upstream or downstream of the tempering device. When the yarn tension is measured upstream of the tempering device, it will be necessary that the measuring occur in the draw zone, in which also the tempering device is arranged. When the yarn tension is measured downstream of the tempering device, the measuring may again occur directly below the tempering device, but also with a godet interposed. It has shown that even in subsequent processing zones, for example, in the takeup zone, the adjusted level of the yarn tension will undergo a change, when the heat transfer varies (see, not yet published German Application P 43 00 633.7). However, it is necessary that the yarn speed be substantially constant from the end of the tempering device to the measuring point of the yarn tension, i.e., there must be a defined advance of the yarn between the tempering device and the measuring point, so that the yarn tension cannot be changed by additional influences.
In this instance, one may proceed in such a manner that the actual values of the yarn tension measured at the measuring point are compared with a predeterminable (possibly time-dependent) desired value, with correcting signals for controlling the godet temperature being determined from the variations of the actual values of the yarn tension from the desired value. Basis for a (time-dependent or constant) desired value to be predetermined may be, for example, empirical values, such as are obtained from an evaluation of recorded production data, or the mean value of such empirical values. When processing the registered variations of the tension from the desired value, it will be advantageous to consider a tolerance range, which may likewise be established based on empirical values.
The measuring signals originating from the variations in the yarn tension and converted into correcting signals allow to modify, in accordance with the invention, the temperature of the tempering device, which is predetermined by a central control unit, so that the yarn tension does not leave a tolerance range which has been predetermined for the chronological progression of the yarn tension.
BRIEF DESCRIPTION OF THE DRAWING
Referring now to embodiments of the apparatus of the present invention as illustrated in the drawing, the invention is described in more detail.
In the drawing:
FIG. 1 is a schematic view of a spin draw system with a draw zone between two godets and the device for measuring the yarn tension downstream of the second godet;
FIG. 1A is a diagram of the heating control system for the two godets shown in FIG. 1;
FIG. 2 is a schematic view of a spin draw system as in FIG. 1, however, with the device for measuring the yarn tension being arranged in the draw zone;
FIG. 3 is a schematic view of a spin draw system without godets and with a tubular heater and the device for measuring the yarn tension being arranged downstream of the tubular heater;
FIG. 4 shows a draw system with hot a plate;
FIG. 5 shows a spin draw system with a controlled cooling shaft and delivery godet as well as a device for measuring the yarn tension downstream of the godet; and
FIG. 6 is a schematic view of a spin draw system as in FIG. 2, however with a heated godet upstream of the draw zone.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Schematically illustrated in FIG. 1 is a draw system 1 represented only by a spin system 3, a draw zone 2 defined by two godets 4 and 5, and a takeup 6. Arranged between draw roll or godet 5 and takeup 6 forming the outlet end of draw zone 2 is a device 7 for measuring the yarn tension, for example, a yarn tension sensor 8 equipped with an inline yarn tension measuring head as described in the not yet published German Application P 43 00 633.7. This device 7, 8 for measuring the yarn tension is connected via a signal line 22 with an electronic evaluation unit 11, in which the yarn tension fluctuations measured by device 7 for detecting the yarn tension are compared with desired values and converted into correcting values, and supplied to the signals originating from a central control unit 10.
FIG. 1A is a schematic view of a godet heating system with a temperature control for the two godets 4 and 5. The uniform control signals which are generated in central control unit 10, for example, for all processing positions 1 of a machine, of which only one is shown, advance via a line 23 to the electronic evaluation unit 11 associated to each draw system, in which these signals receive the correction signals. The thus modified signals are input in the temperature, control units 20 and 21 associated to the two godets 4 and 5 with heaters 12 and 13.
The temperature values which are generated by temperature sensors 14, 15 arranged in godets 4, 5 are converted, for example digitized, into signals measuring converters 16A, 16B, and advance via measuring transformers 17A, 17B likewise to temperature control units 20, 21, which allow to define--based on both the signals originating from the correcting value generator and the actual value signals--the amount of the energy supply to the godet heating system, which is effected by two HF supplies 18, 19 associated to heaters 12, 13.
In this manner, the basic adjustment serving to predetermine a constant godet temperature is modified such that changes in the yarn temperatures leading to fluctuations in the yarn tension are corrected.
FIGS. 2 to 6 illustrate further embodiments of the draw system in accordance with the invention.
Thus, the subject matter of FIG. 2 is a draw system, which differs from that shown in FIG. 1 in that the device 7 for detecting the yarn tension is provided between the two godets 4 and 5, of which the second one can be heated, and that the yarn tension fluctuations are measured within draw zone 2.
FIG. 3 illustrates an embodiment of a spin draw system in accordance with the invention without godets. Between spin system 3 and takeup 6, the yarn passes through a tubular heater 24. The device 7, 8 for measuring the yarn tension is provided between tubular heater 24 and takeup 6. The signals generated by same from the fluctuations in the yarn tension advance via signal line 22, and the temperature signals generated by a temperature sensor 27 arranged in tubular heater 24 advance via a signal line 31 to electronic evaluation unit 11, where the desired values predetermined by central control unit 10 and, thus, energy supply 29 of the tubular heater are modified as a function of the actual value signals originating from the measuring of the yarn tension and the measuring of the temperature. If, as a further development, a godet is provided between the end of tubular heater 24 and takeup 6, it will be possible to arrange the device 7, 8 for detecting the yarn tension between tubular heater 24 and the godet (not shown), or between the latter and takeup 6.
As a tubular heater 24 such may be used which has a fixed length and controls the heating effect on the yarn by changing the temperature in the interior of tubular heater 24. It is also possible to use a tubular heater 24 with an inside temperature which is kept constant, and in which the change of the heating effect on the yarn necessary to correct the yarn tension fluctuations occurs as a result of changing the length of the heating tube. Accordingly, it is then possible to use the correcting signals, which originate from measuring the yarn tension, which advance via signal line 22 to electronic evaluation unit 11, and which are then further transmitted to change the length of the tubular heater as a function of the yarn tension.
A further embodiment of the draw system in accordance with the invention is shown in FIG. 4. The possibly partially oriented yarn is supplied over a deflection roll 28, and advances over a first godet 4 into draw zone 2, where is heated by being guided over a hot plate 25. It is then withdrawn by draw roll 5 and after passing through device 7, 8 for measuring the yarn tension, and after converting the measured tension variations into correcting signals, it reaches takeup 6. The signals generated by device 7, 8 advance via signal lines 22 to electronic evaluation unit 11, where they are used, together with the correcting signals originating from temperature monitor 27, for the correction of the desired value signals originating from central control unit 10 and, thus, for the energy supply via a schematically indicated connecting line 29.
Finally, shown in FIG. 5 is a schematic view of a spin draw system equipped in accordance with the invention, which differs from the foregoing embodiments in that the device for influencing the yarn temperature is a cooling device 26 (air flow) with a controllable cooling effect, which is arranged substantially subjacent spin system 3 and monitored by a temperature sensor 27. The device 7, 8 for measuring the yarn tension is arranged downstream of the cooling device and connected via a signal line 22 and an electronic evaluation unit 11 with the device for controlling the cooling effect of cooling device 26.
In the illustrated embodiment, the cooling device is a cooling tube 26 with air supply openings provided in its wall. Associated to the latter is at least one adjustable throttle or shutter. Accordingly, the signals originating from device 7, 8 for measuring the yarn tension are transmitted via a signal line 22, to a device not shown for adjusting possibly several throttles or shutters via a control line 30, the device being controlled via electronic evaluation unit 11.
It should further be noted that the bundle of filaments shown in the drawing of FIG. 5, must be cooled before being combined to a yarn to such an extent that the filaments do no longer stick to one another, i.e., a yarn guide causing them to combine is arranged preferably in or at the outlet end of cooling shaft 26.
Shown in FIG. 6 is yet another embodiment of a draw system 1 similar to that of FIG. 2. Here again, the device 7 for detecting the yarn tension is provided between the two godets 4 and 5, and the yarn tension fluctuations are measured within draw zone 2. In this embodiment the first godet 4 is heated.
The invention has been described with reference to draw and spin draw systems illustrated in the attached drawing. It is however not limited to the illustrated and described embodiments, but can be used with success in all draw systems equipped with a device for influencing the yarn temperature for purposes of improving the quality of drawn products. | A draw process is described, in which yarns in particular of thermoplastic plastics are drawn by influencing their temperature, so as to improve the yarn properties. The process can be employed in a spin process or in a subsequent improvement step. In accordance with the invention, the temperature of the temperature modulating device is controlled as a function of a yarn tension signal, which is obtained within or downstream of the draw zone. | 3 |
This application is a division of the applicant's co-pending application, Ser. No. 507,300 filed June 24, 1983 now U.S. Pat. No. 4,524,960 which is a continuation-in-part of Ser. No. 245,970, filed Mar. 20, 1981 now abandoned for Adjustable Mounting Means.
BRIEF SUMMARY OF THE INVENTION
This invention relates to workpiece locating and clamping apparatus, and, more particularly, to an improved adjustable jig incorporating combined magnetic and mechanical means for adjustably mounting the jig on a workpiece support whereby the jig may be utilized to locate and maintain the correct positional relationship between components of work during assembly and manufacture thereof on a workpiece support. While the jig embodying the present invention is particularly adapted for use in the manufacture of prefabricated wooden roof and floor truss configurations for residential and commercial structures, it will be understood that the present invention is applicable to other uses.
As is well known in the art, in the manufacture of prefabricated wooden roof and floor truss configurations, the wooden components of the truss configurations, such as the chords and webs, are initially clamped in the desired position between a clamp and an associated stop on a relatively large table or other workpiece support after which connector plates are embedded in the wooden components of the truss configuration at the joints of the truss components while the truss components are held on the support in the clamped condition whereby the components of the truss configuration are permanently joined together. Heretofore, the clamps and stops have usually been mounted on the workpiece support through the agency of bolts which pass through the clamps or stops and project through slots or holes in the support, the bolts being retained by female threaded members, such as conventional nuts. In such prior devices, when it is desired to change the set up to accomodate a different size or type of truss, in order to adjust the clamps or stops relative to the support, it has been necessary to loosen the bolts, move the clamps or stops to the desired new position, and then retighten the bolts when the clamps or stops are in the selected adjusted location. Moreover, after the bolts have been tightened, it has not been possible to make small or fine adjustments in the positions of the clamps or stops relative to the support without again loosening the bolts, making the small or fine adjustments, and then retightening the bolts again thereby increasing the time, labor and expense required to install and adjust the clamps, stops and the like on the workpiece support.
An object of the present invention is to overcome the aforementioned as well as other disadvantages in prior devices of the indicated character, such as prior clamps, stops and the like and the means for mounting the same on a workpiece support, and to provide an improved adjustable jig particularly adapted for use in locating and maintaining the correct positional relationship between components of work during the assembly and manufacture thereof.
Another object of the present invention is to provide an improved means for adjustably mounting clamps, stops and the like on a workpiece support.
Another object of the present invention is to provide an improved adjustable jig incorporating improved means for mounting the jig on a workpiece support which means is self retaining and which permits installation and adjustment of the jig with a minimum of time, labor and expense.
Another object of the present invention is to provide an improved adjustable jig incorporating combined magnetic and mechanical means for adjustably mounting the jig on a workpiece support.
Another object of the present invention is to provide an improved adjustable jig incorporating improved means for adjusting the positional relationship of the jig with respect to a workpiece support.
Still another object of the present invention is to provide an improved adjustable jig that is economical to manufacture and assemble, durable, efficient, and reliable in operation.
The above as well as other objects and advantages of the present invention will become apparent from the following description, the appended claims and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top plan view illustrating a plurality of adjustable jigs embodying the present invention, showing the same installed on a workpiece support adjacent a conventional roof truss configuration;
FIG. 2 is an enlarged top plan view of a portion of the structure illustrated in FIG. 1;
FIG. 3 is an enlarged top plan view of one of the embodiments of the present invention illustrated in FIG. 1;
FIG. 4 is a bottom plan view of the structure illustrated in FIG. 3;
FIG. 5 is a side elevational view, with portions in cross section, of the structure illustrated in FIG. 3;
FIG. 6 is a top plan view of another embodiment of the invention;
FIG. 7 is a side elevational view, with portions in cross section, of the structure illustrated in FIG. 6;
FIG. 8 is a top plan view of another embodiment of the invention;
FIG. 9 is a side elevational view, with portions in cross section, of the structure illustrated in FIG. 8;
FIG. 10 is a top plan view of another embodiment of the present invention, with portions broken away for clarity of illustration, and illustrating the clamp mechanism in the locked position;
FIG. 11 is a top plan view of a portion of the structure illustrated in FIG. 10, and illustrating the clamp mechanism in the released position;
FIG. 12 is a cross sectional view of the clamp mechanism illustrated in FIG. 10, taken on the line 12--12 thereof;
FIG. 13 is a side elevational view of a portion of the structure illustrated in FIG. 10;
FIG. 14 is a side elevational view of the handle end portion of the structure illustrated in FIG. 10;
FIG. 15 is a top plan view of still another embodiment of the present invention;
FIG. 16 is a side elevational view of a portion of the structure illustrated in FIG. 13, and showing, in dotted lines, the stop in a raised position;
FIG. 17 is an enlarged cross sectional view of the detent incorporated in the embodiment of the invention illustrated in FIG. 15; and
FIG. 18 is a side elevational view of the structure illustrated in FIG. 15, showing the same in an adjusting position.
DETAILED DESCRIPTION
Referring to the drawings, one embodiment of the invention is illustrated in FIGS. 1 through 5 thereof, and is comprised of an adjustable jig, generally designated 10, incorporating a clamp, generally designated 12, that may be adjustably mounted on a work- piece support, generally designated 14. The clamp 12, which will be described hereinafter in greater detail, is intended to depict a wide variety of conventional clamps which are commercially available and which include a body 16, and a movable clamp 18 carried by the body 16 and having an abutment surface 20 at the free end thereof. A clamp actuating member 22 is provided which is connected to the movable clamp 18 and which enables the movable clamp 18 and its associated abutment surface 20 to be advanced into engagement with a workpiece, generally designated 24, as will be described hereinafter in greater detail. A clamp release means 26 is also provided which is operatively connected to the clamp 18, the clamp release means enabling disengagement of the clamp 18 from the workpiece when the work is completed as will also be described hereinafter in greater detail. The clamp 12, including the body 16, is preferably formed of steel or other suitable material having sufficient strength to withstand the forces exerted thereon. The workpiece support 14 is formed of magnetic material, such as steel, which may be in the form of a plate, and includes a substantially flat surface 28 upon which the jig 10 is mounted as will be described hereinafter in greater detail. The workpiece support 14 also defines a plurality of spaced passageways, such as 30, 32 and 34. The longitudinal axes of the passageways extend in a direction substantially perpendicular to the plane of the surface 28 and the passageways may be spaced at any desired distance relative to each other. For example, the passageways may be disposed in rows and columns with the longitudinal axes of the passageways spaced approximately one inch apart.
The adjustable jig 10 also includes a plurality of permanent magnets, such as 36, 38, 40 and 42, which are mounted in open bottom recesses 44 and 46 defined by housings 48 and 50, respectively. The housings 48 and 50, in turn, are mounted on opposite sides of and fixed to the body 16 of the clamp as shown in FIGS. 3 and 4. The housings 48 and 50 are formed of non-magnetic material, such as aluminum, and the magnets 36, 38, 40 and 42 are preferably retained in the recesses 44 and 46 defined by the housings 48 and 50 through the agency of a suitable potting compound 52. The permanent magnets disposed in each of the housings 48 and 50 may have a combined holding power of several hundred pounds acting in a direction perpendicular to the surface 28 of the workpiece support 14 when the magnets are disposed in engagement with the surface 28 of the workpiece support. It will be understood however that the holding power of the magnets in a direction parallel to the plane of the surface 28 is much less than the holding power of the magnets in a direction perpendicular to the surface 28.
As shown in FIGS. 3, 4 and 5, in this embodiment of the invention, a generally U-shaped base 54 is provided which is fixed to the end portion 56 of the body 16 of the clamp remote from the abutment surface 20. The generally U-shaped base 54 includes a pair of elongate, laterally spaced leg portions 58 and 60 which extend in spaced substantially parallel relationship and which are joined at one end thereof by a transverse portion 62 which is fixed to the adjacent ends of the leg portions 58 and 60 by any suitable means. The opposite ends of the legs 58 and 60 are fixed to the end portion 56 of the body of the clamp by a bolt 66 which passes through the legs 58 and 60 and through the body 16 of the clamp, the bolt 66 being retained by a nut 68.
The base 54 defines an elongate channel 70 which is open at the top and bottom of the base while the ends of the channel 70 are closed at one end by the body 16 of the clamp and at the opposite end by the transverse member 62. An adjustable block 72, in the form of a parallelepiped, is provided which is mounted for longitudinal movement in the channel 70 defined by the base 54, the block 72 defining an internally threaded passageway 74 adapted to receive an elongate externally threaded screw 76 which extends longitudinally of the channel. One end portion of the screw 76 bears against the end portion 56 of the body of the clamp while the opposite end portion of the screw passes freely through a non-threaded opening 78 defined by the transverse portion 62 of the base, the screw being constrained against longitudinal movement by a knurled handle 80 which bears against the outer surface 82 of the transverse portion 62 of the base. With such a construction, rotation of the screw 76 through the agency of the handle 80 in one direction causes the block 72 to advance in the channel toward the body of the clamp while rotation of the screw in the opposite direction causes the block to retract in the channel toward the transverse portion 62 of the base.
A pin 84 is provided which is fixed to the block 72 and which projects outwardly therefrom as illustrated in FIG. 5. The pin 84 is preferably formed of steel or other suitable material having sufficient strength to withstand the forces exerted thereon and the pin is adapted to be received selectively in any of the passageways such as 30, 32 and 34 defined by the workpiece support 14.
With such a construction, the pin 84 may be inserted in any one of the passageways defined by the workpiece support 14 whereby the base 54 and the clamp 12 are located in the approximate desired position for use in clamping components of the workpiece. The handle 80 may then be manually rotated so as to advance or retract the block 72 and the pin 84 carried thereby whereby the abutment surface 20 may be located at the precise desired position. The above described construction also permits the entire jig 10 including the base 54 and the clamp 12 to be moved angularly about the longitudinal axis of the pin 84 to compensate for any irregularities that may be presented by the various components of the workpiece. The permanent magnets prevent the clamp 12, incorporated in the jig 10, from lifting off of the surface 28 of the workpiece support 14 while the pin 84 prevents longitudinal movement of the clamp in a plane parallel to the plane of the surface 28 of the workpiece support.
FIG. 1 illustrates the manner in which clamps 12 incorporated in jigs embodying the present invention may be utilized to clamp components, such as chords 86 and webs 88 of a wooden truss, generally designated 90, between the clamp and a stop 112 provided on the workpiece support 14. Stops 112 embodying the present invention will also be described hereinafter in greater detail, but it will be understood that other types of stops may be utilized if desired.
FIG. 2 illustrates the manner in which connector plates 94 are embedded in the wooden components of the truss configuration at the joints of the truss components while the truss components are held on the workpiece support in the clamped condition whereby the components of the truss configuration are permanently joined together.
If it is desired to manufacture a different type of truss utilizing components with different dimensions, the jig 10 may be easily moved to another position on the workpiece support by tilting the permanent magnets and simultaneously lifting the pin from the passageway in which the pin has previously been inserted in the workpiece support so that the magnets are released from the workpiece support. The entire jig including the base 54 and the clamp 12 may then be moved to a new location on the workpiece support after which the pin 84 is inserted in a passageway at the new desired location and the clamp adjusted to the exact desired position in the manner previously described.
Another embodiment of the invention is illustrated in FIGS. 1, 6 and 7, and is comprised of an adjustable jig, generally designated 110, incorporating a stop, generally designated 112, that may be adjustably mounted on the workpiece support 14. The stop 112 illustrated in the drawings is intended to depict a wide variety of conventional stops and includes a body 116 having an abutment surface 120 on one side thereof adapted to engage a workpiece, such as the workpiece 24. The stop 112 is preferably formed of steel or other suitable material having sufficient strength to withstand the forces exerted thereon.
The adjustable jig 110 includes the plurality of permanent magnets, such as 36, 38, 40 and 42, which are mounted in the open bottom recesses 44 and 46 defined by the housings 48 and 50, respectively. The housings 48 and 50, in this embodiment of the invention, are mounted on the rear side of the stop body 116 which is opposite the abutment surface 120 as shown in FIGS. 6 and 7. As previously mentioned, the housings 48 and 50 are formed of non- magnetic material, such as aluminum, and the magnets such as 36, 38, 40 and 42 are preferably retained in the recesses 44 and 46 defined by the housings 48 and 50 through the agency of a suitable potting compound 52. The permanent magnets disposed in each of the housings 48 and 50 may have a combined holding power of several hundred pounds acting in a direction perpendicular to the surface 28 of the workpiece support 14 when the magnets are disposed in engagement with the surface 28 of the workpiece support 14. It will be understood however that the holding power of the magnets in a direction parallel to the plane of the surface 28 is much less than the holding power of the magnets in a direction perpendicular to the surface 28.
As shown in FIGS. 6 and 7, in this embodiment of the invention, a base 154 is provided which is fixed to the rear side 156 of the stop body 116 opposite the abutment surface 120. In this embodiment of the invention, the base 154 includes a pair of elongate laterally spaced leg portions 158 and 160 which extend in spaced substantially parallel relationship and which are joined at one end thereof by a transverse portion 162 which is fixed to the adjacent ends of the leg portions 158 and 160 by any suitable means. The opposite end portions of the legs 158 and 160 are also fixed to a bearing block 165 by any suitable means.
The base 154 defines an elongate channel 170 which is open at the top and bottom of the base while the ends of the channel 170 are closed at one end by the bearing block 165 and at the opposite end by the transverse member 162. An adjustable block 172, in the form of a parallelepiped, is provided which is mounted for longitudinal movement in the channel 170 defined by the base 154, the block 172 defining an internally threaded passageway 174 adapted to receive an elongate externally threaded screw 176 which extends longitudinally of the channel 170. One end portion of the screw 16 bears against the bearing block 165 while the opposite end portion of the screw 176 passes freely through a non-threaded opening 178 defined by the transverse portion 162 of the base, the screw being constrained against longitudinal movement by a knurled handle 180 which bears against the outer surface 182 of the transverse portion 162 of the base. With such a construction, rotation of the screw 176 through the agency of the handle 180 in one direction causes the block 172 to advance in the channel toward the body of the stop while rotation of the screw in the opposite direction causes the block to retract in the channel toward the transverse portion 162 of the base.
A pin 184, similar to the pin 84 previously described, is provided which is fixed to the block 172 and which projects outwardly therefrom. The pin 184 is also preferably formed of steel or other suitable material having sufficient strength to withstand the forces exerted thereon and the pin is adapted to be received selectively in any of the passages, such as 30, 32 and 34, defined by the workpiece support 14. With such a construction, the pin 184 may be inserted in any one of the passageways defined by the workpiece support 14 whereby the base 154 and the stop 112 are located in the approximate desired position for use in holding components of the workpiece. The handle 180 may then be manually rotated so as to advance or retract the block 172 and the pin 184 carried thereby whereby the abutment surface 120 may be located at the precise desired position. The above described construction also permits the entire jig 110 including the base 154 and the stop 112 to be moved angularly about the longitudinal axis of the pin 184 to compensate for any irregularities that may be presented by the various components of the workpiece. The permanent magnets prevent the stop 112, incorporated in the jig 110, from lifting off of the surface 28 of the workpiece support while the pin 184 prevents longitudinal movement of the stop in a plane parallel to the plane of the surface 28 of the workpiece support 14.
FIG. 1 illustrates the manner in which stops 112 incorporated in jigs embodying the present invention may be utilized to hold components, such as the chord 86 and the web 88 of the wooden truss 90 between a clamp and an associated stop 112 provided on a workpiece support 14.
If it is desired to manufacture a different type of truss utilizing components with different dimensions, the entire jig including the stop 112 may be easily moved to another position on the workpiece support by tilting the permanent magnets and simultaneously lifting the pin 184 from the passageway in which the pin has previously been inserted in the workpiece support so that the magnets are released from the workpiece support. The entire jig including the base 154 and the stop 112 may then be moved to a new location on the workpiece support after which the pin 184 may be inserted in a passageway at the desired new location and the stop adjusted to the exact desired position in the manner previously described.
Another embodiment of the invention is illustrated in FIGS. 8 and 9, and is comprised of an adjustable jig, generally designated 210, incorporating the clamp 12, that may be adjustably mounted on the workpiece support 14. The clamp 12 includes the body 16, the movable clamp 18 carried by the body 16 and the abutment surface 20 disposed at the free end of the moveable clamp 18. The clamp 12 also includes the actuating member 22 which enables the clamp 18 and its associated abutment surface 20 to be advanced into engagement with a workpiece. The clamp also includes the clamp release means 26 which enables disengagement of the clamp 18 from the workpiece when the work is completed.
This embodiment of the invention also includes the plurality of permanent magnets, such as 36, 38, 40 and 42, which are mounted in the open bottom recesses 44 and 46 defined by the housings 48 and 50, respectively, in the manner previously described. The housings 48 and 50, in turn, are mounted on opposite sides of and fixed to the body 16 of the clamp as previously described.
As shown in FIGS. 8 and 9, in this embodiment of the invention, the bases, such as 54 and 154, are eliminated, and a pin 284 is provided which extends through the rear end portion of the body 16 of the clamp and outwardly therefrom whereby the pin may be received selectively in any of the passageways such as 30, 32 and 34 defined by the workpiece support 14. With such a construction, the pin 284 may be inserted in any one of the passageways defined by the workpiece support 14 whereby the jig 210 may be located in the desired position on the workpiece support for use in clamping components of the workpiece. It will be appreciated that since this embodiment of the invention does not include means for adjusting the position of the pin 284 relative to the abutment surface 20, closer spacing of the passageways, such as 30, 32 and 34 defined by the workpiece support 14, may be provided to enable precise positioning of the jig on the workpiece support.
If it is desired to manufacture a different type of roof truss utilizing components with different dimensions, the jig 210 may be easily moved to another position on the workpiece support by lifting the pin 284 from the passageway in which the pin has previously been inserted, and tilting the permanent magnets so that the magnets are released from the workpiece support. The entire jig may then be moved to a new location on the workpiece support after which the pin 284 may be inserted in a passageway at the new desired location. It will also be understood that a stop, as distinguished from a clamp, may be constructed in the same manner as this embodiment of the invention utilizing the permanent magnets and a fixed position pin, as distinguished from a movable position pin as described hereinabove.
Another embodiment of the invention is illustrated in FIGS. 10 through 14, and is comprised of an adjustable jig, generally designated 310, which incorporates a clamp 312, and which may be adjustably mounted on the workpiece support 14. The clamp 312 includes a box beam section body 316, and a moveable clamp 318 carried by the body 316 and having an abutment surface 320 at the free end thereof. A clamp actuating member 322 is provided which is connected to the moveable clamp 318 through the agency of an over-center locking and release mechanism, generally designated 325, whereby the clamp 318 and its associated abutment surface 320 may be manually advanced into clamping engagement with and released from a workpiece. As shown in FIGS. 10, 11 and 12, the clamp actuating member 322, which is constructed in the form of a lever, carries a journal 327 which is welded or otherwise fixed to the lever, the journal being mounted for pivotal movement on a pin 329 fixed to the bottom wall of the box beam sectioned body 316. The clamp actuating member 322 is also pivotally connected, by a pin 331, to one end portion of a bifurcated arm 333 while the opposite end portion of the arm 333 is pivotally connected to a rod 335 by a pin 337. The opposite end portion of the rod 335 extends into a box beam section support member 339 forming part of the clamp 312, the curved section 341 of the clamp, which defines the surface 320, being welded or otherwise fixed to the support member 339. The rod 335 is connected to the support member 339 through the agency of a pin 343 which is fixed to the rod 335 and which extends into a slot 345 defined by the top wall 347 of the support member 339 whereby limited movement of the rod 335 relative to the support member 339 is permitted. A coil spring 349 is provided one end portion of which bears against the inner end of the support member 339 while the opposite end portion of the spring bears against a split ring 351 which surrounds the inner end portion of the rod 335 and the adjacent portion of the arm 333. The split ring 351 is connected to both the rod 335 and the arm 333 by the pin 337. The spring 349 enables the jig to accommodate dimensional tolerances of dimensional lumber.
With the components of the clamp and over-center locking and release mechanism 325 disposed in the positions illustrated in FIG. 10, the forces exerted on the clamp are transmitted through the pins 343, 337 and 327, the axis of the pin 331 being over-center or to the right, as viewed in FIG. 10, of a line extending between the axes of the pins 337 and 327. A clamp release means 326 is also provided which enables disengagement of the clamp 318 from the workpiece when the work is completed. The clamp release means 326 is comprised of a generally L-shaped lever 353 having a flange portion 355 and a leg portion 357, the flange portion 355 being adapted to bear against the end 359 of the lever 322 and the side 361 of the arm 333. The leg portion 357 is pivotally connected, by a pin 363 to the flange portions 365 and 367 of a generally U-shaped bracket, generally designated 369, which is welded or otherwise fixed to the side wall 371 of the body 316. A manual actuating knob 373 is fixed to the outer end portion of the leg 357. With such a construction, pressing the knob 373 causes the L-shaped lever 353 to pivot about the axis of the pin 363 so that the flange portion 355 of the lever bears against the end 359 of the lever 322 and the side 361 of the arm 333 and pushes the pin 331 over-center and to the left, as viewed in FIGS. 10 and 11, so as to release the clamp from the workpiece. The structure, manner of operation and results obtained by the clamp actuating member 22 and the clamp release means 26, previously described, are the same as the structure, manner of operation and results obtained by the clamp actuating member 322 and the clamp release means 326, respectively.
The clamp 312 and the body 316 are preferably formed of steel or other suitable material having sufficient strength to withstand the forces exerted thereon. In this embodiment of the invention, the adjustable jig 310 also includes a plurality of permanent magnets, such as 336, 338, 340 and 342 which are mounted in housings 348 and 350, respectively. The housings 348 and 350, in turn, are mounted on opposite sides of and fixed to the body 316 through the agency of bolts such as 375 and 377 the shank portions of which extend through counterbored passageways 379 defined by the housings. The internal diameters of the counterbored passageways 379 are slightly larger in diameter than the outside diameters of the bolts so that limited movement of the housings and the magnets carried thereby is permitted relative to the body 316. For example the internal diameters of the passageways may be 1/16 of an inch greater in diameter than the maximum corresponding dimensions of the associated head and shank portions of the associated bolt. Such a construction enables limited movement of the housings and associated magnets relative to the body 316 to accommodate irregularities in the surface of the workpiece support 14. The housings 348 and 350 are preferably formed of non-magnetic material, such as aluminum, and the magnets 336, 338, 340 and 342 are preferably retained in the housings through the agency of a suitable potting compound. The permanent magnets disposed in each of the housings 348 and 350 may have a combined holding power of several hundred pounds acting in a direction perpendicular to the surface 28 of the workpiece support 14 when the magnets are disposed in engagement with the surface 28 of the workpiece support 14. It will be understood however that the holding power of the magnets in a direction parallel to the plane of the surface 28 is much less than the holding power of the magnets in a direction perpendicular to the surface 28.
In this embodiment of the invention, a generally U-shaped base portion 354 is provided which is formed integrally with the body 316. The generally U-shaped base portion 354 includes a pair of elongate, laterally spaced leg portions 358 and 360 which extend in spaced substantially parallel relationship and which are joined at one end thereof by a transverse portion 362 which is fixed to the adjacent end portions of the legs 358 and 360 by any suitable means. The opposite end portion of the legs 358 and 360 are formed integrally with the body 316.
The base portion 354 of the jig 310 defines an elongate channel 370 which is open at the top and bottom of the base portion while the ends of the channel 370 are closed at one end by the transverse member 362 and at the opposite end by a block 366. An adjustable block 372, in the form of a parallelepiped, is provided which is mounted for longitudinal movement in the channel 370 defined by the base portion 354, the block 372 defining an internally threaded passageway 374 adapted to receive an elongate externally threaded screw 376 which extends longitudinally of the channel. One end portion of the screw 376 bears against the block 366 while the opposite end portion of the screw passes freely through a non-threaded opening 378 defined by the transverse portion 362, the screw being constrained against longitudinal movement by a knurled handle 380 which bears against the outer surface 382 of the transverse portion 362. With such a construction, rotation of the screw 376 through the agency of the handle 380 in one direction causes the block 372 to advance in the channel toward the clamp 312 while rotation of the screw in the opposite direction causes the block to retract in the channel toward the transverse portion 362.
A pin 384 is provided which is fixed to the block 372 and which projects outwardly therefrom. The pin 384 is preferably formed of steel or other suitable material having sufficient strength to withstand the forces exerted thereon and the pin 384 is adapted to be received selectively in any of the passageways such as 30, 32 and 34 defined by the workpiece support 14. As shown in FIGS. 10 and 14, ribs 390 and 392 are fixed to opposite sides of the base 316 near the handle 380 to facilitate manual lifting of the jig 310. With such a construction, the pin 384 may be inserted in any one of the passageways defined by the workpiece support 14 whereby the jig 310, including the clamp 312, is located in the approximate desired position for use in clamping components of the workpiece. The handle 380 may then be manually rotated so as to advance or retract the block 372 and the pin 384 carried thereby whereby the abutment surface 320 may be located at the precise desired position. The above described construction also permits the entire jig 310 to be moved angularly about the longitudinal axis of the pin 384 to compensate for any irregularities that may be presented by the various components of the workpiece. The permanent magnets prevent the clamp 312 incorporated in the jig 310 from lifting off of the surface 28 of the workpiece support 14 while the pin 384 prevents longitudinal movement of the jig 310 in a plane parallel to the plane of the surface 28 of the workpiece support.
If it is desired to manufacture a different type of truss utilizing components with different dimensions, the jig 310 may be easily moved to another position on the workpiece support by tilting the permanent magnets and simultaneously lifting the pin 384 from the passageway in which the pin has previously been inserted in the workpiece support so that the magnets are released from the workpiece support. The entire jig 310 may then be moved to a new location on the workpiece support after which the pin 384 is inserted in a passageway at the new desired location and the clamp adjusted to the exact desired position in the manner previously described. As previously mentioned, since the housings which carry the magnets are connected to the body 316 in a manner which permits limited relative movement between the housings and the body, the magnets can accomodate irregularities in the surface of the workpiece support.
Another embodiment of the invention is illustrated in FIGS. 15 through 18, and is comprised of an adjustable jig, generally designated 410, which may be adjustably mounted on the workpiece support 14 and which incorporates a stop, generally designated 412. In this embodiment of the invention, the stop 412 is of generally channel shaped configuration, in plan view, and includes a web portion 416 and integral flange portions 417 and 418, the web portion 416 having a curved abutment surface 420 adapted to engage a workpiece. The stop 412 is preferably formed of steel or other suitable material having sufficient strength to withstand the forces exerted thereon. The adjustable jig 410 also includes a plurality of permanent magnets, such as 436, 438, 440 and 442 which are mounted in housings 448 and 450, respectively. The housings 448 and 450, in turn are mounted on opposite sides of and fixed to a base 454 through the agency of bolts, such as 475 and 477, the shank portions of which extend through counterbored passageways 479 defined by the housings. The internal diameters of the counterbored passageways 479 are slightly larger in diameter than the outside diameters of the bolts so that limited movement of the housings and magnets carried thereby is permitted relative to the base 454. For example, the internal diameters of the counterbored passageways may be 1/16 of an inch greater in diameter than the maximum corresponding dimensions of the associated head and shank portions of the associated bolt. Such a construction enables limited movement of the housings and the magnets carried thereby relative to the base 454 to accomodate irregularities in the surface of the workpiece support 14. The housings 448 and 450 are preferably formed of non-magnetic material, such as aluminum, and the magnets 436, 438, 440 and 442 are preferably retained in the housings through the agency of a suitable potting compound. The permanent magnets disposed in each of the housings 448 and 450 may have a combined holding power of several hundred pounds acting in a direction perpendicular to the surface 28 of the workpiece support 14 when the magnets are disposed in engagement with the surface 28 of the workpiece support 14, the holding power of the magnets in a direction parallel to the plane of the surface 28 being less than the holding power of the magnets in a direction perpendicular to the surface 28.
In this embodiment of the invention, the base 454 includes a pair of elongate laterally spaced leg portions 458 and 460 which extend in spaced parallel relationship and which are joined at one end thereof by a transverse portion 462 which is fixed to the adjacent ends of the leg portions 458 and 460 by any suitable means. The opposite end portions of the legs 458 and 460 are also fixed to a bearing block 465 by any suitable means.
The base 454 defines an elongate channel 470 which is open at the top and bottom of the base while the ends of the channel 470 are closed at one end by the bearing block 465 and that the opposite end by the transverse member 462. An adjustable block 472, in the form of a parallelpiped, is provided which is mounted for longitudinal movement in the channel 470 defined by the base 454, the block 472 defining an internally threaded passageway 474 adapted to receive an elongate externally threaded screw 476 which extends longitudinally of the channel 470. One end portion of the screw 476 bears against the bearing block 465 while the opposite end portion of the screw 476 passes freely through a non-threaded opening 478 defined by the transverse portion 462 of the base, the screw being constrained against longitudinal movement by a knurled handle 480 which bears against the outer surface 482 of the transverse portion 462 of the base. With such a construction, rotation of the screw 476 through the agency of the handle 480 in one direction causes the block 472 to advance in the channel toward the stop 412 while rotation of the screw in the opposite direction causes the block to retract in the channel toward the transverse portion 462 of the base.
A pin 484, similar to the pins previously described, is provided which is fixed to the block 472 and which projects outwardly therefrom. The pin 484 is also preferably formed of steel or other suitable material having sufficient strength to withstand the forces exerted thereon and the pin is adapted to be received selectively in any of the passsages, such as 30, 32 and 34, defined by the workpiece support 14. With such a construction, the pin 484 may be inserted in any one of the passageways defined by the workpiece support 14 whereby the base 454 and the stop 412 are located in the approximate desired position for use in holding components of the workpiece. The handle 480 may then be manually rotated so as to advance or retract the block 472 and the pin 484 carried thereby whereby the abutment surface 420 may be located at the precise desired position.
In this embodiment of the invention, the base 454 also includes integral outwardly projecting block portions 459 and 461 which extend in a direction perpendicular to the leg portions 458 and 460 and which are integrally joined thereto by any suitable means. The flange portions 417 and 418 of the stop 412 are pivotally connected to the block portions 459 and 461 through the agency of axially aligned pivot pins 481 and 483 fixed to the block portions 459 and 461, respectively. The radius of curvature of the surface 420 of the stop 412 extends from the aligned axes of the pivot pins 481 and 483. With such a construction, pressure exerted against a workpiece remains constant if the stop 412 is pivoted upwardly, as shown in dotted lines in FIG. 16, with the result that a workpiece may be lifted slightly off the support 14 to enable a connector plate to be inserted thereunder while constant pressure is exerted on the workpiece by the stop 412.
In this embodiment of the invention, a detent, generally designated 490, is provided having an externally threaded body portion 492 which threadably engages an internally threaded passageway 494 defined by the web portion 416 of the stop 412. The detent 490 also includes a ball 496 which is disposed in a blind passageway 498 and biased by a spring 500, the end 502 of the body being crimped or otherwise reduced in diameter to retain the ball in the passageway 498. With such a construction, the stop 412 may be pivoted or cocked toward the workpiece support 14 about the aligned axes of the pivot pins so that the ball 496 of the detent engages the lower edge 504 of the bearing block 465 to hold the stop in the position illustrated in FIG. 18. With the stop 412 in such a position, the magnets are held a slight distance away from the workpiece support 14 so that the entire jig 410 may be moved easily relative to the workpiece support 14 and manually positioned at the desired location on the workpiece support. The magnets are then pushed downwardly to hold the jig in the selected position. The above described construction also permits the entire jig 410 including the base 454 and the stop 412 to be moved angularly above the longitudinal axis of the pin 484 to compensate for any irregularities that may be presented by the various components of the workpiece. The permanent magnets prevent the stop 412, incorporated in the jig 410, from lifting off of the surface 28 of the workpiece support while the pin 484 prevents longitudinal movement of the stop in a plane parallel to the plane of the surface 28 of the workpiece support 14, generally triangularly shaped gusset plates 506 and 508, disposed at the intersections of the block portions 459 and 461 with the leg portions 458 and 460, respectively, being provided to facilitate manual lifting of the jig 410 and manual manipulation thereof relative to the support 14.
While preferred embodiments of the invention have been illustrated and described, it will be understood that various changes and modifications may be made without departing from the spirit of the invention. | An adjustable jig incorporating combined magnetic and mechanical means for adjustably mounting the jig on a workpiece support whereby the jig may be utilized to locate and maintain the correct positional relationship between components of work during assembly and manufacture thereof. | 8 |
BACKGROUND OF THE INVENTION
This invention relates to caster sockets and is particularly directed to the formation of a socket which has improved resistance to abuse and simplifies the installation in an article of furniture.
A great many casters are mounted with the swivel post fitted into a hole bored into the leg or member of the article needing casters for rendering it movable. While the hole can be made to fit the swivel post in its original condition, the forces imposed will soon cause the swivel post to loosen and cause damage or enlarge the hole. Some casters are mounted in sockets which are held in the furniture by screws, and the screws usually extend through an external flange which in time will work the screws loose. These caster mountings are fine when new, but in time will work loose and often will permanently damage the furniture so that efforts to effect repairs is expensive or even not practical.
Furniture of current designs is especially difficult to caster in view of the extensive use of chipboard material which is easily damaged by screws or nails used with the types of caster sockets heretofore available. However, the caster socket of this invention is arranged with means to engage the article at opposed areas so that the initial fit is relatively undisturbed by rough usage.
It is an important object of this invention to provide a caster socket with the greatest ability to withstand hard usage by forming the socket with sufficient surface contact area to restrict the unit loading so that the surrounding body of material of the article is able to retain its original condition for long periods of time.
Other important objects of this invention are to provide an inexpensive yet strong caster socket which can be installed easily and is easily replaceable; to provide means for avoiding the use of screws and for relocating holding means so that the usual forces imposed on a caster socket are removed from the holding means; to provide a caster socket molded of materials that have the necessary strength and are capable of being plated or treated so as to harmonize with the surface texture and color of the article in which it is mounted; and to provide a caster socket requiring a simple slot or notch to receive it so that face and back flanges are able to abut the margins of the slot or notch with a large enough area of contact to keep the unit loads at an advantageous low value so that the stress is not likely to damage the caster socket or article of furniture.
A presently preferred embodiment of the caster socket includes a body formed with an elongated socket open at one end to receive the swivel post of a caster, a pair of flanges which extend along opposite sides of the body and beyond the end opposite the socket opening so that the body and the flanges form seats to receive the article to which the caster is to be applied, and means on one of the flanges to mark an area thereof to receive securing means which holds the caster socket in operative position. The caster socket is formed of moldable plastic material as a unitary article and is applied by being mounted in a slot or similar opening in the article of furniture so that the flanges and socket body absorb the loads, and securing means engaged between a flange and the adjacent surface of the furniture is substantially free of the sheer and tension stresses heretofore normally imposed by conventional types of caster sockets.
BRIEF DESCRIPTION OF THE DRAWINGS
The preferred embodiment of this invention is shown in the accompanying drawings, wherein:
FIG. 1 is a fragmentary perspective view of an article of furniture having an end panel in which the present caster socket is incorporated;
FIG. 2 is a fragmentary section view taken at line 2--2 in FIG. 1 of a left hand caster socket;
FIG. 3 is a fragmentary section view taken at line 3--3 in FIG. 1 of a right hand caster socket;
FIG. 4 is a fragmentary elevation of the furniture panel with the caster socket in position, the views being taken at line 4--4 in FIG. 3;
FIG. 5 is a longitudinal section view of the caster socket showing the swivel post socket and the upper seat, the view being taken at line 5--5 in FIG. 4; and
FIG. 6 is a view of the back side of the caster socket as seen along 6--6 in FIG. 5.
DETAILED DESCRIPTION OF THE EMBODIMENTS
FIG. 1 shows a portion of a mobile cart 10 which has an end panel 11 and a connecting shelf board 12. The opposite end panel is not shown since it will be the same as panel 11 but reversed with respect to its inner and outer faces. A description of the structure associated with panel 11 will be the same for the opposite end panel that is not shown. In general, caster sockets 13 and 14 are mounted in suitable bottom open notches in the lower margin 15 of panel 11, and each socket receives a suitable caster 16, which in this case is of the ball type. It is necessary to construct or form the caster sockets 13 and 14 for right hand and left hand assembly so that the casters 16 can be located close to the outer vertical margins of the panel 11. However, in a different article of furniture, it may not be necessary to have right and left parts.
Turning now to FIG. 2, the left hand caster socket 13 is shown mounted in a notch 17 near the vertical margin 11A of the panel 11. The socket 13 is a one-piece molded member having a front face flange 18, a back face flange 19, and an intervening body 20 formed with a socket bore 21 sized to receive the usual swivel post (not shown) of the caster 16. The back face flange 19 is formed with a side extension 19A having spaced ribs 22 which act to denote a section of the extension in which securing means 23 should be located. In the present case, the securing means 23 are staples set by a suitable stapling gun to drive the staple prongs through the back face 19 and into the end panel 11.
In FIG. 3 it can be seen that the right hand socket 14 is mounted in a notch 24 near the vertical margin 11B of the panel 11. The socket 14 is a one-piece molded member having a front face flange 25, a back face flange 26, and an intervening body 27 having a socket bore 28 to receive the usual swivel post of caster 16. The back face flange 26 of the socket 14 is provided with a side extension 26A on which spaced ribs 29 are formed to denote an area for the insertion of securing means 23 such as staples.
The views of FIGS. 4, 5 and 6 present more detailed disclosure of socket 14. It is to be noted that the front and back face flanges 25 and 26 project above the intervening body 27 to form a seat to engage the inner closed end 24A (FIG. 5) of the notch 24. The body 27 occupies the notch 24 while the face 25 conceals the margins of the notch and presents a pleasing surface to view. The face and back flanges embrace the end panel surface on three sides of the notch 24 so that a very secure mounting of the socket results. The side extension 26A and the spaced ribs 29 furnish a convenient way to attach the socket by use of staples, the elongated ribs guiding the stapling gun.
The socket 13 of FIG. 2 is mounted in the panel 11 in the same manner as just described for socket 14. In each socket, the body 20 or 27 has a cavity 30 to reduce the amount of material needed in the molding thereof. A suitable material for the sockets may be Dow Corning general duty T grade Cycolac plastic which may be surface plated so as to have the front face flanges 18 or 25 treated to harmonize or contrast with the surface treatment for the end panel 11.
The foregoing description has set forth a presently preferred embodiment of a caster socket having an elongated body formed with a caster swivel post receiving socket, face and back flanges projecting outwardly beyond the body to form surfaces abutting and seating in a receiving notch or other opening in an article of furniture, and means on the back flange to locate means to secure the socket in position. The present socket provides an extended surface area around the elongated body and between the flanges so that the loads and side thrust forces caused by moving the article of furniture on the casters will be well distributed for reducing or eliminating the tendency of the socket to loosen and dig into the surfaces of the receiving notch. It is an especially important feature that the present socket is easily installed in a simple notch and is capable of easy removal by extracting the securing staples. | A caster socket for articles of furniture for mounting in a receiving slot in the article so that face and back flanges enclose the slot and locate a body which receives the caster swivel post and the back flange has a portion with indexing means to positively locate a stapling gun for driving staples through the back flange to retain the caster socket in operative position. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
The present invention is a further improvement upon the method disclosed in U.S. Ser. No. 731,053 filed on Oct. 8, 1976, by H. Franz et al. entitled "Improved Electroless Gold Plating Bath."
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates broadly to the art of electroless deposition of metallic films onto nonmetallic substrates. More particularly, the invention relates to a method for improving the color and durability of gold-coated articles.
2. Description of the Prior Art
In the art of depositing noble metal coatings onto nonmetallic surfaces, U.S. Pat. No. 3,300,328 to Luce discloses an aqueous electroless gold plating bath comprising a gold compound, an ammonium or alkali metal sulphite or meta-bisulphite complexing agent, and a hydrazine or hydroxylamine reducing agent. Gold films are deposited in about 40 minutes at elevated temperatures.
A more rapid method of depositing gold films onto nonmetallic substrates is described by Levy in U.S. Pat. No. 3,515,571. A preferably neutral gold solution is prepared by dissolving in water a gold salt such as gold chloride, and complexing the free gold ions in excess of 10 -16 gram ions per liter with suitable coordinating ligands such as alkali metal carbonates, alkali metal hydroxides, ammonia and amines. Gold films may be deposited on nonmetallic substrates in about one minute at ambient temperatures by contacting a receptive surface with the above gold solution and a second solution of a hydrazine reducing agent. Levy suggests the use of the resultant gold coated articles as conductors, electrodes, and mirrors.
U.S. Pat. No. 3,484,263 to Kushihashi et al. discloses a method for forming a homogeneous semi-transparent gold coating on glass. The method involves contacting a sensitized glass surface with an alkaline aqueous solution of a gold salt, a reducing agent and an alkali carbonate to promote reduction at a temperature not to exceed 10° C. After about 0.5 to 5 minutes contact, the contacting interface is subjected to radiation of 2500 - 5000 Angstroms to reduce the gold salt to a gold coating with a thickness of 150 - 500 Angstroms.
In U.S. Ser. No. 731,053, filed on Oct. 8, 1976, Franz et al., disclose an improved method for depositing uniform gold films by contacting a receptive nonmetallic substrate with a solution of complexed gold ions and a reducing agent. The improvement involves preparing the gold solution by adding a concentrated solution of a gold salt to a concentrated solution of a complexing agent with heating. A further improvement involves using sodium carbonate as the complexing agent and buffering the gold solution with sodium bicarbonate.
SUMMARY OF THE INVENTION
The present invention provides a method for producing gold coated articles having a more intense pure gold color and superior abrasion and adhesion properties compared with gold coated articles prepared according to previously known methods.
A uniform gold film is deposited on a receptive nonmetallic substrate. For example, a glass sheet is cleaned, sensitized and activated by methods common in the art of electroless deposition and a gold film is deposited by contacting the surface with a solution of gold ions and a reducing agent. According to the present invention, the gold coated article is then contacted with a solution of silver ions and a reducing agent to deposit a silver film over the gold film resulting in a coated article having a more intense pure gold color and superior abrasion and adherence properties compared with an article coated with only a gold film.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Sheets of glass, particularly soda-lime-silica glass having a thickness of about 7/32 inch, are prepared for coating. First, the surface to be coated is cleaned, preferably by a blocking operation carried out with rotating felt blocks which gently abrade the surface with an aqueous slurry of a commercial cleaning compound. A suitable continuous line apparatus for washing, rinsing and sweeping the surface is shown in U.S. Pat. No. 3,723,158 to Miller et al.
After the surface to be coated is cleaned, it is contacted with a dilute aqueous solution of a sensitizing agent, preferably stannous chloride. After a brief period of contact under ambient conditions, the sheet is rinsed, preferably with deionized water, and activated. Activation may be accomplished by contacting the sensitized surface with a solution of silver ions and a reducing agent to deposit a thin catalytic silver film of such thickness as lowers the luminous transmittance of the sheet to about 60 percent or less. However, the preferred method of activation is to contact the sensitized surface with a dilute solution of palladium chloride.
After the sheet is rinsed, a gold film is deposited on the activated surface. In a most preferred embodiment, a gold solution is used which comprises about 1 to 6 grams per liter gold chloride and about 6 to 36 grams per liter sodium carbonate prepared according to the method disclosed in U.S. Ser. No. 731,053, filed on Oct. 8, 1976, by Franz et al. entitled "Improved Electroless Gold Plating Bath" which disclosure is incorporated herein by reference. Hydrazine reducing agents are preferred, particularly hydrazine tartrate in solutions of about 0.5 to 5 grams per liter. A surfactant, for example sodium dodecylbenzene sulfonate, may be added to a solution of the reducing agent to enhance the uniformity of the gold film.
The gold film is deposited by contacting the activated surface of the substrate substantially simultaneously with separate solutions of complexed gold ions and a reducing agent. A preferred method is a spray method employing a double nozzled spray gun. Sufficient gold is deposited to lower the luminous transmittance of the sheet to about 39 to 44 percent for preferred articles of the present invention.
Following deposition of the gold film, the surface is rinsed and a silver film is deposited over the gold film. A preferred method is again a spray method employing a double nozzled spray gun to contact the gold coated surface substantially simultaneously with a silver solution and a reducing solution. The silver solution is preferably an alkaline aqueous solution comprising about 0.15 to 15 grams, preferably about 0.5 to 5 grams, per liter of silver nitrate and about 0.45 to 60 milliliters, preferably about 1.5 to 20 milliliters, per liter of ammonium hydroxide (28 to 30 percent aqueous solution). The reducing solution comprises about 0.5 to 10 grams per liter of reducing agent, preferably about 1 to 2 grams per liter dextrose.
Sufficient silver is deposited over the gold to achieve the desired final luminous transmittance. A preferred article, according to the present invention, for use in architectural glazing applications has a final luminous transmittance of about 20 percent. The preferred article has a more intense pure gold color and superior durability compared with an article similarly produced with only a gold film.
The present invention will be further understood from the descriptions of specific examples which follow.
EXAMPLE I
Glass sheets are cleaned using an aqueous slurry of cerium oxide and a felt block. The surface to be coated is rinsed thoroughly, sensitized with a dilute aqueous solution of stannous chloride, and rinsed again. The sensitized surface is then activated with a dilute solution of palladium chloride and rinsed once more.
The activated surface is coated with a gold film by spraying through a double nozzled spray gun a gold solution containing 2 grams per liter chlorauric acid (HAuCL 4 . 3H 2 O) and 12 grams per liter sodium carbonate (Na 2 CO 3 anhydrous), and a reducing solution containing 2 grams per liter hydrazine tartrate and 0.02 grams per liter of 60 percent sodium dodecyl benzene sulfonate (available as Richonate 60B from the Richardson Company, Des Plaines, Ill. 60018). The solutions are sprayed until the luminous transmittance of the coated article is approximately 40 percent.
The gold-coated sheet is rinsed thoroughly and coated with a film of silver by spraying simultaneously a silver solution containing 1.25 grams per liter silver nitrate (AgNO 3 ), 0.37 grams per liter sodium hydroxide (NaOH), 3.75 milliliters per liter ammonium hydroxide (28 percent NH 4 OH), and a reducing solution of 0.63 grams per liter dextrose. The solutions are sprayed until the luminous transmittance of the coated articles is about 20 percent.
The article coated with a gold-silver composite film has a more intense pure gold color and superior abrasion resistance and adherence characteristics compared with articles coated with only a gold film.
EXAMPLE II
Glass sheets ae cleaned, sensitized and activated as in Example I. A solution of 2 grams of gold chloride in 100 milliliters of water is added, with stirring, to a solution of 12 grams of sodium carbonate in 100 milliliters of water maintained at a temperature of about 150° F. The resultant solution is diluted to one liter and buffered at a pH of about 9 by the addition of 30 grams of sodium bicarbonate.
A gold film is deposited as in Example I. The gold coated article is then overcoated with silver to a final luminous transmittance of about 20 percent. The color of the resultant article coated with the silver-over-gold composite film is compared in Table I with the color of an article coated by the same method but with gold only. Tristimulus X, Y and Z values were measured relative to a white standard with a Large Sphere Color-Eye Colorimeter manufactured by Instrument Development Laboratories.
TABLE I______________________________________Color-Eye Readings For Silver-Gold Coated ArticleCompared With Readings For Gold Coated ArticleReading Silver-Gold Gold Only______________________________________Tristimulus X 70 43Tristimulus Y 62 35Tristimulus Z 30 18______________________________________
The above examples are offered only to illustrate the present invention. Various modifications which will become known to those skilled in the art are included within the scope of the present invention which is limited only as set forth as follows in the claims. | Uniform gold films having an intense pure gold color and superior abrasion and adhesion properties are prepared by first depositing a gold film on a nonmetallic substrate by a known method, preferably electroless deposition, then depositing a silver film over the gold by electroless deposition. | 8 |
This application is a continuation-in-part of U.S. patent application Ser. No. 08/313,435, filed Sep. 27, 1994, which is a continuation-in-part of U.S. patent application Ser. No. 08/081,317, filed Nov. 8, 1993, now U.S. Pat. No. 5,428,164 which is a continuation-in-part of U.S. patent application Ser. No. 07/635,256, filed Dec. 28, 1990, now U.S. Pat. No. 5,159,083.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to certain aminomethyl phenylimidazole derivatives which selectively bind to brain dopamine receptor subtypes. This invention also relates to pharmaceutical compositions comprising such compounds. It further relates to the use of such compounds in treating affective disorders such as schizophrenia and depression as well as certain movement disorders such as Parkinsonism. Furthermore compounds of this invention may be useful in treating the extrapyramidal side effects asssociated with the use of conventional neuroleptic agents. The interaction of aminomethyl phenylimidazole derivatives of the invention with dopamine receptor subtypes is described. This interaction results in the pharmacological activities of these compounds.
2. Description of the Related Art
Schizophrenia or psychosis is a term used to describe a group of illnesses of unknown origin which affect approximately 2.5 million people in the United States. These disorders of the brain are characterised by a variety of symptoms which are classified as positive symptoms (disordered thought, hallucinations and delusions) and negative symptoms (social withdrawal and unresponsiveness). These disorders have an age of onset in adolescence or early adulthood and persist for many years. The disorders tend to become more severe during the patients lifetime and can result in prolonged institutionalization. In the U.S. today, approximately 40% of all hospitalized psychiatric patents suffer from schizophrenia.
During the 1950's physicians demonstrated that they could sucessfully treat psychotic patients with medications called neuroleptics; this classification of antipsychotic medication was based largely on the activating (neuroleptic) properties of the nervous system by these drugs. Subsequently, neuroleptic agents were shown to increase the concentrations of dopamine metabolites in the brain suggesting altered neuronal firing of the dopamine system. Additional evidence indicated that dopamine could increase the activity of adenylate cyclase in the corpus striatum, an effect reversed by neuroleptic agents. Thus, cumulative evidence from these and later experiments strongly suggested that the neurotransmitter dopamine was involved in schizophrenia.
One of the major actions of antipsychotic medication is the blockade of dopamine receptors in brain. Several dopamine systems appear to exist in the brain and at least three classes of dopamine receptors appear to mediate the actions of this transmitter. These dopamine receptors differ in their pharmacological specificity and were originally classified upon these differences in the pharmacology of different chemical series. Butyrophenones, containing many potent antipsychotic drugs were quite weak at the dopamine receptor that activated adenylate cyclase (now known as a D1 dopamine receptor). In contrast, they labelled other dopamine receptors (called D2 receptors) in the subnanomolar range and a third type D3 in the nanomolar range. Phenothiazines possess nanomolar affinity for all three types of dopamine receptors. Other drugs have been developed with great specificity for the D1 subtype receptor.
Recently, a new group of drugs (such as sulpiride and clozapine) have been developed with a lesser incidence of extrapyramidal side effects than classical neuroleptics. In addition, there is some indication that they may be more beneficial in treating negative symptoms in some patients. Since all D2 blockers do not possess a similar profile, hypotheses underlying the differences have been investigated. The major differences have been in the anticholinergic actions of the neuroleptics as well as the possilility that the dopamine receptors may differ in motor areas from those in the limbic areas thought to mediate the antipsychotic responses. The existence of the D3 and other as yet undiscovered dopamine receptors may contribute to this profile. Some of the atypical compounds possess similar activity at both D2 and D3 receptors. The examples of this patent fall into this general class of molecules.
Using molecular biological techniques it has been possible to clone cDNAs coding for each of the pharmacologically defined receptors. There are at least two forms of D1, and two forms of D2 dopamine receptors. In addition, there is at least one form of D3 dopamine receptor and at least one form of D4 dopamine receptor. Examples from the aminomethyl phenylimidazole series of this patent possess differential affinities for each receptor subtype.
Schizophrenia is characterized by a variety of cognitive dysfunctions and patients perform less well than other groups on most cognitive or attentional tasks. The positive and negative symptom dimensions of schizophrenia are also associated with distinct cognitive deficits. In general, positive symptoms (disordered thought processes, hallucinations and decisions) are related to auditory processing impairments including deficits in verbal memory and language comprehenion. Negative symptoms (social withdrawal and unresponsiveness) are related more to visual/motor dysfunctions including poorer performance on visual memory, motor speed and dexterity tasks.
There disorders have an age of onset in adolescence or early adulthood and persist for many years. The interaction of frontal and septo-hippocampal brain systems, and failures of information processing and self monitoring have been theorized as the basis of positive symptoms. Negative symptoms are thought to arise from abnormalities in the interactions of frontal and striatal systems. Since cognitive disturbances are present in most of the patients diagnosed as schizophrenia, it has been theorized that to understand the pathogenesis and etiology of schizophrenia we must understand the basic dysfunction of the cognitive disorder.
The cognitive disturbances found in schizophrenia include, but are not limited to, various verbal and visual memory deficits. There are various neurocognitive tasks for both animals and humans that have been developed to assess memory deficits, as well as memory enhancements, of various treatments. Many of the neurocognitive behavioral tasks are modulated or mediated by neural activity within the hippocampal brain system noted above.
Drug substances that interact with the hippocampus are capable of modulating memory in animals. Certain memory paradigms employed in animals have construct and predictive validity for memory assessment in humans. In animals (rodents), paradigms such as the Step-Down Passive Avoidance Task assay or the Spatial Water Maze Task assay reliably detect deficits produced by certain drugs in humans. For example, commonly prescribed benzodiazepine anxiolytics and sedative hypnotics are known to produce memory impairment in humans, including varying degrees of anterograde amnesia (depending on the exact drug). In the step-down passive avoidance paradigm, these very same drugs disrupt the memory of animals given the compounds during the information acquisition or processing period. Likewise, benzodiazepines disrupt information processing and memories in the spatial water maze task in rodents. Thus, these animal models can be used to predict the memory impairing effects of certain compounds in humans. Conversely, these same animal models can predict the memory improving or enhancing effects of compounds in humans. Although fewer in number, drugs that improve memory in humans (e.g., nootroprics, beta carbolines) produce memory enhancing effects in rats in these models. Therefore, the spatial water maze and step-down passive avoidance paradigms in rodents are useful in predicting memory impairing and memory enhancing effects of test compounds in humans.
SUMMARY OF THE INVENTION
This invention provides novel compounds of Formula I which interact with dopamine receptor subtypes.
The invention provides pharmaceutical compositions comprising compounds of Formula I. The invention also provides compounds useful in treating affective disorders such as schizophrenia and depression as well as certain movement disorders such as Parkinsonism. Furthermore compounds of this invention may be useful in treating the extrapyramidal side effects asssociated with the use of conventional neuroleptic agents. Accordingly, a broad embodiment of the invention is directed to a compound of Formula I: ##STR3## and the pharmaceutically acceptable non-toxic salts thereof wherein R 1 and T are the same or different and represent hydrogen, halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms;
M is ##STR4## where R 2 is hydrogen or straight or branched chain lower alkyl having 1-6 carbon atoms, or R 1 and R 2 together may represent --(CH 2 ) n .sbsb.1 where n 1 is 1, 2, or 3;
X and Z are the same or different and represent hydrogen, halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, straight or branched chain lower alkoxy having 1-6 carbon atoms or SO 2 R 6 where R 6 is straight or branched chain lower alkyl having 1-6 carbon atoms;
Y is hydrogen, halogen, amino, or straight or branched chain lower alkyl having 1-6 carbon atoms;
R 3 is hydrogen or, straight or branched chain lower alkyl having 1-6 carbon atoms, or R 3 and R 4 together may represent --(CH 2 ) n .sbsb.2 -- where n 2 is 3 or 4; and
R 4 and R 5 are the same or different and represent hydrogen, straight or branched chain lower alkyl having 1-6 carbon atoms, or phenylalkyl or pyridylalkyl where each alkyl is straight or branched chain alkyl having 1-6 carbon atoms; or
R 2 and R 5 together may represent --(CH 2 ) n .sbsb.3 -- where n 3 is 2 or 3; or
NR 4 R 5 represents 2-(1,2,3,4-tetrahydroisoquinolinyl), or 2-(1,2,3,4-tetrahydroiso-quinolinyl) mono or disubstituted with halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms; or ##STR5## where W is N or CH;
R 7 is hydrogen, phenyl, pyridyl or pyrimidinyl, hydrogen, phenyl, pyridyl or pyrimidinyl, each of which may be mono or disubstituted with halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms; or
W--R 7 is oxygen or sulfur; and
n is 1, 2, or 3.
These compounds are highly selective partial agonists or antagonists at brain dopamine receptor subtypes or prodrugs thereof and are useful in the diagnosis and treatment of affectire disorders such as schizophrenia and depression as well as certain movement disorders such as Parkinsonism. Furthermore compounds of this invention may be useful in treating the extrapyramidal side effects asssociated with the use of conventional neuroleptic agents.
The compounds of the invention, such as, for example, 2-Phenyl-4(5)- (4-(2-pyrimidinyl)-piperazin-1-yl)-methyl!-imidazole dihydrochloride (compound 23), 2-Phenyl-4(5)- (4-(2-pyridyl)-piperazin-1-yl)-methyl!-imidazole dihydrochloride (Compound 24), and 2-Phenyl-4(5)- (4-phenyl-piperazin-1-yl)-methyl!-imidazole dihydrochloride (Compound 47), are antagonists binding to dopamine D4 receptors in both the rat and human hippocampus.
As noted above, the hippocampus is associated with both schizophrenia, and general memory processes in humans. In rodents, compound 23 produces memory enhancing effects in both the step-down passive avoidance assay as well as in the spatial water maze assay. Without being bound by a particular theory, it is believed that the D 4 receptors located in the hippocampus mediate the memory enhancing effects of the compounds of the invention. Therefore, since (1) compound 23 is active in animal models that are predictive of cognition enhancement, and specifically enhancement of memory and learning, and (2) compound 23 binds to D 4 receptors in the hippocampus, the D 4 class of dopamine antagonists, including the compounds of the invention, are useful for enhancing memory in humans.
Thus, the invention further provides methods for enhancing cognition, and specifically learning and memory, in mammals. These methods comprise administering to a mammal such as a human a compound of the invention, such as, for example, a compound of formula V, VI, VII, or XII, in an amount effective to enhance cognition.
BRIEF DESCRIPTION OF THE DRAWING
FIGS. 1A-G show representative aminomethyl phenylimidazoles of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The novel compounds encompassed by the instant invention can be described by general formula I: ##STR6## and the pharmaceutically acceptable non-toxic salts thereof wherein R 1 and T are the same or different and represent hydrogen, halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms;
M is ##STR7## where R 2 is hydrogen or straight or branched chain lower alkyl having 1-6 carbon atoms, or R 1 and R 2 together may represent --(CH 2 ) n .sbsb.1 where n 1 is 1, 2, or 3;
X and Z are the same or different and represent hydrogen, halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, straight or branched chain lower alkoxy having 1-6 carbon atoms or SO 2 R 6 where R 6 is straight or branched chain lower alkyl having 1-6 carbon atoms;
Y is hydrogen, halogen, amino, or straight or branched chain lower alkyl having 1-6 carbon atoms;
R 3 is hydrogen or, straight or branched chain lower alkyl having 1-6 carbon atoms, or R 3 and R 4 together may represent --(CH 2 ) n .sbsb.2 -- where n 2 is 3 or 4; and
R 4 and R 5 are the same or different and represent hydrogen, straight or branched chain lower alkyl having 1-6 carbon atoms, or phenylalkyl or pyridylalkyl where each alkyl is straight or branched chain alkyl having 1-6 carbon atoms; or
R 2 and R 5 together may represent --(CH 2 ) n .sbsb.3 -- where n 3 is 2 or 3; or
NR 4 R 5 represents 2-(1,2,3,4-tetrahydroisoquinolinyl), or 2-(1,2,3,4-tetrahydroiso-quinolinyl) mono or disubstituted with halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms; or ##STR8## where W is N or CH; and
R 7 is hydrogen, phenyl, pyridyl or pyrimidinyl, hydrogen, phenyl, pyridyl or pyrimidinyl, each of which may be mono or disubstituted with halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms; or
W-R 7 is oxygen or sulfur; and
n is 1, 2, or 3.
The present invention further encompasses compounds of Formula II: ##STR9## wherein R 1 is hydrogen, halogen,hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms;
M is ##STR10## where R 2 is hydrogen or, straight or branched chain lower alkyl having 1-6 carbon atoms, or R 1 and R 2 together may represent --(CH 2 ) n .sbsb.1 where n 1 is 1, 2, or 3;
X is hydrogen, halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, straight or branched chain lower alkoxy having 1-6 carbon atoms or SO 2 R 6 where R 6 is straight or branched chain lower alkyl having 1-6 carbon atoms;
R 3 is hydrogen or straight or branched chain lower alkyl having 1-6 carbon atoms, or R 3 and R 4 together may represent --(CH 2 ) n .sbsb.2 -- where n 2 is 3 or 4; and
R 4 and R 5 are the same or different and represent hydrogen, straight or branched chain lower alkyl having 1-6 carbon atoms, phenylalkyl or pyridylalkyl where each alkyl is straight or branched chain lower alkyl having 1-6 carbon atoms; or
R 2 and R 5 together may represent --(CH 2 ) n .sbsb.3 -- where n 3 is 2 or 3; or
NR 4 R 5 represents 2-(1,2,3,4-tetrahydroisoquinolinyl) or 2-(1,2,3,4-tetrahydroiso-quinolinyl) mono or disubstituted with halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms; or ##STR11## where W is N or CH; and
R 7 is hydrogen, phenyl, pyridyl or pyrimidinyl, or hydrogen, phenyl, pyridyl or pyrimidinyl, each of which may be mono or disubstituted with halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms; or
W--R 7 is oxygen or sulfur; and
n is 1, 2, or3.
The present invention also encompases compounds of Formula III: ##STR12## wherein R 1 is hydrogen, halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms;
M is ##STR13## where R 2 is hydrogen or, straight or branched chain lower alkyl having 1-6 carbon atoms, or R 1 and R 2 together may represent --(CH 2 ) n .sbsb.1 where n 1 is 1, 2, or 3;
R 3 is hydrogen, or straight or branched chain lower alkyl having 1-6 carbon atoms, or R 3 and R 4 together may represent --(CH 2 ) n .sbsb.2 -- where n 2 is 3 or 4; or
R 4 and R 5 are the same or different and represent hydrogen, straight or branched chain lower alkyl having 1-6 carbon atoms, aryl straight or branched chain lower alkyl having 1-6 carbon atoms or R 2 and R 5 together may represent --(CH 2 ) n .sbsb.3 -- where n 3 is 2 or 3; or
NR 4 R 5 represents 2-(1,2,3,4-tetrahydroisoquinolinyl), or 2-(1,2,3,4-tetrahydroiso-quinolinyl) mono or disubstituted with halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms; or ##STR14## where W is N or CH; and
R 7 is hydrogen, phenyl, pyridyl or pyrimidinyl; or hydrogen, phenyl, pyridyl or pyrimidinyl mono or disubstituted with
halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms; or
W--R 7 is oxygen or sulfur; and
n is 1,2, or 3.
In addition, the present invention encompasses compounds of Formula IV: ##STR15## wherein M is ##STR16## where R 2 is hydrogen or, straight or branched chain lower alkyl having 1-6 carbon atoms, or R 1 and R 2 together may represent --(CH 2 ) n .sbsb.1 where n 1 is 1, 2, or 3;
X is hydrogen, halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, straight or branched chain lower alkoxy having 1-6 carbon atoms, or SO 2 R 6 where R 6 is straight or branched chain lower alkyl having 1-6 carbon atoms;
R 3 is hydrogen, or straight or branched chain lower alkyl having 1-6 carbon atoms, or R 3 and R 4 together may represent --(CH 2 ) n .sbsb.2 -- where n 2 is 3 or 4; and
R 4 and R 5 are the same or different and represent hydrogen, straight or branched chain lower alkyl having 1-6 carbon atoms, phenylalkyl or pyridylalkyl where each alkyl is straight or branched chain lower alkyl having 1-6 carbon atoms; or
R 2 and R 5 together may represent --(CH 2 ) n .sbsb.3 -- where n 3 is 2 or 3; or
NR 4 R 5 represents 2-(1,2,3,4-tetrahydroisoquinolinyl), or 2-(1,2,3,4-tetrahydroiso-quinolinyl) mono or disubstituted with halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms; or ##STR17## where W is N or CH; and
R 7 is hydrogen, phenyl, pyridyl or pyrimidinyl, hydrogen, phenyl, pyridyl or pyrimidinyl, mono or disubstituted with halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms; or
W--R 7 is oxygen or sulfur; and
n is 1, 2, or 3.
The invention also provides compounds of formula V: ##STR18## wherein: R 1 and T independently represent hydrogen, halogen, hydroxy, lower alkyl, or lower alkoxy;
X, Y and Z independently represent hydrogen, halogen, hydroxy, lower alkyl, lower alkoxy, or --SO 2 R 6 where R6 is lower alkyl; and
E is CH or nitrogen.
The invention also provides compounds of formula VI: ##STR19## wherein: R 1 represents hydrogen, halogen, hydroxy, lower alkyl, or lower alkoxy; and
E is CH or nitrogen.
The invention provides compounds of formula VII: ##STR20## wherein: E is CH or nitrogen.
The invention also provides compounds of formula VIII: ##STR21## wherein: R 1 and T independently represent hydrogen, halogen, hydroxy, lower alkyl, or lower alkoxy;
X, Y and Z independently represent hydrogen, halogen, hydroxy, lower alkyl, lower alkoxy, or --SO 2 R 6 where R6 is lower alkyl;
n is 0 or 1; and
A and Q are the same or different and represent CH or nitrogen.
The invention also provides compounds of formula IX: ##STR22## wherein: n is 0 or 1; and
A and Q are the same or different and represent CH or nitrogen.
The invention also provides compounds of formula X: ##STR23## wherein: E is CH or nitrogen.
The invention also provides compounds of formula XI: ##STR24## wherein: R 1 , T, X, Y and Z independently represent hydrogen or lower alkyl; and E represents CH or nitrogen.
The invention also provides compounds of formula XII: ##STR25## wherein: R 1 , T, X, Y and Z independently represent hydrogen or lower alkyl; and
E represents CH or nitrogen.
The invention also provides compounds of formula XIII: ##STR26## wherein R 1 and T independently represent hydrogen, halogen, hydroxy, lower alkyl, or lower alkoxy; and
X, Y and Z independently represent hydrogen, halogen, hydroxy, lower alkyl, lower alkoxy, or --SO 2 R 6 where R6 is lower alkyl.
n is 0 or 1.
The invention also provides compounds of formula XIV: ##STR27## wherein: R 1 and T independently represent hydrogen, halogen, hydroxy, lower alkyl, or lower alkoxy; and
X, Y and Z independently represent hydrogen, halogen, hydroxy, lower alkyl, lower alkoxy, or --SO 2 R 6 where R6 is lower alkyl.
The invention further provides compounds of formula XV: ##STR28## wherein: R is halogen, alkoxy having 1-6 carbon atoms, or hydroxy;
R 1 and T independently represent hydrogen, halogen, hydroxy, lower alkyl, or lower alkoxy;
X, Y and Z independently represent hydrogen, halogen, hydroxy, lower alkyl, lower alkoxy, or --SO 2 R 6 where R 6 is lower alkyl; and
E is CH or nitrogen.
Preferred compounds of Formula XV are those where R 1 , T, X, Y, and Z are hydrogen. Particularly preferred compounds of Formula XV are those where R 1 , T, X, Y, and Z are hydrogen, E is nitrogen, and R is hydroxy, fluorine, or methoxy.
The invention provides compounds of formula XVI: ##STR29## wherein: R is halogen, alkoxy having 1-6 carbon atoms, or hydroxy;
E is CH or nitrogen.
Preferred compounds of Formula XVI are those where E is nitrogen. Particularly preferred compounds of Formula XVI are those where E is nitrogen and R is hydroxy, fluorine, or methoxy.
The invention also provides compounds of formula XVII: ##STR30## wherein: R is halogen, alkoxy having 1-6 carbon atoms, or hydroxy.
Preferred compounds of Formula XVII are those where R is hydroxy, fluorine, or methoxy.
Non-toxic pharmaceutical salts include salts of acids such as hydrochloric, phosphoric, hydrobromic, sulfuric, sulfinic, formic, toluene sulfonic, hydroiodic, acetic and the like. Those skilled in the art will recognize a wide variety of non-toxic pharmaceutically acceptable addition salts.
Representative compounds of the present invention, which are encompassed by Formula I, include, but are not limited to the compounds in FIG. I and their pharmaceutically acceptable salts. The present invention also encompasses the acylated prodrugs of the compounds of Formula I. Those skilled in the art will recognize various synthetic methodologies which may be employed to prepare non-toxic pharmaceutically acceptable addition salts and acylated prodrugs of the compounds encompassed by Formula I.
By alkyl or lower alkyl in the present invention is meant straight or branched chain alkyl groups having 1-6 carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, and 3-methylpentyl.
By alkoxy or lower alkoxy in the present invention is meant straight or branched chain alkoxy groups having 1-6 carbon atoms, such as, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentoxy, 2-pentyl, isopentoxy, neopentoxy, hexoxy, 2-hexoxy, 3-hexoxy, and 3-methylpentoxy.
By halogen in the present invention is meant fluorine, bromine, chlorine, and iodine.
The pharmaceutical utility of compounds of this invention are indicated by the following assays for dopamine receptor subtype affinity.
Assay for D2 and D3 recentor binding activity
Striatial tissue is dissected from adult male Sprague Dawley rats or BHK 293 cells are harvested contianing recombinantly produced D2 or D3 receptors. The sample is homogenized in 100 volumes (w/vol) of 0.05M Tris HCl buffer at 4° C. and pH 7.4. The sample is then centrifuged at 30,000×g and resuspended and rehomogenized. The sample is then centrifuged as described and the final tissue sample is frozen until use. The tissue is resuspended 1:20 (wt/vol) in 0.05M Tris HCl buffer containing 100 mM NaCl.
Incubations are carried out at 48° C. and contain 0.5 ml of tissue sample, 0.5 nM 3H-raclopride and the compound of interest in a total incubation of 1.0 ml. Nonspecific binding is defined as that binding found in the presence of 10-4M dopamine; without further additions, nonspecific binding is less than 20% of total binding. The binding characteristics of examples of this patent are shown in Table 1 for Rat Striatal Homogenates.
TABLE I______________________________________Compound Number.sup.1 IC.sub.50 (uM)______________________________________1 0.9008 0.01116 0.01419 0.10021 0.01824 0.62026 0.200______________________________________ .sup.1 Compount numbers relate to compounds shown in FIG. I.
Compounds 8, 16 and 21 are particularly preferred embodiments of the present invention because of their potency in binding to dopamine receptor subtypes.
The compounds of general formula I may be administered orally, topically, parenterally, by inhalation or spray or rectally in dosage unit formulations containing conventional non-toxic pharmaceutically acceptable carriers, adjuvants and vehicles. The term parenteral as used herein includes subcutaneous injections, intravenous, intramuscular, intrasternal injection or infusion techniques. In addition, there is provided a pharmaceutical formulation comprising a compound of general formula I and a pharmaceutically acceptable carrier. One or more compounds of general formula I may be present in association with one or more non-toxic pharmaceutically acceptable carriers and/or diluents and/or adjuvants and if desired other active ingredients. The pharmaceutical compositions containing compounds of general formula I may be in a form suitable for oral use, for example, as tablets, troches, lozenges, aqueous or oily suspensions, dispersible powders or granules, emulsion, hard or soft capsules, or syrups or elixirs.
Compositions intended for oral use may be prepared according to any method known to the art for the manufacture of pharmaceutical compositions and such compositions may contain one or more agents selected from the group consisting of sweetening agents, flavoring agents, coloring agents and preserving agents in order to provide pharmaceutically elegant and palatable preparations. Tablets contain the active ingredient in admixture with non-toxic pharmaceutically acceptable excipients which are suitable for the manufacture of tablets. These excipients may be for example, inert diluents, such as calcium carbonate, sodium carbonate, lactose, calcium phosphate or sodium phosphate; granulating and disintegrating agents, for example, corn starch, or alginic acid; binding agents, for example starch, gelatin or acacia, and lubricating agents, for example magnesium stearate, stearic acid or talc. The tablets may be uncoated or they may be coated by known techniques to delay disintegration and absorption in the gastrointestinal tract and thereby provide a sustained action over a longer period. For example, a time delay material such as glyceryl monosterate or glyceryl distearate may be employed.
Formulations for oral use may also be presented as hard gelatin capsules wherein the active ingredient is mixed with an inert solid diluent, for example, calcium carbonate, calcium phosphate or kaolin, or as soft gelatin capsules wherein the active ingredient is mixed with water or an oil medium, for example peanut oil, liquid paraffin or olive oil.
Aqueous suspensions contain the active materials in admixture with excipients suitable for the manufacture of aqueous suspensions. Such excipients are suspending agents, for example sodium carboxymethylcellulose, methylcellulose, hydropropylmethylcellulose, sodium alginate, polyvinylpyrrolidone, gum tragacanth and gum acacia; dispersing or wetting agents may be a naturally-occurring phosphatide, for example, lecithin, or condensation products of an alkylene oxide with fatty acids, for example polyoxyethylene stearate, or condensation products of ethylene oxide with long chain aliphatic alcohols, for example heptadecaethyleneoxycetanol, or condensation products of ethylene oxide with partial esters derived from fatty acids and a hexitol such as polyoxyethylene sorbitol monooleate, or condensation products of ethylene oxide with partial esters derived from fatty acids and hexitol anhydrides, for example polyethylene sorbitan monooleate. The aqueous suspensions may also contain one or more preservatives, for example ethyl, or n-propyl p-hydroxybenzoate, one or more coloring agents, one or more flavoring agents, and one or more sweetening agents, such as sucrose or saccharin.
Oily suspensions may be formulated by suspending the active ingredients in a vegetable oil, for example arachis oil, olive oil, sesame oil or coconut oil, or in a mineral oil such as liquid paraffin. The oily suspensions may contain a thickening agent, for example beeswax, hard paraffin or cetyl alcohol. Sweetening agents such as those set forth above, and flavoring agents may be added to provide palatable oral preparations. These compositions may be preserved by the addition of an anti-oxidant such as ascorbic acid.
Dispersible powders and granules suitable for preparation of an aqueous suspension by the addition of water provide the active ingredient in admixture with a dispersing or wetting agent, suspending agent and one or more preservatives. Suitable dispersing or wetting agents and suspending agents are exemplified by those already mentioned above. Additional excipients, for example sweetening, flavoring and coloring agents, may also be present.
Pharmaceutical compositions of the invention may also be in the form of oil-in-water emulsions. The oily phase may be a vegetable oil, for example olive oil or arachis oil, or a mineral oil, for example liquid paraffin or mixtures of these. Suitable emulsifying agents may be naturally-occurring gums, for example gum acacia or gum tragacanth, naturally-occurring phosphatides, for example soy bean, lecithin, and esters or partial esters derived from fatty acids and hexitol, anhydrides, for example sorbitan monoleate, and condensation products of the said partial esters with ethylene oxide, for example polyoxyethylene sorbitan monoleate. The emulsions may also contain sweetening and flavoring agents.
Syrups and elixirs may be formulated with sweetening agents, for example glycerol, propylene glycol, sorbitor or sucrose. Such formulations may also contain a demulcent, a preservative and flavoring and coloring agents. The pharmaceutical compositions may be in the form of a sterile injectable aqueous or oleaginous suspension. This suspension may be formulated according to the known art using those suitable dispersing or wetting agents and suspending agents which have been mentioned above. The sterile injectable preparation may also be sterile injectable solution or suspension in a non-toxic parentally 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'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 diglycerides. In addition, fatty acids such as oleic acid find use in the preparation of injectables.
The compounds of general formula I may also be administered in the form of suppositories for rectal administration of the drug. These compositions can be prepared by mixing the drug with a suitable non-irritating excipient which is solid at ordinary temperatures but liquid at the rectal temperature and will therefore melt in the rectum to release the drug. Such materials are cocoa butter and polyethylene glycols.
Compounds of general formula I may be administered parenterally in a sterile medium. The drug, depending on the vehicle and concentration used, can either be suspended or dissolved in the vehicle. Advantageously, adjuvants such as local anaesthetics, preservatives and buffering agents can be dissolved in the vehicle.
Dosage levels of the order of from about 0.1 mg to about 140 mg per kilogram of body weight per day are useful in the treatment of the above-indicated conditions (about 0.5 mg to about 7 g per patient per day). The amount of active ingredient that may be combined with the carrier materials to produce a single dosage form will vary depending upon the host treated and the particular mode of administration. Dosage unit forms will generally contain between from about 1 mg to about 500 mg of an active ingredient.
It will be understood, however, that the specific dose level 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, route of administration, and rate of excretion, drug combination and the severity of the particular disease undergoing therapy.
An illustration of the preparation of compounds of the present invention is given in Scheme I. Those having skill in the art will recognize that the starting materials may be varied and additional steps employed to produce compounds encompassed by the present invention. ##STR31## where R 1 and T are the same or different and represent hydrogen, halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms;
M is ##STR32## where R 2 is hydrogen or straight or branched chain lower alkyl having 1-6 carbon atoms, or R 1 and R 2 together may represent --(CH 2 ) n .sbsb.1 where n 1 is 1, 2, or 3;
X and Z are the same or different and represent hydrogen, halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, straight or branched chain lower alkoxy having 1-6 carbon atoms or SO 2 R 6 where R 6 is straight or branched chain lower alkyl having 1-6 carbon atoms;
Y is hydrogen, halogen, amino, or straight or branched chain lower alkyl having 1-6 carbon atoms;
R 3 is hydrogen or, straight or branched chain lower alkyl having 1-6 carbon atoms, or R 3 and R 4 together may represent --(CH 2 ) n .sbsb.2 -- where n 2 is 3 or 4; and
R 4 and R 5 are the same or different and represent hydrogen, straight or branched chain lower alkyl having 1-6 carbon atoms, or phenylalkyl or pyridylalkyl where each alkyl is straight or branched chain alkyl having 1-6 carbon atoms;
R 2 and R 5 together may represent --(CH 2 ) n .sbsb.3 -- where n 3 is 2 or 3; or NR 4 R 5 represents 2-(1,2,3,4-tetrahydroisoquinolinyl), or 2-(1,2,3,4-tetrahydroiso-quinolinyl) mono or disubstituted with halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms; or ##STR33## where W is N or CH;
R 7 is hydrogen, phenyl, pyridyl or pyrimidinyl, hydrogen, phenyl, pyridyl or pyrimidinyl, each of which may be mono or disubstituted with halogen, hydroxy, straight or branched chain lower alkyl having 1-6 carbon atoms, or straight or branched chain lower alkoxy having 1-6 carbon atoms; or
W--R 7 is oxygen or sulfur; and
n is 1, 2, or 3.
The invention is illustrated further by the following examples which are not to be construed as limiting the invention in scope or spirit to the specific procedures and compounds described in them. ##STR34##
A mixture of 5-Bromo-o-anisaldehyde (6.45 g), hydroxylamine hydrochloride (2.2 g), sodium acetate (4.1 g) and acetic acid (20 mL) was heated at 100° C. with stirring for 1 h. Acetic anhydride was added (20 mL) and the mixture was refluxed for 8 h. The reaction mixture was poured onto ice water and the mixture was made basic by the careful addition of 50% sodium hydroxide. The product was extracted with ether, the ether extracts were dried over magnesium sulfate and the sovent was removed in vacuo. The residue was crystallized from ether/hexane to afford 5-Bromo-2-methoxy-benzonitrile.
EXAMPLE II ##STR35##
A mixture of 5-Bromo-2-methoxy-benzonitrile (4.0 g), 3A molecular selves (5 g) and anhydrous methanol (60 mL) was saturated with HCl gas at room temperature and allowed to stand at room temperature for 24 h. The solvent was removed in vacuo and the residue taken up in 75 mL of anhydrous methanol and saturated with ammonia gas at room temperature. The reaction mixture was then heated at 80° C. for 4 h in a sealed tube. The sovent was removed in vacuo, the reaction mixture was diluted with 3N HCl and washed with ethyl acetate to remove unreacted nitrile. The aqueous layer was made basic with 50% NaOH and the product was extracted three times with 10% methanol in methylene chloride. The combined organic extracts were dried over magnesium sulfate and the sovents removed in vacuo to afford 5-Bromo-2-methoxy-benzamidine as a glassy solid. ##STR36##
To a solution of 1,1,1,3,3,3-hexamethyldisilazane (20 g) in dry ether (150 mL) was added 2.4M n-butyllithium in hexane (5 mL). After 10 min at room temperature, 2,3-Dimethoxybenzonitrile (16.3 g) was added in one portion and the mixture was kept at room temperature for 16 h. The reaction mixture was the poured onto excess 3N HCl. The aqueous layer was separated, basified with 50% NaOH and the product was exuacted three times with 10% methanol in methylene chloride. The combined organic extracts were dried over magnesium sulfate and the solvents removed in vacuo to afford 2,3-Dimethoxy-benzamidine as a glassy solid.
EXAMPLE IV ##STR37##
A mixture of 5-Bromo-2-methoxy-benzamidine (1.5 g), 1,3-dihydroxy-acetone dimer (1.0 g), ammonium chloride (1.3 g), tetrahydrofuran (3 mL) and concentrated aqueous ammonium hydroxide (10 mL) was heated at 90° C. for 3 h. The reaction mixture was chilled on ice and the precipitated product was collected and recrystallized from methanol to afford 2-(5-Bromo-2-methoxyphenyl)-5-hydroxymethyl-imidazole as a yellow solid.
EXAMPLE V ##STR38##
A mixture of 2-(5-Bromo-2-methoxyphenyl)-5-hydroxymethyl-imidazole (500 mg) and thionyl chloride (1.5 mL) was heated at 80° C. for 1 h. Ether (15 mL) was added and the resulting solid was collected and washed with ether. This solid was added in one portion to a mixture of dimethylamine (3 mL), isopropanol (15 mL) and methylene chloride (30 mL) and the mixture was stirred for 20 min. The solvents were removed in vacuo and the residue was dissolved in 2N HCl and washed two times with ethyl acetate. The aqueous layer was made basic with 50% NaOH and the product was extracted with methylene chloride. The organic extracts were dried over magnesium sulfate, the solvents removed in vacuo, and the residue was treated with ethanolic HCl/ether to afford 2-(5-Bromo-2-methoxyphenyl)-4(5)- (N,N-dimethyl)-aminomethyl!-imidazole dihydrochloride (Compound 1), m.p. 242°-243° C.
EXAMPLE VI
The following compounds were prepared essentially according to the procedure described in Examples I-V:
(a) 2-Phenyl-4(5)- (N,N-dimethyl)aminomethyl!-imidazole dihydrochloride (Compound 2), m.p. 259°-260° C.
(b) 2-Phenyl-4(5)-(piperidinomethyl)-imidazole dihydrochloride (Compound 3), m.p. 245°-247° C.
(c) 2-Phenyl-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 4), m.p. 239°-240° C.
(d) 2-(2-Methoxyphenyl)-4(5)- (N,N-dimethyl)aminomethyl!-imidazole dihydrochloride (Compound 5) melting at °C.
(e) 2-(3-Methoxyphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 6), m.p. 115°-117° C.
(f) 2-(2,3-Dimethoxyphenyl)-4(5)- (N,N-dimethyl)aminomethyl!-imidazole dihydrochioride (Compound 7), m.p. 220°-221 ° C.
(g) 2-(2,3-Dimethoxyphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 8), m.p. 200°-202° C.
(h) 2-(3-Methoxyphenyl)-4(5)- (N,N-diethyl)aminomethyl!-imidazole dihydrochloride (Compound 9), m.p. 213°-214° C.
(i) 2-(3-Fluorophenyl)-4(5)- (N,N-dimethyl)aminomethyl!-imidazole dihydrochloride (Compound 10), m.p. 211°-214° C.
(j) 2-(2-Fluorophenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 11), m.p. 241°-244° C.
(k) 2-(3-Methylphenyl)-4(5)- (N,N-dimethyl)aminomethyl!-imidazole dihydrochloride (Compound 12), m.p. 231°-234° C.
(l) 2-(2-Fluorophenyl)-4(5)- (N,N-dimethyl)aminomethyl!-imidazole dihydrochloride (Compound 13), m.p. 246°-247° C.
(m) 2-(4-Fluorophenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 14), m.p. 237°-239° C.
(n) 2-(2-Methoxyphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 15), m.p. 239°-241° C.
(o) 2-(5-Bromo-2,3-dimethoxyphenyl)-4(5)- (N,N-dimethyl)aminomethyl!-imidazole dihydrochloride (Compound 16), m.p. 194°-194° C.
(p) 2-(5-Bromo-2-methoxyphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 17), m.p. 242°-243°-° C.
(q) 2-(5-Bromo-2,3-dimethoxyphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 18).
EXAMPLE VII ##STR39##
A mixture of 2-Phenyl-5-hydroxymethyl-imidazole (350 mg) and thionyl chloride (1 mL) was heated at 80° C. for 1 h. The excess thionyl chloride was removed in vacuo and the residue was dissolved in 20 mL of methylene chloride. This solution was added to a mixture of triethylamine (1 mL) and 1-(2-methoxyphenyl)-piperazine (410 mg) in methylene chloride (20 mL) and the mixture was stirred for 20 min. The solvents were removed in vacuo and the residue was dissolved in 2N HCl and washed two times with ethyl acetate. The aqueous layer was made basic with 50% NaOH and the product was extracted with methylene chloride. The organic extracts were dried over magnesium sulfate, the solvents removed in vacuo, and the residue was crystallized from ethyl acetate to afford 2-Phenyl-4(5)- (4-(2-methoxyphenyl)-piperazin-1-yl)-methyl!-imidazole (Compound 19), m.p. 105°-107° C.
EXAMPLE VIII
The following compounds were prepared essentially according to the procedure described in Example VII:
(a) 2-(4-Fluorophenyl)-4(5)- (4-(2-methoxyphenyl)-piperazin-1-yl)-methyl!-imidazole (Compound 20), m.p. 95°-97° C.
(b) 2-(2,3-Dimethoxyphenyl)-4(5)- (4-(2-methoxyphenyl)-piperazin-1-yl)-methyl!-imidazole dihydrochloride (Compound 21), m.p. 217°-218° C.
(c) 2-(3-Chlorophenyl)-4(5)- (4-(2-methoxyphenyl)-piperazin-1-yl)-methyl!-imidazole dihydrochloride (Compound 22), m.p. 198°-199° C.
(d) 2-Phenyl-4(5)- (4-(2-pyrimidinyl)-piperazin-1-yl)-methyl!-imidazole dihydrochloride (Compound 23), m.p. 246°-248° C.
(e) 2-Phenyl-4(5)- (4-(2-pyridyl)-piperazin-1-yl)-methyl!-imidazole dihydrochloride (Compound 24), m.p. 176°-177° C.
(f) 2-Phenyl-4(5)- (4-benzyl-piperidin-1-yl)-methyl!-imidazole dihydrochloride (Compound 25), m.p. 234°-236° C.
(g) 2-Phenyl-4(5)- (4-phenyl-piperidin-1-yl)-methyl!-imidazole dihydrochloride (Compound 26), m.p. 238°-240° C.
(h) 2-Phenyl-4(5)- (1,2,3,4-tetrahydroisoquinolin)-2-yl-methyl!-imidazole dihydrochloride (Compound 27).
EXAMPLE IX
The following compounds were prepared essentially according to the procedures described in Examples I-VII:
(a) 2-(2,3-Dimethoxyphenyl)-4(5)- (1,2,3,4-tetrahydroisoquinolin)-2-yl-methyl!-imidazole dihydrochloride (Compound 28), m.p. 205°-207° C.
(b) 2-(4-Methoxyphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 29).
(c) 2-(3,4-Dimethoxyphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 30).
(d) 2-(3-Methoxyphenyl)-4(5)- (N-methyl)aminomethyl!-imidazole dihydrochloride (Compound 31).
(e) 2-(5-Chloro-2-methoxyphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole (Compound 32), m.p. 88°-89° C.
(f) 2-(5-Chloro-2-methoxyphenyl)-4(5)- (N,N-dimethyl)aminomethyl!-imidazole dihydrochloride (Compound 33), m.p. 231°-233° C.
(g) 2-(5-Chloro-2-methoxyphenyl)-4(5)- (N-methyl)aminomethyl!-imidazole dihydrochloride (Compound 34), m.p. 225°-227° C.
(h) 2-(5-Chloro-2-methoxyphenyl)-4(5)- (N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 35), m.p. 184°-186° C.
(i) 2-(5-Chloro-2-benzyloxyphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 36), m.p. 118°-123° C.
(j) 2-(2-Benzyloxyphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 37), m.p. 199°-200° C.
(l) 2-(3-Ethylphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 38), m.p. 234°-235° C.
(m) 2-(5-Chloro-2-methoxyphenyl)-4(5)- (N-methyl-N-(-4-chlorobenzyl))aminomethyl!-imidazole dihydrochloride (Compound 39), m.p. 186°-188° C.
(n) 2-(5-Chloro-2-hydroxyphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 40), m.p. 227°-228° C.
(o) 2-(5-Bromo-2-benzyloxyphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 41).
(p) 2-(5-Ethyl-2-methoxyphenyl)-4(5)- (N-methyl-N-benzyl)aminomethyl!-imidazole dihydrochloride (Compound 42), m.p. 114°-115° C.
(q) 2-(5-Chloro-2-methoxyphenyl)-4(5)- (4-(2-methoxyphenyl)-piperazin-1-yl)-methyl!-imidazole dihydrochloride (Compound 43) melting at 138°-143° C.
(r) 2-(5-Chloro-2-methoxyphenyl)-4(5)- (4-phenyl-piperidin-1-yl)-methyl!-imidazole dihydrochloride (Compound 44), m.p. 138°-143° C.
(s) 2-(2,3-Dimethoxyphenyl)-4(5)- (4-(2-methoxyphenyl)-piperidin-1-yl)-methyl!-imidazole dihydrochloride (Compound 45).
(t) 2-phenyl-4(5)- (4-(2-pyridyl)-piperidin-1-yl)-methyl!-imidazole dihydrochloride (Compound 46).
(u) 2-phenyl-4(5)- (4-phenyl-piperazin-1-yl)-methyl!-imidazole dihydrochloride (Compound 47).
EXAMPLE X ##STR40##
2-Phenyl-4(5)-hydroxymethylimidazole (300 g, 0.17 mmol) was dissolved in 5 mL of thionyl chloride and the mixture was briefly heated to reflux. After concentration on a rotary evaporator, chloroform was added and the resulting solution reconcentrated. The residue was dissolved in 5 mL of chloroform and 335 mg of 1-(5-methoxy-2-pyrimidinyl)piperazine (prepared essentially according to the procedure described in J. Chem. Soc., 4590, 1960) and 2 mL of triethylamine were added. After 20 min., the reaction mixture was washed with 1N NaOH solution, dried and concentrated. The resulting material was taken up in a solution of 2 equivalents of maleic acid in 2 mL of isopropanol after which 3 mL of isopropanol was added. Filtration of the resulting solid provided 870 mg of 2-phenyl-4(5)- 4((2-{50-methoxypyrimidinyl})piperazinyl-1)methyl!imidazole dimaleate (86%).
EXAMPLE XI ##STR41##
2-Phenyl-4(5)-hydroxymethylimidazole (200 g) was dissolved in 5 mL of thionyl chloride and the mixture was briefly heated to reflux. After concentration on a rotary evaporator, chloroform was added and the resulting solution reconcentrated. The residue was dissolved in 5 mL of chloroform and 210 mg of 1-(5-fluoro-2-pyrimidinyl)piperazine (prepared essentially according to the procedure described in Chem. Pharm. Bull., 39:2298, 1991) and 1 mL of triethylamine were added. After 20 min., the reaction mixture was washed with 1N NaOH solution, dried and concentrated. Silica chromatography, eluting with 10% methanol in chloroform, provided 175 mg of 2-phenyl-4(5)- 4-((2-{5-fluoropyrimidinyl})piperazin-1-yl)methyl!imidazole. The dimaleate salt was crystallized from isopropyl alcohol (m.p. 185°-186° C.).
EXAMPLE XII ##STR42##
To a solution of 2-phenyl-4(5)- 4-((2-{methoxypyrimidinyl})piperazin-1-yl)methyl!imidazole (Example X) (0.37 g) in dry chloroform (8 mL) was added boron tribromide solution 11.5 mL of 1.0N BBr 3 in methylene chloride). The resulting mixture was refluxed for 4 hours, poured onto ice and ammonium hydroxide and extracted with chloroform. The organic extracts were dried (Na 2 SO 4 ) and concentrated. The product was purified by preparative thin layer chromatography eluting with 10% methanol in chloroform to provide 75 mg of 2-phenyl-4(5)- 4-((2-{hydroxypyrimidinyl})piperazin-1-yl)methyl!imidazole. The dioxalate salt was prepared in ethyl alcohol (m.p. 214°-216° C.).
EXAMPLE XIII
The receptor binding activity of Compounds 23, 24, and 47 was determined for the D2 and D3 receptors essentially as described above. Receptor binding activity of Compounds 23, 24, and 47 for the D4 receptor was determined according to the following assay. This receptor binding activity is shown below in Table II.
Clonal cell lines expressing the human dopamine D4 receptor subtype were harvested in PBS and the cells centrifuged and the pellets stored at -80° C. until used in the binding assay. The pellets were resuspended and the cells lysed at 4° C. in 50 mM Tris pH 7.4 buffer containing 120 mM NaCl, 1 mM EDTA and 5 mM MgCl 2 . The homogenate is centrifuged at 48000×g for 10 minutes at 4° C. The resulting pellet is resuspended in fresh buffer and centfifuged again. After resuspension of the pellet in fresh buffer at 100 ml aliquot is removed for protein determination. The remaining homogenate is centrifuged as above, the supernatant removed and the pellet stored at 4° C. until needed at which time it is resuspended to a final concentration of 625 mg/ml (250 mg per sample) with 50 mM Tris buffer (pH 7.4) and 120 mM NaCl just prior to use. Incubations were carried out for 60 minutes at 25° C. in the presence of 0.1 nM 3 H! YM-09151-2. The incubation was terminated by rapid filtration through Whatman GF/C filters and rinsed with 2×4 ml washes of chilled 50 mM Tris (pH 7.4) and 120 mM NaCl. Non-specific binding was determined with 1 mM spiperone and radioactivity determined by counting in an LKB beta counter. Binding parameters were determined by non-linear least squares regression analysis, from which the inhibition constant (Ki) could be calculated for each test compound. In general, compounds of the accompanying examples were tested in the above assay, and all were found to possess a Ki value for the displacement of 3 H!YM-09151-2 from the human dopamine D4 receptor subtype of below 500 nM.
TABLE II______________________________________Receptor Binding Activity (Ki, nM) Dopamine ReceptorCompound No. D2 D3 D4______________________________________47 239 169 523 1033 8200 2.724 1029 123 0.85______________________________________
EXAMPLE XIV
SUMMARY
The effects of 2-phenyl-4(5)- (4-(2-pyrimidyl)-piperazin-1-yl)methyl!-imidazole dihydrochloride (Compound 23) and clozapine were evaluated in the following models of learning and memory: a step-down passive avoidance task assay and a modified Morris water maze assay Separate groups of male Sprague Dawley rats were pretreated with either Compound 23 or clozapine prior to training in these tasks. The control compound, clozapine, produced an acquisition deficit in the passive avoidance task at the two highest doses tested (1.0, 2.0 mg/kg) but produced no significant deficits in retention. Clozapine produced no deficits in the water maze task at the doses tested. In the step-down passive avoidance assay animals that received the 0.25 mg/kg dose of Compound 23 showed significant improvement in memory compared to the vehicle group. Likewise in the modified Morris water maze, animals that received the 0.03, 0.25 and the 1.0 mg/kg dose of Compound 23 showed significant improvement in task retention compared to the vehicle group. These data show that Compound 23 does not impair learning, but enhances learning in animals.
Method
Non-naive male Sprague Dawley rats (SASCO St. Louis) weighing between 2000-300 grams, were housed in groups of three in a temperature and humidity controlled vivarium having a 12 hour light/dark cycle. Animals had ad lib access to food and water.
Compound 23 was dissolved in 50% Polyethylene glycol (PEG) and administered in a dose range of 0.03-1.0 mg/kg. Clozapine was dissolved in 50% PEG and administered in a dose range of from 0.25 to 2 mg/kg. Both drugs were administered intravenously 5 minutes prior to training in both learning tasks
Apparatus:
Step-Down Passive Avoidance:
A step-down passive avoidance platform 4 (cm)×7 (cm) was placed in the center of an electrified gris floor, which was contained within a large (45×45×50 cm) white translucent plexiglas enclosure having a closable lid. The bars of the grip were spaced 1.5 cm apart and were wired to a BRS-LVE shock generator/scrambler which was set to deliver a 2 mA 6 second shock. Four passive avoidance boxes were automated by customer software (Labview) and commercial interface modules (National Instruments) connected to a computer The timing and delivery of the shock as well as the latency to step down and the number of trials taken to reach criterion during training was under the control of the computer. All testing was done in the presence of 62 db white noise.
Modified Morris Water Maze:
A water maze apparatus consisted of a circular tank (120 cm in diameter and 56 cm in height) having a black interior. The tank was surrounded by external visual cues which consisted of a black and white checkered wall, a black and white striped wall, a while wall and a blue panel. The tank was filled with water (18°-20° C.) to a height of 52 cm and was divided into four quadrants (North, South, East and West). A black circular plexiglas platform (with black rubber top) was placed in the northeast quadrant approximately 1 cm below the surface of the water. The submerged platform was 51 cm in height and had a diameter of 9 cm. Training and testing was conducted in the presence of a 62 db white noise source and under dim light conditions.
Procedure:
1. Passive Avoidance:
Acquisition Training:
After pretreatment with clozapine, Compound 23 or control (vehicle), the animal was placed on the platform which automatically started a timer. When the animal stepped off the platform it automatically received the footshock. Following each shock the animal was removed from the box and placed in its cage for a one minute intertrial interval and then returned to the platform. Training was terminated when the animal remained on the platform for 120 Seconds. Immediately after training the animal was returned to its home cage in a vivarium.
Retention Testing:
Testing was conducted approximately 24 hours after training, Drug-free animals were placed on the platform in the box in which they were trained and the latency to step down onto the unshocked floor was recorded for one trial. The animal was allowed a maximum of 120 seconds to step down.
2. Modified Morris Water Maze:
Acquisition Training:
Acquisition training in this task assay consisted of either four or six training trials. The four trial procedure detects cognitive enhancing effects of drugs while the six trial procedure detects drugs that produce learning deficits in this task assay Compound 23 was tested in the water maze using a four trial procedure and clozapine using a six trial training procedure. Each animal was placed on the platform in the tank for 20 trials separated by an intertrial interval of 2 minutes. The starting position was pseudo-randomly varied but was the same order for each animal. During the ITI (intertrial interval) the animal was dried off and placed near a heat source (heat lamp). The latency to reach the submeged platform on each trial was measured and animals were allowed to remain on the platform for 10 seconds once they reach it. Since the platform was submerged just below the surface of the water, the animal was required to use the external visual cues surrounding the tank (distal cues) to locate the platform.
Retention Training:
On the following day, each animal was individually tested for retention in one trial. All animals were placed in the "SOUTH" starting position and latency to find the submerged platform was recorded.
Results
Passive Avoidance:
There were no significant differences for acquisition between the vehicle group and animals treated with Compound 23. Animals that received 0.25 mg/kg dose of Compound 23 remained on the platform for a significantly longer time during retest than the vehicle animals. Animals that received the 1.0 mg/kg and 2.0 mg/kg doses of clozapine showed a significant deficit in acquisition compared to the vehicle group. There were no significant differences in retention between clozapine treated animals and the vehicle group.
Water Maze:
The difference between the first trial and the retest trial (latency to locate the platform on the following day) revealed significant improvement in retention relative to controls at the 0.03 mg/kd, 0.25 mg/kg and the 1.0 mg/kg dose of Compound 23. However, the difference between the scores of trial 1 and the retest trial for animals that received clozapine revealed no significant differences.
These results indicate that compound 23 improved memory in mammals. These results further show that compound 23 also enhances learning in mammals. Thus, the compounds of the invention are useful for enhancing cognition in mammals and can be used in methods for enhancing cognition, specifically learning and memory, in mammals.
The invention and the manner and process of making and using it, are now described in such full, clear, concise and exact terms as to enable any person skilled in the art to which it pertains, to make and use the same. It is to be understood that the foregoing describes preferred embodiments of the present invention and that modifications may be made therein without departing from the spirit or scope of the present invention as set forth in the claims. To particularly point out and distinctly claim the subject matter regarded as invention, the following claims conclude this specification. | This invention encompasses compounds of the formulas: ##STR1## where R 1 R 3 , R 4 , R 6 , X, Y, and Z are T are variables; and
M is ##STR2## where R 2 is a variable; or R 1 and R 2 together may represent --(CH 2 ) n .sbsb.1 where n .sbsb.1 is 1, 2, or 3.
These compounds are highly selective partial agonists or antagonists at brain dopamine receptor subtypes or prodrugs thereof and are useful in the diagnosis and treatment of affective disorders such as schizophrenia and depression as well as certain movement disorders such as Parkinsonism. Furthermore compounds of this invention may be useful in treating the extrapyramidal side effects asssociated with the use of conventional neuroleptic agents. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No. 60/712,777 filed on Aug. 31, 2005, entitled “Electrical Box For Concrete Walls”.
FIELD OF THE INVENTION
[0002] The present invention relates generally to an electrical outlet box for housing electrical fixtures such as a switch or a receptacle. More particularly, the present invention relates to an improved electrical outlet box for use on concrete wall.
BACKGROUND OF THE INVENTION
[0003] It has long been known to house electrical fixtures such as switches and receptacles in an electrical outlet box. The outlet box permits the insertion of electrical wires into the box which are terminated to electrical fixtures. The fixtures then may be mounted to the box which provides protection to the fixtures as well as the wires terminated therein. The outlet box is then mounted to a wall at a convenient location to provide access. Most outlet boxes accommodate one or more electrical fixtures, which terminate standard 110 volt electrical wires.
[0004] Outlet boxes are available in a variety of configurations and sizes. The selection of which type of box to use is dependant upon the specifics of the application. The most commonly employed box is a single-gang outlet box, also referred to as a standard outlet box. The single-gang box is ideal for applications in which only one receptacle is required for the application. Standard outlet boxes have opening dimensions of approximately 3″×2¼″ and are available in a variety of depths. Double-gang and triple-gang boxes are also available, and they typically have the capacity to hold two and three receptacles respectively. A four inch (4″) square box is also commonly employed for multiple receptacle applications.
[0005] Typically, outlet boxes are mounted by affixing mounting ears to a wall stud or other structural member. However, for some applications, such as exterior uses, there is a requirement to install electrical boxes on poured concrete walls, wherein the outlet box, may be mounted within a concrete structure. This is accomplished by attaching the box to a form in the desired location. The form is usually a wooden temporary structure used to contain the poured concrete in the desired shape that is removed after the concrete has hardened. The outlet box remains in the concrete after removal of the form.
[0006] It is necessary when using an electrical box in such an application to insure that it is securely affixed to the form to resist being displaced during the concrete pour. Presently, electrical boxes used by many contractors for installation in concrete walls are not well adapted for use in concrete wall. Specifically, the prior art boxes lack features thereby making them difficult to use in concrete wall applications, or result in additional work for the contractor. For example, many prior art boxes lack ears or other suitable attachment means for firmly and securely attaching the electrical box to the wooden form prior to pouring the concrete. This can result in the contractor having to use less than suitable means to attach the box to the form which can result in a misplaced box, or one that moved during the concrete pour and subsequently became filled with concrete that the contractor must remove in order to utilize the box.
[0007] Therefore, it would be desirable to have an electrical box for use in concrete walls, incorporating features for securely mounting the electrical box to a form, such that it remains stable and firmly attached to the form during the concrete pouring process. Additionally, it is desirable that the electrical box used in a concrete wall prevent infiltration of concrete into the interior of the box during the concrete pouring process, thereby preventing the box from becoming filled with concrete and thus unusable. It is further desirable that the electrical box can be easily modified to extend the open front perimeter of the box after the concrete is poured and hardened such that the perimeter will be flush with the finished wall surface to conform to electrical code requirements.
SUMMARY OF THE INVENTION
[0008] Applicant has overcome the shortcomings of prior art outlet box with the present invention by incorporating features for securely attaching the electrical box to a concrete form and further includes a built in extension device that can be pulled out from the front of the box to increase the depth of the box, once it is set in place without the need for attaching a separate extension.
[0009] The present invention therefore provides an electrical outlet box for accommodating an electrical fixture comprising a generally rectangular box having a back wall, a perimetrical side wall surrounding said back wall defining an open front face and a box interior, said side wall comprised of a first and second set of generally parallel spaced apart wall portions; and a slidable extension nested within said generally rectangular box, that can be moved from within the generally rectangular box to an extended position beyond the open front face.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a perspective view of the electrical box according to the present invention, with the slide extension in a retracted position.
[0011] FIG. 2 is a perspective view of the electrical box according to the present invention, with the slide extension in an extended position.
[0012] FIG. 3 is a cross sectional view of a typical installation of the electrical box of the current invention with the concrete forms in place along section 3 - 3 of FIG. 1 .
[0013] FIG. 4 is a cross sectional view of a typical installation of the electrical box of the current invention with the concrete forms removed along section 3 - 3 of FIG. 1 .
[0014] FIG. 5 is a cross sectional view of a typical installation of the electrical box of the current invention with a finish surface installed over the concrete along section 5 - 5 of FIG. 2 .
[0015] FIG. 6 is a top cross sectional view of the electrical box according to the present invention, with the slide extension in a retracted position along section 6 - 6 of FIG. 1 .
[0016] FIG. 7 is a top cross sectional view of the electrical box according to the present invention, with the slide extension in an extended position along section 7 - 7 of FIG. 2 .
[0017] FIG. 8 is a perspective view of the interior of the electrical box according to the present invention.
[0018] FIGS. 9A and 9B are close-up side and top views respectively of a component part of the electrical box according to the present invention.
[0019] FIG. 10 is a cross sectional perspective view of an alternate embodiment of the electrical box of the current invention, with the slide extension in a retracted position along section 6 - 6 of FIG. 1 .
[0020] FIG. 11 is a cross sectional perspective view of an alternate embodiment of the electrical box of the current invention, with the slide extension in an extended position along section 7 - 7 of FIG. 2 .
[0021] FIG. 12 is a perspective cross sectional view of the electrical box according to the present invention, with the slide extension in a retracted position along section 6 - 6 of FIG. 1 .
[0022] FIG. 13 is a perspective cross sectional view of the electrical box according to the present invention, with the slide extension in an extended position along section 7 - 7 of FIG. 2 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0023] There will be detailed below the preferred embodiments of the present invention with reference to the accompanying drawings. Like members are designated by like reference characters in all figures.
[0024] Turning now to FIG. 1 , there is shown an embodiment of the outlet box of the present invention. It should be noted that the present invention is shown and described with respect to a single gang outlet box, however the invention can be adapted to multiple gang boxes such as for example a double or triple gang box. The single gang embodiment shown and described, is exemplary and not meant to be limiting to single gang version.
[0025] There is shown an outlet box 100 which is generally a rectangular member having a back wall 102 , a pair of spaced apart side walls 104 extending from back wall 102 , and opposed top and bottom walls 106 and 108 . Back wall 102 , side walls 104 and top and bottom walls 106 and 108 form a box interior 110 having an open front face 112 which accommodates therein an electrical fixture. Open front face 112 has a dimension substantially equivalent to the opening of a single-gang outlet box. The interior length and width of the opening will vary depending on if receptacle mounting flanges disposed on the box are interior or exterior to the box opening. However, the outlet box depicted here is illustrative and not intended to be limiting. It will be appreciated that it would be apparent to have an outlet box according to the present invention having alternate dimensions according to the application of such outlet box. Also visible in the interior of electrical box 100 is slideable extension 113 . The extension 113 is shown in the retracted position within the box. As will be further shown and described with respect to FIG. 6 , in the retracted position, the extension is held in place by protrusion 115 cooperatively engaging cavity 111 . When the extension is pulled outside the box 100 , the protrusion 115 snaps into a cavity 117 in side wall 104 and cooperatively engages the cavity 117 to lock the extension in place. Box 100 is provided with at least two cavities 111 for the retracted position and cavities 117 for the extended position on opposite side walls 104 which engage a similar number of protrusions 115 on extension 113 .
[0026] As is well known in the art, outlet box 100 may include one or more access openings, typically known as knockouts 114 which permit entry of electrical wires and cables (not shown) into box interior 110 . In addition, knockouts 114 include secondary smaller knockouts 115 , centrally positioned on knockout 114 . Knockout 127 is oval in shape and adapted to receive the blade of a straight blade screwdriver. Knockout 127 seals electrical box 100 against the infiltration of concrete during the pour. In use the installer of electrical box 100 would first remove knockout 127 with a straight blade screw driver, then insert the blade into the opening resulting from the removal of knockout 127 and pry out knockout 114 .
[0027] The exterior surfaces of side walls 104 include nails 116 and 118 respectively which allow the box to be secured to a concrete form or the like by driving the nails into the form prior to the concrete being poured. The nails 116 and 118 are attached to the box 100 by collars 119 , which permit the nails to slide with respect to the box 100 . Therefore, the nails can be hammered forward into a form as the open front face 112 is pressed against a form. In addition, each nail 116 , 118 is scored or notched 121 to create a stress raiser. The stress raiser is used to facilitate breaking the nail 116 , 118 after the form has been removed and the electrical box 100 set in concrete. The score mark 121 is positioned along the nail's length such that it aligns with the open front face 112 when the nail is fully extended into the form. In that way, when the form is removed, the score mark is even with the cured concrete and can be broken off flush with the concrete wall. The interior surfaces of extension 113 include component retaining flanges 120 and 122 which include threaded apertures 124 for receiving fasteners, usually screws, to securely mount electrical components within the outlet box. In addition, flange 125 is provided, extending from back wall 102 beyond bottom wall 108 and top wall 106 (not visible in this view). Flange 125 provides an additional anchor point for the electrical box 100 to mechanically be affixed to the concrete.
[0028] Turning now to FIG. 2 , there is shown the electrical box 100 according to the present invention wherein extension 113 is shown in the extended position. In the extended position, the extension 113 , protrudes beyond open front face 112 . By extending the extension 113 , the protrusion 115 comes into cooperative alignment with cavity 117 . The protrusion 115 then snaps into cavity 117 in side wall 104 and locks the extension 113 in place.
[0029] Turning now to FIG. 3 , there is shown a cross sectional view of the electrical box along section 3 - 3 , according to the present invention showing a typical installation of an outlet box 100 in a concrete wall application. FIG. 3 shows a side view of the electrical box 100 encased within forms 302 and 304 . The front form 302 and rear form 304 are used to retain poured concrete 306 to construct a vertical wall. As is well known, such forms may be constructed of wood stud, planks or sheets such as plywood. Electrical box 100 is fastened to front form 302 . The outlet box 100 must be securely fastened to the form when the concrete 306 is poured. The electrical box 100 is nailed to the form by driving the nails 116 , 118 through apertures provided on exterior collars 119 of electrical box into the form. Secure attachment of the box 100 to the form 302 maintains the box 100 in proper position during the concrete pour.
[0030] Also shown in FIG. 3 is a ground screw 308 , which is positioned at the rear of the electrical box 100 along back wall 102 for attaching a ground connection to an electrical device installed in electrical box 100 . Also visible in the side view are nails 116 which pass through collar 119 . A wire is inserted into the electrical box 100 through knockout holes 114 , which would be fitted with a connector (not shown). The wire would typically be inserted through a conduit (not shown) which would be fastened to the connector. The wires can be installed before or after the concrete is poured. It should be noted that the wire can be routed into the electrical box through knockout holes 114 positioned on any wall of the electrical box, such as for example side wall 104 or back wall 102 . In another embodiment, wires could also be affixed within electrical box 100 by way of a locking clamp (not shown) for firmly affixing the wire such as, for example Romex cable. The locking clamp would typically include a screw which is tightened to clamp the wire in place and prevent it from being pulled out during the construction process. The side view of FIG. 3 further shows extension 113 in a retracted position. Furthermore, as can be seen the extension 113 has a semicircular cutout 314 which corresponds to the position of the knockout hole 114 . In that way, when the extension is in the retracted position as shown in FIG. 3 , it does not interfere with the use of the knockout hole 114 . Also seen in the side cross sectional view are protrusion 115 snaps of extension 113 and cavity 117 in side wall 104 . In this view can be seen that when extension 113 is in the retracted position, protrusion 115 and cavity 117 are not cooperatively engaged, but are aligned such that the translational movement of extension 113 will bring protrusion 115 into cooperative engagement with cavity 117 to lock the extension 113 in place. Nails 116 and 118 are shown in an extended position, protruding through form 302 , and thereby holding electrical box 100 flush against the form 302 , such that when the form in removed, the box interior is accessible to the contractor to access wires and install electrical components.
[0031] Turning now to FIG. 4 , there is shown the electrical box 100 according to the present invention in a typical installation wherein the concrete has hardened, and the forms are removed. In this view the concrete wall front 402 and rear 404 surface are exposed. Removal of the forms also exposes the front of outlet box, as well as nails 116 and 118 used to affix the electrical box to front form 302 . The removal of the forms exposes the shank and point of the nails 116 and 118 . In accordance with the present invention, as will be explained further with reference to the FIG. 9 , the shank of fastener nails 116 and 118 which extends beyond concrete front wall 402 can be removed by grasping the extended shank and forcibly bending the shank from side to side, thereby causing the shank to break at the stress raiser score mark or notch 121 .
[0032] Turning now to FIG. 5 , there is shown a cross sectional view along section 5 - 5 of the electrical box 100 according to the present invention in a typical installation wherein the wall finishing material 502 , such as for example sheetrock has been installed on wall front 402 . In this view extension 113 is shown in the extended position, wherein protrusion 115 of extension 113 and cavity 117 in sidewall 104 are in cooperative engagement, thereby locking the extension 113 in place. To extend the electrical box according to the current invention, the contractor need only pull extension 113 out from the electrical box 100 and snap it in place by aligning the protrusion 115 with cavity 117 . This process is easier and less time consuming than prior art methods, which require an extension piece to be affixed to the front of the electrical box usually by screwing the extension onto the electrical box. In the extended position, it can be seen that electrical box 100 flanges 120 and 122 are aligned with the outside plane 504 of wall finishing material 502 . Furthermore, it can be seen that extension 113 extends electrical box 100 to fully cover the gap from the front open front face 112 to the outside plane 504 of finishing material 502 in conformance with electrical code requirements.
[0033] Turning now to FIG. 6 , there is shown top cross sectional view of electrical box 100 along section 6 - 6 of FIG. 1 . In this view, extension 113 is shown in the retracted position, wherein protrusion 115 is visible extending from extension side wall 602 , and into cavity 111 in electrical box sidewall 104 . Protrusion 115 is formed of a resilient tab that angles slightly away from the plane of extension sidewall 602 and is biased to exert a force toward sidewall 104 . In the retracted position, the extension is held in place by protrusion 115 cooperatively engaging cavity 111 .
[0034] Cavity 117 is visible in sidewall 104 , located toward open from face 112 with respect to protrusion 115 . The cavity 117 corresponds in size to protrusion 115 such that when the translational movement of extension 113 moves protrusion 115 into alignment with cavity 117 , the resilient tab moves outward into cavity 117 thereby locking extension 113 in the extended position. In addition, the wall 606 of cavity 111 is angled to provide a ramp for protrusion 115 to disengage from cavity 111 when the installer exerts a force on extension 113 to pull the extension out from electrical box 100 . In this way the force required to pull out the extension is minimized, while still securely locking the extension in the retracted position prior to use.
[0035] Turning now to FIG. 7 , there is shown top cross sectional view of electrical box 100 along section 7 - 7 of FIG. 2 . In this view, extension 113 is shown in the extended position, wherein protrusion 115 is visible extending from extension sidewall 602 , into cavity 117 thereby locking extension 113 in the extended position. As is depicted in FIGS. 6 and 7 , the distance 702 that extension 113 extends from open front face 112 corresponds to the positioning of protrusion 115 and cavity 117 . The placement of protrusion 115 can thus be modified to provide for a longer or shorter extension distance 702 . The closer to the inside edge 704 of extension 113 that protrusion is placed, the longer the distance 702 from open front face 112 of electrical box 100 to the extension front edge 706 . In this way, the electrical box 100 according to the present invention can be adapted to use for various thickness finishing material 502 . It is typical that sheetrock of ½″, ⅝″ or ¾″ is used in most applications, however other variations are possible. For example, the electrical box 100 according to the current invention can be adapted for use where sheetrock is overlaid with another material such as ceramic or stone tile. In this type of application, protrusions 115 will be located on extension sidewall 602 at a distance from inside edge 704 such that extension 113 extends to a distance corresponding to the depth of the finish material layers 502 .
[0036] Turning now to FIG. 8 , there is shown a front perspective view of the electrical box 100 according to the current invention. Shown in this view is the electrical box interior 110 . In this view, knockouts 114 are visible on the top 106 and bottom 108 of electrical box 100 . All knockouts on the box according to the present invention are design to withstand the conditions specific to the use of electrical boxes in a concrete wall. All knockouts 114 are punched to the outside of electrical box 100 , to prevent the knockout opening from the force of the poured concrete pressing against the outside of the electrical box during construction. Furthermore, as previously mentioned, knockouts 114 incorporate a smaller oval or oblong shaped knockout 127 located centrally within knockouts 114 . Knockouts 127 are punched to the inside of the box to facilitate its opening by the contractor, and are adapted to receive a flat head screw driver blade. The contractor installing an electrical box according to the current invention can therefore have a sealed electrical box that will prevent concrete from infiltrating into the box interior 110 . Once the contractor has removed knockout 127 the contractor can use the oblong hole obtained to pry open knockout 114 with a screw driver.
[0037] Also shown in FIG. 8 is tab 804 for mounting grounding screws 806 , located on back wall 102 . Tab 804 is comprised of a frangible slit 808 on back wall 102 . The tab 804 provides the contractor with additional room to secure the ground wire to the electrical box, once the concrete has been poured and hardened. In typical conditions it is difficult to screw the grounding screws in fully to where the head touches the bottom of the box because the screw cannot penetrate the hardened concrete outside the box. To eliminate that difficulty, tab 804 in the electrical box 100 according to the present invention can be bent forward by the user after the box is installed and the concrete hardened. In that way, there will be enough room behind the screws to fully screw in the grounding screws and affix the ground wires.
[0038] Turning to FIG. 9 there is a shown a close-up view of side view 9 A and top view 9 B of nails 116 and 118 used to secure electrical box 100 to a concrete form by driving the nails into the form prior to the concrete being poured. Each nail 116 , 118 is scored 121 to create stress raiser. In side view 9 A, the score 121 is shown as a “v” shaped cut extending partially through the shank of nails 116 and 118 and creates a stress raiser, which can be seen in FIG. 9B as a slit in the side of nails 116 and 118 . The stress raiser is used to facilitate breaking the nail after the form has been removed and the electrical box 100 set in concrete. To that end, the score mark 121 is positioned along the nails' length such that it corresponds to the open front face 112 when the nail is fully extended into the form. In that way, when the form is removed, the score mark is even with the cured concrete and can be broken off flush with the concrete wall.
[0039] Turning now to FIG. 10 , there is shown top cross sectional view of an alternate embodiment of electrical box 100 along section 6 - 6 of FIG. 1 . In this view, extension 113 is shown in the retracted position, wherein protrusion 115 is visible extending from extension side wall 602 , and bearing against electrical box sidewall 104 . Protrusion 115 is formed of a resilient tab that angles slightly away from the plane of extension sidewall 602 and is biased to exert a force against sidewall 104 . In the retracted position, the extension is held in place by the friction between protrusion 115 and sidewall 104 .
[0040] Cavity 117 is visible in sidewall 104 , located toward open from face 112 with respect to protrusion 115 . The cavity 117 corresponds in size to protrusion 115 such that when the translational movement of extension 113 moves protrusion 115 into alignment with cavity 117 , the resilient tab moves outward into cavity 117 thereby locking extension 113 in the extended position.
[0041] Turning now to FIG. 11 , there is shown top cross sectional view of electrical box 100 along section 7 - 7 of FIG. 2 . In this view, extension 113 is shown in the extended position, wherein protrusion 115 is visible extending from extension sidewall 602 , into cavity 117 thereby locking extension 113 in the extended position. As is depicted in FIGS. 6 and 7 , the distance 702 that extension 113 extends from open front face 112 corresponds to the positioning of protrusion 115 and cavity 117 . The placement of protrusion 115 can thus be modified to provide for a longer or shorter extension distance 702 . The closer to the inside edge 704 of extension 113 that protrusion is placed, the longer the distance 702 from open front face 112 of electrical box 100 to the extension front edge 706 . In this way, the electrical box 100 according to the present invention can be adapted to use for various thickness finishing material 502 . It is typical that sheetrock of ½″, ⅝″ or ¾″ is used in most applications, however other variations are possible. For example, the electrical box 100 according to the current invention can be adapted for use where sheetrock is overlaid with another material such as ceramic or stone tile. In this type of application, protrusions 115 will be located on extension sidewall 602 at a distance from inside edge 704 such that extension 113 extends to a distance corresponding to the depth of the finish material layers 502 .
[0042] Turning now to FIG. 12 , there is shown a perspective view of the electrical box 100 along section 6 - 6 of FIG. 1 . In this view, extension 113 is shown in the retracted position, wherein protrusion 115 is visible extending from extension side wall 602 , and into cavity 111 in electrical box sidewall 104 . Protrusion 115 is formed of a resilient tab that angles slightly away from the plane of extension sidewall 602 and is biased to exert a force toward sidewall 104 . In the retracted position, the extension is held in place by protrusion 115 cooperatively engaging cavity 111 .
[0043] Cavity 117 is visible in sidewall 104 , located toward open from face 112 with respect to protrusion 115 . The cavity 117 corresponds in size to protrusion 115 such that when the translational movement of extension 113 moves protrusion 115 into alignment with cavity 117 , the resilient tab moves outward into cavity 117 thereby locking extension 113 in the extended position. In addition, the wall 606 of cavity 111 is angled to provide a ramp for protrusion 115 to disengage from cavity 111 when the installer exerts a force on extension 113 to pull the extension out from electrical box 100 . In this way the force required to pull out the extension is minimized, while still securely locking the extension in the retracted position prior to use.
[0044] Turning now to FIG. 13 , there is shown a perspective cross sectional view of electrical box 100 along section 7 - 7 of FIG. 2 . In this view, extension 113 is shown in the extended position, wherein protrusion 115 is visible extending from extension sidewall 602 , into cavity 117 thereby locking extension 113 in the extended position. As is depicted in FIGS. 6 and 7 , the distance 702 that extension 113 extends from open front face 112 corresponds to the positioning of protrusion 115 and cavity 117 . The placement of protrusion 115 can thus be modified to provide for a longer or shorter extension distance 702 . The closer to the inside edge 704 of extension 113 that protrusion is placed, the longer the distance 702 from open front face 112 of electrical box 100 to the extension front edge 706 . In this way, the electrical box 100 according to the present invention can be adapted to use for various thickness finishing material 502 . It is typical that sheetrock of ½″, ⅝″ or ¾″ is used in most applications, however other variations are possible. For example, the electrical box 100 according to the current invention can be adapted for use where sheetrock is overlaid with another material such as ceramic or stone tile. In this type of application, protrusions 115 will be located on extension sidewall 602 at a distance from inside edge 704 such that extension 113 extends to a distance corresponding to the depth of the finish material layers 502 .
[0045] It will be appreciated that the present invention has been described herein with reference to certain preferred or exemplary embodiments. The preferred or exemplary embodiments described herein may be modified, changed, added to or deviated from without departing from the intent, spirit and scope of the present invention. It is intended that all such additions, modifications, amendments, and/or deviations be included within the scope of the claims appended hereto. | An electrical outlet box for accommodating an electrical fixture comprising a generally rectangular box having a back wall, a perimetrical side wall surrounding said back wall defining an open front face and a box interior, said side wall comprised of a first and second set of generally parallel spaced apart wall portions; and a slidable extension nested within said generally rectangular box, that can be moved from within the generally rectangular box to an extended position beyond the open front face. | 7 |
CROSS-REFERENCE TO RELATED APPLICATION
The subject matter disclosed hereinafter relates generally to the subject matter in copending application No. 07/321,420 now allowed.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method for frequency-shifting the modulus of the transfer function of a digital filter having a transversal structure and also relates to devices for carrying out said method.
Filters for the frequency of electric signals are employed in many fields of electronics and especially for processing radar signals, for example in order to eliminate fixed echoes or in order to detect echoes having predetermined characteristics such as a radial velocity. This mode of processing is employed, for example, in coherent Doppler radars having constant ambiguous velocity pulses which make it possible by virtue of the Doppler effect to detect the moving obstacles which give rise to radar signals of small amplitude in the midst of stationary obstacles corresponding to radar signals of large amplitude. In fact, in these pulse radars, the waves received after reflection from moving obstacles are affected by a phase which varies from one repetition period to the next whereas the waves received from the stationary obstacles are not subject to such a phase-shift variation. In consequence, the signals corresponding to moving obstacles have, after demodulation, components which vary sinusoidally at a frequency fd called the Doppler frequency which is related to the radial velocity v and to the wavelength e of the radar by the formula Fd=2v/e. The signals which correspond to stationary obstacles have a constant amplitude and their spectrum is constituted by a series of discrete lines at the frequencies 0, Fr, 2Fr, . . . nFr, Fr being the repetition frequency of the emitted pulses. Moreover, the spectrum of signals corresponding to moving obstacles is composed of discrete lines of the type mFr -+Fd.
As may accordingly be understood, it is possible to eliminate the signals corresponding to the stationary obstacles by employing a filter for removal of fixed echoes which does not permit transmission of signals having a frequency 0, Fr, 2Fr, . . . nFr. It is also desirable in certain radars such as air traffic surveillance radars to eliminate the moving obstacles which have low Doppler velocities with respect to the velocities of the echoes of interest such as clouds, for example, or else fluctuating stationary obstacles which have a certain Doppler velocity such as trees shaken by the wind. These different low-velocity parasitic echoes are better known as "clutter".
These examples show that it would be an advantage to provide in the radar field filters having a function of transfer along the axis of frequencies which could be easily and simply modified so as to eliminate not only the fixed or pseudo-fixed echoes but also those whose radial velocity is very different from that of the targets of interest.
2. Description of the Prior Art
In radars, filters are frequently designed in digital form. In other words, the signals to be filtered are sampled at a frequency equal to the repetition frequency of the pulses emitted by the radar, whereupon the amplitude of the samples is coded in order to obtain a succession of digital codes. Finally, these codes are multiplied by coefficients having values which define the characteristics of filtering to be obtained.
These so-called digital filters are formed, for example, by means of memories placed in series which record in each case the codes of all the samples of a repetition period, by means of multiplier circuits placed at the output of said memories in order to multiply the codes read from the associated memory by a suitable coefficient and by means of an adder circuit for summing the codes resulting from the multiplications.
Digital filters of this type can be employed in fields other than radar, for example in the field of high-fidelity signals, especially when such signals are in digital form. In these fields, there also exists a need to modify the transfer function of the filters on the axis of frequencies without thereby modifying the structure of the filters to any extensive degree, for example in order to extend the rejection band of the filter.
SUMMARY OF THE INVENTION
One object of the present invention is therefore to implement a method which makes it possible in a transversal filter to frequency-shift the modulus of the transfer function of said filter.
Another object of the invention is to provide devices for implementation of the method which are easy to construct in respect of certain values of the frequency shift.
The invention relates to a method for frequency-shifting by a value Fd the modulus of the transfer function of a transversal filter having n cells, the coefficients of multiplication of which are KO . . . , Ki . . . , Kn, the method being distinguished by the fact that it consists in multiplying the coefficient of order i by a factor
.sub.e j(n-i)r
with i varying from 0 to n and
r=2πFd·Tr
if Tr is the repetition period of the samples applied to the transversal filter so as to obtain new coefficients K'O . . . K'i . . . K'n.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of a transversal filter for removal of fixed echoes;
FIG. 2 is a diagram showing the modulus of the transfer function of the transversal filter of FIG. 1;
FIG. 3 is a vector diagram showing two positions of a radar signal vector in the complex plane;
FIG. 4 is a diagram of the canonical structure of a transversal filter in accordance with the invention;
FIG. 5 is a diagram showing the modulus of the transfer function of a transversal filter in accordance with the invention, which eliminates the echoes of Doppler frequencies in the vicinity of -Fr/4;
FIG. 6 is a diagram showing the modulus of the transfer function of a transversal filter in accordance with the invention which eliminates the Doppler frequency echoes in the vicinity of +Fr/4; and
FIG. 7 is a diagram of construction of two transversal filters at the frequencies +Fr/4 and -Fr/4.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention will be described in a particular application which is that of filtering of radar signals.
In operations which involve processing of these signals, it is known to filter them, especially in order to eliminate fixed echoes, by making use of a device which is shown in the schematic diagram of FIG. 1. This device includes a plurality of delay lines such as, for example, three delay lines LR1, LR2 and LR3 disposed in series, each delay line being intended to introduce a time-delay equal to the repetition period Tr of the emitted pulses having a frequency Fr. Each delay-line output as well as the input of the first delay line LR1 is connected respectively to a multiplication or weighting circuit M0, M1, M2 and M3 in which the amplitude of the signal is multiplied or weighted respectively by a coefficient K0, K1, K2 and K3. The outputs of the multiplication circuits are connected to a summing circuit S which forms the sum of the weighted signals so as to obtain a filtered signal. In order to eliminate the fixed echoes, the values of the coefficients K0, K1, K2 and K3 can be respectively 1, -3, 3 and -1 and the frequency transfer function of a filter of this type is of the form
|sin πFd·Tr|.sup.3
where Fd is the Doppler frequency of the echo. The modulus of the frequency response curve of a filter of this type is given by the diagram of FIG. 2. In the field of radars, a filter of this type is known as a transversal filter and is of the type involving cancelation on four pulses, designated as a four-pulse canceler transversal filter.
In modern radars, a filter of this type is of digital design, which means that the video-frequency signals of the radar are sampled at the frequency Fr and coded digitally in order to obtain codes Xi. These codes are recorded in memories which realize the delay lines LR1, LR2, and LR3 of FIG. 1. The multiplication circuits M0, M1, M2 and M3 as well as the summing circuit S are also realized digitally so that, in respect of a code Xi at the input of the delay line or memory LR1, a code Si is obtained at the output of the circuit S.
More precisely, at a given instant ti+3, the signal S i+3 at the output of the summing circuit S will be given by:
S.sub.i+3 =K0·X.sub.i+3 +K1·X.sub.i+2 +K2·X.sub.i+1 +K3 X.sub.i
where:
X i is the amplitude of the sample at the instant t of recurrence of order (i),
X i+1 is the amplitude of the sample at the instant t of recurrence of order (i+1), that is to say one period Tr later,
X i+2 is the amplitude of the sample at the instant t of recurrence of order (i+2), that is to say two periods Tr later,
X i+3 is the amplitude of the sample at the instant t of recurrence of order (i+3), that is to say three periods Tr later.
The samples X i to X i+3 therefore correspond to a radar signal produced by a distance box located at a predetermined distance from the radar antenna which is equal to t/C if C is the velocity of light.
The objective proposed by the invention is to shift the transfer function of said filter, the frequency response of which is shown in FIG. 2, along the axis of frequencies by a value f, this shift being obtained in a simple manner with a minimum of additional means.
FIG. 3 makes it possible to understand the step involved in the present invention. In this figure, a radar signal Xi having a recurrence i can be represented in the form of a vector Vi defined by its components I and Q in the complex plane: Xi=Ii+JQi. At the following recurrence (i+1), the vector will have become Vi+1 and will correspond to the vector Vi o but with a rotation r=2πFd/Fr if Fd is the Doppler frequency of the echo. It will accordingly be apparent that this echo would be seen as a fixed echo if, at each recurrence, it was phase-shifted through the angle r through which it would have rotated, which is equivalent to multiplying the radar signal:
X.sub.i by 1
X.sub.i+1 by e.sup.-jr
X.sub.i+2 by e.sup.-2jr
X.sub.i+3 by e.sup.-3jr
One will thus have obtained a frequency translation of the filter for elimination of the fixed echoes by a value Fd. One way of carrying out a translation of this type is to perform the multiplications at the input of the transversal filter of FIG. 1, that is to say by providing upstream of the delay line LR1 a multiplication circuit 10 which has been represented by a dashed-line rectangle. A solution of this type results in a multiplication circuit 10 which is fairly complex since the coefficient changes at each recurrence and which is fairly costly in the number of logic circuits and in processing time.
In the device in accordance with the invention, a multiplication circuit 10 of this type is no longer necessary and is replaced by new values K'0, K'1, K'2, and K'3 of the multiplication coefficients employed in the circuits M'0 to M'3. These values are fixed and, in the case of certain values of the frequency Fd, are easy to establish digitally.
The mathematical developments which follow are intended to determine the coefficients K'0 to K'3. To this end, recourse is had to the z transform which is, for example, defined in Chapter II of the book entitled "Les Filtres Numeriques" by R. Boite and H. Leich and published by Masson in 1980.
The z transform of a discrete time signal (x n ) is defined by the series: ##EQU1##
In the case of a radar signal, x n corresponds to the series of samples which are separated from each other by a repetition period Tr.
The properties of the z transform make it possible to demonstrate that the transfer function H(z) of the filter of FIG. 1 (without the multiplier circuit 10) is written in the form:
H(z)=K0+K1·z.sup.-1 +K2·z.sup.-2 +K3·z.sup.-3 (2)
If the multiplier circuit 10 is introduced, said transfer function is written in the form:
Hi(z)=K0·C.sub.i+3 +K1·C.sub.i+2 ·z.sup.-1 +K2·C.sub.i+1 ·z.sup.-2 +K3·C.sub.i ·z.sup.-3
In this form, Ci=(e jr ) i =(e j2 πFd/Fr) i
The modulus Hi(z) is then given by
Hi(z)=K0·e.sup.j3r +K1·e.sup.j2r ·z.sup.-1 +K2·e.sup.jr ·z.sup.-2 +K 3·z.sup.-3
which corresponds to a filter having a transfer function H'(z) such that
H'(z)=K0·e.sup.j3r +K1·e.sup.j2r ·z.sup.-1 +K2·e.sup.jr ·z.sup.-2 +K3·z.sup.-3 (3)
A comparison of formulae (2) and (3) shows that, in order to achieve the frequency shift fd of the modulus of the transfer function, it is sufficient to modify the coefficients of the multiplier circuits M0 to M3 so that they become
K'0=K0·e.sup.j3r
K'1=K119 e.sup.j2r
K'2=K2·e.sup.jr
K'3=K3
FIG. 4 gives the canonical structure of a transversal filter in the case of weighting carried out on four pulses. In this figure, the delay lines LR1 to LR3 of FIG. 1 are represented schematically by operators Z1 to Z3 in series, each of which forms the transform z -1 , which corresponds to producing a time-delay Tr of each sample X i since:
z.sup.-1 =e.sup.-j2πFd·Tr
The input of the operator circuit Z1 as well as the outputs of the operator circuits Z1, Z2 and Z3 are connected to multiplier circuits M'0 to M'3 which perform respectively the multiplication by the coefficients K'0 to K'3. The outputs of the multiplier circuits M'0 to M'3 are connected to an adder circuit S' which delivers a filtered signal S' i+3 defined by:
S'.sub.i+3 =K'0·X.sub.i+3 +K'1·X.sub.i+2 +K'2·X.sub.i+3 +K3·X.sub.i
that is to say a signal from which the echoes having frequencies Fd have been eliminated.
The description of the invention has been made in the particular case of a transversal filter for processing four pulses but it is clear that the invention can be carried into effect in the case of any number of pulses. Thus, in the case of a number L of pulses to be processed simultaneously, we have the following z transfer functions in accordance with the structures:
(A) conventional structure for elimination of fixed echoes: ##EQU2## (B) structure with multiplications at the head end ##EQU3## (C) structure with multiplication at the output ##EQU4##
It is accordingly observed that Hi(z) and H'(z) have the same modulus, which means that the same filtering is performed with the structure (C) as with the structure (B) if consideration is given only to the modulus but, in the structure (C), the coefficients no longer depend on the order of the sample in the repetition period and are therefore fixed values.
It is worthy of note that, for certain values of the Doppler frequency Fd with respect to the repetition frequency Fr, one obtains values of the coefficients K'0 to K'3 which are whole numbers leading to simple multiplications. This is accordingly the case when Fd is equal to +Fr/4 or to -Fr/4. In the first case, the four coefficients K'0 to K'3 can be respectively equal to one of the following four groups:
-(-j, 3, 3j, -1)
-(1, 3j, -3, -j)
-(j, -3, -3j, 1)
-(-1, -3j, 3, j)
In the second case, they can be respectively equal to:
-(j, 3, -3j, -1)
-(1, -3j, -3, j)
-(-j, -3, 3j, 1)
-(-1, 3j, 3, -j)
In the first case, the modulus of the frequency transfer function H'(f) is given by the curve 12 of FIG. 5 which corresponds to the curve 11 of elimination of the fixed echoes of FIG. 2 but displaced by -Fr/4 on the axis of frequencies. A transfer function of this type, the maximum value of transmission of which is at +Fr/4, makes it possible to eliminate the echoes corresponding to the Doppler frequencies in the vicinity of -Fr/4.
In the second case, the modulus of the frequency transfer function H'(f) is given by the curve 13 of FIG. 6 which corresponds to the curve 11 of elimination of the fixed echoes but displaced by +Fr/4 on the axis of frequencies. This transfer function, the maximum value of transmission of which is at -Fr/4, enables the filter to eliminate the echoes corresponding to the Doppler frequencies in the vicinity of +Fr/4.
FIG. 7 is a diagram of a digital filtering device for carrying out the method of the invention in the case of simultaneous frequency shifts +Fr/4 and -Fr/4 with processing on four pulses by means of three memories each forming a delay line.
The signal to be filtered is presented in the form of its two real and imaginary components I and Q respectively which are first processed in two separate channels, then within a common portion. Each separate channel has a memory 20 (or 21) which is constituted, in the case of simultaneous treatment on four samples, by three identical elementary memories 22, 24, 26 (or 23, 25, 27) each memory being intended to record, in the case of a radar signal, the codes of the samples corresponding to a repetition period Tr. The outputs of the memories 22 and 24 (or 23 and 25) are connected respectively to adder circuits 28 and 30 (or 29 and 31) which perform the operation of multiplication by the coefficient 3.
The common portion comprises adder circuits 32 to 39 and two circuits for calculation of modulus. The adder circuits 32 to 35 and 36, 39 have a (+) direct input and a (-) complementary input which forms the complement of the code which is applied thereto. More precisely, the (-) inputs of the adder circuits 32 to 35 are connected respectively:
to the output of the memory 26,
to the output of the adder circuit 31,
to the input of the memory 22,
to the output of the memory 27.
Similarly, the (+) inputs of the adder circuits 32 to 35 are connected respectively:
to the output of the adder circuit 28,
to the input of the memory 23,
to the output of the adder circuit 30,
to the output of the adder circuit 29.
Each output of the adder circuits 32 to 35 is connected to one of the two inputs of one of the adder circuits 36 to 39. Thus the output of the adder circuit 32 is connected to the (+) inputs of the adder circuits 36 and 37; the output of the adder circuit 33 is connected to the (-) input of the circuit 36 and to the (+) input of the circuit 37; the output of the circuit 34 is connected to the (+) input of the circuit 38 and to the (-) input of the circuit 31; finally, the output of the circuit 35 is connected to the (+) input of the circuits 38 and 39.
The outputs 42 and 45 of the circuits 36 and 39 are connected to the two inputs of the computing circuit of the modulus 41 and the outputs 43 and 44 are connected to the two inputs of the modulus calculation circuit 40.
If the references I0, I1, I2 and I3 respectively designate the codes of the samples at the input of the memory 22 and at the outputs of the memories 22, 24 and 26 and if the references Q0, Q1, Q2 and Q3 designate the codes of the samples at the input of the memory 21 and at the outputs of the memories 23, 25 and 27, it is apparent that we have the following codes at the output of the circuits 36 to 39:
at the output 42 of the adder circuit 36:
-I3+3I1-Q0+3Q2;
at the output 45 of the adder circuit 39:
-Q3+3Q1+I0-3I2;
at the output 43 of the adder circuit 37:
-I3+3I1+Q0-3Q2;
at the output 44 of the adder circuit 38:
-Q3+3Q1-I0+3I2.
It has been shown in the foregoing that, in order to obtain a filter known as a +Fr/4 filter, it was necessary in accordance with the invention to multiply the complex samples X3, X2, X1, X0 by the respective coefficients -1, 3j, 3, -j and to perform a summation of the results of multiplications, namely to obtain:
-1(I3+jQ3)+3j(I2+jQ2)+3(I1+jQ1)-j(Io+jQo)
that is:
-I3+3I1+Q0-3Q2+j(-Q3+3Q1-I0+3I2),
which corresponds in the case of the real portion to the output 43 of the circuit 37 and in the case of the imaginary portion to the output 44 of the circuit 38.
In regard to the so-called -Fr/4 filter, the respective coefficients which have been indicated in the foregoing are -1, -3j, 3 and j in the case of the complex samples X3, X2, X1, X0. At the output of the summing circuit S' of FIG. 4, there is obtained:
-1 (I3+jQ3)-3j(I2+jQ2)+3(I1+jQ1)+j(Io+jQo) namely:
-I3+3I1-Q0+3Q2+j (-Q3+3Q1+I0-3I2), which
corresponds in the case of the real portion to the output 42 of the circuit 36 and in the case of the imaginary portion to the output 45 of the circuit 39.
In consequence of the foregoing, the circuit 40 for computing the modulus therefore gives the modulus of the signal corresponding to the +Fr/4 filter whilst the circuit 41 gives the modulus of the signal corresponding to the -Fr/4 filter. The description which has just been made with reference to FIG. 7 shows that the application of the invention to particular cases of filters leads to simple digital devices which are easy to construct and make use only of elementary circuits.
The invention has been described in connection with a particular application in the field of radars. However, it is understood that the invention applies to filtering of all types of electric signals on condition that they are sampled at a frequency at least equal to twice the maximum frequency of the useful spectrum so as to obtain the samples Xi separated by time intervals equal to the sampling period.
As will be readily apparent, in order to obtain a filter having a given transfer function by implementing the present invention, it is possible to place in parallel a plurality of transversal filters in accordance with the invention and each transversal filter has a suitable transfer function in order to ensure that the sum of transfer functions finally results in the requisite global transfer function. | The invention relates to a method for frequency-shifting the modulus of the transfer function of a transversal filter.
In a transversal filter having three delay lines Z1, Z2 and Z3 in series and four multipliers M'0 to M'3, the multiplier coefficients K0 to K3 of which are intended to eliminate the signals at frequencies in the vicinity of zero frequency and integral multiples of the repetition frequency Fr of the samples X i , the method consists in replacing the multiplier coefficients K0 to K3 by coefficients K'0 to K'3 which are deduced from the first by multiplying them by fixed coefficients
e.sup.3jr, e.sup.2jr, e.sup.jr and 1 with r=2πFd/Fr.
The invention is applicable in particular to the elimination of certain undesirable echoes from radar signals. | 6 |
CROSS-REFERENCE TO OTHER APPLICATIONS
This is a National Phase of International Application No. PCT/SG2004/000371, filed on Nov. 17, 2004, which claims priority from U.S. Provisional Patent Application No. 60/520,643, filed on Nov. 18, 2003.
FIELD OF INVENTION
This invention relates to a method of actuating and an actuator, and refers particularly, though not exclusively, to an electrokinetic actuator and method for fluids. The use of such a method and actuator is particularly relevant, though not exclusively so, for compressing gases or vapour, for transporting gases and vapors, for delivering non-conducting, non-polar liquids in micro-scaled channels, and for enhancing mixing in microfluidics.
BACKGROUND
Electroosmosis is an electrokinetic phenomenon that occurs when an electrolyte fluid interacts with solid surfaces causing a charged layer to form at the interface between the solid and the liquid. Immobilized electric charges develop at the surface of the solid surface in contact with the electrolyte fluid due to electro-chemical phenomena. The surface charge leads to the formation of an electric double layer (“EDL”) by influencing the distribution of counter-ions and co-ions in the electrolyte fluid. In a diffuse layer of the EDL, the counter-ions predominate over the co-ions to neutralize the surface charge. As such, the local net charge density is not zero. A Columbic force is exerted on the ions within the EDL when an electric field is applied tangentially along the charged surface. Consequently, an electroosmotic flow (EOF) results whereby the migration of mobile ions will carry the adjacent and bulk liquid phase by viscosity.
The build-up of pressure as a result of electroosmosis facilitates the transport and manipulation of liquids in microfluidic devices for biomedical applications. These principles have been applied in the operation of many electroosmotic pumps. Such electroosmotic pumps work without movable mechanical parts, consequently improving durability and minimizing difficulties in production. Such electroosmotic pumps are essential for biochemical analyses as they enable the pumping of liquids over a wide range of fluid conductivities.
Given that electroosmosis is essentially a surface dominated phenomenon, the use of a porous structure with a high surface area-to-volume ratio can enhance the pressure-building capacity. Paul et al. [1998 Electrokinetic generation of high pressures using porous microstructures in: Proceedings of the Micro Total Analysis Systems '98 Workshop, Banff, Canada] proposed a method to generate high pressure using DC electroosmosis through a microchannel packed with microparticles. The pressure of 10 atm at 1.5 kV applied voltage has been achieved using fused-silica capillaries packed with charged 1.5 μm silica beads. S. Zeng et al, [Fabrication and Characterization of Electroosmotic Micropupms, Sensors and Actuators B 2001, 79, 107-114] fabricated an electroosmotic pump that can generate maximum pressures in excess of 20 atm or maximum flow rates of 3.6 μl/min by applying a 2 kV electric voltage over 5.4 cm long, 500-700 μm in diameter fused-silica capillaries packed with 3.5 μm silica particles. S. Yao et al, [A Large Flowrate Electroosmotic Pump with Micro Pores, Proceedings of IMECE, ASME, 2001, New York, N.Y.] developed an electroosmotic pump for a large flowrate with micro pores which can generate a maximum flowrate of 7 ml/min and a maximum pressure of 2.5 atm for 200V applied potential. In a recent development, L. Chen et al, [Generating High-Pressure Sub-Microliter Flow Rate in Packed Microchannel by Electroosmotic Force: Potential Application in Microfluidic Systems, Sensors and Actuators B 2003 88 260-265] developed a pump made of microchannels packed with porous fine dielectric material, which can generate a maximum pressure of 15 MPa.
The aforementioned sampling of documents show that the use of electroosmotic principles are commonly employed in micro-fluid pumping. Thus far, there has been no disclosure of the application of electroosmotic principles for actuation.
SUMMARY
According to a first preferred aspect there is provided a method of actuating, comprising: filling at least a portion of a tube with a liquid containing electrolytes, the tube having an inner surface that is electrically chargeable when in contact with the liquid; positioning an object in fluid communication with the liquid in the tube; and applying an electrical field along a lengthwise axis across the tube at said portion for producing a pressure in the liquid. The inner surface is advantageously electrically chargeable due to electrochemical phenomena. The pressure in the liquid exerts a force on the object so as to actuate the object. The tube may preferably be selected from a capillary tube or a micro-capillary tube. It is preferable that the tube has an open end and the object is in fluid communication with the liquid in the tube through the open end.
Preferably, there is an additional plurality of tubes each at least partially filled with a liquid containing electrolytes in fluid communication with the object, The plurality of tubes may be formed in a porous material. It is preferable that the porous material may be made from electrically non-conducting material such as silica or ceramic. The porous material may advantageously have one or more material properties such as a porous structure, micro capillaries, small particles, electrically non-conductive, and hydrophilic.
The electric field may be generated from AC or DC power supplies. It is advantageous that the DC power supply is linked to an on-off frequency controller. Advantageously, the pressure in the liquid is caused by electroosmotic flow.
A higher force on the object may be generated by preferably adopting techniques like using porous material with small pore sizes, using porous material with large cross-sectional areas, using a lower concentration of the liquid containing electrolytes, or by generating a stronger electric field.
There is also provided an actuator comprising: a tube with an inner surface and at least partially filled with a liquid containing an electrolyte, the inner surface being electrically chargeable when in contact with the liquid; an electric field generator for generating a field along a lengthwise axis of the tube for inducing a pressure in the tube; and an object in fluid communication with the liquid such that the pressure in the liquid exerts a force on the object for actuating the object. The inner surface may be electrically chargeable due to electrochemical phenomena and the pressure in the liquid exerts a force on the object so as to move the object. The tube may preferably be selected from either a capillary tube or a micro-capillary tube. Advantageously, the tube has an open end and the object is in fluid communication with the liquid in the tube through the open end. There may be an additional plurality of tubes each at least partially filled with a liquid, the liquid containing electrolytes in fluid communication with the object. The plurality of tubes may be formed in a porous material. The porous material may preferably be made from electrically non-conducting material selected from silica or ceramic. Advantageously, the porous material may have material properties such as hydrophilic, electrically non-conductive, porous structure, micro capillaries, and small particles.
The electric field generator may generate either AC or DC power. Preferably, the DC power supply is linked to an on-off frequency controller. In addition, The pressure in the liquid is preferably caused by electroosmotic flow.
A higher force on the object may be generated by adopting techniques such as using porous material with small pore sizes, using porous material with large cross-sectional areas, using a lower concentration of the liquid containing electrolytes, or by generating a stronger electric field.
Preferably, a housing defines a chamber containing the tube, and a cylinder in fluid communication with the chamber. The tube may be in the cylinder and the object may be a piston slideably mounted in the cylinder. It is preferable that the piston is biased to resist a force exerted thereon from the tube. The actuator may further comprising a displacement amplifier operatively connected to the piston.
Preferably, the piston has silicone seals. The actuator may further include a compensating piston to prevent a drop of pressure in the porous material. The actuator may advantageously further include a vent in the housing for allowing the exchange of air within the chamber.
DESCRIPTION OF DRAWINGS
In order that the invention may be better understood and readily put into practical effect, there shall now be described by way of non-limitative example only preferred embodiments of the present invention, the description being in reference to the accompanying illustrative drawings in which:
FIG. 1 is a schematic diagram of a preferred embodiment;
FIG. 2 is a graph of pressure gradient against time in a micro-capillary of a preferred embodiment when a DC electric field is applied;
FIG. 3 is a graph of pressure gradient against ratio of the hydraulic diameter of a micro-capillary to a reference diameter with a geometric size of 40×100 μm when a DC electric field is applied;
FIG. 4 is a graph of pressure gradient against characteristic moments in a micro-capillary of a preferred embodiment when an AC electric field is applied; and
FIG. 5 is a graph of pressure gradient against ratio of applied frequency to characteristic frequency f* in a micro-capillary of a preferred embodiment when an AC electric field is applied.
DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to FIG. 1 , there is provided a schematic diagram of an electrokinetic actuator 20 . The actuator 20 may have a housing 22 . The housing 22 may be of different cross-sectional shapes, such as, for example, circular, rectangular, approximating a square, polygonal, and the like. The housing 22 has a circular cross section forming a cylinder.
The housing 22 defines a chamber 21 that encases hydraulic fluid 19 , a primary cylinder 24 and a secondary cylinder 26 . The primary cylinder 24 and the secondary cylinder 26 have different bore diameters. The hydraulic fluid 19 acts as a damping medium. The primary cylinder 24 has a larger bore than the secondary cylinder 26 . Correspondingly, a primary piston 28 in the primary cylinder 24 has a larger diameter than a secondary piston 30 . There is also a primary retaining spring 32 and a secondary retaining spring 34 in the primary 24 and secondary 26 cylinders respectively. The primary retaining spring 32 prevents the primary piston 28 from contacting a top end 40 of the primary cylinder 24 and to return the primary piston 28 to a resting position. Similarly, the secondary retaining spring 34 prevents the secondary piston 30 from contacting a top end 48 of the secondary cylinder 26 and to return the secondary piston 30 to a resting position.
The primary 24 and secondary 26 cylinders may be connected as shown in FIG. 1 . The top end 40 of the primary cylinder 24 may have an opening (not necessarily central) joining to a bottom end 42 of the secondary cylinder 26 . The primary 24 and secondary 26 cylinders may be filled with hydraulic fluid that flows within the chambers of both the primary 24 and secondary 26 cylinders. The hydraulic fluid may also line the walls of the chambers of both the primary 24 and secondary 26 cylinders as a lubricating film. The hydraulic fluid may be contained primarily towards the top end 40 of the primary cylinder 24 and the bottom end 42 of the secondary cylinder 26 . The primary piston 28 and the secondary piston 30 may include at least one circumferential-seal 44 to prevent hydraulic fluid from leaking to other portions of the chambers of the primary 24 and secondary 26 cylinders. The circumferential seal may be made of silicone or other suitable materials.
Electroosmosis is ordinarily associated with DC (direct current) electric field, which is used to generate a steady-state mono-directional electroosmotic flow. An AC (alternating current) electric field may also be applied to induce electroosmosis. However, the electroosmotic flow then becomes time and frequency dependent, with an oscillating flow direction. A frequency-dependent excitation electric field may be applied across a non-conductive capillary with single sealed ends to induce electroosmosis. Each capillary may be filled with an aqueous liquid. Since each capillary is sealed at one end, there is no net flow of ions and this builds up the pressure in each capillary. This pressure can be converted into an actuating force.
In a preferred embodiment of the present invention, the primary cylinder 24 may contain hundreds or thousands of microcapillaries bundled together in a lower end 36 of the primary cylinder 24 . For ease of fabrication, a porous material 38 (as shown) filled/soaked with an electrically conducting or an aqueous solution may be used in place of the microcapillary bundles. The porous material 38 may be made of electrically non-conducting materials.
Mathematical models have been developed to analyze the frequency-dependent electroosmotic flow in empty or packed microcapillaries. The corresponding Navier-Stokes equation is solved using the Green's function method and the complete Poisson-Boltzmann equation governing the EDL potential field is solved under an analytical scheme for arbitrary zeta potentials. When both capillary ends are closed, the oscillating flow independently generated by the AC electroosmosis is balanced by the oscillating counter-flow.
While operating the electrokinetic actuator 20 , an AC power supply 46 (or any sinusoidal power supply) with a switch 47 may be applied across the porous material 38 which is filled/soaked with an electrically conducting, any aqueous liquid, or any ionic solution such as, for example, demonized water. With the AC power supply 46 turned on, an oscillating electrical field generated causes the ions in porous channels of the porous material 38 to flow in an oscillating manner. As the porous channels of the porous material 38 simulates closed channels, the oscillating electrical field causes the liquid flow at the central part of these porous channels in the porous medium 38 to change direction often, creating a high pressure gradient in the porous channels in the porous medium 38 . This high pressure gradient generates a high back pressure in the porous channels in the porous medium 38 . The back pressure in the porous channels in the porous medium 38 may be used to push/move the primary piston 28 in the primary cylinder 24 . The primary piston 28 compresses the hydraulic fluid in the top end 40 of the primary cylinder 24 and the bottom end 42 of the secondary cylinder 26 . The compressed hydraulic fluid then pushes/moves the secondary piston 30 of the secondary cylinder 26 .
The secondary piston 30 may be connected to an actuation cylinder 50 that provides linear actuation to external applications/devices. The difference in the bore sizes of the primary cylinder 24 and the secondary cylinder 26 creates a displacement amplifier effect because of the non-compressitivity of the hydraulic fluid. The volume of hydraulic fluid forced out of the primary cylinder 24 by the movement of the primary piston 28 will be the same volume of hydraulic fluid forced in the secondary cylinder 26 . The smaller bore size of the secondary cylinder 26 compared to the bore size of the primary cylinder 24 allows the actuator 20 to be used in situations where large amplitudes of actuation are required. Based on the principle of conservation of fluid, the amplitude of actuation of the actuating cylinder 50 is the amplitude of motion of the primary piston 28 multiplied by the square of the diameter ratio of the primary piston 28 and the secondary piston 30 . Hence, it can be seen that a slight movement by the primary piston 28 would induce a significant movement of the actuation piston 50 , especially if the diameter ratio of the primary piston 28 and the secondary piston 30 is large. The converse is true when the secondary piston 30 falls from its highest position.
In an alternative embodiment, a DC power supply instead of an AC power supply may be used to work the actuator 20 . The DC power supply may be linked to an on-off frequency controller that provides necessary on-off modulation for the system to simulate the sinusoidal oscillating patterns of an AC power supply. The DC power supply should preferably be of high voltage because of the high electric field required. The actuation frequency may be specified using the on-off frequency controller.
The lower end 36 of the primary cylinder 24 may include a compensating piston 52 . The compensating piston 52 may be used to prevent the drop of pressure in the porous channels of the porous material 38 during the operation of the actuator 20 due to the displacement of the primary piston 28 .
A vent 54 may be incorporated at the lower end 36 of the primary cylinder 24 . The vent 54 may be used to facilitate the movement of the compensating piston 52 . The vent 54 allows the compensating piston 52 to return to its rest position when the primary piston 28 returns to its own rest position by exposing the void in the housing 22 created by the movement of the compensating piston 52 to atmospheric pressure.
Simulations have been carried out to determine the characteristics of different parameters in a sealed micro-capillary during frequency-dependent electroosmotic flow. The simulations and calculations were carried out based on a set of fixed parameters. The working fluid was NaCl (sodium chloride) with valence of 1 at 293 K and with density, viscosity and dielectric constant of 10000 kg/m 3 , 9×10 −4 Ns/m 2 and 80, respectively. The reference velocity was set at 1 mm/s and the electric field for both DC and AC were applied with a field strength of 1000V/m. The characteristic hydraulic diameter of the micro-capillary was set at 57 μm. Other important parameters were a characteristic time t*=155.3 μs with a corresponding eigen-frequency of f*=6.44 kHz.
FIG. 2 shows that in the instance of a DC electric field applied to a micro-capillary, the highest magnitude of the pressure gradient ( 80 ) is generated during time first instant immediately after the application of an electric field. It can be seen from FIG. 2 that the pressure gradient gradually decreases thereafter and eventually attains a steady state of a low pressure gradient.
FIG. 3 shows a graph of pressure gradient against a ratio of a hydraulic diameter of a micro-capillary to a reference diameter with a geometric size of 40×100 μm when a DC electric field is applied. The negative gradient of FIG. 3 suggests that as the size of the micro-capillary increases, the magnitude of the pressure generated in the chamber decreases.
FIGS. 4 and 5 show the behaviour in the micro-capillary that occurs when an AC supply electric field is applied to a micro-capillary. FIG. 4 shows a graph of pressure gradient against characteristic moments in a micro-capillary of a preferred embodiment of the present invention when an AC electric field is applied. FIG. 4 shows that at higher excitation frequencies, for example, when f=10f*, the larger the oscillation in values of the pressure gradient.
FIG. 5 shows a graph of pressure gradient against a ratio of applied frequency to characteristic frequency f* in a micro-capillary of a preferred embodiment of the present invention when an AC electric field is applied. As denoted in FIG. 5 , the supply frequency should exceed the characteristic frequency f* in order to attain a high pressure gradient within a micro-capillary. It can also be seen that when the ratio of applied frequency to characteristic frequency f* (dimensionless excitation frequency) exceeds the value of 100, the magnitude of the pressure gradient increases linearly with the magnitude of the dimensionless excitation frequency, and correspondingly, the supply frequency.
The force required for the actuation of the primary piston 28 may depend on various factors. Higher forces may be attained by utilizing a porous medium 38 with small pores sizes. It should be noted that the overlapping of EDLs should be avoided to maximize the amount of force generated. Other approaches to attaining greater forces include using a lower concentration of the electrolyte solution, using a larger cross-sectional area of a porous column, and using a stronger electric field. Forces in excess of 2 KN may be obtainable from the use of a 0.1 m diameter porous column.
The actuator 20 is a simple design with few moving parts that is not complicated in construction. Each actuator 20 requires minimal maintenance, if any. The materials used to manufacture the actuator 20 may include metals, silica, ceramic and plastics. The materials used and the corresponding material costs would be determined by the environment that the actuator 20 is employed at The cost of manufacture would be low as the actuator 20 may be manufactured using existing manufacturing techniques and technology.
The actuator 20 is an energy-efficient device. Although the applied voltage to generate an electric field is relatively high, the current drawn is low and correspondingly, power consumption is low as well.
The actuator 20 may be used in a myriad of different applications ranging from situations that require precision micro actuation, to situations that require large displacement linear actuation such as in a linear motor. It may be unnecessary to use a displacement amplifier in the actuator 20 for precision micro actuation. The actuation may be obtained directly from the primary piston 28 .
The actuator 20 may be used in applications involving linear actuations. The actuation may be in nano, micro or macro scales. The actuator 20 may also be used for positioning in relevant fields of applications.
The actuator 20 may be used as a precision actuator as its actuation can correspondingly be controlled precisely since the displacement of the actuator 20 is proportional to the applied electric field strength. As such, the actuator 20 may be employed to replace piezo-actuators. The actuator 20 may also be employed in a hard disk drive to position the head arms to different tracks on the surface of the platter during the writing/retrieval of data. Similarly, the actuator 20 may be used as a precision micro-actuator in cameras, microscopes or any applications that require precision linear or possibly even rotational actuation. For larger amplitudes, of actuation, a linear displacement amplifier (as described earlier) may be used to amplify the amplitude of displacement.
In an alternative application, the actuator 20 may be employed as a linear motor. It may be possible to generate larger linear displacements from the actuator with the aid of a mechanical displacement amplifier. The actuator 20 may be used in various scales as a linear motor in delivering linear actuations such as, for example, driving linear air compressors or refrigeration compressors for air-conditioners or refrigerators or in a miniature refrigeration system for CPU cooling. The fabrication of the miniature refrigeration compressor may be possible because of the miniaturisation of the actuator 20 . The actuator 20 may also be used for hydraulic or pneumatic actuations.
The actuator 20 may also be used for precision positioning applications. As the pressure generated by such actuators 20 may attain very high levels (in excess of 100 atmospheric pressures), it may thus be suitable for applications in static and dynamic nano, micro and macro positioning, depending on the design parameters of the actuator 20 .
Whilst there has been described in the foregoing description preferred embodiments of the present invention, it will be understood by those skilled in the technology concerned that many variations or modifications may be made to details of design or construction without departing from the present invention.
The present invention extends to all features disclosed either individually, or in all possible permutations and combinations. | A method of actuating, comprising: filling at least a portion of a tube ( 21 ) with a liquid ( 19 ) containing electrolytes, the tube ( 21 ) having an inner surface that is electrically chargeable when in contact with the liquid ( 19 ); positioning an object ( 28 ) in fluid communication with the liquid in the tube; and applying an electrical field ( 46 ) along a lengthwise axis across the tube at said portion for producing a pressure in the liquid. The pressure in the liquid exerts a force on the object so as to actuate the object ( 28, 30 ). An actuator ( 20 ) is also disclosed. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of the filing date of U.S. Provisional Application No. 61/420,481, filed Dec. 7, 2010, entitled LONG WEAR COSMETIC COMPOSITIONS CONTAINING POSS THERMOPLASTIC ELASTOMERS, the disclosure of which is hereby incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] Cosmetic manufacturers continuously explore new avenues in search of cosmetic ingredients and combinations thereof that will fill the always needed gaps of longer wear, richness of color, comfort and non-tackiness. Cosmetic formulations are sought that provide long-lasting, durable wear, preferably one or more days, removable by the consumer whenever desired, and exhibit a rich and natural-looking color. In response to this need, the cosmetics art has developed numerous extended wear technologies, among them formulations that contain a combination of solid pigments, silicone resins such as organosiloxanes and diorganopolysiloxanes. Although these types of formulations have extended wear performance, they have also been found to be tacky or sticky during or after product application, and even cause unpleasant sensations of tautness, making these cosmetics uncomfortable to wear. It has also been found that a film formed on the skin after application is too rigid also causing unpleasant sensations such as, for example, during facial movements. Beyond issues of tackiness and comfort, silicone-based cosmetic formulations have also been limited from the standpoint of providing a relatively long-lasting rich and natural-looking color to keratinous tissue. Organic pigments are desirable in this respect because they provide a very rich intensity that inorganic pigments tend to lack. However, since most organic colorants are water-soluble, it is difficult to incorporate them into long-wearing cosmetics which is further complicated when the user comes into contact with water from perspiration, raindrops, etc. Use of organic pigments is also compromised from the standpoint that since they are not compatible in non-aqueous systems at appreciable concentrations, they cannot be used in amounts large enough to impart significant color to the composition.
[0003] Therefore, there is a remaining need in the cosmetics art to provide long-wearing cosmetic compositions based on film-forming silicone resins and which also provide non-tackiness, greater comfort and a long-lasting color effect.
BRIEF SUMMARY OF THE INVENTION
[0004] The present invention provides novel cosmetic compositions and methods of making up keratinous tissue in a way that preserves long-wear but also greater comfort, reduced tackiness and enriched color. The present invention exploits the use of polyhedral oligomeric silsequioxanes (POSS)-grafted polyolefins.
[0005] Accordingly, a first aspect of the present invention is directed to a cosmetic composition that contains a polymer having a chain that contains a polyolefin, and a polyhedral oligomeric silsesquioxane (POSS) grafted onto the polymer chain, a solvent and at least one other cosmetically acceptable ingredient. In some embodiments, wherein monomeric POSS (the POSS molecule that is reacted with the polyolefin) includes a functional group reactive with a vinyl group on the polyolefin, and the POSS is grafted onto the polymer chain via the functional group. In other embodiments, monomeric POSS includes a polymerizable functional group, and the polymer chain further includes the polymerized functional group such that the POSS is grafted onto the polymer chain via the polymerized functional group (the polymerizable functional moiety becomes integrated into the polymer backbone). In other embodiments, more than one polyolefin component is present. Thus, the polymers of the present invention include random and non-random copolymers, and block copolymers and terpolymers.
[0006] A second aspect of the present invention is directed to a method for making up keratinous tissue, which entails applying to the keratinous tissue (e.g., skin, lips, eyelids, hair, nails) a cosmetic composition that contains a polymer having a chain that contains a polyolefin, and a polyhedral oligomeric silsesquioxane (POSS) grafted onto the polymer chain, a solvent and at least one other cosmetically acceptable ingredient.
[0007] A third aspect of the present invention is directed to a method for making a cosmetic composition, which includes formulating a composition containing a polymer having a chain that includes a polyolefin, and a POSSPOSS grafted onto the polymer chain, a solvent and at least one other cosmetically acceptable ingredient, into a cosmetic composition.
[0008] The POSS component provides the benefits of long wear but without compromising with respect to comfort, tackiness and color enrichment. The polyolefin component of the polymer has a molecular weight of about 1,000 to about 200,000 daltons, and a relatively low glass transition temperature (Tg) (e.g., less than about 25 C.). Without intending to be bound by any particular theory of operation, Applicants believe that backbone of the relatively low Tg polyolefin provides adequate tackiness and adhesive properties that causes aggregation, resulting in excellent comfort and adhesion both to skin and colorants, but without a prolonged tacky sensation.
DETAILED DESCRIPTION
[0009] Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients and/or reaction conditions are to be understood as being modified in all instances by the term “about,” meaning within 10% to 15% of the indicated number.
[0010] “Keratinous tissue”, as used herein, includes but is not limited to, skin, hair and nails.
[0011] “Substituted” as used herein, means comprising at least one substituent. Non-limiting examples of substituents include atoms, such as oxygen atoms and nitrogen atoms, as well as functional groups, such as hydroxyl groups, ether groups, alkoxy groups, acyloxyalky groups, oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups, amine groups, acylamino groups, amide groups, halogen-containing groups, ester groups, thiol groups, sulphonate groups, thiosulphate groups, siloxane groups, and polysiloxane groups. The substituent(s) may be further substituted.
[0012] “Volatile”, as used herein, means having a boiling point of less than about 100° C. “Non-volatile”, as used herein, means having a flash point of greater than about 100° C.
[0013] As used herein, the terms “at least one”, “a”, and “an” mean one or more and thus include individual components as well as mixtures/combinations.
[0014] “Long wear” compositions as used herein, refer to compositions where color remains the same or substantially the same as at the time of application, as viewed by the naked eye, after an extended period of time. Long wear properties may be evaluated by any method known in the art for evaluating such properties. For example, long wear may be evaluated by a test involving the application of a composition to human hair, skin or lips and evaluating the color of the composition after an extended period of time. For example, the color of a composition may be evaluated immediately following application to hair, skin or lips and these characteristics may then be re-evaluated and compared after a certain amount of time. Further, these characteristics may be evaluated with respect to other compositions, such as commercially available compositions.
[0015] “Hardness” as used herein, refers to the resistance of a composition to penetration. Hardness may be evaluated according to a method of penetrating a probe into the composition and in particular using a texture analyzer (for example TA-XT2i from Rheo) equipped with an ebonite cylinder of height 25 mm and diameter 8 mm. The hardness measurement is carried out at 20° C. at the center of 5 samples of the composition. The cylinder is introduced into each sample of composition at a pre-speed of 2 mm/s and then at a speed of 0.5 mm/s and finally at a post-speed of 2 mm/s, the total displacement being 1 mm. The recorded hardness value is that of the maximum peak observed.
The POSS-Grafted Polyolefins
[0016] Polyolefin Component:
[0017] The polyolefin component of the polymers of the present invention (and in the case of block copolymers, the total polyolefin component) has a molecular weight of from about 1,000 to about 200,000 daltons. In general, the polyolefin component has a glass transition temperature (Tg) less than about 25° C. The term “glass transition temperature” generally refers to the temperature at which the amorphous material changes from a glassy solid state to a rubbery state. This temperature may be measured by standard techniques in the art, such as DSC (Differential Scanning calorimetry), e.g., according to the ASTM D3418-97 standard. As used herein, the term “about” as it is used in the specific context of Tg allows for imprecision in the use of a particular technique, or the variation between or among various techniques, in determining Tg. Thus, the term provides variability in the order of ±2° C. Polyolefin/POSS polymers wherein the polyolefin has a Tg in this range contribute to desirable cohesive properties, and particularly to particulate colorants, producing colored cosmetic compositions that exhibit excellent wear. This property of the polyolefin component also results in a polymer that exhibits excellent aggregation characteristics, producing cosmetic compositions that exhibit excellent tackiness and comfort.
[0018] The polyolefins for use in the present invention are non-silicone based polymers. They have the values of elastic or storage modulus G′, at frequency of 1 Hz and 25° C., as measured by Dynamic Mechanical Analyzer (DMA), that generally ranges from about 1 Mpa to about 100 Mpa, or higher. See, “ An introduction to rheology ” by H. A. Barnes, J. F. Hutton and K. Walters, pages 46 to 54 (published by Elsevier 1989). The polyolefins have a refractive index (RI) which, in general, is greater than 1.46. Representative examples of polyolefins that may be present in the polymers of the present invention include polyethylene, polypropylene, polyisobutene, polybutene, polyisoprene, polybutadiene, polycycloalkenes (e.g., polycyclooctene) and poly-hydrocarbon-dienes [e.g., pentylene-dienes, and olefinic copolymers thereof]. More than one polyolefin component may be present (e.g., polyethylene/polypropylene, styrene/butadiene/styrene, polyethylene/polypropylene/styrene and polycyclooctene/styrene).
[0019] The POSS Component:
[0020] The other component of the polymers of the present invention is a polyhedral oligomeric silsesquioxane (POSS), which is a general name to describe organic-inorganic materials with a cubic caged (“complete” or “incomplete”) core structure that contains silicon and oxygen atoms, with a silicon to-oxygen ratio of 1 to 1.5. See, Johshi, et al., J. Macromolecular Sci, Part C: Polym. Rev. 2004, 44, 389; Wang, et al., J. Inorg. Organomet. Polym. 2001, 11, 123. The POSS core is surrounded by peripheral groups off each silicon atom (also referred to as a POSS periphery), which can consist of a wide variety of non-reactive and reactive functional groups alike, including for example, aliphatic, aromatic, or aryl groups, as well as any other functional groups provided that the derivatized POSS is not rendered unacceptable for cosmetic purposes.
[0021] In some embodiments, the POSS molecules have the complete cage structure of Formula I formula III which have 8 and 6 silicon atoms respectively, as follows:
[0000]
[0022] In other embodiments, one or even two of the oxygen bridges between successive silicon atoms are broken or missing, in which case the “POSS” is referred to as having an “incomplete” case structure. Representative examples include the three-dimensional cage structures illustrated in Formulas IIA-E, IVA-E and V, as follows:
[0000]
[0023] In Formula IVA, the number of Si atoms in the cage is 10, in Formula IVB, the number of Si atoms is 10 and in Formula IVC, the number of Si atoms in the cage is 12. In Formulae IVD and IVE, the number of Si atoms in the cage or core is 16. In the “incomplete” cage structure shown in Formula V, one or more of the oxygen bridges between successive silicon atoms is broken or missing. Even though Formula IVC is shown with specific R groups, the structure is not limited to that exact molecule—the R groups may include other substituents as disclosed hereinbelow.
[0024] To make the POSS-grafted polyolefins of the present invention, the POSS periphery must contain a functional group reactive with pendant vinyl groups on various polyolefin backbones, and/or a functional group that is itself polymerizable and can become integrated into the polyolefin backbone. These reactive groups may be linked directly or indirectly to the Si atom in the POSS (e.g., the reactive group may be attached to an “R” group). Thus, the polymers of the present invention include POSS grafted onto homo-polyolefins, and polyolefin copolymers including polyolefin block copolymers and terpolymers that contain, in addition to the polyolefin component(s), blocks of the polymerized functional group. For purposes of the present invention, both types of embodiments are embraced by the term “grafted”. These groups are described in the context of the immediately succeeding section on methods of making the polymers. Other substituents that may be included in the POSS periphery are discussed thereafter. The POSS-grafted polyolefins may be cross-linked or non-crosslinked.
Methods of Making the POSS-Grafted Polyolefins
[0025] The polyolefins grafted with POSS may be synthesized in accordance with a variety of synthetic techniques known in the art. See, generally, Wu, et al., J. Macromolec. Sci. Part C: Polymer Reviews 19:25-63 (2009). For example, the POSS-polyolefin polymers may be in the form of random or non-random copolymers, diblock and triblock copolymers and tadpole-shaped copolymers.
[0026] In some embodiments, the POSS is derivatized with a polymerizable moiety that is capable of being integrated into the polyolefin backbone. Suitable polymerizable moieties include ethylenically unsaturated groups (e.g., alkenyl groups and preferably vinyl groups) and epoxy groups. Ethylenically unsaturated groups, especially those that can be polymerized by means of a free radical mechanism e.g., substituted and unsubstituted acrylates, methacrylates, alkenes and acrylamides, are preferred. Norbornene and styrene are two such examples of such polymerizable moieties. Other examples include functional silicones—for example, silanes (Si—H), and silanols, hydroxy, urethane, acrylate, vinyl, amides, MQ or T groups, functional acrylates, functional polyamides, PVK, PVA, PS, PEG, PPG, polysaccharides or modified starch, functional block copolymers, functional polyesters and polyesters, fluorinated polymers and wax. Persons skilled in the art would be able to select yet other polymerizable moieties e.g., from among the POSS substituents disclosed herein, and in the scientific literature. Thus, in these embodiments, the monomeric derivatized POSS and the olefin(s) are reacted together to form olefin-POSS copolymers (and in the case of two olefins, terpolymers). See, Seurer, et al., Macromol. Chem. Phys. 209:1198-1209 (2008), which describes a synthetic procedure in which POSS, linked to a diene such as norbornene, via a POSS periphery containing ethyl, isobutyl or phenyl groups, was polymerized with ethylene and propylene, thus making ethylene/propylene/POSS terpolymers via ring-opening metathesis polymerization (ROMP), and using the polymerization catalyst ethyl(bis-indenyl)hafnium dichloride.
[0027] In other embodiments, POSS can be grafted onto polyolefin backbones that as a result of the polymerization of the olefin (such as isoprene and butadiene), have pendant (also known as “dangling”) vinyl groups (e.g., 1,2-butadienes). In these embodiments, the POSS periphery is derivatized with a functional group reactive with the vinyl group on the polyolefin backbone. This type of polymerization can be practiced using a Zieglar-Natta scheme (see, e.g., Bhowmich, et al, Handbook of Elastomers, 2 nd Ed., Marcel Dekker, Inc., New York 2001) using polymerization initiators including for example, benzoyl peroxide, azobisisobutyronitrile (AIBN), the initiators available from Akzo Nobel under the tradenames Trigonox® and Perkadox® e.g., Trigonox 21S (tert-butyl peroxy-2-ethylhexanoate), Trigonox 25C75 (tert-Butyl peroxypivalate), Trigonox 141 (2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane), and Perkadox 16 (di(4-tert-butylcyclohexyl) peroxydicarbonate). See, for example, Chun, et al., Mat. Res. Soc. Symp. Proc. 661:K.K.10.8.1-K.K.10.8.6 (2001), which reports dimethyl silane-POSS grafted onto a polyisoprene-polystyrene block copolymer. See, also, Fu, et al., Macromolecules 37:5211-18 (2004); Drazkowski, et al., Macromolecules 39:1854-63 (2006); and Drazkowski, et al., Macromolecules 40:2798-2805 (2007), which report grafting of styrene-butadiene-styrene triblock copolymers grafted with the following octameric POSS ([Si 9 O 12 ]) derivatives, each containing a single silane functional group (i.e., ((CH 2 ) 3 SiMe 2 (C 6 H 4 )(SiMe 2 H)) and an “R” group, as follows: cyclopentyl (i.e., (c-C 5 H 9 ); cyclohexyl; cyclohexenyl; and phenyl; and isobutyl, respectively.
[0028] Even further, Zheng, et al., J. Poly. Sci. Part A: Polymer Chemistry 39:2920-28 (2001), report a two-step synthetic route for the preparation of PE-POSS copolymers, via ROMP of cyclooctene and a POSS having a periphery containing a single norbornene group and 7 cyclopentyl groups (also referred to as cyclopentyl-POSS-norbornene macromonomer 1-[−(5-norbornen-2-yl)ethyl]-3,5,7,9,11,13,15-heptacyclopentylpentacylclo[9.5.1.1.1.1]octasiloxane), using Grubb's catalyst, wherein a large degree of control over incorporation of the POSS monomer was achieved by use of diimide reduction which completely removed unsaturated units from the polymer backbone. In Zheng, et al., Macromolecules 34(23):8034-39 (2001), control over the incorporation of cyclopentyl-POSS-norbornene macaromonomer with ethylene and also with propylene using classical metallocene catalysts. In Zheng, et al., Macromolecules 37(23):8606-11 (2004), polymerization of cyclopentyl-POSS-norbornene macaromonomer with polybutadiene using Grubb's catalyst, wherein the resultant polymers formed two-dimensional lamellar-like nanostructures of assembled cubic silsesquioxanes, is reported.
[0029] Synthesis of tadpole-shaped (monochelic) POSS-containing hybrid (alkyne-terminated) polystyrene via CuBr-catalyzed click coupling is reported in Zhang, et al., Polymer 51(10):2133-39 (2010).
[0030] Persons skilled in the art would be able to select yet other functional groups reactive with vinyl groups e.g., from among the POSS substituents disclosed herein, and in the scientific literature.
[0031] In some embodiments, the polyolefin component is a block copolymer containing units of polyethylene and polypropylene, and the POSS component contains 8, 10 or 12 Si atoms, wherein one of the “R” groups is the reactive group or the polymerizable functional group, and all other R substituents are isobutyl or a cycloalkyl or cycloalkenyl (or wherein the reactive group or the polymerizable functional group is directly attached to an R substituent which thus serves as a linker).
Other POSS Substituents
[0032] In addition to the functional group reactive with a vinyl group and/or a polymerizable functional group, the POSS may have any substituent (including non-reactive and additional reactive groups) as described hereinbelow. For example, the POSS may have at least one M, D or T subunit.
[0033] The “M” unit can be represented by the structure:
[0000]
[0034] The “D” subunit can be represented as:
[0000]
[0035] The symbol “T” denotes the trifunctional subunit, (CH 3 )SiO 3/2 and can be represented as:
[0000]
[0036] Preferably, at least four of the Si atoms in the POSS structure are “completely saturated.” Most preferably, all of the Si atoms are bound, through oxygen atoms, to three other Si atoms within the cage as shown in Formulas I, III and IVA, thus all the Si atoms are “completely saturated.” While illustrated in Formula I as Si atoms, the groups at each corner may be the same or different and may be one or more atoms or groups including, without limitation, silicon, silane, siloxane, silicone or organometallic groups.
[0037] Any methyl group can be replaced in the “M”, “D” and/or “T” subunits with another functional or R group. As non-limiting examples, one or more methyl groups could be replaced with another alkyl group, alkene, alkyne, hydroxyl, thiol, ester, acid, ether. In one embodiment, the “IR groups” of the present invention include, without limitation, one or more of the following: methyl, ethyl, propyl, isobutyl, isooctyl, phenyl, cyclohexyl, cyclopentyl, —OSi(CH 3 ) 2 —CH 2 —CH 2 —(CF 2 ) 5 CF 3 , —(CH 2 ) 3 SH, N + (CH 3 ) 3 , O—N + CH 3 ) 3 , —OH, —(CH 2 ) n N + H 3 X— wherein n is 0-30 and X is a counter ion,
[0000]
[0038] Preferably, the R group is an isooctyl group. These substituent groups may be bound directly to the cage structure or may be bound through a bridging molecule such as an azo, diazo, epoxy or halogen containing material.
[0039] For example, the one remaining bond of each silicon of Formula I, III and IVA can bind to a variety of substituents or groups specified, as “R” groups (R 1 -R 8 ), ((R 1 -R 6 ) in Formula III). In some embodiments illustrated in Formulas II, IVB and V a POSS molecule in which one or two of the oxygen bridges between adjacent silicon molecules have been eliminated, a greater number of R groups are possible. When a POSS having 8 Si atoms is employed, it is preferred that no more than two of these inter-silicon connections (oxygen bridges) be eliminated. However, it is possible to eliminate as many as three such bridges (Formula IIE). More preferably, only a single oxygen bridge would be eliminated (Formula IIA). As stated above, the Si molecules not completely bound may have one or more additional positions available for binding additional substituents. In the case of a single missing side, the POSS molecule may include additional R group R 9 and R 10 , which may be the same or different as the R group R 1 -R 8 . When 2 or 3 bridges are missing, the POSS molecule may include additional R groups R 9 , R 10 , R 11 and R 12 (as appropriate), which all may be the same or different and may be the same as the groups identified for R 1 -R 8 .
[0040] In general, R groups (for example, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 as shown in the figures and any other R groups appropriate) can be the same or different and may be reactive or nonreactive groups. They may be, in replacing a methyl or H, for example, hydroxy (—OH), alkane derivatives (missing a hydrogen) also known as alkyl groups (other than methyl), alkenyl groups also referred to as derivatives of alkenes (having one or more double bonds), usually missing an H where they are bound to Si in POSS or to some other molecule, alkynyl groups also referred to as derivatives of alkynes (having one or more triple bonds) usually missing an H where they are bound to Si in POSS or to some other molecule, aryl groups (either the 6-carbon ring of benzene or the condensed 6-carbon rings of other aromatic derivatives such as naphthalene) also referred to as derivatives of arenes, usually missing an H where they are bound to Si in POSS or to some other molecule, acyl groups (organic acids without the OH group, e.g., CH 3 CO— or C 6 H 5 CO—), alkoxy groups (alkyl radicals attached to the remainder of a molecule by oxygen), such as methoxy, ester groups, acid groups, acrylate groups, alkyl acrylate groups, hydroxy groups, halogens, amino groups, alkylamino groups, aminoalkyl groups, groups containing one or more tertiary or quaternary nitrogens, silicone containing groups, sulfur containing groups, epoxides, azo groups, diazo groups, halogens, cyclic compounds which can undergo ring opening polymerization or ring opening metathesis polymerization. R groups may also be monomers or polymers where POSS will be used as a pendant substituent of the polymer. Acrylates and cationic polymers providing conditioning properties are provided in one embodiment.
[0041] Where appropriate, any of these R groups may themselves be substituted or unsubstituted, saturated or unsaturated, linear or branched. Possible substitutions include C 1 -C 30 alkyl groups, C 1 -C 30 alkenyl groups, C 1 -C 30 alkynyl groups, C 6 -C 18 aryl groups, acyl groups, alkoxy groups, carboxy groups, ester groups, acrylate groups, alkyl acrylate groups, trihydroxy groups, amino groups, alkylamino groups including mono and dialkylamino groups, mono and dihydroxy alkylamino groups, cyano groups, aminoalkyl groups, groups containing one or more tertiary or quaternary nitrogens, silicone containing groups, sulfur and/or phosphorous containing groups, SO 2 X, SO 2 X, where X is H, methyl or ethyl, epoxides, azo groups, diazo groups, halogens, cyclic compounds which can undergo ring opening polymerization or ring opening metathesis polymerization (ROMP). Indeed, any group which can be attached to a corner of a POSS molecule can be used.
[0042] When these R groups are carbon containing fatty acids or fatty alcohols, aromatic or cyclic groups, they generally may contain between six and 50 carbon atoms and may be saturated or unsaturated, substituted as discussed above or unsubstituted and branched or linear, as appropriate for a given group.
[0043] More specifically, possible R groups include, without limitation, hydroxy groups including mono or poly hydroxy groups, phenols, alkoxy, hydroxy alkyls, silanes, amino and in particular, quats, halosilanes, epoxides, alkyl carbonyls, alkanes, haloalkyls, halogens, acrylates, methacrylates, thiols, nitriles, norbornenyls, branched alkyl groups, polymers, silanes, silanols, styryls and thiols. In a single POSS molecule of Formula I, R 1 could be H, R 2 —OH, R 3 —NH 2 , R 4 —CH 2 CH 2 N + CH 3 (OCH 2 CH 3 ) CH 2 CH 2 CH 3 , R 5 —CH 2 CH 2 CHOCH 2 (epoxide), R 6 —OC(CH 3 ) 3 , R 7 —OOC(CH 2 ) 16 CH 2 and R 8 could be Cl. This is a hypothetical example, merely to illustrate that each of the R groups can be derivatized separately and to emphasize the wide variety of possible substitutions.
[0044] In one embodiment, these POSS molecules are not completely substituted with the same R groups (e.g., not all R 1 -R 6 , R 1 -R 8 , R 1 -R 10 or R 1 -R 12 (and any other R groups, as appropriate, given the number of Si atoms and available bonds in a given POSS molecule) are methyl, isobutyl or phenyl, etc.). This is particularly preferred for POSS molecules that have the structure of Formula I. Moreover, when a POSS molecule having 8 Si subunits, as depicted in Formula I, is employed, at least one of the R groups is a group other than a methyl.
[0045] Also contemplated under the term POSS is the family of commercially available compounds available from Hybrid Plastics, 18237 Mount Baldy Circle, Fountain Valley, Calif. 92708-6117 and Mayaterials, Inc. P.O. Box 87, South Lyon, Mich. 48178-0087.
[0046] Otherwise, POSS compounds with various R groups are well known in the literature. They are described in a number of U.S. patents including, for example, U.S. Pat. Nos. 5,047,492; 5,389,726; 5,484,867; 5,589,562; 5,750,741; 5,858,544; 5,939,576; 5,942,638; 6,100,417; 6,127,557; 6,207,364; 6,252,030; 6,270,561; 6,277,451; 6,362,279; and 6,486,254. These patents describe in detail various methods of producing the basic POSS cage structure and various derivatives thereof.
[0047] The amount of POSS-grafted polyolefin present in the cosmetic compositions of the present invention generally varies from about 1 to about 50%, and in some embodiments from about 5 to about 30% by weight, based on the total weight of the composition.
Solvents
[0048] Suitable solvents (also “carriers”) for the POSS-grafted polyolefins are most typically non-aqueous or anhydrous in nature. The solvent should also be non-reactive with and in the presence of the POSS-grafted polyolefin as well as be cosmetically acceptable for purposes of use in a cosmetic or personal care product. Otherwise, they may be polar or non-polar, volatile or non-volatile, or aqueous or non-aqueous in nature.
[0049] Representative volatile solvents include non-polar volatile hydrocarbon-based oils (which as used herein, refers to oil containing only hydrogen and carbon atoms), silicone oils (optionally comprising alkyl or alkoxy groups that are pendant or at the end of a silicone chain), and fluoro oils. Suitable hydrocarbon-based oils include isoparaffins, e.g., branched alkanes containing 8-16 carbon atoms, such as isododecane (also known as 2,2,4,4,6-pentamethylheptane), and petroleum distillates. Suitable volatile silicone oils may include linear or cyclic silicones containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. Examples include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexadecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, decamethyltetrasiloxane and heptamethyloctyltrisiloxane.
[0050] Representative polar volatile solvents may also be used, examples of which include C 2 to C 5 alcohols, such as ethanol, ethyl 3-ethoxypropionate and isohexyl neopentanoate.
[0051] Representative non-polar non-volatile solvents include polyalphaolefins, which include ethylene derivatives oligomerized into even-numbered carbon polyalphaolefins e.g., C 6 -C 14 olefins such as polydecene and polymers of C 6 , C 8 , C 12 and C 14 olefins. The polyolefins have a molecular weight (MW) generally ranging from about 280 to about 11,500, and a viscosity (CPs at about 20° C.) generally ranging from about 7 to about 32,500. They may also be hydrogenated. In some embodiments, the non-volatile polyolefin solvent may be obtained commercially from Exxon Chemicals under the tradename PureSyn™, e.g., PureSyn™ 2 (MW about 283), PureSyn™ 4 (MW about 432), PureSyn™ 6 (MW about 570), PureSyn™ 8 (MW about 611), PureSyn™ 150 (MW about 3980) and PureSyn™ 300 (MW about 4870) (INCI name: hydrogenated polydecene). The viscosities of these polymers are about 8, about 33, about 64, about 103, about 4179 and about 8400, respectively. PureSyn™ 100 (MW about 2939, viscosity about 3900, INCI name:hydrogenated C6-14 olefin polymers) and PureSyn™ 1000 (MW about 11,500, viscosity about 32,400, INCI name: polydecene) may also be useful.
[0052] Representative examples of non-volatile silicone oils which may be suitable for use as solvents/carriers include polydimethylsiloxanes (PDMSs), that are optionally phenylated, such as phenyltrimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenylmethyldimethyltrisiloxanes, diphenyldimethicones, phenyldimethicones and polymethylphenylsiloxanes, optionally substituted with aliphatic and/or aromatic groups, or optionally fluorinated; polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes (in particular polyoxyethylene or copoly(oxyethylene/oxypropylene) blocks or grafts such as dimethicone polyols); fluorosilicones and perfluorosilicone oils such as perfluoroalkyl polydimethylsiloxanes and perfluoroalkyl polymethylphenylsiloxanes; and silicones bearing both hydrophobic hydrocarbon-based groups (for example C 2 -C 30 alkyl groups) and polyoxyethylenated or copoly(oxyethylenated/oxypropylenated) blocks or grafts, such as alkyldimethicone copolyols. Other non-volatile silicone oils that may be useful as solvents/carriers in the inventive compositions include dimethicone polymers available from Dow Corning under the name Dow Corning 200® Fluid and have viscosities ranging from 5 to 600,000 centistokes, the Viscasil series of polyalkylsiloxanes (General Electric Company) and the Dow Corning 200 series (Dow Corning Corp.), the polymethylphenyl siloxanes having viscosities of from about 15 to about 65 centistokes at 25° C. such as, for example, those available as SF 1075 methyl-phenyl fluid (General Electric Company) and 556 Cosmetic Grade Fluid (Dow Corning Corp.), polyethersiloxane copolymers such as a polyoxyalkylene ether copolymer having a viscosity of about 1200 to 1500 centistokes at 25° C., including for example, SF1066 organosilicone surfactant (General Electric Company).
[0053] The amount of solvent present in the cosmetic compositions of the present invention generally varies from about 10% to about 90%, and in some embodiments from about 20 to about 80% by weight, based on the total weight of the composition.
[0054] In view of the solubility of the POSS-grafted polyolefins, cosmetic compositions in which the POSS-grafted polyolefins may be formulated typically fall into two general categories, namely anhydrous-based compositions, and multiphasic compositions or emulsions, that include two or more phases, typically aqueous and oil-based, wherein the discrete (e.g., continuous and discontinuous) phases are dispersible by the presence of an emulsifier or other cosmetic ingredient with emulsifying properties.
[0055] Anhydrous compositions are typically characterized in that aside from an amount of water present in a pre-made commercial cosmetic ingredient, there is typically no added water. For purposes of the present invention, added water may be present in amounts of no more than 10%, 5%, 2% or even 1%, based on the total weight of the composition. Representative examples of anhydrous cosmetic compositions include non-compressed and compressed powders (such as foundation, and sticks), pastes, water-proof mascara, lipstick and lipgloss. Examples of non-anhydrous compositions include gels, lotions, solutions, foams and creams.
[0056] In addition to the POSS-grafted polyolefin and non-aqueous solvent, these compositions typically contain at least one additional cosmetic ingredient, including for example, structuring agents such as waxes and non-wax polymers, hydrophobic and hydrophilic gelling agents, and powders/fillers.
[0057] Emulsions typically contain, in addition to the POSS-grafted polyolefin and the solvent, at least one other phase e.g., a fatty or oil phase (that typically contains a liquid fatty phase and/or a fatty substance that is at least partially solid at room temperature (20° C.-25° C.)), or water, and an emulsifier or other cosmetic ingredient with emulsifying properties.
Structuring Agents
[0058] The function of this ingredient is to structure (that is, thicken and/or increase the viscosity of) the product, and particularly an oil phase thereof, in order to form a solid product. Structuring agents that may be useful in the present invention include polyorganosiloxane-containing polymers, non-silicone-polyamide copolymers, waxes, and mixtures thereof. Polyorganosiloxane-containing polymers can generally be described as polymers chosen from homopolymers and copolymers, preferably, with a weight-average molecular mass ranging from about 500 to about 2.5×10 6 or more, comprising at least one moiety comprising: at least one polyorganosiloxane group comprising, preferably, from 1 to about 10,000 organosiloxane units in the chain of the moiety or in the form of a graft, and at least two groups capable of establishing hydrogen interactions are provided. Non-silicone-polyamide copolymers include those known in the trade as Uniclear or Sylvaclear. These non-silicone polyamides have different terminal end groups, such as ester terminated, known as Uniclear 80 or 100, such as amide terminated, known as Sylvaclear A200, and such as polyalkyleneoxy terminated, known as Sylvaclear AF1900 as well as ester terminated polyesteramides. Such non silicone polyamides are commercially available, for instance, from Arizona Chemical Company, Jacksonville, Fla.
[0059] Suitable waxes are those generally used in cosmetics and dermatology. Representative examples of waxes include those of natural animal, plant or mineral origin, for instance beeswax, carnauba wax, candelilla wax, ouricury wax, Japan wax, cork fiber wax, sugar cane wax, paraffin wax, lignite wax, microcrystalline waxes, lanolin wax, montan wax, ozokerites and hydrogenated oils such as hydrogenated jojoba oil as well as waxes of synthetic origin, for instance polyethylene waxes derived from the polymerization of ethylene, waxes obtained by Fischer-Tropsch synthesis, fatty acid esters and glycerides that are solid at 40° C., for example, at above 55° C., silicone waxes such as alkyl- and alkoxy-poly(di)methylsiloxanes and/or poly(di)methyl-siloxane esters that are solid at 40° C., for example, at above 55° C. Waxes approved for food use include ozokerite, rice wax and the waxes referenced in the Codex alimentary.
[0060] In general, the amount of structuring agent ranges from about 0.1 to about 30% and in some embodiments from about 0.5 to about 10% by weight, based on the total weight of the composition.
Gelling Agents
[0061] These ingredients also referred to as gellants, thickeners or thickening agents, may be hydrophobic (and if water is present, hydrophilic) in nature. Representative examples of oil- or fatty-phase-compatible thickeners that may be suitable for use in the present invention may be polymeric or mineral-based. The thickener may cause gelling via chemical reticulation and agents that gel via physical reticulation. Modified clays may be used as thickeners, including hectorites modified with an ammonium chloride of a C10 to C22 fatty acid, such as hectorite modified with distearyldimethylammonium chloride, also known as quaternium-18 bentonite, such as the products commercially available from Rheox under the tradename Bentone 34, or from Southern Clay under the tradenames Claytone XL, Claytone 34 and Claytone 40, the modified clays known as quaternium-18 benzalkonium bentonites and commercially available from Southern Clay under the tradenames Claytone HT, Claytone GR and Claytone PS, the clays modified with stearyldimethylbenzoylammonium chloride, known as stearalkonium bentonites, such as those commercially available from Southern Clay under the tradenames Claytone APA and Claytone AF, and from Rheox under the tradename Baragel 24. Other mineral thickeners include silica, such as fumed silica.
[0062] Representative examples of hydrophilic or aqueous-compatible thickeners that may be useful in the present invention include polysaccharides and gums, e.g., natural gums, xanthan gum, sclerotium, carrageenan and pectin; polysaccharide resins such as starch and its derivatives, for example tapioca starch, polyvinylpyrrolidone (PVP), polyvinyl alcohol, crosslinked polyacrylic acids and acrylates (e.g., Carbopol 982), hydrophobically-modified acrylates (e.g., Carbopol 1382); polyacrylamides such as, for example, the crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide/C13-C14 isoparaffin/Laureth 7) and Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyltaurate copolymer/isohexadecane/polysorbate 80) by SEPPIC; 2-acrylamido-2-methylpropanesulphonic acid polymers and copolymers, that are optionally crosslinked and/or neutralized; cellulose derivatives such as hydroxyethylcellulose, sodium carboxymethylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, ethyl cellulose and hydroxymethyl cellulose; hyaluronic acid and its salts, clays such as montmorillonites, hectorites, bentonites, and laponites, polyglyceryl (meth)acrylates polymers commercially available from Hispano Quimica or Guardian under the tradenames “Hispagel” and “Lubragel”, crosslinked acrylamide polymers and copolymers, such as those commercially available from Hoechst under the tradenames “PAS 5161” and “Bozepol C”, and crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymers such as those commercially available from Allied Colloid under the tradename “Salcare S.C.95”.
[0063] The gelling agent or thickener is typically present in an amount ranging from about 0.01% to about 10% by weight, in some embodiments from about 0.1% to about 5% by weight, based on the total weight of the composition.
Powders/Fillers
[0064] These ingredients may be obtained from various sources (e.g., mineral or organic), and have any number of shapes (e.g., lamellar or spherical). Representative examples of fillers/powders that may be useful in the present invention include polyamide (Nylon) particles and especially the microbeads sold under the tradename Orgasol by the company Atochem, or nylon fibres; polyethylene powders; microspheres based on acrylic copolymers, such as those made of ethylene glycol dimethacrylate/lauryl methacrylate copolymer sold by the company Dow Corning under the tradename Polytrap; the polymethyl methacrylate microspheres sold under the tradename Microsphere M-100 by the company Matsumoto or under the tradename Covabead LH 85 by the company Wackherr; melamine-formaldehyde or urea-formaldehyde resin particles; poly(tetrafluoroethylene) particles; ethylene-acrylate copolymer powders, for instance those sold under the tradename Flobeads by the company Sumitomo Seika Chemicals; expanded powders such as hollow microspheres and especially microspheres formed from a terpolymer of vinylidene chloride, acrylonitrile and methacrylate, and sold under the tradename Expancel by the company Kemanord Plast under the references 551 DE 12 (particle size of about 12 μm and mass of a unit volume of 40 kg/m 3 ), 551 DE 20 (particle size of about 30 μm and mass of a unit volume of 65 kg/m 3 ) and 551 DE 50 (particle size of about 40 μm), or the polyacrylonitrile microspheres sold under the tradename Micropearl F 80 ED by the company Matsumoto; powders of natural organic materials such as starch powders, especially of crosslinked or non-crosslinked maize, wheat or rice starch, such as the powders of starch crosslinked with octenylsuccinate anhydride, sold under the tradename Dry-Flo by the company National Starch, and cellulose microbeads; and silicone resin microbeads, such as those sold under the tradename Tospearl by the company Toshiba Silicone, especially Tospearl 240.
[0065] The amount of filler/powder generally ranges from about 0.1% to about 25% and in some embodiments from about 1% to about 20% by weight, based on the total weight of the composition.
Fatty Phase Ingredients
[0066] In addition to the non-aqueous solvent, at least one cosmetically or dermatologically acceptable and, in general, physiologically acceptable oil may be present. As used herein, the term “oil” means any fatty substance that is in liquid form at room temperature and atmospheric pressure. Oils that may be suitable for use in the present invention include both volatile and nonvolatile oils.
[0067] The volatile or nonvolatile oils are typically selected from hydrocarbon-based oils, silicone oils, and fluoro oils. The term “hydrocarbon-based oil” refers to oil mainly containing hydrogen and carbon atoms and possibly oxygen, nitrogen, sulfur and/or phosphorus atoms.
[0068] Representative categories of non-volatile hydrocarbon-based oils include fatty acids, linear or branched hydrocarbons of plant, mineral, or plant origin, and synthetic oils such as esters and ethers, fatty alcohols and fatty amides.
[0069] Examples of fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid, erucic acid, brassidic acid, cetoleic acid, lignoceric acid and nervonic acid.
[0070] Examples of linear or branched hydrocarbons of mineral origin include mineral oils (e.g., paraffin), petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam, perhydrosqualene and squalane.
[0071] Examples of hydrocarbon-based plant oils include triglycerides consisting of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C4 to C24, these chains possibly being linear or branched, and saturated or unsaturated, e.g., heptanoic or octanoic triglycerides, groundnut oil, babassu oil, coconut oil, grapeseed oil, cottonseed oil, corn oil, corn germ oil, mustard seed oil, palm oil, rapeseed oil, sesame seed oil, soybean oil, sunflower oil, wheatgerm oil, canola oil, apricot oil, mango oil, castor oil, shea oil, avocado oil, olive oil, sweet almond oil, peach kernel oil, walnut oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy seed oil, pumpkin oil, marrow oil, blackcurrant seed oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passionflower oil, musk rose oil or shea butter oil and alternatively caprylic/capric acid triglycerides.
[0072] Representative examples of synthetic esters and ethers, in particular of fatty acids, such as oils of formulae R1COOR2 and R1 OR2 in which R1 represents the residue of a fatty acid or of a fatty alcohol comprising from 8 to 29 carbon atoms and R2 represents a branched or unbranched hydrocarbon chain comprising from 3 to 30 carbon atoms, such as, for example, purcellin oil, octyl palmitate, isopropyl lanolate, 2-octyldodecyl stearate, 2-octyldodecyl erucate or isostearyl isostearate; hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate or heptanoates, octanoates or decanoates of fatty alcohols; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters, such as pentaerythrityl tetraisostearate; or lipophilic derivatives of amino acids, such as isopropyl lauroyl sarcosinate (INCI name). Yet other examples include C 12 -C 15 alkyl benzoates such as those sold under the tradenames “Finsolv TN” and “Witconol TN” by the company Witco, and 2-ethylphenyl benzoate, for instance the product sold under the name X-TEND 226® by the company ISP, triglycerides such as dicaprylyl carbonate (e.g., Cetiol CC, sold by Cognis), and oxyethylenated or oxypropylenated fatty esters and ethers.
[0073] Fatty alcohols which may be useful in the present invention tend to be liquid at room temperature and have a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms. Representative examples thus include 2-octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2-undecylpentadecanol.
[0074] Representative examples of fatty amides include isopropyl lauroyl sarcosinate such as the product sold under the tradename “Eldew SL-205” by the company Ajinomoto).
[0075] Representative examples of volatile hydrocarbon-based oils include oils containing from 8 to 16 carbon atoms, and especially branched C8-C16 alkanes (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane and isohexadecane.
[0076] Examples of nonvolatile silicone oils that may be useful in the present invention include nonvolatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising alkyl or alkoxy groups that are pendent and/or at the end of a silicone chain, these groups each containing from 2 to 24 carbon atoms, phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes and 2-phenylethyl trimethylsiloxysilicates, and dimethicones or phenyltrimethicones with a viscosity of less than or equal to 100 cSt.
[0077] Representative examples of volatile silicone oils that may be useful in the present invention include volatile linear or cyclic silicone oils, especially those with a viscosity ≦8 centistokes (8×10 −6 m 2 /s) and especially containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. Specific examples include dimethicones with a viscosity of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.
[0078] Representative examples of volatile fluoro oils that may be suitable for use in the present invention include nonafluoromethoxybutane and perfluoro-methylcyclopentane.
[0079] The amount of oil that may present in the compositions generally ranges from about 5% to about 99% and in some embodiments, from about 10% to about 80% by weight, based on the total weight of the composition.
[0080] The fatty phase may contain any other standard fat-soluble or fat/oil-dispersible additive such as waxes and other polymeric structuring agents, and pasty compounds or substances, which as used herein, refer to fatty compounds with a reversible solid/liquid change of state and containing, at a temperature of 25° C., a liquid fraction and a solid fraction. Examples of pasty compounds, such as polyol esters, are described in U.S. Patent Application Publication 2010/0015074 A1.
[0081] The amount of fatty phase (including both liquids and solids), exclusive of emulsifier and hydrophobic gelling agent, that may present in the compositions generally ranges from about 5% to about 80% and in some embodiments, from about 10% to about 50% by weight, based on the total weight of the composition.
Emulsifiers
[0082] Representative examples of emulsifiers that may be particularly suitable for use in the present invention include non-ionic amphiphilic lipids and anionic amphiphilic lipids.
[0083] Nonionic Amphiphilic Lipids:
[0084] The nonionic amphiphilic lipids of the invention are preferably chosen from 1) silicone surfactants; 2) amphiphilic lipids that are fluid at a temperature of less than or equal to 45° C., chosen from the esters of at least one polyol chosen from the group formed by polyethylene glycol comprising from 1 to 60 ethylene oxide units, sorbitan, glycerol comprising from 2 to 30 ethylene oxide units, polyglycerols comprising from 2 to 15 glycerol units, and of at least one fatty acid comprising at least one saturated or unsaturated, linear or branched C 8 -C 22 alkyl chain; 3) mixed esters of fatty acid or of fatty alcohol, of carboxylic acid and of glycerol; 4) fatty acid esters of sugars and fatty alcohol ethers of sugars; 5) surfactants that are solid at a temperature of less than or equal to 45° C., chosen from fatty esters of glycerol, fatty esters of sorbitan and oxyethylenated fatty esters of sorbitan, ethoxylated fatty ethers and ethoxylated fatty esters; and 6) block copolymers of ethylene oxide (A) and of propylene oxide (B).
[0085] The silicone surfactants which can be used according to the invention are silicone compounds comprising at least one oxyethylene chain —OCH 2 CH 2 — and/or oxypropylene chain —OCH 2 CH 2 CH 2 —. As silicone surfactants which can be used according to the present invention, mention may be made of those disclosed in documents U.S. Pat. No. 5,364,633 and U.S. Pat. No. 5,411,744.
[0086] The silicone surfactant used according to the present invention is preferably a compound of formula (VI):
[0000]
[0000] in which:
R 1 , R 2 and R 3 , independently of each other, represent a C 1 -C 6 alkyl radical or a radical —(CH 2 ) x —(OCH 2 CH 2 ) y —(OCH 2 CH 2 CH 2 ) z —OR 4 , at least one radical R 1 , R 2 or R 3 not being an alkyl radical; R 4 being a hydrogen, an alkyl radical or an acyl radical; A is an integer ranging from 0 to 200; B is an integer ranging from 0 to 50; with the proviso that A and B are not simultaneously equal to zero; x is an integer ranging from 1 to 6; y is an integer ranging from 1 to 30; and z is an integer ranging from 0 to 5.
[0087] According to one preferred embodiment of the invention, in the compound of formula (VI), the alkyl radical is a methyl radical, x is an integer ranging from 2 to 6 and y is an integer ranging from 4 to 30.
[0088] As examples of silicone surfactants of formula (VI), mention may be made of the compounds of formula (VII):
[0000]
[0000] in which A is an integer ranging from 20 to 105, B is an integer ranging from 2 to 10 and y is an integer ranging from 10 to 20.
[0089] As examples of silicone surfactants of formula (VI), mention may also be made of the compounds of formula (VIII):
[0000] H—(OCH 2 CH 2 ) y —(CH 2 ) 3 —[(CH 3 ) 2 SiO] A′ —CH 2 ) 3 —(OCH 2 CH 2 ) y —OH (VIII)
[0000] in which A′ and y are integers ranging from 10 to 20.
[0090] Compounds of the invention which may be used are those sold by the company Dow Corning under the names DC 5329, DC 7439-146, DC2-5695 and Q4-3667. The compounds DC 5329, DC 7439-146 and DC2-5695 are compounds of formula (II) in which, respectively, A is 22, B is 2 and y is 12; A is 103, B is 10 and y is 12; A is 27, B is 3 and y is 12.
[0091] The compound Q4-3667 is a compound of formula (VIII) in which A is 15 and y is 13.
[0092] The amphiphilic lipids that are fluid at a temperature of less than or equal to 45° C. are, in particular: the isostearate of polyethylene glycol of molecular weight 400, sold under the name PEG 400 by the company Unichema; diglyceryl isostearate, sold by the company Solvay; glyceryl laurate comprising 2 glycerol units, sold by the company Solvay; sorbitan oleate, sold under the name Span 80 by the company ICI; sorbitan isostearate, sold under the name Nikkol SI 10R by the company Nikko; and α-butylglucoside cocoate or α-butylglucoside caprate, sold by the company Ulice.
[0093] The mixed esters of fatty acid or of fatty alcohol, of carboxylic acid and of glycerol, which can be used as surfactants in the cosmetic composition according to the invention, may be chosen in particular from the group comprising mixed esters of fatty acid or of fatty alcohol with an alkyl chain containing from 8 to 22 carbon atoms, and of α-hydroxy acid and/or of succinic acid, with glycerol. The α-hydroxy acid may be, for example, citric acid, lactic acid, glycolic acid or malic acid, and mixtures thereof.
[0094] The alkyl chain of the fatty acids or alcohols from which are derived the mixed esters which can be used in the cosmetic composition of the invention may be linear or branched, and saturated or unsaturated. They may especially be stearate, isostearate, linoleate, oleate, behenate, arachidonate, palmitate, myristate, laurate, caprate, isostearyl, stearyl, linoleyl, oleyl, behenyl, myristyl, lauryl or capryl chains, and mixtures thereof.
[0095] As examples of mixed esters which can be used in the cosmetic composition of the invention, mention may be made of the mixed ester of glycerol and of the mixture of citric acid, lactic acid, linoleic acid and oleic acid (CTFA name: Glyceryl citrate/lactate/linoleate/oleate) sold by the company Hills under the name Imwitor 375; the mixed ester of succinic acid and of isostearyl alcohol with glycerol (CTFA name: Isostearyl diglyceryl succinate) sold by the company Hills under the name Imwitor 780 K; the mixed ester of citric acid and of stearic acid with glycerol (CTFA name: Glyceryl stearate citrate) sold by the company Hills under the name Imwitor 370; the mixed ester of lactic acid and of stearic acid with glycerol (CTFA name: Glyceryl stearate lactate) sold by the company Danisco under the name Lactodan B30 or Rylo LA30.
[0096] Fatty acid esters of sugars, which can be used as surfactants in the cosmetic composition according to the invention, are preferably solid at a temperature of less than or equal to 45° C. and may be chosen in particular from the group comprising esters or mixtures of esters of C 8 -C 22 fatty acid and of sucrose, of maltose, of glucose or of fructose, and esters or mixtures of esters of C 14 -C 22 fatty acid and of methylglucose.
[0097] The C 8 -C 22 or C 14 -C 22 fatty acids forming the fatty unit of the esters which can be used in the cosmetic composition of the invention comprise a saturated or unsaturated linear alkyl chain containing, respectively, from 8 to 22 or from 14 to 22 carbon atoms. The fatty unit of the esters may be chosen in particular from stearates, behenates, arachidonates, palmitates, myristates, laurates and caprates, and mixtures thereof. Stearates are preferably used.
[0098] As examples of esters or mixtures of esters of fatty acid and of sucrose, of maltose, of glucose or of fructose, mention may be made of sucrose monostearate, sucrose distearate and sucrose tristearate and mixtures thereof, such as the products sold by the company Croda under the name Crodesta F50, F70, F110 and F160 having, respectively, an HLB (hydrophilic lipophilic balance) of 5, 7, 11 and 16; and examples of esters or mixtures of esters of fatty acid and of methylglucose which may be mentioned are methylglucose polyglyceryl-3 distearate, sold by the company Goldschmidt under the name Tego-care 450. Mention may also be made of glucose or maltose monoesters such as methyl o-hexadecanoyl-6-D-glucoside and o-hexadecanoyl-6-D-maltoside.
[0099] The fatty alcohol ethers of sugars, which can be used as surfactants in the cosmetic composition according to the invention, are solid at a temperature of less than or equal to 45° C. and may be chosen in particular from the group comprising ethers or mixtures of ethers of C 8 -C 22 fatty alcohol and of glucose, of maltose, of sucrose or of fructose, and ethers or mixtures of ethers of a C 14 -C 22 fatty alcohol and of methylglucose. These are in particular alkylpolyglucosides.
[0100] The C 8 -C 22 or C 14 -C 22 fatty alcohols forming the fatty unit of the ethers which may be used in the cosmetic composition of the invention comprise a saturated or unsaturated, linear alkyl chain containing, respectively, from 8 to 22 or from 14 to 22 carbon atoms. The fatty unit of the ethers may be chosen in particular from decyl, cetyl, behenyl, arachidyl, stearyl, palmityl, myristyl, lauryl, capryl and hexadecanoyl units, and mixtures thereof, such as cetearyl.
[0101] As examples of fatty alcohol ethers of sugars, mention may be made of alkylpolyglucosides such as decylglucoside and laurylglucoside, which is sold, for example, by the company Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearyl glucoside optionally as a mixture with cetostearyl alcohol, sold for example, under the name Montanov 68 by the company SEPPIC, under the name Tego-care CG90 by the company Goldschmidt and under the name Emulgade KE3302 by the company Henkel, as well as arachidyl glucoside, for example in the form of a mixture of arachidyl alcohol and behenyl alcohol and arachidyl glucoside, sold under the name Montanov 202 by the company SEPPIC.
[0102] The surfactant used more particularly is sucrose monostearate, sucrose distearate or sucrose tristearate and mixtures thereof, methylglucose polyglyceryl-3 distearate and alkylpolyglucosides.
[0103] The fatty esters of glycerol which may be used as surfactants in the cosmetic composition according to the invention, which are solid at a temperature of less than or equal to 45° C., may be chosen in particular from the group comprising esters formed from at least one acid comprising a saturated linear alkyl chain containing from 16 to 22 carbon atoms and from 1 to 10 glycerol units. One or more of these fatty esters of glycerol may be used in the cosmetic composition of the invention.
[0104] These esters may be chosen in particular from stearates, behenates, arachidates and palmitates, and mixtures thereof. Stearates and palmitates are preferably used.
[0105] As examples of surfactants which can be used in the cosmetic composition of the invention, mention may be made of decaglyceryl monostearate, distearate, tristearate and pentastearate (CTFA names: Polyglyceryl-10 stearate, Polyglyceryl-10 distearate, Polyglyceryl-10 tristearate, Polyglyceryl-10 pentastearate), such as the products sold under the respective names Nikkol Decaglyn 1-S, 2-S, 3-S and 5-S by the company Nikko, and diglyceryl monostearate (CTFA name: Polyglyceryl-2 stearate), such as the product sold by the company Nikko under the name Nikkol DGMS.
[0106] The fatty esters of sorbitan which may be used as surfactants in the cosmetic composition according to the invention are solid at a temperature of less than or equal to 45° C. and are chosen from the group comprising C 16 -C 22 fatty acid esters of sorbitan and oxyethylenated C 16 -C 22 fatty acid esters of sorbitan. They are formed from at least one fatty acid comprising at least one saturated linear alkyl chain containing, respectively, from 16 to 22 carbon atoms, and from sorbitol or from ethoxylated sorbitol. The oxyethylenated esters generally comprise from 1 to 100 ethylene glycol units and preferably from 2 to 40 ethylene oxide (EO) units.
[0107] These esters may be chosen in particular from stearates, behenates, arachidates, palmitates, and mixtures thereof. Stearates and palmitates are preferably used.
[0108] As examples of surfactants which can be used in the cosmetic composition of the invention, mention may be made of sorbitan monostearate (CTFA name: sorbitan stearate), sold by the company ICI under the name Span 60, sorbitan monopalmitate (CTFA name: sorbitan palmitate), sold by the company ICI under the name Span 40, and sorbitan tristearate 20 EO (CTFA name: polysorbate 65), sold by the company ICI under the name Tween 65.
[0109] The ethoxylated fatty ethers that are solid at a temperature of less than or equal to 45° C., which may be used as surfactants in the cosmetic composition according to the invention, are preferably ethers formed from 1 to 100 ethylene oxide units and from at least one fatty alcohol chain containing from 16 to 22 carbon atoms. The fatty chain of the ethers may be chosen in particular from behenyl, arachidyl, stearyl and cetyl units, and mixtures thereof, such as cetearyl. Examples of ethoxylated fatty ethers which may be mentioned are behenyl alcohol ethers comprising 5, 10, 20 and 30 ethylene oxide units (CTFA names: beheneth-5, beheneth-10, beheneth-20, beheneth-30), such as the products sold under the names Nikkol BB5, BB10, BB20 and BB30 by the company Nikko, and stearyl alcohol ether comprising 2 ethylene oxide units (CTFA name: steareth-2), such as the product sold under the name Brij 72 by the company ICI.
[0110] The ethoxylated fatty esters that are solid at a temperature of less than or equal to 45° C., which may be used as surfactants in the cosmetic composition according to the invention, are esters formed from 1 to 100 ethylene oxide units and from at least one fatty acid chain containing from 16 to 22 carbon atoms. The fatty chain in the esters may be chosen in particular from stearate, behenate, arachidate and palmitate units, and mixtures thereof. Examples of ethoxylated fatty esters which may be mentioned are the ester of stearic acid comprising 40 ethylene oxide units, such as the product sold under the name Myrj 52 (CTFA name: PEG-40 stearate) by the company ICI, as well as the ester of behenic acid comprising 8 ethylene oxide units (CTFA name: PEG-8 behenate), such as the product sold under the name Compritol HD5 ATO by the company Gattefosse.
[0111] The block copolymers of ethylene oxide (A) and of propylene oxide (B), which may be used as surfactants in the cosmetic composition according to the invention, may be chosen in particular from block copolymers of formula (IX):
[0000] HO(C 2 H 4 O) x (C 3 H 6 O) y (C 2 H 4 O) z H (IX)
[0000] in which x, y and z are integers such that x+z ranges from 2 to 100 and y ranges from 14 to 60, and mixtures thereof, and more particularly from the block copolymers of formula (I) having an HLB value ranging from 2 to 16.
[0112] These block copolymers may be chosen in particular from poloxamers and in particular Poloxamer 231, such as the product sold by the company ICI under the name Pluronic L81 of formula (XI) in which x=z=6, y=39 (HLB 2); Poloxamer 282, such as the product sold by the company ICI under the name Pluronic L92 of formula (XI) in which x=z=10, y=47 (HLB 6); and Poloxamer 124, such as the product sold by the company ICI under the name Pluronic L44 of formula (XI) in which x=z=11, y=21 (HLB 16).
[0113] Among the nonionic amphiphilic lipids that are preferably used are polyethylene glycol isostearate (8 mol of ethylene oxide), diglyceryl isostearate, polyglyceryl monolaurate and monostearate comprising 10 glycerol units, sorbitan oleate, and sorbitan isostearate.
[0114] Anionic Amphiphilic Lipids:
[0115] The anionic amphiphilic lipids of the invention are chosen in particular from Alkyl ether citrates, Alkoxylated alkenyl succinates, Alkoxylated glucose alkenyl succinates, and Alkoxylated methylglucose alkenyl succinates.
[0116] The alkyl ether citrates which may be used as surfactants in the cosmetic composition according to the invention may be chosen in particular from the group comprising monoesters, diesters or triesters formed from citric acid and from at least one oxyethylenated fatty alcohol comprising a linear or branched, saturated or unsaturated alkyl chain containing from 8 to 22 carbon atoms, and comprising from 3 to 9 ethoxylated groups, and mixtures thereof. Specifically, it is possible to use a mixture of one or more of these citrates in the cosmetic composition of the invention.
[0117] These citrates may be chosen, for example, from the mono-, di- and triesters of citric acid and of ethoxylated lauryl alcohol, comprising from 3 to 9 ethoxylated groups, which are sold by the company Witco under the name Witconol EC, in particular Witconol EC 2129 which is predominantly a dilaureth-9 citrate, and Witconol EC 3129 which is predominantly a trilaureth-9 citrate.
[0118] The alkyl ether citrates used as surfactants are preferably used in a form neutralized to a pH of about 7, the neutralizing agent being chosen from inorganic bases such as sodium hydroxide, potassium hydroxide or ammonia, and organic bases such as monoethanolamine, diethanolamine, triethanolamine, 1,3-aminomethylpropanediol, N-methylglucamine, basic amino acids such as arginine and lysine, and mixtures thereof.
[0119] The alkenyl succinates which may be used as surfactants in the cosmetic composition of the invention are, in particular, ethoxylated and/or propoxylated derivatives and they are preferably chosen from the compounds of formula (X) or (XI):
[0000] HOOC—(HR)C—CH 2 —COO-E (X)
[0000] HOOC—(HR)C—CH 2 —COO-E-O—CO—CH 2 —C(HR′)—COOH (XI)
[0000] in which the radicals R and R′ are chosen from linear or branched alkenyl radicals containing from 6 to 22 carbon atoms, and E is chosen from oxyethylene chains of formula (C 2 H 4 O) n in which n ranges from 2 to 100, oxypropylene chains of formula (C 3 H 6 O) n in which n′ ranges from 2 to 100, random or block copolymers comprising oxyethylene chains of formula (C 2 H 4 O) n and oxypropylene chains of formula (C 3 H 6 O) n′ such that the sum of n and n′ ranges from 2 to 100, the oxyethylenated and/or oxypropylenated glucose groups comprising on average from 4 to 100 oxyethylene and/or oxypropylene units distributed on all the hydroxyl functions, the oxyethylenated and/or oxypropylenated methylglucose groups comprising on average from 4 to 100 oxyethylene and/or oxypropylene units distributed on all the hydroxyl functions.
[0120] In formulae (X) and (XI), n and n′ are average values and are thus not necessarily integers. A value of n ranging from 5 to 60 and even more preferably from 10 to 30 is advantageously chosen.
[0121] The radical R and/or R′ is advantageously chosen from linear alkenyl radicals containing from 8 to 22 and preferably from 14 to 22 carbon atoms. It may be, for example, the hexadecenyl radical containing 16 carbon atoms or the octadecenyl radical containing 18 carbon atoms.
[0122] The compounds of formulae (X) and (XI) described above, in which E is chosen from oxyethylene chains, oxypropylene chains and copolymers comprising oxyethylene chains and oxypropylene chains, may be prepared in accordance with the description given in documents WO-A-94/00508, EP-A-107199 and GB-A-2 131 820, which are incorporated herein for reference.
[0123] The acid function —COOH in the surfactants of formulae (I) and (II) is generally in the cosmetic composition of the invention in a form which is neutralized with a neutralizing agent, the neutralizing agents being chosen, for example, from inorganic bases such as sodium hydroxide, potassium hydroxide or ammonia, and organic bases such as monoethanolamine, diethanolamine, triethanolamine, 1,3-aminomethylpropanediol, N-methylglucamine, basic amino acids such as arginine and lysine, and mixtures thereof.
[0124] As examples of surfactants which can be used in the cosmetic composition of the invention, mention may be made of hexadecenyl succinate 18 EO (compound of formula X with R=hexadecenyl, E=(C 2 H 4 O) n , n=18), hexadecenyl succinate 45 EO (compound of formula X with R=hexadecenyl, E=(C 2 H 4 O) n , n=45), dihexadecenyl succinate 18 EO (compound of formula XI with R=R′=hexadecenyl, E=(C 2 H 4 O) n , n=18), dihexadecenyl glucose succinate 10 EO (compound of formula XI with R=R′=hexadecenyl, E=oxyethylenated glucose containing 10 oxyethylene groups), dihexadecenyl glucose succinate 20 EO (compound of formula XI with R=R′=hexadecenyl, E=oxyethylenated glucose containing 20 oxyethylene groups), dioctadecenyl methylglucose succinate 20 EO (compound of formula II with R=R′=octadecenyl, E=oxyethylenated methylglucose containing 20 oxyethylene groups), and mixtures thereof.
[0125] Depending on its more hydrophilic or more lipophilic nature, the nonionic or anionic amphiphilic lipid may be introduced into the aqueous phase or into the oily phase of the cosmetic composition.
[0126] Other Emulsifiers:
[0127] Cationic and amphoteric emulsifiers may also be useful.
[0128] The amount of emulsifier generally ranges from about 0.01 to about 20% and in some embodiments from about 0.1 to about 10% by weight, based on the total weight of the composition.
Aqueous Phase
[0129] In addition to water, an aqueous phase may also include water-miscible or at least partially water-miscible compounds, such as polyols or lower C2 to C8 monoalcohols, such as ethanol and isopropanol. “Polyol” should be understood as meaning any organic molecule comprising at least two free hydroxyl groups, examples of which include glycols, such as butylene glycol, propylene glycol, isoprene glycol, glycerol and polyethylene glycols, such as PEG-8, sorbitol and sugars, such as glucose. The aqueous phase may further include any other water-soluble, cosmetically acceptable ingredient.
[0130] The amount of aqueous phase (water, water-miscible solvents and other aqueous components) generally ranges from about 0.1 to about 50% and in some embodiments from about 1 to about 30% by weight, based on the total weight of the composition.
[0131] The cosmetic compositions of the present invention may also contain at least one further cosmetically acceptable ingredient, which to the extent they are not already mentioned in connection with any specific category of composition, are typically selected from colorants, photoprotective agents (e.g., U.V. filters), secondary film-formers, fillers, cosmetically active agents, and/or cosmetic additives. These ingredients are selected based on several factors, including for example, their compatibility with the POSS-grafted polyolefin and the solvent system, and the intended overall effect of the composition.
[0132] Representative examples of all the forementioned cosmetic ingredients are provided below.
Additional Film-Forming Polymers
[0133] These ingredients may be present in the inventive compositions, specifically selected depending on their compatibility with the POSS-polyolefin and the solvent. Broadly, film-forming polymers include synthetic polymers (of the free-radical type or the poly-condensate type), and polymers of natural origin. Of the term “free-radical film-forming polymer,” it is meant a polymer obtained by polymerization of unsaturated, e.g., ethylenically unsaturated monomers, capable of homopolymerization. Representative examples of these polymers that may be suitable for use in the present invention include vinyl polymers or copolymers, e.g., acrylic polymers. Vinyl film-forming polymers result from the polymerization of ethylenically unsaturated monomers containing at least one acidic group (e.g., α, β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid), esters of the acid monomers (e.g., (meth)acrylates, such as (meth)acrylates of an alkyl, such as a C1-C30 and preferably C1-C20 alkyl, (meth)acrylates of an aryl, such as a C6-C10 aryl, and (meth)acrylates of a hydroxyalkyl, such as a C2-C6 hydroxyalkyl) and amides of the acid monomers (e.g., (meth) acrylamides, including N-alkyl (meth)acrylamides, such as a C2-C12 alkyl such as N-alkyl(meth)acrylamides, N-ethylacrylamide, N-t-butylacrylamide, N-t-octylacrylamide and N-undecylacrylamide). Vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers selected from vinyl esters and styrene monomers, or copolymerization wherein these monomers are polymerized with the aforementioned acid, ester or amide monomers.
[0134] Representative examples of film-forming polycondensates that may be useful in the present invention include polyurethanes, polyesters, polyesteramides, polyamides, epoxy ester resins and polyureas.
[0135] The polymers of natural origin, which may be optionally modified, typically include shellac resin, sandarac gum, dammar resins, elemi gums, copal resins and cellulosic polymers.
[0136] Representative examples of specific oil/lipid-soluble film-forming polymers which may be suitable for use in the present invention include polyalkylenes, e.g., polybutene; alkylcelluloses with a linear or branched, saturated or unsaturated C1-C8 alkyl radical, e.g., ethylcellulose and propylcellulose; copolymers of vinylpyrrolidone (VP), e.g., copolymers of VP and C3-C20 alkenes, e.g., VP/vinyl acetate, VP/ethyl methacrylate, VP/eicosene, VP/hexadecene, and VP/styrene. Yet other oil/lipid-soluble film-forming polymers that may be useful include silicone resins, such as cross-linked polyorganosiloxanes and silicone resin copolymers. Block copolymers may also be useful (e.g., film-forming linear block ethylenic polymers which contain at least a first block and at least a second block with different glass transition temperatures that are linked together via an intermediate block containing at least one constituent monomer of the first block and at least one constituent monomer of the second block).
[0137] The film-forming polymer may also be present in an inventive composition in the form of particles dispersed in an aqueous phase (e.g., a (meth)acrylates copolymer) or in a non-aqueous solvent phase, which is generally known as a latex or pseudo latex.
[0138] Specific examples of representative polymers, including commercially available film-forming polymers are described in U.S. Patent Application Publication 2010/0278770 A1.
[0139] Additional film-forming polymers may be present in amounts generally ranging from about 0.1 to about 50% and in some embodiments from about 0.2 to about 40% by weight, based on the total weight of the composition.
Colorants
[0140] Colorants may be chosen from the lipophilic dyes, hydrophilic dyes, traditional pigments, and nacres usually used in cosmetic or dermatological compositions, and mixtures thereof. The coloring agent may have any shape, such as, for example, spheroidal, oval, platelet, irregular, and mixtures thereof. Pigments may optionally be surface-treated e.g., with silicones (e.g., inorganic pigments may be coated with simethicone), perfluorinated compounds, lecithin, and amino acids.
[0141] The liposoluble dyes include, for example, Sudan Red, D&C Red 17, D&C Green 6, soybean oil, Sudan Brown, D&C Yellow 11, D&C Violet 2, D&C Orange 5, quinoline yellow and annatto. The water-soluble dyes are, for example, beetroot juice or methylene blue.
[0142] The pigments may be chosen from white pigments, colored pigments, inorganic pigments, organic pigments, coated pigments, uncoated pigments, pigments having a micron size and pigments not having a micron size. Among the inorganic pigments that may be mentioned are titanium dioxide, optionally surface-treated, zirconium oxide, zinc oxide, cerium oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydrate, and ferric blue. Among the organic pigments which may be mentioned are carbon black, pigments of D&C type, lakes based on cochineal carmine, lakes based on barium, lakes based on strontium, lakes based on calcium, and lakes based on aluminum.
[0143] The nacreous pigments may, for example, be chosen from white nacreous pigments such as mica coated with titanium and mica coated with bismuth oxychloride, colored nacreous pigments such as titanium mica with iron oxides, titanium mica with, for example, ferric blue and/or chromium oxide, titanium mica with an organic pigment of the type mentioned above, as well as nacreous pigments based on bismuth oxychloride, interferential pigments, and goniochromatic pigments.
[0144] Colorants are generally present in an amount ranging from about 0.01% to about 20% and in some embodiments from about 0.1% to about 10%, by weight, based on the total weight of the composition.
Photoprotectants
[0145] These ingredients which are also referred to as U.V. filters, can be organic or inorganic (or physical) agents. Representative examples of organic photoprotective agents that may be suitable for use in the present invention include dibenzoylmethane derivatives, e.g., butylmethoxydibenzoylmethane; cinnamic derivatives, e.g., ethylhexyl methoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate, DEA methoxycinnamate, diisopropyl methylcinnamate, and glyceryl ethylhexanoate dimethoxycinnamate; para-aminobenzoic acid derivatives, e.g., PABA, ethyl PABA, ethyl dihydroxypropyl PABA, ethylhexyl dimethyl PABA, glyceryl PABA, and PEG-25 PABA; salicylic derivatives, e.g., homosalate, ethylhexyl salicylate, dipropyleneglycol salicylate, and TEA salicylate; β,β-diphenylacrylate derivatives, e.g., octocrylene and etocrylene; benzophenone derivatives, e.g., benzophenone-1, benzophenone-2, benzophenone-3 (also known as oxybenzone), benzophenone-4, benzophenone-5, benzophenone-6, benzophenone-8, benzophenone-9, benzophenone-12, and n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl) benzoate; benzylidenecamphor derivatives, e.g., 3-benzylidene camphor, 4-methylbenzylidene camphor, benzylidene camphor sulfonic acid, camphor benzalkonium methosulfate, terephthalylidene dicamphor sulfonic acid, and polyacrylamidomethyl benzylidene camphor; phenylbenzimidazole derivatives, e.g., phenylbenzimidazole sulfonic acid, and disodium phenyl dibenzimidazole tetrasulfonate; phenylbenzotriazole derivatives, e.g., drometrizole trisiloxane and methylene bis-benzotriazolyl tetramethylbutyl-phenol; triazine derivatives, e.g., bis-ethylhexyloxyphenol methoxyphenyl triazine, ethylhexyl triazone, diethylhexyl butamido triazone, 2,4,6-tris(dineopentyl 4′-aminobenzalmalonate)-s-triazine, 2,4,6-tris(diisobutyl 4′-aminobenzalmalonate)-s-triazine, 2,4-bis(n-butyl 4′-aminobenzoate)-6-(aminopropyl-trisiloxane)-s-triazine, and 2,4-bis(dineopentyl 4′-aminobenzalmalonate)-6-(n-butyl 4′-aminobenzoate)-s-triazine; anthranilic derivatives, e.g., menthyl anthranilate; imidazoline derivatives, e.g., ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate; benzalmalonate derivatives, e.g., polyorganosiloxane comprising benzalmalonate functional groups; 4,4-diarylbutadiene derivatives, e.g., 1,1-dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene; benzoxazole derivatives, e.g., 2,4-bis[5-1-(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine; and merocyanine derivatives, e.g., octyl 5-(N,N-diethylamino)-2-phenylsulfonyl-2,4-pentadienoate.
[0146] Preferred organic photoprotectants include octocrylene, homosalate, butylmethoxydibenzoylmethane, and ethylhexyl methoxycinnamate.
[0147] Representative inorganic photoprotectants are typically pigments formed of metal oxides which may or may not be coated (and which typically have a mean particle size between about 5×10 −3 μm and 100×10 −3 μm. Specific examples include pigments formed of titanium oxide, iron oxide, zinc oxide, zirconium oxide, and cerium oxide.
[0148] Representative examples of commercially available organic and inorganic photoprotective agents that may be useful in the present invention are disclosed, for example, U.S. Patent Application Publication 2010/0190740 A1.
[0149] Photoprotectants are generally present in an amount ranging from about 0.5 to about 50%, and in some embodiments from about 1 to about 40% by weight, based on the total weight of the composition.
[0000] Cosmetic Active Agents and other Additives
[0150] The compositions of the present invention may further contain at least one cosmetically active agent representative examples of which include anti-inflammatory agents, defoaming agents, emollients, vitamins, keratolytic and desquamating agents, α-hydroxy acids, depigmenting agents, salicylic acid, retinoids, hydrocortisone, natural extracts, steroids, anti-bacterial agents, enzymes, flavanoids, soothing agents, mattifying agents, trace elements and essential fatty acids. Aside from the forementioned fillers/powders, colorants, dispersion agents and photoprotectants, the compositions of the present invention may further contain at least one cosmetic additive representative examples of which include emollients, moisturizers, fibers, preservatives, chelators (such as EDTA and salts thereof, particularly sodium and potassium salts), antioxidants (e.g., BHT, tocopherol), essential oils, fragrances and neutralizing or pH-adjusting agents (e.g., sodium hydroxide). These ingredients may be selected for compatibility with aqueous or non-aqueous solvents (e.g., aqueous or fatty phase).
[0151] Cosmetic active agents and other cosmetic additives may present in the compositions in amounts generally ranging from about 0.01 to about 40% and in some embodiments from about 0.05 to about 30% by weight, based on the total weight of the composition.
[0152] The invention will now be discussed in terms of the following non-limiting examples. Unless otherwise specified, all parts are by weight.
Examples 1 and 2
Compositions Containing Colorant
[0153]
[0000]
PHASE
TRADE NAME
EXAMPLE1
EXAMPLE2
A
PE-PP-POSS iBu
11.52
0
12
PE-PP-POSS Ph12
0
11.50
Isododecane
73
73.01
Benton Gel
4.42
4.42
B
Color pigment
3.98
3.98
Isododecane
7.08
7.08
TOTAL
100.00
100.00
[0154] The two polyolefin/POSS polymers used in both exemplified compositions are disclosed in Seurer et al., Macromol. Chem. Phys. 209:1198-1209 (2008). The cosmetic compositions described in the Table were made according to the following procedure: in phase A, the POSS containing polymer was dissolved in isododecane and the solution was stirred at 80-90° C.; after the solution became homogeneous, it was allowed to cool to room temperature; the bentone gel was added as in Phase A; and Phase B containing color pigment in isododecane, was added, with mixing for a couple of minutes until the composition became uniform. After drawing down the solution of examples 1 and 2, thus allowing the solvent to evaporate, the color films that formed were non-tacky, water-proof and showed good color transfer resistance.
[0155] All publications cited in the specification, both patent publications and non-patent publications are indicative of the level of skill of those skilled in the art to which this invention pertains. All these publications are herein incorporated by reference to the same extent as if each individual publication were specifically and individually indicated as being incorporated by reference.
[0156] Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims. | Disclosed are cosmetic compositions and methods of making up keratinous tissue in a way that preserves long-wear but also greater comfort, reduced tackiness and enriched color, and which entail use of polyhedral oligomeric silsequioxanes (POSS)-grafted polyolefins. | 0 |
BACKGROUND
Manufacturing operations have significantly evolved in complexity through the integration of sophisticated automation devices and associated methods. Gains have been realized both in productivity and reliability as past reliance on human judgment and manipulation has been replaced by processor-based systems.
An example of this is manifested in the production equipment used in processing thin disc substrates that are made into storage media for data storage devices like disc drives. During storage and transit these discs are preferably stored for safekeeping in plastic caddies that individually support and spatially separate a plurality of the discs. The caddy also preferably longitudinally aligns the discs along their centroid axes to facilitate the use of automated end effectors to pick and place the discs from and to the caddy during processing steps.
The caddy preferably has a top cover that engages a cassette body to form a sealed enclosure that protects the discs inside from contamination during storage and transit. What is lacking is a top cover that is conceived to be optimal for using automated processing equipment to remove and replace it. It is to that needed improvement in the art that the claimed embodiments are directed.
SUMMARY
Claimed embodiments are generally directed to an apparatus and associated method for handling a disc caddy.
In some embodiments the disc caddy is characterized by a disc cassette having opposing longitudinal side walls joined to opposing lateral end walls forming a substantially rectangular structure defining open first and second ends. A first removable cover is provided for closing the first end, and a second removable cover is provided for closing the second end. The second removable cover defines barb members that latchingly engage respective strikes defined by the first removable cover that extend substantially parallel to the end walls. The disc cassette also has protuberant features defining reference hold-down surfaces, and the first removable cover defines clearance apertures through which the hold-down surfaces extend.
These and various other features and advantages which characterize the claimed embodiments will become apparent upon reading the following detailed description and upon reviewing the associated drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric depiction of a disc caddy that is constructed in accordance with related art solutions.
FIG. 2 is an isometric depiction of a disc cassette constructed in accordance with the claimed embodiments.
FIG. 3 is an isometric depiction of a caddy constructed in accordance with the claimed embodiments.
FIG. 4 is an end elevational depiction of the caddy of FIG. 3 showing retractable end effectors engaging the protuberant hold-down surfaces that are defined by the disc cassette.
FIG. 5 depicts one end of the top cover and the bottom cover in the manner that they are operably latched together as in FIG. 3 , but with the disc cassette not shown for clarity sake.
FIG. 6 is a cross sectional view taken along the line 6 - 6 in FIG. 5 depicting the top cover and bottom cover latched together.
FIG. 7 is a view similar to FIG. 6 but depicting an end effector having displaced the top cover flaps relative to the bottom cover to unlatch the covers.
FIG. 8 is a view similar to FIG. 7 but depicting the end effector having lifted the top cover away from the disc cassette.
FIG. 9 is an end elevational depiction of the lower end of the flap in FIG. 6 .
FIG. 10 is a view similar to FIG. 9 but depicting an alternative equivalent construction of the claimed embodiments.
FIG. 11 is a flowchart depicting steps in practicing a method for CADDY HANDLING in accordance with embodiments of the present invention.
DETAILED DESCRIPTION
Turning to the FIGS. generally, and for now particularly to FIG. 1 which depicts a caddy 100 that is constructed in accordance with attempted solutions in the related art. The caddy 100 has a disc cassette 102 into which the discs are longitudinally stacked, and a top cover 104 that seals a top opening in the disc cassette 102 for protecting the discs from contamination and/or debris during storage and transit.
Although not shown, typically the caddy 100 also includes a bottom cover to seal a bottom opening in the disc cassette 102 . The bottom opening is sometimes used to access the discs inside the disc cassette 102 during picking and placing them, and sometimes used as a drain when the discs are subjected to a chemical bath. However, even when a bottom opening is not needed, the bottom opening with bottom cover combination is preferable to a solid bottom because removing the bottom cover facilitates cleaning the disc cassette 102 during normal use.
FIG. 1 shows that to remove the top cover 104 the opposing flaps 106 are pulled away from the disc cassette 102 so that they are outwardly-angled with respect to the medial portion of the top cover 104 . Likewise, when attaching the top cover 104 the medial portion must be matingly engaged with the top opening while holding the tabs 106 outwardly angled from the ends of the disc cassette 102 . While this construction might be adequate for manually removing and replacing the top cover 104 , as depicted, it is not suited for use with automated processing equipment. That is, grasping the outwardly-angled flaps 106 does not reliably position the medial portion of the top cover 104 for placement. Even if that shortcoming were resolved, the motions necessary to remove and attach the top cover 104 are generally not optimal for automating the process.
FIG. 2 depicts a disc cassette 110 that is constructed in accordance with the claimed embodiments. The disc cassette 110 has opposing longitudinal walls 112 , 114 defining slots 116 for receiving a plurality of discs (not depicted) in a spaced apart configuration. Opposing end walls 113 , 115 are connected to the longitudinal walls 112 , 114 to define a substantially rectangular structure with an open top and an open bottom.
In this illustrative embodiment the disc cassette 110 also has two protuberant features 118 extending from a lower end of the longitudinal walls 112 , 114 . The protuberant features 118 define substantially laterally directed reference hold-down surfaces 120 .
FIG. 3 depicts a caddy 123 of the claimed embodiments, which includes the disc cassette 110 , a top cover 122 , and a bottom cover 124 to cover the top and bottom openings thereof, respectively. The top cover 122 has a medial 126 portion sized in relation to the top opening in the disc cassette 110 . Flaps 128 depend from each of proximal and distal ends of the medial portion 126 to cover openings in the end walls 113 , 115 that are contiguous to the top opening of the disc cassette 110 .
The bottom cover 124 defines apertures 127 through which the protuberant features 118 extend. FIG. 4 is an end view of the caddy 123 depicting how automated retractable fingers 130 contactingly engage the reference hold-down surfaces 120 to assert a hold-down force on the disc cassette 110 against a reference surface 132 , such as at a disc load/unload station.
It will be noted that the retention of the covers 122 , 124 is enhanced by making them latchingly engage each other, sandwiching the disc cassette 110 therebetween. FIG. 5 depicts the top cover 122 and the bottom cover 124 latched together as they are in FIG. 3 , but with the disc cassette 110 not shown to more clearly depict the bottom cover 124 defining an aperture 134 that is sized to receivingly engage a distal end of the flap 128 . FIG. 6 is a cross sectional view along the line 6 - 6 in FIG. 5 , showing the flap 128 defines a barb 136 at a distal end thereof. The distal end is guided into the aperture 134 by a sharp point and tapered edge of the barb surface 138 that is directed toward the distal end. The tapered edge terminates at an abrupt shoulder that latchingly engages against a strike surface 140 adjoining the edge of the aperture 134 . The flap 128 is aligned with the aperture 134 such that it is biased to the latching engagement position of FIG. 6 once the barb 136 passes beyond the strike surface 140 .
Preferably, the barb surface 138 is directed away from the disc cassette 110 as illustrated, so that as FIG. 7 shows an end effector 142 affecting an unlatching force F 1 directed toward the disc cassette 110 displaces the lower portion of the flap 128 to clearingly disengage the barb 136 from the strike surface 140 . The flap 128 is provided with a protuberant surface 144 , and the end effector 142 is made to matingly engage the protuberant surface 144 . FIG. 8 shows that this permits asserting F 1 while also asserting a lifting force F 2 with the end effector 142 to lift the top cover 122 away from the disc cassette 110 . Although in these embodiments the end effector 142 is described as asserting the forces F 1 , F 2 to unlatch and remove the top cover 122 , in equivalent alternative embodiments the disc cassette 110 could be moved relative to a fixed end effector 142 to accomplish removal of the top cover 122 .
FIG. 9 is an end elevational depiction of the lower portion of FIG. 6 , showing that in the illustrative embodiments the strike surface 140 continuously engages the barb surface 138 in the latching engagement of the top and bottom covers 122 , 124 . FIG. 10 depicts alternative embodiments wherein the strike surface 140 is segmented, such that it discontinuously engages the barb surface 138 in the same latching engagement. FIG. 10 permits using an end effector that is configured to matingly engage the barb surface 138 itself in the gap 146 to unlatch and remove the tope cover 122 in the manner described above, but where the end effector engaged the protuberant feature 144 . Engaging the barb surface 138 itself means that the protuberant feature 144 can be eliminated, simplifying construction of the top cover 124 .
Given the aforedescribed structure, FIG. 11 is a flowchart depicting programming steps in an automated method 200 for CADDY HANDLING in accordance with embodiments of the present invention. The method 200 begins in block 202 with positioning the caddy in a desired load/unload position. In block 204 retractable end effectors engage the protuberant features at the lower end of the disc cassette to affix the caddy at the load/unload position. In block 206 another set of end effectors move toward each other and pressingly engage against the downwardly extending flaps of the top cover to unlatch the top cover from the bottom cover. Finally, while maintaining the opposing bias on the flaps from the operation of step 206 , the end effectors are also lifted in unison to carry the top cover away from the disc cassette.
It is to be understood that even though numerous characteristics and advantages of various embodiments have been set forth in the foregoing description, together with details of the structure and function of various embodiments, this description is illustrative only, and changes may be made in detail, especially in matters of structure and arrangements of parts within the principles of the present embodiments to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed. For example, the particular elements may vary in type or arrangement without departing from the spirit and scope of the present embodiments.
In addition, although the embodiments described herein are described in relation to handling data storage discs, it will be appreciated by those skilled in the art that the claimed subject matter is not so limited and various other component handling systems employing a portable component caddy can utilize the present embodiments without departing from the spirit and scope of the claimed embodiments. | A disc caddy and associated method for handling is characterized by a disc cassette having opposing longitudinal side walls joined to opposing lateral end walls forming a substantially rectangular structure defining open first and second ends. A first removable cover is provided for closing the first end, and a second removable cover is provided for closing the second end. The second removable cover defines barb members that latchingly engage respective strikes defined by the first removable cover that extend substantially parallel to the end walls. The disc cassette has protuberant features defining reference hold-down surfaces, and the first removable cover defines clearance apertures through which the hold-down surfaces extend. | 6 |
BACKGROUND TO THE INVENTION
Thermal insulation is a widely used method of reducing undesirable heat gains or losses to a minimum. One extremely efficient method of providing thermal insulation is to use an evacuated enclosure such as disclosed in U.S. Pat. Nos. 4,546,798, and 3,680,631. However, such evacuated enclosures usually involve the use of walls of fragile glass, or heavy and expensive metals. Expensive vacuum pumps are necessary and the time required to pump the enclosure down to the required vacuum level can be excessive, in many applications. While such materials and costs can be justified in sophisticated applications such as chemical plants, oil gathering and the aerospace industry, etc., they are totally unacceptable in the requirements for the mass production of consumer goods.
For instance a non-limiting example is in the manufacture of domestic or "semi-industrial" refrigerators where, for economy of energy consumption, it is necessary to thermally insulate the cold storage space. This is presently accomplished by the use of sheets of foamed plastic material. Unfortunately the production of this foamed plastic makes use of chlorinated hydrocarbons whose widescale use is considered to be an ecological disaster and legislation is gradually being introduced to drastically reduce or eliminate their use.
In an attempt to provide an alternative insulating medium to foamed plastic it has been proposed to utilize plastic bags filled with a fibrous or powdered insulating medium and subsequently evacuated. However there have been found problems of gas permeation through the plastic bag causing loss of vacuum and hence thermal insulation. Creating the original vacuum is a lengthy process due to restricting conductances through pumping tubulations. Outgassing of the components during life again contributing to loss of vacuum is a problem. A getter device, to maintain the vacuum has been suggested but it must be heated, to cause it to sorb gases, at temperatures higher than the melting point of the plastics used.
OBJECTS OF THE PRESENT INVENTION
It is therefore an object of the present invention to provide an improved process for the manufacture of a vacuum insulating structure.
It is another object of the present invention to provide an improved process for the manufacture of a vacuum insulating structure having reduced manufacturing costs.
It is yet another object of the present invention to provide an improved process for the manufacture of a vacuum insulating structure using mainly plastic material.
It is still a further object of the present invention to provide an improved process for the manufacture of a vacuum insulating structure not requiring the use of chlorinated hydrocarbons.
Another object of the present invention is to provide an improved vacuum insulating structure.
These and other objects and advantages of the present invention will become evident to those skilled in the art by reference to the following description and drawings wherein;
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram useful in understanding a preferred method of the present invention.
FIG. 2 is a block diagram useful in understanding an alternative preferred method of the present invention.
FIG. 3 is a schematic partially cutaway view of a vacuum insulation structure being manufactured according to a method of the present invention.
FIG. 4 shows a glass phial useful in the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The method of the present invention for the manufacture of a vacuum insulating structure of the present invention comprises the steps of: flowing a getterable purge gas from a purge gas source which is in fluid contact with said vacuum insulated structure via a purge gas inlet attached to the vacuum insulating structure. Atmospheric air within the insulating structure is thereby expelled through a purge gas outlet attached to the insulating structure, thus producing a purged vacuum insulating structure. The purge gas outlet is closed and the getterable purge gas remaining in the purged vacuum insulating structure is removed by means of a purge gas removal means in fluid contact with the vacuum insulating structure via purge gas sorption conduit to produce a residual gas pressure of less than about 1 mbar within the vacuum insulating structure. The purge gas sorption conduit is then closed and the residual gas is then contacted with a residual gas getter material situated within the vacuum insulating structure.
Referring now to the drawings and in particular to FIG. 1 there is shown a block diagram 100 which will be used to describe one preferred method for the manufacture of a vacuum insulating structure of the present invention. In this case the purge gas source and the purge gas removal means are a single hydrogen storage device 102. The purge gas being used as the getterable gas is hydrogen. Hydrogen is the preferred purge gas as it has a higher flow rate under molecular flow conditions than other gases. Furthermore it is believed to have a chemical cleaning action. Suitable hydrogen storage devices are commercially available for instance from HWT Gesellschaft fur Hydrid und Wasserstoff Technik mbH, Germany as model number "KL 114-5." These hydrogen storage devices generally contain metallic hydrides such as those disclosed in German Patent Publication No. 3,210,381 published May 19, 1983 the entire disclosure of which is incorporated herein by reference. Particularly suitable are the hydrided alloys described in Examples 2, 3, 4, and 5 appearing in Columns 5 and 6 of that publication. These hydrogen storage devices release hydrogen at above atmospheric pressure upon heating and re-sorb hydrogen upon cooling. Hydrogen storage device 102 is therefore provided with a heating means (not shown) which may be an electric heating coil situated within the hydrogen storage device 102 or wrapped around the device itself. Alternatively heating may be accomplished simply by immersing the hydrogen storage device 102 within a bath (not shown) of hot water. In operation the hydrogen storage device 102, containing for example metallic hydrides such as ZrH or TiH, is heated to above ambient temperature and upon opening valve 104 hydrogen at above atmospheric pressure is caused to flow through purge gas inlet 106 attached in insulating structure 108 within which it is desired to produce a vacuum and hence a vacuum insulating structure. The above atmospheric pressure of hydrogen thereby expells atmospheric air from within insulating structure 108 through a purge gas outlet 110 also attached to the insulating structure 108. Thus there is produced a purged vacuum insulating structure 112. Purge gas outlet 110 is then crimped to produce a cold welded pressure and vacuum tight seal. The hydrogen storage device 102 is then cooled to remove getterable hydrogen purge gas remaining in the purge gas inlet 106 and the vacuum insulating structure 108 to produce a residual gas pressure of less than about 1 mbar. Valve 104 is closed and then purge gas inlet 106, which in this case also functions as a purge gas sorption conduit is crimped to produce a pressure and vacuum tight seal. The residual gas is then contacted with a residual gas getter material 114 which further reduces the residual gas pressure to about 10 -2 mbar or less and maintains this pressure throughout the life of the vacuum insulating structure.
Referring now to FIG. 2 there is shown a block diagram 200 which will be used to describe an alternative preferred method for the manufacture of a vacuum insulating structure 208 of the present invention. In this case there is provided a separate purge gas source 202 which may be either a high pressure hydrogen gas cylinder or a hydrogen storage device as described above. Valve 204 allows purge gas from purge gas source 202 to flow through a purge gas inlet 206 in fluid contact with vacuum insulating structure 208, thereby expelling atmospheric air through a purge gas outlet 210 also attached to the vacuum insulating structure 208 thus producing a purged vacuum insulating structure. Purge gas outlet 210 is again closed in a pressure and vacuum tight manner. Valve 204 is closed and valve 212 is opened to connect purge gas removal means 214 via a purge gas sorption conduit 216 in fluid contact with the vacuum insulating structure 208. Purge gas removal means 214 may comprise a getter material. Any getter material which can remove the getterable hydrogen purge gas remaining in the purged vacuum insulating structure 208 to produce a residual gas pressure of less than about 1 mbar may be used. The preferred getter material is a non-evaporable getter alloy; most preferably a getter material chosen from the group consisting of;
(a) an alloy of from 5-30% Al balance Zr,
(b) an alloy of from 5-30% Fe balance Zr,
(c) an alloy of from 5-30% Ni balance Zr, and
(d) Zr-M 1 -M 2 alloys wherein M 1 is vanadium and/or niobium and M 2 is nickel and/or iron.
The purge gas sorption conduit 216 is then sealed in a vacuum tight manner and the residual gas is contacted with a residual gas getter material 218 situated within the vacuum insulating structure 208.
Referring now to FIG. 3 there is shown a schematic partially cut-away view 300 of a vacuum insulating structure 302 being manufactured according to a method as described in conjunction with FIG. 1.
Purge gas source and purge gas removal means are a single hydrogen storage device 304 connected to the vacuum insulating structure 302 by means of purge gas inlet 306 provided with valve 308. The vacuum insulating structure 308 has four hollow tubes 310, 310', 310", 310'", preferably of plastic material but possibly also of thin metal. Hollow tubes 310, 310', 310", 310'" form a substantially rectangular framework. Hollow tube 310 which is connected to purge gas inlet 306 contains a series of gas flow holes such as the holes 312, 312', which face inwardly towards the volume 314 defined by hollow tubes 310, 310', 310", 310'". Hollow tube 310" also contains similar inwardly facing gas flow holes (not shown) and is connected to a purge gas outlet 318. Thin plates of plastic or metal 316, 316' are attached in a gas tight manner to the hollow plastic tubes 310, 310', 310", 310'" further defining volume 314. Volume 314 is filled with an insulating material 315 such as fiber glass or diatomaceous earth. This serves both as an additional insulating element and also prevents deformation of the insulating structure due to either high or low pressures. If, however, excessively high pressures should occur within volume 314 due to a rapid introduction of hydrogen from storage device 304, external containment means can be provided whose rigidity is such as to support the temporary high pressure created within volume 314 thus impeding outward curvature, or even rupture, of plates 316, 316'.
If the four tubes 310, 310', 310", 310'" and the plates 316, 316' are plastic, it is preferable that all plastic parts be metallized to improve thermal insulation and also to reduce permeation of atmospheric gases into the vacuum insulating structure 302. Hollow tubes 310, 310" are provided with appendages 320, 320' respectively, and each containing a rupturable container in the form of glass phials 322, 322'. The glass phials 322, 322' contain a residual gas getter material. The manufacturing method as described for FIG. 1 is used to produce a vacuum insulating structure. A low temperature (about 100° C.) degassing stage, may be used either before and/or during purging. Preferably the residual gas getter material is a pre-activated getter material chosen from the group consisting of;
(a) an alloy of from 5-30% Al balance Zr,
(b) an alloy of from 5-30% Fe balance Zr,
(c) an alloy of from 5-30% Ni balance Zr, and
(d) Zr-M 1 -M 2 alloys wherein M 1 is vanadium and/or niobium and M 2 is nickel and/or iron.
The rupturable container is a glass phial 322 as shown in FIG. 4. If appendages 320, 320' are of relatively flexible plastic material then the glass phial 322 can be ruptured by mechanical means. Alternatively the glass phial may have a weakened area 324 round which a metal wire 326 is formed and upon heating by radio frequency induction heating the phial 322 can be broken; thus contacting the residual gas getter material 328 with the residual gas.
It is to be noted that, besides the above mentioned example related to the manufacture of refrigerators other examples of the use of vacuum insulating panels are in vehicle walls such as automobiles and in particular refrigerated trucks, in aeroplanes and also in buildings such as for "under window" panels in modern buildings which externally appear to be all glass.
Although the invention has been described in considerable detail with reference to certain preferred embodiments designed to teach those skilled in the art how best to practice the invention, it will be realized that other modifications may be employed without departing from the spirit and scope of the appended claims. | A method is described for the manufacture of a vacuum insulating structure intended mainly, but not exclusively, for use in such domestic appliances as refrigerators or freezers as well as for vehicle walls including aeroplanes and in buildings. A hollow plastic or metal panel is purged to atmospheric air by means of a getterable gas. Vacuum is produced by removing the purge gas and the vacuum is subsequently maintained by contacting the residual gas with a getter material. A vacuum insulating structure thus manufactured is also described. | 5 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application is a Continuation-In-Part of U.S. Nonprovisional patent application Ser. No. 10/191,250, filed on Jul. 8, 2002, entitled VIDEO GAME CONSOLE AND CASHLESS METHOD OF USE.
SUMMARY OF THE INVENTION
[0002] The current invention relates to an improved video game console. More specifically, the current invention discloses and describes a video game console, which is designed to be quickly and easily reconfigured for changing games, and a cashless method for playing a game on said console. Furthermore, the current invention presents a game counting process and application. Finally, a secure gaming information storage and retrieval system is presented.
BACKGROUND OF THE INVENTION
[0003] In 1974 the world first witnessed the beginning of what was to be a new revolution in entertainment. It was in that year that “Pong” a video game depicting a ping-pong game was first introduced. Once the consumer public was overtaken, the industry has been on an odyssey to continually entertain and captivate their enthusiasts. As technology became more advanced, so did the games and the machines which play them. The machines have taken us from “Pong” through three-dimensional graphics and virtual reality. What has also continued to grow is the extraordinary revenue generated by the video game industry. Today, complex and sophisticated games are commonplace. Since the humble beginnings, video gaming has blossomed into a multi-billion dollar a year industry. Commercial video games, of the kind usually found in arcades and played on a pay-per-game basis, are still the backbone of the industry. These commercial machines are usually large, sturdy, and have the most sophisticated games. There is one major drawback. When a machine is assembled and configured, it is most often for one specific game. When that game no longer has the same popularity, the owner is forced to discard the entire unit. Attempts have been made, with varying degrees of success, to reconfigure older consoles to run newer games. Most of the time, the reconfigurations are logistically difficult to perform, and there are limitations as to the extent of reconfiguration possible. Also, reconfiguration of video game consoles can be costly. Oftentimes, it is easier and more cost effective to simply discard the unwanted console and purchase a new game. One such limitation is the user controls. They may or may not be compatible with multiple games. This can be illustrated using two very well known games from the past. The game Centipede is played with a track ball control, while the game Pac Man is played with a joystick. In order to change from one of these games to another, the control panel must be changed. Most video game consoles are not designed for the control panel to be changed. If there are opportunities to change, it is at a great expense of time and effort. The current invention is designed to overcome the difficulties of reconfiguration.
[0004] It is an object of the invention to provide a novel video game console that is easily reconfigured.
[0005] It is another object of the invention to provide a video game console in which the control panel is easily detachable.
[0006] It is another object of the invention to provide a video game console in which the control panel can be quickly and easily interchanged.
[0007] It is yet another object of the invention for the entire video game drawer to be easily disconnected and interchanged.
[0008] It is another object of the invention to provide a video game console in which the control panel can be interchanged to easily adapt to numerous games.
[0009] It is another object of the invention to provide a video game console in which the game played is quickly and easily changed.
[0010] It is another object of the invention to provide a video game console in which the game played is interfaced from a circuit board placed within the machine.
[0011] It is another object of the invention to provide a video game console in which the circuit board has quick connects and disconnects to both the control panel and display.
[0012] It is another object of the invention to provide a video game console which can be played with or without the use of currency.
[0013] It is another object of the invention to provide a video game console, which can be played without the use of currency or tokens. The user uses a computer read only chip to deduct money from a chip in which money was deposited and the value stored on the chip.
[0014] It is another object of the invention for the cashless system to be used with a casino gambling machine, wherein debits are deducted from the stored cash value on a semiconductor chip, and winnings are credited to said chip.
[0015] It is another object of the invention to introduce a game count parameter for use in determining winnings entitlement. The game count, which determines the number of games played by a user, shall be recorded on removable media that can be transported among a group of properly configured and receptive machines.
[0016] It is another object of the invention to introduce a game-playing method using said game count.
[0017] It is another object of the invention to introduce an interface module that communicates game playing information between said game console and removable media.
[0018] It is another object of the invention to provide an accounting of promotional credit owed to patrons of retail establishments and automated vending systems.
[0019] It is another object of the invention to provide a physical security mechanism to retain the semiconductor chip carrier in the game playing console during game operation. This carrier acts as protective packaging for the chip.
[0020] It is another object of the invention to provide data security capabilities using encryption, biometric data, and personal identification information stored locally or retrieved from remote resources.
[0021] It is another object of the invention to provide wired or wireless data communication capabilities for the purpose of monitoring game playing conditions and for adherence to legal and tax regulations.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] FIG. 1 is the front view of the assembled console.
[0023] FIG. 2 is a person sitting at the console.
[0024] FIG. 3 is the console showing removable computer motherboard.
[0025] FIG. 4 is the console showing removable and interchangeable game controls.
[0026] FIG. 5 shows removal of the monitor and game housing from the console stand.
[0027] FIG. 6 is a schematic showing the integration of multiple game circuit boards within a single unit.
[0028] FIG. 7 a & 7 b are diagrams showing the chip carrier, indicating placement of the I-Chip semiconductor device including its Input/Output mechanism. The chip reader and some of the related components are also shown.
[0029] FIG. 8 a - FIG. 8 c are diagrams showing the internal mechanism of the I-Chip reader device.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0030] The current invention allows a user to access commercial pay-for-play video consoles, without the need for depositing currency or tokens. There is a commercially available product called the “I Chip” available from Dallas Semiconductor, Dallas, Tex. The chip is described in U.S. Pat. No. 6,085,983, incorporated herein by reference. This patent describes a secure monetary system, by which monetary deposit information is stored on said chip. The current invention has produced novel software for performing the monetary transfer. A copy of one embodiment is submitted on CD-ROM and the contents are incorporated herein by reference. It is this novel software that provides a method for use of the established technology in a previously unexplored arena of commerce.
[0031] The commercial video arcade has been a major icon in our society for the previous 20+ years. Conventionally, patrons would use change machines to receive either quarters or tokens. Then, they would proceed from machine to machine with pockets filled with coins. The novel video game apparatus described herein would completely eliminate the need for any coins. Additionally, a method for transacting video gaming without the need for coins is sought as part of the invention. The method would be carried out as follows: A patron would enter an arcade or other appropriate area where commercial pay-for-play games are available. The patron would obtain a holder, which has a permanently mounted semiconductor chip. The patron would proceed to a terminal, which has mounted a standard dollar bill reader as is commonly known and used in commerce. The terminal would also have appropriately formed first and second conductive surfaces, which are combined to form a cavity appropriate for the insertion of the semiconductor chip. For the purposes of this invention, these combined conductive surfaces will be referred to as the chip receiver. The patron then inserts the semiconductor chip into a chip receiver. The chip receiver is interfaced, through said novel software, to provide a method transaction. The patron will deposit a desired amount of currency into the dollar bill reader, and the amount of deposit is subsequently stored on a chip. The patron will then remove the semiconductor chip and proceed to a gaming machine. The gaming machine can be any suitable electronic gaming device (or gaming system). Said gaming devices and gaming systems can include, but are not limited to: video arcade games, gaming machines, gambling machines, casino games, video gambling games, automated vending systems, I-chip interface equipped satellite signal and CATV receiver systems, and computers with an I-chip interface reader attached. The method is directed to removing a user initiated amount of currency and receiving credit on the desired gaming device. Internet game play and merchandise purchase using a gaming device with an I-chip reader is also supported. It should be understood that the desired gaming device will have a chip receiver and appropriate software for initiating and completing the transaction. Once the chip receiver transmits the presence of the chip, the software provides a method for the circuit board to read the stored information and ascertain if there is any monetary value on the chip. This is done using the aforementioned software. Each video game also has appropriate software to read the monetary information stored on the chip, and deducts appropriate amounts for games played. The user approaches a machine, inserts the semiconductor chip into the chip receiver, selects the amount of game credits desired, and starts playing.
[0032] Another novel feature of the current invention provides for the return of unused credits. An example is a patron that selects for two games to be played, and at the completion of the first game, desires to play a different game, or not play any more. The patron can have the game credits refunded and the monetary value restored to his semiconductor chip. Thus the current invention provides for a novel method for the commercial video patron to play multiple games, without the need for currency, coins or tokens.
[0033] In another embodiment, the software will place a series of award points onto the chip. In many arcades, tickets are awarded for attaining certain levels of scores on the games. These award tickets are then redeemed for prizes. This embodiment would eliminate the need for these award tickets. Alternatively, in a casino setting, the patron will have winnings deposited onto the chip. The patron will then redeem the total winnings at a cashier for cash or a cashiers check.
[0034] In another embodiment, the software may be used to track a patron's usage to determine the relative popularity of various games. The data relating to a patrons activity may include, but would not be limited to amount of time played, amount of money played, amount of winnings earned, or any combination thereof.
[0035] In another embodiment, casino or “gaming” games are equipped to receive payment from a user using the semiconductor chip. Additionally, in a casino atmosphere where allowable by law, the winnings of a patron may be credited onto the users chip. The user would cash in the winnings by going to a cashier and having the chip read for a current monetary value, and receiving compensation, in the form of a cash, check, or other appropriate payment for the value recorded on the chip.
[0036] In situations where earnings from gaming are highly regulated by Government, some jurisdictions only permit winnings of up to a fixed dollar amount or some multiple of a fixed dollar amount per game played. In these situations, it might be extremely helpful to know the number of games that had been played by a patron in order to permit earnings commensurate with the allowable award limits. Toward this end, the present invention provides a means for keeping an electronic game count. As an example, Florida statute permits an arcade amusement center to dispense a merchandise or prize value no greater than $0.75 for each game played. If, for example, a patron purchases $100 worth of games at $0.10 per game, then the patron is entitled to play 1000 games and the maximum merchandise value, in Florida, may not exceed $750.00 after completing those 1000 games. If, after playing 10 games, the patron wins the jackpot, then the entitlement is for a merchandise value not greater than $7.50. Not until all 1000 games are played is the patron entitled to a merchandise or prize with an equivalent value of $750.00. Therefore, the ability to accurately determine the number of games played (game count) is essential to the legal operation of the game center.
[0037] Current patrons of an amusement center in the state of Florida buy a set of tokens from a concession. Game winnings are tabulated by counting tickets dispensed from the game machine or by the use of script writers. The sum of the tickets represent the merchandise or prize that the customer is entitled to receive. Problems with these methods include miscounting and dispensing machine malfunctions causing inconvenience, earnings loss, and disagreements between patrons and management. Additional problems with this method include increased maintenance costs for machines with ticket dispensers. The present invention provides an improved system, allowing a patron to insert a portable chip carrier into a receptive gaming machine prior to play allowing an electronic record of the game count to be stored into a non-volatile memory. This operation has the added advantage of allowing eligibility for merchandise and prizes to be transferred from one game machine to the next.
[0038] An extension to the embodiments described in the previous paragraphs relates to promotional credit received for purchase of commercial goods. In this scenario, the game count would reflect the quantity of merchandise of a given type purchased by a customer. As an example, a soft-drink vendor or manufacturer may award a cash value or cash-equivalent prize after purchase of a quantity of a name-brand soda. This entitlement may be entered into the semiconductor chip for later redemption. Deductions and credits can be automatically registered on the chip by a reader and its associated circuitry and processes as awards are redeemed and received, respectively. The method of purchase could be made through traditional retail establishments, automated vending machines, or through Internet purchases using computer systems outfitted with appropriately configured chip reader devices. In a similar manner, retail services, such as car washing services, could be outfitted with appropriate chip reader systems and configured to convey award entitlement based on the number of times the services were purchased.
[0039] It is also envisioned that keeping an accurate game count might facilitate State and Federal tax collection. Game playing information could be electronically transmitted from the game playing system to State offices for purposes of tax assessment. One way that current systems tax patrons is at the time that currency or tokens are entered into the game playing system by including taxes in the cost of game play. This method is readily supported using the I-chip system described herein by deducting the appropriate value electronically from the device.
[0040] Example source code that increments a game count for the present invention and calculates bonus-time is shown below.
If ((GameIndex==1) && (STATUS==1))) { //changed Delay_10ms(50); GameCount++; GameIndex=0; If (isTournament) { tLong = GetRawTime( ) − TimeStart; If (tLong > BonusTime) { BonusTime=0; } else if (tLong>0) { BonusTime=BonusTime−tLong; } SaveBalance( );
[0041] The game count is recorded onto a removable media, such as the I-chip, and displayed on the game video display during game play. The source code that displays the game count is shown below.
If (Show_Balance) { clear_screen( ); PrintHeader( ); PrintBalance( ); CoverPts( ); } else { // just show game count on bottom of screen x=7; y=1; setXY( ); FillRow( ); x=7; y=1; setXY( ); inverse=1; sprintf(buffer,”Game Count: %1d”,GameCount); print(buffer); }
[0042] The video console itself has been improved to provide several unique characteristics that are not found on commercially available machines. The control panels of commercially available video gaming equipment are not easily changed. If there were a machine capable of changing the game, it would be limited to interchange based on the control panel. It has been discovered that one is able to form the control panel onto a detachable door. Said detachable door is able to be unlocked and removed from the body of the console. The electronic and/or computer circuitry mounted to the board for both the controls and the semiconductor chip are designed so they may be disconnected from the video and electrical interfaces by means of a quick connect/disconnect mechanism. In forming the machine with the quick connect/disconnect, the entire drawer assembly may be removed and the commercial video game machine can be quickly and easily reconfigured to play another game. The electronic circuitry for individual games can be stored in the circuitry mounted to the board.
[0043] In another embodiment, the games are computer based and generated.
[0044] In another embodiment, the control panel also is removable and interchangeable by means of standard quick connect/disconnect. In this manner, if the game board already contains the appropriate programming for running multiple games, only the controls need be changed to accommodate the games' control requirements. The machine is readily changeable and reconfigurable to facilitate the change of games and controls.
[0045] Another feature of the console provides for the easy removal of the video monitor housing. Again, because the machine has electronic quick connect/disconnect, the monitor can be easily separated from its computer and electronic connections. The monitor is secured to the base with a plurality of mounting screws or other appropriate mounting means. The size, type, and number of mountings are easily ascertained and assigned by the machine designer and is determined by methods commonly known in the art.
[0046] Another embodiment provides for the mounting of more than one game circuit board within the video game assembly. The games may be interchanged externally, or internally by changing the connection using the quick connect/disconnect. The advantage of this embodiment is that it does not limit the owner of the console in the offering of games to the consumers.
[0047] In another embodiment the unit is portable and removable from the lower cabinet. In this embodiment, the machine can be placed on a tabletop, countertop or bar.
[0048] FIG. 1 shows the video console 100 with lower cabinet 102 that supports upper cabinet 104 . Lower cabinet 102 may incorporate a footrest 106 for use when user is seated at the console. Incorporated into upper cabinet 104 is a video display 108 for viewing the game. Game drawer assembly 300 is mounted into upper cabinet 104 and locked and unlocked at 320 by any commonly used locking mechanism.
[0049] FIG. 2 shows a patron seated in front of the video console 100 with the aforementioned elements. Also shown in FIG. 2 is the electrical power cord 504 , which connects to an appropriate source of electricity 502 .
[0050] FIG. 3 shows the removal of the game drawer assembly 300 . The drawer is disconnected from the video game console by removing both the electronic quick disconnect output 318 , which supplies power to the power supply 316 which in turn delivers current to printed circuit board 308 . Printed circuit board 308 is mounted onto drawer 300 . Complete removal game drawer assembly 300 also requires removal of electronic quick disconnect input 314 from the electronic quick disconnect output 312 which supplies the signal to the video display. The game drawer assembly 300 also has mounted a speaker 306 suitable for providing appropriate audio for the game being played. The game drawer assembly 300 further contains a kill switch 322 and kill switch wires 324 , which leads to the display 326 . The kill switch provides a means of security by providing a mechanism by which the machine becomes disabled, either temporarily or permanently in order to prevent unauthorized access to any of the components housed within the console. The display can be a light emitting diode (LED), liquid crystal display (LCD) or any other suitable display. Mounted under display 326 is a circuit board 328 , which provides the signal for the display 326 . Mounted directly under display 326 is a chip receiver 330 . The chip receiver is of appropriate size and shape to allow for the insertion of a mounted semiconductor chip. This allows for the patron to prepurchase a monetary value, which is stored on the chip. The video console has appropriate software, which allows for the circuitry to read the monetary value stored on the semiconductor chip, deduct an amount as determined by the user, and receive credit on the video game. FIG. 3 also shows varied embodiments of the game drawer. Game drawer 332 shows one possible configuration. Game drawer 334 shows an embodiment wherein the controls 302 have a joystick. Game drawer 336 shows even another embodiment showing the arrangement of the controls. These embodiments are given by way of example and are in no way intended to be limiting in their scope.
[0051] FIG. 4 shows another embodiment by which only the user controls dismount from the board and provide a means for reconfiguring the console. In this embodiment more than one circuit board is mounted within the console and the reconfiguring of the game is achieved by manually or electronically switching boards, and by changing the user controls, which are mounted to the drawer of the console.
[0052] FIG. 5 shows the console 100 and depicts the mounting of upper cabinet 104 onto lower cabinet 102 . The mounting in one embodiment can be conventional mounting screws 402 . The mounting can be by any appropriate means.
[0053] One advantage of the use of the I-chip by Dallas Semiconductor is that it is possible to embed the integrated circuit in a portable chip carrier that can be conveniently placed into a gaming machine prior to game play. A chip carrier 600 for this application has been designed, as shown in FIG. 7 a . The I-chip 602 is shown embedded in the carrier, with electrical contacts rising above the surface of the carrier. A corresponding reader 604 has been designed to accept the carrier for reading and writing relevant game playing and user identification information from/to the I-chip. Important game playing information may include monetary data (funds remaining, money played, and winnings earned), game count, time/date played, and bonus time earned. User identification information can be stored and accessed for security screening. Such information might include encryption, biometric data, photographic, and third party identification information such as passport or driver's license numbers. One application of such information is the restriction of fund access without proper identification. As an example, a fingerprint reader device connected to the I-chip reader may require matching with fingerprint data stored on the I-chip before allowing access to the funds stored on the I-chip.
[0054] The portable chip carrier reader communicates with other game playing system components through a set of electrical contacts 606 and 608 . Insertion of the chip carrier into the reader toggles a switch 610 that initiates data communication with the I-chip. The switch also activates a motor driven mechanical locking device 612 that blocks the withdrawal of the carrier from the gaming machine during play. A fully inserted carrier is shown in FIG. 7 b.
[0055] FIG. 8 a through FIG. 8 c show details of the electrical and mechanical operation of the reader assembly. Insertion of the chip carrier into the reader engages an electrical switch 610 that initiates exchange of information between the game module and the I-chip- 602 . It also initiates operation of an electric stepper motor 612 that actuates a rod 614 to extend 616 , blocking movement of the carrier during game play, as shown in FIG. 8 a . A simplified diagram of the operation that initiates communication between the I-chip and the game playing console is shown in FIG. 8 b . The manual movement of the chip carrier 600 into the reader 604 causes an open switch 618 to close 620 , allowing current to flow between the I-chip and the game playing console. The electrical connections, shown collectively 622 in this diagram, make contact with the electrodes on the I-chip. Details of the electrical contact between the I-chip electrodes and the electrodes on the reader are shown in FIG. 8 c . The ground electrode 624 and data electrode 628 on the I-chip are separated by an electrical insulator 626 . As the carrier 600 is inserted, a metal spring 630 , that is also connected to chassis ground 632 , is forced open and maintains electrical contact with the ground electrode 624 . Electrical contact is made between electrode 634 on the reader and the larger diameter I-chip electrode 628 . The I-chip is an integrated circuit module specifically designed to securely handle monetary transactions using a two electrode data communications channel. Having only 2 electrodes makes interconnection with the chip relatively simple and reliable. While only electrically conductive contact has been described with regard to communication between the game playing system and the I-chip carrier, it should be understood that such communication can be achieved by a wide range of other mechanical and electromagnetic means. These communication means are intended to be included in the scope of this invention.
[0056] The invention can also be used with wired or wireless data communication capabilities for the purpose of monitoring game playing conditions and for communication with State and Federal agencies to help adhere to legal and tax regulations. Appropriate networking equipment and protocols would need to be fitted.
[0057] It should be understood that the I-chip by Dallas Semiconductor is but one semiconductor device that can be specified for use with the present invention. Other competing devices with similar characteristics are applicable, as are future versions of the described semiconductor device.
[0058] These are provided by way of example and are in no means intended to limit the scope of the invention. While the invention has been described in its preferred form or embodiment with some degree of particularity, it is understood that this description has been given only by way of example and that numerous changes in the details of construction, fabrication, and use, including the combination and arrangement of parts, may be made without departing from the spirit and scope of the invention. | A novel video game console and method of use are disclosed and described. The invention also presents a game counting process and application thereof. A secure gaming information storage system is also detailed. | 6 |
TECHNICAL FIELD OF THE INVENTION
The technical field of this invention is emulation hardware particularly for highly integrated digital signal processing systems.
BACKGROUND OF THE INVENTION
Advanced wafer lithography and surface-mount packaging technology are integrating increasingly complex functions at both the silicon and printed circuit board level of electronic design. Diminished physical access to circuits for test and emulation is an unfortunate consequence of denser designs and shrinking interconnect pitch. Designed-in testability is needed so the finished product is both controllable and observable during test and debug. Any manufacturing defect is preferably detectable during final test before a product is shipped. This basic necessity is difficult to achieve for complex designs without taking testability into account in the logic design phase so automatic test equipment can test the product.
In addition to testing for functionality and for manufacturing defects, application software development requires a similar level of simulation, observability and controllability in the system or sub-system design phase. The emulation phase of design should ensure that a system of one or more ICs (integrated circuits) functions correctly in the end equipment or application when linked with the system software. With the increasing use of ICs in the automotive industry, telecommunications, defense systems, and life support systems, thorough testing and extensive real-time debug becomes a critical need.
Functional testing, where the designer generates test vectors to ensure conformance to specification, still remains a widely used test methodology. For very large systems this method proves inadequate in providing a high level of detectable fault coverage. Automatically generated test patterns are desirable for full testability, and controllability and observability. These are key goals that span the full hierarchy of test from the system level to the transistor level.
Another problem in large designs is the long time and substantial expense involved in design for test. It would be desirable to have testability circuitry, system and methods that are consistent with a concept of design-for-reusability. In this way, subsequent devices and systems can have a low marginal design cost for testability, simulation and emulation by reusing the testability, simulation and emulation circuitry, systems and methods that are implemented in an initial device. Without a proactive testability, simulation and emulation plan, a large amount of subsequent design time would be expended on test pattern creation and upgrading.
Even if a significant investment were made to design a module to be reusable and to fully create and grade its test patterns, subsequent use of a module may bury it in application specific logic. This would make its access difficult or impossible. Consequently, it is desirable to avoid this pitfall.
The advances of IC design are accompanied by decreased internal visibility and control, reduced fault coverage and reduced ability to toggle states, more test development and verification problems, increased complexity of design simulation and continually increasing cost of CAD (computer aided design) tools. In the board design the side effects include decreased register visibility and control, complicated debug and simulation in design verification, loss of conventional emulation due to loss of physical access by packaging many circuits in one package, increased routing complexity on the board, increased costs of design tools, mixed-mode packaging, and design for produceability. In application development, some side effects are decreased visibility of states, high speed emulation difficulties, scaled time simulation, increased debugging complexity, and increased costs of emulators. Production side effects involve decreased visibility and control, complications in test vectors and models, increased test complexity, mixed-mode packaging, continually increasing costs of automatic test equipment and tighter tolerances.
Emulation technology utilizing scan based emulation and multiprocessing debug was introduced more than 10 years ago. In 1988, the change from conventional in circuit emulation to scan based emulation was motivated by design cycle time pressures and newly available space for on-chip emulation. Design cycle time pressure was created by three factors. Higher integration levels, such as increased use of on-chip memory, demand more design time. Increasing clock rates mean that emulation support logic causes increased electrical intrusiveness. More sophisticated packaging causes emulator connectivity issues. Today these same factors, with new twists, are challenging the ability of a scan based emulator to deliver the system debug facilities needed by today's complex, higher clock rate, highly integrated designs. The resulting systems are smaller, faster, and cheaper. They have higher performance and footprints that are increasingly dense. Each of these positive system trends adversely affects the observation of system activity, the key enabler for rapid system development. The effect is called “vanishing visibility.”
FIG. 1 illustrates the trend in visibility and control over time and greater system integration. Application developers prefer the optimum visibility level illustrated in FIG. 1 . This optimum visibility level provides visibility and control of all relevant system activity. The steady progression of integration levels and increases in clock rates steadily decrease the actual visibility and control available over time. These forces create a visibility and control gap, the difference between the optimum visibility and control level and the actual level available. Over time, this gap will widen. Application development tool vendors are striving to minimize the gap growth rate. Development tools software and associated hardware components must do more with less resources and in different ways. Tackling this ease of use challenge is amplified by these forces.
With today's highly integrated System-On-a-Chip (SOC) technology, the visibility and control gap has widened dramatically over time. Traditional debug options such as logic analyzers and partitioned prototype systems are unable to keep pace with the integration levels and ever increasing clock rates of today's systems. As integration levels increase, system buses connecting numerous subsystem components move on chip, denying traditional logic analyzers access to these buses. With limited or no significant bus visibility, tools like logic analyzers cannot be used to view system activity or provide the trigger mechanisms needed to control the system under development. A loss of control accompanies this loss in visibility, as it is difficult to control things that are not accessible.
To combat this trend, system designers have worked to keep these buses exposed. Thus the system components were built in a way that enabled the construction of prototyping systems with exposed buses. This approach is also under siege from the ever-increasing march of system clock rates. As the central processing unit (CPU) clock rates increase, chip to chip interface speeds are not keeping pace. Developers find that a partitioned system's performance does not keep pace with its integrated counterpart, due to interface wait states added to compensate for lagging chip to chip communication rates. At some point, this performance degradation reaches intolerable levels and the partitioned prototype system is no longer a viable debug option. In the current era production devices must serve as the platform for application development.
Increasing CPU clock rates are also limiting availability of other simple visibility mechanisms. Since the CPU clock rates can exceed the maximum I/O state rates, visibility ports exporting information in native form can no longer keep up with the CPU. On-chip subsystems are also operated at clock rates that are slower than the CPU clock rate. This approach may be used to simplify system design and reduce power consumption. These developments mean simple visibility ports can no longer be counted on to deliver a clear view of CPU activity. As visibility and control diminish, the development tools used to develop the application become less productive. The tools also appear harder to use due to the increasing tool complexity required to maintain visibility and control. The visibility, control, and ease of use issues created by systems-on-a-chip tend to lengthen product development cycles.
Even as the integration trends present developers with a tough debug environment, they also present hope that new approaches to debug problems will emerge. The increased densities and clock rates that create development cycle time pressures also create opportunities to solve them. On-chip, debug facilities are more affordable than ever before. As high speed, high performance chips are increasingly dominated by very large memory structures, the system cost associated with the random logic accompanying the CPU and memory subsystems is dropping as a percentage of total system cost. The incremental cost of several thousand gates is at an all time low. Circuits of this size may in some cases be tucked into a corner of today's chip designs. The incremental cost per pin in today's high density packages has also dropped. This makes it easy to allocate more pins for debug. The combination of affordable gates and pins enables the deployment of new, on-chip emulation facilities needed to address the challenges created by systems-on-a-chip.
When production devices also serve as the application debug platform, they must provide sufficient debug capabilities to support time to market objectives. Since the debugging requirements vary with different applications, it is highly desirable to be able to adjust the on-chip debug facilities to balance time to market and cost needs. Since these on-chip capabilities affect the chip's recurring cost, the scalability of any solution is of primary importance. “Pay only for what you need” should be the guiding principle for on-chip tools deployment. In this new paradigm, the system architect may also specify the on-chip debug facilities along with the remainder of functionality, balancing chip cost constraints and the debug needs of the product development team.
FIG. 2 illustrates a prior art emulator system including four emulator components. These four components are: a debugger application program 110 ; a host computer 120 ; an emulation controller 130 ; and on-chip debug facilities 140 . FIG. 2 illustrates the connections of these components. Host computer 120 is connected to an emulation controller 130 external to host 120 . Emulation controller 130 is also connected to target system 140 . The user preferably controls the target application on target system 140 through debugger application program 110 .
Host computer 120 is generally a personal computer. Host computer 120 provides access the debug capabilities through emulator controller 130 . Debugger application program 110 presents the debug capabilities in a user-friendly form via host computer 120 . The debug resources are allocated by debug application program 110 on an as needed basis, relieving the user of this burden. Source level debug utilizes the debug resources, hiding their complexity from the user. Debugger application program 110 together with the on-chip trace and triggering facilities provide a means to select, record, and display chip activity of interest. Trace displays are automatically correlated to the source code that generated the trace log. The emulator provides both the debug control and trace recording function.
The debug facilities are preferably programmed using standard emulator debug accesses through a JTAG or similar serial debug interface. Since pins are at a premium, the preferred embodiment of the invention provides for the sharing of the debug pin pool by trace, trigger, and other debug functions with a small increment in silicon cost. Fixed pin formats may also be supported. When the pin sharing option is deployed, the debug pin utilization is determined at the beginning of each debug session before target system 140 is directed to run the application program. This maximizes the trace export bandwidth. Trace bandwidth is maximized by allocating the maximum number of pins to trace.
The debug capability and building blocks within a system may vary. Debugger application program 110 therefore establishes the configuration at runtime. This approach requires the hardware blocks to meet a set of constraints dealing with configuration and register organization. Other components provide a hardware search capability designed to locate the blocks and other peripherals in the system memory map. Debugger application program 110 uses a search facility to locate the resources. The address where the modules are located and a type ID uniquely identifies each block found. Once the IDs are found, a design database may be used to ascertain the exact configuration and all system inputs and outputs.
Host computer 120 generally includes at least 64 Mbytes of memory and is capable of running Windows 95, SR-2, Windows NT, or later versions of Windows. Host computer 120 must support one of the communications interfaces required by the emulator. These may include: Ethernet 10T and 100T; TCP/IP protocol; Universal Serial Bus (USB); Firewire IEEE 1394; and parallel port such as SPP, EPP and ECP.
Host computer 120 plays a major role in determining the real-time data exchange bandwidth. First, the host to emulator communication plays a major role in defining the maximum sustained real-time data exchange bandwidth because emulator controller 130 must empty its receive real-time data exchange buffers as fast as they are filled. Secondly, host computer 120 originating or receiving the real-time data exchange data must have sufficient processing capacity or disc bandwidth to sustain the preparation and transmission or processing and storing of the received real-time data exchange data. A state of the art personal computer with a Firewire communication channel (IEEE 1394) is preferred to obtain the highest real-time data exchange bandwidth. This bandwidth can be as much as ten times greater performance than other communication options.
Emulation controller 130 provides a bridge between host computer 120 and target system 140 . Emulation controller 130 handles all debug information passed between debugger application program 110 running on host computer 120 and a target application executing on target system 140 . A presently preferred minimum emulator configuration supports all of the following capabilities: real-time emulation; real-time data exchange; trace; and advanced analysis.
Emulation controller 130 preferably accesses real-time emulation capabilities such as execution control, memory, and register access via a 3, 4, or 5 bit scan based interface. Real-time data exchange capabilities can be accessed by scan or by using three higher bandwidth real-time data exchange formats that use direct target to emulator connections other than scan. The input and output triggers allow other system components to signal the chip with debug events and vice-versa. Bit I/O allows the emulator to stimulate or monitor system inputs and outputs. Bit I/O can be used to support factory test and other low bandwidth, non-time-critical emulator/target operations. Extended operating modes are used to specify device test and emulation operating modes. Emulator controller 130 is partitioned into communication and emulation sections. The communication section supports host communication links while the emulation section interfaces to the target, managing target debug functions and the device debug port. Emulation controller 130 communicates with host computer 120 using one of industry standard communication links outlined earlier herein. The host to emulator connection is established with off the shelf cabling technology. Host to emulator separation is governed by the standards applied to the interface used.
Emulation controller 130 communicates with the target system 140 through a target cable or cables. Debug, trace, triggers, and real-time data exchange capabilities share the target cable, and in some cases, the same device pins. More than one target cable may be required when the target system 140 deploys a trace width that cannot be accommodated in a single cable. All trace, real-time data exchange, and debug communication occurs over this link. Emulator controller 130 preferably allows for a target to emulator separation of at least two feet. This emulation technology is capable of test clock rates up to 50 MHZ and trace clock rates from 200 to 300 MHZ, or higher. Even though the emulator design uses techniques that should relax target system 140 constraints, signaling between emulator controller 130 and target system 140 at these rates requires design diligence. This emulation technology may impose restrictions on the placement of chip debug pins, board layout, and requires precise pin timings. On-chip pin macros are provided to assist in meeting timing constraints.
The on-chip debug facilities offer the developer a rich set of development capability in a two tiered, scalable approach. The first tier delivers functionality utilizing the real-time emulation capability built into a CPU's mega-modules. This real-time emulation capability has fixed functionality and is permanently part of the CPU while the high performance real-time data exchange, advanced analysis, and trace functions are added outside of the core in most cases. The capabilities are individually selected for addition to a chip. The addition of emulation peripherals to the system design creates the second tier functionality. A cost-effective library of emulation peripherals contains the building blocks to create systems and permits the construction of advanced analysis, high performance real-time data exchange, and trace capabilities. In the preferred embodiment five standard debug configurations are offered, although custom configurations are also supported. The specific configurations are covered later herein.
SUMMARY OF THE INVENTION
Triggers are used to turn on or off various streams for tracing target processor activity. Triggers can be either synchronous or asynchronous to the pipeline. Synchronous triggers follow all the rules of the pipeline. Asynchronous triggers may be generated at any time. Examples of some of the violations are: while the central processing unit is stalled and during an illegal instruction boundary. These triggers have to be realigned to the pipeline for the user to use the information effectively.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other aspects of this invention are illustrated in the drawings, in which:
FIG. 1 illustrates the visibility and control of typical integrated circuits as a function of time due to increasing system integration;
FIG. 2 illustrates an emulation system to which this invention is applicable (prior art);
FIG. 3 illustrates in block diagram form a typical integrated circuit employing configurable emulation capability (prior art);
FIG. 4 is a timing diagram illustrating the process of servicing a trace trigger during a central processing unit stall; and
FIG. 5 is a timing diagram illustrating the process of servicing a trace trigger at an invalid instruction boundary.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
When the streams are switched on or off using the triggers, markers are generated. Various streams are synchronized using markers called sync points. The sync points provide a unique identifier field and a context to the data that will follow it. All streams may generate a sync point with this unique identifier. The information in the sync point is valid only at a legal instruction boundary.
FIG. 3 illustrates an example of a prior art one on-chip debug architecture embodying target system 140 . The architecture uses several module classes to create the debug function. One of these classes is event detectors including bus event detectors 210 , auxiliary event detectors 211 and counters/state machines 213 . A second class of modules is trigger generators including trigger builders 220 . A third class of modules is data acquisition including trace collection 230 and formatting. A fourth class of modules is data export including trace export 240 , and real-time data exchange export 241 . Trace export 240 is controlled by clock signals from local oscillator 245 . Local oscillator 245 will be described in detail below. A final class of modules is scan adaptor 250 , which interfaces scan input/output to CPU core 201 . Final data formatting and pin selection occurs in pin manager and pin micros 260 .
The size of the debug function and its associated capabilities for any particular embodiment of a system-on-chip may be adjusted by either deleting complete functions or limiting the number of event detectors and trigger builders deployed. Additionally, the trace function can be incrementally increased from program counter trace only to program counter and data trace along with ASIC and CPU generated data. The real-time data exchange function may also be optionally deployed. The ability to customize on-chip tools changes the application development paradigm. Historically, all chip designs with a given CPU core were limited to a fixed set of debug capability. Now, an optimized debug capability is available for each chip design. This paradigm change gives system architects the tools needed to manage product development risk at an affordable cost. Note that the same CPU core may be used with differing peripherals with differing pin outs to embody differing system-on-chip products. These differing embodiments may require differing debug and emulation resources. The modularity of this invention permits each such embodiment to include only the necessary debug and emulation resources for the particular system-on-chip application.
The real-time emulation debug infrastructure component is used to tackle basic debug and instrumentation operations related to application development. It contains all execution control and register visibility capabilities and a minimal set of real-time data exchange and analysis such as breakpoint and watchpoint capabilities. These debug operations use on-chip hardware facilities to control the execution of the application and gain access to registers and memory. Some of the debug operations which may be supported by real-time emulation are: setting a software breakpoint and observing the machine state at that point; single step code advance to observe exact instruction by instruction decision making; detecting a spurious write to a known memory location; and viewing and changing memory and peripheral registers.
Real-time emulation facilities are incorporated into a CPU mega-module and are woven into the fabric of CPU core 201 . This assures designs using CPU core 201 have sufficient debug facilities to support debugger application program 110 baseline debug, instrumentation, and data transfer capabilities. Each CPU core 201 incorporates a baseline set of emulation capabilities. These capabilities include but are not limited to: execution control such as run, single instruction step, halt and free run; displaying and modifying registers and memory; breakpoints including software and minimal hardware program breakpoints; and watchpoints including minimal hardware data breakpoints.
Consider the case of tracing processor activity and generating timing, program counter and data streams. Table 1 shows the streams generated when a sync point is generated. Context information is provided only in the program counter stream. There is no order dependency of the various streams with each other. However, within each stream the order cannot be changed between sync points.
TABLE 1
Timing stream
PC stream
Data stream
Timing sync point,
PC sync point,
Data sync point,
id = 1
id = 1
id = 1
Timing data
PC data
Memory Data
Timing data
Memory Data
Timing data
PC data
Memory Data
PC data
Timing data
Memory Data
Timing sync point,
PC sync point,
Data sync point,
id = 2
id = 2
id = 2
The triggers are handled differently depending upon the particular trace stream. For the data trace stream the trigger is evaluated instantaneously. For the program counter trace and the timing trace streams, the triggers are handled a little differently. Service of a trace trigger is not held during stall cycles as long as it is at a valid instruction boundary. This helps the user characterize the length of the stalls. It is completely possible for a stream to be turned on or off during an entire stall window.
This timing is illustrated in FIGS. 4 and 5 . In FIG. 4 , a trigger input signal (trigger_in) is received during a central processing unit stall time (cpu_stall). The effective service of the trigger (trigger effective) and the tracing activity occurs immediately even during the central processing unit stall time. In FIG. 5 , a trigger input (trigger_in) occurs during a central processing unit stall time (cpu_stall). The effective service of the trigger (trigger effective) and the tracing activity is held past the end of the central processing unit stall time until a valid instruction boundary period.
The advantage of this approach is that one can profile with accuracy the total number of stall cycles that occurred This does not impact an illegal instruction boundary. Trace triggers can never be generated then because there is no valid information that can be sent with the sync point. between the trace trigger and the start of tracing activity. | A method of trace collection in a data processor begins trace data collection even if a trace trigger is received during an interval when a central processing unit is stalled. Trace data collection is deferred if a trace trigger is received during an interval of an invalid instruction boundary until a valid instruction boundary. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to surfactant mixtures with improved dermatological compatibility which contain alkyl oligoglucosides having a selected chain length composition.
2. Statement of Related Art
Alkyl oligoglycosides, especially alkyl oligoglucosides, are nonionic surfactants which are acquiring increasing significance by virtue of their excellent detergent properties and their high ecotoxicological compatibility. The production and use of these substances have been described just recently in a number of synoptic articles of which the articles by H. Hensen in Skin Care Forum, 1, (October 1992), D. Balzer and N. Ripke in Seifen-Ole-Fette-Wachse 118, 894 (1992) and B. Brancq in Seifen-Ole-Fette-Wachse 118, 905 (1992) are cited as representative.
Although alkyl oligoglucosides are extremely mild on the skin, there is still a growing need for substances having further improved dermatological compatibility. For example, attempts have been made in the past to improve the dermatological compatibility of alkyl oligoglucosides by addition of amphoteric surfactants.
A starting point for the production of particularly high-performance alkyl oligoglucosides is to mix species differing in their chain length. For example, it is proposed in hitherto unpublished patent application U.S. Ser. No. 07/876,967 (Henkel Corp.) to mix two alkyl oligoglucosides having chain lengths of C 8-10 and C 12-16 in a ratio of 50:50 to 90:10 parts by weight. However, this application teaches using a mixing ratio of 60:40 to 80:20, i.e. using the short-chain species in excess.
DE-A1 40 05 958 (Huls) describes a liquid foaming cleaning preparation which may contain 3 to 40% by weight of a C 7-10 alkyl oligoglucoside and 3 to 40% by weight of a C 11-18 alkyl oligoglucoside (ad 100% by weight water). It is proposed to use the relatively short-chain and relatively long-chain species in a ratio by weight of 10:90 to 50:50 and preferably in a ratio of 17:83 to 33:67. There is no reference in this document to particular advantages arising out of the dermatological compatibility of the mixture.
In the past, alkyl oligoglucosides differing in their chain length have been mixed primarily with a view to obtaining optimal performance properties. Although the mixtures according to the prior art may be satisfactory, for example, in regard to their foaming and cleaning power, their dermatological compatibility is not optimal.
Now, the problem addressed by the present invention was to provide new mixtures of alkyl oligoglucosides differing in their chain lengths which would be free from the disadvantages mentioned above.
DESCRIPTION OF THE INVENTION
The present invention relates to ultramild surfactant mixtures containing
a) 5 to 12% by weight of an alkyl oligoglucoside corresponding to formula (I):
R.sup.1 --O--(G).sub.p (I)
in which R 1 is a C 6-12 alkyl radical, G is a glucose unit and p is a number of 1.3 to 1.8 and
b) 88 to 95% by weight of an alkyl oligoglucoside corresponding to formula (II):
R.sup.2 --O--(G).sub.p (II)
in which R 2 is a C 10-18 alkyl radical, G is a glucose unit and p is a number of 1.3 to 1.8.
It has surprisingly been found that products showing particularly high dermatological compatibility can be obtained within a very narrow mixing range of alkyl oligoglucosides differing in their chain length. Although similar mixtures of short-chain and long-chain alkyl oligoglucosides in a ratio of 10:90 are mentioned as lower limits in DE-A1 40 05 958 (Huls), the selection made in accordance with the present application is both new and inventive because neither the mixtures as such nor the surprising effect associated with them have been described before and because the teaching of the cited document points in the direction of mixing ratios at which the advantageous dermatological compatibility is no longer present.
Alkyl oligoglucosides
Alkyl oligoglucosides are known substances which may be obtained by the relevant methods of preparative organic chemistry. EP-A1-0 301 298 and WO 90/3977 are cited as representative of the extensive literature available on this subject.
The index p in general formulae (I) and (II) indicates the degree of oligomerization (DP degree), i.e. the distribution of monoglucosides and oligoglucosides and is a number of 1.3 to 1.8. Whereas p in a given compound must always be an integer and, above all, may assume a value of 1.3 to 1.6, the value p for a certain alkyl oligoglucoside is an analytically determined calculated quantity which is generally a broken number.
The alkyl radical R 1 may be derived from primary alcohols containing 6 to 12 and preferably 8 to 10 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, undecyl alcohol and lauryl alcohol and technical mixtures thereof such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxosynthesis. C 6-12 alkyl oligoglucosides (DP=1.3 to 1.6), which are obtained as first runnings in the separation of technical C 8-18 coconut oil fatty alcohol by distillation and which contain essentially C 8-10 alkyl radicals, are preferred. Alkyl oligoglucosides corresponding to formula (I) which have the following C chain distribution in the alkyl radical are particularly preferred:
C 6 :0-5% by weight
C 8 :40-66% by weight
C 10 :30-59% by weight
C 12 :0-6% by weight
The alkyl radical R 2 may be derived from primary alcohols containing 10 to 18 and preferably 12 to 16 carbon atoms. Typical examples are capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, arachyl alcohol, behenyl alcohol and technical mixtures thereof which may be obtained as described above. Alkyl oligoglucosides based on hydrogenated C 10-18 coconut oil alcohol (DP=1.3 to 1.6), in which the alkyl radicals essentially contain 12 to 16 carbon atoms, are preferred. Alkyl oligoglucosides corresponding to formula (II) which have the following C chain distribution in the alkyl radical are particularly preferred:
C 10 :0-3% by weight
C 12 :60-75% by weight
C 14 :21-30% by weight
C 16 :0-12% by weight
C 18 :0-3% by weight
Production of the mixtures
The alkyl oligoglucosides corresponding to formulae (I) and (II) may be mixed by methods known per se. For example, the concentrated pastes may be stirred with one another at an elevated temperature of 40° C. and may be diluted to the in-use concentration during making up into end products. However, dilute solutions may also be mixed with one another in the same way. This entails a purely mechanical operation involving no chemical reaction.
In one preferred embodiment of the invention, however, the relatively short-chain alkyl oligoglucosides may also be added to the relatively long-chain alkyl oligoglucosides during their production, for example before the final bleaching step. In addition, it is possible--taking the differences in reactivity into account--to acetalize fatty alcohols of suitable chain composition with glucose by methods known per se and thus to produce the mixtures in situ. In both these cases, uniform products are obtained.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 plots total irritation scores for mixtures of alkyl oligoglycosides. The data are summarized in Table 1.
COMMERCIAL APPLICATIONS
The surfactant mixtures according to the invention are distinguished by particularly high dermatological compatibility and do not irritate the skin, even in the form of 50% by weight aqueous pastes.
Surfactants
The surfactant mixtures according to the invention may be used together with other anionic, nonionic, cationic and/or amphoteric or zwitterionic surfactants.
Typical examples of anionic surfactants are alkyl benzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride sulfates, fatty acid amide (ether) sulfates, sulfosuccinates, sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids, fatty acid isethionates, sarcosinates, taurides, alkyl oligoglucoside sulfates, alkyl (ether) phosphates and vegetable or animal protein hydrolyzates or condensation products thereof with fatty acids. Where the anionic surfactants contain polyglycol ether chains, they may have a conventional homolog distribution although they preferably have a narrow homolog distribution.
Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkyl phenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, alk(en)yl oligoglycosides, fatty acid glucamides, polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates. Where the nonionic surfactants contain polyglycol ether chains, they may have a conventional homolog distribution although they preferably have a narrow homolog distribution.
Typical examples of cationic surfactants are quaternary ammonium compounds and quaternized difatty acid trialkanolamine esters.
Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
All the surfactants mentioned are known compounds. Information on the structure and production of these substances can be found in relevant synoptic works, cf. for example J. Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin 1987, pp. 54-124 or J. Falbe (ed.), "Katalysatoren, Tenside und Mineraloladditive", Thieme Verlag, Stuttgart, 1978, pp. 123-217.
Surface-active preparations
The present invention also relates to the use of the surfactant mixtures according to the invention for the production of surface-active preparations, more particularly laundry detergents, dishwashing detergents and cleaning products and also hair-care and personal-care products, in which they may be present in quantities of 1 to 99% by weight and preferably in quantities of 5 to 30% by weight, based on the particular preparation. The following are typical examples of such preparations:
Powder-form universal detergents containing 10 to 30% by weight--based on the detergent--of the mixture according to the invention of alkyl oligoglucosides corresponding to formulae (I) and (II) and anionic, nonionic, cationic and/or amphoteric or zwitterionic surfactants and, optionally, other typical auxiliaries and additives.
Liquid universal detergents containing 10 to 70% by weight--based on the detergent--of the mixture according to the invention of alkyl oligoglucosides corresponding to formulae (I) and (II) and anionic, nonionic, cationic and/or amphoteric or zwitterionic surfactants and, optionally, other typical auxiliaries and additives.
Liquid light-duty detergents containing 10 to 50% by weight--based on the detergent--of the mixture according to the invention of alkyl oligoglucosides corresponding to formulae (I) and (II) and anionic, nonionic, cationic and/or amphoteric or zwitterionic surfactants and, optionally, other typical auxiliaries and additives.
Liquid cleaning and disinfecting preparations containing 10 to 30% by weight--based on the preparation--of the mixture according to the invention of alkyl oligoglucosides corresponding to formulae (I) and (II) and anionic, nonionic, cationic and/or amphoteric or zwitterionic surfactants and, optionally, other typical auxiliaries and additives.
Hair shampoos containing 10 to 30% by weight--based on the shampoo--of the mixture according to the invention of alkyl oligoglucosides corresponding to formulae (I) and (II) and anionic, nonionic, cationic and/or amphoteric or zwitterionic surfactants and, optionally, other typical auxiliaries and additives.
Hair rinses containing 10 to 30% by weight--based on the hair rinse--of the mixture according to the invention of alkyl oligoglucosides corresponding to formulae (I) and (II) and anionic, nonionic, cationic and/or amphoteric or zwitterionic surfactants and, optionally, other typical auxiliaries and additives.
Foam baths containing 10 to 30% by weight--based on the foam bath--of the mixture according to the invention of alkyl oligoglucosides corresponding to formulae (I) and (II) and anionic, nonionic, cationic and/or amphoteric or zwitterionic surfactants and, optionally, other typical auxiliaries and additives.
Syndet soaps containing 10 to 50% by weight--based on the soap--of the mixture according to the invention of alkyl oligoglucosides corresponding to formulae (I) and (II) and anionic, nonionic, cationic and/or amphoteric or zwitterionic surfactants and, optionally, other typical auxiliaries and additives.
Detergents and cleaning products based on the detergent mixtures according to the invention may contain, for example, builders, salts, bleaches, bleach activators, optical brighteners, redeposition inhibitors, solubilizers, foam inhibitors and enzymes as auxiliaries and additives.
Typical builders are sodium aluminium silicates (zeolites), phosphates, phosphonates, ethylenediamine tetraacetic acid, nitrilotriacetate, citric acid and/or polycarboxylates. Suitable salts or diluents are, for example, sodium sulfate, sodium carbonate or sodium silicate (waterglass). Typical individual examples of other additives are sodium borate, starch, sucrose, polydextrose, TAED, stilbene compounds, methyl cellulose, toluene sulfonate, cumene sulfonate, long-chain soaps, silicones, mixed ethers, lipases and proteases.
Hair shampoos, hair lotions or foam baths based on the detergent mixtures according to the invention may contain, for example, emulsifiers, oil components, fats and waxes, thickeners, superfatting agents, biogenic agents, film formers, fragrances, dyes, pearlescers, preservatives and pH regulators as auxiliaries and additives.
Typical oil components are such substances as paraffin oil, vegetable oils, fatty acid esters, squalene and 2-octyl dodecanol. Suitable fats and waxes are, for example, spermaceti, beeswax, montan wax, paraffin and cetostearyl alcohol. Superfatting agents may be selected from such substances as, for example, polyethoxylated lanolin derivatives, lecithin derivatives and fatty acid alkanolamides, the fatty acid alkanolamides also serving as foam stabilizers. Suitable thickeners are, for example, polysaccharides, more particularly xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also relatively high molecular weight polyethylene glycol monoesters and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinyl pyrrolidone and electrolytes, such as sodium chloride and ammonium chloride. Biogenic agents are understood to be, for example, vegetable extracts, protein hydrolyzates and vitamin complexes. Typical film formers are, for example, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives and similar compounds. Suitable preservatives are, for example, formaldehyde solution, p-hydroxybenzoate or sorbic acid. Suitable pearlescers are, for example, glycol distearic acid esters, such as ethylene glycol distearate, and also fatty acid monoglycol esters. The dyes used may be selected from any of the substances which are permitted and suitable for cosmetic purposes, as listed for example in the publication "Kosmetische Farbemittel" of the Farbstoffkommission der Deutschen Forschungsgemeinschaft, published by Verlag Chemie, Weinheim, 1984. These dyes are typically used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.
The following Examples are intended to illustrate the invention without limiting it in any way
EXAMPLES
I. Alkyl oligoglucosides used
Comp. I:
C 8-10 alkyl oligoglucoside
C chain distribution in the alkyl radical: 45% C 8 , 55% C 10
DP degree: 1.59
Plantaren® APG 225, a product of Henkel KGaA, Dusseldorf, FRG
Comp. II:
C 12-16 coconut oil alkyl oligoglucoside
C chain distribution in the alkyl radical: 68% C 12 , 26%
C 14 , 6% C 16
DP degree: 1.38-1.53
Plantaren® APG 600, a product of Henkel KGaA, Dusseldorf, FRG
All the products were used in the form of 50% by weight aqueous pastes.
II. Application Examples
Irritation of the skin was determined by OECD Method No. 404 and EEC Directive 84/449 EEC, Part B.4. The total irritation scores shown were compiled from the irritation scores obtained after 24, 48 and 72 hours. The total irritation score determined in comparison test C1 for a 100% C 12-16 alkyl oligoglucoside (DP=1.38) was put at 100% and the total irritation scores obtained in the other tests were related to that score.
The results are set out in Table 1 and FIG. 1.
TABLE 1______________________________________Results of performance tests Comp. I Comp. II Total irritation scoreEx. % by weight % by weight DP % rel.______________________________________1 7 93 1.38 672 10 90 1.38 623 10 90 1.41 604 10 90 1.53 525 12 88 1.38 59C1 0 100 1.38 100C2 0 100 1.45 95C3 0 100 1.53 95C4 17 83 1.38 72C5 20 80 1.38 80C6 33 67 1.38 75C7 40 60 1.38 64C8 60 40 1.38 62C9 63 37 1.38 70C10 80 20 1.38 72C11 90 10 1.38 75C12 100 0 1.38 78C12 100 0 1.59 71______________________________________ | An ultramild surfactant mixture consisting of
a) from about 5 to about 12% by weight of at least one alkyl oligoglucoside corresponding to formula (I):
R.sup.1 --O--(G).sub.p (I)
in which R 1 is an alkyl radical containing 8 to 10 carbon atoms, G is a glucose unit and p is a number of 1.3 to 1.8; and
b) from about 88 to about 95% by weight of at least one alkyl oligoglucoside corresponding to formula (II):
R.sup.2 --O--(G).sub.p (II)
in which R 2 is an alkyl radical containing 12 to 16 carbon atoms, G is a glucose unit and p is a number of 1.3 to 1.8.
Also, finished compositions containing the above surfactant mixture. | 1 |
FIELD OF THE INVENTION
[0001] The present invention relates generally to blood monitoring devices, and, more particularly, to a test patch for painlessly obtaining a sample of blood.
BACKGROUND OF THE INVENTION
[0002] It is often necessary to quickly and painlessly obtain a sample of blood and perform a quick analysis of the blood. One example of a need for painlessly obtaining a sample of blood is in connection with a blood glucose monitoring system where a user must frequently use the system to monitor the user's blood glucose level.
[0003] Those who have irregular blood glucose concentration levels are medically required to regularly self-monitor their blood glucose concentration level. An irregular blood glucose level can be brought on by a variety of reasons including illness such as diabetes. The purpose of monitoring the blood glucose concentration level is to determine the blood glucose concentration level and then to take corrective action, based upon whether the level is too high or too low, to bring the level back within a normal range. The failure to take corrective action can have serious implications. When blood glucose levels drop too low—a condition known as hypoglycemia—a person can become nervous, shaky, and confused. That person's judgment may become impaired and that person may eventually pass out. A person can also become very ill if their blood glucose level becomes too high—a condition known as hyperglycemia. Both conditions, hypoglycemia and hyperglycemia, are both potentially life-threatening emergencies.
[0004] One method of monitoring a person's blood glucose level is with a portable, hand-held blood glucose testing device. A prior art blood glucose testing device 100 is illustrated in FIG. 1. The portable nature of these devices 100 enables the users to conveniently test their blood glucose levels wherever the user may be. The glucose testing device contains a test sensor 102 to harvest the blood for analysis. The device 100 contains a switch 104 to activate the device 100 and a display 106 to display the blood glucose analysis results. In order to check the blood glucose level, a drop of blood is obtained from the fingertip using a lancing device. A prior art lancing device 120 is illustrated in FIG. 2. The lancing device 120 contains a needle lance 122 to puncture the skin. Some lancing devices implement a vacuum to facilitate the drawing of blood. Once the requisite amount of blood is produced on the fingertip, the blood is harvested using the test sensor 102 . The test sensor 102 , which is inserted into a testing unit 100 , is brought into contact with the blood drop. The test sensor 102 draws the blood to the inside of the test unit 100 which then determines the concentration of glucose in the blood. Once the results of the test are displayed on the display 106 of the test unit 100 , the test sensor 102 is discarded. Each new test requires a new test sensor 102 .
[0005] One problem associated with some conventional lancing devices is that there is a certain amount of pain associated with the lancing of a finger tip. Diabetics must regularly self-test themselves several time per day. Each test requires a separate lancing, each of which involves an instance of pain for the user.
[0006] Another problem associated with some conventional lacing devices is that the lacerations produced by the lances are larger than necessary and consequently take a greater time to heal. The greater the amount of time for the wound to heal translates into a longer period of time in which the wound is susceptible to infection.
[0007] Another problem associated with some conventional blood glucose monitoring devices is that the user's blood physically contacts the elements within the testing unit. Cross-contamination can be a problem if the monitoring device is used by more than one user such as a clinical setting.
SUMMARY OF THE INVENTION
[0008] According to one embodiment of the present invention, a test strip is provided for use in the determination of the concentration of a chemical in blood. The test strip comprises an array of microneedles and a test area. Each microneedle is adapted to puncture skin and to draw blood. The test area is in fluid communication with the microneedles. The test area contains a reagent adapted to produce a reaction indicative of the concentration of the chemical in blood.
[0009] The above summary of the present invention is not intended to represent each embodiment, or every aspect, of the present invention. Additional features and benefits of the present invention will become apparent from the detailed description, figures, and claims set forth below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] Other objects and advantages of the invention will become apparent upon reading the following detailed description in conjunction with the drawings in which:
[0011] [0011]FIG. 1 is a top view of a prior art blood glucose testing device;
[0012] [0012]FIG. 2 is a perspective view of a prior art lance;
[0013] [0013]FIG. 3 is a perspective view of a microneedle patch according to one embodiment of the present invention;
[0014] [0014]FIG. 4 is a cross-sectional view of the embodiment of the microneedle patch illustrated in FIG. 3;
[0015] [0015]FIG. 5 is another cross-sectional view of the embodiment of the microneedle patch illustrated in FIG. 3;
[0016] [0016]FIG. 6 is a collection point of a microneedle according to a second alternative embodiment of the present invention;
[0017] [0017]FIG. 7 is a collection point of a microneedle according to a third alternative embodiment of the present invention;
[0018] [0018]FIG. 8 is a collection point of a microneedle according to a forth alternative embodiment of the present invention;
[0019] [0019]FIG. 9 is an embodiment of a blood glucose monitoring device for use in conjunction with a microneedle patch according to a sixth alternative embodiment of the present invention;
[0020] [0020]FIG. 10 is an embodiment of a blood glucose monitoring device for use in conjunction with a microneedle patch according to a seventh alternative embodiment of the present invention;
[0021] [0021]FIG. 11 is an embodiment of a blood glucose monitoring system according to an eighth alternative embodiment of the present invention; and
[0022] [0022]FIG. 12 is an embodiment of a blood glucose monitoring system according to a ninth alternative embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0023] Referring now to FIG. 3, a hollow microneedle patch 200 according to one embodiment of the present invention is illustrated. The microneedle patch 200 comprises a plurality of hollow microneedles 202 coupled to a test chamber 204 . Blood is moved through each of the plurality of microneedles 202 by capillary action to the test chamber 204 . In the illustrated embodiment of the present invention, the plurality of hollow microneedles 202 are arranged in a twenty by twenty array so that the microneedle patch 200 includes four hundred hollow microneedles 202 . The microneedle patch 200 is used to lance a user's skin and to harvest a sample of blood. Essentially, the microneedle patch 200 integrates the prior art test sensor 102 and the lance 120 (discussed in conjunction with FIGS. 1 and 2) into a single unit.
[0024] Each microneedle penetrates the skin to a depth of about two-hundredths of an inch (0.005 inch). The microneedles 202 extend below the surface of the skin a distance sufficient to collect a sample of blood from the outermost layer of capillaries. The skin's outer layer, called the stratum corneum, does not contain any nerve endings. The first extensive nerve layer is disposed below the outermost layer of capillaries. Because each of the microneedles 202 do not contact any nerves, the lancing of the skin and the collection of blood is essentially painless. Further, because the lacerations created in the skin are much smaller that those created by a conventional lance, the risk of infection is lessened and the healing of the lacerations is expedited. The precise dimensions of the microneedles 202 and the microneedle 200 patch are a function of several variables including the amount of blood to be harvested and the type of blood glucose analysis to be used in conjunction with the microneedle patch 200 .
[0025] Referring now to FIGS. 4 and 5, the microneedle patch 200 is illustrated pressed onto a user's skin 206 causing each of the microneedles 202 to penetrate the skin 206 . Each of the microneedles 202 are hollow and have a collection point 208 and an outlet 210 . The outlet 210 of each microneedle 202 is coupled to the test chamber 204 . After penetrating the skin 206 , blood 212 is collected though the collection point 208 of each of the microneedles 202 . The blood 212 is moved though an interior 214 of the hollow microneedles 202 by capillary action to the test chamber 204 . The requisite volume of blood 212 necessary for accurate testing is dependent on the type of glucose analysis employed. For example, the applicant has found that at least approximately one micro-liter of blood 212 is necessary to employ electrochemical analysis to determine the blood glucose concentration. Each of the plurality of microneedles 202 draws a portion of the requisite volume of blood 212 into the test chamber 204 where the analysis occurs.
[0026] A reagent 215 is incorporated in the test chamber 204 of the microneedle patch 200 . Once blood is moved into the test chamber 204 , the glucose in the blood 212 reacts with the reagent 215 in the test chamber 204 to produce a detectable signal. That signal is then measured by a sensor which can measure the concentration of the glucose in the blood 212 based on the signal. The specific reagent 215 incorporated into the test chamber 204 is a function of the type of sensing employed to determine the concentration of glucose in the blood 212 .
[0027] In operation, a user can measure the concentration of the user's blood by pressing the microneedle patch 200 onto the user's skin. Each of the microneedles 202 lances the skin 206 . A quantity of blood 212 is moved by capillary action from the collection point 208 of each microneedle 202 to the test chamber 204 . The glucose in the blood 212 reacts with a reagent 215 incorporated into the test chamber 204 producing a signal indicative of the blood glucose concentration. That signal is then measured with an appropriate sensor in a blood glucose analyzer to determine the concentration of glucose in the user's blood. Once the blood glucose analyzer measures the signal produced by the reaction, the microneedle patch 200 can be discarded.
[0028] An advantage to the use of the microneedle patch 200 is that blood never comes into contact with the blood glucose analyzer. Therefore, in addition to self-testing, the microneedle patch 200 may be used at a clinical level because cross-contamination is not an issue. For example, a doctor may use a single blood glucose analyzer to test the blood glucose concentration for that doctor's patients. One microneedle patch 200 would be used for each patient. The microneedle patch is pressed onto the patient's skin and the signal produced by the reaction within the microneedle patch 200 is read by a blood glucose analyzer which never contacts the patient's blood. The blood glucose analyzer can be used again while the use microneedle patch 200 , containing the sample of blood, is discarded.
[0029] Referring to FIGS. 6, 7 and 8 , three alternative embodiments of the collection point of each microneedle 202 is illustrated. Each microneedle 202 of the present invention is generally shaped as a hollow cylinder having cylindrical walls 230 . In FIG. 6, the collection point of the microneedle 202 is an angled collection point 232 . A plane parallel to the angled collection point 232 is disposed at an angle relative to the longitudinal axis of the microneedle 202 .
[0030] In another alternative embodiment, the microneedle 202 has a generally concave collection point 234 as illustrated in FIG. 7. The generally cylindrical walls 230 of the microneedle 202 are formed upwardly sloping radially away from the longitudinal axis of the microneedle 202 at the collection point 234 .
[0031] In still another alternative embodiment, the microneedle 202 has a generally convex collection point 236 is illustrated in FIG. 8. In the embodiment illustrated in FIG. 8, the generally cylindrical walls 230 of the microneedles 202 are formed downwardly sloping radially away from the longitudinal axis of the microneedle 202 at the collection point 236 . The shape of the alternative embodiments of the collections points illustrated in FIGS. 6 - 8 reduces surface tension at the collection point of the microneedle 202 thus facilitating the movement of blood from the collection point through the hollow microneedle 202 to the test chamber 104 .
[0032] Colorimetric analysis is one type of analysis that can be utilized with the microneedle patch 200 of the present invention. The reaction of the glucose and a specific reagent produces a change in color, or a colorimetric reaction, which is indicative of the amount of glucose in the blood. That color change can be compared to a color chart, wherein the colors on the color chart were obtained using blood having a known glucose concentration, to determine the blood glucose concentration. The color change in the test chamber 204 caused by the reaction of the glucose and the reagent 215 can be read with a spectrophotometric instrument incorporated into a glucose monitoring device for use with the patch 200 . In such an embodiment where colorimertic sensing is employed, a back side 218 (FIG. 4) of the test sensor 204 may be transparent allowing the glucose monitoring device to optically detect the color change.
[0033] Alternatively, electrochemical analysis is another type of analysis which may be utilized in conjunction with the microneedle patch 200 of present invention to determine the concentration of glucose in a user's blood. In such an embodiment, the test chamber 104 includes a pair of electrodes. In electrochemical analysis, the change in current across the electrodes caused by the reaction of the glucose and the reagent is indicative of the concentration of the glucose in the blood. The reaction of the glucose and the reagent creates an oxidation current at the electrode which is directly proportional to the user's blood glucose concentration. This current can be measured by an appropriate sensor implemented in an glucose monitoring device for use with the patch 200 . The glucose monitoring device can then communicate to the user the blood glucose concentration. Both calorimetric and electrochemical testing systems are described in detail by commonly-owned U.S. Pat. No. 5,723,284 entitled “Control Solution and Method for Testing the Performance of an Electrochemical Device for Determining the Concentration of an Analyte in Blood” which is incorporated herein by reference in its entirety.
[0034] Referring now to FIG. 9, a glucose monitoring device 300 having a calorimetric sensor (a spectrophotometric instrument) 302 which may used in conjunction with the microneedle array patch 200 is illustrated. The test chamber 204 of the microneedle array patch 200 contains appropriate reagents designed to react with glucose in a manner to produce a change in color indicative of the glucose concentration in the user's blood. The glucose monitoring device 300 having a colorimetric sensor 302 determines the glucose concentration and informs the user of the result. The monitoring device 300 is activated with a switch 304 . After the microneedle array patch 200 is pressed onto the user's skin and the requisite amount of time has past for the reaction to occur, the monitoring device 300 is brought into close proximity to the microneedle array patch 200 to read the colorimetric signal produced by the reaction. The test chamber 204 has a transparent back cover 218 allowing the calorimetric sensor 302 in the monitoring device 300 to optically read the signal. The monitoring then determines the blood glucose concentration and communicates those results to the user via a display 306 . The microneedle patch 200 can then be removed and discarded.
[0035] Alternatively, electrochemical sensing can be employed in conjunction with the microneedle array path of the present invention. FIG. 10 illustrates a suitable monitoring device 320 which can be used in conjunction with an embodiment of the microneedle patch 200 designed for electrochemical sensing. The embodiment of the microneedle patch 200 designed for electrochemical sensing contains a pair of electrodes 352 . The blood glucose monitoring device 320 contains a pair of corresponding electrodes 353 (shown in FIG. 12). The blood glucose monitoring device 350 is activated with a switch 354 . Once the microneedle patch 200 is pressed onto a users skin and a requisite amount of time has passed for the electrochemical reaction to occur, the electrodes 352 of the monitoring device are bought into contact with the corresponding electrodes 353 on the microneedle patch 200 . The results of the blood glucose analysis are communicated to the user via a display 356 .
[0036] Referring now to FIG. 11, another application of the microneedle patch 200 of the present invention is in an integrated blood glucose monitoring system 350 which integrates the microneedle array patch 200 and a blood glucose analyzer into a single instrument. The integrated blood glucose monitoring system contains a plurality of microneedle patches 200 and when activated moves a new microneedle patch 200 to the test end 352 of the system 350 . In operation, a user would activate the system 350 with a switch 354 . A new microneedle patch 200 is advanced to the test end 352 of the system 350 . The user would then press the test end 352 of the system against the user's skin causing each of the microneedles 202 in the array of microneedles 202 to lance the user's skin and to harvest the blood sample. Once the requisite blood sample has been obtained and the requisite time has elapsed for the reaction in the test chamber 204 of the microneedle patch 200 to occur, the blood glucose monitoring system 350 determines the blood glucose concentration and communicates the result to the user via a display 356 . The used microneedle array patch is then ejected from the system 350 . Both electrochemical sensing and colorimetric sensing as well as other types of blood glucose analysis may be implemented within the blood glucose monitoring system 350 of the present invention.
[0037] Referring now to FIG. 12, another alternative embodiment of the present invention is illustrated wherein the microneedle patch 200 has an adhesive 360 disposed on an upper surface 362 of the microneedle patch 200 in an another alternative embodiment of the present invention. The adhesive 360 holds the microneedle patch 200 against a user's skin 206 . The adhesive 360 is useful in an embodiment of the microneedle patch 200 wherein a longer period of time is required for the harvesting of the blood sample and then the occurrence of the reaction between the glucose in the blood and the reagent disposed in the test chamber 204 . Also illustrated in FIG. 12 are the pair of electrodes 353 disposed in the test chamber 203 .
[0038] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings and will be described in detail herein. It should be understood, however, that it is not intended to limit the invention to the particular forms disclosed, but, to the contrary, the intention is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the invention as defined by the appended claims. | A test strip is provided for use in the determination of the concentration of an a chemical in blood. The test strip comprises a plurality of microneedles and a test area. Each microneedle is adapted to puncture skin and to draw blood. The test area is in fluid communication with the microneedles. The test area contains a reagent adapted to produce a reaction indicative of the concentration of the chemical in blood. | 0 |
FIELD OF THE INVENTION
This invention pertains in general to circuitry for reducing transient electrical noise in alternating current circuits, and more particularly to circuitry for attenuating high-frequency electrical noise produced by the closing of contacts in electro-mechanical relays.
BACKGROUND OF THE INVENTION
Circuitry consisting of resistive, inductive, and capacitive elements (RLC circuits) has long been used to attenuate transient noise in direct current electrical circuits. However, it has not always been possible to successfully employ RLC circuits to attenuate noise alternating current circuits, due to the high rate of change of voltage with respect to time inherent in alternating current circuits. For example, in a 165 volt root-mean-square (rms) 8,000 hertz application, it was found difficult to attenuate noise having a frequency above one-hundred mega-hertz.
Therefore a need exists for noise attenuation circuitry that will protect sensitive integrated circuit components from being damaged by transient high-frequency noise generated by electro-mechanical relays.
OBJECT, FEATURES, AND ADVANTAGES
It is a primary objective of the present invention to protect sensitive integrated circuit components in alternating current circuits from being damaged by transient high-frequency noise generated by the closing of electro-mechanical relay contacts.
It is a feature of the present invention to place metal oxide field effect transistors (MOSFETs) in series between the electro-mechanical relay and sensitive integrated circuit components.
It is a feature of the present invention to utilize a photocoupler to electrically isolate the direct current relay circuit (which energizes the electro-mechanical relay coil) from all other circuits.
It is a feature of the present invention to utilize a floating ungrounded rectifying circuit incorporating a zener diode to provide voltage-stabilized direct current for activating the MOSFETs.
It is a feature of the present invention to utilize a RLC circuit to delay the activation of the light emitting diode in the photocoupler.
It is a feature of the present invention to utilize a RLC circuit to delay the activation of the MOSFETs.
It is an advantage of the present invention that the inherent safety and reliability of an electro-mechanical relay is combined with the inherent low noise characteristics of semiconductor devices.
SUMMARY OF THE INVENTION
The noise attenuating circuit illustrated consists of a photocoupler (a light-emitting diode and a phototransistor), a step-down transformer having a secondary center tap, two MOSFETs, one zener diode, two diodes, two capacitors, and six resistors. When the foregoing elements, together with an electro-mechanical relay, are connected together via the illustrated circuit they comprise a new and useful device combining the safety features of the relay with the electrical quietness of a purely semiconductor device.
In essence the function of the electro-mechanical relay is reduced to that of a safety block, the function of contact closing being taken over by the time-delayed semiconductor devices.
BRIEF DESCRIPTION OF THE DRAWINGS
The sole FIGURE is a schematic diagram showing the noise attenuating circuit of the present invention, which is connected to an electro-mechanical relay shown enclosed within the dashed rectangle.
DRAWING REFERENCE NUMERALS
10 noise attenuating circuit
11 input terminal for alternating current
12 relay input lead
13 relay output lead
14 output terminal for alternating current
15 input terminal for direct current
16 coil input lead
17 coil ground lead
18 common electrical ground
20 electro-mechanical delay
21 relay mechanical contacts
22 electro-mechanical relay coil (5.0 henrys)
24 photocoupler (TIL-111 Optocoupler)
26 light emitting diode
28 phototransistor
30 first metal oxide silicon field effect transistor (IRH 450)
32 second metal oxide silicon field effect transistor (IRH 450)
34 step-down transformer with center tap on secondary
35 center tap floating ground
36 zener diode (15 volt)
38 first diode (1N4002)
40 second diode (1N4002)
42 first capacitor (0.22 μf)
44 second capacitor (1.0 μf)
46 first resistor (750Ω)
48 second resistor (750Ω)
50 third resistor (30 kΩ)
52 fourth resistor (30 kΩ)
54 fifth resistor (10 kΩ)
56 sixth resistor (2 kΩ)
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the schematic diagram of the sole FIGURE, there is shown the noise attenuating circuit 10 of the present invention, connected to a normally-open electro-mechanical relay 20 shown enclosed within the dashed rectangle.
Relay 20 is connected in series between AC input terminal 11 and first MOSFET 30 by relay input lead 12 and relay output lead 13 respectively. First MOSFET 30 is next connected in series with second MOSFET 32, which is in turn connected in series to AC output terminal 14.
The coil input lead 16 of relay coil 22 is connected to DC input terminal 15; the coil ground lead 17 is connected to common ground 18. A light-emitting diode (LED) 26 and a first capacitor 42 are connected to each other in parallel; then they are connected in series with sixth resistor 56 across the two leads 16 and 17 of relay coil 22. The LED 26 along with phototransistor 28 are elements of photocoupler 24, which serves to electrically isolate the direct current relay coil circuit from other circuits.
The primary side of a center-tap step-down transformer 34 is connected between the AC input relay lead 12 and common ground 18; a first diode 38 is connected to one end of the secondary side, and a second diode 40 is connected to the other end. The opposite ends of the two diodes 38 and 40 are connected together and to the first end of fifth resistor 54. A zener diode 36 is connected between the secondary side center tap floating ground 35 of transformer 34 and the second end of resistor 54. A rectified voltage-stabilized direct current is thus established across the connections of zener diode 36. This rectified direct current is transmitted (via phototransistor 28, and thence via a voltage activation delay network for the field effect transistor 30 and 32 consisting of third resistor 50, fourth resistor 52, and second capacitor 44) to bias both the gate of first MOSFET 30 (via an associated first resistor 46) and the gate of second MOSFET 32 (via an associated second resistor 48).
In operation, when a direct current (DC) voltage is applied (across DC terminal 15 and common ground 18) to relay coil 22, the contacts 21 of relay 20 close, passing alternating current (AC) voltage to first MOSFET 30. The AC voltage (applied across AC terminal 11 and common ground 18) is stepped down by transformer 34, and then full-wave rectified by first diode 38 and second diode 40; the zener diode 36 limits the magnitude of this rectified voltage (which will be applied to the gates of first MOSFET 30 and second MOSFET 32). The current activation delay network (consisting of sixth resistor 56 and first capacitor 42) for the light-emitting diode (LED) 26 delays the rise of direct current in the LED 26 of photocoupler 24. As the current in LED 26 rises, the phototransistor 28 within photocoupler 24 turns on, transmitting rectified voltage (via the voltage activation delay network for the field effect transistors) to the gates of first MOSFET 30 and second MOSFET 32.
The values for the components are selected so that the delay produced lasts longer than the bouncing of the delay contacts 21; hence the AC output (across AC output terminal 14 and common ground 18) will not transmit any of the high-frequency noise usually generated by relay contacts 21 closing. Values for the components (or other descriptive information) that were used for a breadboard prototype are given, in parentheses, in the preceding list of drawing reference numerals. The step-down transformer 34 was built on a 52168-1A core, with 581 turns on the primary and 116 turns on the secondary. For the breadboard prototype, the frequencies generated by the turn-on transient of first MOSFET 30 and second MOSFET 32 was on order of 1 MHz, compared to frequencies above 100 MHz produced by the relay 20 alone. When first MOSFET 30 and second MOSFET 32 turned on, they turned on in the time span on the order of a microsecond, which is very slow compared to the nanosecond rise times produced by bouncing contacts.
The foregoing method of reducing high-frequency electrical noise is applicable in a system that has vulnerable integrated circuit components, and where safety dictates that relay contacts shall be in series with the AC power source. This allows the relay contacts to act as safety blocks, while at the same time protecting the downstream components from high-frequency contact noise.
While this invention has been described in conjunction with a preferred embodiment thereof, it is obvious that modifications and changes therein may be made by those skilled in the art without departing from the scope of this invention as defined by the claims appended hereto. | An electrical noise reduction circuit which includes field-effect transiss and a photocoupler, for use in alternating current circuits in conjunction with an electro-mechanical relay. The circuit essentially reduces the function of the electro-mechanical relay to that of a safety block, the function of contact closing being taken over by the time-delayed semiconductor devices of the noise reduction circuit. | 7 |
BACKGROUND OF THE INVENTION
The present invention relates to disc screen apparatuses for sorting, by size, particulate matter such as wood chips, and the like. It more specifically relates to discs for such apparatuses and methods for forming such discs.
Disc screens have been used for many years to sort a variety of objects by size, such as wood chips, coal, coke, grain, beets, leaves, sticks and potato chips. For example, uniform high yield wood pulp requires correctly sized and composed wood chips. Examples of disc screens are those shown in the following U.S. patents. These patents and all other patents and publications mentioned herein are hereby incorporated by reference in their entireties.
______________________________________U.S. Pat. No. Patentee______________________________________4,037,723 Wahl et al.4,239,119 Kroell4,301,930 Smith4,376,042 Brown4,377,474 Lindberg4,452,694 Christensen et al.4,538,734 Gill4,579,652 Bielagus4,653,648 Bielagus4,658,964 Williams4,658,965 Smith4,703,860 Gobel et al.4,741,444 Bielagus4,755,286 Bielagus4,795,036 Williams______________________________________
Generally speaking, these disc screens include a frame and a plurality of rotating parallel shafts mounted within the frame. Each of the shafts has a plurality of spaced apart discs mounted thereon. The discs on adjacent shafts intermesh and rotate side-by-side with a fixed critical distance between the intermeshed discs. These disc screens typically have an entrance end perpendicular to the longitudinal axes of the shafts. Opposite the entrance end is an exit end which is adjacent to a discharge port. Each shaft rotates in a downstream direction to transport matter along the discs from the entrance end to the exit end.
In operation, the particulate matter to be sorted is dropped from above the disc screen along the entrance end. The downstream shaft rotation carries the larger pieces of particulate matter across the upper surface of the screen to the discharge port. The smaller size particulate matter falls due to gravity through the critical fixed distance spaces between the intermeshing discs for collection below the disc screen. Generally, the shafts of the disc screens are coplanar and rotate in a horizontal plane.
Some devices have utilized the disc screen in an inclined position. For example, if the entrance end is at a higher level, gravity assists in transporting the larger particles over the upper surface of the disc screen. Other disc screen arrangements have linked inclined and horizontal disc screen sections, with a continuous path of travel along the upper surface of the linked sections.
The critical spacing between the intermeshing discs depends upon the disc spacing along adjacent shafts. Various methods have been used to maintain the required disc spacing on a given shaft. Many devices utilize spacers, such as washers, between adjacent plate-like disc. Close axial tolerances must be maintained on both spacers and discs to minimize the cumulative error over the length of a shaft. Close tolerance requirements, however, increase the cost of such assemblies.
Other devices use discs having hubs projecting outwardly from one or both sides of the disc which butt against the adjacent hub or disc. Some hubbed discs are die cast and susceptible to fracture from porosity and other material impurities. Die cast discs are generally thicker, heavier to handle, and expensive due to the increased material required, however. Many of these earlier devices have used bearings having cast bearing housings to mount the rotating shaft to the frame. These cast bearing housings usually have oversized mounting bolt holes to facilitate shaft alignment. Vibrations encountered during operation can loosen the mounting bolts, allowing the bearing housing to shift. Thus the critical spacing is not maintained.
For shaft assemblies having a plurality of spaced apart discs mounted upon a cylindrical shaft, there is an undesirable tendency for the discs to rotate relative to the shaft and/or relative to each other. This undesirable rotation impedes the flow of the particulate matter across the screen. A variety of notch and key methods have been used to prevent this rotation. Examples thereof are shown in the previously-listed '723 patent to Wahl, the '734 patent to Gill and the '119 patent to Kroell. Another method has been to weld the discs to the shaft to prevent the rotation and maintain axial alignment. The welding of the discs is a time consuming process, however, due to the close tolerances often involved and may also heat warp the discs. A prior art disc and disc screen assembly which remedies many of the problems has been commercially available from Mill Services and Manufacturing, Inc. of Hattiesburg, Miss. under the trademark "SoloDisc," which can be used in a flat screen or a V-screen replacement shaft assembly. This prior art disc screen assembly allows the discs to be readily fitted upon a shaft during initial assembly, retrofitting and replacement. The shaft assembly has a minimal number of parts and has minimal disc wobble resulting. This prior art system is illustrated in FIGS. 1-5 generally at 100 and is described below.
Referring to FIGS. 1 and 2 it is seen that a shaft 102 is driven by a belt drive (a "Gates Poly Chain GT" drive--see e.g., U.S. Pat. No. 4,605,389) extending over a sheave 104. The belt drive thereby directly drives the entire shaft (a "live" shaft) through a bearing 106 and which in turn drives a pipe roll 108. Thus the pipe roll 108 is secured to and rotatable with the shaft. A plurality of individual stepped discs 110 are slipped into place on the roll and held therein by the locking slots, by the stepped relation of the discs, and by the compression lock nut 112 securable thereto. Also illustrated in the FIG. 2 are the male fixed end cap 114, the female compression ring 116, the lock washer 117 and the shaft seal 118 of shaft assembly 100.
The prior art disc 110 shown in isolation FIGS. 3-5, comprises a disc plate 122 having teeth 124 about its outer perimeter and a double stepped spacing and nesting sleeve shown generally at 126 integrally formed with the plate. The first step 128 is sized diametrically to slidably receive the tubular shaft (108). The second step 130 interconnects the first step 128 with the plate 122 and is diametrically sized to slidably receive the first step of a preceding disc. Thus, the adjacent precedingly and subsequently assembled discs are nested together by their overlapping steps. This sleeve 126 spaces the discs 110 at the desired distance.
A stop 132 and a stop engaging surface 134 are provided on the two-stepped sleeve 126. The stop 132 is formed as a shoulder defined by the outer radius of the bend in the sleeve 126 connecting the second step 130 with the disc plate 122. The stop engaging surface is shown by the shoulder stop 132 located at the outer periphery of the diametrical transition between the first and second steps 128, 130. When assembled, the shoulder of one disc engages the shoulder stop of the adjacent disc to maintain a desired spacing between adjacent discs. Separate spacers are thus not required to maintain disc spacing. The desired spacing is determined from the disc plate thickness and the maximum size of acceptable particles. In other words, the critical space equals one-half the difference between the desired spacing and the disc thickness. Thus, the axial length of the first step on a preceding disc should be long enough to extend under the second step but not so long as to interfere with the first step of the next disc.
After the discs have been assembled on the shaft, the lock nut 112 is tightened, forcing the compression collar inward and the shoulders of the discs into engagement with the shoulder stops of the preceding discs. The lock washer 117 prevents further rotation of the lock nut 112 and maintains the axial alignment of the discs. Thus no welding, which is not only time consuming but may also heat warp the disc, is needed. Each of the discs is provided with an inwardly projecting key or dimple 140 on the first step 128 of the disc which then slides onto a longitudinal groove on the outer surface of the tubular shaft thereby preventing relative rotation of the discs.
These discs were manufactured from ductile steel using a three-step draw die. At the first draw die step the center opening was punched through the disc, a slight draw of around 71/2 millimeters for the double stepped sleeve was formed and the outer diameter of the disc was punched. The second die punched the draw to form the double stepped sleeve. A third punch formed the teeth on the outer diameter of the disc. These teeth were chrome plated in a subsequent operation. In a fourth forming step a slide punch placed the anti-rotation dimple or key in the first step of the sleeve. The disc assemblies were assembled with the teeth on adjacent discs staggered to assist in pulling apart the mat of particulate matter conveyed thereon. The dimple was thus located positively or fixed relative to the teeth. (Examples of prior art die stamping procedures for other articles are disclosed in U.S. Pat. Nos. 3,707,133 and 3,834,212.)
Thus with the discs slid into place on the shaft and held together by the end clamping means, the stop of one disc is adjacent the shoulder stop of the adjacent disc. Since both of these surfaces are curved rounded surfaces, as best shown in FIG. 5, the contact between the shoulder and the stop, when viewed in cross-section, is essentially only a point contact, or when viewed in three dimensions is a circle line contact, the line having a maximum width of generally only one thirty-second of an inch. This provides for only a ball joint type of coacting relationship, allowing one surface to roll against the other, that is, allowing the discs to wobble.
Although as a practical matter this prior art screen functioned effectively, commercially they were not as successful as desired due to this wobble. The customer requires uniform spacing with extremely tight tolerances, and IFOs having an accuracy of twenty thousandths of an inch are preferred. No method, even the "SoloDisc", was known for consistently providing these accurate IFOs in a system without any undesirable wobbling of the disc.
In fact since such a system was thought not possible, the trend in sorting machines has been away from disc screens and to spiral and diamond roll-type screens. Examples of such are the "DynaGage Bar Screen" available from Rader Companies, which is a division of Beloit Corporation and has a headquarters in Portland, Oreg. It includes z gauge bars. The slots between the bars establish the maximum particle thickness that will pass through the screen. When activated the eccentricity of the shafts causes each deck to oscillate independently. Another recent design also available from Rader Companies is the "Raderwave Fines Screen", which has a series of parallel shafts located beneath a flexible perforated screen deck. A wave-like motion is created on the material on the screen when the shafts rotate. The pins and chips are thereby apparently suspended, the fines (undersized chips) migrate through the perforations and acceptable fiber travels across the screens.
Another example is the "ChipManager PST" available from Evergreen Engineering, Inc. of Eugene, Oreg. and disclosed in U.S. Pat. No. 4,376,042. A further system also available from Evergreen Engineering is their "ChipManager VSF". It uses a small horizontal disc screen head of an existing system to thereby split the infeed mass and more thoroughly remove fines and overthicks.
SUMMARY OF THE INVENTION
Accordingly it is a principal object of the present invention to provide an improved disc screen assembly which is easy to manufacture, assemble and repair.
Another object of the present invention is to provide an improved disc construction which is easy to manufacture and which reliably and consistently maintains an accurate spacing between adjacent discs and which prevents disc wobble.
A further object of the present invention is to provide a novel method of manufacturing these improved discs.
Directed to achieving these objects, an improved disc construction is herein disclosed. It is formed as a one-piece metal stamping having perimeter teeth and a central opening through which it can be assembled onto shafts at exact predetermined spacing. These shaft and disc assemblies are arranged in parallel rows to make a rotating screen for sorting wood chips for the paper industry. The disc includes a plate having a toothed perimeter and a sleeve integrally formed with the plate and projecting out from one face thereof. The sleeve is formed as a two-stepped arrangement having an exterior stop and an interior shoulder stop, both formed as angled flat surfaces. When the sleeves are assembled onto the shaft, the stop of one sleeve engages the shoulder stop of an adjacent sleeve over a wide area and thereby accurately positions and holds the plates at the desired spaced relation. There are generally between one hundred and one hundred and forty-three, or typically one hundred and sixteen, discs per shaft and generally between five and twenty-two, or typically sixteen, shafts per screen.
Other objects and advantages of the present invention will become more apparent to those persons having ordinary skill in the art to which the present invention pertains from the foregoing description taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational view of a prior art disc screen shaft assembly, with a central portion thereof broken away for illustrative purpose.
FIG. 2 is an exploded perspective view of the shaft assembly in FIG. 1.
FIG. 3 is an elevational view of the prior art disc of the shaft assembly of FIG. 1 and illustrated in isolation.
FIG. 4 is a side elevational view of the disc of FIG. 3.
FIG. 5 is an enlarged view taken on circle 5 of FIG. 4.
FIG. 6 is a sectional view, similar to FIG. 5, of a pair of discs of the present invention illustrated in an assembled position; these discs are in other non-illustrated aspects the same as that shown in FIG. 3.
FIG. 7 is a sectional fragmentary view of a first die of the present invention illustrating the blank piercing and drawing step of the present invention for forming the disc(s) of FIG. 6.
FIG. 8 is a sectional fragmentary view of a second die of the present invention illustrating the trimming and piercing step for the present disc.
FIG. 9 is a sectional fragmentary view of a third die of the present invention illustrating the coining and extruding step.
FIG. 10 is a sectional fragmentary view of the die in FIG. 9 illustrated in the flattening and resizing mode and step.
FIG. 11 is a sectional view of a fourth die of the present invention illustrating the keyway lance forming step.
FIG. 12 is a cross-sectional view of the shaft tubing of the present invention, similar to that shown in FIG. 1 except having a pair of keyways provided.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The disc screen assembly of the present invention differs only in a few small, but extremely important, aspects over that illustrated in FIGS. 1-5. These differences focus on the construction of the disc itself and primarily the two-stepped sleeve component thereof. The relevant portion of the disc construction of the present invention is shown in FIG. 6, and the invention embodied therein will become apparent when compared to the stepped-sleeve arrangement of the prior art illustrated in FIG. 5. It is seen in the disc 200 in FIG. 6 that a pair of parallel flat surfaces 202, 204 are formed disposed at angles of forty-five degrees relative to the center line of the disc, or when mounted on the shaft to the center line of the shaft. The inner flat 202 forms a shoulder at the transition between the first inner step 206 of the disc and the toothed disc plate 208. The exterior flat 204 forms a stop at the transition between the inner step 206 and the outer step 210. Each of these flats is between 3/16 and 1/4 inch, or approximately one-quarter inch, wide and defines a frusto-conical surface when viewed in three dimensions. Thus, with the discs 200, 200' slid into place on the shaft and held thereon by the first step, the top side of the outer step 208 slides under the disc plate 210' of the adjacent disc 200' such that the shoulder 202' of one disc 200' abuts against the stop 204 of the adjacent disk 200. These large flat surfaces provide a wide area of contact. When the discs are clamped together on the shaft and the shaft is rotated in a screening operation, the discs accordingly do not wobble due to this wide flat contact. The flats 202, 204 are arranged at forty-five degrees relative to the center line of the rotating shaft to provide the maximum surface contact area between adjacent discs. Other angles in a mating relationship are also within the scope of the present invention.
Both of these flat areas, that is, the shoulder 202 and the stop 204 of each disc, are formed simultaneously with a coining die, as shown in FIG. 9 at 220. The preferred material for these discs 200 is a cold or hot rolled sheet of A1008, A1006 or A1003 steel, 3/16ths of an inch thick and in a 201/2 by 201/2 inch square. A uniform metal thickness in any one lot is desirable to minimize variations. Where there is a wide range in thickness variations, however, the parts should be sorted in groups and these variations adjusted for during the coining operation.
The process for forming the disc is described below, and details of each of the dies follow this process description.
(1) The first, second and third dies 222, 224, 220 are set up for the particular spacing or IFO being produced.
(2) The square steel sheet 226 is place in the first die 222, which is shown in FIG. 7, where with a five-hundred ton hydraulic press with cushion, the center opening is pierced and a preliminary draw is made.
(3) The part 230 is then placed in the second die 224, which is shown in FIG. 8, where with the operation of an eight-hundred ton press, the teeth are trimmed and the center is repierced.
(4) The part 234 is then placed in the third die 220, which is shown in FIG. 9, where using a five-hundred ton hydraulic press with cushion, the flats 202, 204 are coined and the part extruded. Continual inspection is needed, the outboard stop rails on each side of the die can be built up as needed and the stack height controlled by utilizing shimming stop rails and/or by varying the press tonnage.
(5) The disc par(s) is (are) mounted on a stack check fixture disposed on a large surface area and height measurements are made using an eighteen-inch digital count zero reset dial height gauge fitted with a 0.030 dial indicator. Eleven discs are stacked with their hubs upward on the check fixture and clamped snug with a spider and draw bolt. The indicator is set at zero on the top surface of the tooth on the bottom disc and the height is read on the top surface of the tooth of the uppermost disc. These readings are repeated for at least four equal places around the periphery of the disc. These readings are then averaged and divided by ten, and a stack-height tolerance per disc of only plus or minus 0.002 inch is permitted.
(6) The die 220 of FIG. 9 is converted to a one-degree overbend flattening mode using flattening rings, as shown in FIG. 10, and a top shim is installed to apply tonnage to the flat rather than the hub area of the disc. The part 240 is positioned in this die (modified die 220), a five-hundred ton hydraulic press with cushion is applied and the flange area is thereby flattened.
(7) The part is removed from the over-form die of FIG. 20 and is furnace carburized. Parts are stacked in the furnace, axis vertically, with spacer rings and top and bottom caps to minimize distortion and to restrict carbonaceous atmosphere to the tooth area only.
(8) The part is then induction hardened in the tooth area.
(9) The part is flattened and the hub resized in the coin die of FIG. 9 set up in the flattening mode and using a five-hundred ton hydraulic press with cushion. The disc should be flat after the hardening and finishing operations, and this is greatly dependent on the chemical and physical properties of the material; the hardness and carbon content are variables which need to be controlled. The hole is being restruck after heat treatment to round it up.
(10) The part is inspected again, similar to step (5) above.
(11) The keyway 238 is then formed in the die 239 of FIG. 11 using a one-hundred ton press.
Referring to FIG. 7, the construction and operation of the first die 222 will be explained. The flat metal piece 226 is located on the stop guides 240 of the lower press part. The upper press part includes the upper die set 241, the female draw die 242, the shim 243, the stripper plate 244 and the blank punch 245. The lower press part includes the lower spacer or shim 246, the lower die set or shoe 247, the draw punch 248, the mounting plate 249, the blank die 250 and the draw ring 256. The mounting plate 249 holds the blank die 250 in place. As the die is coming down, the stripper plate 244 is pushed out by springs so that it is at the level, at the bottom of the female draw die 242. As the upper part is pressed down by the press, the blank punch 245 pierces or cuts the center opening or hole, and punches out a round slug which drops down and out the bottom. As the draw is drawn down, the metal flows away from the center, away from the blank punch 248. As the die continues further down, it draws the Z-shaped cross-section, the preliminary sleeve draw 254, by pushing against the draw ring 256 and bottoming against the spacer 246. At that point, the die is working against the pressure from the press cushion through the pressure pin 260. When the press opens up, the pressure from the pins 260 raises the part up and moves it out to an accessible position. The stripper ring 244 strips it out of the top. The parallel member 264 positioned directly beneath the lower die set 240 raises it up so that the scrap can be removed.
The part 230 is removed from the first die 222 and turned upside down so that the "hat" is facing downward and placed in the second die 224 as depicted in FIG. 8. The upper part of this die is shown by the upper die set 270, a trim punch 272 secured thereto, an upper stripper plate 274 secured thereto by the shoulder screw 276 with a spring 278 disposed therebetween, and the return punch 280 secured to the upper die set by a shoulder screw 282. The part 230 is laid on the trim punch 272 and is in contact with the trim die. As the upper part is brought down, the teeth are cut by the trim punch 272 at the same time as the center hole is repierced. The upper stripper plate 274 strips it off. The hole is to be repierced, since after the hole is blanked in the die 222 of FIG. 7 and the draw 254 is made, the hole becomes larger or smaller depending upon the size of the draw. The deeper the draw, the larger the hole becomes. The holes are to be the same when the part is completed from the die 224 of FIG. 8 so that all parts will have the same extrusion or extrude length.
Although the teeth could be trimmed or cut after the flats 202, 204 have been coined, that would entail an additional operation. It is thus desirable to combine the teeth trimming with the repiercing in the same operation, as is done herein. The lower die set 290 comprises the plate member at the bottom of FIG. 8 and a shoulder screw 292 holds the mounting plate 294, spring 296, and stripper plate 298 to it. The trim punch 272 cuts the teeth forming a small piece of scrap 300. When the die 224 is opened, the stripper plate 298 shoves the scrap 300 upwards and strips it off. The stripper plate 298 is operated by the action of the spring 296. The screws 302 hold the trim punch 303 to the lower die set with the spacer plate 304 disposed therebetween, the spacer plate being made with inner and outer sections.
The disc part produced by the die of FIG. 8 is dropped into the coin and extrude die 220 of FIG. 9 and on the upper coin ring 312. The upper members of this die are the upper die set 310, an upper coin punch 316, a spacer 318 and a coin and extrude punch 320. A shoulder screw 322 holds the lower coin ring 324 to the mounting plate 326. The pressure pad 330 applies pressure to the part 234 and hold it. The coin and extrude punch 320 is spaced as needed by spacer 318 of the appropriate thickness depending on how deep the part is to be pushed, that is, the millimeter size being made. Thus, for the deepest part, the spacer 318 is needed and for the shallowest part it is not needed. As the upper part of the die comes down, it is coining the two flats 202, 204 at the same time while extruding the part to form the tip of the outer step 208. In other words, it is extruding the portion that fits around the shaft. The pressure pin 332 lifts the part out, after being formed, by applying pressure against the lifter plate or pad 334. The pressure pin 332, which is on a cushion, thus raises up and lifts the part out of the lower die part.
Especially for larger discs on the order of nineteen inches in diameter, the coining step of FIG. 9 makes the flange, or disc plate 210 of the disc bow upwards, like a dish or cymbal. The draw is deeper in the center and the plate flanges tend to bow upwards on the outside. This cupping is greater across the grain of the plate. This is undesirable and thus the flange or plate 210 is flattened in the die of FIG. 9 after the flats have been coined to within a few (six to fourteen) thousandths of an inch. The upper die set applies pressure to the upper form die 332 through the spring 300 with a spacer 334 disposed between the upper die set and the upper form die. The lower form die 336 is secured to the top of the mounting plate 338, which in turn is secured to the top of the lower die set 340. The lifter pads 334 are shown in two parts at the top of the pressure pin 332. FIG. 10 is basically the same as FIG. 9 except the upper form die 332 and the lower form die 336 have a one degree negative slope as shown by angle 342.
The flattened part is then removed from the die of FIG. 10 and subsequently placed in the die 239 of FIG. 11 to form the keyway 238. This die includes a lower die shoe 350 and secured thereto by a socket head cap screw 352 is the keyway die 354. The lower slide 356 is biased away from the keyway die 354 by a spring, 358, and the key punch 360 is secured to the lower slide by a flat head screw 366. A T-shaped cam 367 is secured to the underneath side of the upper die set 368 by a socket head cap screw 369. The pusher ring 370 is similarly secured to the underneath side by a shoulder screw 372, and pushes the part down against the lifter ring 374. As the upper die set 368 comes down, the cam 367 acts against the lower slide 356, pushing it inward, or to the right as shown in FIG. 11, against the bias of the spring 358. It thereby pushes the key punch 360 against the part, forming the keyway 238. In other words, the keyway punch 360 defines the keyway die male member and the female member is defined by the keyway die 354. The retainer plate 378 keeps the key punch 360 into the slide 356. The dowel pin 380 indicates the center line of the die 239. The lifter ring 374 is secured to the lower die shoe by shoulder screws 384, and raises the part up and down. When the part is dropped into the die, the ring 374 raises it up by the spring 386. This die can make different size parts. This flexibility is illustrated by the upper dotted line 388 which represents a ten millimeter part whereas the solid lines 389 show a seven millimeter part.
It is desirable to stagger the teeth of adjacent discs on a shaft to help separate the matted material conveyed thereon. Thus the present invention provides for a pair of parallel longitudinal grooves 390, 392 formed on the shaft tube as shown in FIG. 12, and disposed at forty-five degrees relative to one another. The discs are slid onto the shaft with the keyways or dimples of adjacent discs being fitted alternatingly in the grooves. IFOs are between two and ten millimeters, where two is typical for fine screen and seven and a half for chip screen, and accuracies of ±0.020 (twenty thousandths) are obtainable with this invention, which meets the commercial demand requirements.
From the foregoing description, it will be evident that there are a number of changes, adaptations and modifications of the present invention which come within the province of those skilled in the art. However, it is intended that all such variations not departing from the spirit of the invention be considered as within the scope thereof as limited solely by the claims appended hereto. | A die stamp formed disc construction including a toothed plate and a two-stepped sleeve integrally formed thereon. The sleeve has coined or stamped interior and exterior forty-five degree flats. The flats are accurately positioned so that, with the discs received through their central openings and clamped together onto the rotation shaft, the interior flat of one disc is held directly against the exterior flat of the adjacent disc thereby accurately and consistently positioning and holding the toothed plates of adjacent discs in spaced relation and preventing disc wobble. | 1 |
REFERENCE TO CROSS-RELATED APPLICATIONS
This application is a continuation-in-part of application Ser. No. 461,683, filed Apr. 17, 1974, now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to coated glass fiber bundles suitable for rubber reinforcement, and more particularly relates to glass fiber cord having substantially complete individual filament encapsulation with a resorcinol formaldehyde and elastomer coating composition containing a material which retards the degradation of the coated cord during exposure to heat and moisture.
It has long been recognized that glass fiber material makes an ideal reinforcement for rubber products such as automobile tires and the like. In preparing glass fiber material for such applications, the individual glass fibers and groups of glass fibers in the form of strand, rope, cord, roving, fabric and the like are coated with a rubber adhesive to aid in bonding the glass to the elastomeric material to be reinforced. The rubber adhesive generally comprises a resin and an elastomeric material to link between the glass and the main body of material being reinforced. Generally, in the production of fiber glass reinforcing cords or other bundle forms, individual fibers are coated with a sizing and then the fibers are brought together in bundle form. The bundle is then coated by dipping or otherwise contacting it with a coating mixture containing an elastomeric latex and a homogeneous resinous component. Commonly, the sizing contains a coupling agent such as a silane, a lubricant and other ingredients to assist in the handling of the cord during processing.
The term "elastomer", as used herein, is intended to mean and include both synthetic and natural rubber. "Natural rubber", as used herein, is the elastic solid obtained from the sap or latex of the Hevea tree, the major constituent being the homopolymer of 2-methyl-1,3-butadiene (isoprene). "Synthetic rubber", as used herein, is meant to encompass polymers based upon at least 2 percent of a conjugated unsaturated monomer, the conjugation being in the 1 to 3 position in the monomer chain and the final polymer in its uncured state having an extensibility of at least 200 percent and a memory of at least 90 percent when stretched within the extensibility limits and released instantaneously. The conjugated, unsaturated monomers which are used in the preparation of synthetic rubber are, but are not limited to, chloroprene, butadiene, isoprene, cyclopentadiene, dicyclopentadiene and the like. Other olefins capable of free radical, anionic, or cationic interpolymerization into the polymer chain with the conjugated unsaturated monomer are useful in forming synthetic rubbers. These olefins are typically monoethylenically unsaturated monomers. Monoethylenically unsaturated as used herein is characterized by the monomer having one CH=C< group. These monoethylenically unsaturated monomers are, but not limited to, the acrylic monomers such as methacrylic acid, acrylic acid, acrylonitrile, methacrylonitrile, methylacrylate, methylmethacrylate, ethylacrylate, ethylmethylacrylate and the like; monoolefinic hydocarbons such as ethylene, butylene, propylene, styrene, alpha-methylstyrene and the like; and other functional monounsaturated monomers such as vinylpyridine, vinylpyrollidone and the like functional vinylic monomers.
Glass fibers are excellent reinforcing materials and are distinguishable from other fibrous reinforcing materials such as natural and synthetic organic fibers in that glass fibers do not become elongated or deformed under stress to the extent that other fibers do. Unlike other fibers, particular combinations of glass fibers with encapsulating coatings cooperate to yield reinforcing materials that have greater tensile strength than either the glass or coating material alone. While other materials, which are subject to substantial stress elongation, are essentially limited in tensile strength to the basic strength of the bare fibers, even if coated, properly coated glass fibers have greater strength than the glass alone. For example, the low modulus of elasticity of glass may be exploited to provide reinforced tires having superior road performance if an appropriate coating medium is provided to transfer stresses to all fibers in the glass fiber cord so that loading throughout is substantially uniform. This phenomenon is illustrated by the observation that a typical, uncoated glass fiber cord (G-75, 5/0, filament count 2,000 i.g. 2,000 filament strands of G fibers of about 38 × 10.sup. -5 inch diameter, 7,500 yards per pound) has a tensile strength of about 35 to 40 pounds by ASTM test D578-52, but, when coated with a resorcinol formaldehyde latex coating, such a cord has a tensile strength of about 50 to 70 pounds.
Unfortunately, when exposed to a warm, moist environment, coated glass fiber cords lose strength. After about 1 week of exposure at 120°F. and 95 percent relative humidity, the coated cord described above has a strength of only 35 to 40 pounds. The strength degradation is observed even when the exposure is in a typical warehouse which is dark and not affected by any particular oxidizing atmosphere. The problem is surprising in view of the fact that rubber and elastomer materials themselves are not found to degrade significantly in warm, moist environments absent the influence of ultraviolet light, ozone and higher temperatures. The loss of strength in resorcinol formaldehyde elastomer coated glass fiber cord does not appear to be explained as conventional oxidation for it would be expected that a substantial amount of resorcinol formaldehyde (which has antioxidative characteristics) would protect the elastomer from degradation. It has been found that the addition of typical antioxidants such as phenols, amines and the like do not protect the elastomer adequately from such degradation.
During the course of experimenation, it was found that a material containing 2,6-ditert-butyl-4-phenylphenol absorbed on a diatomaceous earth imparted moisture resistance to the adhesive coated glass fiber bundles in moist environments when used at a 0.4 percent by weight level based on the total elastomer content of the coating composition. This product containing the above phenolic compound and the diatomaceous earth has found much commercial success. Naturally, it was assumed that the phenolic compound was responsible for this improvement in tensile strength after aging due to its known antioxidative and antidegradative properties. However, further investigation surprisingly revealed that the improvement in the aged bundles' tensile strength was due to the treated diatomaceous earth.
It has been necessary in the past to avoid the degradation of elastomer coated glass fiber materials by providing a moisture barrier such as a polyethylene bag about them and providing a desiccant such as a silica gel with the stored materials. Even when this expensive protective storage is employed, it is necessary to expose the coated glass fiber cord during processing such as weaving to moisture laden atmosphere and degradation can then occur. This is an expensive and unsatisfactory solution to the problem. As is described below, a satisfactory solution has been discovered.
SUMMARY OF THE INVENTION
A glass fiber bundle is provided with a coating containing a rubber adhesive comprising a combination of phenolic resin, an elastomer and further containing a treated diatomaceous earth having no 2,6-ditert-butyl-4-phenylphenol therein which enables the cord to retain tensile strength even after prolonged exposure to a moist environment for example, in an environment of 95 percent relative humidity and about 100°F. for a period of at least 8 days. Particular inhibition of moisture induced degradation is observed in partially cured rubber adhesives which retain a capacity for further curing when embedded in an elastomeric material.
Diatomaceous earth is a hydrous opaline form of silica which consists of the skeletons of one celled plants of the class Bacillarieae. These Bacillarieae are enclosed in two overlapping valves of which the cell wall is siliceous in nature thereby constituting the skeleton which is deposited on the floor, below the body of water in which the plants grow, after the organic portion of the plants decay.
These skeletal remains known as diatoms are mined commercially and subsequently used for a plurality of purposes. The diatoms, in some cases, are treated chemically to alter there chemical and physical properties to render them adaptable for particular uses. Among the chemical treatments of diatoms is their hydrothermal reaction with hydrated lime to produce hydrocalcium silicate. Additionally, hydromagnesium silicate is produced by much the same process. Both the hydrocalcium silicate and hydromagnesium silicate are useful in the practice of the instant invention to inhibit moisture induced degradation of the cured rubber adhesive encapsulated glass fibers.
These treated diatomaceous earths are characterized by low bulk densities ranging from 5.5 pounds per cubic foot to 15 pounds per cubic foot and surface areas from 95 square centimeters per gram to 180 square centimeters per gram and are sold by Johns-Mansville Corporation under the names of MICRO-CEL and CELKATE for the hydrocalcium silicates and the hydromagnesium silicates respectively.
Typically, the chemical analysis of the diatomaceous earths useful in the practice of the invention are: for the lime treated diatomaceous earths;SiO 2 49-67%CaO 22-28%Al 2 O 3 2.1-3.8%Fe 2 O 3 1.0-1.3%MgO 0.4-0.6%Na 2 O + K 2 O 1.2-1.6%loss on ignition 14.0-18.5%
and for the magnesium oxide treated diatomaceous earth a typical chemical analysis is as follows:
SiO.sub.2 66%CaO 1.0%Al.sub.2 O.sub.3 4.3%Fe.sub.2 O.sub.3 1.6%MgO 16.6%Na.sub.2 O + K.sub.2 O 1.0%loss on ignition 9.1%
The above are typical chemical analysis and it is understood that other ranges of compositions are within the scope of the invention inasmuch as they are considered by those skilled in the art to be within the compositional ranges of calcium and magnesium treated diatomaceous earths.
Glass fiber bundles in the form of strands, yarns, cords and fabrics, formed from fiber bundles are impregnated with rubber adhesive coatings containing elastomeric latices, both natural and synthetic, such that the fibers are substantially encapsulated with coating and a continuous interconnecting body of coating exists throughout the bundle and about the entire bundle. The coating is provided to interact and adhere to a host material being reinforced, such as rubber. A broad range of elastomeric latices have been used to form the strands, yarns, and cords in glass fiber bundles. Particular elastomeric latices suited for use in this invention include styrene-butadiene-vinylpyridine terpolymers, neoprene, polyisoprene, butyl rubber, butadiene-styrene-copolymers (styrene-butadiene-rubber), acrylonitrile-butadiene-vinylpyridine terpolymers and the like.
Useful resins employed in this invention include resorcinol formaldehyde resins, phenol formaldehyde resins, and the like. Both the resole and novolac type phenolic aldehyde resins have been found to be useful in forming the rubber adhesive coating. The resole resins being characterized by the formation of the resin induced by base catalysis and the novolac resins being characterized by their formation by acid catalysis. Generally, the resole resins are more highly methylolated than the novolacs. The choice between the resole or novolac resin in the rubber adhesive coating composition is contingent on the other materials used in the coating composition itself and the desired properties of the final cord. Rubber adhesive systems which are useful in the practice of the invention include those disclosed in U.S. Pat. Nos. 2,691,614, 2,817,616, and 2,822,311 which are incorporated herein by reference and made a part hereof.
Host material suitable for reinforcement by the coated fiber bundles of this invention and which are resistant to moisture attack include natural rubber and synthetic rubbers as hereinbefore defined and additionally other highly extensible materials such as polyurethane rubber, and like rubbers not based on conjugated unsaturated monomeric materials.
Preferably included on each glass fiber filament is a dual-functional coupling agent such as a silicon containing organic compound or a Werner complex which establishes a bond with the glass through the metal atom and a bond with the rubber adhesive through the organic radicals attached to the metal atom.
Typically useful reactants in the form of silane coupling agents are but not limited to, gamma aminopropyltriethoxy silane, N-bis (beta hydroxyethyl)-gamma-aminopropyltriethoxy silane, N-beta (amino-ethyl gamma-aminopropyltrimethoxy silane, (CH 3 O) 3 Si (CH 2 ) 3 NH (CH 2 ) 2 NH (CH 2 ) 2 COOCH 3 , gamma-glycidoxypropyltrimethoxy silane, vinyltriacetoxy silane, gamma-methacryloxypropyltrimethoxy silane, vinyltriethoxy silane, vinyltris (betamethoxyethoxy) silane, beta (3,4-epoxycyclohexyl) ethyltrimethoxy silane and the like. Typical of the sizes which may be applied to the glass fibers of this invention are the sizes disclosed in U.S. Pat. Nos. 3,437,517, and 3,459,585 which are incorporated herein by reference and made a part hereof.
Generally, in the application of the functional components to the bare glass, other components will be present in the sizing and coating mixtures or in the combined sizing and coating mixtures. Residue of materials added to ease processing such as textile lubricants, emulsifiers, wetting agents, catalysts and the like remain in the finished coated glass fiber bundles. A description of the materials added to aid in processing will serve to identify constituents which may be found in the final article and will serve to describe at least some typical methods for producing a coated glass fiber bundle suited for rubber reinforcement and resistance to degradation induced and accelerated by moisture. Typically materials which may be present include the following: vegetable oil, amylose starch, amylopectine starch, fatty acid amides, ammonia soluble carboxyl-containing polymers, such as acrylic interpolymers and carboxylated elastomers, cellosolves, alkali metal salts, oxy-and phenoxypolyalcohols, imidazoline reaction products, ethylene oxide derivatives of sorbitol esters, polyethylene glycol, polyols, such as sorbitol and mannitol, polyethylene, polypropylene and the like.
To the elastomer and resin-containing coating may be added waxes, paraffinic or microcrystalline, to aid in lubrication of the cord during processing and to provide resistance to sun checking, that is, rubber degradation caused by exposure to ultraviolet light. Microcrystalline waxes have found particular utility in the compositions of this invention. It has been observed that during the curing of coatings on glass fiber materials that microcrystalline waxes are substantially retained without any noticeable loss due to smoke evolution as has been observed when paraffin waxes are employed.
Typically, the glass will be coated using aqueous mixtures containing the functional coating materials. The glass may be sized and coated with a single mixture or the glass may be sized by any conventional or known sizing method using commonly known materials and then later coated as a fiber bundle to produce the article herein described. Also, treatment may include heat cleaning or other removal of lubricants, starches, oils and the like after sizing and before coating filament bundles to produce the articles herein disclosed. When sizing and coating from a single mixture, it has been found useful to include an ammonia soluble, carboxyl-containing polymer to stabilize the mixture as described in U.S. Pat. No. 3,853,605, entitled "Coating Composition and Process for Preparing and Applying the Coating Composition to Glass Fibers" by Dennis M. Fahey, assigned to the present assignee and incorporated herein by reference.
It will be understood that organic solvents may be used with or in lieu of water in the aqueous mixtures described above. Although the detailed description provided herein is limited to aqueous systems, it will be appreciated by those skilled in the art that preparation of the articles of this invention using organic solvents is contemplated as well.
A preferred method of producing the coated glass fiber bundles of this invention is to contact a continuous bundle, for example, strand which has previously been sized, with a highly concentrated elastomeric latex and resin-containing aqueous coating bath further containing, as an essential ingredient, a treated diatomaceous earth and having no 2,6-ditert-butyl-4-phenylphenol present as hereinbefore described; and then to dry the coating within and about the bundle and then cure the coating residing within and about the bundle to produce a coated cord suitable for rubber reinforcement. A particularly advantageous method for producing the glass fiber bundles of this invention is based upon the method described in U.S. Pat. No. 3,619,252 entitled "Manufacture of Elastomer Coated Glass Fibers", by Alfred M. Roscher, which is incorporated herein by reference. This invention is particularly applicable to glass fiber filament bundles having complete filament encapsulation and having a relatively high ratio of coating weight to glass weight such as disclosed in application Ser. No. 328,160, now abandoned, filed Jan. 31, 1973, and entitled "Improved Fiber Glass Cord for Reinforcing Rubber and Method for Making Same", by Norman G. Bartrug, assigned to the present assignee and incorporated herein by reference.
A plurality of glass fiber strands each having a slight twist to provide strand integrity, which have previously been sized, are combined in parallel relation and passed through a guide in tangential contact across motor driven rollers. The rollers are partially immersed in an aqueous rubber dip or emulsion, and these rollers pick up this coating material when rotated. The coating, which is picked up, is brought into contact with the glass fiber strands, coating and impregnating the combined bundle of strands. Relaxation of tension in the combined bundle of strands opens the spacing between fibers and between strands enhancing impregnation of the dip or coating into the bundle. The total impregnation is limited by the volume available between the fibers and strands and by the volume of coating solids in the total dip volume which fills the voids in the bundle. High solids concentration in the dip is utilized when it is desired to obtain full impregnation with rubber adhesive and not merely with water. Typically, the resin and elastomeric latex fraction of the aqueous dip will exceed about 28% weight solids and preferably will be between 30% and 40% by weight.
After contacting the fiber glass bundle with the rubber adhesive concentrated dip for sufficient time to fully impregnate the bundle with the water and solids-containing dip, the bundle is passed through a dielectric heater or drying oven. The drying oven is so designed and operated that water is removed rapidly from inside the bundle as well as from the surface of the bundle without substantial migration of the solids from the interior to the surface of the bundle and without excessive blistering.
The dried, glass fiber bundle is then subjected to heat to partially cure the rubber adhesive coating throughout the bundle. It is preferable to partially cure the coating while the coated fiber remains separate and to complete the curing of the coating on the glass fiber bundle when it is embedded in the rubber being reinforced during the curing of the rubber in the final article.
A second method for making the glass fiber bundles of this invention is based upon the method described in U.S. Pat. No. 3,718,448 entitled "Fiber Forming and Coating Process", by Warren W. Drummond and Donald W. Denniston, which is assigned to the present assignee and is incorporated herein by reference and made a part hereof.
Upon forming, individual glass fibers are drawn over a roller coater, such as is described in U.S. Pat. No. 2,873,718. An aqueous rubber adhesive dip having the treated diatomaceous earth included within the coatings of this invention is applied to the fibers passing over the roller.
The coated fibers are brought together into strands and are dried. Drying is accomplished by passing the strands through a dielectric oven, a hot gas or convection oven, or an infrared radiant heating chamber. Strands of glass fibers are brought together into cords or rovings and are further heated to partially cure the resin and latex and bond the strands together into a bundle. Following this, if additional elastomer coating is desired, the composite glass fiber bundle may be further coated or impregnated with additional coating.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawing
FIG. 1 illustrates a method utilized to prepare elastomer coated glass fiber material of the instant invention; and
FIG. 2 is a diagrammatic illustration of the interior of the dielectric oven utilized to dry the impregnated cords.
DESCRIPTION OF PREFERRED EMBODIMENTS
A coating mixture free of 2,6-ditert-butyl-4-phenylphenol is prepared having the following composition:
Table I______________________________________ Preferred Com- Range Parts position PartsIngredients by Weight by Weight______________________________________GENTAC Latex (styrene-butadiene vinyl pyridine15:70:15 41% solids inwater) 1,140-2,100 1,400GENFLO Latex (styrene-butadiene 50:50 41% solidsin water) 0-800 467water 600-1,000 870NH.sub.4 OH 28% -- 4PENACOLITE Resin (resorcinol-formaldehyde novolac resin,0.6 formaldehyde 1 resorcinol,70% solids in water) 80-245 134Formalin (37% formaldehyde) 20-120 56water 10-70 39MOBILCER Q wax (micro-crystalline wax 50% solidsin water) 0-400 76.5treated diatomaceousearth 0.05-50 1.5______________________________________
On a solids basis, the novolac comprises 9 to 12 percent by weight, the formaldehyde 1.4 to 2.5 percent by weight, the combined elastomer 82 to 86 percent by weight, the styrene-butadiene vinyl pyridine being from 61 to 87 percent by weight and the styrene-butadiene ranging from 0 to 25 percent by weight and the treated diatomaceous earth from about 0.02 to about 1 percent by weight. Solids content of the preferred coating dips ranges from about 27 percent to 38 percent by weight of the solution, with the preferred composition having about 32 percent by weight solids.
The mixture is prepared by adding the larger volume of water to a premixed tank followed by the addition of ammonium hydroxide while stirring and then adding the novolac to this mixture while stirring, and continuing stirring until complete dissolution of the resin occurs. The styrene-butadiene vinyl pyridine is added to a batch tank and to it is added the styrene-butadiene rubber, if any, with stirring until complete dissolution occurs followed by continued stirring for about 5 minutes. The premix is then added to the batch tank with stirring which is continued for 5 minutes after addition of the premix. The formaldehyde is then added to the mixture, and the mixture is stirred for 10 minutes. To this is added a solution of the wax with the minor amount of water shown in the above table, and the coating mixture is then allowed to age for at least 2 hours before use.
Glass fiber cord (G-75,5/0, filament count 2,000), which has been sized according to the method for sizing during forming described in U.S. Pat. No. 2,728,972, is coated with the above coating. The sizing present on the glass may be any typical size containing a coupling agent as described above. The preferred size and that used in the examples, unless otherwise indicated is the size described in U.S. Pat. Ser. No. 3,655,353 entitled "Glass Fiber Size", of Charles E. Nalley and Joe B. Lovelace, assigned to the present assignee and here incorporated by reference and made a part hereof.
The resulting coated yarn has an excellent appearance indicating apparent uniform coating distribution throughout. The yarn is freely flexible and when bonded in rubber is found to have excellent adhesion. The rubber coated yarn combination has excellent tensile strength retention and flex resistance.
Preferred embodiments of the resulting coated fiber glass cord have the coating present in an amount of from about 15 to 50 percent by weight and preferably from about 15 to 40 percent by weight of the glass in the cord bundle which may be determined from conventional loss on ignition analysis. Within the dried coating on the cord, the individual constituents comprise on a water-free basis in percents by weight of the coating the following proportions: styrene-butadiene vinyl pyridine terpolymer from about 46 to about 90 percent; novolac resole or phenol-formaldehyde resin from about 10 to about 15 percent; calcium or magnesium silicate in the form of a calcium or magnesium treated diatomaceous earth from about 0.02 to about 5 percent and preferably about 1 percent and microcrystalline wax from about 5 to about 15 percent.
The following examples will further illustrate in detail the nature of this invention.
EXAMPLE I
Several coating dips were prepared having the composition indicated in Table I as the preferred composition. There was no 2,6-ditert-butyl-4-phenylphenol present in these coating dips. The coating composition except for the calcium or magnesium silicate component in the form of treated diatomaceous earth are the same.
In this example, the calcium silicate used is MICRO-CEL E produced by Johns-Manville the analysis of which is as follows:
Component Percentage______________________________________SiO.sub.2 54.3CaO 25.1Al.sub.2 O.sub.3 3.6Fe.sub.2 O.sub.3 1.2MgO 6.5Na.sub.2 O + K.sub.2 O 1.3loss on ignition 14______________________________________
Samples of glass fiber cord, G-75, 5/0 which has been sized in accordance with a size having the following composition:
Parts byIngredients Weight grams______________________________________Polypropylene emulsion con-taining 25% by weight of poly-propylene (molecular weight6,300) and 6% by weight ofpolyvinyl alcohol (Evanol 52-22sold by DuPont) 500imidazolamine (Emery Industries1,200-136) 200Methyacryloxypropyltrimethoxysilane 250acetic acid 8silicone defoamer (SAG 470) 3.8water sufficient to make 10 gallons______________________________________
The above sizing composition was applied to the fibers during formation in accordance with the method described in U.S. Pat. No. 3,655,353.
Referring to the drawings in detail, FIG. 1 shows a creel 1 having mounted thereon a plurality of bobbins 3 containing glass fiber strands 5. Each of the glass fiber strands 5 is coated with a sizing material comprising a lubricant, binder and coupling agent. Furthermore, as is conventional, each of the glass fiber strands 5 has imparted therein a 0.5 turn per inch twist to provide strand integrity and resistance to fuzzing during initial handling or processing prior to being coated and impregnating with elastomeric material.
The strands 5 are combined in parallel relation and passed through a ceramic guide 7, in tangential contact across motor driven rotating rollers or dip applicators 9, to a motor driven rotating wiper roller or pulley 11. The rollers or dip applicators 9 are partially suspended in an aqueous rubber dip or emulsion 13 contained within vessels or tanks 15. The dip applicators 9 are driven counter to the direction of travel of the strands 5 to improve the coating and impregnation thereof. The pickup of rubber dip 13 by the applicators 9 and strands 5 is more than sufficient to coat and impregnate the strands with the desired final amount of rubber dip or adhesive material 13. The wiper roller or pulley 11 is driven with the direction of travel of the strands 5 and serves to change the direction of the strands with care to avoid removing rubber dip or adhesive material 13, except in excess of that required to obtain the beneficial effects of coating.
From the wiper roller or pulley, the coated, impregnated strands are passed vertically through a dielectric heater or drying oven 17, wherein water and other volatile constituents of the rubber dip 13 are driven off, and removed from the dielectric oven 17 by means of a blower 19. A suction device (not shown) could be used in lieu of or in addition to the blower 19 and would preferably be located adjacent the upper or exit end of vertically arranged dielectric oven 17. The construction of a typical dielectric heating or drying oven, suitable for use with the present invention, is shown more fully in FIG. 2.
Referring to FIG. 2, there is shown a diagrammatic representation of dielectric heater 17 comprising a vertically arranged series of spaced electrodes 25 electrically connected to a suitable power source (not shown) to produce an alternating, high frequency electrical field 27 between successive oppositely charged electrodes. As the strands 5, coated and impregnated with aqueous rubber dip 13, traverse across but not contacting the electrodes 25 and through fields 27, the liquid component of the dip, water, which has a higher dielectric constant than the solid component, is electrically activated to produce a uniform heating action throughout dip material 13. The rate and amount of electrical activation or dielectric heating is controlled to the extend of removing or volatilizing substantially all of the liquid component of the aqueous dip material while leaving the solid component substantially unaffected. The coated and impregnated strands 5, as they leave dielectric heater 17, are free of bubbles and sufficiently dry and free of tack for the purpose of further processing the strands over rolls, pulleys or the like without fear of stripping off coating material and/or depositing coating material on supporting and conveying elements or the like.
Thereafter, the coated strands pass upwardly and then traverse through a hot gas oven 21 or other suitable heating device to partially cure or react the solid component of the adhesive 13. Following attainment of the desired degree of cure, the adhesive coated fiber glass strands are removed from the oven 21 and collected on a suitable take-up device 23.
Samples of fiber glass cord prepared according to the description above were evaluated to determine cord strength according to ASTM procedure D578-52 modified by replacement of Scott Spino clamps C33975 with G61-4D-0 clamps covered on cord contact surfaces with electrical tape. Following the initial testing of the samples of cord the samples were aged for varying times and after aging, the samples were tested according to this modified ASTM test for strength. Test results and aging periods are summarized in Table II.
Moisture aging is accomplished by placing coated cord samples on a tray in a sealed box about 2 feet × 3 feet × 4 feet with the tray about one inch from the floor of the box, maintaining liquid water on the floor of the box, and holding the box in a thermostatically controlled heating room maintained at 120°F. Periodic checks of relative humidity in the box indicate a relative humidity of 90-95 percent. The interior of the box is dark. Samples are held in such a box for various periods then are removed and tested for strength.
EXAMPLE II
Example I was repeated except that the MICRO-CEL E was substituted with MICRO-CEL B diatomaceous earth having the following analysis:
Component Percentage______________________________________SiO.sub.2 52.9CaO 22.6Al.sub.2 O.sub.3 3.6Fe.sub.2 O.sub.3 1.2MgO 0.4Na.sub.2 O + K.sub.2 O 1.3ignition loss 18.0______________________________________
Tensile aging results are reported in Table II following.
EXAMPLE III
Example I was repeated except that MICRO-CEL E was substituted with MICRO-CEL T-26 having the following analysis:
Component Percentage______________________________________SiO.sub.2 54.3CaO 25.1Al.sub.2 O.sub.3 3.6Fe.sub.2 O.sub.3 1.2NgO 0.5Na.sub.2 O + K.sub.2 O 1.3ignition loss 14.0______________________________________
The results of the tensile aging test is reported in Table II following.
EXAMPLE IV
Example I is repeated except that MICRO-CEL E diatomaceous earth is substituted with CELKATE T-21 having the following chemical analysis:
Component Percentage______________________________________SiO.sub.2 66.4CaO 1.0Al.sub.2 O.sub.3 4.3Fe.sub.2 O.sub.3 1.6NgO 16.6Na.sub.2 O + K.sub.2 O 1.0ignition loss 9.1______________________________________
The results of the tensile aging test are reported in Table II following.
EXAMPLE V: CONTROL
Example I was repeated except that no diatomaceous earth was added to the coating mixture. Table II summarizes the results of the testing of Examples I through V.
TABLE II______________________________________TENSILE STRENGTH IN POUNDSAGED AT LEAST 16 24 32 48Example No. Initial days days days days______________________________________ I 60 54 54 53 55II 63 54 57 53 55III 62 -- 56 55 54IV 61 58 58 56 48 V 66 37 -- -- --______________________________________
It is evident from Table II that cords prepared according to this invention substantially retain their strength after exposure to a moist environment compared with cords which do not contain calcium silicate or magnesium silicate in the form of treated diatomaceous earths.
Considering the severity of the aging conditions employed, cords are considered to have substantially retained their initial strength if after 16 days of exposure as described above the cords retain at least 70 and preferably 75 percent of their strength. It will be noted from Table II that only those samples prepared according to this invention substantially retain their strength. Samples prepared without the addition of the diatomaceous earths have not been found to exhibit the strength retention found for the coated cords of this invention.
While the above examples have been conducted using a specific coating composition, it is to be understood that other coating compositions may be used which are known to those skilled in the art and additionally the treated diatomaceous earths can be incorporated into a combined sizing and coating composition to form an improved glass fiber bundle having increased tensile strength retention.
While the present invention has been described with reference to particular preferred embodiments, it will be appreciated by those skilled in the art that variations may be employed without departing from the spirit of the invention and the invention is only to be limited insofar as is set forth in the accompanying claims. | Glass fiber filament bundles such as cords for rubber reinforcement are impregnated and coated with an elastomer composition such that the coated cord maintains adhesion and tensile strength even in a moist environment due to the inclusion in the coating of a chemically treated diatomaceous earth. These chemically treated diatomaceous earths contain a major portion of an alkali earth metal silicate. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to improvements in a DC to AC power inverter. More specifically, the present invention relates to improvements in a load demand sensing circuit of the inverter, a quiescent operating current and feedback circuit for the inverter, and an automatic power factor correction circuit of the inverter.
2. Description of the Prior Art
Heretofore DC to AC inverters were turned on after a load was applied to the inverter, and it was necessary to sense a load applied to the inverter before turning on the inverter. This was typically done by sensing a load using a DC bias on the AC circuit while the AC output of the inverter was turned off and isolated. By sensing a DC current, one could determine if a load had been placed on the inverter. In this way, once a predetermined DC current was sensed, the inverter was turned on, and AC power was delivered to the load. At the same time, a relay was activated to isolate the DC bias so as not to harm the DC current sensing circuit. After the inverter was turned on to supply AC power to the load an AC current sensing circuit was actuated to sense the AC power applied and to keep the AC power output of the inverter turned on.
Once the AC current had fallen below a predetermined value, the AC output power of the inverter was turned off and the DC bias and current sensing circuit was reapplied to the output lines of the inverter.
When using a DC bias and a DC current sensing circuit coupled to the output lines of the inverter to detect the presence of a load, any basically alternating current device such as a wall clock or doorbell transformer appeared as a large load to the DC current sensing circuit because such devices appeared as a short circuit to the DC bias. Accordingly, the inverter was turned on to supply AC current and the AC sensing circuit was sensitive enough to stay on after the DC current sensing circuit caused the inverter to be turned on. Additionally, the AC current sensing circuit was very sensitive so as to detect minute AC current loads which in the case of an old electrical wiring installation, could cause the inverter to stay on even if the actual load is removed. This was due to leakage current in the old electrical wiring. Moreover there were times when long lines to a power tool had sufficient leakage current so as to indicate to the AC current sensing circuit a load which in actuality did not exist.
As will be described in greater detail hereinafter, the inverter of the present invention provides a self-detecting, load demand circuit which cyclically energizes the inverter while at the same time sensing AC current draw from the inverter. If AC current draw is sensed, the load demand circuit is constructed to keep the inverter energizing logic in an on mode to keep the inverter energized.
Heretofore DC to AC power inverters of the class B, C, D or E type, namely those which utilize an SCR, required relatively high input currents at no load. A no load current draw is necessary to establish a capacitor commutation charge in the capacitor circuitry associated with the SCR s. Typically resistive loading is provided to establish the required current draw. Of course, the current drained off the battery is dissipated in the resistors, thereby reducing the batteries useful capability.
As will be described in greater detail hereinafter, the inverter of the present invention provides a feedback circuit through the SCRs establishing satisfactory capacitory communication charge. The current is then, via the primary winding and a feedback winding, stepped to a higher voltage and rectified and returned to the battery. In this way, the current drawn for satisfactory SCR operation is fed back to the battery to significantly decrease battery drain and increase the efficiency of the inverter in a standby or no load mode.
While previous power factor correction circuits have worked well, particularly with smaller capacity inverters, of say 5 kilowatts, such circuits have not worked well with a larger inverter, say on the order of 12 kilowatts.
Also heretofore disadvantages had been incurred with previous power factor correction circuitry. More specifically, previous power factor correction circuitry was not sensitive to light reactive loads and did not feed enough leading power factor correction for large reactive loads such as could be used with a 12 kilowatt inverter. This was due to the fact that the power factor correction was switched in only at the end of a half cycle. As will be described in greater detail hereinafter, the inverter of the present invention includes automatic power factor correcting circuitry which supplies full time leading power factor correction, which is very sensitive to light reactive loads, and works well with inverters of greater than 5 kilowatts capacity.
SUMMARY OF THE INVENTION
According to the invention, there is provided in a DC to AC power inverter of the class B,C,D, or E type which includes a battery, at least one power SCR and associated capacitor circuitry and at least one input winding on a main transformer core and which requires a quiescent current to establish operating current for capacitor commutation charge, the improvement comprising circuit means for feeding current generated by the quiescent current back to the battery; said circuit means including an isolated feedback winding on the main transformer core and rectifying means coupled directly between said feedback winding and the battery; and said feedback winding having a slightly higher number of turns than said input winding such that a voltage slightly higher than the battery voltage is generated across said feedack winding so that there is a current draw by the battery from said feedback winding sufficient to establish said quiescent current through the input winding for quiescent operation required for capacitor commutation charge.
Further, according to the invention, there is provided in a DC to AC power inverter of the class B,C,D or E type which includes a battery, at least one power SCR and associated capacitor circuitry, and at least one input winding on a main transformer core, which also has thereon at least one secondary output winding, the improvement comprising selfdetecting load demand circuit means coupled to a line from said output winding for cyclically energizing the inverter, for sensing a minimum AC load across said secondary winding, and upon sensing a minimum AC load, for holding said inverter in an energized state until less than a minimum AC load is sensed during an energizing cycle; said load demand circuit means including a current transformer circuit having a primary winding comprised of at least one turn formed by a line from one end of the output secondary winding; and a multi-turn secondary winding, such that a load current flowing through said line generates a voltage across said secondary winding; means for cyclically energizing said inverter; means for sensing a load current flowing in the output secondary winding; and, means for holding said inverter in an energized state when and while a minimum load current is flowing through the output secondary winding, said energizing means including a timer which supplies an enable signal every few seconds to said holding means.
Still further, according to the invention there is provided in a DC to AC power inverter of the class B,C,D or E type which includes a battery, at least one power SCR and associated capacitor circuitry, a main transformer core, at least one input winding on the main transformer core, and at least one output secondary winding on the main transformer core, the improvement comprising automatic power factor correction circuitry for supplying full time leading power factor correction to a load, said automatic power factor correction circuitry being sensitive to light reactive loads and including a power factor correction capacitor, switching means in series with said capacitor and operable to place said power factor correction capacitor in parallel with the load on said output secondary winding, a signal source in said inverter producing a signal having a frequency greater than the inverter output frequency, means for differentiating said signal, first circuit means coupled to said differentiated signal and coupled to the voltage across the load, said first circuit means having a dv/dt sensing circuit and and an output coupled to said switching means and being operable to operate said switching means to place said power factor correction capacitor in parallel with the load on a trailing edge of a cycle of the inverter output waveform when a dv/dt above a certain threshold dv/dt is sensed by said sensing circuit, and second circuit means connected to have an input voltage proportional to an inductive reactive load and an input coupled to said differentiated signal, the output of said second circuit means also being coupled to said switching means, and said second circuit means being operable to operate said switching means to hold said power factor correction capacitor in parallel with the load after the dv/dt sensed by said sensing circuit has fallen below said threshold dv/dt as long as the load is connected to the inverter.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block schematic diagram of a portion of the electrical circuit of the inverter of the present invention and shows therein the self-detecting load demand circuitry of the present invention coupled to the inverter energizing logic.
FIG. 2 is a schematic electrical circuit diagram of another portion of the inverter of the present invention and shows the main transformer of the inverter including the feedback loading circuit, the power SCRs and the associated capacitor circuitry which are coupled to the circuitry shown in FIG. 1.
FIG. 3 is a schematic circuit diagram of the circuitry coupled to the output secondary winding of the main transformer shown in FIG. 2 and shows the automatic power factor correcting circuit of the inverter of the present invention.
FIG. 4 is a simplified schematic circuit diagram of the feedback loading circuit of the inverter of the present invention.
FIG. 5 is a simplified block schematic circuit diagram of the self-detecting load demand circuit of the inverter of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIGS. 1, 2 and 3, there is illustrated therein the DC to AC power inverter of the present invention which is generally identified by the reference numeral 10 and which includes control circuitry 12 and inverter energizing logic 14 which are shown in FIG. 1. The control circuitry 12 and the energizing logic 14 are of conventional design. As shown in FIG. 1, an output 16 from a self-detecting load demand circuit 18 constructed and operated in accordance with the teachings of the present invention as will be described in greater detail hereinafter, is coupled to an input 20 of the inverter energizing logic 14.
As shown, the control circuitry 12 is coupled by lines 21-26 to the two power SCRs 28 and 30 and associated capacitor circuitry 32 and 34 shown in FIG. 2 which are coupled to first and second input windings 36 and 38 on a main transformer core 40 shown in FIG. 2.
Also coupled to the main transformer core 40 is a feedback loading circuit 42 constructed and operated in accordance with the teachings of the present invention as will be described in greater detail hereinafter.
As shown in FIG. 2, the main transformer core also has a secondary winding 44 thereon which has two sections 46 and 48 and a center tap 50 and 52. It will be appreciated that a modified AC square wave 240 volt 60 Hz waveform is generated across the secondary winding 44 with 120 volts appearing across the output secondary winding section 46 and 120 volts appearing across the output secondary winding section 48.
As shown in FIGS. 2 and 3, output lines 50-53 from the secondary winding 44 are coupled to an automatic power factor correction circuit 60 constructed and operated in accordance with the teachings of the present invention as will be described in greater detail hereinafter.
As shown in FIG. 3 a sensing circuit 64 of the control circuitry 12 is coupled across lines 50, 51 and 53 and is coupled by lines 65 and 66 to the control circuitry 12 shown in FIG. 1.
Also an isolating transformer circuit 67 is coupled to lines 51 and 53 and has output lines 68 and 69 which are coupled to the self-detecting load demand circuit 18 in FIG. 1. The isolating transformer 67 functions as an AC current load sensing circuit as will be described in greater detail hereinafter in connection with the description of the load demand circuit 18 and forms a part of the load demand circuit 18.
The load connected to the inverter is connected to output terminals 70, 71 and 73 at the ends of lines 50, 51 and 53 as shown in FIG. 3, and more particularly between terminals 70 and 73 if 240 volts are desired or terminal 71 and terminal 70 or 73 if 120 volts are desired.
Referring now to FIGS. 2 and 4 the feedback loading circuit 42 forming part of the inverter 10 of the present invention includes a feedback coil 82 that has a few more turns than the input windings 36 and 38. Typically, the feedback coil has approximately 4% more turns than either of the input windings 36 and 38, with the turns ratio typically being 41 turns in each of the input coils or windings 36 and 38 and 43 turns in the feedback coil or winding 82. The output of the feedback winding 82 is rectified by a full wave diode bridge rectifying circuit 84 forming part of the feedback loading circuit 42. Output leads 86 and 88 from the rectifying bridge circuit 84 are coupled respectively to the positive input 90 of the battery 92 and system ground 94.
In operation, the higher voltage generated across the feedback winding 82 by reason of the slightly higher number of turns therein causes a current draw from the feedback winding 82 through the rectifying bridge 84 to the battery 92. In the meantime, of course, current is being drawn from the battery for energizing the input windings 36 and 38 and the current drawn by the feedback winding 82 is sufficient to establish the necessary quiescent operating current through the input windings 36 and 38 which passes through the SCR s 28 and 30 and associated capacitor circuitry 32 and 34. Such current is typically 6 amps and is sufficient to maintain the necessary commutation charge on the capacitors in the capacitor circuits 32 and 34 necessary to provide the modified square wave current in the input or primary windings 36 and 38 for generating a modified square wave output voltage in the secondary winding 44.
At the same time, by establishing a current draw to the battery by reason of a higher voltage feedback coil 82, a minimum power drain is incurred during the quiescent operating state of the inverter 10 than would be incurred if a resistive load was inserted in the inverter circuit for establishing the quiescent operating current through the input windings 36 and 38.
Referring now to FIG. 5 and to FIGS. 1 and 3, the self-detecting load demand circuit 18 includes the isolating transformer 67 which has a primary winding 100 comprised of one turn 101 of line 51 and one turn 103 of line 53 such that the primary winding 100 has two turns 101 and 103 therein. A secondary winding 104 of the isolating transformer 67 typically has 175 to 350 turns therein and is coupled to a current sensing and latching circuit 106.
The version of the load demand circuit 18 shown in FIG. 5 also includes a timer circuit 108 and a OR gate 110. As shown, the current sensing and latching circuit 106 and the timer 108 are fed with eight volts from a regulated supply.
In the operation of the load demand circuit 18 shown in FIG. 5, the timer 108 which is typically a 555 timer circuit supplies a "turn-on" signal every few seconds via output line 112 to the OR gate 110, which "turn-on" signal is passed through the OR gate to output 16 of the circuit 18 and thereby to input 20 of the inverter on/off logic 14 to turn on the inverter. Once the inverter 10 is turned on, any load current flowing in line 51 and/or line 53 will generate an input voltage to the transformer 67 which is then multiplied by the multiturn secondary winding 104 to provide a voltage input to the current sensing and holding circuit 106. Circuit 106 rectifies the voltage and holds that voltage on an output line 114 from the current sensing and holding circuit 106 which is fed to the OR gate 110, thereby to maintain an output signal at the output 16, which is supplied to the input 20 of the inverter on/off logic 14 for maintaining the inverter 10 turned on while there is a load on the inverter 10, namely across terminals 71 and 70; 73 and 70 or 71 and 73.
Typically, the timer 108 is constructed and arranged to supply a turn on signal every 1 to 3 seconds to the OR gate 110.
Turning now to FIG. 1, it will be appreciated that the current sensing and holding function of the current sensing and holding circuit 106 and the gating function of the OR gate 110 are carried out by an operational amplifier 120 and a NAND gate 112.
As shown, the input lines 68 and 69 from the secondary winding 104 of the transformer 67 are fed to a full wave diode bridge rectifier 124. The output of the rectifier 124 is fed through a voltage clipping Zener diode 125, for over-voltage protection, to one section 126 of the operational amplifier 120 as shown. The other section 128 is utilized for a different purpose than load demand and will not be further described. The output from the section 126 of the operational amplifier 120 is then supplied to one input 130 of NAND gate 122 while the output line 112 from the timer 108 is fed to another input 132 of the NAND gate 122.
It will be understood that the operational amplifier 120 in conjunction with the NAND gate 122 and associated resistors, capacitors and diodes as shown will provide a OR gating function so that the inverter energizing (on/off) logic 14 will be energized every time a logic signal is supplied by the timer 108 via line 112 to the NAND gate 122, and that when sufficient AC current draw is sensed by the operational amplifier 120, the signal applied to the input 130 of the NAND gate 122 is such as to maintain an "inverter-on" signal at the input 20 of the inverter energizing logic 14.
The timer 108 supplies an output pulse sufficient to maintain the inverter on for at least one cycle. If no threshold current is detected by the operational amplifier 120 after the one cycle, the inverter energizing logic 14 is de-energized and maintained off for 1-3 seconds before another sample cycle takes place upon generation of another "on" signal from the timer 108.
When a sufficient threshold current is detected, meaning that a load has been coupled across two of the output terminals 70, 71, 73, the operational amplifier 120 holds the NAND gate 122 in a state where it produces an inverter "on" signal at the output 16 thereof which is supplied to the input 20 of the inverter energizing logic 14.
Referring now to FIG. 3, the automatic power factor correcting circuitry 60 is supplied with a 120 Hz square wave signal at an input 140 thereof. This 120 Hz signal is generated within the inverter 10 and then supplied to the input 140 and through resistor 142 to a comparator 144 which receives a reference voltage via a line 146 which is supplied from a plus eight volt source through a dropping resistor 148. The output of the comparator 144 is then differentiated through a capacitor 150 and resistor 152 and supplied to one input 154 of a first NAND gate 156 of a first, detecting circuit 158 and an input 160 of a second NAND gate 162 of a second, holding circuit 164.
As will be described in greater detail below, the first, detecting circuit 158 and the second, holding circuit 164 are utilized to operate a switching circuit 168 when a large reactive load is sensed connected across two terminals 70, 71 and 73. When such a highly reactive load is sensed coupled across two terminals 70, 71 and 73, the switching circuit 168 is energized to energize a coil 170 of a relay so as to close relay contacts 171 and 172 thereof to short out a high isolating resistance circuit 174 which is connected in series with a deQing resistor 176 and a power factor correcting capacitor 178 connected across lines 51 and 53. In this respect, when the first detecting circuit 158 senses a high dv/dt at the trailing edge of one cycle, the switching circuit 168 is energized to energize the relay 170 to short circuit the isolating resistance circuit 174 to place the deQing resistor 176 and power factor correcting capacitor 178 in parallel with the load. The dv/dt signal sensed disappears once the capacitor 178 is put in the circuit so that the second, holding circuit 164 is provided for holding the switching circuit 168 in an energized condition for at least one half cycle and this is accomplished by sensing the voltage across the deQing resistor 176 which is related to the amount of inductance in the load connected across two output terminals 70, 71 and 73.
Also as will be described in greater detail hereinafter the use of a 120 Hz signal, which is twice the frequency of the 60 Hz modified square wave output waveform from the inverter 10, ensures that the decision whether to activate the switching circuit 168 will only be made at the trailing end of a half cycle on the 60 Hz modified square output waveform.
Returning now to the first detecting circuit 158, it has already been described that a signal twice the frequency of the output waveform is generated by conventional means, as by an oscillator, supplied to the comparator 144, and compared with a reference voltage. When the 120 Hz signal exceeds the reference voltage, an output pulse is generated at the output of the comparator 44 and differentiated by the capacitor 150-resistor 152 circuit. This differentiated signal is supplied to the input 154 of the NAND gate 156. In the meantime, a dv/dt sensing circuit comprising an isolating transformer 180 having a primary winding 182 connected across the output secondary winding section 46 senses the voltage across the load, and such voltage is reflected in the secondary winding 184 of the transformer 180. A dv/dt sensing circuit comprised of a capacitor 186 and potentiometer 188 are connected across the secondary winding 184. When a voltage spike is added to the output voltage by an inductive reactive load discharging energy back into the circuit, the fast rate of voltage rise of the voltage spike, is sensed by the dv/dt sensing circuit comprised of capacitor 186 and potentiometer 188.
A similar dv/dt sensing circuit is disclosed in my previously mentioned copending application, the disclosure of which is incorporated herein by reference.
A wiper blade 190 of the potentiometer 188 is coupled through a diode 192 and an RC circuit 194 to another input 196 of the NAND gate 156. Now when there is a sufficiently large dv/dt signal sensed at the wiper blade 190 and supplied to the input 196 of the NAND gate 156, at the same time a pulse from differentiated 120 Hz signal is supplied to the input 154 of the NAND gate 156, a momentary low is present at an output 198 of the NAND gate 156. This low is supplied to a fast attack, slow release circuit 200 which then supplies a signal to input 201 of NAND gate 202 which forces output 203 thereof high to turn on a transistor 204 of the switching circuit 168. When transistor 204 is turned on, coil 170 is energized to close the relay contacts 171 and 172 to short out the isolating resistance circuit 174 thereby to couple the deQing resistor 176 and power factor correcting capacitor 178 across the load.
The fast attack, slow release circuit 200 comprised of a resistor, capacitor and diode as shown, lengthens the time when a low signal is applied to input 201 of NAND gate 202 thereby to maintain a high at output 203 of NAND gate 202 for a desired length of time.
Once the deQing resistor 176 is coupled across the load, a voltage is generated thereacross which is related to the amount of inductance in the inductive reactive load. This voltage is supplied to a primary winding 208 of an isolating transformer 210 having a secondary winding 212 which is coupled to a full wave diode rectifying bridge 214. The output from the diode rectifying bridge 214 is supplied via line 216 to a potentiometer 218. A wiper blade 220 of the potentiometer 218 supplies part of the rectified voltage from the rectifier bridge 214 to an input 222 of a comparator 224 which also has applied thereto the reference voltage on the line 146. When the voltage supplied to input 222 of comparator 224 exceeds the voltage on line 146, an output signal is supplied by the comparator 224 to another input 226 of the NAND gate 162 in the second, holding circuit 164 which also received the differentiated 120 Hz signal at its other input 160.
This causes an output signal to be generated at output 228 of NAND gate 162 which is supplied to an input 230 of a one shot circuit 232. The one shot circuit 232 then supplies an inverted, longer duration output pulse at its output 234 to another input 236 of the NAND gate 202. Typically this output pulse has a duration of 8.3 milliseconds which is equivalent to one half cycle of a 60 Hz signal. This will then cause a high to be generated at the output 203 of the gate 202 which is supplied to the base of the transistor 204 to maintain the base of the transistor 204 on for the following half cycle of the output waveform from the inverter 10.
As a result, the first, detecting circuit 158 serve to first detect a high dv/dt and when such as high dv/dt is detected a power factor correcting capacitor 178 and deQing resistor 176 are coupled in parallel with the load. Then, the second holding circuit 164 operates to maintain the power factor correcting capacitor 178 and deQing resistor 176 coupled across the load for at least one half cycle of the inverter output waveform.
From the foregoing description it will be apparent that the power inverter 10 of the present invention and more particularly the minimum feedback loading circuit 42 thereof, the self-detecting load demand circuit 18 thereof, and the automatic power factor correcting circuitry 60 thereof provide a number of advantages, some of which have been described above and others of which are inherent in the invention.
Also it will be apparent to those skilled in the art that modifications can be made to the power inverter 10 and circuits 42, 18 and 60 thereof without departing from the teachings of the invention. Accordingly, the scope of the invention is only to be limited as necessitated by the accompanying claims. | The DC to AC power inverter is of the class B, C, D or E type and includes a battery, at least one power SCR and associated capacitor circuitry, at least one input winding on a main transformer core and at least one output secondary winding on the transformer core. Such inverter requires a quiescent current to establish operating current for capacitor commutation charge and includes a feedback loading circuit for feeding current generated by the quiescent current back to the battery. The inverter also includes a self-detecting load demand circuit coupled to a line from said output winding for cyclically energizing the inverter, for sensing a minimum AC load and for holding said inverter in an energized state until less than a minimum AC load is sensed during an energizing cycle. Further the invention includes automatic power factor correction circuitry for supplying full time leading power factor correction to a load, with the automatic power factor correction circuitry being sensitive to light reactive loads. | 8 |
[0001] The invention relates to the field of PRRS viruses and infectious clones obtained from PRRS viruses. Furthermore, the invention relates to vaccines and diagnostic assays obtainable by using and modifying such infectious clones of PRRS viruses.
[0002] Porcine reproductive and respiratory syndrome virus (PRRSV) is a positive-strand RNA virus that belongs to the family of arteriviruses together with equine arteritis virus (EAV), lactate dehydrogenase-elevating virus (LDV) and simian hemorrhagic fever virus (Meulenberg et al., 1993). Recently, the International Committee on the Taxonomy of Viruses has decided to incorporate this family in a new order of viruses, the Nidovirales, together with the Coronaviridae (genomic length 28 to 30 kb), and Toroviridae (genomic length 26 to 28 kb). The order Nidovirales represents enveloped RNA viruses that contain a positive-stranded RNA genome and synthesize a 3′ nested set of subgenomic RNAs during replication. The subgenomic RNAs of coronaviruses and arteriviruses contain a leader sequence which is derived from the 5′ end of the viral genome. The subgenomic RNAs of toroviruses lack a leader sequence. Whereas the ORFs 1a and 1b, encoding the RNA dependent RNA polymerase, are expressed from the genomic RNA, the smaller ORFs at the 3′ end of the genomes of Nidovirales, encoding structural proteins, are expressed from the subgenomic mRNAs.
[0003] A replicon herein is defined as derived from a recombinant nucleic acid. Although genomic information regarding PRRSV is now emerging, it is for example not known where deletions or modifications in the PRRSV genome can be located so that the resulting recombinant nucleic acid can be used as a functional replicon allowing in vivo RNA replication, be it in (complementary) cells expressing essential (PRRS) viral proteins (such as polymerase or structural (envelope) proteins or not, or allowing independent in vivo RNA replication in animals, such as pigs, after vaccination with a vaccine comprising a nucleic acid encoding such a PRRS replicon.
[0004] PRRSV (Lelystad virus) was first isolated in 1991 by Wensvoort et al. (1991) and was shown to be the causative agent of a new disease now known as porcine reproductive respiratory syndrome (PRRS). The main symptoms of the disease are respiratory problems in pigs and abortions in sows, sometimes complicated by sow-mortality. Although the major outbreaks, such as observed at first in the US in 1987 and in Europe in 1991, have diminished, this virus, in its various virulent or less-virulent forms, still causes major economic losses in herds in the US, Europe, and Asia.
[0005] PRRSV preferentially grows in alveolar lung macrophages (Wensvoort et al., 1991). A few cell lines, such as CL2621 and other cell lines cloned from the monkey kidney cell line MA-104 are also susceptible to the virus. Some well known PRRSV strains are known under accession numbers CNCM I-1102, I-1140, I-1387, I-1388, ECACC V93070108, or ATCC VR 2332, VR 2385, VR 2386, VR 2429, VR 2474, and VR 2402. The genome of PRRSV is 15 kb in length and contains genes encoding the RNA dependent RNA polymerase (ORF1a and ORF1b) and genes encoding structural proteins (ORFs 2 to 7; Meulenberg et al., 1993 and Meulenberg et al., 1996). ORF5 encodes the major envelope glycoprotein, designated GP 5 . The ORFs 2, 3, and 4 encode glycoproteins designated GP 2 , GP 3 , and GP 4 , respectively. These glycoproteins are less abundantly present in purified virions of the Lelystad virus isolate of PRRSV. The GP 5 protein forms a di-sulfide-linked heterodimer with the membrane protein M encoded by ORF6. The nucleocapsid protein N is encoded by ORF7. The analysis of the genome sequence of PRRSV isolates from Europe and North America, and their reactivity with monoclonal antibodies has proven that they represent two different antigenic types. The isolates from these continents are genetically distinct and must have diverged from a common ancestor relatively long ago (Murtaugh et al., 1995).
[0006] Pigs can be infected by PRRSV via the oronasal route. Virus in the lungs is taken up by lung alveolar macrophages and in these cells replication of PRRSV is completed within 9 hours. PRRSV travels from the lungs to the lung lymphnodes within 12 hours and to peripheral lymphnodes, bone marrow and spleen within 3 days. At these sites, only a few cells stain positive for viral antigen. The virus is present in the blood during at least 21 days and often much longer. After 7 days antibodies to PRRSV are found in the blood. The combined presence of virus and antibody in PRRS infected pigs shows that the virus infection can persist for a long time, albeit at a low level, despite the presence of antibody. During at least 7 weeks the population of alveolar cells in the lungs is different from normal SPF lungs.
[0007] PRRSV needs its envelope to infect pigs via the oronasal route and the normal immune response of the pig thus entails among others the production of neutralising antibodies directed against one or more of the envelope proteins; such antibodies can render the virus non-infective. However, once in the alveolar macrophage, the virus also produces naked capsids, constructed of RNA encapsidated by the M and/or N protein, sometimes partly containing any one of the glycoproteins. The intra- and extracellular presence of these incomplete viral particles or (partly) naked capsids can be demonstrated by electron microscopy. Sometimes, naked capsids without a nucleic acid content can be found. The naked capsids are distributed through the body by the bloodstream and are taken up from the blood by macrophages in spleen, lymphnodes and bonemarrow. These naked but infectious viral capsids can not be neutralised by the antibodies generated by the pig and thus explain the persistence of the viral infection in the presence of antibody. In this way, the macrophage progeny from infected bonemarrow cells is spreading the virus infection to new sites of the body. Because not all bonemarrow macrophage-lineage cells are infected, only a small number of macrophages at peripheral sites are infected and produce virus. PRRSV capsids, consisting of ORF7 proteins only, can be formed in the absence of other viral proteins, by for instance infection of macrophages with a recombinant pseudorabies-ORF7 vector virus. The PRV virus was manipulated to contain ORF7 genetic information of PRRSV. After 18 hours post infection, the cytoplasm of infected cells contains large numbers of small, empty spherical structures with the size of PRRS virus nucleocapsids.
[0008] Although live-attenuated and killed PRRSV vaccines are now available, it has been shown that in general these are not immunogenic enough or are too virulent for specific groups of pigs, i.e. for young piglets or sows in the third trimester of pregnancy. It is clear that a PRRSV vaccine that is not sufficiently immunogenic will not stand up in the market. However, several of the existing immunogenic vaccines are not safe illustrating the need for attenuated PRRSV vaccines with reduced virulence.
[0009] Furthermore, again under specific circumstances, several of the existing vaccines spread within a population, and may inadvertently infect other pigs that need not or should not be vaccinated, illustrating the need for non-spreading PRRSV vaccines.
[0010] Furthermore, the existing vaccines can in general not be distinguished from wild type field virus, illustrating the need for a so-called marker vaccine, obtained for example by mutagenesis of the genome, so that vaccinated pigs can be distinghuished from field virus-infected pigs on the basis of differences in serum antibodies.
[0011] In addition, PRRS vaccines, being so widely used throughout the world, and being in general not infectious to other animals but pigs, would be attractive candidate vaccines to carry foreign antigens derived from other (porcine) pathogens to provide for protection against those other pathogens, illustrating the need for PRRSV carrier or vector vaccines allowing vaccination against those other pathogens or allowing positive marker identification.
[0012] It goes without saying, that PRRSV vaccines combining one or more of these features would be preferred. It is an object of the present invention to provide solutions to these needs.
[0013] The invention provides a porcine reproductive and respiratory syndrome virus (PRRSV) replicon having at least some of its original PRRSV nucleic acid deletions, herein also comprising substitutions, said replicon capable of in vivo RNA replication, said replicon further having been deprived of at least some of its original PRRSV nucleic acid and/or having been supplemented with nucleic acid derived from a heterologous micro-organism.
[0014] Surprisingly, it has been found that the genome of PRRSV can be deprived of quite a large amount of its nucleic acid. An independent and functional PRRSV replicon capable of independent in vivo RNA replication can still exist if the stretch, or fragments thereof, of nucleic acid encoding the ORF2-ORF6, but not an essential element from the ORF7 protein, is deleted and/or modified. Having a replicon wherein such a large stretch of nucleic acid has been deleted or modified opens up a large capacity for the addition to said replicon of heterologous nucleic acid from any other organism than PRRSV, thereby providing a PRRSV vector replicon with large carrier capacities. Herewith, the inventor provides identification of specific nucleic acid regions in the genome of porcine reproductive and respiratory syndrome virus, that are important for attenuation of the virus, for making it non- or little spreading or for the introduction of a marker, without crippling the viral nucleic acid so much that it can no longer provide in vivo RNA replication. Furthermore, the inventor demonstrates that a PRRSV replicon can be used as vector for the expression of foreign antigens, preferably derived from other (porcine) pathogens, allowing vaccination against those other pathogens and allowing positive marker identification. The minimal sequence requirements for a PRRSV replicon or PRRSV vector replicon as provided by the invention are essential elements comprising the 5′ noncoding region-ORF1a-ORF1b-ORF7-3′ noncoding region, (e.g. from the PRRSV polymerase region) whereby the ORF7 coding region can be deleted further for example according to the data shown in FIG. 2. In a preferred embodiment, the invention provides a PRRSV replicon or vector at least comprising essential elements from the PRRSV polymerase region for example as described below and/or comprising at least nucleic acid derived from a essential region of 44 nucleotides between nucleotides 14642 to 14686 in the ORF7 gene (as identified in the nucleic acid sequence of the Lelystad virus isolate of PRRSV, however, the skilled person can easily determine by alignment wherein in any other PRRSV genome said essential element is located).
[0015] In another preferred embodiment, the invention provides a PRRSV replicon comprising at least nucleic acid derived from essential sequence elements from ORF1a and ORF1b, or from the PRRSV polymerase region and having nucleic acid from ORF2, ORF 3, ORF 4, ORF 5, ORF 6, or non-essential elements from ORF7 deleted, allowing insertion of foreign nucleic acid, thereby providing a PRRSV vector replicon having foreign antigen coding capacities. This in contrast to WO98/55626 where the homologous polymerase is replaced with a heterologous Arteriviral one to express ORF2-ORF7, essentially without disclosing expression of foreign antigens derived from other (porcine) pathogens to provide for protection against those other pathogens allowing vaccination against those other pathogens (let alone wherein the PRRSV genome nucleic acid encoding foreign antigens may be located for providing a PRRSV vector replicon or which essential sequence elements should remain).
[0016] The replicase polyprotein of PRRSV encoded by ORF1 is thought to be cleaved in 13 processing end-products (designated nonstructural proteins—nsps) and a large number of intermediates. The polyprotein is cleaved by protease domains located in nsp1α, nsp1β, nsp2 and nsp4. Essential PRRSV RNA-dependent RNA polymerase and nucleoside triphosphate-binding/RNA Helicase motifs were identified in nsp9 and nsp10, respectively. Another conserved (essential) domain was found in nsp11, a conserved Cys/His-rich domain was found in nsp10. It has for example been shown that the latter protein plays a role in subgenomic mRNA synthesis.
[0017] In a further embodiment, the invention provides a PRRSV replicon capable of independent in vivo RNA replication wherein said replicon is a RNA transcript of an infectious copy cDNA. It has been shown for many positive strand RNA viruses that their 5′ and/or 3′ noncoding regions contain essential signals that control the initiation of plus- and minus-strand RNA synthesis. It was not determined for PRRSV whether these sequences alone are sufficient for replication. As for most RNA viruses, PRRSV contains a concise genome and most of the genetic information is expected to be essential. Furthermore, the maximum capacity for the integration of foreign genes into the PRRSV genome is not yet known. An extra limitation is that the ORFs encoding the structural proteins of PRRSV are partially overlapping. The introduction of mutations in these overlapping regions often results in two mutant structural proteins and therefore is more often expected to produce a nonviable virus.
[0018] The production of an infectious clone allowed us to analyse replication signals in the genome of PRRSV. In this study we have mapped cis-acting sequence elements required for replication by introducing deletions in the infectious clone. Surprisingly, we have shown that also cis-acting sequence elements from the region of the genome encoding structural proteins are essential for proper replication. We have shown that transcripts derived from cDNA clones lacking the ORF7 gene are not replicated. A more systematic deletion analysis showed that a region of 44 nucleotides between nucleotides 14642 to 14686 in the ORF7 gene was essential for replication of RNA of PRRS. This was an interesting finding, since the sequences essential for replication of most positive strand RNA viruses are present in the 5′ and 3′ noncoding regions. It is an important finding for studies who's aim is to develop viral replicons which can only be rescued in complementing cell lines expressing the deleted ORFs. The minimal sequence requirements for these RNAs are located in the 5′ noncoding region-ORF1a-ORF1b-ORF7-3′ noncoding region. Viral RNA's or replicons containing these sequence elements supplemented with a selection of fragments from other PRRSV open reading frames or fragments of open reading frames expressing antigens of other (heterologous) pathogens can be packaged into virus particles when the proteins essential for virus assembly are supplied in trans. When these particles are given to pigs, for example as vaccine, they will enter specific host cells such as macrophages and virus- or heterologous antigens are expressed and induce immune responses because of the replicating RNA. However, since the RNA does not express (all) the proteins required for packaging and the production of new particles, the replicon can not spread further, creating an extremely efficient, but safe and not-spreading recombinant vaccine effective against PRRSV and/or heterologous pathogens.
[0019] In a preferred embodiment, the invention provides a replicon according to the invention incapable of N-protein capsid formation. For example, two Cys residues are present at positions 27 and 76 in the N protein sequence and mutating or deleting Cys-27 and Cys-76 from the N protein inhibits the production of infectious particles of PRRSV. The ORF7 gene encoding the N protein was mutated as such that the Cys residues were substituted for Asn and Leu residues, respectively, however, substitution with another amino acid, or deletion of the coding sequence, leads to the desired result as well, as for example can be seen below.
[0020] The Cys-27 and Cys-76 mutations were subsequently introduced in the infectious clone pABV437 of the Lelystad virus isolate of PRRSV, resulting in plasmids pABV534-536 (Cys-27→Asn) and pABV472-475 (Cys-76→Leu). RNA was transcribed from these mutated infectious clones and transfected to BHK-21 cells. The structural proteins were properly expressed, these mutant RNAs were replicated and subgenomic RNAs synthesized. However, infectious particles were not secreted, since the transfer of the supernatant of the transfected BHK-21 cells to macrophages did not result in the production of viral proteins in the macrophages nor in the induction of a cpe.
[0021] Thus, these residues are essential for a proper structure or function or both of the N protein in virus assembly of PRRSV. The N protein is involved in the first steps in virus assembly, the binding of the viral genomic RNA and formation of the capsid structure. Since transcripts of genomic length cDNA clones containing the Cys-27 and/or Cys-76 deletion replicated at the wild type level, the mutations in the Cys residues destroy the binding of the RNA by the N protein. Alternatively, they induce a different structure of the N protein that inhibits the formation of proper capsids. The defect in the encapsidation of the viral RNA genome can be complemented by wild type N protein transiently expressed or continuously expressed in a (BHK-21) cell line. In this way a virus is produced that is able to complete only one round of infection/replication. Therefore such a virus is considered to be a very safe vaccine for protection against PRRSV in pigs.
[0022] In another example, the invention provides a replicon incapable of N-protein capsid formation wherein substitutions in the genome encoding the N protein area containing two antigenic regions designated B and D inhibited the production of infectious virus particles. The B region comprises amino acids 25-30 (QLCQLL), D region; amino acids 51-67 (PEKPHFPLAAEDDIRHH) and amino acids 80-90 (ISTAFNQGAGT) of the N protein of PRRSV. The corresponding sites in VR2332 and other American strains are found when the N proteins of these strains are aligned. Since RNA replication and subgenomic mRNA synthesis appeared to be at the wild type level, these mutations most likely prevented the formation of proper capsids by the N protein.
[0023] The invention furthermore provides a replicon according to the invention wherein a marker allowing serological discrimination has been introduced. For example, mutagenesis of a single amino acid in the D region (Asp-62 or a.a. corresponding thereto) of protein N results in a replicon that has a different MAb binding profile from PRRSV and all other PRRSV viruses. Such a replicon induces a different spectrum of antibodies in pigs, compared to these other PRRSV isolates. Therefore it can be differentiated from field virus on the basis of serum antibodies and is an excellent mutant for further development of marker vaccines against PRRSV.
[0024] The above example involves a subtle modification resulting in a replicon useful for a marker vaccine. However, more extensive changes are now also possible, knowing that it is allowed to partly or fully delete the nucleic acid encoding the structural proteins 2, 3, 4, 5, and/or 6 without tampering with the replicative properties of the resulting replicon. A PRRSV replicon lacking one or more (antigenic) fragments of these structural proteins has the advantage that no immune respons, more specifically no antibodies, against these deleted fragments will be formed, for example after vaccination with a vaccine comprising such a replicon. Again, such a replicon induces a different spectrum of antibodies in pigs, compared to wild type PRRSV. Therefore it can be differentiated from field virus on the basis of serum antibodies and is an excellent mutant for further development of marker vaccines against PRRSV.
[0025] Furthermore, the invention provides a replicon comprising a nucleic acid modification in a virulence marker of PRRSV. Virulence markers of PRRSV have not been elucidated, despite the fact that various differences in virulence have been observed. However, for successfully attenuating a PRRSV or replicon thereof, such knowledge helps in selecting the least virulent, but most immunogenic replicon or virus possible. Now that it is known that deleting or modifying the ORF2 to ORF 6 region is possible without effecting the in vivo RNA replicative properties, such virulence markers can easily be detected. For example, the invention provides replicon comprising a nucleic acid modification in ORF 6 encoding the membrane spanning M-protein. It has been found that the membrane protein is influencing the virus assembly, the stability of the virus, or the virus entry in macrophages, all factors contributing to the virulence of PRRSV. The M protein is the most conserved structural protein among arteriviruses and coronaviruses. The protein is an integral membrane protein containing three N-terminal hydrophobic membrane spanning domains (Rottier, 1995). The protein spans the membrane three times leaving a short N-terminal domain outside the virion and a short C-terminal domain inside the virion. The M protein of coronaviruses was shown to play an important role in virus assembly (Vennema et al., 1996), but was then not determined to be a virulence factor. In particular, the invention provides a replicon wherein said modification modifies protein M in between its second and third membrane spanning fragment, essential in determining virulence of a specific PRRSV isolate. For example, the invention provides a replicon comprising vABV575. A Thr-59→Asn mutation is located between the second and third membrane spanning fragment of M in vABV575. This mutation influences virus assembly, the stability of the virus, or virus entry in the PAMs.
[0026] The invention furthermore provides a replicon according to the invention wherein said heterologous micro-organism comprises a pathogen. Since PRRSV specifically infects macrophages, it can be used as a vector for the delivery of important antigens of other (respiratory) agents to this specific cell of the immune system. The infectious cDNA clone enables us to introduce site specific mutations, deletions and insertions into the viral genome.
[0027] In a preferred embodiment, the invention provides a replicon wherein said pathogen is a virus. We have successfully used PRRSV as a vector for the expression of a foreign protein anigen, an HA epitope of the haemagglutinin of influenza A virus. Recombinant PRRSV vector replicons were engineered that produced the HA tag fused to the N- or C-terminus of the N protein. In addition, an PRRSV mutant was created that contained the HA-tag as well as the protease 2A of foot-and-mouth-disease virus (FMDV) fused to the N terminus of the N protein.
[0028] Furthermore, the invention provides a vaccine comprising a replicon or vector replicon according to the invention. PRRSV vaccines are now provided with specified antigenicity or immunogenicity that are in for example in addition safe enough for specific groups of pigs, i.e. for young piglets or sows in the third trimester of pregnancy.
[0029] Furthermore, the invention provides non-spreading PRRSV vaccines, comprising a replicon or vector replicon for example incapable of N-protein capsid formation, or incapable of further infection due to the absence of (fragments of) structural proteins encoded by ORF 2 to 6, without hampering its in vivo RNA replication properties, thereby allowing the production of proteins against which an immune response is desired.
[0030] Furthermore, the invention provides a vaccine that can be distinguished from wild type field virus, a so-called marker vaccine, obtained for example by mutagenesis of the genome, so that vaccinated pigs can be distinguished from field virus-infected pigs on the basis of differences in serum antibodies.
[0031] In addition, PRRS vaccines, being so widely used throughout the world, and being in general not infectious to other animals but pigs, are now provided as vector vaccines to carry foreign antigens derived from other (porcine) pathogens, allowing vaccination against those other pathogens and allowing positive marker identification.
[0032] Use of a vaccine according to the invention is especially useful for vaccinating pigs, sine the PRRSV is in general very host specific and replicates in macrophages of pigs, thereby targeting an important antigen presenting cell of the immune system.
[0033] The invention is further explained in the detailed description, without limiting the invention.
DETAILED DESCRIPTION
[0034] 1. Mutation of Cys-27 and Cys-76 in the N Protein Inhibits the Production of Infectious Particles of PRRSV
[0035] The nucleocapsid protein N (expressed by ORF7) is present as a monomer in purified virions of PRRSV. However, in some experiments we also detected a homodimer of N. For instance when the N protein was immunoprecipitated from purified virions with N-specific MAbs and electrophorezed on a sodium dodecyl sulfate polyacrylamide gel (SDS-PAGE), a protein of 15 kDa was predominantly observed under reduced conditions, whereas a homodimer of 30 kDa was predominantly observed under nonreduced conditions (Meulenberg et al., 1996). However, when compounds such as N-methyl maleimide or iodoacetamide were used to prevent the formation of nonspecific disulfide bonds, these dimers of N were not detected. This indicated that dimers of N are formed due to the formation of nonspecific disulfide bonds during the processing of cell lysates for analysis. Two cystein residues are present in the N protein sequence. The question raised which of the cysteine residues was responsible for the formation of nonspecific disulfide bonds and whether the cysteine residues are important for the structure and function of the N protein. To answer this question we mutated the two cystein residues individually in the infectious cDNA clone of PRRSV and studied the infectivity of the resulting mutant viral genomic RNAs.
[0036] 2. Introduction of a Marker in the N Protein
[0037] The N protein of PRRSV contains 4 antigenic sites, designated A-D (Meulenberg et al., 1998). Two sites, B and D, contain epitopes that are conserved in European and North American isolates of PRRSV. To produce viruses that can be serologically distinguished from wild type viruses, mutations in the B and D domain that disrupt the binding of N-specific MAbs were introduced in the infectious cDNA clone of PRRSV. Transcripts of the resulting mutant full length cDNA clones were analyzed for RNA replication by detecting the expression of structural proteins and production of infectious virus.
[0038] 3. Elucidation of Replication Signals Present in the Region Encoding Structural Proteins of Lelystad Virus
[0039] Positive strand RNA viruses contain 5′ and 3′ noncoding regions which are essential for replication. The RNA sequences at the 5′ and 3′ end usually have a specific secondary structure which is recognized by the viral RNA dependent RNA polymerase to initiate positive and negative strand synthesis and in the case of arteriviruses subgenomic RNA synthesis. We deleted the ORF7 gene from the infectious clone of PRRSV (Meulenberg et al., 1998) in a first attempt to generate a defective RNA replicon that could be complemented for production of infectious particles, when transfected to a cell expressing the N protein. The ORF7 gene was precisely deleted, without affecting the 3′ noncoding region of the virus. Surprisingly, the RNA of this deletion mutant did not replicate in BHK-21 cells. This suggested that RNA replication signals are present in the coding region of ORF7. The purpose of this study was to further localize these replication signals. By expensive deletion analysis of the coding region and upstream sequences of ORF7 we were able to identify a region of 44 nucleotides in the ORF7 gene that is important for replication of RNA of PRRSV.
[0040] 4. Production of an Attenuated PRRSV Virus by Deletion of the NdeI Site in ORF6.
[0041] Recently, we have established an infectious clone cDNA clone of PRRSV (Meulenberg et al., 1998). The full length cDNA clone contains two NdeI sites, the first at nucleotide 12559 (ORF3) and the second at nucleotide 14265 (in ORF6) in the genome sequence. To facilitate mutagenesis and exchange of fragments in the region encoding the structural proteins (ORFs 2 to 7) of the virus, we destroyed the second NdeI site by PCR-directed mutagenesis. This resulted in an amino acid substitution at position 59 in the M protein (Thr→Asn). The growth properties of the virus produced from the mutated full length cDNA clone containing a unique NdeI site was analysed.
[0042] 5. Lelystad Virus as a Vector for the Expression of Foreign Antigens or Proteins.
[0043] The generation of an infectious cDNA clone of PRRSV (Meulenberg et al., 1998) is a major breakthrough in PRRSV research and opens up new possibilities for the development of new viral vectors. Since PRRSV specifically infects macrophages, it can be used as a vector for the delivery of important antigens of other (respiratory) agents to this specific cell of the immune system. The infectious cDNA clone enables us to introduce site specific mutations, deletions and insertions into the viral genome. However, it is still not known which regions of the PRRSV genome are essential or allow mutagenesis. As for most RNA viruses, PRRSV contains a concise genome and most of the genetic information is expected to be essential. Furthermore, the maximum capacity for the integration of foreign genes into the PRRSV genome is not yet known. An extra limitation is that the ORFs encoding the structural proteins of PRRSV are partially overlapping. The introduction of mutations in these overlapping regions results in two mutant structural proteins and therefore is more often expected to produce a nonviable virus.
[0044] The aim of this study was to identify regions in the PRRSV genome that allow the introduction of foreign antigens that will be exposed to the immune system of the pig after infection with the mutant virus. In a first approach we have selected a small epitope of 9 amino acids of human haemagglutinin of influenza A for expression in PRRSV.
[0045] METHODS
[0046] Cells and Viruses
[0047] BHK-21 cells were grown in BHK-21 medium (Gibco BRL), completed with 5% FBS, 10% tryptose phosphate broth (Gibco BRL), 20 mM Hepes pH 7.4 (Gibco BRL) and 200 mM glutamine, 100 U/ml penicillin and 100 μg/ml streptomycin. Porcine alveolar lung macrophages (PAMs) were maintained in MCA-RPMI-1640 medium, containing 10% FBS, 100 μg/ml kanamycin, 200 U/ml penicillin and 200 μg/ml streptomycin. Virus stocks were produced by serial passage of recombinant PRRSV viruses secreted in the culture supernatant of tranfected BHK-21 cells on PAMs. Virus was harvested when PAMs displayed cytopathic effect (cpe) usually 48 hours after infection. Virus titers (expressed as 50% tissue culture infective doses [TCID 50 ] per ml) were determined on PAMs using end point dilution (Wensvoort et al., 1986).
[0048] Mutagenesis
[0049] 1. Mutagenesis of Cys-27 and Cys-76.
[0050] The Cys-27 was mutated to Asn by PCR-directed mutagenesis with primers LV108 and LV97. The sequences of primers used in this study are listed in Table 1 . The generated PCR fragment was digested with HpaI and PflmI and inserted in the ORF7 gene in pABV431 digested with the same enzymes. This resulted in plasmid pABV451 The Cys-76 was mutated to Leu by PCR-directed mutagenesis with primers LV108 and LV100. The generated fragment was digested with HpaI and ClaI and inserted in the ORF7 gene in pABV431 digested with the same enzymes. This resulted in pABV452. The mutated ORF7 genes were subsequently transferred to the genomic-length cDNA clone pABV437(Meulenberg et al., 1998) with the unique HpaI (nt 14581) and PacI (nt 14981) site, to create plasmids pABV534-536 (Cys-27→Asn) and plasmids pABV472-475 (Cys-76→Leu; FIG. 1).
[0051] 2. Mutagenesis of Antigenic Site B and D in the N Protein
[0052] Antigenic sites B (amino acids 25-30) and D (amino acids 51-67 and 80-90) of the N protein of PRRSV were mutated by substitution of the amino acids in this region for the corresponding amino acids of respectively EAV and LDV. Plasmids pABV455, pABV463, and pABV453 containing these respective mutation were described previously in Meulenberg et al. (1998). In addition, the Asp at position 62 in the D region of the N protein was mutated to a Tyr in a PCR with primers LV108 and LV188. The sequences of these primers are shown in Table 1. The PCR fragment was digested with HpaI and ClaI and inserted in the ORF7 gene in pABV431 digested with the same enzymes. This resulted in pABV582. The ORF7 genes containing the mutations were inserted in pABV437 using the unique HpaI (nt 14581) and PacI (nt 14981) (FIG. 1).
[0053] 3: Creation of Deletion Mutants in the Full-Length cDNA Clone of PRRSV
[0054] Several deletions were made in the full-length cDNA clone of pABV437 of PRRSV (FIG. 2). First, ORF2, ORF3, ORF4, ORF5 and the 5′ half of ORF6 were deleted. pABV437 was digested with EcoRI and NheI and the sites were made blunt with Klenow fragment (Pharmacia Biotech). The fragment was purified and ligated. This resulted in clone plasmid pABV594. Second, ORF7 was deleted from the infectious copy of PRRSV. For this purpose, the infectious full-length cDNA clone pABV442 that contains a SwaI restriction site directly downstream of the stopcodon of ORF7, was digested with HpaI and SwaI and ligated. This resulted in clone plasmid pABV521. Third, to delete the 3′ end of ORF6, PCR-mutagenesis was performed with primers LV198 and LV199. The primers used in PCR-mutagenesis are listed and described in Table 1. The generated product was digested with HpaI and NheI and ligated in the corresponding sites of pABV437. This resulted in plasmid pABV627. Fourth, several deletions in and upstream of the coding region of ORF7 were made. PCR-mutagenesis was performed with forward primers LV188-191 or LV195-197 and reversed primer LV112. The generated products were digested with HpaI and PacI and ligated in the same restriction sites of pABV437, resulting in plasmids pABV602-605 and pABV625-627. Plasmids were transformed to Escherichia coli DH5α and grown at 32° C. and 20 μg kanamycin per ml. For each construct two clones containing fragments of two independent PCRs were sequenced to confirm the correct sequence of the clones. The resultant mutants are shown in FIG. 2.
[0055] 4. Mutagenesis of the NdeI Site at Position 14265 in the Infectious cDNA Clone pABV437 of PRRSV
[0056] To mutate the NdeI site at position 14265 a fragment of 1.7 kb was amplified by PCR using primers LV27 (nt 12526) and LV182 (nt 14257; Table 1) Primer LV182 contains an AseI site. AseI and NdeI have compatible ends, but ligation of their ends to each other destroys both restriction sites. The PCR fragment was digested with NdeI and AseI and ligated in pABV437 digested with NdeI. The full length clone pABV575 (FIG. 3) that contained the PCR fragment in the proper orientation, lacked the NdeI site at position 14265 and had no other mutations between 12559 and 14265 due to PCR errors was selected for further analysis.
[0057] 5: Construction of Full-Length Genomic cDNA Mutants of PRRSV Encoding an Antigenic HA tag
[0058] PCR-mutagenesis was used to create mutants in the infectious clone of PRRSV. First, a sequence of 27 nucleotides encoding an epitope of the human haemagglutinin of influenza A (HA-tag; Kolodziej et al., 1991) was introduced directly downstream of the start codon of ORF7 in the PacI mutant of the genome-length cDNA clone of Lelystad Virus (pABV437; Meulenberg et al., 1998). Two sequential PCRs were performed with primers LV192 and LV112 and with primers LV193 and LV112. Primers used to create the PCR-fragments are listed and described in Table 1. Second, both this HA-tag and a sequence of 51 nucleotides encoding the protease 2A of FMDV (Percy et al., 1994) were introduced directly downstream of the startcodon of ORF7. Two sequential PCR-reactions were performed with primers LV139 and LV112 and with LV140 and LV112. Third, the HA-tag was introduced at the 31 end of the ORF7 gene in a PCR with primers LV108 and LV194. The three PCR fragments obtained were digested with HpaI and PacI and ligated into pABV437 digested with the same enzymes. Standard cloning procedures were performed essentially as described in Sambrook et al., (1989). Plasmids were transformed into Escherichia coli DH5α and grown at 32° C. and 20 μg kanamycin per ml. For each construct two clones containing fragments of two independent PCRs were sequenced to confirm the correct sequence of the clones. Introduction of the HA epitope at the 5′ end of ORF7 resulted in the generation of clone pABV525, introduction of both the HA-tag and the protease 2A at the 5′ end of ORF7 resulted in clone pABV523, and the introduction of the HA-epitope at the 3′ end of ORF7 resulted in clone pABV526 (FIG. 4).
[0059] Sequence Analysis
[0060] The generated cDNA clones were analyzed by oligonucleotide sequencing. Oligonucleotide sequences were determined with the PRISM Ready Dye Deoxy Terminator cycle sequencing kit and the automatic sequencer (Applied Biosystems).
[0061] In Vitro Transcription and Transfection of RNA
[0062] Full-length genomic cDNA clones and derivatives thereof were linearized with PvuI, which is located directly downstream of the poly(A) stretch. The linearized plasmids were precipitated with ethanol and 1.5 μg of these plasmids was used for in vitro transcription with T7 RNA polymerase by the methods described for SFV by Liljeström and Garoff (1991). The in vitro transcribed RNA was precipitated with isopropanol, washed with 70% ethanol and stored at −20° C. until use.
[0063] BHK-21 cells were seeded in 35-mm wells (approximately 10 6 cells/well) and were transfected with 2.5 μg in vitro transcribed RNA mixed with 10 ml lipofectin in optimem as described earlier (Meulenberg et al., 1998). Alternatively, RNA was introduced in BHK-21 cells in 20-mm wells with 0.5 μg in vitro transcribed RNA mixed with 2 ml lipofectin in optimem. The medium was harvested 24 h after transfection, and transferred to CL2621 cells or PAMs to rescue infectious virus. Transfected and infected cells were tested for expression of PRRSV proteins by an immunoperoxidase monolayer assay (IPMA), essentially as described by Wensvoort et al. (1986). Monoclonal antibodies (MAbs) 122.14, 122.1, and 126.3 directed against respectively the GP 3 , GP 4 , M protein (van Nieuwstadt et al., 1996) were used for staining in this assay. A panel of MAbs (122.17, 125.1, 126.9, 126.15, 130.2, 130.4, 131.7, 131.9, 138.22, WBE1, WBE4, WBE5, WBE6, SDOW17, NS95, and NS99) directed to four different antigenic sites A-D were used to study the expression of the N protein (Meulenberg et al., 1998). MAb 12CAS was used to detect the expression of the HA-epitope and was purchased from Boehringer Mannheim. In addition, we analyzed the expression of PRRSV proteins by metabolic labeling of transfected or infected cells, followed by immunoprecipitation using specific monoclonal antibodies or peptide sera directed to the structural proteins of PRRSV, as described by Meulenberg et al (1996).
[0064] Sequence Analysis of Genomic RNA of Recombinant Viruses
[0065] The culture supernatant of the PAMs infected with passage 3 of the HA-expressing viruses was used to analyze viral RNA by RT-PCR. A volume of 500 μl proteinase K buffer (100 mM Tris-HCl [pH 7.2], 25 mM EDTA, 300 mM NaCl, 2% [wt/vol] sodium dodecyl sulfate) and 0.2 mg Proteinase K was added to 500 μl supernatant. After incubation for 30 minutes at 37° C., the RNA was extracted with phenol-chloroform and precipitated with ethanol. The RNA was reverse transcibed with primer LV76. Then, PCR was performed with primers LV37 and LV112 to amplify fragments of vABV523 and vABV525 and with primers LV37 and LV75 to amplify fragments of vABV526 (Table 1). Sequence analysis was performed to determine whether the mutant viruses at passage 4 still contained the inserted foreign sequences.
[0066] Results
[0067] 1. Mutation of Cys-27 and Cys-76 in full length cDNA clone pABV437 Two Cys residues are present at positions 27 and 76 in the N protein sequence. The ORF7 gene encoding the N protein was mutated as such that the Cys residues were substituted for Asn and Leu residues, respectively. The Cys-27 and Cys-76 mutations were subsequently introduced in the infectious clone pABV437 of the Lelystad virus isolate of PRRSV, resulting in plasmids pABV534-536 (Cys-27→Asn) and pABV472-475 (Cys-76→Leu; FIG. 1). RNA was transcribed from these mutated infectious clones and transfected to BHK-21 cells. These cells stained positive with N-specific MAbs in IPMA. Analysis of the N protein synthesized by pABV534-536 and pABV472-475 in immuno precipitation and SDS-PAGE indicated that its apparent molecular weight was similar to the wild type N protein and migrated at 15 kDa under reducing conditions. Next we analyzed the N protein under nonreducing conditions in the absence of N-methyl maleimide or iodoacetamide. Under these conditions, the N protein expressed by pABV472-475 (Cys-76→Leu) resembled the wild type N protein and was mainly detected as a dimer, whereas the N protein expressed by pABV534-536 (Cys-27→Asn) was detected as a monomer. This indicated that the Cys residue at position 27 was responsible for the formation of nonspecific disulfide bonds. The production of other structural proteins such as GP 3 , GP 4 , and M was also detected in IPMA and immuno precipitation after transfection of full length RNA from plasmids pABV534-536 (Cys-27→Asn) and pABV472-475 (Cys-76→Leu: FIG. 1). Since the structural proteins were properly expressed, these mutant RNAs were replicated and subgenomic RNAs synthesized. However, infectious particles were not secreted, since the transfer of the supernatant of the transfected BHK-21 cells to PAMs did not result in the production of viral proteins in the PAMs nor in the induction of a cpe. Therefore both Cys residues are essential for a proper structure or function or both of the N protein in virus assembly.
[0068] 2. Characterization of Full Length cDNA Clones containing Mutations in Antigenic Sites of the N Protein of PRRSV
[0069] Site B (amino acids 25-30) and D (amino acids 51-67 and 80-90) are two antigenic regions that are conserved in European and North American PRRSV isolates. When we mutated site B and D by substituting their amino acid sequence for the corresponding amino acids of the LDV or EAV N protein, the binding of the N protein by respectively B-specific and D-specfic MAbs was disrupted (Meulenberg et al., 1998). To produce a PRRSV virus that is antigenically different from PRRSV field viruses, we introduced the ORF7 genes containing a mutated B or D region in our infectious clone pABV437. This resulted in pABVS27-533, containing a mutated B site (amino acids 25-30), pABV537-539 containing a mutated D domain (amino acids 51-67), and pABV512-515 containing a mutated D domain (amino acids 80-90) (FIG. 1). When RNA of these full length clones was transfected to BHK-21 cells, these cells stained positive with N-specific MAbs at 24 h after transfection. As expected, the N protein expressed by pABV527-533 was recognized by A-, C-, and D-specific MAbs, but not by B-specific MAbs. On the other hand the N protein expressed by pABV537-539 and pABV512-515 was recognized by A-, B-, and C-specific MAbs but not by D-specific MAbs. The staining of cells transfected with the RNA derived from pABVS27-533 , pABV537-539 and pABV512-515 with MAbs directed against GP 3 , GP 4 , and M, was similar to that observed in transfections with RNA derived from wild type pABV437. This suggested that RNA replication and subgenomic mRNA synthesis were not affected by the mutations. When the supernatant of the cells transfected with RNA derived from pABV527-533, pABV537-539 and pABV512-515 was transferred to PAMs, cpe was not produced. Most likely, the mutations in the B and D region destroyed the function of the N protein in the formation of a proper capsid structure.
[0070] Since the mutation of 4 amino acids in domain B and 5 or 9 amino acids in domain D did not allow the generation of infectious particles we then created a more subtle mutation of 1 amino acid in the D region. We introduced an Asp-62 to Tyr mutation in the N-protein in the infectious clone of PRRSV. The amino acid Asp-62 in the PRRSV N protein was mutated to Tyr by PCR directed mutagenesis and transferred to pABV437, resulting in pABV600. RNA transcribed from pABV600 was tranfected to BHK-21 cells. These cells stained positive with MAbs directed against GP 3 , GP 4 , M and N. At 24 h after transfection, suggesting that the RNA was replicated and subgenomic mRNAs were synthesized. When the supernatant of the BHK-21 cells transfected with transcripts from pABV600 was transferred to PAMs, cpe was detected at 2-3 days after inoculation. The infected cells stained positive with PRRSV specific MAbs, which further confirmed that infectious virus was produced. Therefore, the mutation of Asp-62 to Tyr in the N protein is tolerated in the virus and does not destroy the function of the N protein. The mutant virus VABV600 was further typed with a panel of N-specific MAbs (Table 2). Not only the binding of D-specific MAb SDOW17, but also the binding of D-specific MAbs 130.2, 130.4, 131.7, and 131.9 and WBE1 to vABV600 was greatly reduced. If hybridoma culture supernatant of these MAbs was diluted to 0.3-0.5 μg IgG/ml bright staining was observed for wild type PRRSV, but no staining could be observed for vABV600. However, when the IgG of MAbs 130.2, 130.4, 131.7, and 131.9 was purified and used more concentrated (10 μg IgG/ml) faint staining was observed. Staining of vABV600 with A- and B-specific MAbs was comparable to PRRSV. These data indicated that we have created a virus that is antigenically different from wild type PRRSV or North American PRRS viruses.
[0071] 3: Identification of Replication Signals at the 3′ End of the PRRSV Genome
[0072] In order to determine cis-acting sequences that are essential signals for RNA replication (plus and/or minus strand synthesis and/or subgenomic mRNA synthesis), several deletions were made in the infectious cDNA clone and transcripts derived from these deletion mutants were analysed for replication in BHK-21 cells. When transcripts from pABVS21, lacking the entire ORF7 gene were transfected to BHK-21 cells, the expression of the N-protein could not be detected in IPMA (FIG. 2). Interestingly, these transcripts were also defective in the expression of other structural proteins, such as GP 3 , GP 4 and M. This indicated that these RNAs were not replicated and did not produce subgenomic RNAs. On the other hand, the deletion of ORF2, ORF3, ORF4, ORF5 and the 5′ end ORF6 from the infectious copy (pABV594) resulted in viral RNA that was still capable of replication. Therefore, replication signals are present in the coding region of ORF7 and not in the coding region of ORF's 2-6. To test this and further locate the regions involved in replication, mutants containing smaller deletions in ORF7 were constructed. The transcripts of these constructs were tested for their ability to replicate by detecting the expression of PRRSV proteins in IPMA of transfected BHK-cells (FIG. 2). From these results, it could be concluded that essential signals for replication of the PRRSV genome are present between nucleotides 14643 to 14687. Viral RNAs lacking this region were defective in replication.
[0073] 4. Analysis of Full Length cDNA Clone pABV575 Lacking the NdeI Site in ORF6
[0074] A full length cDNA clone, pABV575, was created that had a unique NdeI site at position 12559 due to mutation of the second NdeI site at position 14265 by PCR. RNA was produced from pABV575 and transfected to BHK-21 cells together with RNA from its parent clone pABV437. At 24 h after transfection with pABV575 RNA and pABV437 RNA an equal number of cells stained positive in IPMA with M-specific and N-specific MAbs (FIG. 3). Furthermore, the intensity of the staining was similar. However, when the supernatant of the transfected BHK-21 cells was transferred to PAMs and incubated for 24 h, the number of cells infected by vABV575 was much lower than that observed for vABV437. Furthermore, the cpe developed much slower in the PAMs inoculated with vABV575 than with vABV437. Although the replication of the RNA and synthesis of the subgenomic RNAs of vABV575 in BHK-21 appeared to be at the wild type level, the virus that is produced was less infectious for macrophages. This was most likely due to the amino acid mutation in the M protein (Thr→Asn) that resulted from the destruction of the NdeI site at position 14265.
[0075] 5: Introduction of an HA-Tag in the Infectious Clone of PRRSV
[0076] An epitope of the haemagglutinin of influenza A (HA-tag; Kolodziej et al., 1991) was expressed by different recombinant PRRSV viruses. The HA epitope was chosen as foreign antigen for expression in PRRSV mainly for two reasons; First, the tag has a limited size (27 nucleotides), which reduces the chance to disturb the replication of the virus or the expression or function of the protein to which it is fused. Second, antibodies to detect the expression of this epitope are available. The HA-tag was introduced at the 5′ end of ORF7 (pABV525), and at the 3′ end of ORF7 (pABV526; FIG. 4) as such that it did not induce mutations in other ORFs. We expected to get high expression of the foreign antigen by inserting it in the ORF7 gene, because subgenomic messenger RNA7(encoding ORF7) is most abundantly produced in infected cells. Since we could not predict the influence of the HA-epitope on the function and the structure of the N protein, we created an additional in frame insertion of the 16-amino acid self-cleaving 2A protease of foot-and-mouth disease virus (FMDV; Percy et al., 1994). This protease was introduced downstream of the HA-tag at the 5′ end of ORF7, which resulted in clone pABV523 (FIG. 4). We expected that this would result in the expression of a polyprotein, which could be proteolytically cleaved to release both the HA-tag and the N-protein.
[0077] 5. Analysis of Recombinants of PRRSV Expressing the HA Epitope
[0078] First, the expression of the structural proteins by the various transcripts from the recombinant full-length cDNA clones was tested in IPMA. BHK-21 cells, transfected with transcripts of pABV523, 525, and 526 stained positive with MAbs directed against GP 3 , GP 4 , the M protein, and the N protein, which indicated that these PRRSV proteins were properly expressed (FIG. 4). The cells also stained positive with a MAb directed against HA, indicating that the HA epitope was expressed by all three RNAs. Therefore, the HA-expressing transcripts replicated in BHK-21 cells. In addition, the N-protein to which the HA-tag was fused was still expressed by the mutant RNAs.
[0079] To examine whether the transcripts of pABV523, 525 and 526 were able to produce infectious virus, the culture supernatant of transfected BHK-21 cells was used to infect PAMs.
[0080] PAMs not only stained positive with MAbs directed against the PRRSV proteins GP 3 , GP 4 , M protein and N protein in IPMA, but also with MAb 12CA5 directed against the HA epitope. However, when PAMs were double stained, both with MAbs against the HA-tag and the N protein, we also detected PAMs which could only be stained with the MAb against the N protein but not with that against the HA-tag. For viruses derived from pABV525 and pABV526 the percentage of cells that stained only with N-specific Mabs was higher than for the viruses derived form pABV523, which contained the additional protease 2A. This indicated that the HA-tag directly attached to the N- or C-terminus of the N protein disturbed to some extent either the packaging of the viral RNA or the infectivity of the virus. However, when the protease 2A was introduced to cleave the HA-tag from the N protein by the protease 2A, the fitness of the resulting virus (vABV523) was not or hardly reduced (FIG. 4). The recombinant viruses were designated vABV523, vABV525 and vABV526.
[0081] Analysis of protease 2A activity in vABV523 The activity of the protease 2A was further analyzed by radioimmunoprecipitation. Besides a 15 kDa protein, an additional protein of approximately 18 kDa was immunoprecipitated with N-specific MAb 122.17 from cells transfected with transcripts of pABV523. The 15 kDa protein was similar in size to the wild type N protein; the 18 kDa protein resembled the expected size of the polyprotein of HA-protease 2A-N. These data indicated that protease 2A of FMDV is able to cleave the HA-protease 2A-N polyprotein in the cell, which results in the release of the HA-tag from the N protein.
[0082] 5.Growth Characteristics of HA-Expressing Viruses
[0083] The amount of virus produced by BKH-21 cells transfected with transcripts from pABV437 and pABV523 was generally higher than that produced by BHK-21 cells transfected with transcripts from pABV525 and pABV526.
[0084] Serial passage of HA-expressing viruses on PAMs resulted in stocks of vABV523, vABV525, and vABV526 with titers of approximately 10 7 TCID 50 /ml. It needs to be resolved whether the HA-expressing viruses have the same growth properties as the wild type virus of the infectious copy of PRRSV (vABV437). This will be studied in growth curves.
[0085] 5. Analysis of the Stability of HA-Expressing Viruses.
[0086] To determine the stability of HA-expressing viruses, viral RNA was examined at passage 4. For this purpose, RT-PCR was performed on isolated viral RNA. Part of the ORF7 gene, the site at which the HA-tag was inserted, was amplified by PCR and the obtained fragments were analyzed on agarose gel. We obtained two fragments for vABV523 and vABV525 and one fragment for vABV526. Sequence analysis of the most abundantly amplified fragment showed that vABV523 at passage 4 still contained the properly inserted nucleotide sequence encoding the HA-tag and the protease 2A gene. In contrast, both vABV525 and vABV526 had lost the inserted nucleotide sequence encoding the HA-tag.
[0087] 1. Mutation of Cys-27 and Cys-76 in the N Protein Inhibits the Production of Infectious Particles of PRRSV
[0088] In this study we have found that mutation of Cys-27→Asn and Cys-76→Leu in the N protein of PRRSV interferes with the production of infectious particles in BHK-21 cells. We conclude that these residues are essential for a proper structure or function or both of the N protein in virus assembly of PRRSV. The N protein is involved in the first steps in virus assembly, the binding of the viral genomic RNA and formation of the capsid structure. Since transcripts of genomic length cDNA clones containing the Cys-27→Asn and Cys-76→Leu replicated at the wild type level, the mutations in the Cys residues destroy the binding of the RNA by the N protein. Alternatively, they induce a different structure of the N protein that inhibits the formation of proper capsids. The defect in the encapsidation of the viral RNA genome can be complemented by wild type N protein transiently expressed or continuously expressed in a (BHK-21) cell line. In this way a virus is produced that is able to complete only one round of infection/replication. Therefore such a virus is considered to be a very safe vaccine for protection against PRRSV in pigs.
[0089] 2. Introduction of a Marker in the N Protein of PRRSV.
[0090] The aim of this study was to create mutant PRRS viruses that can be serologically differentiated from field virus and therefore may be promising mutants for marker vaccine development against PRRSV. The N protein was chosen as a first candidate for mutagenesis to create a virus with a serologic marker since many studies have shown that the N protein is the most antigenic protein of PRRSV. For example, pigs infected with PRRSV develop strong antibody responses against the N protein of PRRSV (Meulenberg et al., 1995). In addition, the N protein contains two antigenic regions designated B and D that are conserved in European and US PRRSV isolates and MAbs directed to these regions are available (Meulenberg. et al., 1998). Here, we have demonstrated that mutation of 4 amino acids in site B to corresponding amino acids of the EAV N protein and mutation of 5 or 9 amino acids in domain D to corresponding amino acids of the LDV N protein inhibited the production of infectious virus particles. Since RNA replication and subgenomic mRNA synthesis appeared to be at the wild type level, these mutations most likely prevented the formation of proper capsids by the N protein. However, mutagenesis of a single amino acid in the D region (Asp-62→Tyr) resulted in virus vABV600 that had a different MAb binding profile from PRRSV and all other PRRSV Viruses. vABV600 induces a different spectrum of antibodies in pigs, compared to these other PRRSV isolates. Therefore vABV600 can be differentiated from field virus on the basis of serum antibodies and is an excellent mutant for further development of marker vaccines against PRRSV.
[0091] 3: Elucidation of Replication Signals in ORF7 of Lelystad Virus
[0092] It has been shown for many positive strand RNA viruses that their 5′ and/or 3′ noncoding regions contain essential signals that control the initiation of plus- and minus-strand RNA synthesis. It was not yet determined for PRRSV whether these sequences alone are sufficient for replication. The production of an infectious clone allowed us to analyse replication signals in the genome of PRRSV. In this study we have mapped cis-acting sequence elements required for replication by introducing deletions in the infectious clone. We have shown that transcripts derived from cDNA clones lacking the ORF7 gene are not replicated. A more systematic deletion analysis showed that a region of 44 nucleotides between nucleotides 14644 to 14687 in the ORF7 gene was important for replication of RNA of PRRSV. This was an essential interesting finding, since the sequences essential for replication of most positive strand RNA viruses are present in the 5′ and 3′ noncoding regions. It is also an important finding for studies who's aim is to develop viral replicons which can only be rescued in complementing cell lines expressing the deleted ORFs. The minimal sequence requirements for these RNAs are 5′ noncoding region-ORF1a-ORF1b-ORF7-3′ noncoding region. Viral RNA s or replicons containing these sequence elements supplemented with a selection of fragments from other PRRSV open reading frames or fragments of open reading frames expressing antigens of other (heterologous) pathogens can be packaged into virus particles when the proteins essential for virus assembly are supplied in trans. When these particles are given to pigs, for example as vaccine, they will enter specific host cells such as macrophages and virus- or heterologous antigens are expressed and induce immune responses because of the replicating RNA. However, since the RNA does not express (all) the proteins required for packaging and the production of new particles, the replicon can not spread further, creating an extremely efficient, but safe and not-spreading recombinant vaccine effective against PRRSV and/or heterologous pathogens.
[0093] 4. Production of an Attenuated PRRSV Virus by Deletion of the NdeI Site in ORF6.
[0094] In this study we have produced a mutant PRRS virus vABV575 that had different growth characteristics in PAMs compared to the parent strain vABV437. Whereas no difference in the expression of structural proteins in BHK-21 cells by RNAs of vABV575 or vABV437 was observed, the vABV575 virus produced in BHK-21 cells infected PAMs slower than vABV437. The growth kinetics of vABV575 need to be analyzed further by performing growth curves in PAMs. In the cDNA clone pABV575, that was used to produce vABV575, the NdeI site at position 14265 in ORF6 was mutated. This resulted in an amino acid change of Thr-59->Asn in the M protein. The mutated M protein was still bound by M-specific MAb 126.3. The M protein is the most conserved structural protein among arteriviruses and coronaviruses. The protein is an integral membrane protein containing three N-terminal hydrophobic membrane spanning domains (Rottier, 1995). The protein spans the membrane three times leaving a short N-terminal domain outside the virion and a short C-terminal domain inside the virion. The M protein of coronaviruses was shown to play an important role in virus assembly (Vennema et al., 1996). The Thr-59→Asn mutation is located between the second and third membrane spanning fragment of M in AB575. This mutation influences virus assembly, the stability of the virus, or virus entry in the PAMs.
[0095] 5. Expression of the HA Epitope in Recombinant PRRSV viruses
[0096] In this study we have successfully used PRRSV as a vector for the expression of a foreign antigen, an HA epitope of the haemagglutinin of influenza A virus. Recombinant PRRSV viruses were engineered that produced the HA tag fused to the N- or C- terminus of the N protein. In addition, a PRRSV mutant was created that contained the HA-tag as well as the protease 2A of FMDV fused to the N terminus of the N protein. The protease 2A was functionally active in the context of the PRRSV virus, and cleaved the HA-tag from the N protein. This resulted in an N protein that is identical to the wild type N protein, except for the first and second amino acids (Met and Ala) that are lacking in the mutant. Genetic analysis of passage 4 of the recombinant viruses indicated that the mutant virus containing both the HA-tag and the protease 2A was more stable than the mutant viruses expressing the HA-N-fusion proteins. Apparently, the lack of the first methionine? and mutation of the second amino acid at the N-terminus of N is better tolerated by the virus than the addition of the HA-tag of 9 amino acids to the N- or C-terminus of N. Further genetic and functional analysis needs to be done to explain the differences in stability observed for these viruses. In addition, pigs need to be infected with these HA-expressing mutants to determine whether antibody responses are induced against the HA epitope.
[0097] The ORF7 gene was selected for insertion of the HA-tag mainly for two reasons; (I) The subgenomic RNA7 expressing this gene is the most abundant subgenomic RNA produced in infected cells and (II) the HA-tag could be inserted without mutating other ORFs since ORF7 has very little overlap with ORF6 at the 5′ end and no overlap with other ORFs at the 3′ end. However, similar constructs can be made by introducing the HA-tag and protease 2A at the 5′ end of ORP2 and at the 5′ end of ORF5 without affecting other ORFs.
[0098] The successful expression of the HA-tag in combination with the protease 2A at the 5′ end of ORF7 creates new opportunities to express other foreign antigens such as the E2 protein of hog cholera virus, or B cell epitopes of parvo virus by PRRSV. Since PRRSV specifically infects macrophages, cells of the immune system that have antigen presentation and processing capacities, PRRSV might be an excellent vector for the expression of antigens and induction of immunity to these antigens in the pig.
LEGENDS TO THE FIGURES
[0099] [0099]FIG. 1. Properties of full length cDNA clones of PRRSV containing mutations in the ORF7 gene. The mutated ORF7 genes were inserted in infectious cDNA clone pABV437 with the unique HpaI and PacI site that are indicated. The plasmid (pABV) numbers of the resulting constructs are shown. RNA replication was determined by detecting the expression of structural proteins in IPMA after transfection of the transcripts of the full length cDNA clones in BHK-21 cells. N protein production was determined in IPMA or immunoprecipitation. Production of infectious virus was established by transfer of the supernatant of transfected BHK-21 cells to PAMs and detection of cpe.
[0100] [0100]FIG. 2. Properties of full length cDNA clones of PRRSV containing deletions in the region encoding the structural proteins of LV in order to elucidate the presence of replication signals in this region. The deleted regions (dotted bars), the regions of ORF7 still present (dark bars) and the plasmid (pABV) numbers of the resulting clones are shown. RNA replication was determined by detecting the expression of structural proteins, and the expression of the N-protein in particular, both in IPMA. Production of infectious virus was established by infecting PAMs with the supernatant of transfected BHK-21 cells. IPMA was performed to detect the expression of LV-proteins.
[0101] [0101]FIG. 3. Properties of infectious cDNA clone pABV575. This clone was constructed by mutation of the NdeI site at position 14265 in ORF6. RNA replication was determined by detecting the expression of structural proteins in IPMA after transfection of the transcripts of the full length cDNA clones in BHK-21 cells. Production of infectious virus was established by transfer of the supernatant of transfected BHK-21 cells to PAMs and detection of cpe.
[0102] [0102]FIG. 4. Introduction of an antigenic marker in the infectious clone of PRRSV. The insertion of the HA tag and protease 2A sequence in plasmids pABV 525, 523 and 526 is indicated. RNA replication was determined by detecting the expression of structural proteins in IPMA after transfection of the transcripts of the full length cDNA clones. The expression of N and HA was also determined in IPMA. Production of infectious virus was established by transfer of the supernatant of transfected BHK-21 cells to PAMS and detection of cpe.
References
[0103] 1. Liljeström, P. and Garoff, H. (1991). A new generation of animal cell expression vectors based on the Semliki Forest virus replicon. Biotechnol. 9, 1356-1361.
[0104] 2. Kolodziej, P. A. and Young, R. A. Epitope tagging and protein surveillance. 1991. Methods Enzymol. 194, 508-519
[0105] 3. Meulenberg, J. J. M., Bende, R. J., Pol, J. M., Wensvoort, G., and Moormann, R. J. M. (1995). Nucleocapsid protein N of Lelystad virus: expression by recombinant baculovirus, immunological properties, and suitability for detection of serum antibodies. Clin. Diagn. Laboratory Immunol. 2, 652-656.
[0106] 4. Meulenberg, J. J. M., Hulst, M. M., de Meijer, E. J., Moonen, P. L. J. M., den Besten, A., de Kluyver, E. P., Wensvoort, G., and Moormann, R. J. M. (1993). Lelystad virus, the causative agent of porcine epidemic abortion and respiratory syndrome (PEARS) is related to LDV and EAV. Virology 192, 62-74.
[0107] 5. Meulenberg, J. J. M., and Petersen-den Besten, A. (1996). Identification and characterization of a sixth structural protein of Lelystad virus: The glycoprotein GP 2 encoded by ORF2 is incorporated in virus particles. Virology 225, 44-51.
[0108] 6. Meulenberg, J. J. M., Bos-de Ruijter, J. N. A, van de Graaf, R., and Wensvoort, G., and R. J. M. Moormann. (1998) Infectious transcripts from cloned genome-length cDNA of porcine reproductive and respiratory syndrome virus. J. of Virology 72, 380-387.
[0109] 7. Meulenberg, J. J. M., van Nieuwstadt, A. P., van Essen-Zandbergen, A., Bos-de Ruijter, J. N. A., Langeveld, J. P. M., and Meloen, R. H. (1998) Localization and fine mapping of antigenic sites on the nucleocapsid protein N of porcine reproductive and respiratory syndrome virus with monoclonal antibodies. Virology, 252, 106-114.
[0110] 8. Murtaugh, M. P., Elam, M. R., and Kakach, L. T., (1995). Comparison of the structural protein coding sequences of the VR-2332 and Lelystad virus strains of the PRRS virus. Arch. Virol. 140, 1451-1460.
[0111] 9. Percy, N., Barclay, W. S., Garcia-Sastre, A. and Palese, P. Expression of a foreign protein by influenza A virus. 1994 . J. Virol. 68: 4486-4492
[0112] 10. Rottier, P. J. M. (1995) The coronavirus membrane protein, p. 115-139. In: S. D. Siddell (ed.), The coronaviridae. Plenum Press, New York, N.Y.
[0113] 11. Sambrook, J., Fritsch, E. F. and Maniatis, T. Molecular cloning a laboratory manual. 1989. 2nd edition, Cold Spring Harbor Laboratory, Cold Spring Harbor, N.Y.
[0114] 12. van Nieuwstadt, A. P., Meulenberg, J. J. M., van Essen-Zandbergen, A., Petersen-den Besten, A., Bende, R. J., Moormann, R. J. M., and Wensvoort, G. (1996). Proteins encoded by ORFs 3 and 4 of the genome of Lelystad virus (Arteriviridae) are structural proteins of the virion. J. Virol. 70, 4767-4772.
[0115] 13. Wensvoort, G., Terpstra, C., Pol, J. M. A., Ter Laak, E. A., Bloemraad, M., de Kluyver, E. P., Kragten, C., van Buiten, L., den Besten, A., Wagenaar, F., Broekhuijsen, J. M., Moonen, P. L. J. M., Zetstra, T., de Boer, E. A., Tibben, H. J., de Jong, M. F., van't Veld, P., Groenland, G. J. R., van Gennep, J. A., Voets, M. Th., Verheijden, J. H. M., and Braamskamp, J. (1991). Mystery swine disease in the Netherlands: the isolation of Lelystad virus. Vet. Quart. 13, 121-130.
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TABLE 1 Primers used in PCR-mutagenesis and sequencing Sense (+) Primer (nt.) Sequence primer a antisense(-) Purpose LV97 5′CATTGCACCCAGCAACGGTTCAGTTGT 3′ − Cys-27→Asn LV100 5′CGTCTGGATCGATTGCAAGAGGAGGGA 3′ − Cys-76→Leu LV188 5′TCTGGATCGATTGCAAGCAGAGGGAGCGTTCAGTCTGGG − Asp-62→Tyr TGAGGTGGTGCCGGATGTCATATTCAGCAG 3′ LV27 5′GATTGGATCCAACACATCATTCGAGCTG 3′ + Δ Ndel LV182 5′GGATTGAAAATGCAATTAATTCATGTAT 3′ − Δ Ndel 118U250 (14755) 5′CAGCCAGGGGAAAATGTGGC 3′ − Sequencing LV37 (14340) 5′GATTGGATCCACCATGGAGTCATGGAAGTTTATCACT 3′ + Sequencing LV75 (15088) 5′TCTAGGAATTCTAGACGATCG 3′ − Sequencing LV76 (15088) 5′TCTAGGAATTCTAGACGATCG(T) 40 3′ − RT-PCR LV82 (14703) 5′AGCAACCTAGGGGAGGACAG 3′ + Sequencing LV108 (14566) 5′GGAGTG GTTAA CCTCGTCAAGTATGGCCGGTAAAAACCAGAGCC 3′ + ORF7-HA LV112 (14958) 5′CCATTCACCTGACTG TTTAATTAA CTTGCACCCTGA 3′ − Pacl site LV139 (14609) 5′AACTTTGACCTTCTCAAGTTGGCCGGCGACGTCGAGTCCAA + 1 st HA-prot-ORF7 CCCAGGGCCCGGTAAAAACCAGAGCCAGAA 3′ LV140 (14609) 5′GAGTG GTTAAC CTCGTCAAGTATGGCCGGTAAATACCCATACGAT + 2 nd HA-prot-ORF7 GTTCCAGATTACGCT0AACTTTGACCTTCT 3′ LV188 (14687) 5′ACGTGC GTTAAC TAAGGTGCAATGATAAAGTCCCA 3′ + Δ 99 nt. 5′ORF7 LV189 (14796) 5′ACGTGC GTTAAC TAAATCCGGCACCACCTCACCCA 3′ + Δ 198 nt. 5′ORF7 LV190 (14885) 5′ACGTGC GTTAAC TAAGGGAAGGTCAGTTTTCAGGT 3′ + Δ 297 nt. 5′ORF7 LV191 (14936) 5′ACGTGC GTTAAC TAACGCCTGATTCGCGTGACTTC 3′ + Δ 348 nt. 5′ORF7 LV192 (14609) 5′AAATACCCATACGATGTTCCAGATTACGCTAACCAGAGCCA 3′ + 1 st HA-ORF7 LV193 (14609) 5′AGTG GTTAAC CTCGTCAAGTATGGCCGGTAAA TACCCATACG 3′ = 2 nd HA-ORF7 LV194 (14971) 5′ACTGT TTAATTAA GCGTAATCTGGAACATCGTA − ORF7-HA TGGGTAACTTGCACCCTG 3′ LV195 (14642) 5′ACGTGC GTTAAC TAACCGATGGGGAATGGCCAG 3′ + Δ 55 nt 5′ORF7 LV196 (14642) 5′GGAGTG GTTAAC CTCGTCAAGTAACCGATGGGGAATGGCCAG 3′ + Δ 45 nt 5′ORF7 LV197 (14597) 5′ACGTGC GTTAAC GGCCGGTAAAAACCAGAGC 3′ + Δ 10 nt 3′ORF6 LV198 (141333) 5′GCTCGT GCTAGC CTTTAGCATCACATACAC 3′ + Δ 54 nt 3′ORF6 LV199 (14596) 5′CTTGACGA GGTTAAC TGGTACTAGAGTGCC 3′ − Δ 54 nt 3′ORF6
[0118] [0118] TABLE 2 Staining of LV4.2.1, vABV600 (Asp-62→Tyr mutation), ATCCVR2332-like PRRSV containing an Asp61→ Tyr mutation in the N protein, and ATCC-VR2332 with various N-specific MAbs in IPMA vABV600 ATCCVR2332- (Asp-62→ like (Asp61→ MAb Site LV4.2.1 Tyr) Tyr) ATCC-VR2332 138.22 A + + − − NS99 B + + + + 122.17 D ++ ++ ++ ++ 130.2 D ++ − 1) − + 130.4 D ++ − 1) − + 131.7 D ++ − 1) − + 131.9 D ++ − 1) − + SDOW17 D ++ − 1) − 1) ++ WBE1 D + − − − WBE4 D ++ ++ − − WBE5 D ++ ++ − − WBE6 D ++ ++ − − VO17 ? − − + +
[0119] [0119]
1
29
1
6
PRT
Porcine reproductive and respiratory syndrome virus
1
Gln Leu Cys Gln Leu Leu
1 5
2
17
PRT
Porcine reproductive and respiratory virus
2
Pro Glu Lys Pro His Phe Pro Leu Ala Ala Glu Asp Asp Ile Arg His
1 5 10 15
His
3
11
PRT
Porcine reproductive and respiratory virus
3
Ile Ser Thr Ala Phe Asn Gln Gly Ala Gly Thr
1 5 10
4
26
DNA
Artificial Sequence
PCR Primer
4
cattgcaccc agaactggtt cagttg 26
5
27
DNA
Artificial Sequence
PCR Primer
5
cgtctggatc gattgcaaga ggaggga 27
6
69
DNA
Artificial Sequence
PCR Primer
6
tctggatcga ttgcaagcag agggagcgtt cagtctgggt gaggtggtgc cggatgtcat 60
attcagcag 69
7
28
DNA
Artificial Sequence
PCR Primer
7
gattggatcc aacacatcat tcgagctg 28
8
28
DNA
Artificial Sequence
PCR Primer
8
ggattgaaaa tgcaattaat tcatgtat 28
9
20
DNA
Artificial Sequence
PCR Primer
9
cagccagggg aaaatgtggc 20
10
37
DNA
Artificial Sequence
PCR Primer
10
gattggatcc accatggagt catggaagtt tatcact 37
11
21
DNA
Artificial Sequence
PCR Primer
11
tctaggaatt ctagacgatc g 21
12
22
DNA
Artificial Sequence
PCR Primer
12
tctaggaatt ctagacgatc gt 22
13
20
DNA
Artificial Sequence
PCR Primer
13
agcaacctag gggaggacag 20
14
44
DNA
Artificial Sequence
PCR Primer
14
ggagtggtta acctcgtcaa gtatggccgg taaaaaccag agcc 44
15
36
DNA
Artificial Sequence
PCR Primer
15
ccattcacct gactgtttaa ttaacttgca ccctga 36
16
72
DNA
Artificial Sequence
PCR Primer
16
aactttgacc ttctcaagtt ggccggcgac gtcgagtcca acccagggcc cggtaaaaac 60
cagagccaga ag 72
17
75
DNA
Artificial Sequence
PCR Primer
17
gagtggttaa cctcgtcaag tatggccggt aaatacccat acgatgttcc agattacgct 60
aactttgacc ttctc 75
18
35
DNA
Artificial Sequence
PCR Primer
18
acgtgcgtta actaaggtgc aatgataaag tccca 35
19
35
DNA
Artificial Sequence
PCR Primer
19
acgtgcgtta actaaatccg gcaccacctc accca 35
20
35
DNA
Artificial Sequence
PCR Primer
20
acgtgcgtta actaagggaa ggtcagtttt caggt 35
21
35
DNA
Artificial Sequence
PCR Primer
21
acgtgcgtta actaacgcct gattcgcgtg acttc 35
22
41
DNA
Artificial Sequence
PCR Primer
22
aaatacccat acgatgttcc agattacgct aaccagagcc a 41
23
42
DNA
Artificial Sequence
PCR Primer
23
agtggttaac ctcgtcaagt atggccggta aatacccata cg 42
24
51
DNA
Artificial Sequence
PCR Primer
24
actgtttaat taagcgtaat ctggaacatc gtatgggtaa cttgcaccct g 51
25
33
DNA
Artificial Sequence
PCR Primer
25
acgtgcgtta actaaccgat ggggaatggc cag 33
26
42
DNA
Artificial Sequence
PCR Primer
26
ggagtggtta acctcgtcaa gtaaccgatg gggaatggcc ag 42
27
31
DNA
Artificial Sequence
PCR Primer
27
acgtgcgtta acggccggta aaaaccagag c 31
28
30
DNA
Artificial Sequence
PCR Primer
28
gctcgtgcta gcctttagca tcacatacac 30
29
30
DNA
Artificial Sequence
PCR Primer
29
cttgacgagg ttaactggta ctagagtgcc 30 | The invention relates to the field of PRRS viruses and infectious clones obtained from PRRS viruses. Furthermore, the invention relates to vaccines and diagnostic assays obtainable by using and modifying such infectious clones of PRRS viruses. The invention provides a porcine reproductive and respiratory syndrom virus (PRRSV) replicon having at least some of its original PRRSV nucleic acid deleted, said replicon capable of in vivo RNA replication, said replicon further having been deprived of at least some of its original PRRSV nucleic acid and/or having been supplemented with nucleic acid derived from a heterologous microorganism. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a Divisional of U.S. application Ser. No. 11/529,400, filed Sep. 29, 2006, now U.S. Pat. No. 7,538,208, which is a Divisional of U.S. application Ser. No. 10/813,908, filed Mar. 26, 2004, now U.S. Pat. No. 7,232,569, which is a Continuation of U.S. application Ser. No. 10/416,902, filed May 15, 2003, now abandoned, which is a 371 of International Application No. PCT/CA01/01589, filed Nov. 15, 2001, which claims the benefit of U.S. Provisional Application No. 60/248,864, filed Nov. 15, 2000, each of which is herein incorporated by reference in its entirety.
FIELD OF THE INVENTION
This invention relates to bacterial secretion systems, and in particular to a newly identified and characterized type III secretion system in Aeromonas salmonicida . The invention also encompasses the use of components of the novel secretion system in immunoprotection against A. salmonicida infection, as well as other diagnostic and therapeutic uses thereof.
BACKGROUND OF THE INVENTION
Various publications are referenced throughout this publication, and full citations for each of these publications are provided at the end of the Detailed Description.
Aeromonas salmonicida , a Gram-negative, facultatively anaerobic, non-motile, rod shaped bacterium, growing at temperatures around 20° C., is the etiological agent of furunculoses in salmonids, causing most severe economic losses in production farms of salmon and trout. The disease is characterized in the sub-acute or chronic form by the presence of haemorrhagic necrotic lesions in the gills, gut and muscle, while in the acute form fish die apparently from toxaemia without showing particular external signs.
Due to the high contagiousity of the disease and the high mortality in salmon of all ages, particularly in the sea water growers, large amounts of antibiotics are used in closed and open waters for therapy of furunculoses (Munro and Hastings, 1993). Vaccination has become an important strategy to control furunculoses in fish farms (Ellis, 1997). However, the currently applied whole cell antigen vaccines seem to show considerable variability in efficacy, the origin of which remains currently unexplained (Thornton et al., 1993).
Knowledge of the mechanisms of pathogenicity of A. salmonicida , and in particular of the main virulence factors involved, is essential in the development of efficient strategies to prevent outbreaks of furunculoses caused by A. salmonicida . Currently, several potential virulence factors of A. salmonicida have been reported, including a surface-layer protein (Chu et al., 1991), the hemolysins ASH1, ASH3, ASH4 (Hirono and Aoki, 1993), salmolysin (Titball and Munn, 1985), the serine protease AspA (Whitby et al., 1992) and the glycerolipid-cholesterol acyltransferase (GCAT) (Lee and Ellis, 1990), but their role in pathogenesis is unclear and many of them seem not to play a primary role in virulence. This was demonstrated by A. salmonicida strains with deletion mutants of the GCAT and aspA genes which had no influence on virulence of the strains in inducing furunculoses.
SUMMARY OF THE INVENTION
A new ADP-ribosylating toxin named AexT ( Aeromonas exoenzyme T) encoded by the gene aexT was identified in a virulent strain of A. salmonicida. A. salmonicida strains that were propagated for several passages on culture medium had lost expression of AexT, but still retained the aexT gene. AexT shows amino acid sequence similarity to the ADP-ribosyltransferase toxins ExoS and ExoT of Pseudomonas aeruginosa which are secreted by a type III-dependent secretion mechanism (Yahr et al., 1996). Regulation of aexT was shown to be dependent on contact with fish cells and could also be induced by Ca 2+ depletion of the medium. The aexT gene was found to be preceded by a consensus sequence for binding of a transcriptional activator known in P. aeruginosa as ExsA which is involved in type III mediated gene expression (Frank, 1997).
Based on these observations, we used broad range gene probes to identify in A. salmonicida a novel type III secretion system by means of the gene acrD (Aeromonas calcium response D) encoding a transmembrane spanning protein. The acrD gene has a high similarity to IcrD, a protein of the Yersinia sp. which is an inner membrane protein of the type III secretion apparatus in Yersinia sp. The acrD gene is flanked by further typical type III secretion genes which were designated acr1, acr2, acr3, acr4, acrD, acrR, acrG, acrV, and acrH, and which show significant similarity to pcr1, pcr2, pcr3, pcr4, pcrD, pcrR, pcrG, pcrV, and pcrH of Pseudomonas aeruginosa and to tyeA, sycN, yscX, yscY, lcrD, lcrR, lcrG, IcrV, and IcrH of Yersinia enterocolitica . All these genes play a predominant role in building up the type III secretion apparatus in the respective bacterium, including the regulation of the low calcium response (LCR) and chaperon functions. The genes isolated from A. salmonicida belong to the analogue of the virA operon, which is central in the type III secretion pathway of many Gram-negative pathogens of human, animals and plants (Fenselau et al., 1992; Gough et al., 1992; Michiels and Cornelis, 1991).
We have also determined that the type III secretion system in A. salmonicida is located on a 84 kb plasmid which is rapidly lost upon growth in culture medium. Biosynthesis of AcrV in A. salmonicida , the analogue to LcrV in Yersinia , requires as a trigger either low Ca 2+ conditions or contact with fish cells. Upon infection with A. salmonicida expressing AcrV, the cultured cells undergo significant morphological changes. Cultures derived from originally virulent A. salmonicida strains, which had lost the type III secretion genes including AcrV, lost virulence as they did not affect rainbow trout gonad cells morphologically after infection. Concomitantly to loss of the type III secretion genes, these cultures lost the expression of the aexT gene which specifies the ADP-ribosylating toxin of A. salmonicida.
Rainbow trout gonad cells infected with the virulent A. salmonicida and incubated in antiserum directed against recombinant AcrV-His protein could be protected from the toxic effect and showed only weak morphological changes. AcrV, which belongs to the type III secretion proteins is a determinative factor involved in virulence mechanisms of A. salmonicida , and is expected to provide new insights into basic mechanisms of pathogenicity of bacterial species. The components of the type III secretion system of A. salmonicida may be used as antigens for the development of sub-unit vaccines against infection of fish by A. salmonicida.
In one embodiment, the invention comprises an isolated 5.7 kb nucleic acid segment (SEQ ID NO:10) containing the type III secretion genes of A. salmonicida . In another embodiment, the invention comprises a nucleic acid segment that encodes protein having the amino acid sequence of SEQ ID NOS:1, 2, 3, 4, 5, 6, 7, 8, and 9, including variants that retain either biological activity or immunogenicity or both. Due to the degeneracy of the genetic code and the possible presence of flanking nucleic acid fragments outside of the coding regions, it will be understood that many different nucleic acid sequences may encode the amino acid sequence of SEQ ID NO NOS:1, 2, 3, 4, 5, 6, 7, 8, or 9, and variants, and that all such sequences would be encompassed within the scope of the present invention.
In a further embodiment, the invention relates to the use of AcrV as an immunogen, and to the use of AcrV in a recombinant or traditional vaccine to reduce the incidence of infection by A. salmonicida.
In another embodiment, the invention provides a means of diagnosing A. salmonicida , or other bacteria found to contain AcrV homologues, by the detection of the AcrV protein or the homologous proteins.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a genetic map of the type III secretion genes found in A. salmonicida . Boxes with arrowheads indicate open reading frames (ORFs). The size of the different genes (in kilobases) is shown by the scale bar. A restriction map containing restriction enzymes SacI, PstI, NotI, BamHI, and SalI is shown. Abbreviation used: acr, Aeromonas calcium response.
FIG. 2 is a segregation curve of A. salmonicida JF2267. An A. salmonicida JF2267 LB-culture was first incubated 2½ hrs at 19° C. and then at 22° C. for 7 hrs. Colony-blotting was performed to analyze the LB-culture at 10 different time points for positive, respectively negative colonies.
FIG. 3 shows a pulsed-field gel electrophoresis of A. salmonicida strain JF2267, and strain JF2397. (Lane 1) JF2267, undigested. (Lane 2) JF2397, undigested. (Lane 3) JF2267 digested with NotI. (Lane 4) JF2397 digested with NotI. (Lane 5) Low Range PFG Marker (New England Biolabs).
FIG. 4 shows infection of fish cells with A. salmonicida ATCC 33658 T , JF2267, and JF2397. RTG-2 cells infected with JF2267 (A), ATCC 33658 T (B), JF2397 (C), and pure PBS (D). RTG-2 cells infected with JF2267 and monospecific polyclonal antibodies against AcrV were protected (E), whereas RTG-2 cells infected with JF2267 and anti-AcrV preserum (F) were not. Pictures were taken 24 hrs after infection, respectively 21 hrs after the protection assay under a phase contrast microscope.
FIG. 5 shows low Ca 2+ response induced AcrV expression in A. salmonicida JF2267. The picture shows an immunoblot reacted with specific rabbit anti-AcrV antiserum. Strains ATCC33658 T (lane 2), JF2267 (lane 3) and JF2397 (lane 4) were grown in Ca 2+ depleted medium, harvested by centrifugation and analyzed on 15% SDS PAGE followed by immunoblotting. Lane 1 contains purified recombinant AcrV-His protein as a control.
DETAILED DESCRIPTION
A 5.7 kb segment containing type III secretion genes of A. salmonicida that were cloned and sequenced correspond to the per locus (Pseudomonas calcium response) of Pseudomonas aeruginosa (Frank, 1997; Yahr et al., 1997b) and the virA operon and genes of the following operon of Yersinia enterocolitica (Cheng and Schneewind, 2000; Iriarte and Cornelis, 1999; Plano et al., 1991; Skrzypek and Straley, 1993; Motin et al., 1994; Price and Straley, 1989) and other Gram-negative animal and plant pathogens (Fenselau et al., 1992; Gough et al., 1992; Michiels and Cornelis, 1991). The most conserved gene at this locus was revealed to be the acrD gene encoding the AcrD protein, which showed 82% identical aa to the transmembrane spanning core proteins LcrD of the injectisome of the Y. enterocolitica type III secretion apparatus and PcrD of the injectisome of the P. aeruginosa type III secretion apparatus (Yahr et al., 1997b; Plano et al., 1991). Due to this high similarity, we conclude AcrD to have the analogous functions in the injectisome of the A. salmonicida type III secretion pathway.
The least conserved protein encoded on the cloned and analyzed segment is AcrV, which shows only 35% identical aa to PcrV of P. aeruginosa and 37% identity to LcrV of Y. enterocolitica . The main role of LcrV and PcrV, and accordingly also of AcrV, is assumed to be involved in sensing the bacterium-host interactions (Sawa et al., 1999; Bergman et al., 1991). We therefore interpret the significantly higher dissimilarity between AcrV and LcrV or PcrV, compared to the other gene products of the type III secretion locus (Table 3), to be due to the host specificity which seems to be determined by AcrV, LcrV or PcrV.
Our analyses revealed the A. salmonicida type III secretion genes to be located on a plasmid of 84 kb. The plasmid was shown to be lost very easily in standard growth media, in particular after a slight raise in growth temperature. Concomitant to the loss of the type III genes in A. salmonicida , we detected the loss in virulence of the strain as measured by the infection of RTG-2 fish cell cultures, as well as the loss of production of ADP-ribosylating toxin aexT in supernatants and bacterial cell pellets of low Ca 2+ response induced A. salmonicida cultures. It is also noted that AexT biosynthesis induced by contact of A. salmonicida with RTG-2 fish cells disappeared in those strains or subcultures that had lost the type III secretion genes. Expression of the aexT gene must therefore be regulated by a mechanism which is dependent on type III secretion genes. In this context it must be noted that several genes of the type III secretion pathway of Yersinia spp., in particular LcrV, are down regulated and secretion and production of effector proteins is completely blocked in the presence of millimolar amounts of Ca 2+ (Forsberg et al., 1987). It also became apparent from tissue culture infection models that the absence of Ca 2+ in vitro mimics a yet undefined signal that is received by Yersinia species when they are adherent to eukaryotic cells and that induce both type III secretion genes and effector molecules such as YopE and Yops (Cornelis, 1998).
The dependence of aexT expression on type III secretion mechanism was also indicated by the presence of a consensus sequence upstream the aexT toxin gene in A. salmonicida , which shows full homology to the binding site of a transcriptional activator, known in P. aeruginosa as ExsA, which is involved in type III dependent gene expression (Frank, 1997). The expression of aexT in A. salmonicida is thus dependent on a functional type III secretion mechanism. The lack of production of AexT as detected in the type strain of A. salmonicida ATCC33658 T as well as in the strain JF2397 which was derived from an originally virulent A. salmonicida strain, JF2267, in spite of the presence of a functional aexT gene, must therefore be due to the loss of the type III secretion pathway.
The AcrV protein of the novel type III secretion pathway of A. salmonicida plays an important role in pathogenesis by its role as a sensor and regulator of the system, as shown in other type III secretion systems. An important role in the secretion-related regulatory role in the low Ca 2+ response of Y. pestis is attributed to LcrV, which is localized to the bacterial surface and required for targeting of Yops of Y. pestis (Fields and Straley, 1999; Nilles et al., 1997). In addition, it was postulated that LcrV is also secreted by a special pathway which results its localization in the cytosol of infected cells but not the surrounding medium (Fields and Straley, 1999). Using a tissue cell model, it was shown that antiserum directed against LcrV prevented Y. pestis from injecting the Yop effector molecules into the host cells (Pettersson et al., 1999; Hueck, 1998). Active immunization of mice with recombinant LcrV antigen efficiently protected mice against challenge with Y. pestis (Leary et al., 1995). Our results showed that antibodies directed against recombinant AcrV, the analogous protein to LcrV, protected fish RTG-2 cells from damage caused by virulent A. salmonicida strain JF2267 and demonstrated that the AcrV plays an important role in type III secretion pathway mediated virulence of A. salmonicida.
The newly found type III secretion pathway plays a central role in pathogenicity of A. salmonicida via the secretion and direct injection of the ADP-ribosylating toxin AexT into the target cells. Loss of the type III secretion pathway, which is frequently observed, is due to the instability of a kb plasmid under culture conditions. Furthermore, loss of type III secretion genes such as acrD and acrV abolished expression of the aexT gene, and led to loss of virulence of A. salmonicida . As shown, surface exposed gene products of this type III secretion pathway, in particular AcrV, are potent candidates for new vaccines for the immune prophylaxis of fish against furunculosis.
The invention is further described by way of the following examples and results, which are not to be considered as limiting the scope of the invention. It will be appreciated by those skilled in the art, in light of this disclosure, that many changes can be made in the specific embodiments disclosed without departing from the scope of the invention.
EXAMPLES AND RESULTS
Materials and Methods
Bacterial Strains, Growth Conditions and Cloning Vectors:
A. salmonicida strains are listed in Table 1. A. salmonicida type strain ATCC 33658 T was purchased from the American Type Culture Collection. A. salmonicida strain JF2267 was freshly isolated from an arctic char ( Savelinus alpinus ) showing typical symptoms of furunculoses. A. salmonicida strain JF2397 was derived from strain JF2267 by repeated single colony isolations after each of nine passages propagated on LB agar medium at 22° C. for two days each passage. A. salmonicida strains were routinely cultured on blood agar plates (Trypticase soy agar supplemented with 0.1% CaCl 2 and 5% sheep blood) at 19° C. unless otherwise mentioned.
TABLE 1
A. salmonicida used in this study and presence of acrD
Strain
origin
acrD a)
ATCC33658
American Type Culture Collection, Type strain
−
JF2267
Char ( Savelinus alpinus ), Switzerland
+
JF2397
Laboratory strain, derivative of JF2267
−
CC-23
Salmon, Norway
+
CC-24
Salmon, Norway
+/− b)
CC-27
Salmon, Norway
+
CC-29
Salmon, Scotland, UK
+
CC-30
Salmon, Canada
+
CC-34
Salmon, Canada
+
MT 44
Spontaneous non virulent mutant
−
CC-63
Salmon, Canada
+
CC-72
Salmon, Canada
+
a) As determined by Southern blot hybridization.
b) Very weak hybridization signal indicating that only a minor part of the population of the culture contains the acrD gene.
Liquid cultures of A. salmonicida were made by inoculation of Tripticase soy broth (TSB) (2.75 g/100 ml Tripticase soy broth without Dextrose (BBL® 11774, Becton Dickinson AG, Basle, Switzerland), 0.1% Glycerol, 0.1 M L-Glutamic acid pH 7.3) with fresh culture from solid medium and subsequent growth for 18 h at 19° C. For growth in Ca 2+ -restricted medium, TSB was supplemented with 10 mM Nitrilotriacetic acid (Titriplex I, Merck 1.08416, Darmstadt, Germany).
For cloning and expression of cloned genes, Escherichia coli strains. XL1-blue (recA1 endA1, gyrA96 thi-1 hsdR17supE44 relA1 lac [F′ proAB lacI q ZΔM15 Tn10 (Tet T )] (Bullock et al., 1987), and BL21 (DE3) (F′dcm ompT hsdS(r B -m B -) gal λDE3)) (Studier et al., 1990) respectively, were used. Plasmid pBluescriptII-SK − (Stratagene, La Jolla, Calif., USA) was used as basic cloning vector. For the construction of genes encoding poly-Histidine fusion proteins and their expression, plasmid pETHIS-1, a T7 promoter based expression vector (Schaller et al., 1999) was used. E. coli strains were grown at 37° C. in Luria-Bertani broth (LB) supplemented when necessary with ampicillin (50 μg/ml) for selection and maintenance of recombinant plasmids. When blue-white selection with pBluescriptIISK − was performed, 125 μM X-Gal medium was supplemented with 5-bromo-4-chloro-3-indolyl-β-D-thiogalacto-pyranoside.
Preparation of Genomic DNA, Cloning and Sequencing Procedures:
Genomic DNA of A. salmonicida was extracted by the guanidium hydrochloride method (Pitcher et al., 1989). A partial gene library of, A. salmonicida JF2267 was constructed by cloning agarose gel purified SacI-SalI digested fragments of 4 to 6 kb size into vector pBluescriptII-SK − using standard procedures (Ausubel et al., 1999). Recombinant plasmids were screened by colony blot (Ausubel et al., 1999) using digoxigenin (DIG)-labeled DNA probes as described previously (Braun et al., 1999). Plasmids from A. salmonicida were purified using the method of Birnboim and Doly (Birnboim and Doly, 1979).
To construct a genomic library from A. salmonicida JF2267, 0.1 μg of DNA partially digested with Sau3a was ligated to ZapExpress BamHI prepared arms (Pharmacia, Uppsala, Sweden) and packed into phage Lambda. Two-hundred μl of freshly grown XL1-blue MRF′ cells (Pharmacia) resuspended in 10 mM MgSO 4 were infected with the packed phages during 15 min at 37° C. Three ml of preheated (50° C.) Top Agarose (LB-broth containing 0.7% Agarose) supplemented with IPTG and X-Gal for blue/white selection were added and the mixture was poured onto an LB-Agar plate. Plates were incubated overnight at 37° C. and then used for screening of plaques. Positive plaques were cut out and stored overnight at 4° C. in 0.5 ml SM-buffer (100 mM NaCl, 8 mM MgSO 4 , 50 mM Tris, pH 7.5, and 0.01% gelatine) containing 20 μl chloroform. 20 ml overnight cultures of XL1-blue MRF′ grown in LB supplemented with 0.2% maltose and 10 mM MgSO 4 and 20 ml XLOLR cells (Pharmacia) grown in LB media were centrifuged for 5 min at 4,000 rpm and resuspended in 10 mM MgSO 4 to a final OD 600 =1. Two-hundred μl the XL1-blue MRF′ cells were added to 250 μl of the SM-buffer containing the positive phages and 1 μl (10 7 pfu) ExAssist™ helper phage. This mixture was incubated 15 min at 37° C. and 3 ml LB-broth were added and shaken another 3 hrs at 37° C. The cultures were then heated for 15 min at 70° C., centrifuged during 15 min at 5,700 rpm, 4° C., and the supernatant containing the pBK-CMV phagemid filamentous phage was decanted into fresh tubes. Two-hundred μl XLOLR cells were mixed with 100 μl supernatant and incubated for 15 min at 37° C., 300 μl LB-broth were added and the culture was incubated for another one hr at 37° C. Two-hundred μl of this culture were plated on LB-plates containing 50 mg/l kanamycin overnight at 37° C. Colonies were picked and mini-preps (using the QIAprep Spin Miniprep kit, Qiagen AG, Basle, Switzerland) performed for plasmid purification.
For sequencing, subclones of sequential DNA segments were generated with a double-stranded nested deletion kit (Pharmacia LKB, Biotechnology AB, Uppsala, Sweden). Sequencing was done with the dRhodamine Terminator Cycle Sequencing Kit (Applied Biosystems, Foster City, Calif.) according to the manufacturer's protocol using either T3 and T7 primers flanking the cloned inserts in pBluescriptII-SK − or customer-synthesized internal primers. All sequences were determined on both strands. Reaction products were analyzed on an ABI Prism 310 genetic analyzer (Applied Biosystems).
Sequence Data Analyses:
Sequence alignment and editing were performed by using the software Sequencer (Gene Codes Corporation, Ann Arbor, Mich., USA). Comparisons of DNA sequences and their deduced amino acid sequences with EMBL/GenBank and NBRF databases were performed using the programs BLASTN, BLASTX and BLASTP (Altschul et al., 1990). Potentially antigenic segments of AcrV were determined using the software ProtScale (Bairoch et al., 1995) and the software Coils output (Lupas et al., 1991). The molecular masses of the protein and its theoretical isoelectric pH (pI) were calculated by using ProtParam tool (Gill and von Hippel, 1989). Transmembrane prediction of the protein were made by using Tmpred (Hofmann and Stoffel, 1993).
PCR Amplifications and Preparations of DIG-labeled Gene Probes:
Template DNA was produced either by extraction of genomic DNA or by preparation of lysates from bacterial colonies. Lysates were obtained by resuspending five colonies of the corresponding bacterial cultures in 200 μl lysis buffer (100 mM Tris-HCl, pH 8.5, 0.05% Tween 20 (Merck), 0.24 mg/ml proteinase K (Roche Diagnostics, Rotkreuz, Switzerland) dissolved in pyrogen-free water, filtered through a 0.22 μm low protein binding membrane filter) followed by subsequent incubation for 60 min at 60° C. and 15 min at 97° C. Lysates were then cooled on ice and used as PCR templates.
PCR amplifications were performed with either a PE9600 or PE2400 automated thermocycler with MicroAmp tubes (Applied Biosystems). The reaction was carried out in a 50 μl reaction mix (10 mM Tris-HCl, pH 8.3, 1.5 mM MgCl 2 , 50 mM KCl, 0.005% Tween 20, 0.005% NP-40 detergent, 170 μM of each deoxinucleoside triphosphate (dATP, dCTP, dGTP, dTTP), 0.25 μM of each primer, 2.5 units Taq DNA polymerase (Roche Diagnostics)), and 100 ng of template DNA or 5 μl lysate. For the production of DIG-labeled probes, PCR mixtures were supplemented with 40 μM digoxigenin-11-dUTP (Roche Diagnostics). PCR conditions were as follows: 3 min at 94° C. followed by 35 cycles of 30 s at 94° C., 1 min at the corresponding annealing temperature (Table 2), and 30 s at 72° C. In addition, an extension step of 7 min at 72° C. was added at the end of the last cycle in order to ensure fall length synthesis of the fragments.
TABLE 2 Oligonucleotide primers Residue Nos. of SEQ ID Annealing Name Sequence a 5′ to 3′ NO: 10 b temp. ° C. AslcrD-L c GCCCGTTTTGCCTATCAA 1159-1176 60 (SEQ ID NO: 16) AslcrD-R c GCGCCGATATCGGTACCC 2028-2011 60 (SEQ ID NO: 17) AcrV-L c TTCGTCGGCTGGCTTGATGT 4144-4163 58 (SEQ ID NO: 18) AcrV-R c GAACTCGCCCCCTTCCATAA 4734-4715 58 (SEQ ID NO: 19) AsacrVt-L d gg gaattc GATGAGCACAATCCCTGACTAC 4104-4125 57 (SEQ ID NO: 11) AsacrVt-R d at gcggccgc AAATTGCGCCAAGAATGTCG 5188-5169 57 (SEQ ID NO: 12) AsacrVN′-R d tc gcggccgc ACCCTTTACGCTGATTGTC 4555-4537 57 (SEQ. ID NO: 13) AsacrVC′-L d cg gaattc GTTGCGGGATGAGCTGGCAG 4554-4573 57 (SEQ. ID NO: 14) AsacrVC′-R d tc gcggccgc ACTCGGCTTCTATGCCACTC 4987-4968 57 (SEQ. ID NO: 15) a Lowercase letters indicate nucleotides added to create restriction enzyme recognition sites (underlined) for cloning. b Based on nucleotide sequence of A. salmonicida JF2267 c Primer used for gene probe preparation d Primer used for amplification of gene acrV, acrV-N, and acrV-C respectively
Curing of Type III Secretion Genes from A. Salmonicida:
In order to study the segregation of the type III secretion genes in A. salmonicida strain JF2267, the strain was inoculated in LB-broth at a density of A 600 =0.08 and incubated 2½ hrs at 19° C. Then the culture was split in two. One part was kept for continued growth at 19° C., while the other part was incubated at 22° C. Samples were taken at different time points from both cultures and spread on LB-agar medium. The plates were then incubated at 19° C. for 24 hrs. Subsequently, colony blot hybridizations were performed using gene probes to determine the loss of specific genes.
Pulsed-field Gel Electrophoresis (PFGE):
The bacterial strains A. salmonicida JF2267 and JF2397 were grown on LB agar for one day at room temperature. Then bacterial suspensions in 10 mM Tris, 10 mM EDTA, pH 8.0, sterile, were prepared to a final OD 600 of 5. Three-hundred μl of 1.5% Sea Kem gold agarose (FMC Bioproducts, Maine, USA) in 100 mM Tris, 100 mM EDTA, pH 8.0, was added to 300 μl of bacterial cell suspension. Plugs were immediately poured in sterile moulds and kept on ice until hardened. The plugs were then incubated at 50° C. overnight in sterile 1.5 ml 0.5 M EDTA, 1% N-lauroylsarcosin, 2 mg/ml proteinase K (Roche Diagnostics), pH 8.0, by shaking. The next day, the plugs were thoroughly washed 5 times over the whole day at room temperature in sterile TE buffer (10 mM Tris, 1 mM EDTA, pH 8.0) and stored in sterile 0.5 M EDTA, pH 8.0, at 4° C. until further use. To digest the plugs they were first incubated in 4× Buffer H (Roche Diagnostics) for 10 min at 22° C. Then the plugs were incubated at 37° C. by shaking for 7½ hrs in 2× Buffer H containing 40 U of NotI (Roche Diagnostics). They were then placed into the slots of a 1% Sea Kem gold agarose gel in 0.5×TBE and sealed with 1% Sea Kem gold agarose. The gel was then equilibrated in 0.5×TBE at 12° C. using an Electrophoresis CHEF-DR® III system (BioRad Laboratories, Hercules, Calif., USA). To separate NotI DNA fragments, the field was 6V/cm, having an angle of 12°, starting with 1 s and ending with 12 s. The duration of the PFGE was 14 hrs and it was performed at 12° C. The gel was stained 30 min at room temperature in water containing 0.5 μg/ml ethidium bromide, washed two times with water and analyzed under a UV-light. Additionally, the gel was further used for Southern-blotting.
Southern-blot Analyses:
Southern-blotting was done by alkaline transfer onto positively charged nylon membranes (Roche Diagnostics) with an LKB 2016 VacuGene vacuum blotting pump (Pharmacia LKB). To depurinate the agarose gels they were incubated for 10 min in 0.25 M HCl, and subsequent transfer was performed with 0.4 M NaOH for 1½ hrs. After blotting, membranes were baked for 30 min at 80° C. under vacuum. After at least one hr of prehybridization, hybridization was carried out in 5×SSC (1×SSC in 0.15 M NaCl plus 0.015 M sodium citrate)-1% blocking reagent (Roche Diagnostics)-0.1% N-lauroylsarcosine sodium salt-0.02% sodium dodecyl sulphate (SDS) at 68° C. overnight, using DIG-labeled DNA as probe. Membranes were washed under nonstringent conditions twice for 5 min each with 50 ml of 2×SSC-0.1% SDS per 100 cm 2 at 22° C., followed by medium-high-stringency washing twice for 15 min each with 50 ml of 0.2×SSC-0.1% SDS per 100 cm 2 at 68° C. The membranes were then processed with phosphatase-labeled anti-DIG antibody (Roche Diagnostics) according to the manufacturer's protocol. Signals were produced with chemiluminescent substrate (CSPD, Roche Diagnostics).
Pulsed-field gels were treated for Southern-blotting by using the same solutions as described above. To depurinate the agarose gels efficiently, they were incubated for 20 min in 0.25 M HCl, and then equilibrated for 20 min in 0.4 M NaOH. Transfer was performed for 3 hrs and the gels were treated as described above.
Expression and Purification of His-tailed Fusion Protein AcrV:
Oligonucleotide primers used to amplify the whole acrV gene are given in Table 2. The PCR reactions were carried out as described above with the exception of using Pwo DNA polymerase (Expand Long Template PCR System kit, Roche Diagnostics) instead of Taq DNA polymerase and genomic DNA of A. salmonicida JF2267. The PCR products were purified by using the High Pure™ PCR Product Purification Kit (Roche Diagnostics) as described by the manufacturer's protocol. Then the acrV PCR product was cloned into pGEM-T vector (Promega, Madison, Wis. USA), having 3′-T overhangs at the insertion sites, as described in the manufacturer's protocol and transformed into E. coli strains XL-1 Blue. The resulting plasmid was designated pJFFIVB873. The cloning of the PCR products into pGEM-T vector was used to provide efficient restriction of the subcloned fragments. Plasmid pJFFIVB873 was then digested with EcoRI and NotI, and the DNA fragment was inserted into the T7-promoter-based expression vector pETHIS-1 (Schaller et al., 1999). The resulting plasmid, pJFFETHISacrV4 was purified and controlled by DNA sequencing to assure the fusions with the vector's poly-His codons and then transformed into Escherichia coli BL21 (DE3) cells (Novagen) for expression. Expression was induced by addition of 1 mM IPTG to cultures and incubation continued for another 3 h. The cells were sedimented by centrifugation at 3000×g for 10 min, resuspended in 5 ml PN buffer (50 mM NaH 2 PO 4 , pH 8.0, 300 mM NaCl), sonicated with a microtip for 4 min with the power output control at 1 and a duty cycle of 50% (1 s pulses) in a Branson Sonifier 250 (Branson Ultrasonics, Danbury, Conn., USA). Then guanidine hydrochloride was added to a final concentration of 6 M and was incubated overnight at 4° C. on a shaker. The mixture was loaded onto a prewashed 2.5 ml bed volume Ni 2+ chelation chromatography column (Qiagen) and washed once more with 30 ml PNG buffer (50 mM NaH 2 PO 4 , pH 8.0, 300 mM NaCl, 6 M guanidine hydrochloride). Step elutions of the proteins were performed by adding 10 ml PNG buffer at each different pH (7.0, 6.0, 5.5, 5.0, and 4.5) and fractions of 1 ml were collected. The fractions were dialyzed and analyzed on 15% PAGE. The purified fusion proteins were eluted at pH 4.5.
Production of Monospecific Rabbit Anti-AcrV Antibodies and Immunoblot Analyses:
Monospecific, polyclonal antibodies directed against AcrV were obtained by immunizing rabbits subcutaneous with 80 μg of recombinant polyhistidine-tailed AcrV protein in 200 μl PN buffer and 150 μl NaCl (0.85%) mixed with 350 μl Freund's complete adjuvant (Difco Laboratories, Detroit, Mich., USA) followed by a booster immunization with the same amount of protein in Freund's incomplete adjuvant (Difco)3 weeks later. The animals were bled 22 d after the booster immunization according to standard protocols (Harlow and Lane, 1988).
Infection of Fish Cell Cultures with A. Salmonicida:
Rainbow trout ( Oncorhynchus mykiss ) gonad cells (RTG-2, ATCC CCL-55) were grown in 75 cm 2 tissue culture flasks (Techno plastic products AG, Trasadingen, Switzerland) at 22° C. in minimum essential medium (GibcoBRL Life Technologies, Basel, Switzerland) supplemented with 2 mM L-glutamine (GibcoBRL), 1Xnon-essential amino acids (GibcoBRL), 3 g/l sodium bicarbonate and 10% foetal bovine serum. Three days before infection the cells were trypsinized and 4 mio cells were seeded into a 25 cm 2 tissue culture flask. Monolayered RTG-2 cells were infected with A. salmonicida cells resuspended in phosphate buffered saline (PBS) pH 7.4 at a multiplicity of infection of 20:1 or 2:1 (bacteria/fish cells). As a control also 100 μl of pure PBS pH 7.4 were added to cultured fish cells. After 24 hrs of infection at 15° C. the fish cells were photographed under a green filtered phase contrast microscope (Aixovert 100, Zeiss, Jena, Germany). To detach the cultured cells from the flask, the flask was shaken by hand. The suspended cells were centrifuged for 5 min at 4,000 rpm. Lysis of the fish cells was performed in 100 μl distilled water with two subsequent freeze thawing steps and verified by microscopy. The lysed fish cells were used for further analyzes on Western-blots.
Protection Assay Using Rabbit Antiserum AcrV:
RTG-2 fish cells were grown as described above. Two days before infection 20 million of trypsinized RTG-2 fish cells were seeded into 24 well culture plates (1.9 cm 2 ) (Techno plastic products AG, Trasadingen, Switzerland). Rabbit antiserum directed against AcrV as well as control preserum were decomplemented for 30 min at 56° C. A fresh culture of A. salmonicida (at end exponential growth phase) was washed and resuspended in PBS pH 7.4 and mixed with either preserum or anti AcrV antiserum at a ratio of 1:1, 1:10, 1:100, 1:1000 or 1:10,000. Bacteria were incubated with the serum at 18° C. for 30 min. The opsonized bacteria were added to the fish cells in a ratio of 20:1 or 2:1 (bacteria/fish cells). After 21 hrs of infection at 15° C. the fish cells were photographed as described before and inspected for morphological changes.
SDS-PAGE and Immunoblot Analysis:
Proteins were separated by polyacrylamide gel electrophoresis (SDS-PAGE) as described by Laemmli (Laemmli, 1970) using 15% or 10% polyacrid gels and transferred to a nitrocellulose membrane (BioRad Laboratories). For immunoblotting, Western-blots were blocked with 1% milk buffer for at least one hour and then incubated with the rabbit antiserum AcrV (1:2000) or with the rabbit preserum (1:1000) in milk buffer overnight at 4° C. The membranes were then washed thoroughly with water before phosphatase-labelled conjugate (Goat anti-Rabbit IgG (H+ L) [cat. no. 075-1506], Kirkegaard & Perry, Gaithersburg, Md., USA) diluted 1:2000 in milk buffer was added. The reaction was visualized 90 min later by incubation with BCIP-NBT (Ausubel et al., 1999).
EXAMPLES/RESULTS
Cloning and Sequence Analysis of the virA Locus of a Type III Pathway of A. salmonicida
Analysis of A. salmonicida strain JF2267 with an array of broad range probes for detection of type III secretion pathways revealed a strong signal with the lcrD subset of the probes, indicating the presence of a new type III secretion pathway. Subsequent Southern-blot analyses showed a 4.8 kb fragment of SacI-SalI digested genomic DNA of strain JF2267 reacting with the lcrD probe. This fragment was cloned on vector pBluescriptII-SK − leading to plasmid pJFFIVB638 which was subsequently sequenced. DNA sequence analyses revealed the presence of eight open reading frames (ORF) ( FIG. 1 ) which showed strong similarity to the genes encoded on the virA operon of the type III secretion pathway of Yersinia pestis and Pseudomonas aeruginosa . In analogy to the Y. pestis genes, we named them acr1, acr2, acr3, acr4, and acrD (Aeromonas calcium response ( FIG. 1 )). They are located on a single operon followed by a transcription termination signal similar to the virA operon of Y. pestis, Y. enterocolitica and Pseudomonas aeruginosa (Boland et al., 1996; Iriarte and Cornelis, 1999; Plano et al., 1991; Cornelis, 1998; Yahr et al., 1997a). The similarities of the genes acr1, acr2, acr3, acr4 and acrD with the analogues in Y. enteroclitica and in P. aeruginosa are given in Table 2. Downstream lcrD we identified a locus with a canonical promoter sequence followed by further genes named acrR, acrG, and acrV on a separate operon ( FIG. 1 ) according to the corresponding genes in Y. pestis (Table 3) (Barve and Straley, 1990; Skrzypek and Straley, 1993; Nilles et al., 1998). The ORF of the putative acrV gene seemed to be incomplete on the 4.8 kb SacI-SalI fragment of pJFFIVB638, and represented only the 5′-half of the gene. The remaining part of acrV and part of acrH located downstream of acrV were cloned separately from the λ phage gene library of A. salmonicida as an overlapping clone which was obtained by screening the gene library using a gene probe for the 5′-half of acrV which was produced by PCR with primers AcrV-L and AcrV-R (Table 2). The resulting plasmid based on vector pBK-CMV was designated pJFFIVB832. From this plasmid, a 0.9 kb SalI fragment containing the 3′ end of acrV and part of the downstream gene acrH was subcloned on pBluescriptII-SK and designated pJFFIVB828.
TABLE 3 A. salmonicida type III proteins compared to analogues in P. aeruginosa and in V. entercolitica Protein in Analogue in Similarity/ Genbank Analogue in Similarity/ Genbank A. salmonicida P. aeruginosa identity a Access. Nr. Y. enterocolitica identity a Access. Nr. Proposed function Acr1 Pcr1 80/60 AF019150 TyeA 83/69 AF102990 part of the translocation-control apparatus, required for selective translocation of Yops Acr2 Pcr2 63/44 AF019150 SycN 77/62 AF102990 chaperone for YopN Acr3 Pcr3 62/47 AF019150 YscX 69/54 AF102990 part of the type III secretion apparatus, secretion of Yop Acr4 Pcr4 66/55 AF019150 YscY 64/52 AP102990 part of the type III secretion apparatus, secretion of Yop AcrD PcrD 90/82 AF019150 LcrD 90/82 X87771 inner membrane spanning protein of type III secretion AcrR PcrR 68/58 AF019150 LcrR 71/58 AF102990 AcrG PcrG 63/46 AF010149 LcrG 64/42 AF102990 regulation of low calcium response AcrV PcrV 50/35 AF010149 LcrV 53/37 X96797 regulation of low calcium response, sensor suppression of TNFá and Interferon ã, protective antigen AcrH PcrH 78/65 AF010149 LcrH (SycD) 79/58 AF102990 regulation of low calcium response, chaperon for YopD, secretion a Given as % of similar/identical amino acids
Instability of the Genes Belonging to the Type III Pathway in A. Salmonicida:
When we analyzed the different A. salmonicida strains with a specific probe for acrD, we discovered by using Southern blot hybridization that the acrD gene was present only in strain JF2267 but not in the derivative strain JF2397 which had undergone nine passages of subsequent single colony cloning isolation. Additionally, the type strain of A. salmonicida , ATCC33658 T , did not show a signal with the acrD probe. However, several A. salmonicida strains that were freshly isolated from salmon and trout with furunculoses did contain acrD (Table 1). These results indicate that the type III secretion pathway of A. salmonicida may be lost easily. In order to get an estimate on the loss of the type III secretion genes, we have analyzed the kinetics of disappearance of acrD after a shift of growth temperature of strain JF2267 from 19° C. to 22° C. Colony hybridization with the acrV probe revealed that in a fresh culture of strain JF2267, the acrD gene was present in all cells grown at 19° C. After the shift to 22° C., acrD was still present for further 5½ hrs, following which it was lost very rapidly within less than 1 hr ( FIG. 2 ). Taking into account the generation time of 2 h for A. salmonicida under the given growth conditions, the acrD gene was lost within two generations. To analyze the loss of acrD further, undigested and NotI digested genomic DNA of A. salmonicida strain JF2267 and of the acrD deficient derivative strain JF2397 were submitted to pulse field gel electrophoresis (PFGE) and subsequent Southern blot hybridization with the acrD probe. PFGE analyses of total undigested DNA revealed the presence of two large plasmids in strain JF2267 while in strain JF2397 only one of the two plasmids was seen ( FIG. 3 ). Digestion of the total DNA from these two strains with the rarely cutting enzyme NotI revealed the lack of a 84 kb band in strain JF2397 compared to JF2267 as the sole detectable difference ( FIG. 3 ). Southern-blot hybridization of the DNA on this gels with the acrD probe confirmed the larger plasmid and the 84 kb NotI fragment of strain JF2267 to contain acrD gene. Neither the remaining large plasmid in JF2397 nor any of its NotI fragments hybridized with the AcrV probe. This indicates that the type III secretion genes, or at least the virA operon thereof, are located on a large plasmid in the size range of 84 kb.
Presence of acrD in A. salmonicida Strains:
In order to assess the presence of the acrD gene in various A. salmonicida strains, DNA samples extracted from A. salmonicida Type strain ATCC 33658 and various field strains isolated from salmon or char were digested with restriction enzymes SalI and SacI, separated by 0.7% agarose gel electrophoresis, blotted onto nylon membranes and hybridized with the acrD gene probe. The Southern blot revealed the presence of the acrD gene on a 4.8 kb fragment in all strains except in the type strain ATCC 33658, the laboratory strain JF2397 which was used for the type III secretion genes, and A. salmonicida strain MT44 known to be a virulent for trout. One field strain, # 24, showed a very weak hybridization signal indicating that the culture contains acrD only in a minor population of the cells (Table 1).
Infection of RTG-2 Fish Cells and Protection of Cell Damage with Anti-AcrV Antiserum:
Freshly cultured A. salmonicida strain JF2267 was used to infect RTG-2 cells. After 24 hrs of incubation the fish cells were rounded up and also detached from the plastic support ( FIG. 4A ). In contrast cells infected with A. salmonicida type strain ATCC 33658 T or strain JF2397 ( FIGS. 4B and C), both known to be devoid of acrD and acrV, showed no morphological changes at all in spite of a massive multiplication of the bacteria in the cultures. RTG-2 fish cells which were incubated with PBS buffer as control showed no morphological changes like the cells infected with the acrD and acrV deficient strains JF2397 or ATCC 33658 T ( FIG. 4D ).
In order to study further the role of the newly detected type III secretion pathway in virulence of A. salmonicida , we incubated strain JF 2267 with monospecific polyclonal anti-AcrV antibodies prior to infection of RTG-2 fish cell cultures. When RTG-2 fish cells were infected with strain JF2267 that was incubated with rabbit anti-AcrV antibodies diluted 1:1 or 1:10, the characteristic morphological changes of the cells were reduced, significantly affecting only 20% of the cells or less ( FIG. 4E ) compared to the infection with non-treated strain JF 2267 ( FIG. 4A ) or to the infection with JF 2267 that was pretreated with serum from the same rabbit taken before immunization ( FIG. 4F ). Titration of the anti-AcrV serum showed that protection of about 50% of the RTG-2 cells could still be reached with a serum dilution of 1:100, while further dilutions had no visible effect in protection.
Expression of AcrV in A. salmonicida:
The expression of AcrV in A. salmonicida strain JF2267 was assessed by immunoblots using AcrV-His antibodies. When A. salmonicida was grown under standard culture conditions in TSB medium, no AcrV protein could be detected from total cells nor from culture supernatant of strain JF 2267, nor in the control of strains JF2397 and ATCC33658 T . However, when the cells are submitted to a low Ca 2+ response by chelating free Ca + ions in the growth medium by the addition of 10 mM NTA, we detected AcrV with anti-AcrV antibodies in the pellet of JF2267 as a protein of about 37 kDa ( FIG. 5 ) but not in strains JF2397 and ATCC33658 T , which are both devoid of the AcrV gene ( FIG. 5 ). No AcrV protein could be detected in the supernatants of cultures from strains JF2267, JF2397 and ATCC33658 T , grown in Ca 2+ depleted medium.
When strain JF2267 was grown under standard culture conditions (containing free Ca 2+ ions) and then put in contact with RTG-2 cells at a ratio 2:1 (bacteria:cells) for 30 minutes, the AcrV protein could be monitored on immunoblots reacting with anti-AcrV, similar to cultures from Ca 2+ depleted medium.
Recombinant AcrV Vaccine Trial
Materials
Vaccine Formulations:
1. The AcrV vaccine was formulated using recombinant, Histidine-tagged AcrV resuspended in 10 mM phosphate buffer, pH 7.0, to 112.5 μg/mL. Four parts of this protein solution were mixed with one part oil adjuvant for a final AcrV concentration of 90 μg/mL The dose for testing was 0.1 mL, or 9 μg/fish.
2. The commercial comparator vacciuc was serial 4-13 of the vaccine MultiVacc4 (Bayotek International Ltd.).
3. The placebo (control) vaccine consisted of phosphate buffered saline (PBS) (10 mM phosphate, 150 mM NaCl, pH 7.2).
4. All vaccines were maintained at 4° C. until use.
Methods
Trial Design:
Fish (rainbow trout Oncorhynchus mykiss ) that have been determined to be pathogen free and are at least 15 g in size are held for at least one-week pre vaccination for acclimation purposes. During the acclimation period the fish are offered 1% body weight in salmonid fish food every day, however they are denied food 24 hours pre and post-vaccination.
At least 50 fish are vaccinated 0.1 mL of AcrV vaccine via intra-peritoneal (IP) injection, or 0.2 mL of the commercial vaccine MutiVacc4. At the same time a group of at least 50 fish from the same stock are mock vaccinated with 0.1 mL of PBS. Vaccinated fish are then held for a period of at least 350-degree days to allow specific immune response generation in an acclimation tank with a continuous flow of water at a temperature of 12-13° C. The fish are offered 1% body weight in salmonid fish food daily until 24 hours pre-challenge and post-challenge.
After at least 350-degree days post vaccination 50 fish per group were challenged by IP injection with a pre-determined concentration of virulent Aeromonas salmonicida . The dosage depends on the source of the fish and the water temperature (this is determined empirically immediately prior to challenge of test fish). The identical procedure is performed with the placebo vaccinated control fish. The fish are observed daily for mortality for 21 days post challenge and the cause of mortality assessed and examined to ensure that mortality is attributed to the challenge organism. After 24 hours post-challenge the fish are again offered 1% body weight in salmonid fish feed daily. Tanks are maintained with a continuous flow of water at a temperature of 12-13° C. For a challenge series to be considered satisfactory; all challenge groups must meet the following criteria:
1. At least 70% of the non-immunized controls must die within 21 days of challenge. 2. A relative percent survival (RPS) of no less than 25% must be achieved for the challenge disease before a vaccine is considered even partially efficacious for this disease.
RPS[=1−(% mortality vaccinates/% mortality controls)]×100
Developed from: The Rules Governing Medicinal Products in the European Union, Volume VII, Guidelines for the testing of veterinary medicinal products. 1994. Specific Requirements for the Production and Control of Live and Inactivated Vaccines Intended for Fish. Section 3.2. Potency.
Results:
Group % Mortality RPS PBS 82 — AcrV 49 40 MultiVacc4 30 63
There was a strong challenge with 82% control mortalities.
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Thornton, J. C., Garduno, R. A., Carlos, S. J. and Kay, W. W.: Novel antigens expressed by Aeromonas salmonicida grown in vivo. Infect. Immun. 61 (1993) 4582 4589.
Titball, R. W. and Munn, C. B.: The purification and some properties of H-lysin from Aeromonas salmonicida . J. Gen. Microbiol. 131 (1985) 1603 1609.
Whitby, P. W., Landon, M. and Coleman, G.: The cloning and nucleotide sequence of the serine protease gene (aspA) of Aeromonas salmonicida ssp. salmonicida. FEMS Microbiol. Lett. 78 (1992) 65 71.
Yahr, T. L., Goranson, J. and Frank, D. W.: Exoenzyme S of Pseudomonas aeruginosa is secreted by a type III pathway. Mol. Microbiol. 22 (1996) 991 1003.
Yahr, T. L., Mende-Mueller, L. M., Friese, M. B. and Frank, D. W.: Identification of type III secreted products of the Pseudomonas aeruginosa exoenzyme S regulon. J. Bacteriol. 179 (1997b) 7165 7168.
Yahr, T. L., Mende-Mueller, L. M., Friese, M. B. and Frank, D. W.: Identification of type III secreted products of the Pseudomonas aeruginosa exoenzyme S regulon. J. Bacteriol. 179 (1997a) 7165 7168. | Disclosed is a newly identified and characterized type III secretion system in Aeromonas salmonicida . The invention also encompasses the use of components of the novel secretion system in immunoprotection against A. salmonicida infection, as well as other diagnostic and therapeutic uses thereof. | 2 |
CROSS-REFERENCES TO RELATED APPLICATIONS
This application claims benefit of the following patent application(s) which is/are hereby incorporated by reference: U.S. Provisional Patent Application No. 61/408,379, filed Oct. 29, 2010.
A portion of the disclosure of this patent document contains material that is subject to copyright protection. The copyright owner has no objection to the reproduction of the patent document or the patent disclosure, as it appears in the U.S. Patent and Trademark Office patent file or records, but otherwise reserves all copyright rights whatsoever.
BACKGROUND OF THE INVENTION
The present invention relates generally to High Intensity Discharge (HID) lamps and electronic ballasts for powering such lamps. More particularly, the present invention relates to various embodiments of an inrush protection circuit for use in an electronic ballast for powering an HID lamp.
Generally stated, an HID electronic ballast includes a tank circuit which stores energy so that the ballast can continue to power the load (i.e., an HID lamp) for a certain period of time even if the input power source to the ballast is disconnected for some reason, such as a black out. This function is required because an HID lamp will not restart immediately after extinguishing until it is cooled down. To minimize operational inconvenience, the ballast should not extinguish the lamp during very short-term black outs, in the order of tens of milliseconds.
A second function of the tank circuit is to smooth out the AC input ripple so that an output power regulation circuit which connects to the tank circuit can regulate the output to the HID lamp without having any adverse effect from the input ripple. The higher the capacitance in the tank circuit, the lower the AC ripple that will appear on the rectified bus voltage, but the higher the spike current to charge the tank circuit capacitor.
In designs where a high spike current is presented to charge the tank circuit capacitor when the power is initially applied, the spike current needs to be controlled. This spike current is also known in the art as an inrush current. Generally, the inrush current needs to be less than a certain value to avoid problems such as, for example, the welding of switches or terminals which are incorporated within the ballast due to the high peak current, or to prevent the circuit breaker which is in series with the input power source and the lighting fixtures from becoming active.
A common method for preventing excessive inrush current is to add resistive impedance into the circuit of the ballast. The resistive impedance limits the peak of the inrush current at initial power up. At the same time, a switch is added in parallel with the resistive impedance. The switch will be turned on to short the resistive impedance when the tank circuit has been charged up enough not to have too high peak current even with the shorted resistive impedance. In this configuration, the inrush current flows through the resistive impedance, while in normal operation the input current flows through the switch. This circuit arrangement which limits the inrush current and bypasses the inrush current limiting element for normal operation is called an inrush protection circuit.
FIG. 1 shows a first example of an inrush protection circuit 11 in a ballast 1 as conventionally known in the art having a boost chopper as a PFC (Power Factor Correction) circuit. This inrush protection circuit 11 is relatively simple. The switching element Q 1 is passively controlled. DB 1 is the diode bridge and it rectifies the AC input power source. R 1 is a resistor which is provided along the low potential side (i.e., ground, or alternatively stated the negative terminal of the circuit) of the rectified input voltage. Q 1 is a MOSFET switch and is coupled in parallel with resistor R 1 .
R 2 and R 3 are resistors which divide the rectified input voltage and provide the voltage at the gate of switch Q 1 . C 2 is a capacitor coupled across the gate of switch Q 1 . L 1 , D 1 , and Q 2 are an inductor, diode and MOSFET, respectively, and they collectively form a boost chopper PFC circuit. C 0 is a film capacitor which can carry the high frequency current for the PFC circuit. C 1 is an electrolytic capacitor and it is further part of the tank circuit of the ballast. Capacitor C 1 has enough capacitance to deliver power to the load, which includes the output power regulation circuit, for a certain period of time when the input power source is disconnected in normal operation. The capacitance is also large enough to filter out the AC ripple voltage after rectification.
When the input power source is connected to the ballast, the gate voltage of switch Q 1 is gradually charged up by the rectified input voltage, depending on the divider ratio between resistors R 2 and R 3 , and further depending on the time constant between resistor R 2 and capacitor C 2 . When switch Q 1 is off, the inrush current delivered from the input power source to charge up capacitor C 1 , the tank circuit, flows through a circuit loop consisting of diode-bridge DB 1 , inductor L 1 , diode D 1 , capacitor C 1 , and R 1 as the resistive impedance. The peak of the inrush current is mainly controlled by resistor R 1 . At the same time, capacitor C 1 is also being charged up by the boost chopper. When the gate voltage of the switch Q 1 exceeds the threshold voltage of the switch Q 1 , switch Q 1 turns on. After switch Q 1 turns on, the input current flows through switch Q 1 instead of resistor R 1 . If capacitor C 1 is charged up more than the peak of the input voltage when switch Q 1 turns on, no high peak charging current flows through C 1 and switch Q 1 .
There are three design parameters for this inrush protection circuit which may be given primary consideration. The first is that the time constant of resistor R 2 and capacitor C 2 should be large enough not to turn on switch Q 1 right away after the input power source is connected. The second one is that the gate voltage of switch Q 1 should be higher than the turn-on threshold voltage of switch Q 1 during normal operation so that switch Q 1 does not carry any unintended loss. The third one is the time constant of resistor R 3 and capacitor C 2 should be as short as possible, so that switch Q 1 can turn off when the input power is removed.
However, because switch Q 1 is controlled passively, the discharging time of the gate voltage of switch Q 1 when the input power source is disconnected depends primarily on the time constant of resistor R 3 and capacitor C 2 , which cannot be very small due to the second of the design constraints mentioned above. That is, switch Q 1 will stay on for a relatively long time after the input power source is disconnected. If the input power source is momentarily disconnected during normal operation due to for example blackout, etc., the ballast will continue to deliver energy to the HID lamp from capacitor C 1 . The voltage on capacitor C 1 will reduce sharply. In this situation, because of the switch Q 1 being on, there is no resistive impedance in series in the input circuit, and the inrush current may be very high when the input power source is reconnected. This high inrush current flows through the switching element Q 1 to charge the tank circuit C 1 , which is a major concern not only for the inrush current itself, but also for the operational reliability of switch Q 1 .
FIG. 2 shows another example of an inrush protection circuit 21 configuration alongside a boost chopper as the PFC circuit in an electronic ballast 2 . This inrush protection circuit 21 is more intelligent compared with the example 11 shown in FIG. 1 , but also more expensive. The turn-on of switch Q 1 is passively controlled by the input voltage, while the turn-off of switch Q 1 is actively controlled by signal IC 2 - 1 (- 2 ). In addition to the circuit arrangement of the previous example, the controller IC 1 is needed to sense the voltage across C 1 and forces switch Q 1 to turn off when the voltage on capacitor C 1 becomes low by shorting capacitor C 2 with signal IC 2 - 2 . R 4 is a resistor provided to regulate the current of IC 2 - 1 .
When the input power source is connected to the ballast 2 , the gate voltage of switch Q 1 is gradually charged up in substantially the same way as in the example of FIG. 1 . When the input power source is disconnected, switch Q 1 can be turned off immediately and no high peak inrush will occur whenever the input power source is re-connected.
However, as previously stated this circuit 21 is more expensive because of the added components controllers IC 1 and IC 2 . The circuit arrangement is also more complex. Controller IC 1 may be utilized for other functions of the ballast, such as the output power regulating controller, but the design layout may be difficult since controller IC 1 now needs to be dedicated not only to the output side of the ballast but also to the input side. Controller IC 1 is also required to have one extra pin to control controller IC 2 . An isolated device, controller IC 2 , such as an opto-coupler is needed because the circuit GND which connects to controller IC 1 is the drain of switch Q 1 , not the source.
The conventionally known examples 11 and 21 as described herein are therefore either lacking in certain desired functionality or prohibitively expensive and complex.
BRIEF SUMMARY OF THE INVENTION
In various embodiments of the present invention arrangements of an inrush protection circuit are provided which may be simple and inexpensive, yet satisfy the required functions which limit the inrush current during the entire operation of the ballast.
In an embodiment, an electronic ballast with an inrush protection circuit of the present invention includes a diode bridge to rectify an AC input voltage from an AC power source and a power factor correction circuit having a first capacitor coupled across high and low potential sides of the rectified AC input voltage. A tank circuit includes a second capacitor effective to store electricity provided from the power factor correction circuit and further coupled across a load. A first resistor is positioned along the low potential side of the rectified AC input voltage and between the diode bridge and the power factor correction circuit. A switching element is coupled in parallel with the first resistor. An input voltage dividing network is made up of second and third resistors. A first node between the second and third resistors is further coupled to the gate of the switching element. A third capacitor is coupled in parallel with the third resistor to provide a smoothed DC voltage to the gate of the switching element. A discharging circuit is coupled in series between the third capacitor and the high potential side of the rectified AC input voltage, and arranged to conduct discharging current from the third capacitor to the first capacitor when the voltage across the first capacitor is less than the voltage across the third capacitor. The power factor correction circuit is effective to deliver current from the first capacitor to the second capacitor until the voltage across the third capacitor discharges below a first predetermined voltage when the AC input voltage is removed from the circuit.
In another embodiment, an inrush protection circuit is provided for an electronic ballast for powering HID lamps. A first resistor is positioned along a low potential side of the circuit and a switching element coupled in parallel with the first resistor. Second and third resistors are coupled in series and are effective to receive DC input power from a DC source, with a first node between the second and third resistors further coupled to the gate of the switching element. A capacitor is coupled in parallel with the third resistor to provide a smoothed DC voltage to the gate of the switching element. A discharging circuit includes a diode and a fourth resistor coupled in series between the first node and the high potential side of the circuit, and is arranged to conduct discharging current from the capacitor until the voltage across the capacitor discharges below a predetermined voltage after the DC input power is removed from the circuit.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIG. 1 is a simplified circuit diagram of an electronic ballast with an inrush protection circuit as previously known in the art.
FIG. 2 is a simplified circuit diagram of another electronic ballast with an inrush protection circuit as previously known in the art.
FIG. 3 is a simplified circuit diagram of an embodiment of the electronic ballast with an inrush protection circuit of the present invention.
FIG. 4 is a more detailed circuit diagram of the ballast with the previously known inrush protection circuit of FIG. 1 .
FIG. 5 is a more detailed circuit diagram of the ballast with the inrush protection circuit of FIG. 3 .
DETAILED DESCRIPTION OF THE INVENTION
Throughout the specification and claims, the following terms take at least the meanings explicitly associated herein, unless the context dictates otherwise. The meanings identified below do not necessarily limit the terms, but merely provide illustrative examples for the terms. The meaning of “a,” “an,” and “the” may include plural references, and the meaning of “in” may include “in” and “on.” The phrase “in one embodiment,” as used herein does not necessarily refer to the same embodiment, although it may.
The term “coupled” means at least either a direct electrical connection between the connected items or an indirect connection through one or more passive or active intermediary devices.
The term “circuit” means at least either a single component or a multiplicity of components, either active and/or passive, that are coupled together to provide a desired function.
The term “signal” means at least one current, voltage, charge, temperature, data or other signal.
The terms “switching element” and “switch” may be used interchangeably and may refer herein to at least: a variety of transistors as known in the art (including but not limited to FET, BJT, IGBT, JFET, etc.), a switching diode, a silicon controlled rectifier (SCR), a diode for alternating current (DIAC), a triode for alternating current (TRIAC), a mechanical single pole/double pole switch (SPDT), or electrical, solid state or reed relays. Where either a field effect transistor (FET) or a bipolar junction transistor (BJT) may be employed as an embodiment of a transistor, the scope of the terms “gate,” “drain,” and “source” includes “base,” “collector,” and “emitter,” respectively, and vice-versa.
Terms such as “providing,” “processing,” “supplying,” “determining,” “calculating” or the like may refer at least to an action of a computer system, computer program, signal processor, logic or alternative analog or digital electronic device that may be transformative of signals represented as physical quantities, whether automatically or manually initiated.
Referring generally to FIGS. 3 and 5 , embodiments of an inrush protection circuit in accordance with the present invention may be described herein. Where the various figures may describe embodiments sharing various common elements and features with other embodiments, similar elements and features are given the same reference numerals and redundant description thereof may be omitted below.
Referring first to FIG. 3 , an embodiment of an inrush protection circuit 31 of the present invention includes a discharging circuit 32 having a resistor R 5 and a diode D 2 which are connected in series between the gate of switch Q 1 and the high side of the rectified input voltage. Resistor R 5 is selected to have a value much smaller than resistor R 3 while diode D 2 is selected to have the same voltage rating as DB 1 .
When the input voltage source is disconnected, the voltage across capacitor C 0 will go to zero almost immediately because the PFC circuit is still functioning and delivering power from capacitor C 0 to capacitor C 1 . When the voltage across capacitor C 0 becomes less than the gate voltage of switch Q 1 , which is the same as the voltage of capacitor C 2 , capacitor C 2 starts to discharge through a discharge loop defined by resistor R 5 , diode D 2 , capacitor C 0 , and switch Q 1 . Because capacitor C 0 continues to deliver power to PFC, capacitor C 0 is not charged up by the discharging of capacitor C 2 . The discharging current from capacitor C 2 continues flowing through capacitor C 0 via resistor R 5 , diode D 2 and switch Q 1 . The time constant of the loop may be much smaller than the time constant of capacitor C 2 and resistor R 3 so that switch Q 1 can turn off much faster in comparison with the circuit as shown in FIG. 1 . By doing so, switch Q 1 can turn off before the voltage of capacitor C 1 becomes low. The inrush current may be limited by resistor R 1 when the input power comes back after a momentarily drop. Both diode D 2 and resistor R 5 do not require any high current rating since they only discharge the gate voltage of switch Q 1 , and are thereby relatively inexpensive.
In various embodiments of an inrush protection circuit as may be described in further detail herein, the allowed inrush current may be set to 15 A peak, for explanatory purposes only and not for the purpose of otherwise limiting the scope of the present invention.
As the conventional example of the ballast and inrush protection circuit as shown in FIG. 4 and the example of the ballast and inrush protection circuit of the present invention as shown in FIG. 5 are substantially similar in various aspects but for some added circuit components in the example of FIG. 5 , a detailed explanation with regards to the circuit of FIG. 4 may be undertaken first and may apply generally as well to the circuit of FIG. 5 except where otherwise stated.
FIG. 4 shows the conventional example of a 150 W electronic HID ballast design with an inrush protection circuit. The load, including the power regulation circuit which is the buck converter, is connected to capacitor C 1 . The output power to the load including the power regulation circuit is 158 W in normal operation. The power regulation circuit regulating the average current from capacitor C 1 to the load is fixed in normal operation. The input voltage can vary from 120V˜277V. Diode bridge DB 1 is composed of four (4) diodes, such as type S3K from Fairchild. Resistor R 1 is selected to be 25 ohms and is connected in parallel with switch Q 1 , which may be a type STB26NM60N from ST Microelectronics. Resistor R 2 is divided into four (4) resistors of 464 k ohm each. The 12V zener diode ZD 1 is connected in parallel with resistor R 3 to clamp the voltage across resistor R 3 to 12V across the entire range of the input voltage. Resistor R 3 is selected to be 243 kohm and capacitor C 2 is selected to be 0.47 μF so that capacitor C 2 can be charged up to 12V across the entire range of the input voltage, which is enough to operate switch Q 1 without having any unintended loss in normal operation. Inductor L 1 , switch Q 2 , and diode D 1 collectively form the boost chopper PFC circuit. The output voltage to capacitor C 1 is boosted up to 465V so that the PFC circuit can be functional across the entire range of the input voltage during normal operation. Capacitor C 0 is the input capacitor of the PFC circuit and the capacitance is set to 1.0 μF. Capacitor C 1 is the tank circuit of the ballast and the capacitance is set to 75 μF.
According to the given specifications for the switch Q 1 , switch Q 1 can carry 15 A when the gate voltage is more than 5V. When the input power source is connected, capacitor C 2 is gradually charged up by the rectified input voltage through resistors R 2 a ˜R 2 d . It takes about 20 ms to be charged up to 5V if the input voltage is 277V. The charging time, tc, is calculated by the following equation:
tc
=
-
0.47
uF
*
464
Kohm
*
4
*
Ln
(
1
-
5
V
(
277
V
*
2
*
2
pi
)
*
464
Kohm
*
4
(
464
Kohm
*
4
+
243
Kohm
)
On the other hand, capacitor C 1 is almost fully charged through resistor R 1 up to the rectified input voltage (or even more due to the boost chopper) after 20 ms. Therefore, no high peak inrush current will occur after 20 ms even if switch Q 1 is turned on. With 120V input voltage, it takes about 47 ms to charge capacitor C 2 up to 5V. The charging time tc is calculated by the following equation:
tc
=
-
0.47
uF
*
464
Kohm
*
4
*
Ln
(
1
-
5
V
(
120
V
*
2
*
2
pi
)
*
464
Kohm
*
4
(
464
Kohm
*
4
+
243
Kohm
)
Capacitor C 1 is therefore charged up to the rectified input voltage (or even more due to the boost chopper) at this time, and thus the inrush protection circuit even with the circuit arrangement of FIG. 4 is functional when the input power source is initially connected.
However, when the input voltage is disconnected, it takes about 100 ms to discharge capacitor C 2 from 12V to 5V through resistor R 3 . This discharging time, td, may be calculated using the following equation:
td
=
-
0.47
uF
*
243
Kohm
*
Ln
(
5
V
12
V
)
On the other hand, the voltage across capacitor C 1 is dropping lower and lower because capacitor C 1 keeps delivering the required current to the power regulation circuit, which is a fixed average current in normal operation as mentioned above, even without input power source. Therefore, the voltage across capacitor C 1 can be below the peak input voltage, which is 391V (=277*√{square root over (2)}), in about 16.3 ms. The time t_C 1 @391 Vdc may be calculated using the following equation:
t_C1
@
391
Vdc
=
(
465
V
-
391
V
)
*
75
uF
*
465
V
158
W
If the input power source comes back between 16.3 ms (when the capacitor C 1 voltage is below the peak of the input voltage) and 100 ms (when switch Q 1 is still on), the inrush current with very high peak will flow through switch Q 1 and C 1 without having any resistive impedance.
An embodiment of an inrush protection circuit 31 of the present invention as shown in FIG. 5 includes a discharging circuit 32 with only two components in addition to the above mentioned example of an inrush protection circuit arrangement. One is a 19.1 kohm resistor R 5 and the other is a diode D 2 : M1F80 from Shindengen, which are connected in series between C 2 and the high side of the rectified input voltage. They are actually in parallel with resistors, R 2 a ˜R 2 d , so difficulties in the design layout may be substantially reduced.
When the input voltage is disconnected during normal operation, the voltage across capacitor C 0 may approach zero immediately because the boost chopper is still functional. Then, the voltage across capacitor C 2 can start discharging not only flowing through resistor R 3 but also largely flowing through a discharge loop defined by resistor R 5 , diode D 2 , and capacitor C 0 because the time constant of resistor R 5 and capacitor C 2 is much smaller than the time constant of resistor R 3 and capacitor C 2 . As mentioned above, because the boost chopper circuit is functional, capacitor C 0 is never charged up so that the discharging current from capacitor C 2 can keep flowing through capacitor C 0 . With the above circuit arrangement, the discharging time of capacitor C 2 is less than 8 ms from 12V to 5V. The discharging time, t_C 2 _discharge, may be calculated using the following equation:
t — C 2_discharge=−0.47 uF*19.1 Kohm*Ln(5V/12V)
Switch Q 1 will turn off or otherwise cannot deliver more than 15 A in 8 ms after the input power source is disconnected. In other words, the inrush protection circuit is already functional before the voltage across capacitor C 1 drops below the peak of the input voltage, 391V, due to a lack of input power. No peak inrush current higher than 15 A will occur even if the input is reconnected. Actually, in accordance with design parameters for the electronic ballast, the boost chopper circuit may be required to remain functional at least for 8 ms after the input power source is disconnected.
The foregoing embodiment is merely exemplary and is not to be construed as limiting the present invention. The description of the present invention is intended to be illustrative, and not to limit the scope of the claims. Many alternatives, modifications, and variations will be apparent to those skilled in the art.
The illustrations of the embodiments described herein are intended to provide a general understanding of the structure of the various embodiments. The illustrations are not intended to serve as a complete description of all of the elements and features of apparatus and systems that utilize the structures or methods described herein. Many other embodiments may be apparent to those of skill in the art upon reviewing the disclosure. Other embodiments may be utilized and derived from the disclosure, such that structural and logical substitutions and changes may be made without departing from the scope of the disclosure. Accordingly, the disclosure and the figures are to be regarded as illustrative rather than restrictive.
One or more embodiments of the disclosure may be referred to herein, individually and/or collectively, by the term ‘invention’ merely for convenience and without intending to voluntarily limit the scope of this application to any particular invention or inventive concept. Moreover, although specific embodiments have been illustrated and described herein, it should be appreciated that any subsequent arrangement designed to achieve the same or similar purpose may be substituted for the specific embodiments shown. This disclosure is intended to cover any and all subsequent adaptations or variations of various embodiments. Modification of the above embodiment, and other embodiments not specifically described herein, will be apparent to those of skill in the art upon reviewing the description.
The previous detailed description has been provided for the purposes of illustration and description. Thus, although there have been described particular embodiments of the present invention of a new and useful “Electronic Ballast with Inrush Protection Circuit,” it is not intended that such references be construed as limitations upon the scope of this invention except as set forth in the following claims. | An inrush protection circuit is provided for an electronic ballast for powering HID lamps. A first resistor is positioned along a low potential side of the circuit and a switching element coupled in parallel with the first resistor. Second and third resistors are coupled in series and effective to receive DC input power from a DC source, with a first node between the second and third resistors further coupled to the gate of the switching element. A capacitor is coupled in parallel with the third resistor to provide a smoothed DC voltage to the gate of the switching element. A discharging circuit includes a diode and a fourth resistor coupled in series between the first node and the high potential side of the circuit, and is arranged to conduct discharging current from the capacitor until the voltage across the capacitor discharges below a predetermined voltage after the DC input power is removed from the circuit. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of provisional application 61/685,317 filed on Mar. 15, 2012. This application is also a Divisional Application of Ser. No. 13/506,458 filed Apr. 20, 2012.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable
DESCRIPTION OF ATTACHED APPENDIX
Not Applicable
DESCRIPTION OF FIGURES
NONE
BRIEF DESCRIPTION OF INVENTION
This Invention discloses a process for making anionic ether amine derivatives the reaction of ether amines with 3-chloro 2-hydroxpropyl sulfonic acid sodium salt (CHPSAS) or monosodium chloroacetate (MSCA). The ether amines may be derived from natural products such as animal, marine or vegetable oils or from petroleum derived raw materials.
The invention provides the following advantages:
a) manufactured without the use of a costly and environmental problematic sulfonation processes that use sulfur trioxide, oleum or chlorosulfonic acids, b) the ether amine sulfonates or carboxylates of the present invention can be used under harsh environmental conditions since it is resistant to high temperature decomposition, and compatible with high electrolyte concentrations, c) the bulky, branched structure of the ether amine sulfonate or carboxylate of the present invention reduces the adsorption of the surfactant onto a substrate. This is of extreme importance in the case of Enhanced Oil Recovery (EOR) applications. d) the product can be made using petroleum based raw materials or using plant based, naturally derived, renewable resources as raw material, including but not limited to palm oil, rapeseed oil, canola oil, jatropha oil, crambe oil, sunflower seed oil, to insure a steady supply of environmentally safe, green surfactant, e) provides low interfacial tension (IFT) for a wide range of the oil and brine. Other advantages to the present invention will become apparent through the description and examples that follow.
DETAILED DESCRIPTION OF THE INVENTION
The reaction of the present invention uses ether amines as one of the starting materials with the structure shown below:
where
R=C1-C30 alkane, or C1-C30 alkenyl, or C4-C18 alkylphenol or C4-C18 dialkylphenol, R′=H, C1-C30 Alkane, C1-C30 Alkenyl, or R—(X)x(Y)y, R″=H, C1-C30 Alkane or C1-C30 Alkenyl, At least one of R′ or R″=H, X=methyloxirane, Y=oxirane, X and Y can be present in either order, or be a mixture of the two x÷y=1 to 100.
Ether amines are available from several manufacturers including Huntsman Chemical under the trade name Jeffamine™. CHPSAS is produced by the reaction of epichlorohydrin with sodium bisulfite as is well documented in the literature. MSCA can be obtained as a commercial product or it can be generated from chlorosulfonic acid and alkali as is well known in the literature.
The ether amines are reacted with CHPAS or MSCA at 50-150° C. and optionally in the presence of water and/or other mutual solvents. Mutual solvents include but are not limited to: water, ethylene glycol monobutyl ether, C1-C8 alkoxylated alcohol, glycerin, ethylene glycol and propylene glycol. The reaction generally takes from 2 to 12 hours for completion depending on the composition of the R, R′ and R″ groups as well as the amount of oxirane and/or methyloxirane present in the starting ether amine, and the reaction temperature.
The proposed structure of the final ether amine derivative of the present invention is shown below:
[Figure 2 Structure of the Anionic Ether Amine of the Present Invention]
where;
R=C1-C30 alkane, C1-C30 alkenyl, C4-C18 alkylphenol, or C4-C18 Dialkylphenol;
R′=H, C1-C30 Alkane, C1-C30 Alkenyl or, R—(X)x(Y)y;
R′″=H or OH;
X=methyloxirane;
Y=oxirane;
X and Y can be present in either order, or be a mixture of the two;
X+y=1 to 100;
z=0 or 1;
Z=SO 3 M or COOM;
M=H, Na, K, NH4.
The reaction of a mono ether amine with CHPSAS of the present invention is shown below. MSCA may be substituted for CHPSA to give the corresponding carboxylate.
R=C, C1-C30 alkane, C1-C30 alkenyl, C4-C18 alkylphenol, or C4-C18 Dialkylphenol;
X=methyloxirane;
Y=oxirane;
X and Y can be present in either order, or be a mixture of the two;
x+y=1 to 100.
The reaction of a diether amine with CHPSAS of the present invention is shown below. The reaction can also be carried out using MSCA instead of CHPSAS to give the corresponding carboxylate:
where:
R=C1-C30 alkane, C1-C30 alkenyl, C4-C18 alkylphenol, or C4-C18 Dialkylphenol; X=methyloxirane; Y=oxirane; X and Y can be present in either order, or be a mixture of the two; x+y=1 to 100,
The ether amine derivatives of the present invention provide excellent solubilities in aqueous solutions containing mono and divalent cations. They also provide low surface tension and interfacial tension between the aqueous and hydrocarbon phases. They provide low adsorption onto the reservoir rock surfaces. They are stable at elevated temperatures and in acidic, neutral and alkaline solutions. They can be used in various applications including but not limited to oil field, Enhanced Oil Recovery, detergents, mining, industrial cleaning, coatings, paper, and lubricants.
Example 1
99.0 g (0.200 Moles) of an ether amine where R is C12-14 alkane, y=8, x=0, R′ and R″ are both H is added to a 250 ml three-necked round-bottom flask fitted with a stirrer, a reflux condenser and a thermocouple to control the temperature of a heating mantle on which the flask rests. To this is added 50.0 g of ethylene glycol monobutyl ether (mutual solvent), 50.0 g water, 41.2 g (0.210 Moles) CHPSAS. The contents are stirred and allowed to react at 80° C. and the progress of the reaction is monitored by measuring the sodium chloride formed through the reaction. After the chloride value has leveled off and is approaching t the completion of the reaction, 10.0 g 50% sodium hydroxide is added to neutralize the product to pH 7-10.
Table 1 shows the progress of the reaction as followed by me/g chloride formed. The theoretical amount of chloride formed if the reaction were complete is 0.799 me/g.
TABLE 1
Progress of Ether Amine Reaction
Elapsed time, hr
Chloride, me/g
% completion
1
0.53
66
2
0.63
79
3*
0.64
79
4
0.71
89
5
0.74
93
6
0.79
99
*NaOH added after 3 hours reaction time at 80° C.
Example 2
Evaluation of Sample from Example 1 Above as an EOR Surfactant to Reduce the Interfacial Tension
This example described the IFT results obtained for a crude oil and a solution of the composition of the present invention in seawater. It is well known by those familiar with the art that a low interfacial tension reaching less than 0.02 mN/m is preferred to mobilize the oil from the microscopic capillaries in the reservoir rock where it is trapped. A synthetic sea water sample was prepared according to the formulation shown in Table 2.
TABLE 2
Synthetic Seawater Composition
Ingredient
% by wt
NaCl
2.75
MgCl 2 •6H 2 O
0.65
CaCl 2 •2H 2 O
0.54
Water
96.06
A sample of 0.1 wt % and, 0.2 wt % solutions of the formulation from Example 1 were prepared in the synthetic seawater described in Table 2. The interfacial tension of the surfactant solutions against a Southeast Asian crude oil with API gravity of 28.4 was measured at 90° C. and the results are shown in Table 3 below.
TABLE 3
IFT and Stability of the Ether Amine Sulfonate
Surfactant
IFT, mN/m, @ 90° C.
IFT, mN/m @ 90° C.
conc., wt %
Initial
Aging @ 90° C. for 4 Weeks
0.10
0.0047
0.0051
0.20
0.0052
0.0064
The results show that the compositions of the present invention provide ultra-low IFT and they are stable at high temperature. They are suitable as surfactants for Chemical Enhanced Recovery. The compositions of the Invention may be combined with one or more various additives known to the art including but not limited to co-surfactants, co-solvents, brines, alkalis, viscosifying agents, buffers, chelating agents and brine. They are then injected into a subterranean reservoir containing residual hydrocarbons to improve the recovery of these hydrocarbons. The aqueous solution containing the surfactant of the present invention is injected into one or more injection wells and the oil is recovered from one or more production wells. The injection wells(s) and the production well(s) may be the same or they may be different wells.
Further embodiments and alternative embodiments of various aspects of the present invention may be apparent to those skilled in the art in view of this description. Accordingly, this description is to be construed as illustrative only and is for the purpose of teaching those skilled in the art the general manner of carrying out the invention. It is to be understood that the forms of the invention shown and described herein are to be taken as the presently preferred embodiment. Elements and materials may be substituted for those illustrated and described herein, parts and processes may be reversed, and certain features of the invention may be utilized independently, as would be apparent to those skilled in the art after having benefited by this description of the invention. Changes may be made in the elements described herein without departing from the spirit and scope of the invention as described in the flowing claims. In addition, it is to be understood that features described herein independently may, in certain embodiments, be combined.
While the invention has been described in connection with a preferred embodiment, it is not intended to limit the scope of the invention to the particular form set forth, but on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims. | The process for making amphoteric surfactants derived from ether amine s is described. The ether amines may be derived from natural products such as animal, marine or vegetable oils or from petroleum derived raw materials. The application of these amphoteric surfactants to the recovery of residual oil by Enhanced Oil Recovery methods is disclosed. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
The subject application relates to copending applications as follows:
U.S. Pat. application Ser. Nos. 07/373,078, filed June 29, 1989; and 07/375,074, filed July 3, 1989
The application for Serial No. 07/375,074 is particularly relevant.
BACKGROUND OF THE INVENTION
The present invention relates generally to oxidation resistant coatings formed of alloys of titanium and aluminum. More particularly, it relates to such coatings formed of alloys of titanium and aluminum which have been modified both with respect to stoichiometric ratio and with respect to chromium and tantalum addition.
It is known that as aluminum is added to titanium metal in greater and greater proportions the crystal form of the resultant titanium aluminum composition changes. Small percentages of aluminum go into solid solution in titanium and the crystal form remains that of alpha titanium. At higher concentrations of aluminum (including about 25 to 35 atomic %) an intermetallic compound Ti 3 Al is formed. The Ti 3 Al has an ordered hexagonal crystal form called alpha-2. At still higher concentrations of aluminum (including the range of 50 to 60 atomic % aluminum) another intermetallic compound TiAl, is formed having an ordered tetragonal crystal form called gamma. Coatings formed of the gamma compound, as modified, is the subject matter of the present invention. Also, the invention concerns titanium aluminide alloy structures which are coated by gamma TiAl modified by chromium and tantalum.
The alloy of titanium and aluminum having a gamma crystal form, and a stoichiometric ratio of approximately one, is an intermetallic compound having a high modulus, a low density, a high thermal conductivity, favorable, although not extraordinary, oxidation resistance, and good creep resistance.
The relationship between the modulus and temperature for TiAl compounds to other alloys of titanium and in relation to nickel base superalloys is shown in FIG. 5. As is evident from the figure, the TiAl has the best modulus of any of the titanium alloys. Not only is the TiAl modulus higher at higher temperature but the rate of decrease of the modulus with temperature increase is lower for TiAl than for the other titanium alloys. Moreover, the TiAl retains a useful modulus at temperatures above those at which the other titanium alloys become useless. Alloys which are based on the TiAl intermetallic compound are attractive lightweight materials for use where high modulus is required at high temperatures and where good, although not extraordinary, environmental protection is also required.
One of the characteristics of TiAl which limits its actual application to such uses is a brittleness which is found to occur at room temperature. Also, the strength of the intermetallic compound at room temperature can use improvement before the TiAl intermetallic compound can be exploited in certain structural component applications. Improvements of the gamma TiAl intermetallic compound to enhance creep resistance as well as to enhance ductility and/or strength at room temperature are very highly desirable in order to permit use of the compositions at the higher temperatures for which they are suitable.
With potential benefits of use at light weight and at high temperatures, what is most desired in the TiAl compositions which are to be used is a combination of strength and ductility at room temperature. A minimum ductility of over one percent is acceptable for some applications of the metal composition but higher ductilities are much more desirable. A minimum strength for a composition to be useful is about 50 ksi or about 350 MPa. However, materials having this level of strength are of marginal utility for certain applications and higher strengths are often preferred for some applications.
The stoichiometric ratio of gamma TiAl compounds can vary over a range without altering the crystal structure. The aluminum content can vary from about 50 to about 60 atom percent. The properties of gamma TiAl compositions are, however, subject to every, significant as a result of relatively small changes of one percent or more in the stoichiometric ratio of the titanium and aluminum ingredients. Also, the properties are similarly significantly affected by the addition of relatively similar small amounts of ternary elements.
I have now discovered that further improvements can be made in the gamma TiAl intermetallic compounds and particularly in oxidation resistance, by incorporating therein a combination of additive elements so that the composition not only contains a ternary additive element but also a quaternary additive element.
Furthermore, I have discovered that the composition including the quaternary additive element has a uniquely desirable combination of properties which include a substantially improved strength, a desirably high ductility, a significantly improved creep resistance, and a remarkably valuable oxidation resistance. In fact, the oxidation resistance is so high that the material can be used as a coating layer on other titanium aluminide alloys of lower oxidation resistance.
PRIOR ART
There is extensive literature on the compositions of titanium aluminum including the Ti 3 Al intermetallic compound, the TiAl intermetallic compounds and the Ti 3 Al intermetallic compound. A patent, U.S. Pat. No. 4,294,615, entitled Titanium Alloys of the TiAl Type contains an extensive discussion of the titanium aluminide type alloys including the TiAl intermetallic compound. As pointed out in the patent in column 1, starting at line 50, in discussing TiAl's advantages and disadvantages relative to Ti 3 Al:
"It should be evident that the TiAl gamma alloy system has the potential for being lighter inasmuch as it contains more aluminum. Laboratory work in the 1950's indicated that titanium aluminide alloys had the potential for high temperature use to about 1000° C. But subsequent engineering experience with such alloys was that, while they had the requisite high temperature strength, they had little or no ductility at room and moderate temperatures, i.e., from 20° C. to 550° C. Materials which are too brittle cannot be readily fabricated, nor can they withstand infrequent but inevitable minor service damage without cracking and subsequent failure. They are not useful engineering materials to replace other base alloys."
It is known that the alloy system TiAl is substantially different from Ti 3 Al (as well as from solid solution alloys of Ti) although both TiAl and Ti 3 Al are basically ordered titanium aluminum intermetallic compounds. As the '615 patent points out at the bottom of column 1:
"Those well skilled recognize that there is a substantial difference between the two ordered phases. Alloying and transformational behavior of Ti 3 Al resemble those of titanium, as the hexagonal crystal structures are very similar. However, the compound TiAl has a tetragonal arrangement of atoms and thus rather different alloying characteristics. Such a distinction is often not recognized in the earlier literature."
The '615 patent does describe the alloying of TiAl with vanadium and carbon to achieve some property improvements in the resulting alloy. In Table 2 of the '615 patent, two TiAl compositions containing tungsten are disclosed. However, there is no disclosure in the '615 patent of any compositions TiAl containing chromium or tantalum. There is, accordingly, no disclosure of any TiAl composition containing a combination of chromium and tantalum.
A number of technical publications dealing with the titanium aluminum compounds as well as with the characteristics of these compounds are as follows:
1. E.S. Bumps, H.D. Kessler, and M. Hansen, "Titanium-Aluminum System", Journal of Metals, June 1952, pp. 609-614, TRANSACTIONS AIME, Vol. 194.
2 H.R. Ogden, D.J. Maykuth, W.L. Finlay,and R.I. Jaffee, Mechanical Properties of High Purity Ti-AI Alloys", Journal of Metals, February 1953, pp. 267-272, TRANSACTIONS AIME, Vol. 197.
3. Joseph B. McAndrew, and H.D. Kessler, "Ti-36 Pct AI as a Base for High Temperature Alloys", Journal of Metals, Oct. 1956, pp. 1348-1353, TRANSACTIONS AIME, Vol. 206.
This latter paper discloses on page 1353 a composition of titanium-35 weight percent aluminum and 7 weight percent tantalum. On an atomic percent scale this is equivalent to Ti 47 .5 Al 51 Tahd 5. This composition is stated to have an ultimate tensile strength of 76,060 psi and a ductility of about 1.5% and is discussed further below.
A discussion of oxidative influences and the effect of additives, including tantalum, on oxidation is contained starting on page 1350 of the Journal of Metals, October 1956, Transactions AIME.
4. Patric L. Martin, Magdan G. Mendiratta, and Harry A. Lispitt, "Creep Deformation of TiAl and TiAl +Alloys", Metallurgical Transactions A, Volume 14A (October 1983) pp. 2171-2174.
5. P.L. Martin, H.A. Lispitt, N.T. Nuhfer, and J.C. Williams, "The Effects of AIIoying on the Microstructure and Properties of Ti 3 Al and TiAl", Titanium 80, (Published by American Society for Metals, Warrendale, PA), Vol. 2, pp. 1245-1254 .
6. R.A. Perkins, K.T. Chiang, and G.H. Meier, "Formulation of Alumina on Ti-AI Alloys", Scripta METALLURGICA, Vol. 21 (1987) pages 1505-1510.
7. Tokuzo Tsujimoto, "Research, Development, and Prospects of TiAl Intermetallic Compound Alloys", Titanium and Zirconium, Vol. 33, No. 3, 159 (July 1985) pp. 1-19.
8. H.A Lipsitt, "Titanium Aluminites--An Overview", Mat.Res.Soc. Symposium Proc., Materials Research Society, Vol. 39 (1985) pp. 351-364.
9. S.H. Whang et al., "Effect of Rapid Solidification in Ll o TiAl Compound Alloys", ASM Symposium Proceedings on Enhanced Properties in Struc.Metals Via Rapid Solidification, Materials Week (October 1986) pp. 1-7.
10. Izvestiya Akademii Nauk SSSR, Metally. No. 3 (1984) pp. 164-168.
U.S. Pat. No. 4,661,316 to Hashianoto teaches doping of TiAl with 0.1 to 5.0 weight percent of manganese, as well as doping TiAl with combinations of other elements with manganese. The Hashianoto patent does not teach the doping of TiAl with chromium or other combinations of elements including chromium and particularly not a combination of chromium with tantalum.
U.S. Pat. No. 3,203,794 to Jaffee discloses a TiAl composition containing silicon and a separate TiAl composition containing chromium.
Japanese Kokai Patent No. Hei (1989) 298127 describes various titanium aluminide compositions containing separate additions of chromium and niobium as well as other additives.
Canadian Patent 62,884 to Jaffee discloses a composition containing chromium in TiAl in Table 1 of the patent. Jafee also discloses a separate composition in Table 1 containing tantalum in TiAl as well as about 26 other TiAl compositions containing additives in TiAl. There is no disclosure in the Jaffee Canadian patent of any TiAl compositions containing combinations of elements with chromium or combinations of elements with tantalum. There is particularly no disclosure or hint or suggestion of a TiAl compositions containing a combination of chromium and tantalum.
A number of commonly owned patents relating to titanium aluminides have issued. These include U.S. Pat. Nos. 4,836,983; 4,842,817; 4,842,819; 4,842,820; 4,857,268; 4,879,092; 4,897,127; 4,902,474, 4,923,534; and U.S. Pat. No. No. 4,842,817 to S.C. Huang and M.F.X. Gigliotti. U.S. Pat. Nos. 4,842,819 and 4,842,817 concern separate compositions containing chromium and tantalum respectively. Some of these patents include data concerning oxidation resistance of the compositions but none are as outstanding in oxidation resistance as to permit their use as coatings as effective as the coatings of this application.
With regard to the oxidation resistance of the the titanium aluminum compositions, it is recognized that titanium itself is very reactive with oxygen. What results from this reaction is the formation of a spalling oxide scale and the embrittlement of the metal itself. It is recognized that this mode of oxidation is one of the main factors that limits the use of titanium alloys at elevated temperatures. It is recognized that protective coatings which serve as oxygen barriers would enable the titanium alloys to be used for longer times at higher temperatures. We have demonstrated that coatings of the MCr and McrAlY-types can be protective to various substrates at temperatures up to about 850° C. These coatings are not as compatible with titanium aluminide substrates as titanium aluminides protective coatings would be. It is thought that at temperatures above about 850° C. it is possible that diffusion of coating elements of the MCrAlY type coatings into the alloy substrates may result in different surface reactions and may cause problems. However, the alloys which are based on the binary, titanium aluminide have a potential for use and high temperature aircraft components as they have low densities as explained more fully above and can have considerable strength and ductilities at temperatures up to about 1000° C. However, it is recognized that many of these alloys are susceptible to oxidation at these higher temperatures.
BRIEF DESCRIPTION OF THE INVENTION
It is accordingly one object of the present invention to provide titanium base alloy compositions having greater resistance to oxidation.
Another object of the present invention is to provide structures for high temperature high strength use such as in aircraft engines with high resistance to oxidation.
Another object is to provide a metal substrate with a titanium base which has oxidation resistance which approaches or surpasses the oxidation resistance of MCrAlY-type protective layers.
Other objects will be in part apparent and in part pointed out in the description which follows.
In one of its broader aspects objects of the present invention can be achieved by providing a gamma titanium aluminide having chromium and tantalum additives according to the expression:
Ti-Al 46-52 Cr 1-4 Ta 4-8 .
A preferred range of ingredients is according to the expression:
Ti-Al.sub.46-50 Cr.sub.1-4 Ta.sub.5-7 .
A more preferred range of ingredients is according to the expression:
Ti-Al 46-50 Cr 1-3 Ta 6 .
In these expressions, titanium is the balance except for the inevitable impurities.
BRIEF DESCRIPTION OF THE DRAWINGS
The detailed description of the invention which follows will be understood with greater clarity if reference is made to the accompanying drawings in which:
FIG. 1 is a graph in which weight change in milligrams per square centimeter is plotted against the cycled exposure time in hours;
FIGS. 2, 3 and 4 are graphs very similar to the graph of FIG. 1; and
FIG. 5 is a graph illustrating the relationship between modules and temperature for an assortment of alloys.
DETAILED DESCRIPTION OF THE INVENTION
We have made a detailed study of the oxidation behavior of a number of gamma TiAl alloys at temperatures up to 1000° C. In making these studies we have used a rapid thermal cycling technique and test procedure. The rapid cycle testing is a procedure in which the sample is exposed to flowing air at a designated temperature, as for example 850° C. or 1000° C., and the temperature is cycled to the test temperature for 50 minutes and then allowed to cool for 10 minutes. The air flow during such tests is at a rate of 300 milliliters per minute.
In making this series of tests we have found that the oxidation resistance is greatly influenced by the presence of low concentrations of ternary and quaternary elements such as niobium tantalum tungsten, chromium and manganese.
We have found hat when chromium alone is added, the effect on oxidation resistance is deleterious and that the resistance is reduced. We have also found that the oxidation resistance is enhanced by small niobium additions.
When a combination of chromium and niobium is added to a gamma TiAl alloy, as for example Ti-48Al-2Cr-2Nb, alloys are produced which have good physical properties and which are resistant to oxidation to about 850° C. A commonly owned patent. U.S. Pat. No.4,879,092 concerns this alloy composition. We have found that at higher temperatures this composition does produce a spalling oxide scale after an initial induction.
What we have also found to be entirely unique in the range of gamma titanium aluminide alloys having ternary and quaternary additives is a composition containing a small amount of the order of 2 atom percent of chromium and a larger amount of the order of 6 atom percent of tantalum. The oxidation behavior of these alloys is quite unique and is very dependent on the level of the tantalum additive. Extensive studies of this and related compositions have been made and this application for patent is a result of these studies.
In general, we have found that increases in the concentration of the chromium additive result in increases in oxidation resistance but that such increases also result in decrease in ductility. Chromium concentrations of from 1 to 4 atom percent may be used when coupled with tantalum additions of from 4 to 8 atom percent depending on the use application to be made of the alloy.
Similarly with respect to the aluminum ingred:rent, generally the higher the aluminum content of the novel compositions disclosed herein the better the oxidation resistance. However, higher aluminum concentrations can be detrimental to ductility of these compositions.
A principal object of coating end use applications, for example, is to form a coating which has properties the same as or close to those of a titanium aluminide substrate on which the coating is formed. A coating which has a ductility, thermal expansion, or other property or combination of properties close to that of a titanium aluminide substrate, such as Ti-48Al-2Cr-2Nb, for example, is desirable and valuable.
The remarkable novelty and uniqueness of this set of compositions can be best described with reference to the accompanying drawings in which the weight change of an alloy sample is plotted against the time and hours during which the sample was exposed to the cyclic heating at the temperature indicated on the graph.
Referring now first to FIG. 1 a plot of the results of tests of three compositions is set out on the graph. These compositions were tested through one hour heating cycles to 850° C as described above with air flowing at 300 milliliters per minute as indicated in the legend in the figure. The number of cycles of exposure given in time and hours is displayed on the abscissa and the resultant change in weight of the sample is given in milligrams per square centimeter in the ordinate. Zero weight gain is indicated in the ordinate scale and a horizontal line providing a reference value for zero weight gain is marked on the Figure. A sample having the composition Ti-48Al-2Cr-2Ta was tested and as indicated by the marked plot of FIG. 1, first displayed a relatively short weight gain over the first 50 hours of cycle testing and then displayed a very rapid weight loss as the oxide coating spallated and separated from the surface of the sample. The test results ran off the chart at -6 milligrams per square centimeter of sample at about 265 hours of cycle testing.
A sample having a composition Ti-48Al-2Cr-4Ta was tested and this composition displayed a continuing weight gain through about 300 hours of cycle testing with a net gain of about 1 milligram per square centimeter over this period of time. Obviously from the results plotted in FIG. 1, the results obtained with the second composition containing 4 atom percent tantalum represented a remarkable and unique improvement in oxidation resistance when compared to the composition containing 2 atom percent of tantalum.
A third sample having a composition of Ti-48Al-2Cr-6Ta was similarly tested in an hourly cycling test at 850° C. with the flowing air at 300 milliliters per minute. As is evident from the marked plot of FIG. 1, this sample continued to gain weight for the entire 500 hours of the test and the weight gain was less than 1 milligram per square centimeter and was closer to about 75 milligrams per square centimeter.
From the data plotted in FIG. 1 it is accordingly evident that compositions containing 4 atom percent of tantalum or more have a unique and remarkable improvement in resistance to oxidation when compared to the composition having 2 atom percent tantalum or less. The compositions having at least 6 atom percent of tantalum gave the most spectacular oxidation resistance results as is evidence from the plot of FIG. 1. At values of 8 atom percent tantalum and higher, the oxidation resistance is not as favorable as it is for the compositions with less than 8 atom percent tantalum.
Based on these results, we concluded that these compositions can be used as protective coatings on titanium aluminides, as well as on other substrates, which are more susceptible to oxidative attack at elevated temperatures.
Referring next to FIG. 2, a set of data is plotted for tests conducted at 1000.C in flowing air employing the rapid heating cycle regime of the first set of experiments. Weight change is recorded with reference to the line plotted on the figure. The first test was of a sample with a composition Ti-48Al-4Nb. As indicated on the graph, this composition first gained about 1.3 grams per square centimeter in the first 25 hours of testing and then lost weight at a rapid rate with the lost weight results going off the table at about -3 milligrams per square centimeter after about 170 hours of testing.
A second test was performed on a sample having a composition 48Al-2Cr-4Ta and the results of this test are also illustrated in the figure. The initial weight gain of about 2.5 milligrams per square centimeter during the first 70 hours of testing was followed by a decline in weight as the oxide flaked from the surface of the sample and the plot went off the lower scale at about -3 milligrams per square centimeter short of 400 hours of testing. A fourth sample having a composition Ti-24Al-llNb-0.lY was also tested and its fate is also plotted in the graph of FIG. 2. This composition first gained about 3.5 milligrams per square centimeter of sample during the first approximately 135 hours of testing and this gain was followed by an extremely rapid loss of weight with the plot going off the scale at more than 3 milligrams per square centimeter of weight loss at less than 200 hours of testing.
The third sample tested was a sample having a composition Ti-48Al-2Cr-6Ta. As is also evident from the plot this sample continued to gain weight during the entire 500 hour test and the sample had gained approximately 3.6 milligrams per square centimeter of sample after about 500 hours of testing. Accordingly it is evident from the plot of FIG. 2 that the sample having the composition Ti-48Al-2Cr-6Ta was a unique and remarkable sample with reference to oxidation resistance. The fact that the sample continued to gain weight and did not lose weight during the entire 500 hours of cyclic testing at 1000.C indicated that the oxide formed on the sample was not an oxide which spalled and separated from the surface of the sample. It is this characteristic of the oxide which forms on the titanium aluminide sample which contains 2 atom percent of chromium and 6 atom percent of tantalum which makes all the difference in the protective character of the alloy substrate.
A fourth sample had a composition Ti-48Al-2Cr-8Ta. It is evident from the plot of data obtained for this sample that it has oxidation properties less favorable than those for Ti-48Al-2Cr-6Ta but that its oxidation resistance properties are quite high and comparable to those for the composition Ti-48Al-2Cr-4Ta.
Reference is next made to FIG. 3 and to the plots of the results obtained from testing of three different doped titanium aluminide samples at 1000.C using rapid cycling and flowing air as described above.
The first sample was of an alloy having a composition Ti-48Al-8Nb. This sample was tested through the rapid cycle heating tests and the results obtained are plotted on the figure. The sample first gained about 2 milligrams per square centimeter during the first 200 hours of testing and then continuously lost weight due to spallation until the test ran off the chart at about -20 milligrams per square centimeter at about 760 hours of testing.
The second sample contained the composition Ti-48Al-2Cr-2Nb. The sample also gained about 2 milligrams per centimeter of surface area during the first 100 hours of testing and then lost weight during the next 640 hours of testing to go off the chart at about -20 milligrams per square centimeter.
The sample of one of the compositions of the present invention, containing Si-48Al-2Cr-6Ta, was tested and it also gained about 2 milligrams per square centimeter of sample during the first 100 hours of testing. However, unlike the other two samples, this sample continued to gain and failed to lose weight during the next 900 hours of testing so that the final weight of the sample represented an increase of about 4 milligrams per square centimeter during the entire 1000 hours of testing at 1000 C in flowing air during the rapid cycle heating test. This test was essentially a continuation of the test of the same composition as described with reference to FIG. 2. Again, a remarkable unique and novel resistance to oxidation is displayed by the titanium aluminide composition containing the 2 atom percent chromium and 6 atom percent tantalum.
Referring now next to FIG. 4 an effort was made through the series of tests to compare the oxidation resistance of the uncoated titanium aluminide containing 2 atom percent chromium and 6 atom percent tantalum identified as CF163 in the figure with coatings of a number of other conventional oxidation resistance materials onto a substrate of the Ti-48Al-2Cr-6Ta also identified in the FIG. 4 as CF163.
The first material tested was a NiCrAlY coating on the Ti-48Al-2Cr-6Ta substrate. The composition of NiCrAlY is a well known and well established oxidation resistant coating material employed in coating various substrate materials subjected to higher temperature and high stress. In this particular case, the temperature to which the tested sample was heated was 815° C. using the 1 hour rapid cycle testing method described above. As in all other tests set forth in this application air was flowed over the sample at 300 milliliters per minute. The result of the test is plotted in FIG. 4. The NiCrAlY data is represented by the dots in the intermediate curve between the uppermost and lowermost curves of the plot.
The next coating material tested pursuant to this series of tests was the FeCrAlY coating material represented in the graph by the vertical triangle. As is evident from FIG. 4 the data obtained from this test is plotted essentially along the same intermediate curve path as the NiCrAlY data discussed above.
The next coating sample tested was a CoCrWFeNi coating and the data obtained and plotted for this sample is represented by the inverted triangles. As is evident from FIG. 4 the series of inverted triangles again follows the intermediate curve of the figure. In each of these three tests, the weight gain over the 1000 hours of the test was approximately 1.2 milligrams per square centimeter.
The fourth test of this series was carried out with a coating composition of Ni-50Cr coated onto the CF163 base of Ti-48Al-2Cr-6Ta. The solid square data points plotted for this sample appears as the uppermost of the three plotted curves of FIG. 4. The nickle chromide displayed a weight gain which exceeded that of the 3 samples discussed above. The final level of the weight gain of the sample was not greatly different from that of the other samples and a value of about 1.3 milligrams per square centimeter was observed for this sample after it had completed the 1000 hours of rapid cycle heating.
The next sample tested is represented in the data plotted in FIG. 4 by the open squares. This sample, also identified as CF163, is the sample of the Ti-48Al-2Cr-6Ta material which was an uncoated substrate material. As is evident from FIG. 4, the weight gain for this sample was less than half of the weight gain displayed for the other four samples. The weight gain after 1000 hours of testing at 11° C. employing flowing air at 300 milliliters per minute and the 1 hour rapid cycle heating regimen was approximately 0.4 milligrams per square centimeter.
Accordingly the data plotted for the five test the samples as carried out in this testing series demonstrates that the uncoated gamma titanium aluminide alloy having 48 atom percent aluminum, 2 atom percent chromium and 6 atom percent tantalum performs at a remarkably high level of oxidation resistance for a substrate material. It must be realized that each of the other materials of this series is essentially a coating type of material so that the substrate material of the Ti-48Al-2Cr-6Ta is being compared with coating materials. One of the most critically significant differences between an uncoated substrate material and a coated material is that the substrate material possesses sufficient physical and other properties to permit its use as a structural material per se. This contrasts with substrate materials which are employed as structural materials but must be coated with a coating material such as the NiCrAlY or FeCrAlY materials which have properties suitable for use as coatings but which do not themselves possess adequate physical properties to be employed as structural materials. Accordingly, the novel and unique Ti-48Al-2Cr-6Ta material of the subject invention is unique both in that it has the remarkable oxidation resistance displayed in the four graphs discussed above but is also a material which itself serves as a substrate or which itself can serve as a structural material in the articles to be incorporated within a jet engine.
In addition, because of the unique properties which the Ti-48Al-2Cr-6Ta material displays relative to physical properties and oxidation resistance it is possible to employ this novel and unique material as a coating material. This is particularly true for substrate material such as the gamma titanium aluminides of which this material is a member. Accordingly, we have the situation in which the Ti-48Al-2Cr-6Ta material can be applied to a gamma titanium aluminide as a protective oxidation resistant coating for the gamma titanium aluminide material and this coating can be accomplished by plasma spray deposit or by a number of other means.
An oxidation resistance test performed on a sample of Ti-48Al-2Cr-8Ta provided evidence that the oxidation resistance is not as high as that of the Ti-48Al-2Cr-6Ta. However, the Ti-48Al-2Cr-8Ta material had a very superior oxidation resistance making it suitable for use in many applications, similar to the Ti-48Al-2Cr-4Ta material, in which the extraordinary oxidation resistance of the Ti-48Al Ta material is not needed. | It has been found that a titanium aluminide modified with chromium and tantalum in the rates of about Ti-Al 46-56 Cr 1-4 Ta 4-8 has a remarkable and unique antioxidation capability. Because of this unique antioxidation property, this aluminide can be used as a protective coating on other aluminides as well as on the surfaces of other bodies needing atmospheric protection. | 2 |
This application is a division of application Ser. No. 841,427 filed on Aug. 4, 1986 which is a continuation of abandoned patent application Ser. No. 642,654, filed Aug. 21, 1984.
BACKGROUND OF THE INVENTION
1. Field of the Invention:
This invention relates to a power transmission for use in vehicles provided with a continuously variable transmission (hereinafter called "CVT").
2. Description of the Prior Art:
A CVT is used for an excellent power transmission system which is to control continuously speed ratio e(=the output side rotational speed Nout/input side rotational speed Nin) to improve the specific fuel consumption of a vehicle. In a belt type CVT, a belt is trained over a pair of input side pulleys and a pair of output side pulleys, the input and output side pulleys are provided respectively with hydraulic cylinders to control press forces of the input and output side pulleys according to oil pressure supplied to the hydraulic cylinder and oil pressure in the hydraulic cylinder of one of the input and output side pulleys (usually the output side pulleys) provides line pressure which is controlled in relation to the transmission force of the belt by an electromagnetic relief valve to thereby avoid the slip of the belt while restraining the drive loss of an oil pump. However, since the hydraulic cylinder is rotated integrally with the pulley, a centrifugal force acts on a hydraulic medium in the hydraulic cylinder so that actual oil pressure becomes larger than a controllably intended value due to said centrifugal force. This increases the press force of the pulleys, causing the degradation of the transmission efficiency of the CVT and the lives of respective parts of the CVT. For prior corrective measures against such degradation are there a method of offsetting constructionally the centrifugal force itself of the hydraulic medium and a method of providing an oil reservoir in a rotary portion integral with the hydraulic cylinder and detecting an oil pressure value in the oil reservoir as a signal related to the centrifugal force through a Pitot tube to correct the line pressure through a pressure regualting valve on the basis of the detected value. In the former method, however, the offsetting of the produced centrifugal force is limited to about 50% and in the latter method problems are encountered in that the construction is complicated while power loss due to stirring is brought about. Both methods present obstacles against the practical use of prior corrective measures.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a power transmission system for a vehicle having a CVT which is to offset the increment of line pressure due to a centrifugal force without any troubles in the practical use.
According to the present invention is noted the following facts. That is, the increment ΔPl of line pressure Pl caused by the centrifugal force is represented by the following formula; ##EQU1## ω: angular velocity of hydraulic cylinder R2: radius of hydraulic cylinder
R1: radius of boss of hydraulic cylinder
ρ,R2 and R1 are constant irrespective of the running condition of an engine and ω 2 is proportional to the square Nc 2 of the rotational speed Nc of the hydraulic cylinder, so that ΔPl is substituted as the following formula represents;
ΔPl=K·Nc.sup.2 (2)
provided K is a constant.
Thus, in the power transmission system for use in a vehicle according to the present invention which comprises a belt system continuously variable transmission provided with a pair of the input side pulleys arranged opposed to each other to vary the distance therebetween in relation to oil pressure in the hydraulic cylinder, a pair of the output side pulleys arranged opposed to each other to vary the distance therebetween in relation to oil pressure in the hydraulic cylinder, a belt trained over the pairs of the input and output side pulleys to transmit rotational torque and an electromagnetic relief valve for controlling the relief amount of oil sent from an oil pump in relation to an electric control signal to produce line pressure related to the electric control signal so that the line pressure is transmitted to the hydraulic cylinder for one of the input and output side pulleys and an electronic control unit including a central processing unit(CPU) controls the electric control signal of the electromagnetic relief valve, the rotational speed Nc of the hydraulic cylinder to which the line pressure Pl is transmitted is detected by a rotational speed sensor and a product value K·Nc 2 of the square Nc 2 of the detected rotational speed Nc times the constant K is calculated for a correction amount so that the electric control signal of the electromagnetic relief valve is corrected by the electromagnetic control unit to produce the line pressure Pl corrected by this correction amount K·Nc 2 in the electromagnetic relief valve.
Consequently, the increment of the line pressure Pl due to the centrifugal force is offsetted by the decrement of same due to the correction so that the line pressure Pl provides a value meeting the transmission power of the belt as the final result in the hydraulic cylinder to prevent the degradation of the transmission efficiency of the CVT, the increase of drive loss of oil pump, the shortening of lives of respective parts in the CVT or the like. Further, according to the present invention, the addition of construction of the CVT and provision of a Pitot tube are not needed so that the electric control signal of the electromagnetic relief valve is to be varied correspondingly only to the correction amount K·Nc 2 to simplify the construction and facilitate extremely the practical use.
According to the present invention, since the line pressure Pl is corrected by varying the electric control signal of the electromagnetic relief valve, the line pressure Pl is to be more precisely controlled compared with one corrected by the use of control oil pressure.
The accompanying drawings, which are incorporated in and constitute part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph illustrating horse power lines and specific fuel consumption lines on a system of engine load-engine torque coordinates;
FIG. 2 is a graph showing the relationship among throttle position, engine speed and engine output torque;
FIG. 3 a graph showing the relationship between the throttle position and the engine speed which is defined in accordance with the line A of FIG. 2;
FIG. 4 shows a construction of an embodiment in accordance with the present invention;
FIG. 5 is a graph illustrating the relationship between the input and output of an amplifier for a flow rate controlling valve;
FIG. 6 is a graph illustrating the relationship between the input of the flow rate controlling valve and the flow rate of fluid introduced from the flow rate control valve to the hydraulic input servo of the CVT;
FIG. 7 is a graph illustrating the relationship between the input and output of a pressure regulating valve;
FIG. 8 is a graph illustrating the relationship between the input of the pressure regulating valve and line pressure;
FIG. 9 is a block diagram of an embodiment in accordance with the present invention;
FIG. 10 is a flow chart showing an example of a program in accordance with the block diagram of FIG. 9;
FIG. 11 is a graph illustrating the relationship between the speed ratio of the CVT and a line pressure; and
FIG. 12 is a graph illustrating the relationship betweem the rotational speed of the hydraulic cylinder to which the line pressure is supplied and the increment of the line pressure due to a centrifugal force produced in the cylinder.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows equivalent specific fuel consumption lines (solid line) and equivalent horse power lines (broken line) on engine speed-engine output torque. Further the unit of the equivalent horse power line is PS and the unit of the equivalent specific fuel consumption line g/PS.h. The dash-dot line shows the property of a throttle valve when it is fully opened, i.e. running limit of the engine. Line A is one interconnecting points of the minimum specific fuel consumption in each output horse power. When this line was set like line B in the speed ratio of conventional transmissions the specific fuel consumption was not good. According to the present invention the desired horse power of the engine is set as a function of operating amount of a accelerator pedal, i.e. pedalling amount thereof to run an internal combustion engine so that the engine speed and the engine output torque are specified by the line A in each desired horse power.
FIG. 2 shows the relationship between the engine speed and the engine output torque having a parameter of the throttle position of an intake system. A coincides with A shown in FIG. 1, and in the throttle position θth=10° for example the specific fuel consumption becomes minimum with 8.5 kg.m engine output torque and 1250 rpm engine speed. Thus, when the engine is run along the line A, the engine speed is a function of the throttle position θ. When the engine speed as the function of the throttle position θ specified by the line A is assumed to be a desired engine speed Ne', the relationship between the throttle position θ and the desired engine speed Ne' is shown in FIG. 3 (solid line). In FIG. 3, the desired engine speed is corrected by vehicle speed because of optimizing an engine, clutch and CVT system (broken line). Under the normal condition, the desired engine speed Ne' is calculated from the throttle position θ and vehicle speed, and when the speed ratio e of CVT is controlled so that actual engine speed Ne becomes the desired engine speed Ne', then the engine output torque becomes one as specified by the line A in FIG. 1 to run the engine with the minimum specific fuel consumption. In acceleration, the engine torque corresponding to the throttle position θ is generated by the control delay of CVT and thereafter the engine speed Ne becomes the desired engine speed Ne'. Also in deceleration, similarly due to the control delay of CVT, with the engine speed being unchanged, the engine output torque is previously reduced and then the engine speed reduced as the throttle position is displaced toward the closing one. Namely in the transient time, the change in the engine output torque due to the control delay of CVT precedes the change in the engine speed to compensate for the degradation of running performance.
While various mechanisms have been so far proposed for the CVT, an embodiment of a compact belt system CVT with a large capacity of transmitting torque will be described.
In FIG. 4, the output shaft 2 of an internal combustion engine 1 is connected to the input shaft 5 of CVT 4 through a clutch 3. The input shaft 5 and the output shaft 6 of CVT 4 are arranged parallel to each other. The input side fixed pulley 7 is secured fixedly to the input shaft 5 and the input side movable pulley 8 fits axially movably on the outer periphery of the input shaft 5 through splines or ball bearings. The output side fixed pulley 9 is secured fixedly to the output shaft 6 and the output side movable pulley 10 fits axially movably on the outer periphery of the output shaft 6 through splines or ball bearings. Further the pressure receiving area of the movable side pulley is set to provide the input side >the output side, and the fixed and movable pulleys in the input and output sides are arranged axially in the opposite direction to each other. The opposed surfaces of the fixed pulleys 7, 9 and the movable pulleys 8, 10 are formed to be tapered to increase the distances between themselves radially outward so that a belt 11 having an isosceles trapezoidal section is trained over the input and output side pulleys. Thus, as fastening forces on the fixed and movable pulleys are changed, the radial contact positions of the belt 11 on the pulley surfaces are changes continuously. When the contact positions of the belt 11 on the surfaces of the input side pulleys 7, 8 move radially outward, the contact positions of the belt 11 on the surfaces of the output pulleys 9, 10 move radially inward to increase the speed ratio e of CVT 4 ##EQU2## and in the reverse case, e is decreased. Power of the output shaft 6 is transmitted to drive wheels not shown. A throttle position sensor 18 detects the throttle position θ of the intake system. An accelerator pedal is connected to a throttle valve of the intake system so that the engine output horse power becomes a desired function of the pedalling amount of the accelerator pedal. The input and output side rotary angle sensors 20, 21 detect respectively the rotary angles, thus the number of revolution of the disks 7, 10. A pressure regulating valve 24 controls oil amount escaping to an oil path 28 as hydraulic medium sent from a reservoir 26 through an oil path 27 by an oil pump 25 to regulate line pressure Pl in an oil path 29. The line pressure Pl is supplied through the oil path 29 to a hydraulic servo of the output side movable pulley 10. A flow controlling valve 30 controls an inflow and an outflow of oil to the input side movable pulley 8. To maintain the speed ratio e of CVT 4 constant, an oil path 33 is disconnected from a line pressure oil path 31 and a drain oil path 32 branched from the oil path 29, i.e. to maintain the axial position of the input side movable pulley 8 constant for increasing the speed ratio e, oil is supplied from the oil path 31 to 33 to increase a fastening force between the input side pulleys 7, 8. To reduce the speed ratio e, oil pressure in the hydraulic servo of the movable pulley 8 is adapted to communicate to the atmospheric side through the drain oil path 32 for decreasing the thrust between the input side pulleys 7, 8. Oil pressure in the oil path 33 is lower than the line pressure Pl. However, since the working area of a piston in the hydraulic servo of the input side movable pulley 8 is larger than the working area of a piston in the hydraulic servo of the output side movable pulley 10, the fastening force between the input side pulleys 7, 8 is to be made larger than that between the output side pulleys 9, 10. To generate the fastening force for ensuring the torque transmission without any slip of the belt 11 in the output side pulleys 9, 10, the line pressure Pl is controlled by the pressure regulating valve 24 and the fastening force between the input side pulleys 7, 8 is changed by the flow controlling valve 30 to control the speed ratio. An electronic control 38 comprises a D/A (Digital/Analog) converter 40, an input interface 41, an A/D (Analog/Digital) converter 42, a CPU 43, a RAM 44 and a ROM 45 connected to each other by an address data bus 39. The analog output of the throttle position sensor 18 is sent to the A/D converter 42 and pulses of the rotary angle sensors 20, 21 are sent to the input interface 41. The outputs to the flow controlling valve 30 and the pressure regulating valve 24 are sent to the input interface 41. The outputs from the D/A converter 40 are sent to the flow controlling valve 30 and the pressure regulating valve 24 respectively through amplifiers 50, 51.
FIG. 5 shows the relationship between the input voltage and the output current of the amplifier 50 for the flow controlling valve 30, and FIG. 6 shows the relationship between the input current of the flow controlling valve 30 and the flow to the input side hydraulic servo of CVT 4. Thus, the change in the input voltage of the amplifier 50 is proportional to the speed ratio e. FIG. 7 shows the relationship between the input voltage and the output current of the amplifier 51 for the pressure regulating valve 24, and FIG. 8 shows the relationship between the input current of the pressure regulating valve 24 and the line pressure Pl. Thus the line pressure Pl is changed linearly relative to the change in the input voltage of the amplifier 51. Even if the input current of the pressure regulating valve 24 is zero, the line pressure Pl is maintained at Pl1 (Pl1≠0) so that a predetermined oil pressure is supplied to the hydraulic servos of the movable pulleys 8, 10 to ensure the minumum torque transmission in the CVT 4 even when any disconnections or failures of the electronic control 38 take place.
FIG. 9 is a block diagram of an embodiment of the present invention. In a block 55 is calculated the desired engine speed Ne', i.e. desired input rotational speed Nin' of the CVT 4 (Nin'=Ne' in this embodiment) from the throttle position θ and vehicle speed V. Deviation Nin'-Nin of the desired input rotational speed Nin' from the actual input rotational speed Nin of CVT 4 (Nin-Ne' in this embodiment) is obtained at 56. Nin'-Nin is suitably amplified up to Vin in a feedback gain 57 to be sent to the flow controlling valve 30 through the amplifier 50 for the flow controlling valve and feedback controlled so that the speed ratio e of CVT 4, thus the engine speed Ne becomes Ne' with the servo oil pressure of the input side pulley of CVT being changed. In a block 60 is calculated the actual engine output torque Te from the throttle position θ and the actual input rotational speed Nin of CVT 4. As is shown by the equivalent throttle position line in FIG. 2, the actual engine output torque Te is a function of the throttle position θ and the engine speed Ne. While Te may be detected directly by a well-known torque sensor, the torque sensor may be omitted when Te is calculated.
In a block 61, the output voltage Vout to the amplifier 51 for the pressure regulating valve is calculated according to Vout=f(Te, Nin, Nout) from the engine output torque Te, the input and output rotational speed Nin and Nout of CVT 4. The output Vout of the block 61 is sent to the pressure regulating valve 24 through the amplifier 51 for the pressure regulating valve to change the line pressure Pl. As a result, the line pressure Pl is adapted to have the minimum value capable of ensuring the torque transmission by avoiding the slip of the belt 11 so that power loss caused by too much fastening of pulleys of the CVT 4 is to be avoided.
FIG. 10 is a flow chart of a program according to the block diagram in FIG. 9. In step 66 is read the throttle position θ through the input signal from the throttle position sensor 18 and the vehicle speed V from the rotational speed of an output shaft of CVT Nout. In step 67 is calculated the desired input rotational speed Nin' based upon the map of θ'V - Nin' predetermined on the basis of the characteristic line in FIG. 3. In step 68 is read the actual input rotational speed Nin of CVT 4. In step 69 is calculated control voltage Vin sent to the amplifier 50 for flow controlling valve according to Vin=K1(Nin'-Nin), provided K1 is a constant. In step 70 is calculated the engine output torque Te from θ, Nin on the basis of the θ, Nin-Te map which is specified according to the equivalent throttle position line in FIG. 2. In step 71 is calculated the control voltage Vout sent to the amplifier 51 for the pressure regulating valve according to one of the following formulae (3)-(8). ##EQU3## provided K2, K3, K4 and K5 are constants,
Tin is the input torque of CVT 4 defined by one of formulae (9)-(11),
e is speed ratio of belt system CVT 4 (=Nout/Nin),
Nout is rotational speed of the output side hydraulic cylinder,
Ne is engine speed,
Δx is the difference |X'-x| between a desired position x' and an actual position x of the input side or output side pulley,
and
ΔP is a pressure increment allowing for the line pressure and further Tin and Te are in relation of function to each other.
The following formulae (9)-(11) define Tin. ##EQU4##
provided Tcl is torque transmitted from the crankshaft 2 of the engine 1 through the clutch 3 to the input side pulley 7 or 8,
Te is engine torque corresponding to throttle position θ,
ΔTe is an increment of engine torque corresponding to air-fuel ratio reduction of mixture,
K6 and K7 are constants,
dNe/dt is differential value of engine speed Ne with respect to time, and
dNin/dt is differential value of rotational speed Nin of the input side pulley 7 or 8 with respect to time.
Torque transmitted from the belt 11 to the output side pulley 9 or 10 is Tin/e and the belt engaging radius in the output side pulley 9 or 10 is approximately proportional to 1/(1+e). Since the more the transmitted torque Tin/e is increased and the more the belt engaging radius is decreased, the more the belt 11 is likely to slip over the surface of the output side pulley 9 or 10, the controlling accuracy of the line pressure is to be improved by making the line pressure proportional to (Tin/e)·(e+1), i.e. defining Vout as formula (2) to set the line pressure corresponding to the belt transmitted torque and the belt engaging radius.
The output side hydraulic cylinder rotates integrally with output side pulley 10 and a centrifugal force proportional to the square of the rotational speed of the output side hydraulic cylinder, i.e. the rotational speed Nout of the output side pulley 10 acts on oil in the cylinder. Oil pressure in the cylinder is raised by this centrifugal force to produce results similar to the rise of the line pressure. In FIG. 11, solid lines represent an original line pressure Pl i.e. an oil pressure produced by the pressure regulating valve 24. FIG. 12 shows the increment ΔPl of the line pressure Pl due to the centrifugal force produced in the output side hydraulic cylinder. As a result of this final line pressure in the output side hydraulic cylinder is represented by broken lines in FIG. 11. In the prefered embodiment, however, since a corrective term of K3·Nout 2 is added by formula (5), the increment of oil pressure caused by the centrifugal force is to be compensated.
While a pressure regulating valve 24 such as electromagnetic system relief valve controls the sectional areas of flow in the oil pump side port and the line pressure oil path side port according to the input current, the line pressure generated even if these sectional area of flow equal each other varies with the discharge pressure of the oil pump 25, thus the rotational speed Ne of the output shaft 2 of the engine 1 driving the oil pump 25. In formula (6) the corrective term K4·Ne is added so that the error of line pressure accompanying the input pressure change in the pressure regulating valve 24 is to be compensated.
To ensure speed change without any troubles in the transient time, namely rapid speed change, it is necessary to ensure the line pressure in response to the necessary speed change. While the input side or output side movable pulley 8 or 10 moves axially in relation to the speed change, the magnitude of the speed change relates to the difference Δx(|x'-x|) between the desired position x' and the present position x of the input side or output side variable pulley 8 or 10. The difference Δx is to be replaced with the some value of required flow at the flow controlling valve 24. Since the corrective term K5·Δx is added in formula (7), the line pressure is corrected according to the magnitude of the speed change to ensure the rapid speed change in the transient time.
To ensure the torque transmission in any running condition, it is preferable to give a predetermined allowance to the line pressure. The corrective term ΔP for such allowance is added by formula (8) to ensure the torque transmission in any running condition.
The torque Tin of the input side pulley 7 or 8 equals the torque transmitted to the input side pulley 7 or 8 through the clutch 3 provided between the output shaft 2 of the engine 1 and the input shaft 5 of CVT 4. Tin is to be substituted by Tcl according to formula (9).
In CVT 4 the engine output torque is a function of the throttle position θ. However, in warming-up or acceleration, fuel injection amount is increased and the engine output torque is increased to improve the driveability. ΔTe in formula (10) corresponds to the increment of the engine output torque caused by the increase of fuel injection amount, i.e. the decrease of air-fuel ratio of mixture, and the line pressure is to be increased correspondingly to the increment of the engine output torque due to the air-fuel ratio reduction of mixture by introducing ΔTe.
Torque Tin of the input side pulley 7 or 8 varies in relation to the change dNe/dt of the engine speed Ne with respect to time. By introducing the corrective term K6·dNe/dt in formula (10) is to be ensured the torque transmission accommodating the change in torque Tin accompanying dNe/dt.
When the clutch 3 is interposed between the output shaft 2 of engine 1 and the input shaft 5 of CVT 4, the change dNe/dt in the engine speed Ne with respect to time is not equalized to the change dNin/dt in the rotational speed Nin of the input side pulley 7 or 8 with respect to time due to the slip of the clutch 3 so that torque Tin of the input side pulley 7 or 8 accompanying dNin/dt is changed. The corrective term K7·dNin/dt is added in formula (11) to accommodate the change in torque Tin accompanying dNin/dt so that the torque transmission is to be ensured.
It will be apparent to those skilled in the art that various modifications and variations may be made in the elements of the invention without departing from the scope or spirit of the invention. | A belt type continuously valiable transmission (CVT) comprises a pair of input pulleys, a pair of output pulleys and a belt trained over input and output pulleys to transmit power. Each pair of the pulleys has a hydraulic cylinder for pressing the pulleys against the belt. A line pressure used in one cylinder is controlled by adjusting an electric pressure regulating valve. A correction value is calculated which corresponds to the square of the rotational speed of the hydraulic cylinder to which line pressure is supplied. The value of control signal of the pressure regulating valve is corrected in accordance with the correction value, so that the error of the line pressure due to a centrifugal force is compensated for. | 1 |
RELATED APPLICATION
U.S. patent application Ser. No. 358,140, filed Mar. 15, 1982 U.S. Pat. No. 4,478,749 discloses β-lactam antibiotics having an acylamino substituent in the 3-position and a ##STR2## substituent in the 1-position wherein R a is hydrogen, alkyl, substituted alkyl, phenyl or substituted phenyl and R b is hydroxy, alkoxy, (substituted alkyl)oxy, phenyloxy, (substituted phenyl)oxy, alkyl, substituted alkyl, phenyl, substituted phenyl, heteroaryl, amino(--NH 2 ), substituted amino, alkylthio, (substituted alkyl)thio, phenylthio, (substituted phenyl)thio, 1-(ethoxycarbonyloxy)ethoxy, 1,3-dihydro-3-oxo-1-isobenzofuranyloxy, ##STR3## wherein R' is hydrogen or alkyl, R" is alkyl or phenyl, R"' is hydrogen, methyl or phenyl, and R iv is hydrogen or together with R"' is --(CH 2 ) 3 -- or --(CH 2 ) 5 --.
U.S. patent application Ser. No. 381,260, filed May 24, 1982 discloses analogous β-lactams having a ##STR4## substituent.
BACKGROUND OF THE INVENTION
The β-lactam ring, ##STR5## has been known since the late nineteenth century. While knowledge of β-lactam chemistry developed during the early 1900's, it was not until 1929 that Fleming reported in Brit. J. Exper. Pathol., 10, 226 (1929) that a fermentation product of the organism Penicillium notatum had antibiotic properties. The compound which Fleming had worked with was benzylpenicillin, ##STR6## The in vivo activity of benzylpenicillin against various bacteria was reported by Chain et al. in Lancet, 2: 226 (1940).
During the early 1940's research in the field of penicillins was intense. This research focused first on structure elucidation and then on synthetic routes for preparing benzyl penicillin. It was not, however, until the late 1950's that a totally synthetic route was discovered for the preparation of benzyl penicillin.
U.S. Pat. No. 2,941,955, issued June 21, 1960, to Doyle et al., discloses the discovery of 6-aminopenicillanic acid, ##STR7## This patent was followed by U.S. Pat. No. 2,951,839, issued Sept. 6, 1960, also to Doyle et al., which discloses the use of 6-aminopenicillanic acid as a valuable intermediate which could be acylated, using art-recognized procedures, to obtain penicillin derivatives having antibiotic properties. Using 6-aminopenicillanic as a stepping stone, research chemists have prepared numerous penicillin derivatives having antibiotic activity.
The second major class of β-lactam antibiotics is the cephalosporins. In the 1940's a Cephalosporium species was found to produce an antibiotic that had activity against gram-positive and gram-negative bacteria. Work in the 1950's showed that the fermentation product of a Cephalosporium species contained not one, but several antibiotics. One of these antibiotics, cephalosporin C, ##STR8## proved to be an important stepping stone in cephalosporin research. Removal of the acyl group in the 7-position of cephalosporin C yields 7-aminocephalosporanic acid, ##STR9## an intermediate useful for the preparation of numerous acylated compounds which are analogs of cephalosporin C.
The penicillins and cephalosporins are, of course, the most important of the β-lactam antibiotics reported to date. Others have, however, been reported. Stapley et al., Antimicrobial Agents and Chemotherapy, 2(3): 122 (1972) disclose that certain actinomycete cultures isolated from soil produce antibiotics characterized by a methoxy group and D-α-aminoadipic acid on the 7-carbon of the cephem nucleus. The cephamycins, as they are known, have the formula ##STR10## Stapley et al. reported that cephamycin A and cephamycin B each exhibits a similar range of potencies against gram-negative and gram-positive bacteria, and cephamycin C had greater potency against gram-negative bacteria than against gram-positive bacteria. Cephamycin C was reported to be the most active of the three antibiotics.
Scannell et al., The Journal of Antibiotics, XXVII (1): 1 (1975), disclose the isolation from a fermentation broth of Streptomyces species 372A of (S)-alanyl-3-[α-(S)-chloro-3-(S)-hydroxy-2-oxo-3-azetidinyl-methyl]-(S)-alanine, which has the formula ##STR11##
The structure of the above naturally occurring monocyclic β-lactam containing molecule is similar to the structure of the earlier discovered β-lactam containing molecules known as tabotoxins, i.e., ##STR12## wherein X is hydrogen or methyl as reported by Stewart, Nature, 229: 174 (1971), and Taylor et al., Biochem. Biophys. Acta., 286: 107 (1972).
Recently, several novel series of naturally occurring β-lactam antibiotics have been isolated. The nocardicins, nocardicin A and B, are monocyclic β-lactams having the formula ##STR13## as reported by Hashimoto et al., The Journal of Antibiotics, XXIX (9): 890 (1976).
Clavulanic acid, a bicyclic β-lactam antibiotic isolated from fermentation broths of Streptomyces clavuligerus, has the formula ##STR14## i.e., Z-(2R,5R)-3-(β-hydroxyethylidene)-7-oxo-4-oxa-1-azabicyclo[3,2,0]heptane-2-carboxylic acid, as reported by Lloyd et al., J.C.S. Chem. Comm., 266 (1976).
Still another recently isolated β-lactam antibiotic is thienamycin, an antibiotic isolated from the fermentation broths of Streptomyces cattleya. As reported by Albers-Schonberg et al., J.A.C.S., 100: 20, 6491 (1978), thienamycin has the structure ##STR15##
Additional fused β-lactams, olivanic acid derivatives, have recently been isolated from cultures of Streptomyces olivaceus. As disclosed by Brown et al., J.C.S. Chem. Comm., these olivanic acid derivatives have the formulas ##STR16## The isolation of the above antibiotics, and a discussion of their activity, is reported by Butterworth et al., The Journal of Antibiotics, XXXII (4): 294 (1979) and by Hood et al., The Journal of Antibiotics, XXXII (4): 295 (1979).
Another recently isolated β-lactam antibiotic is PS-5, reported by Okamura et al., The Journal of Antibiotics, XXXI: 480 (1978) and The Journal of Antibiotics, XXXII (4): 262 (1979). The structure of this antibiotic, which is produced by Streptomyces cremeus subspecies auratilis, is reported to be ##STR17## Structurally related antibiotics PS-6 and PS-7 are reported in European Patent application Ser. No. 1,567 to have the respective structures ##STR18##
Two recently disclosed series of β-lactam antibiotics are the monocyclic β-lactams having the formulas ##STR19## wherein R a is acyl, R b is hydrogen or alkoxy, R c and R d are various organic substituents, and M.sup.⊖ is a cation. The antibiotics having an --SO 3 .sup.⊕ M.sup.⊖ activating group are disclosed in U.K. patent application No. 2,071,650, published Sept. 23, 1981. The antibiotics having an --O--SO 3 .sup.⊕ M.sup.⊖ activating group are disclosed in U.S. Pat. No. 4,337,197, issued June 29, 1982.
BRIEF DESCRIPTION OF THE INVENTION
This invention is directed to a novel family of β-lactam antibiotics, and to the use of such compounds as antibacterial agents. It has been discovered that the β-lactam nucleus can be biologically activated by a substituent having the formula ##STR20## and pharmaceutically acceptable salts thereof, attached to the nitrogen atom in the nucleus.
β-Lactams having a ##STR21## substituent (or a pharmaceutically acceptable salt thereof) in the 1-position and an acylamino substituent in the 3-position exhibit activity against a range of gram-negative and gram-positive bacteria.
Illustrative members of the novel family of β-lactam antibiotics of this invention are those encompassed by the formula ##STR22## or a pharmaceutically acceptable salt thereof.
As used in formula I and throughout the specification, the symbols are as defined below.
R 1 is acyl;
R 2 is hydrogen or methoxy;
R 3 and R 4 are the same or different and each is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, phenyl, substituted phenyl or a 4,5,6 or 7-membered heterocycle (referred to hereinafter as R 6 ) or one of R 3 and R 4 is hydrogen and the other is azido, halomethyl, dihalomethyl, trihalomethyl, alkoxycarbonyl, 2-phenylethenyl, 2-phenylethynyl, carboxyl, ##STR23## X 1 is azido, amino (--NH 2 ), hydroxy, alkanoylamino, alkylsulfonyloxy, phenylsulfonyloxy, (substituted phenyl)sulfonyloxy, phenyl, substituted phenyl, cyano, --S--X 2 or --O--X 2 ;
X 2 is alkyl, substituted alkyl, phenyl, substituted phenyl, phenylalkyl, (substituted phenyl)alkyl, alkanoyl, substituted alkanoyl, phenylcarbonyl, (substituted phenyl)carbonyl or heteroarylcarbonyl;
one of X 3 and X 4 is hydrogen and the other is hydrogen or alkyl, or X 3 and X 4 when taken together with the carbon atom to which they are attached form a cycloalkyl group;
X 5 is formyl, alkanoyl, phenylcarbonyl, (substituted phenyl)carbonyl, phenylalkylcarbonyl, (substituted phenyl)alkylcarbonyl, carboxyl, alkoxycarbonyl, aminocarbonyl ##STR24## (substituted amino)carbonyl, or cyano (--C.tbd.N); A is --CH═CH--, --CH 2 --CH═CH--, --(CH 2 ) n --, --(CH 2 ) n' --O--, --(CH 2 ) n' --NH--, or --(CH 2 ) n' --S--CH-- 2 ;
n is 0, 1, 2 or 3;
n' is 1 or 2;
X 6 and X 7 are the same or different and each is hydrogen or alkyl, or X 6 is hydrogen and X 7 is amino, substituted amino, acylamino or alkoxy;
R 5 is hydroxyl, alkyl, substituted alkyl, phenyl, substituted phenyl, alkoxy, alkylthio, (substituted alkyl)oxy, (substituted alkyl)thio, phenyloxy, phenylthio, (substituted phenyl)oxy or (substituted phenyl)thio; and
Y is oxygen or sulfur.
Listed below are definitions of various terms used to describe the β-lactams of this invention. These definitions apply to the terms as they are used throughout the specification (unless they are otherwise limited in specific instances) either individually or as part of a larger group.
The terms "alkyl" and "alkoxy" refer to both straight and branched chain groups. Those groups having 1 to 10 carbon atoms are preferred.
The terms "cycloalkyl" and "cycloalkenyl" refer to cycloalkyl and cycloalkenyl groups having 3,4,5,6 or 7 carbon atoms.
The term "substituted alkyl" refers to alkyl groups substituted with one, or more, azido, amino (--NH 2 ), halogen, hydroxy, carboxy, cyano, alkoxycarbonyl, aminocarbonyl, alkanoyloxy, alkoxy, phenyloxy, (substituted phenyl)oxy, R 6 -oxy, mercapto, alkylthio, phenylthio, (substituted phenyl)thio, alkylsulfinyl, or alkylsulfonyl groups.
The terms "alkanoyl", "alkenyl", and "alkynyl" refer to both straight and branched chain groups. Those groups having 2 to 10 carbon atoms are preferred.
The terms "halogen" and "halo" refer to fluorine, chlorine, bromine and iodine.
The term "protected carboxyl" refers to a carboxyl group which has been esterified with a conventional acid protecting group. These groups are well known in the art; see, for example, U.S. Pat. No. 4,144,333, issued Mar. 13, 1979. The preferred protected carboxyl groups are benzyl, benzhydryl, t-butyl, p-methoxybenzyl, and p-nitrobenzyl esters.
The term "substituted phenyl" refers to a phenyl group substituted with 1, 2 or 3 amino(--NH 2 ), halogen, hydroxyl, trifluoromethyl, alkyl (of 1 to 4 carbon atoms), alkoxy (of 1 to 4 carbon atoms), or carboxyl groups.
The expression "a 4,5,6 or 7-membered heterocycle" (referred to as "R 6 ") refers to substituted and unsubstituted, aromatic and non-aromatic groups containing one or more nitrogen, oxygen or sulfur atoms. Exemplary substituents are oxo(=0), halogen, hydroxy, nitro, amino, cyano, trifluoromethyl, alkyl of 1 to 4 carbons, alkoxy of 1 to 4 carbons, alkylsulfonyl, phenyl, substituted phenyl, 2-furylimino ##STR25## benzylimibn and substituted alkyl groups (wherein the alkyl group has 1 to 4 carbons). One type of "4,5,6 or 7-membered heterocycle" is the "heteroaryl" group. The term "heteroaryl" refers to those 4,5,6 or 7-membered heterocycles which are aromatic. Exemplary heteroaryl groups are substituted and unsubstituted pyridinyl, furanyl, pyrrolyl, thienyl, 1,2,3-triazolyl, 1,2,4-triazolyl, imidazolyl, thiazolyl, thiadiazolyl, pyrimidinyl, oxazolyl, triazinyl, and tetrazolyl. Exemplary nonaromatic heterocycles (i.e., fully or partially saturated heterocyclic groups) are substituted and unsubstituted azetincyl, oxetanyl, thietanyl, piperidinyl, piperazinyl, imidazolidinyl, oxazolidinyl, pyrrolidinyl, tetrahydropyrimidinyl, dihydrothiazolyl and hexahydroazepinyl. Exemplary of the substituted 4,5,6 or 7-membered heterocycles are 1-alkyl-3-azetinyl, 2-oxo-1-imidazolidinyl, 3-alkylsulfonyl-2-oxo-1-imidazolidinyl, 3-benzylimino-2-oxo-1-imidazolidinyl, 3-alkyl-2-oxo-1-imidazolidinyl, 3-phenyl (or substituted phenyl)-2-oxo-1-imidazolidinyl, 3-benzyl-2-oxo-1-imidazolidinyl, 3-(2-aminoethyl)-2-oxo-1-imidazolidinyl, 3-amino-2-oxo-1-imidazolidinyl, 3-[(alkoxycarbonyl)amino]-2-oxo-1-imidazolidinyl, 3-[2-[(alkoxycarbonyl)-amino]ethyl]-2-oxo-1-imidazolidinyl, 2-oxo-1-pyrrolidinyl, 2-oxo-3-oxazolidinyl, 4-hydroxy-6-methyl-2-pyrimidinyl, 2-oxo-1-hexahydroazepinyl, 2-oxo-3-pyrrolidinyl, 2-oxo-3-furanyl, 2,3-dioxo-1-piperazinyl, 2,5-dioxo-1-piperazinyl, 4-alkyl-2,3-dioxo-1-piperazinyl, and 4-phenyl-2,3-dioxo-1-piperazinyl.
The term "substituted amino" refers to a group having the formula --NY 1 Y 2 wherein Y 1 is hydrogen, alkyl, phenyl, substituted phenyl, phenylalkyl or (substituted phenyl)alkyl, and Y 2 is alkyl, phenyl, substituted phenyl, phenylalkyl, (substituted phenyl)alkyl, hydroxy, cyano, alkoxy, phenylalkoxy, or amino (--NH 2 ).
The term "substituted alkanoyl" includes within its scope compounds having the formula (substituted alkyl) ##STR26## (wherein "substituted alkyl" is defined above ) and phenylalkanoyl.
The term "acyl" refers to all organic radicals derived from an organic acid (i.e., a carboxylic acid) by removal of the hydroxyl group. Certain acyl groups are, of course, preferred but this preference should not be viewed as a limitation of the scope of this invention. Exemplary acyl groups are those acyl groups which have been used in the past to acylate β-lactam antibiotics including 6-aminopenicillanic acid and derivatives and 7-aminocephalosporanic acid and derivatives; see, for example, Cephalosporins and Penicillins, edited by Flynn, Academic Press (1972), German Offenlegungsschrift No. 2,716,677, published Oct. 10, 1978, Belgian Pat. No. 867,994, published Dec. 11, 1978, U.S. Pat. No. 4,152,432, issued May 1, 1979, U.S. Pat. No. 3,971,778, issued July 27, 1976, U.S. Pat. No. 4,172,199, issued Oct. 23, 1979, and British Pat. No. 1,348,894 published Mar. 27, 1974. The portions of these references describing various acyl groups are incorporated herein by reference. The following list of acyl groups is presented to further exemplify the term " acyl"; it should not be regarded as limiting that term. Exemplary acyl groups are:
(a) Aliphatic groups having the formula ##STR27## wherein R a is alkyl; cycloalkyl; alkoxy; alkenyl; cycloalkenyl; cyclohexadienyl; or alkyl or alkenyl substituted with one or more halogen, cyano, nitro, amino, mercapto, alkylthio, or cyanomethylthio groups.
(b) Carbocyclic aromatic groups having the formula ##STR28## wherein n is 0, 1, 2 or 3; R b , R c , and R d each is independently hydrogen, halogen, hydroxyl, nitro, amino, cyano, trifluoromethyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or aminomethyl; and R e is amino, hydroxyl, a carboxyl salt, protected carboxyl, formyloxy, a sulfo salt, a sulfoamino salt, azido, halogen, hydrazino, alkylhydrazino, phenylhydrazino, or [(alkylthio)thioxomethyl]thio.
Preferred carbocyclic aromatic acyl groups include those having the formula ##STR29## (R e is preferably a carboxyl salt or sulfo salt) and ##STR30## (R e is preferably a carboxyl salt or sulfo salt).
(c) Heteroaromatic groups having the formula ##STR31## wherein n is 0, 1, 2 or 3; R e is as defined above; and R f is a substituted or unsubstituted 5-, 6- or 7-membered heterocyclic ring (heteroaryl group) containing 1,2,3 or 4 (preferably 1 or 2) nitrogen, oxygen and sulfur atoms. Exemplary heterocyclic rings are thienyl, furyl, pyrrolyl, pyridinyl, pyrazolyl, pyrazinyl, thiazolyl, pyrimidinyl, thiadiazolyl and tetrazolyl. Exemplary substituents are halogen, hydroxyl, nitro, amino, protected amino, cyano, trifluoromethyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, or ##STR32##
Preferred heteroaromatic acyl groups include those groups of the above formulas wherein R f is 2-amino-4-thiazolyl, 2-amino-5-halo-4-thiazolyl, 4-aminopyrimidin-2-yl, 5-amino-1,2,4-thiadiazol-3-yl, 2-thienyl, 2-furanyl, or 6-aminopyridin-2-yl.
(d) [[(4-Substituted-2,3-dioxo-1-piperazinyl)carbonyl]amino]arylacetyl groups having the formula ##STR33## wherein R g is an aromatic group (including carbocyclic aromatics such as those of the formula : ##STR34## and heteroaromatics as included within the definition of R f ); and R h is alkyl, substituted alkyl (wherein the alkyl group is substituted with one or more halogen, cyano, nitro, amino or mercapto groups), arylmethyleneamino (i.e., --N═CH--R g wherein R g is as defined above), arylcarbonylamino (i.e., ##STR35## wherein R g is as defined above) or alkylcarbonylamino.
Preferred [[(4-substituted-2,3-dioxo-1-piperazinyl)carbonyl]amino]arylacetyl groups include those wherein R h is ethyl, phenylmethyleneamino or 2-furylmethyleneamino.
(e) (Substituted oxyimino)arylacetyl groups having the formula ##STR36## wherein R g is as defined above and R i is hydrogen, R 6 , alkyl, cycloalkyl, alkylaminocarbonyl, arylaminocarbonyl (i.e., ##STR37## wherein R g is as defined above) or substituted alkyl (wherein the alkyl group is substituted with 1 or more halogen, cyano, nitro, amino, mercapto, alkylthio, aromatic group (as defined by R g ), carboxyl (including salts thereof), amido, alkoxycarbonyl, phenylmethoxycarbonyl, diphenylmethoxycarbonyl, hydroxyalkoxyphosphinyl, dihydroxyphosphinyl, hydroxy(phenylmethoxy)phosphinyl, or dialkoxyphosphinyl substituents).
Preferred (substituted oxyimino)arylacetyl groups include those wherein R g is 2-amino-4-thiazolyl. Also preferred are those groups wherein R i is methyl, ethyl, carboxymethyl, 1-carboxy-1-methylethyl, 2,2,2-trifluoroethyl or 1-carboxycyclopropyl.
(f) (Acylamino)arylacetyl groups having the formula ##STR38## wherein R g is as defined above and R j is ##STR39## amino, alkylamino, (cyanoalkyl)amino, amido, alkylamido, (cyanoalkyl)amido, ##STR40##
Preferred (acylamino)arylacetyl groups of the above formula include those groups wherein R j is amino or amido. Also preferred are those groups wherein R g is phenyl or 2-thienyl.
(g) [[[3-Substituted-2-oxo-1-imidazolidinyl]carbonyl]amino]arylacetyl groups having the formula ##STR41## wherein R g is as defined above and R k is hydrogen, alkylsulfonyl, arylmethyleneamino (i.e., --N═CH--R g wherein R g is as defined above), ##STR42## (wherein R m is hydrogen, alkyl or halogen substituted alkyl), aromatic group (as defined by R g above), alkyl or substituted alkyl (wherein the alkyl group is substituted with one or more halogen, cyano, nitro, amino or mercapto groups).
Preferred [[3-substituted-2-oxo-1-imidazolidinyl]carbonyl]amino]arylacetyl groups of the above formula include those wherein R g is phenyl or 2-thienyl. Also preferred are those groups wherein R k is hydrogen, methylsulfonyl, phenylmethyleneamino or 2-furylmethyleneamino.
The terms "salt" and "salts" refer to basic salts formed with inorganic and organic bases. Such salts include ammonium salts, alkali metal salts like sodium and potassium salts (which are preferred), alkaline earth metal salts like the calcium and magnesium salts, salts with organic bases, e.g., dicyclohexylamine salt, benzathine, N-methyl-D-glucamine, hydrabamine salts, salts with amino acids like arginine, lysine and the like. The nontoxic, pharmaceutically acceptable salts are preferred, although other salts are also useful, e.g., in isolating or purifying the product.
The salts are formed in conventional manner by reacting the free acid form of the product with one or more equivalents of the appropriate base providing the desired cation is in a solvent or medium in which the salt is insoluble, or in water and removing the water by freeze drying. By neutralizing the salt with an insoluble acid like a cation exchange resin in the hydrogen form (e.g., polystyrene sulfonic acid resin like Dowex 50) or with an aqueous acid and extraction with an organic solvent, e.g., ethyl acetate, dichloromethane or the like, the free acid form can be obtained, and, if desired, another salt formed.
β-Lactams having a ##STR43## substituent (or a pharmaceutically acceptable salt thereof) in the 1-position and an amino or acylamino substituent in the 3-position contain at least one chiral center--the carbon atom (in the 3-position of the β-lactam nucleus) to which the amino or acylamino substituent is attached. This invention is directed to those β-lactams which have been described above, wherein the stereochemistry at the chiral center in the 3-position of the β-lactam nucleus is the same as the configuration at the carbon atom in the 6-position of naturally occurring penicillins (e.g., penicillin G) and as the configuration at the carbon atom in the 7-position of naturally occurring cephamycins, (e.g., cephamycin C).
With respect to the preferred β-lactams of formula I, the structural formulas have been drawn to show the stereochemistry at the chiral center in the 3-position. Because of the nomenclature convention, those compounds of formula I wherein R 2 is hydrogen have the S-configuration and those compounds of formula I wherein R 2 is methoxy have the R-configuration.
Also included within the scope of this invention are racemic mixtures which contain the above-described β-lactams.
DETAILED DESCRIPTION OF THE INVENTION
β-Lactams having a ##STR44## substituent (or a pharmaceutically acceptable salt thereof) in the 1-position of the β-lactam nucleus and an acylamino substituent in the 3-position of the β-lactam nucleus have activity against a range of gram-negative and gram-positive organisms.
The ##STR45## substituent (or a pharmaceutically acceptable salt thereof) is essential to the activity of the compounds of this invention.
The compounds of this invention can be used as agents to combat bacterial infections (including urinary tract infections and respiratory infections) in mammalian species, such as domesticated animals (e.g., dogs, cats, cows, horses, and the like) and humans.
For combating bacterial infections in mammals a compound of this invention can be administered to a mammal in need thereof in an amount of about 1.4 mg/kg/day to about 350 mg/kg/day, preferably about 14 mg/kg/day to about 100 mg/kg/day. All modes of administration which have been used in the past to deliver penicillins and cephalosporins to the site of the infection are also contemplated for use with the novel family of β-lactams of this invention. Such methods of administration include oral, intravenous, intramuscular, and as a suppository.
The β-lactams of this invention can be prepared from hydroxamic acids of formula VIII (infra.), which are obtainable from an amino acid having the formula ##STR46## utilizing the methodology disclosed in U.S. Pat. No. 4,337,197. As disclosed therein, the amino group is first protected with a classical protecting group (e.g., t-butoxycarbonyl, benzyloxycarbonyl, o-nitrophenylsulfenyl, etc.), yielding a compound having the formula ##STR47## In formula III, and throughout the specification, the symbol "A 1 " refers to a nitrogen protecting group.
The carboxyl group of a protected amino acid of formula III is then reacted with an amine salt having the formula
Y.sub.3 --O--NH.sub.3.sup.⊕ Cl.sup.⊖, IV
In formula IV, and throughout the specification, the symbol "Y 3 " refers to benzyl, pivaloyl, --CH 2 (NHA)CO 2 alkyl, t-butyl, p-nitrobenzyl, benzhydryl, 2-cyanoethyl, 2-trimethylsilylethyl, trichloroethyl, inter alia. The reaction proceeds in the presence of a coupling agent such as 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide or dicyclohexylcarbodiimide, and yields a compound having the formula ##STR48## The hydroxyl group of a compound of formula V is converted to a leaving group, using, for example, a classical reagent such as methanesulfonyl chloride (methanesulfonyl is referred to hereinafter as "Ms").
The fully protected compound having the formula ##STR49## is cyclized by treatment with base, e.g., potassium carbonate. The reaction is preferably carried out in an organic solvent such as acetone, under reflux conditions, and yields a compound having the formula ##STR50##
Alternatively, cyclization of a compound of formula V can be accomplished without first converting the hydroxyl group to a leaving group. Treatment of a compound of formula V with triphenylphosphine and diethylazodicarboxylate or carbon tetrachloride, triphenylphosphine and a base such as triethylamine, yields a compound of formula VII.
Both of the methods disclosed above for ring closure of a compound of formula V result in the inversion of the stereochemistry at the carbon bonded to the R 3 and R 4 substituents.
Selective reduction of a compound of formula VII (using catalytic hydrogenation if Y 3 is benzyl or by treatment with a base such as sodium sulfide or sodium hydroxide if Y 3 is pivaloyl or with DBU if Y 3 is --CH 2 CH(NHA)CO 2 alkyl) yields the corresponding compound having the formula ##STR51##
Phosphorylation of a hydroxamic acid of formula VIII can be accomplished by first treating the compound with base (e.g., 2,6-lutidine or triethylamine) to generate the corresponding anion and then reacting the salt with a phosphorous derivative having the formula ##STR52## wherein the activating group "Act" is, most preferably, chlorine to yield the corresponding compound having the formula ##STR53## Hydrolysis of a compound of formula X under neutral or mildly acidic conditions yields the corresponding compound having the formula ##STR54##
Alternatively, phosphorylation of a hydroxamic acid of formula VIII can be accomplished by first treating the compound with a base (e.g., 2,6-lutidine) and then reacting it with a phosphorous derivative having the formula ##STR55## wherein R 5 ' is alkyl or alkoxy, to obtain the corresponding compound having the formula ##STR56## Treatment of a compound of formula XIII with an acid-scavenger and drying agent such as bis-trimethylsilylacetamide, followed by treatment with trimethylsilyl bromide, yields an intermediate silyl ester having the formula ##STR57## wherein R 5 " is alkyl or --O--Si(CH 3 ) 3 . A compound of formula XIV is readily converted to a salt of the corresponding compound of formula XI by treatment with aqueous buffer in the range of pH 2.5 to pH 6, with or without an alcohol.
Deprotection of the 3-amino substituent of a compound of formula XI can be accomplished using art-recognized techniques. If, for example, the protecting group is t-butoxycarbonyl, trifluoroacetic acid-anisole can be used to deprotect the amino group. If the protecting group is benzyloxycarbonyl, catalytic (e.g., palladium on charcoal) hydrogenation can be used. If the protecting group is o-nitrophenylsulfenyl, p-toluenesulfonic acid can be used in combination with p-thiocresol. The deprotected compound has the formula ##STR58## and is a key intermediate for preparing the compounds of this invention.
Well known acylation techniques can be used to convert a compound of formula XV to the corresponding compound having the formula ##STR59## Exemplary techniques include reaction with a carboxylic acid (R 1 --OH) or corresponding carboxylic acid halide or carboxylic acid anhydride. The reactions with a carboxylic acid proceed most readily in the presence of a carbodiimide such as dicyclohexylcarbodiimide and a substance capable of forming a reactive intermediate in situ such as N-hydroxybenzotriazole or 4-dimethylaminopyridine. In those instances wherein the acyl group (R 1 ) contains reactive functionality (such as amino or carboxyl groups) it may be necessary to first protect these functional groups, then carry out the acylation reaction, and finally deprotect the resulting product.
The products of formula I wherein R 2 is methoxy can be prepared from the corresponding compound of formula XI wherein A 1 is benzyloxycarbonyl. Halogenating (preferably chlorinating) the amide nitrogen of a compound of formula XI yields a compound having the formula ##STR60## Reagents and procedures of N-chlorinating amides are known in the art. Exemplary reagents are tert.-butyl hypochlorite, sodium hypochlorite, and chlorine. The reaction can be run in an organic solvent (e.g., a lower alkanol such as methanol) or in a two phase solvent system (e.g., water/methylene chloride) in the presence of a base such as sodium borate decahydrate. The reaction is preferably run at a reduced temperature.
Reaction of a compound of formula XVII with a methoxylating agent, e.g., an alkali metal methoxide, yields a compound (in combination with its enantiomer if R 3 and R 4 are the same or if XVII is a racemic mixture) having the formula ##STR61## The reaction can be run in an organic solvent, e.g., a polar organic solvent such as tetrahydrofuran, at a reduced temperature.
Alternatively, a compound of formula XI, wherein A 1 is benzyloxycarbonyl, can be converted to a compound of formula XVIII using a single step procedure. The methoxylating agent can first be mixed with a compound of formula XI and the N-chlorinating reagent then added to the reaction mixture.
Conversion of a compound of formula XVIII to the desired products of formula I can be accomplished using the procedures described above for the conversion of an intermediate of formula XI to a product of this invention.
The following examples are specific embodiments of this invention.
EXAMPLE 1
Methylphosphonic acid, [3S-[3α(Z),4β]]-3-[[(2-amino-4-thiazolyl)(methoxyimino)acetyl]amino]-4-methyl-2-oxo-1-azetidinyl ester, potassium salt
(A) O-Benzyl-α-N-t-butoxycarbonyl-L-threonine hydroxamate
To a stirred solution of 10.95 g (50 mmol) of N-t-butoxycarbonyl-L-threonine in 50 ml of water was added a solution of 8.75 g (55 mmol) of O-benzylhydroxylamine hydrochloride and 50 ml of water, which had been adjusted to pH 4.0 using 2N KOH. After the addition, the pH was adjusted to 4.0, and a solution of 10.55 g (55 mmol) of 1-ethyl-3-[(3-dimethylamino)propyl]carbodiimide hydrochloride (water soluble carbodiimide, in 50 ml of water was added over 10 minutes while maintaining the pH at 4.0-4.5 using 1N HCl. The reaction was continued for 20 minutes in this pH range, and then extracted with ethyl acetate. The ethyl acetate extract was washed at pH 8.5 (aqueous NaHCO 3 ) and then at pH 3.0 (1N HCl), dried (Na 2 SO 4 ), and evaporated to a crystalline residue. Treatment with ethyl acetate-hexane gave 9.60 g of crystalline product.
(B) O-Benzyl-α-N-t-butoxycarbonyl-L-(O-mesylthreonine)hydroxamate
To a stirred solution of O-benzyl-α-N-t-butoxycarbonyl-L-threonine hydroxamate (0.60 g, 29.6 mmol) in 24 ml of dry pyridine at 0°-5° C. under nitrogen was added dropwise 2.63 ml (34 mmol) of methylsulfonyl chloride. The reaction was stirred at this temperature for 4 hours, poured into 250 ml of water, adjusted to pH 3.5 (3N HCl), treated with saturated NaCl solution, and extracted repeatedly with ethyl acetate. The combined ethyl acetate extract was washed with water, then water at pH 7, dried (Na 2 SO 4 ), and evaporated to give 11.68 g of desired product as a crystalline mass.
(C) [3S-(3α,4β)]-3-[[(1,1-Dimethylethoxy)carbonyl]amino]-4-methyl-2-oxo-1-(phenylmethoxy)azetidine
Potassium carbonate (12 g, 0.087 mol) was added to a stirred solution of 11.65 g (0.029 mol) of O-benzyl-α-N-t-butoxycarbonyl-L-(O-mesylthreonine)hydroxamate in 490 ml of acetone under nitrogen and the reaction was refluxed. After 6 hours, the reaction mixture was cooled and filtered through Celite. Evaporation of the filtrate gave a crystalline residue, which was recrystallized from ethyl acetate-hexane to give 4.65 g of crystalline product.
(D) [3S-(3α,4β)]-3-[[(1,1-Dimethylethoxy)carbonyl]amino]-4-methyl-2-oxo-1-hydroxyazetidine
To a solution of [3S-(3α,4β)]-3-[[(1,1-dimethylethoxy)carbonyl]amino]-4-methyl-2-oxo-1-(phenylmethoxy)azetidine (1.22 g, 4 mmole) in 40 ml of methanol was added 10% palladium on charcoal (0.8 g), and the reaction mixture ws reduced at atmospheric pressure for 15 minutes (until hydrogen uptake stopped). The reaction mixture was filtered through Celite and concentrated in vacuo. The solid that was obtained, was dried over P 2 O 5 at 45° C. to yield 0.75 g of product.
(E) Methylphosphonic acid, [3S-(3α,4β)]-3-[[(1,1-dimethylethoxy)carbonyl]amino]-4-methyl-2-oxo-1-azetidinyl ester, potassium salt
[3S-(3α,4β]-3-[[(1,1-Dimethylethoxy)carbonyl]amino]-4-methyl-2-oxo-1-hydroxyazetidine (1.02 g, 4.7 mmole) was partially dissolved in 14 ml of dry dichloromethane and cooled to -10° C. under nitrogen. 2,6-Lutidine (0.6 ml, 4.9 mmole) was then added followed by the dropwise addition of methylphosphonic dichloride (0.62 g, 4.6 mmole) in 5 ml of dichloromethane. After addition, the reaction was stirred at -10° C. for 1 hours. The temperature was allowed to rise to 0° C., and then 20 ml of 0.5M KH 2 PO 4 containing 2 ml of 2N KOH and 15 ml of tetrahydrofuran was added (pH 6.6). This solution was stirred at 0°-15° C. for 5 hours, and the pH was maintained at 4.2 by the addition of 1N KOH. The reaction mixture was concentrated in vacuo to remove solvent and the remainder was lyophilized. The lyophilate was washed with two 200 ml portions of dichloromethane, and the dichloromethane was concentrated in vacuo to yield 1.63 g of crude material. This was dissolved in 5 ml of water (pH 4.5) and passed through 60 ml of Dowex 50 resin (K.sup.⊕, 0.7 meq/ml) to yield 1.03 g of crude product. The product was further purified by chromatography through 80 ml of HP-20 resin using water as eluent. The product which was found to elute in a wide band (500 ml) gave, after lyophilization, 0.4 g of hygroscopic material.
(F) Methylphosphonic acid, [3S-(3α,4β)]-3-amino-2-methyl-4-oxo-1-azetidinyl ester, trifluoroacetic acid salt
Methylphosphonic acid, [3S-(3α,4β)]-3-[[(1,1-dimethylethoxy)carbonyl]amino]-4-methyl-2-oxo-1-azetidinyl ester, potassium salt (0.35 g, 1 mmole) was suspended in 1.5 ml of dichloromethane and 1.25 ml of anisole. The reaction mixture was cooled to -10° C., and trifluoroacetic acid (0.95 ml) was added. This was stirred under nitrogen at -10° C. for 1 hour. The reaction mixture was evaporated in vacuo to a residue, which was evaporated from toluene (twice) to give a viscous oil. Ether was added, and the oil solidified. The ether was decanted and the product was dried in vacuo.
(G) Methylphosphonic acid, [3S-[3α(Z),4β]]-3-[[(2-amino-4-thiazolyl)(methoxyimino)azetyl]amino]-4-methyl-2-oxo-1-azetidinyl ester, potassium salt
1-Hydroxybenzotriazole (0.169 g, 1.1 mmole) and (Z)-(2-amino-4-thiazolyl)(methoxyimino) acetic acid (0.223 g, 1.1 mmole) were dissolved in 3 ml of dry dimethylformamide under nitrogen. this was cooled to 0° C., and N,N'-dicyclohexylcarbodiimide (0.228 g, 1.1 mmole) was added portionwise. After addition, the reaction was stirred at 0° C. for 1 hour. To this was added a solution of methylphosphonic acid, [3S-(3α,4β)]-3-amino-2-methyl-4-oxo-1-azetidinyl ester, trifluoroacetic acid salt in 2 ml of dimethylformamide and 1.1 ml of N,N-diisopropylethylamine at 0° C. The reaction was stirred at 0° C. for 1 hour and then at room temperature overnight. The solution was filtered, and the filtrate was concentrated in vacuo. The residue was dissolved in water (pH 4.5), and the solution was washed with dichloromethane. The aqueous solution was passed through 80 ml of Dowex 50 (K.sup.⊕ 0.7 meq/ml). Partial purification of product was obtained by taking 8 ml fractions. Those fractions that contained product (4-8, 40 ml) were pooled and lyophilized to yield 0.4 g of material which was purified further by chromatography through 150 ml of HP-20 resin using water as eluent. Lyophilization gave 32 mg of desired product containing ca. 0.1-0.2 equivalents of 1-hydroxybenzotriazole; melting point 160°-180° C., dec.
Analysis Calc'd. for C 11 H 15 N 5 O 6 SPK: C, 31.81; H, 3.64; N, 16.86; S, 7.72; P, 7.46, Found: C, 30.24; H, 3.71; N, 16.22; S, 7.23; P, 5.6.
EXAMPLE 2
[3S-[3α(Z),4β]]-2-[[[1-(2-Amino-4-thiazolyl)-2-[[1-[(hydroxymethylphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidine]amino]oxy]-2-methylpropanoic acid, dipotassium salt
(A) Methylphosphonic acid, [3S-(3α,4β)]-3-amino-4-methyl-2-oxo-1-azetidinyl ester, trifluoroacetic acid salt
Methylphosphonic acid, [3S-(3α,4β)]-3-[[(1,1-dimethylethoxy)carbonyl]amino]-4-methyl-2-oxo-1-azetidinyl ester, potassium salt (0.223 g, 0.7 mmole; see example 1E) was suspended in 0.53 ml of anisole and 0.53 ml of dry dichloromethane under nitrogen. Trifluoroacetic acid (1.0 ml) was added dropwise at 0° C., and the reaction mixture was stirred at 0° C. to 5° C. for 2 hours. This was concentrated in vacuo to a residue, which was dried by concentration two times from 30 ml portions of toluene. The crude reaction product was triturated twice with ether to give, upon drying, a solid.
(B) [3S-[3α(Z),4β]]-2-[[[1-(2-Amino-4-thiazolyl)-2-[[1-[(hydroxymethylphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidine]amino]oxy]-2-methylpropanoic acid, diphenylmethyl ester, potassium salt
(Z)-(2-Amino-4-thiazolyl)[[2-(diphenylmethoxy)-1,1-dimethyl-2-oxoethoxy]imino]acetic acid (0.310 g, 0.7 mmole) and 1-hydroxybenzotriazole (0.108 g, 0.7 mmole) were dissolved in 4 ml of dry dimethylformamide under nitrogen. This was cooled to 0° C., and N,N'-dicyclohexylcarbodiimide (0.145 g, 0.7 mmole) was added portionwise. After addition, the reaction was stirred at 0° C. for 1 hour. To this was added a solution of methylphosphonic acid, [3S-(3α,4β)]-3-amino-4-methyl-2-oxo-1-azetidinyl ester, trifluoroacetic acid salt (ca. 0.7 mmole) in 2 ml of dimethylformamide and 0.5 ml of N,N-diisopropylethylamine at 0° C. The reaction was stirred at 0° C. for 1 hour and then at room temperature overnight. The solution was filtered and the filtrate was concentrated in vacuo. The residue was dissolved in 50 ml of dichloromethane and washed with 2 ml of water (pH 4.5). The dichloromethane was concentrated in vacuo to yield 0.581 g of crude product. This was purified partially by dissolving in 20 ml of ethyl acetate and washing with 5 ml portions of KH 2 PO 4 buffer at pH 4.5 (four times). The aqueous washes were lyophilized overnight to give 0.261 g of a residue which was passed through 10 ml of Dowex 50 (K.sup.⊕ 0.7 meq/ml) using water, and lyophilized to give 0.233 g of crude product contaminated with hydroxybenzotriazole.
(C) [3S-[3α(Z),4β]]-2-[[[1-(2-Amino-4-thiazolyl)-2-[[1-[(hydroxymethylphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidine]amino]oxy]-2-methylpropanoic acid, dipotassium salt
[3S-[3α(Z),4β]]-2-[[[1-(2-Amino-4-thiazolyl)-2-[[1-(hydroxymethylphosphinyl)oxy]-2-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidine]amino]oxy-2-methylpropanoic acid, diphenylmethyl ester, potassium salt (0.223 g) was dissolved in 1.8 ml of dichloromethane, 0.5 ml of anisole, and 1.5 ml of trifluoroacetic acid, and stirred under nitrogen at 0° C. for 2 hours. The reaction mixture was concentrated in vacuo and evaporated from toluene twice. The residue was washed with ether:ethyl acetate (1:1) (three times) to give the trifluoroacetic acid salt as a white solid. This was dissolved in 1.5 ml of pH 4.5 0.5M KH 2 PO 4 , and the pH was adjusted to 6.5 with 1N KOH. This aqueous fraction was chromatographed through 80 ml of HP-20 resin with water to give 94 mg of desired product, melting point 60°-70° C.
Analysis Calc'd for C 14 H 18 N 5 O 8 PS.2K.3.75H 2 O: C, 28.35; H, 4.33; N, 11.80; P, 5.22. Found: C, 28.61; H, 3.76; N, 11.45; P, 4.9.
EXAMPLE 3
Methylphosphonic acid, [3S-[3α(R),4β]]-3-[[[[(4-ethyl-2,3-dioxo-1-piperazinyl)carbonyl]amino]phenylacetyl]amino]-4-methyl-2-oxo-1-azetidinyl ester potassium salt
(3S-trans)-3-[[[[(4-Ethyl-2,3-dioxo-1-piperazinyl)carbonyl]amino]phenylacetyl]amino]-1-hydroxy-4-methyl-2-azetidinone (0.22 g, 0.53 mmol; see U.S. Pat. No. 4,337,197) was suspended in 8 ml of dry dichloromethane at -10° C. under nitrogen. 2,6-Lutidine (0.07 ml, 0.6 mmol) was added followed by the dropwise addition of methylphosphonic dichloride in 0.5 ml of dichloromethane. After addition, the reaction was stirred at -10° C. for 2 hours. The temperature was allowed to rise to 0° C., 8 ml of 0.5M KH 2 PO 4 containing 0.6 ml of 2N KOH (pH 6.6) was added and the reaction was stirred at room temperature for 2 hours. The organic layer was separated and the aqueous layer was lyophilized. The lyophilate was washed (3 times) with 100 ml portions of dichloromethane. These washes were concentrated in vacuo, dissolved in 2 ml of water (pH 4.5) and passed through 10 ml of Dowex 50 resin (K.sup.⊕, 0.7 meq/ml) to yield 120 mg of crude product. This was chromatographed through 50 ml of HP-20 resin packed in water; product was eluted with 20% acetone:water. After lyophilization, 62 mg of analytical product was obtained, melting point 175°-180° C., dec.
Analysis Calc'd for C 20 H 25 N 5 O 8 PK.2.25H 2 O: C, 41.85; H, 5.18; N, 12.20; P, 5.40, Found: C, 42.05; H, 5.01; N, 12.08; P, 5.0.
EXAMPLE 4
Methylphosphonic acid, (S)-2-oxo-3-[(phenylacetyl)amino]-1-azetidinyl ester, potassium salt
(S)-N-(1-Hydroxy-2-oxo-3-azetidinyl)-2-phenylacetamide (0.119 g, 0.55 mmole; see U.S. Pat. No. 4,337,197) was dissolved in 3 ml of dry dichloromethane and the solution was cooled to -10° C. under nitrogen. 2,6-Lutidine (0.065 ml, 0.56 mmole) was added, followed by the dropwise addition of a solution of methylphosphonic dichloride in 1 ml of dichloromethane. After addition, the reaction was stirred at -10° C. for 2 hours. The remaining chloro group was hydrolyzed at room temperature with 8 ml of 0.5M KH 2 PO 4 containing 0.6 ml of 1N KOH (pH 6.0). The solution was stirred vigorously for 2 hours. The dichloromethane layer was separated and the aqueous layer was lyophilized. The lyophilate was washed 3 times with 100 ml portions of dichloromethane and with 100 ml of ethanol. These washes were concentrated in vacuo, combined and dissolved in 2 ml of water. The pH of this solution was adjusted to 4.5 with 1N KOH from pH 2.5. This material was passed through 8 ml of Dowex resin (K.sup.⊕, 0.7 meq/ml) to yield 67 mg of crude product. This was placed on 15 ml of HP-20 resin and product was eluted with water. After lyophilization, 20 mg of analytical product was obtained, melting point 135°-140° C., dec.
Analysis Calc'd for C 12 H 14 N 2 O 5 PK.H 2 O: C, 40.64; H, 4.56; N, 7.90; P, 8.73, Found: C, 40.64; H, 4.47; N, 7.89; P, 8.4.
EXAMPLE 5
[3S-[3α(Z),4β]]-2-[[[1-(2-Amino-4-thiazolyl)-2-[[1-[(hydroxymethoxyphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidine]amino]oxy]-2-methylpropanoic acid, dipotassium salt
(A) Methylphosphoric acid, [3S-(3α,4β)]-3-[[(1,1-dimethylethoxy)carbonyl]amino]-4-methyl-2-oxo-1-azetidinyl ester, potassium salt
[3S-(3α,4β)]-3-[[(1,1-Dimethylethoxy)carbonyl]amino]-4-methyl-2-oxo-1-hydroxyazetidine (1.18 g, 5.46 mmole, see example 1D) was partially dissolved in 14 ml of dry dichloromethane and cooled to -70° C. under nitrogen. Triethylamine (0.78 ml, 5.46 mmole) was added followed by the dropwise addition of methyl phosphonic dichloride (0.79 g, 5.46 mmole) in 6 ml of dichloromethane. The reaction mixture was stirred for 1.2 hours while warming from -60° to -30° C. A solution of 0.5M KH 2 PO 4 pH 5.5 buffer (55 ml) was added, and the reaction was stirred vigorously. The reaction flask was removed from the cooling bath and the solution was stirred at ambient temperature for 45 minutes. The pH during this time was maintained at 3.5 to 4.0 by occasional addition of 2N KOH. The aqueous layer was lyophilized. The lyophilate was washed with three 150 ml portions of dichloromethane, and the dichloromethane was concentrated in vacuo to yield the crude triethyl ammonium salt (1.8 g). This was dissolved in water (pH 4.2) and passed through 90 ml of Dowex 50 resin (K.sup.⊕, 0.7 meq/ml) to yield 0.87 g of crude material, which was purified further by chromatography through 100 ml of HP-20 resin packed in water. The product eluted with 20% acetone-water (170 ml) to yield, after lyophilization, 0.22 g of analytically pure material, melting point 143°, dec.
(B) Methylphosphoric acid, [3S-(3α,4β)]-3-amino-4-methyl-2-oxo-1-azetidinyl ester, trifluoroacetic acid salt
Methylphosphoric acid, [3S-(3α,4β)]-3-[[(1,1-dimethylethoxy)carbonyl]amino]-4-methyl-2-oxo-1-azetidinyl ester, potassium salt (0.20 g, 0.57 mmole) was suspended in 0.65 ml of dichloromethane and 0.65 ml of anisole. The reaction mixture was cooled to -10° C., and trifluoroacetic acid (1.3 ml) was added. This was stirred at 0° C. for 1 hour. The solution was concentrated in vacuo to a residue, which was evaporated from benzene (twice) to give a viscous oil. This was triturated with ether to give a white solid, which was dried in vacuo.
(C) [3S-[3α(Z),4β]]-2-[[[1-(2-Amino-4-thiazolyl)-2-[[1-[(hydroxymethoxyphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidine]amino]oxy]-2-methylpropanoic acid, diphenylmethyl ester, potassium salt
(Z)-(2-Amino-4-thiazolyl)[[2-diphenylmethoxy)-1,1-dimethyl-2-oxoethoxy]imino]acetic acid (0.29 g, 0.66 mmole) and 1-hydroxybenzotriazole (0.10 g, 0.66 mmole) were dissolved in 8 ml of dry dimethylformamide (DMF) nitrogen. This was cooled to 0° C., and N,N-dicyclohexylcarbodiimide (0.14 g, 0.66 mmole) was added portionwise. After addition, the reaction was stirred at 0° C. for 1 hour. Methylphosphoric acid, [3S-(3α,4β)]-3-amino-4-methyl-2-oxo-1-azetidinyl ester, trifluoroacetic acid salt (0.57 mmol) in 2 ml of DMF and 0.5 ml of N,N-diisopropylethylamine were added to the activated acid side chain, and the reaction was stirred overnight at room temperature. The solution was filtered, and the filtrate was concentrated in vacuo. The residue was dissolved in 8 ml of water, and the pH was adjusted to 4.5 with 1N KOH. This solution was passed through 100 ml of Dowex 50 (K.sup.⊕, 0.7 meq/ml) using water, and lyophilized to give 0.202 g of crude material contaminated with hydroxybenzotriazole.
(D) [3S-[3α(Z),4β]]-2-[[[1-(2-Amino-4-thiazolyl)-2-[[1-[(hydroxymethoxyphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidine]amino]oxy]-2-methylpropanoic acid, dipotassium salt
[3S-[3α(Z),4β]]-2-[[[1-(2-Amino-4-thiazolyl)-2-[[1-[(hydroxymethoxyphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidine]amino]-oxy]-2-methylpropanoic acid, diphenylmethyl ester, potassium salt was dissolved in 1.8 ml of dichloromethane, 0.5 ml of anisole, and 1.5 ml of trifluoroacetic acid, and stirred under N 2 at -10° C. for 1 hour. The reaction mixture was concentrated in vacuo, and the residue was evaporated from benzene (three times). The residue was washed with ether:ethyl acetate (1:1) and ether:acetonitrile (1:1) to give a white solid. This material was dissolved in 2 ml of pH 5.5, 0.5M KH 2 PO 4 and the pH was adjusted to 6.5 with 1N KOH. This was chromatographed through 100 ml of HP-20 resin with water to give 77 mg of desired product, melting point 178°-185° C., dec.
Calc'd. for C 14 H 18 N 5 SPO 9 K 2 .2.4H 2 O: C, 28.72; H, 3.92; N, 11.96; S, 5.47; P, 5.29, Found: C, 28.72; H, 3.73; N, 11.86; S, 5.51; P, 5.0.
Additional embodiments of compounds following within the scope of this invention are:
[3S-[3α(Z),4α]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[(hydroxymethylphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy]-2-methylpropanoic acid, dipotassium salt
[3S-[3α(Z),4α]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-(hydroxymethoxyphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy]-2-methylpropanoic acid, dipotassium salt
methylphosphonic acid, [3S-[3α(Z),4β]]-3-[[(2-aminothiazolyl)(2,2,2-trifluoroethoxyimino)acetyl]amino]-4-methyl-2-oxo-1-azetidinyl ester
[3S-[3α(Z),4β]]-[[[1-(2-amino-4-thiazolyl)-2-[[1-[(hydroxymethylphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy]acetic acid
methylphosphonic acid, [3S-[3α(Z),4β]]-3-[[(2-amino-4-thiazolyl)[(2-amino-2-oxoethoxy)imino]acetyl]amino]-4-methyl-2-oxo-1-azetidinyl ester
methylphosphonic acid, [3S-(3α,4β)]-3-[[(S)-α-[(aminocarbonyl)amino]-2-thiopheneacetyl]amino]-4-methyl-2-oxo-1-azetidinyl ester
methylphosphonic acid, [3S-(3α,4β)]-3-[(aminophenyacetyl)amino]-4-methyl-2-oxo-1-azetidinyl ester
methylphosphonic acid, [2S-(2α,3β)]-3-[[(phenylsulfo)acetyl]amino]-2-methyl-4-oxo-1-azetidinyl ester
methylphosphonic acid, [3S-[3α(Z),4α]]-3-[[(2-amino-4-thiazolyl)(methoxyimino)acetyl]amino]-4-methyl-2-oxo-1-azetidinyl ester
[3S-[3α(Z),4α]]-[[[1-(2-amino-4-thiazolyl)-2-[[1-[(hydroxymethylphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy]acetic acid
methylphosphoric acid, [3S-[3α(Z),4α]]-3-[[(2-amino-4-thiazolyl)(methoxyimino)acetyl]amino]-4-methyl-2-oxo-1-azetidinyl ester
methylphosphoric acid, [3S-[3α(Z),4α]]-3-[[(2-amino-4-thiazolyl)[(2-amino-2-oxoethoxy)imino]acetyl]amino]-4-methyl-2-oxo-1-azetidinyl ester
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[(hydroxyphenylphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[hydroxy(4-methoxyphenyl)phosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[hydroxy(4-dimethylaminophenyl)phosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[hydroxy(phenylmethyl)phosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[[(azidomethyl)hydroxy]phosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[hydroxy(methoxymethyl)phosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[(hydroxyethylphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[hydroxy(2-propenyl)phosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[(hydroxyphenoxyphosphinyl)oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[hydroxy(4-methylphenoxy)phosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[hydroxy(phenylmethoxy)phosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[(hydroxyethoxy)phosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[(2-fluoroethoxy)hydroxyphosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[hydroxy(methylthio)phosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[(hydroxymethyl)thiophosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[(hydroxyphenyl)thiophosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[(hydroxymethoxy)thiophosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid
[3S-[3α(Z),4β]]-2-[[[1-(2-amino-4-thiazolyl)-2-[[1-[[(hydroxyphenoxy)thiophosphinyl]oxy]-4-methyl-2-oxo-3-azetidinyl]amino]-2-oxoethylidene]amino]oxy-2-methylpropanoic acid | Antimicrobial activity is exhibited by β-lactams having a ##STR1## substituent in the 1-position and an acylamino substituent in the 3-position, or a pharmaceutically acceptable salt thereof; wherein Y is oxygen or sulfur and R 5 is hydroxyl, alkyl, substituted alkyl, phenyl, substituted phenyl, alkoxy, alkylthio, (substituted alkyl)oxy, (substituted alkyl)thio, phenyloxy, phenylthio, (substituted phenyl)oxy or (substituted phenyl)thio. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to and the benefit of U.S. Provisional Patent Application No. 61/087,566 filed Aug. 8, 2008, entitled POLARIZATION-MODULATED TIP ENHANCED OPTICAL MICROSCOPE, which is incorporated by reference herein.
STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] This invention was made with government support under grant DBI-0845193 awarded by the National Science Foundation. The U.S. Government has certain rights to this invention.
BACKGROUND OF THE INVENTION
[0003] 1. The Field of the Invention
[0004] The present invention relates generally to optical microscopy. More particularly, the invention relates to a polarization-modulated tip enhanced optical microscope.
[0005] 2. The Relevant Technology
[0006] Microscopy is the technical field of using microscopes to view samples or objects. There are three well-known branches of microscopy: optical, electron, and scanning probe. Optical and electron microscopy involve the diffraction, refraction, or reflection of electromagnetic radiation incident upon the subject of study, and the subsequent collection of this scattered radiation in order to build up an image of the subject. This process may be carried out by wide field irradiation of the sample (for example, standard light microscopy and transmission electron microscopy) or by scanning of a fine beam over the sample (for example, confocal microscopy and scanning electron microscopy). Scanning probe microscopy involves the interaction of a scanning probe with the surface or object of interest. The development of microscopy revolutionized biology and remains an essential tool in that science, along with many others.
[0007] Optical or light microscopy involves passing light transmitted through or reflected from the sample through a single lens or multiple lenses to allow a magnified view of the sample. More specifically, as light, such as a laser beam, is focused through a lens and onto a sample, the sample fluoresces. That is, as the light is directed onto the sample, the sample absorbs the light and emits light of a different wavelength. The resulting light can be detected directly by the eye, imaged onto a photographic plate, or captured digitally. The single lens with its attachments or the system of lenses and imaging equipment along with the appropriate lighting equipment, sample stage and support make up the basic light microscope.
[0008] While optical microscopy provides many benefits in imaging a sample, the resolution achieved with standard optical microscopy is limited. In particular, because standard optical microscopy uses light to image a sample, structures or features of the sample that are smaller than about half the wavelength of the light focused on the sample cannot be imaged. In biological samples, for example, the focused light is usually within the visible range of light, i.e., 500 to 800 nanometers. This means that sample structures or features that are smaller than 250 to 400 nanometers cannot be resolved or imaged using standard optical microscopy.
[0009] Many solutions have been designed to overcome these inherent limitations of the optical microscope, including tip-enhanced fluorescence microscopy (“TEFM”). TEFM is a type of apertureless near field scanning optical microscope (“ANSOM”) that utilizes fluorescence to generate an image. By aligning the sharp tip of a probe into the focus of a laser beam with axial polarization, enhanced fields are generated at the apex of the tip where the intensity of light is significantly greater than without the probe, analogous to a lightning rod. This field enhancement is tightly confined to the vicinity of the tip apex and has been shown to decay rapidly as r −6 with distance r from the tip apex. Therefore, light intensity measurements even a few nanometers away from the tip are lower than those at the tip and are about the same as if the tip were not present.
[0010] Once the high intensity region is created, it can be used to image nanometer scale features of a sample. When this technique is used to scan and image a sample, a background image is created. The background image is created by the light that is directed onto the sample away from the high intensity light region. This image is the same image that would be achieved by using a standard optical microscope without the addition of the probe tip, and thus the resolution is limited by diffraction. In addition to the background image, however, the high intensity region provides a greater detailed image of the sample within the high intensity region. As the sample is scanned, the more detailed image is superimposed on the background image, thereby providing a more detailed image of the complete sample.
[0011] The high intensity region enables information to be obtained about the distribution, structures, and features of the sample with much better resolution. In fact, the resolution is independent of the wavelength of the laser beam, and is only dependent on the size of the high intensity region. The size of the high intensity region is determined by the sharpness of the probe tip. In this manner, resolution can be achieved down to about 10 nanometers, thereby overcoming the diffraction limit discussed above by a factor of about 25.
[0012] The above identified modified optical microscope works well for imaging isolated molecules or particles on a surface when the molecules or particles are farther apart on average than the size of the laser beam. When they are close together and within the laser beam focus, the background signal goes up because each molecule or particle is fluorescing. However, because the region of higher intensity near the tip is so tightly localized, only one of the molecules or particles experiences the elevated field near the end of the tip. Thus, the more dense the sample is, the more molecules or particles there are within the laser focus, thereby reducing the image contrast because there is only one molecule that is being affected with the high intensity region near the tip, but there are many molecules within the laser that increase the background signal.
[0013] In response to problems associated with this poor contrast, methods for increasing the contrast between the background signal and that of the high intensity region have been developed. For example, in some applications, the probe tip is rapidly vibrated in and out of the region containing the sample to, in essence, rapidly modulate the detected signal. When the tip is moved close to the sample, the high intensity region at the tip's apex causes an increase in the detected signal. In contrast, when the tip is moved away from the sample, the signal returns to the background level. Any sample molecule within the high-intensity region will experience the higher intensity light, and the signal collected from that molecule will increase. However, the molecules outside of the higher intensity region, but within the area illuminated by the laser, will not experience the higher intensity light and the signal collected from them will, therefore, be the same as that resulting from the normal laser beam. In contrast, when the probe tip is moved away from the sample region, the high intensity region is removed from the single molecule, and the signal collected from that single molecule then returns to its normal level resulting from the laser beam.
[0014] In other words, oscillating or vibrating the tip quickly above the sample causes one molecule that is close to the tip to “blink” or fluctuate its fluorescence rate at the same rate that the tip is being oscillated. While one molecule within the high intensity region blinks, the signals given by molecules that are not close to the tip, but which are still within the laser focus, remain unchanged. Therefore, rather than detecting how much light is given off by a sample, the amount of “blinking” by each molecule is detected. In this manner the background signal can be suppressed while focusing on the one blinking molecule.
[0015] While oscillating the tip causes a molecule to blink, the blinking of the molecule is sensitive to the amplitude of the tip's oscillation. If the oscillation amplitude is too small then the fluctuation or blinking of the molecule is too small to detect or separate from the background signal. However, if the oscillation amplitude is too large, then the fluctuations or blinking will only occur for a brief period of time, that fraction of the oscillation period whereby the tip is close to the sample. Thus, there is an optimum oscillation amplitude for the tip. A limitation of the tip-oscillation method summarized above is that this optimum oscillation amplitude is rather large, (˜40 nm), which is sufficiently large as to possibly cause damage or unwanted perturbations to very soft samples, such as the thin membranes that envelope a cell or various organelles within the cell. This limits the utility of the technique when applied to a number of very important biological systems.
[0016] The subject matter claimed herein is not limited to embodiments that solve any disadvantages or that operate only in environments such as those described above. Rather, this background is only provided to illustrate one exemplary technology area where some embodiments described herein may be practiced.
BRIEF SUMMARY OF THE INVENTION
[0017] The present invention relates generally to high resolution optical microscopy techniques. More particularly, the invention provides a system for improved high resolution scanning using a polarization-modulated tip enhanced optical microscope. It would be recognized that the invention has a broad range of applicability. For example, this invention can be applied with apertureless near field scanning optical microscopes that image samples with various scattering processes, including one- and two-photon fluorescence, Raman scattering, infrared spectroscopy, and Rayleigh scattering. Moreover, the scanned samples can be from a variety of different fields such as biology, electronics, semiconductors, organic chemistry, life sciences, biotechnology, nanotechnology, molecular and biological circuits, and others.
[0018] A system for improved high resolution scanning according to exemplary embodiments of the present invention uses a polarization-modulated tip enhanced microscope to selectively generate and remove a high intensity light region near the probe tip. This invention can turn the region of high intensity light off and on without oscillating the probe tip in and out of the focus of the light source, or toward and away from the sample surface. One advantage of this system is that no damage is done to sensitive samples by the oscillations of the polarization-modulated tip.
[0019] An optical microscope according to this invention comprises a light source adapted to generate and emit light, a probe tip with a longitudinal axis that is disposed within the path of the light from the light source, a lens disposed between the light source and the probe tip that is configured to focus the light from the light source onto the probe tip, and a means for changing a polarization of the light from the light source. When the means for changing the polarization of light alternates between a polarization substantially aligned with the longitudinal axis of the probe dip and a polarization traverse to the longitudinal axis of the probe tip, the light will alternately create and remove a region of high intensity light adjacent an end of the probe tip.
[0020] An optical microscope system according to another embodiment of this invention comprises a cantilever with a probe tip coupled to a piezo-electric stack, a light source adapted to emit light, a stage disposed beneath the cantilever, a photodiode configured to receive emitted light from a sample, an objective lens disposed beneath the stage that is configured to focus the light from the light source onto the probe tip, a dichroic mirror aligned to both direct the light from the light source through the objective lens by reflection and to transmit emitted photons from the sample to the photodiode, and a light polarization device adapted for changing a polarization of the light from the light source. When the light polarization device alternates between a polarization substantially aligned with the longitudinal axis of the probe tip and a polarization transverse to the longitudinal axis of the probe tip, the light will alternately create and remove a region of high intensity light adjacent to the end of the probe tip.
[0021] According to another embodiment of this invention, a method for imaging microscopic objects using detection of photons emitted from the objects is disclosed. The method comprises: first, locating a tip of a probe near a sample to influence a rate of emission of electromagnetic energy from the sample; second, focusing light adjacent the tip of the probe; and third, alternating the polarization of the light between a direction substantially aligned with the longitudinal axis of the probe tip and a direction that is generally transverse to the longitudinal axis of the probe tip in order to alternately create and remove a region of high intensity light adjacent the tip of the probe.
[0022] This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
[0023] Additional features and advantages will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the teachings herein. Features and advantages of the invention may be realized and obtained by means of the instruments and combinations particularly pointed out in the appended claims. Features of the present invention will become more fully apparent from the following description and appended claims, or may be learned by the practice of the invention as set forth hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] To further clarify the above and other advantages and features of the present invention, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. It is appreciated that these drawings depict only illustrated embodiments of the invention and are therefore not to be considered limiting of its scope. The invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which:
[0025] FIG. 1 illustrates a schematic representation of an optical microscope system according to an exemplary embodiment of the present invention;
[0026] FIG. 2A illustrates an optical microscope system with two peripheral light rays, each having a particular polarization, being passed through a lens and focused adjacent a probe tip and the resultant polarization of the focused light;
[0027] FIG. 2B illustrates the optical microscope system of FIG. 2A with two peripheral light rays having different polarizations being passed through a lens and focused adjacent a probe tip and the resultant polarization of the focused light;
[0028] FIG. 3A illustrates an optical microscope system with a single peripheral light ray, having a particular polarizations, being passed through a lens and focused adjacent a probe tip, and being reflected back through the lens by a glass slide, and the resultant polarizations of the focused light;
[0029] FIG. 3B illustrates the optical microscope of FIG. 3A with a single peripheral light ray, having a different polarization than in FIG. 3A , being passed through a lens and focused adjacent a probe tip, and being reflected back through the lens by a glass slide, and the resultant polarizations of the focused light;
[0030] FIG. 4A illustrates an optical microscope system with a region of enhanced optical intensity adjacent a probe tip resulting from the polarization of light being passed through a lens;
[0031] FIG. 4B illustrates the optical microscope system of FIG. 4A with light of a different polarization being focused through the lens, thereby eliminating the region of enhanced optical intensity adjacent the probe tip; and
[0032] FIG. 5 illustrates an exemplary microscope arrangement that utilizes the invention described herein.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0033] The present invention relates generally to high resolution optical microscopy systems and techniques. More particularly, the invention provides a system for improved high resolution scanning using a polarization-modulated tip enhanced optical microscope. It would be recognized that the invention has a broad range of applicability. The present invention can be configured to resolve features of a sample on the nanometer scale. Additionally, the present invention can be used to identify different kinds of molecules based on the spectra of light emitted by the molecules when a light is directed onto the sample. The emitted light spectra can be used to identify various features, structures, and characteristics of the sample, even if the sample is a single molecule. Moreover, the present invention maintains most, if not all, of the advantages of using light to image structures, while achieving greater resolution of the sample without being limited by the wavelength of the light used to image the sample or without damaging the sample.
[0034] Depicted in FIG. 1 is a schematic diagram of an optical microscope system 100 according to an exemplary embodiment of the present invention. The embodiment illustrated in FIG. 1 is merely exemplary and is not intended to limit the scope of the present invention. Rather, one of ordinary skill in the art will appreciate that modifications, alternatives, and variations can be made to the embodiment of FIG. 1 without departing from the scope of the present invention.
[0035] As shown, the present optical microscope system 100 includes a probe tip 103 , a lens 105 , a polarizer 107 , and a light source 109 . In an exemplary embodiment, light source 109 comprises a laser. Light source 109 may alternatively comprise one or more lasers, light bulbs, xenon arc lamps, mercury-vapor lamps, and the like. Lens 105 is disposed between light source 109 and probe tip 103 such that lens 105 focuses the light from light source 109 adjacent probe tip 103 . Disposed between lens 105 and light source 109 is polarizer 107 . Polarizer 107 can be any suitable structure or device that can change the polarization of the light from light source 109 . By way of non-limiting examples, polarizer 107 can include a Pockels cell, a liquid crystal device, a retarder, a crystal, a combination thereof, or any other structure(s) or device(s) known in the art that is able to change the polarization of light. The aforementioned polarizers can comprise and function as means for changing a polarization of the light from light source 109 .
[0036] Polarizer 107 is configured to alternate the polarization of the light from light source 109 between a direction generally aligned with an axis of probe tip 103 (referred to herein as longitudinal polarization) and a direction that is generally transverse to the axis of probe tip 103 (referred to herein as transverse polarization). When the light from light source 109 has a generally longitudinal polarization, a region of enhanced light intensity is created adjacent to an end of probe tip 103 . In contrast, when the light from light source 109 has a generally transverse polarization, no region of enhanced light intensity is created adjacent to the end of probe tip 103 .
[0037] In some exemplary embodiments, such as those illustrated in the Figures, the relevant axis of probe tip 103 that is used, in conjunction with the polarization of the incident light, to create the region of enhanced light intensity is a longitudinal axis of the probe tip. In the illustrated embodiments, probe tip 103 is illustrated as being elongated with a longitudinal axis of probe tip 103 being generally perpendicular to the sample plane. It will be appreciated, however, that probe tip 103 can be configured in any number of ways without departing from the spirit and scope of the present invention. For instance, rather than having a pyramidal or other pointed shape that has a longitudinal axis that is perpendicular to the sample plane, probe tip 103 can have a spherical shape. When probe tip 103 has a spherical shape, changing the polarization of the light from light source 109 between longitudinal and transverse polarizations can change the location of the region of enhanced light intensity. For instance, when the light from light source 109 has a longitudinal polarization, a region of enhanced light intensity is created at the lower pole of the probe tip near the sample. When the polarization is changed to a transverse polarization, the region of enhanced light intensity is shifted from the pole to the equatorial plane of the spherically shaped probe tip.
[0038] In light of the disclosure herein, it will be understood that probe tip 103 can be shaped and configured in any suitable manner that allows for the creation and removal of a region of enhanced light intensity as the polarization of the incident light is changed. Thus, the systems and methods of the present invention are generally directed to creating and removing a region of enhanced light intensity near a probe tip and sample in order to image the sample. The specific configuration of the probe tip and the specific polarizations of the incident light are not critical. Rather, present invention is directed to using any probe tip that can cooperate with changing polarizations of light to create and remove the region of enhanced optical intensity, regardless of the specific configuration of the probe tip and the polarizations of the light. Thus, in some embodiments, the region of enhanced light intensity is created when the light's polarization is aligned with a longitudinal axis of the probe tip and removed when the polarization is transverse to the longitudinal axis of the probe tip. In other embodiments, however, the probe tip may be configured to create the region of enhanced light intensity when the light's polarization is transverse to an axis of the probe tip and remove the region when the polarization is aligned with the axis of the probe tip. In still other embodiments, the polarization of the light may create and remove the region of enhanced light intensity without regard to any axis of the probe tip. Therefore, while some embodiments are described herein with polarizations being aligned with or transverse to an axis of the probe tip, it will be appreciated that such descriptions are exemplary only, and not limiting of the scope of the present invention.
[0039] It is not required that light source 109 and polarizer 107 be disposed immediately beneath lens 105 . Instead, in a specific embodiment of the invention, a combination of lenses and mirrors are used to direct the light from light source 109 through polarizer 107 and then subsequently through lens 105 . In one embodiment, the combination of lenses and mirrors includes a beam splitter to split the light from light source 109 , directing only a part of the light through lens 105 . In a separate embodiment the combination of lenses and mirrors includes a dichroic lens which adjusts the light so as to direct it through lens 105 .
[0040] In an exemplary embodiment, lens 105 is a single lens that focuses the light from light source 109 onto probe tip 103 . However, lens 105 may comprise one or more lenses, and may even comprise a complex objective lens.
[0041] In an exemplary embodiment, probe tip 103 has a pyramidal shape and the tip of the pyramid is coated with silver particles. However, other particles or coatings can also be used. For example, such coatings include, among others, semiconductors (e.g., silicon, silicon nitride, diamond, etc.), conductors (e.g., platinum, gold, silver alloys, aluminum, platinum-irridium, cobalt and other metals as well as materials doped to be conductive), as well as other combination of these, and the like.
[0042] Exemplary embodiments of the present invention employ standard optical microscopes with a probe tip positioned within the focused laser beam as described elsewhere herein to create a high intensity light region adjacent to a sample. However, rather than oscillating the probe tip in and out of the laser beam, or toward and away from the sample surface, to create the high intensity light region near the sample, the present invention is directed to creating the high intensity light region without significant oscillations of the probe tip. Nonetheless, the present invention may be accomplished even if the probe tip is oscillated.
[0043] To create the high intensity region near the end of the probe tip, the polarization of the focused laser beam is aligned with the axis of the probe tip. If the polarization is rotated so that it is generally transverse to the axis of the probe tip, as illustrated in FIG. 2A , then the high intensity region will not exist.
[0044] Therefore, even if the probe tip is not oscillated above the sample, but the polarization of the laser beam is rotated from a first polarization to a second polarization, the high intensity region is created and removed from above the sample. Thus, the high intensity region can be controlled through modulating the polarization of the laser beam. As the polarization is modulated, the signal from the single molecule that is near the tip modulates or blinks at the same rate as the polarization.
[0045] The above described method for creating and removing the high intensity region does not require large oscillation amplitudes of the probe tip. In fact, the method does not require any oscillation of the tip at all. While no oscillation is required, small oscillations of the probe tip are acceptable. Eliminating oscillations of the probe tip, or at least minimizing their amplitudes, reduces the likelihood of damaging soft samples. Thus, using the methods and devices of the present invention enables the blinking of sample molecules so that the background signal from the rest of the sample molecules can be suppressed.
[0046] In an exemplary embodiment of the invention, polarizer 107 comprises a Pockels cell, although polarizer 107 alternatively can comprise multiple Pockels cells, a liquid crystal device, a retarder, a crystal, or any other structure or device known in the art that is able to change the polarization of light. A Pockels cell can be used to rotate the laser beam polarization between a first polarization and a second polarization. A Pockels cell has a crystal with some birefringence which gives it the ability to rotate the polarization of light. However, the ability to rotate the polarization is dependent on an electric field that is applied across the crystal. As a laser beam propagates through the crystal, its polarization can either be rotated or not depending on the presence and size of a voltage applied across the crystal. As the presence or size of the voltage across the crystal is changed, the polarization of the light passing through the crystal is rotated. The voltage across the crystal can be changed relatively quickly, thereby allowing the polarization of the laser beam to be changed relatively quickly.
[0047] Thus, the polarization of a laser beam can be rotated 90 degrees simply by switching on and off or changing the voltage across the crystal. In some embodiments, the voltage across the crystal, and hence the polarization of the laser beam, can be changed in less than a nanosecond. As the polarization of the laser beam is rotated, the high intensity region near the probe tip turns on and off, thereby causing the molecule close to the tip to blink as describe herein. The blinking, or fluctuation in signal, from the molecule close to the probe tip enables the nanometer-sized features of the sample to be more clearly imaged because the background signal can be suppressed and the sample is not damaged during the imaging process.
[0048] In one exemplary embodiment, the sharp probe tip 103 comprises an atomic force microscope (“AFM”). The AFM can be of the type referred to as tapping mode (intermittent-contact), contact mode, lateral force mode, or noncontact mode. However, other types of microscopes can be used in conjunction with the present invention, including other types of scanning probe microscopes such as scanning tunneling microscopes (STM) and near-field scanning optical microscopes (NSOM).
[0049] FIGS. 2A and 2B are more detailed illustrations of the resulting light polarizations when light beams of particular polarizations from a light source (not shown) are focused through lens 105 adjacent probe tip 103 . In FIG. 2A , the incoming light rays 111 and 112 have commonly oriented linear polarizations, as seen at the top of FIG. 2A in a depiction of a cross section of a beam of light 121 . After rays 111 and 112 are focused by lens 105 adjacent probe tip 103 , the resulting polarization is generally transverse to the longitudinal axis of probe tip 103 , as demonstrated by arrow 102 . Because the polarization of the focused light is generally transverse to the longitudinal axis of probe tip 103 , a region of enhanced optical intensity adjacent the probe tip 103 is not created.
[0050] In FIG. 2B , however, the incoming light rays 111 and 112 have radial polarization, as seen at the top of FIG. 2A in a depiction of a cross section of a beam of light 123 . After rays 111 and 112 are focused by lens 105 adjacent probe tip 103 , the resulting polarization is along the longitudinal axis of the probe tip 103 , as demonstrated by arrow 102 . The alignment of the resulting polarization and the longitudinal axis of probe tip 103 creates a region of enhanced optical intensity as described previously herein.
[0051] Thus, in this embodiment, where the light incident on probe tip 103 through the lens is radially polarized, a region of enhanced optical intensity is created. By periodically switching between radial polarization and another form of polarization that does not create a region of enhanced optical intensity, such as linear polarization, the high resolution optical scanning described herein can be achieved.
[0052] FIGS. 3A and 3B illustrate another embodiment of the invention herein. FIG. 3A depicts light ray 113 from a light source (not shown). Light ray 113 has linear polarization, as seen at the top of FIG. 3A in a depiction of a cross section of a ray of light 125 . In this embodiment, a glass slide 115 is disposed between lens 105 and probe tip 103 . After being focused by lens 105 , the light ray strikes glass slide 115 at such an angle that total internal reflection occurs and the light ray returns through lens 105 . When the light is polarized as it is in light ray 113 , the resulting polarization adjacent probe tip 103 is along the axis of probe tip 103 (as demonstrated by arrow 102 ), thereby creating a region of enhanced optical intensity.
[0053] FIG. 3B depicts light ray 114 from a light source (not shown). Light ray 114 also has a linear polarization, as seen at the top of FIG. 3B in a depiction of a cross section of a ray of light 127 . However, light ray 114 is polarized at a 90 degree angle from light ray 113 (as can be seen by comparing cross section 127 and cross section 125 ). In FIG. 3B , when light ray 114 is focused by lens 105 such that it strikes glass slide 115 at such an angle that total internal reflection occurs, the resulting polarization adjacent probe tip 103 is generally transverse the axis of probe tip 103 (as demonstrated by arrow 104 pointing into the plane of the page), thereby removing a region of enhanced optical intensity.
[0054] In this embodiment, where glass slide 115 is present and the incident light rays are subject to total internal reflection, only some linearly polarized light will create a region of enhanced optical intensity. Thus, by periodically alternating between different linear polarizations of the light, the high resolution optical scanning described herein can be achieved.
[0055] FIG. 4A illustrates an optical microscope system 300 with a region of enhanced optical intensity 131 adjacent a probe tip 103 . In FIG. 4A , a glass slide 115 is disposed between probe tip 103 and lens 105 . On glass slide 115 is a sample 121 . Depending on the application, the sample 121 can include a biological sample, quantum dots, fluorescently tagged molecules, fluorescently tagged nano- or micro-structures, arrays or components, and the like. Radially polarized light 117 from a light source (not shown) is passed through lens 105 . When the light is focused by lens 105 adjacent probe tip 103 the resulting polarization is along the axis of probe tip 103 , thus creating a region of enhanced optical intensity 131 .
[0056] FIG. 4B illustrates the same optical microscope system 300 as in FIG. 4A . In contrast to FIG. 4A , however, there is not a region of enhanced optical intensity adjacent probe tip 103 because the light 118 being passed through lens 105 is azimuthally polarized. After being focused by lens 105 adjacent probe tip 103 , the resulting polarization is generally transverse the axis of probe tip 103 , and thus no region of enhanced optical intensity is created.
[0057] Thus, in this embodiment, where the light incident on the probe tip through the lens 105 is radially polarized, a region of enhanced optical intensity is created. By alternately switching between radial polarization and another form of polarization, such as azimuthal polarization, the high resolution optical scanning described herein can be achieved.
[0058] It should be noted that optical microscope system 300 can be configured in other arrangements without departing from the scope of the present invention. By way of non-limiting example, rather than illuminating sample 121 from beneath, sample 121 can be illuminated from the side or from above. In such an arrangement, lens 105 and a light source can be positioned above or to the side of sample 121 such that the light is focused on sample 121 from above or from the side of sample 121 . Many samples, and in particular biological samples, are transparent enough to enable viewing or imaging of the samples by passing light through the samples, as illustrated in FIGS. 4A and 4B . However, other samples, such as materials science samples, may be sufficiently opaque that light cannot be passed through them to view or image the sample. Illuminating such samples from the side or from above can enable viewing and imaging of the samples without having to pass light through the samples. Thus, it will be appreciated that the specific arrangement of the microscope system components is not limiting to the present invention so long as the polarization of the illuminating light can be changed to create and remove a region of enhanced light intensity near the sample.
[0059] FIG. 5 illustrates an experimental setup that implements an exemplary embodiment of the invention described herein. As shown, the experimental setup 200 includes a sample stage 169 which has x-y-z movement capability. In other words, sample stage 169 is able to be moved both laterally (so that any part of the surface of stage 169 can be located under microscope 173 ) and up-and-down (so that stage 169 can be positioned at various distances from microscope 173 ). A sample 121 can be placed on the stage 169 for viewing and imaging. Depending on the application, sample 121 can include a biological sample, quantum dots, fluorescently tagged molecules, fluorescently tagged nano- or micro-structures, arrays or components, and the like. Sample 121 can be in liquids, air, inert gas environments, or in vacuum and at specific temperatures (cryogenic, room temperature, warm to extremely high temperatures), depending on the application.
[0060] The system 200 also includes a microscope 173 . In one embodiment, microscope 173 is a tapping mode atomic force microscope, but one of ordinary skill in the art would recognize many other types of microscopes that might be employed with this invention, including any scanning probe microscope. Microscope 173 includes various elements, such as probe 103 , a cantilever 175 to support probe 103 , which is coupled to a piezo-electric stack 165 . Such piezo-stack 165 provides for dithering and z-motion (up and down movement over the top of stage 169 ) of the cantilever. Microscope 173 is also attached to certain control electronics. The control electronics may include a digital synthesizer 163 , a microscope controller 161 , a personal computer (“PC”) 159 , a lock-in amplifier 157 , and a photon counting system (not shown) (collectively, the “signal acquisition and processing apparatus 181 ”). Microscope controller 161 is configured to be able to manipulate and control microscope 173 and its properties. PC 159 contains a display for the data. The purpose of the signal acquisition and processing apparatus 181 is to receive data from the microscope 173 and the photodiode 155 , process the data, and output the data. In one exemplary embodiment, the data is output on PC 159 .
[0061] Aligned with probe 103 is microscope objective lens 105 . Light from light source 109 (which in a specific embodiment is a green He—Ne laser source) is focused on probe tip 103 . The light is directed from light source 109 and is adjusted by way of dichroic mirror 151 through objective lens 105 , which focuses the light beam onto probe tip 103 . Furthermore, the light from light source 109 passes through a polarizer 107 configured to alternate the emitted light between various polarizations. As the sample is scanned over its surface on stage 169 , fluorescence photons emit from sample 121 . Such photons pass through objective lens 105 , through a bandpass filter 153 , and then are detected by avalanche photodiode 155 . In one embodiment of the invention, the emitted photons are focused onto the avalanche photodiode 155 by lens 167 . The avalanche photodiode 155 is connected to the signal acquisition and processing apparatus 181 .
[0062] In order to practice an embodiment of the present invention, light from light source 109 is focused by objective lens 105 adjacent to probe tip 103 (which is part of microscope 173 ). Disposed beneath probe tip 103 is stage 169 , which is configured to receive sample 121 . While FIG. 5 illustrates sample 121 being illuminated from below, as noted herein, sample 121 can be illuminated from the side or from above. In such an arrangement, light source 109 , objective lens 105 , and/or associated components (polarizer 107 , dichroic mirror 151 , etc.) can be positioned above or to the side of sample 121 .
[0063] Before being focused adjacent probe tip 103 , light from light source 109 passes through polarizer 107 . Polarizer 107 is configured to alternate the polarization of light between two or more polarizations. The first polarization is one such that after the light from light source 109 is focused by lens 105 adjacent to probe tip 103 , the resulting polarization creates a region of enhanced optical intensity adjacent probe tip 103 and sample 121 . In the illustrated embodiment, the polarization that creates the enhanced optical intensity is substantially aligned with the longitudinal axis of probe tip 103 . As discussed herein, the specific polarization required to create the region of enhanced optical intensity may depend on the shape and configuration of probe tip 103 . Thus, in some embodiments, the region of enhanced optical intensity may be created when the polarization is not aligned with a longitudinal axis of probe tip 103 .
[0064] The polarization can then be alternated to one or more different polarizations which result in a final polarization that removes the region of enhanced optical intensity adjacent probe tip 103 and sample 121 . In the illustrated embodiment, the polarization of the light that removes the region of enhanced optical intensity generally transverse to the longitudinal axis of probe tip 103 . Depending on the specific configuration of probe tip 103 , the region of enhanced optical intensity may be removed even when the polarization of light is aligned with an axis of probe tip 103 . By alternating polarizations of the light, this region of enhanced optical intensity is created and removed as probe tip 103 is scanned over sample 121 . Signal acquisition and processing apparatus 181 is configured to receive data and create an image of sample 121 as will be understood by one skilled in the art.
[0065] The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope. | Methods and systems for improving high resolution imaging using a polarization-modulated tip enhanced optical microscope. A polarizer is configured to alternately create and remove a region of enhanced optical intensity adjacent the tip of the microscope probe at the focus of a light source. The sample being studied emits photons at specific rates relative to a background rate depending on the existence or nonexistence of the region of enhanced optical intensity. Comparing the rate of emissions when the region of enhanced optical intensity exists to when it does not creates a detailed image of the sample. By not requiring the probe to oscillate, this system enhances the resolution of the microscope without potentially causing damage to the sample. | 1 |
This invention, at least in part, was funded by a grant from the United States Government and the Government has certain rights in the invention.
This is a continuation of application Ser. No. 07/539,842, filed Jun. 18, 1990, now abandoned, which is a continuation in part of application Ser. No. 07/212,573, filed on Jun. 28, 1988, now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to controlling the cellular immune/inflammatory responses, particularly phagocyte-mediated tissue injury and inflammation.
Circulating phagocytic white blood cells are an important component of the cellular acute inflammatory response. It is believed that a number of important biological functions such as chemotaxis, immune adherence (homotypic cell adhesion or aggregation), adhesion to endothelium, phagocytosis, antibody-dependent cellular cytotoxicity, and histaminase and lysosomal enzyme release are mediated by a leukocyte surface glycoprotein receptor, known as complement receptor type 3 (CR3), also known as Mol, CD11b/CD18, Mac-1 or MAM. See, Arnaout et al., J. Clin. Invest. 72:171-179 (1983), and references cited therein; Dana et al., J. Immunol. 137:3259-3263 (1986); Wallis et al., J. Immunol. 135:2323-2330 (1985); Arnaout et al., New Eng. J. Med. 312:457-462 (1985); Dana et al., J. Clin. Invest. 73:153-159 (1984); and Beatty et al., J. Immunol. 131:2913-2919 (1983).
CR3 consists of two noncovalently associated subunits. Kishimoto et al., Cell 48:681-690 (1987); Law et al., Eur. Mol. Biol. Organ. J. 6:915-919 (1987). The alpha subunit has an apparent molecular mass of 155-165 kD and associates in a divalent cation-independent manner with a beta subunit of 95 kD. Todd et al., Hybridoma 1:329-337 (1982). The beta subunit is common to two other leukocyte surface glycoproteins, LFA-1 and p150,95. In addition to sharing the property of binding to the same beta subunit, CR3, LFA-1, and p150,95 leukocyte adhesion molecules require divalent cations to mediate their adhesion functions, and they have homologous NH 2 -termini. Pierce et al., Biochem. Biophys. Acta. 874:368-371 (1986); Miller et al., J. Immunol. 138:2381-2383 (1987).
Monoclonal antibodies have been used to identify at least two distinct functional domains of CR3, one mediating adhesion and the other mediating binding to the complement C3 fragment (iC3b). See, Dana et al., J. Immunol. 137:3259-3263 (1986).
Cosgrove et al., Proc. Nat'l. Acad. Sci. USA 83:752-756 (1986) report a human genomic clone which produces "a molecule(s)" reactive with monoclonal antibodies to CR3α (Mac-1 or OKM1).
Sastre et al., Proc. Nat'l. Acad. Sci. USA 83:5644-5648 (1986) report a mouse genomic clone coding for the α subunit of mouse complement receptor type 3.
It is believed that CR3 and p150,95 mediate enhanced adhesiveness of activated phagocytes through increased expression of these proteins on the surface of activated cells. For example, in granulocytes, these proteins are translocated from intracellular storage pools present in secondary and tertiary granules. Arnaout et al., J. Clin. Invest. 74:1291-1300 (1984); Arnaout et al., New Eng. J. Med. 312:457-462 (1985); Todd et al., J. Clin. Invest. 74:1280-1291 (1984).
Inherited deficiency of CR3 impairs leukocyte adhesion-dependent inflammmatory functions and predisposes to life-threatening bacterial infections. Dana et al., (1984), cited above.
Simpson et al., J. Clin. Invest. 81:624 (1988) disclose that a monoclonal antibody directed to an adhesion-promoting domain of CR3α reduces the extent of cardiac damage in dogs associated with myocardial infarction, presumably by limiting reperfusion injury.
SUMMARY OF THE INVENTION
The invention features human CR3α recombinant peptide. As used herein, human CR3α recombinant peptide is a chain of amino acids derived by expression of recombinant CR3α-encoding cDNA, or by expression of the corresponding synthetic DNA. For convenience, the term peptide is used to include all polypeptides regardless of length, including short polypeptides as well as proteins.
The invention also features human CR3α synthetic peptides that include at least one functional CR3 domain capable of inhibiting a CR3-mediated immune response. As used herein, "synthetic peptide" means a peptide derived by expression of recombinant DNA or by chemical synthesis. "CR3-mediated immune response" includes those functions mentioned above: chemotaxis, immune adherence (homotypic cell adhesion or aggregation), adhesion to endothelium, phagocytosis, antibody-dependent cellular cytotoxicity, and histaminase and lysosomal enzyme release. Inhibition of these immune functions can be determined by one or more of the following inhibition assays as described in greater detail below: cell-cell aggregation, phagocytosis, adhesion to endothelium, and chemotaxis.
Preferably, the peptide's functional domain has an amino acid sequence between 7 and 500 amino acid residues; most preferably, the domain is an amino acid sequence derived from the natural CR3α amino acid region that is homologous to a binding region of the yon Willebrand factor encompassing amino acids 134 through 340; or a peptide having one of the amino acid sequences: DIAFLIDGS; FRRMKEFVS; FKILVVITDGE; VIRYVIGVGDA; YYEQTRGGQVSVCPLPRGRARWQCDAV (fibronectin-like collagen binding domain; IL-2-receptor-like region); or KSTRDRLR. The peptide may also be derived from one or more of the metal binding domains of the CR3α peptide and preferably may be derived from the domains encompassing amino acids 358-412, 426-483, 487-553, or 554-614; most preferably, the peptide has one of the amino acid sequences: DVDSNGSTD, DVNGDKLTD, DLTMDGLVD, or DSDMNDAYL.
In another aspect, the invention features purified DNA encoding human CR3α or a synthetic CR3α peptide as defined above. The purified DNA may be cDNA encoding all of the CR3α peptide or a restriction enzyme fragment encompassing part of the CR3α-coding region, or synthetic DNA.
The invention can be used to control the cellular immune response mediated by CR3, where that response is not desired. The invention is particularly advantageous in that it avoids introduction of proteins of non-human species, such as non-human antibodies, which (particularly after the first administration) can raise undesired immune responses. It specifically provides a method of controlling damage associated with reduced perfusion of heart tissue (e.g. resulting from myocardial infarction) consisting of administering a therapeutic amount of the above described peptide in a suitable, pharmaceutically acceptable vehicle. It also can be used to treat dialysis leukopenia, a disease state characterized by phagocyte-dependent tissue injury.
In one particular embodiment, the peptide is administered as a heterodimer, with the human CR3β peptide, preferably a truncated (soluble) CR3β peptide that includes the extracellular position of the CR3β peptide and lacks the transmembrane portion. Most preferably, the CR3β portion of the heterodimer is a recombinant protein produced by expressing DNA encoding the truncated CR3β peptide.
Other features and advantages of the invention will be apparent from the following description of the preferred embodiments thereof, and from the claims.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The drawing will first briefly be described.
Drawing
FIG. 1 is the cDNA sequence and deduced amino acid sequence of the open reading frame of human CR3α from Arnout et al., J. Cell. Biol. 106:2153-2158 (1988).
CR3α Peptide
The complete human CR3α peptide can be expressed from recombinant DNA encoding the entire α subunit. CR3α peptide fragments according to the invention can be expressed from a cloned restriction enzyme fragment of recombinant DNA or from synthesized DNA. The complete CR3α peptide can be obtained in the following way.
Isolation of a Human CR3α cDNA Clone
A 378 base pair (bp) cDNA clone encoding guinea pig CR3 was used as a probe to isolate three additional cDNA clones from a human monocyte/lymphocyte cDNA library as described in Arnaout et al., Proc. Nat. Aca. Sci. 85:2776 (1988); together these three clones contain the 3,048-base nucleotide sequence encoding the CR3α gene shown in FIG. 1.
In order to express CR3α, a mammalian expression vector can be constructed by assembling the above-described three cDNA clones. Appropriate restriction enzyme sites within the CR3α gene can be chosen to assemble the cDNA inserts so that they are in the same translation reading frame. A suitable basic expression vector can be used as a vehicle for the 3,048 bp complete cDNA fragment encoding the human CR3α peptide; the recombinant cDNA can be expressed by transfection into, e.g., COS-1 cells, according to conventional techniques, e.g., the techniques generally described by Aruffo et al., Proc. Nat'l. Acad. Sci. USA 84:8573-8577 (1987).
Isolation of CR3α Peptide from Mammalian Cells
The CR3α protein can be purified from the lysate of transfected COS-1 cells, using affinity chromatography and lentil-lectin Sepharose and anti-CR3α monoclonal antibody as described by Pierce et al. (1986) cited above and Arnaout et al., Meth. Enzymol. 150:602 (1987). Anti-CR3α monoclonal antibody can be made according to techniques well known in the art using synthetic peptides corresponding to functional domains of the CR3α molecule as the initial immunogen, or it can be purchased from Becton Dickinson, Ortho Pharmaceutical, or other sources.
If the desired CR3α peptide is shorter than the entire protein, DNA encoding the desired peptide can be expressed in the same mammalian expression vector described above using the selected DNA fragment and the appropriate restriction enzyme site, as outlined above. The selected DNA fragment may be isolated according to conventional techniques from one of the CR3α cDNA clones or may be synthesized by standard phosphoamidite methods, as described by Beaucage et al., Tetrahedron Letters 22:1859 (1981).
Characterization of the CR3a Polypeptide
The coding sequence of the complete CR3α protein is preceded by a single translation initiation methionine. The translation product of the single open reading frame begins with a 16-amino acid hydrophobic peptide representing a leader sequence, followed by the NH 2 -terminal phenylalanine residue. The translation product also contained all eight tryptic peptides isolated from the purified antigen, the amino-terminal peptide, and an amino acid hydrophobic domain representing a potential transmembrane region, and a short 19-amino acid carboxy-terminal cytoplasmic domain (FIG. 1). The coding region of the 155-165 kD CR3α (1,136 amino acids) is eight amino acids shorter than the 130-150 kD alpha subunit of p150,95 leukocyte adhesion molecule (1,144 amino acids). The cytoplasmic region of CR3α contains one serine residue that could serve as a potential phosphorylation site. The cytoplasmic region is also relatively rich in acidic residues and in proline (FIG. 1). Since CR3 is involved in the process of phagocytosis and is also targeted to intracellular storage pools, these residues are candidates for mediating these functions. The long extracytoplasmic amino-terminal region contains four metal-binding domains (outlined by broken lines in FIG. 1) that are similar to Ca 2+ -binding sites found in other integrins. Each metal binding site may be composed of two noncontiguous peptide segments and may be found in the four internal tandem repeats formed by amino acid residues 358-412, 426-483, 487-553, and 554-614. The extracytoplasmic region also contains a unique 187-amino acid sequence, beginning at residue 151, which is not present in the homologous alpha subunits of fibronectin, vitronectin, or platelet IIb/IIIa receptors. This sequence is present in the highly homologous alpha subunit of leukocyte p150,95 with 57% of the amino acids identical and 34% representing conserved substitutions. It is known that both Mol and p150,95 have a binding site for complement fragment C3 and this unique region may be involved in C3 binding. This region of CR3α also has significant homology (17.1% identity and 52.9% conserved sustitutions) to the collagen/heparin/platelet GpI binding region of the mature von Willebrande factor (residues 530-713).
The following peptides can be used to inhibit CR3 activity: a) peptide identical to the above-described p150,95-homologous region of CR3α, or a domain thereof, e.g., DIAFLIDGS, FRRMKEFVS, FKILVVITDGE, or VIRYVIGVGDA; b) YYEQTRGGQVSVCPLPRGRARWQCDAV (fibronectin-like collagen binding domain, IL-2-receptor-like region); c) peptides identical to one or more of the four metal binding regions of CR3α, e.g., having one of the following amino acid sequences: DVDSNGSTD, DVNGDKLTD, DLTMDGLVD, DSDMNDAYL; d) peptides substantially identical to the complete CR3α; or e) other CR3α domains, e.g. KSTRDRLR.
A CR3α peptide, such as one of those described above, can be tested in vitro for inhibition in one of the following five assays: iC3b binding; cell-cell aggregation, phagocytosis, chemotaxis, or adhesion to endothelium; or tested in vivo for controlling damage associated with reduced perfusion of heart tissue, as a result of myocardial infarction.
Inhibition of Granulocyte or Phagocyte Adhesion to iC3b-Coated Erythrocytes or Bacteria
The antimicrobial activity of the neutrophil depends to a significant degree on the ability of this cell to establish a firm attachment to its target. For this purpose, neutrophils possess a number of specific cell surface receptors that promote this interaction, such as a receptor which binds to complement C3 (iC3b), e.g. the CR3 receptor. Human neutrophilic polymorphonuclear granulocytes can be isolated from EDTA-anticoagulated blood on Ficoll-Hypaque gradients (Boyum, Scand. J. Clin. Invest. (Suppl.) 21:77 (1968)) modified as described by Dana et al., J. Clin. Invest. 75.:153 (1984)). Phagocytes can be prepared by incubating the mononuclear cell fraction (obtained from Ficoll-Hypaque centrifugation) on plastic petri dishes (Todd et al., J. Immunol. 126:1435 (1981)). Peptides of the invention can be tested for their ability to inhibit iC3b mediated binding of granulocytes to sheep erythrocytes as described in Dana et al., 1984, cited above and Arnaout et al., (1985) cited above.
Inhibition of Phagocytosis
Phagocytosis is an important biological function resulting in clearing of damaged tissue from the body, and in elimination of foreign particles (bacteria, fungi). An in vitro test for inhibition of phagocytosis is described in Arnaout et al., New Eng. J. Med. 306:693 (1982).
Inhibition of Phagocyte Adhesion to Endothelium
Monocytes must cross vascular endothelium during their egress from blood to extravascular tissues. Studies of leukocyte kinetics in animals indicate that acute inflammatory reactions may be marked by a massive increase in transendothelial monocyte/granulocyte traffic. In many chronic inflammatory lesions, perivascular monocytes accumulate in skin windows more slowly than neutrophils, but later become the predominant cell type. In addition monocytes leaving the circulation can rapidly acquire the morphoology of resident tissue macrphages--in some cases within a few hours of their departure from plasma. Thus, vascular endothelium may be considered an important substrate with which monocytes (and granulocytes) must interact during adherence, diapedesis, and differentiation. An in vitro assay for monocyte/granulocyte interaction with the vessel wall consists of binding radiolabeled monocyte/granulocyte preparations to cultured vascular endothelium, as described in Mentzer et al., J. Cell Physiol. 125:285 (1986).
Inhibition Of Chemotaxis
The ability of cells of the immune system to migrate is essential to the cellular immune response that results in tissue inflammation. Therefore, a peptide of the invention can be tested for its ability to inhibit chemotaxis, as described in Dana et al., (1986), cited above.
Cell-Cell Agregation
Granulocyte aggregation will be performed as detailed elsewhere. Arnaout et al., New Engl. J. Med. (1985) cited above. Aggregation will be induced by zymosan-activated autologous serum or with chemotactic peptides, e.g. FMLP. Aggregation will be recorded as incremental change in light transmission [ΔT] using a platelet aggregometer. The reading can be confirmed by phase microscopy.
In Vivo Model for Testing Peptide
Damage to the heart tissue during myocardial infarction can be minimized by administering to an animal an inhibitor of the CR3-mediated immune response. A peptide of the invention may be tested for in vivo effectiveness using animals, e.g., dogs, which have been induced to undergo myocardial infarction. See, e.g. Simpson et al. cited above.
Use
The peptide can be administered intravenously in saline solution generally on the order of mg quantities per 10 kilograms of body weight. The peptide can be administered in combination with other drugs, for example, in combination with, or within six hours to three days after a clot dissolving agent, e.g., Tissue Plasminogen Activator (TPA), Activase, or Streptokinase.
Heterodimer
It may be advantageous to administer the heterodimer formed by the CR3α and CR3β proteins. Expression of the CR3α chain is described elsewhere in this application. Expression of the CR3β chain has been reported by others. See, e.g. Law et al. EMBO J. 6:915-919 (1987); Kishimoto et al. Cell 48:681-690 (1987); Tankum et al. Cell 46:271-282 (1986). The strategies described above or in those reports can be used to obtain CR3β to make such a heterodimer.
Preferably, a secreted form of CR3α/CR3β complex can be produced by co-transfecting COS cells using the cloned CR3α described above and the cloned CR3β. A secreted form of the complex can be produced by known techniques by generating stop codons 5' to the DNA sequences encoding the transmembrane regions of the two subunits. Culture supernatants from COS cells transfected with the combined cDNAs will be used, as described elsewhere, preferably after purification.
Other emobodiments are within the following claims. | The invention features human CR3α recombinant or synthetic peptide capable of inhibiting a CR3-mediated immune response, a purified DNA encoding a human CR3α peptide, and a method of controlling any phagocyte-mediated tissue damage such as that associated with reduced perfusion of heart tissue during acute cardiac insufficiency. As used herein, a human CR3α recombinant peptide is a chain of amino acids derived from recombinant CR3α-encoding cDNA, or the corresponding synthetic DNA. | 2 |
NATURE OF THE INVENTION
This invention relates to a method for purifying and removing trace amounts of mercury from liquid hydrocarbons, particularly natural gas condensate.
PRIOR ART
Trace quantities of mercury are known to exist in natural gas and natural gas condensate, but the significance of these trace quantities has not been recognized until recently. The mercury detected in the produced gas and the associated condensate is now known not to result from well drilling or well completion operations and does not result by accident. The mercury is produced in association with the gas and the condensate and is thought to originate from geologic deposits in which the natural gas occurs. Even in trace quantities however, mercury is an undesirable component. The processing of natural gas in LNG plants requires at some location in the system contact with equipment made primarily of aluminum. This is particularly true after the stages of processing where the gas is treated to remove carbon dioxide and hydrogen sulfide and then is chilled or cooled in aluminum-constructed heat exchangers. Because large volumes of gas must flow through the aluminum heat exchangers they are of massive size and represent a capital investment of several million dollars.
Damage to these exchangers is to be avoided if at all possible. One threat of damage comes from the mercury present in the gas flowing through the heat exchangers. Although the concentration of mercury appears low, its effect is cumulative as it amalgamates with the aluminum. The result is damage to the system such as corrosion cracking leading to equipment failure. Repair is correspondingly difficult because of damage to the welded seams of the aluminum. Replacement of the heat exchangers in an LNG plant represents a large expenditure. The problem of mercury in natural gas is discussed further in U.S. Pat. No. 4,094,777 and French Pat. No. 2,310,795, both of which are incorporated herein by reference.
Several methods have been proposed for absorbing mercury from natural gas. For example, J. E. Leeper in Hydrocarbon Processing, Volume 59, November, 1980, pages 237-240, describes a procedure wherein natural gas is contacted with a fixed bed of copper sulfide on an alumina-silica support to remove the mercury present. The absorbent is regenerated by purging it with gas heated to a temperature of 200°-500° C. Another commercial process is based on contacting the mercury contaminated gas with sulfur supported on activated carbon. According to the Leeper article, the sulfur impregnated activated charcoal process is regarded as the best system for treating a gas stream, particularly one free of heavy hydrocarbons. The reference, Hydrocarbon Processing, Volume 59, November, 1980, pages 237-240, is incorporated herein by reference.
U.S. Pat. No. 4,474,896 discloses the removal of mercury from liquids and gases utilizing a support material containing sulfide species to be contacted with the liquid or gas under treatment.
The presence of mercury contamination in natural gas in turn leads to the formation of mercury-contaminated gas condensate and associated liquid hydrocarbons. Accordingly a primary object of this invention is to provide an improved process for removing trace quantities of mercury present in a hydrocarbon condensate, particularly petroleum gas condensate.
SUMMARY OF THE INVENTION
Briefly stated, this invention comprises reducing the concentration of mercury in a hydrocarbon gas condensate by first contacting the liquid condensate with a solution of an alkali polysulfide and subsequently recovering a liquid hydrocarbon product substantially depleted of mercury.
DESCRIPTION OF THE INVENTION
As stated above, the essence of this invention lies in treating the liquid hydrocarbon (natural gas condensate) containing mercury by contacting it with a solution of an alkali polysulfide. Preferably the alkali polysulfide is sodium polysulfide and the concentration of sulfur in the polysulfide is between 0.1 and 25%. Natural gas condensate can be contacted with the aqueous polysulfide solution in several different ways in batchwise or continuous processes. In one method the condensate is introduced into the bottom of a packed column and the aqueous solution of polysulfide is introduced into the top of the column in countercurrent flow so that the condensate rising through the column thoroughly contacts the aqueous polysulfide solution. The effluent liquid condensate is recovered and further processed to remove any moisture or other material present in the liquid condensate. The temperature at which this process is carried out can be ambient or room temperature, i.e. about 70° F. or higher and the pressure can be atomspheric pressure or higher.
When the alkali polysulfide is sodium polysulfide the aqueous solution should contain between 5.0 and 350.0 grams of sodium polysulfide per liter of water. The liquid hydrocarbons treated according to this invention ordinarily will have an average molecular weight of between 110 and 130.
The polysulfide compound can be a polysulfide of a metal selected from the group consisting of sodium, potassium lithium, rubidium, cesium, magnesium and calcium and the concentration of sulfur in the polysulfide solution between 0.1 and 25 percent by weight.
The liquid hydrocarbon treated according to the process of this invention subsequently is allowed to separate into a hydrocarbon phase and an aqueous phrase. The two phases are then separated and the liquid hydrocarbon phase can be further treated to remove entrained water, etc.
EXAMPLES
In the following examples pentane is used to simulate a petroleum gas condensate because pentane is a major component of gas condensate.
Example 1
One hundred (100) cc. of pentane containing 13 ppb of mercury were mixed with about 1/2 cc. of an aqueous solution of sodium polysulfide containing 22.2% sulfur and shaken vigorously. After the aqueous layer had settled the treated pentane was decanted, washed with water and dried over molecular sieves. The mercury content of the treated and dried pentane was less than 0.01 ppb.
Example 2
One hundred (100) cc. of pentane containing 0.53 ppb mercury were treated as described in Example 1. Similarly the mercury content of the treated and dried pentane was less than 0.01 ppb.
Example 3
One hundred (100) cc. of pentane containing 13 ppb mercury were washed with water and dried over molecular sieves. The mercury content of the treated dry pentane was determined. The mercury content did not change, but remained at 13 ppb.
Example 3 demonstrates that washing pentane with water and dryng it over molecular sieves does not reduce the mercury content of pentane.
Example 4
Example 1 was repeated using an aqueous solution of sodium polysulfide containing 3.5% sulfur. The amount of solution used was 5 cc. Similarly the mercury content of the treated and dried pentane was determined to be less than 0.01 ppb.
The above examples are not intended to limit the scope of the invention but are presented to illustrate the efficiency of the polysulfide in removing mercury from a liquid hydrocarbon. Those skilled in the art will readily recognize that the use of these solutions can be extended to lower or higher concentrations than those given in the above examples. It will, however, be necessary to make sure that solutions containing low sulfur concentrations be given sufficient contact with the hydrocarbon to bring about reaction with mercury. | Liquid hydrocarbons (natural gas condensate) are depleted of contaminating mercury by contacting them with a solution of an alkali polysulfide. | 2 |
RELATED APPLICATIONS
This application is a divisional application of application Ser. No. 10/630,555, filed on Jul. 30, 2003, now U.S. Pat. No. 7,592,428, which is a divisional of application Ser. No. 09/903,068, filed Jul. 11, 2001, now U.S. Pat. No. 6,982,319, which is a divisional of application Ser. No. 09/679,187, filed Oct. 3, 2000, now U.S. Pat. No. 6,331,621, which is a divisional of application Ser. No. 08/436,265, filed Oct. 30, 1995, now U.S. Pat. No. 6,316,217, which is a 35 U.S.C. §371 of PCT/GB93/02367, filed Nov. 17, 1993.
FIELD OF THE INVENTION
This invention relates to proteins having serine/threonine kinase domains, corresponding nucleic acid molecules, and their use.
BACKGROUND OF THE INVENTION
The transforming growth factor-β (TGF-β) superfamily consists of a family of structurally-related proteins, including three different mammalian isoforms of TGF-β (TGF-β1, β2 and β3), activins, inhibins, müllerian-inhibiting substance and bone morphogenic proteins (BMPs) (for reviews see Roberts and Sporn, (1990) Peptide Growth Factors and Their Receptors, Pt.1, Sporn and Roberts, eds. (Berlin: Springer-Verlag) pp 419-472; Moses et al (1990) Cell 63, 245-247). The proteins of the TGF-β superfamily have a wide variety of biological activities. TGF-β acts as a growth inhibitor for many cell types and appears to play a central role in the regulation of embryonic development, tissue regeneration, immuno-regulation, as well as in fibrosis and carcinogenesis (Roberts and Sporn (199) see above).
Activins and inhibins were originally identified as factors which regulate secretion of follicle-stimulating hormone secretion (Vale et al (1990) Peptide Growth Factors and Their Receptors, Pt.2, Sporn and Roberts, eds. (Berlin: Springer-Verlag) pp.211-248). Activins were also shown to induce the differentiation of haematopoietic progenitor cells (Murata et al (1988) Proc. Natl. Acad. Sci. USA 85, 2434-2438; Eto et al (1987) Biochem. Biophys. Res. Commun. 142, 1095-1103) and induce mesoderm formation in Xenopus embryos (Smith et al (1990) Nature 345, 729-731; van den Eijnden-Van Raaij et al (1990) Nature 345, 732-734).
BMPs or osteogenic proteins which induce the formation of bone and cartilage when implanted subcutaneously (Wozney et al (1988) Science 242, 1528-1534), facilitate neuronal differentiation (Paralkar et al (1992) J. Cell Biol. 119, 1721-1728) and induce monocyte chemotaxis (Cunningham et al (1992) Proc. Natl. Acad. Sci. USA 89, 11740-11744). Mullerian-inhibiting substance induces regression of the MUllerian duct in the male reproductive system (Cate et al (1986) Cell 45, 685-698), and a glial cell line-derived neurotrophic factor enhances survival of midbrain dopaminergic neurons (Lin et al (1993) Science 260, 1130-1132). The action of these growth factors is mediated through binding to specific cell surface receptors.
Within this family, TGF-β receptors have been most thoroughly characterized. By covalently cross-linking radio-labelled TGF-β to cell surface molecules followed by polyacrylamide gel electrophoresis of the affinity-labelled complexes, three distinct size classes of cell surface proteins (in most cases) have been identified, denoted receptor type I (53 kd), type II (75 kd), type III or betaglycan (a 300 kd proteoglycan with a 120 kd core protein) (for a review see Massague (1992) Cell 69 1067-1070) and more recently endoglin (a homodimer of two 95 kd subunits) (Cheifetz et al (1992) J. Biol. Chem. 267 19027-19030). Current evidence suggests that type I and type II receptors are directly involved in receptor signal transduction (Seqarini et al (1989) Mol. Endo., 3, 261-272; Laiho et al (1991) J. Biol. Chem. 266, 9100-9112) and may form a heteromeric complex; the type II receptor is needed for the binding of TGF-β to the type I receptor and the type I receptor is needed for the signal transduction induced by the type II receptor (Wrana et al (1992) Cell, 71, 1003-1004). The type III receptor and endoglin may have more indirect roles, possibly by facilitating the binding of ligand to type II receptors (Wang et al (1991) Cell, 67 797-805; López-Casillas et al (1993) Cell, 73 1435-1444).
Binding analyses with activin A and BMP4 have led to the identification of two co-existing cross-linked affinity complexes of 50-60 kDa and 70-80 kDa on responsive cells (Hino et al (1989) J. Biol. Chem. 264, 10309-10314; Mathews and Vale (1991), Cell 68, 775-785; Paralker et al (1991) Proc. Natl. Acad. Sci. USA 87, 8913-8917). By analogy with TGF-β receptors they are thought to be signalling receptors and have been named type I and type II receptors.
Among the type II receptors for the TGF-β superfamily of proteins, the cDNA for the activin type II receptor (Act RII) was the first to be cloned (Mathews and Vale (1991) Cell 65, 973-982). The predicted structure of the receptor was shown to be a transmembrane protein with an intracellular serine/threonine kinase domain. The activin receptor is related to the C. elegans daf-1 gene product, but the ligand is currently unknown (Georgi et al (1990) Cell 61, 635-645). Thereafter, another form of the activin type II receptor (activin type IIB receptor), of which there are different splicing variants (Mathews et al (1992), Science 225, 1702-1705; Attisano et al (1992) Cell 68, 97-108), and the TGF-β type II receptor (TβRII) (Lin et al (1992) Cell 68, 775-785) were cloned, both of which have putative serine/threonine kinase domains.
SUMMARY OF THE INVENTION
The present invention involves the discovery of related novel peptides, including peptides having the activity of those defined herein as SEQ ID Nos. 2, 4, 8, 10, 12, 14, 16 and 18. Their discovery is based on the realisation that receptor serine/threonine kinases form a new receptor family, which may include the type II receptors for other proteins in the TGF-β superfamily. To ascertain whether there were other members of this family of receptors, a protocol was designed to clone ActRII/daf I related cDNAs. This approach made use of the polymerase chain reaction (PCR), using degenerate primers based upon the amino-acid sequence similarity between kinase domains of the mouse activin type II receptor and daf-I gene products.
This strategy resulted in the isolation of a new family of receptor kinases called Activin receptor like kinases (ALK's) 1-6. These cDNAs showed an overall 33-39% sequence similarity with ActRII and TGF-β type II receptor and 40-92% sequence similarity towards each other in the kinase domains.
Soluble receptors according to the invention comprise at least predominantly the extracellular domain. These can be selected from the information provided herein, prepared in conventional manner, and used in any manner associated with the invention.
Antibodies to the peptides described herein may be raised in conventional manner. By selecting unique sequences of the peptides, antibodies having desired specificity can be obtained.
The antibodies may be monoclonal, prepared in known manner. In particular, monoclonal antibodies to the extracellular domain are of potential value in therapy.
Products of the invention are useful in diagnostic methods, e.g. to determine the presence in a sample for an analyte binding therewith, such as in an antagonist assay. Conventional techniques, e.g. an enzyme-linked immunosorbent assay, may be used.
Products of the invention having a specific receptor activity can be used in therapy, e.g. to modulate conditions associated with activin or TGF-β activity. Such conditions include fibrosis, e.g. liver cirrhosis and pulmonary fibrosis, cancer, rheumatoid arthritis and glomeronephritis.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the alignment of the serine/threonine (S/T) kinase domains (I-VIII) of related receptors from transmembrane proteins, including embodiments of the present invention. The nomenclature of the subdomains is accordingly to Hanks et al (1988). The amino acid sequences set forth at amino acids 246-427 of SEQ ID NO: 32, 216-391 of SEQ ID NO: 31, 194-368 of SEQ ID NO: 30, and 1-178 of SEQ ID NO: 33.
FIGS. 2A to 2D shows the sequences and characteristics of the respective primers used in the initial PCR reactions. The nucleic acid sequences are also given as SEQ ID Nos. 19 to 22.
FIG. 3 is a comparison of the amino-acid sequences of human activin type II receptor (Act R-II), mouse activin type IIB receptor (Act R-IIB), human TGF-β type II receptor (TβR-II), human TGF-β type I receptor (ALK-5), human activin receptor type IA (ALK-2), and type IB (ALK-4), ALKs 1 & 3 and mouse ALK-6. See SEQ ID NOS: 30, 31, 32, 10, 2, 4, 6, 8, and 18.
FIG. 4 shows, schematically, the structures for Daf-1, Act R-II, Act R-IIB, TβR-II, TβR-I/ALK-5, ALK's -1, -2 (Act RIA), -3, -4 (Act RIB) & -6.
FIG. 5 shows the sequence alignment of the cysteine-rich domains of the ALKs, TβR-II, Act R-II, Act R-IIB and daf-1 receptors. See positions 34-95 of SEQ ID NO: 2, 35-99 of SEQ ID NO: 4, 61-130 of SEQ ID NO: 6, 34-100 of SEQ ID NO: 8, 36-106 of SEQ ID NO: 10, 30-110 of SEQ ID NO: 30, 29-109 of SEQ ID NO: 31, 51-143 of SEQ ID NO: 32, and 5-101 of SEQ ID NO: 34.
FIG. 6 is a comparison of kinase domains of serine/threonine kinases, showing the percentage amino-acid identity of the kinase domains.
FIG. 7 shows the pairwise alignment relationship between the kinase domains of the receptor serine/threonine kinases. The dendrogram was generated using the Jotun-Hein alignment program (Hein (1990) Meth. Enzymol. 183, 626-645).
BRIEF DESCRIPTION OF THE SEQUENCE LISTINGS
Sequences 1 and 2 are the nucleotide and deduced amino-acid sequences of cDNA for hALK-1 (clone HP57).
Sequences 3 and 4 are the nucleotide and deduced amino-acid sequences of cDNA for hALK-2 (clone HP53).
Sequences 5 and 6 are the nucleotide and deduced amino-acid sequences of cDNA for hALK-3 (clone ONF5).
Sequences 7 and 8 are the nucleotide and deduced amino-acid sequences of cDNA for hALK-4 (clone 11H8), complemented with PCR product encoding extracellular domain.
Sequences 9 and 10 are the nucleotide and deduced amino-acid sequences of cDNA for hALK-5 (clone EMBLA).
Sequences 11 and 12 are the nucleotide and deduced amino-acid sequences of cDNA for mALK-1 (clone AM6).
Sequences 13 and 14 are the nucleotide and deduced amino-acid sequences of cDNA for mALK-3 (clones ME-7 and ME-D).
Sequences 15 and 16 are the nucleotide and deduced amino-acid sequences of cDNA for mALK-4 (clone 8al).
Sequences 17 and 18 are the nucleotide and deduced amino-acid sequences of cDNA for mALK-6 (clone ME-6).
Sequence 19 (B1-S) is a sense primer, extracellular domain, cysteine-rich region, BamHI site at 5′ end, 28-mer, 64-fold degeneracy.
Sequence 20 (B3-S) is a sense primer, kinase domain II, BamHI site at 5′ end, 25-mer, 162-fold degeneracy.
Sequence 21 (B7-S) is a sense primer, kinase domain VIB, S/T kinase specific residues, BamHI site at 5′ end, 24-mer, 288-fold degeneracy.
Sequence 22 (E8-AS) is an anti-sense primer, kinase domain, S/T kinase-specific residues EcoRI site at 5′ end, 20-mer, 18-fold degeneracy.
Sequence 23 is an oligonucleotide probe.
Sequence 24 is a 5′ primer.
Sequence 25 is a 3′ primer.
Sequence 26 is a consensus sequence in Subdomain I.
Sequences 27 and 28 are novel sequence motifs in Subdomain VIB.
Sequence 29 is a novel sequence motif in Subdomain VIII.
DESCRIPTION OF THE INVENTION
As described in more detail below, nucleic acid sequences have been isolated, coding for a new sub-family of serine/threonine receptor kinases. The term nucleic acid molecules as used herein refers to any sequence which codes for the murine, human or mammalian form, amino-acid sequences of which are presented herein. It is understood that the well known phenomenon of codon degeneracy provides for a great deal of sequence variation and all such varieties are included within the scope of this invention.
The nucleic acid sequences described herein may be used to clone the respective genomic DNA sequences in order to study the genes' structure and regulation. The murine and human cDNA or genomic sequences can also be used to isolate the homologous genes from other mammalian species. The mammalian DNA sequences can be used to study the receptors' functions in various in vitro and in vivo model systems.
As exemplified below for ALK-5 cDNA, it is also recognised that, given the sequence information provided herein, the artisan could easily combine the molecules with a pertinent promoter in a vector, so as to produce a cloning vehicle for expression of the molecule. The promoter and coding molecule must be operably linked via any of the well-recognized and easily-practised methodologies for so doing. The resulting vectors, as well as the isolated nucleic acid molecules themselves, may be used to transform prokaryotic cells (e.g. E. coli ), or transfect eukaryotes such as yeast ( S. cerevisiae ), PAE, COS or CHO cell lines. Other appropriate expression systems will also be apparent to the skilled artisan.
Several methods may be used to isolate the ligands for the ALKs. As shown for ALK-5 cDNA, cDNA clones encoding the active open reading frames can be subcloned into expression vectors and transfected into eukaryotic cells, for example COS cells. The transfected cells which can express the receptor can be subjected to binding assays for radioactively-labelled members of the TGF-β superfamily (TGF-β, activins, inhibins, bone morphogenic proteins and mullerian-inhibiting substances), as it may be expected that the receptors will bind members of the TGF-β superfamily. Various biochemical or cell-based assays can be designed to identify the ligands, in tissue extracts or conditioned media, for receptors in which a ligand is not known. Antibodies raised to the receptors may also be used to identify the ligands, using the immunoprecipitation of the cross-linked complexes. Alternatively, purified receptor could be used to isolate the ligands using an affinity-based approach. The determination of the expression patterns of the receptors may also aid in the isolation of the ligand. These studies may be carried out using ALK DNA or RNA sequences as probes to perform in situ hybridisation studies.
The use of various model systems or structural studies should enable the rational development of specific agonists and antagonists useful in regulating receptor function. It may be envisaged that these can be peptides, mutated ligands, antibodies or other molecules able to interact with the receptors.
The foregoing provides examples of the invention Applicants intend to claim which includes, inter alia, isolated nucleic acid molecules coding for activin receptor-like kinases (ALKs), as defined herein. These include such sequences isolated from mammalian species such as mouse, human, rat, rabbit and monkey.
The following description relates to specific embodiments. It will be understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art.
Preparation of mRNA and Construction of a CDNA Library
For construction of a CDNA library, poly (A) + RNA was isolated from a human erythroleukemia cell line (HEL 92.1.7) obtained from the American Type Culture Collection (ATCC TIB 180). These cells were chosen as they have been shown to respond to both activin and TGF-β. Moreover leukaemic cells have proved to be rich sources for the cloning of novel receptor tyrosine kinases (Partanen et al (1990) Proc. Natl. Acad. Sci. USA 87, 8913-8917 and (1992) Mol. Cell. Biol. 12, 1698-1707). (Total) RNA was prepared by the guanidinium isothiocyanate method (Chirgwin et al (1979) Biochemistry 18, 5294-5299). mRNA was selected using the poly-A or poly AT tract mRNA isolation kit (Promega, Madison, Wisconsin, U.S.A.) as described by the manufacturers, or purified through an oligo (dT)-cellulose column as described by Aviv and Leder (1972) Proc. Natl. Acad. Sci. USA 69, 1408-1412. The isolated mRNA was used for the synthesis of random primed (Amersham) cDNA, that was used to make a λgtlO library with 1×10 5 independent cDNA clones using the Riboclone cDNA synthesis system (Promega) and λgtlO in vitro packaging kit (Amersham) according to the manufacturers' procedures. An amplified oligo (dT) primed human placenta λZAPII cDNA library of 5×10 5 independent clones was used. Poly (A) + RNA isolated from AG1518 human foreskin fibroblasts was used to prepare a primary random primed XZAPII cDNA library of 1.5×10 6 independent clones using the RiboClone cDNA synthesis system and Gigapack Gold II packaging extract (Stratagene). In addition, a primary oligo (dT) primed human foreskin fibroblast λgtlO cDNA library (Claesson-Welsh et al (1989) Proc. Natl. Acad. Sci. USA. 86 4917-4912) was prepared. An amplified oligo (dT) primed HEL cell λgtll cDNA library of 1.5×10 6 independent clones (Poncz et al (1987) Blood 69 219-223) was used. A twelve-day mouse embryo λEXIox cDNA library was obtained from Novagen (Madison, Wis., U.S.A.); a mouse placenta λZAPII cDNA library was also used.
Generation of CDNA Probes by PCR
For the generation of cDNA probes by PCR (Lee et al (1988) Science 239, 1288-1291) degenerate PCR primers were constructed based upon the amino-acid sequence similarity between the mouse activin type II receptor (Mathews and Vale (1991) Cell 65, 973-982) and daf-1 (George et al (1990) Cell 61, 635-645) in the kinase domains II and VIII. FIG. 1 shows the aligned serine/threonine kinase domains (I-VIII), of four related receptors of the TGF-β superfamily, i.e. hTβR-II, mActR-IIB, mActR-II and the daf-1 gene product, using the nomenclature of the subdomains according to Hanks et al (1988) Science 241, 45-52.
Several considerations were applied in the design of the PCR primers. The sequences were taken from regions of homology between the activin type II receptor and the daf-1 gene product, with particular emphasis on residues that confer serine/threonine specificity (see Table 2) and on residues that are shared by transmembrane kinase proteins and not by cytoplasmic kinases. The primers were designed so that each primer of a PCR set had an approximately similar GC composition, and so that self complementarity and complementarity between the 3′ ends of the primer sets were avoided. Degeneracy of the primers was kept as low as possible, in particular avoiding serine, leucine and arginine residues (6 possible codons), and human codon preference was applied. Degeneracy was particularly avoided at the 3′ end as, unlike the 5′ end, where mismatches are tolerated, mismatches at the 3′ end dramatically reduce the efficiency of PCR.
In order to facilitate directional subcloning, restriction enzyme sites were included at the 5′ end of the primers, with a GC clamp, which permits efficient restriction enzyme digestion. The primers utilised are shown in FIG. 2 . Oligonucleotides were synthesized using Gene assembler plus (Pharmacia-LKB) according to the manufacturers instructions.
The mRNA prepared from HEL cells as described above was reverse-transcribed into cDNA in the presence of 50 mM Tris-HCl, pH 8.3, 8 mM MgCl 2 , 30 mM KC1, 10 mM dithiothreitol, 2 mM nucleotide triphosphates, excess oligo (dT) primers and 34 units of AMV reverse transcriptase at 42° C. for 2 hours in 40 μl of reaction volume. Amplification by PCR was carried out with a 7.5% aliquot (3 μl) of the reverse-transcribed mRNA, in the presence of 10 mM Tris-HCl, pH 8.3, 50 mM KCl, 1.5 M MgCl 2 , 0.01% gelatin, 0.2 mM nucleotide triphosphates, 1 μM of both sense and antisense primers and 2.5 units of Taq polymerase (Perkin Elmer Cetus) in 100 μl reaction volume. Amplifications were performed on a thermal cycler (Perkin Elmer Cetus) using the following program: first 5 thermal cycles with denaturation for 1 minute at 94° C., annealing for 1 minute at 50° C., a 2 minute ramp to 55° C. and elongation for 1 minute at 72° C., followed by 20 cycles of 1 minute at 94° C., 30 seconds at 55° C. and 1 minute at 72° C. A second round of PCR was performed with 3 μl of the first reaction as a template. This involved 25 thermal cycles, each composed of 94° C. (1 min), 55° C. (0.5 min), 72° C. (1 min).
General procedures such as purification of nucleic acids, restriction enzyme digestion, gel electrophoresis, transfer of nucleic acid to solid supports and subcloning were performed essentially according to established procedures as described by Sambrook et al, (1989), Molecular cloning: A Laboratory Manual, 2 nd Ed. Cold Spring Harbor Laboratory (Cold Spring Harbor, N.Y., USA).
Samples of the PCR products were digested with BamHI and EcoRI and subsequently fractionated by low melting point agarose gel electrophoresis. Bands corresponding to the approximate expected sizes, (see Table 1: ≈460 bp for primer pair B3-S and E8-AS and ≈140 bp for primer pair B7-S and E8-AS) were excised from the gel and the DNA was purified. Subsequently, these fragments were ligated into pUC19 (Yanisch-Perron et al (1985) Gene 33, 103-119), which had been previously linearised with BamHI and EcoRI and transformed into E. coli strain DH5a using standard protocols (Sambrook et al, supra). Individual clones were sequenced using standard double-stranded sequencing techniques and the dideoxynucleotide chain termination method as described by Sanger et al (1977) Proc. Natl. Acad. Sci. USA 74, 5463-5467, and T7 DNA polymerase.
Employing Reverse Transcriptase PCR on HEL mRNA with the primer pair B3-S and E8-AS, three PCR products were obtained, termed 11.1, 11.2 and 11.3, that corresponded to novel genes. Using the primer pair B7-S and E8-AS, an additional novel PCR product was obtained termed 5.2.
TABLE 1 SEQUENCE SEQUENCE IDENTITY SITE OF DNA IDENTITY WITH BETWEEN NAME OF INSERT FRAGMENT IN SEQUENCE mActRII PCR SITE mActRII/hTBRII mActRII/hTBRII and TBR- PRODUCT PRIMERS (bp) CLONES (bp) (%) 11 (%) 11.1 B3-S/E8- 460 460 46/40 42 AS 11.2 B3-S/E8- 460 460 49/44 47 AS 11.3 B3-S/E8- 460 460 44/36 48 AS 11.29 B3-S/E8- 460 460 ND/100 ND AS 9.2 B1-S/E8- 800 795 100/ND ND AS 5.2 B7-S/E8- 140 143 40/38 60 AS
Isolation of cDNA Clones
The PCR products obtained were used to screen various cDNA libraries described supra. Labelling of the inserts of PCR products was performed using random priming method (Feinberg and Vogelstein (1983) Anal. Biochem, 132 6-13) using the Megaprime DNA labelling system (Amersham). The oligonucleotide derived from the sequence of the PCR product 5.2 was labelled by phosphorylation with T4 polynucleotide kinase following standard protocols (Sambrook et al, supra). Hybridization and purification of positive bacteriophages were performed using standard molecular biological techniques.
The double-stranded DNA clones were all sequenced using the dideoxynucleotide chain-termination method as described by Sanger et al, supra, using T7 DNA polymerase (Pharmacia-LKB) or Sequenase (U.S. Biochemical Corporation, Cleveland, Ohio, U.S.A.). Compressions of nucleotides were resolved using 7-deaza-GTP (U.S. Biochemical Corp.) DNA sequences were analyzed using the DNA STAR computer program (DNA STAR Ltd. U.K.). Analyses of the sequences obtained revealed the existence of six distinct putative receptor serine/threonine kinases which have been named ALK 1-6.
To clone cDNA for ALK-1 the oligo (dT) primed human placenta cDNA library was screened with a radiolabelled insert derived from the PCR product 11.3; based upon their restriction enzyme digestion patterns, three different types of clones with approximate insert sizes of 1.7 kb, 2 kb & 3.5 kb were identified. The 2 kb clone, named HP57, was chosen as representative of this class and subjected to complete sequencing. Sequence analysis of ALK-1 revealed a sequence of 1984 nucleotides including a poly-A tail (SEQ ID No. 1). The longest open reading frame encodes a protein of 503 amino-acids, with high sequence similarity to receptor serine/threonine kinases (see below). The first methionine codon, the putative translation start site, is at nucleotide 283-285 and is preceded by an in-frame stop codon. This first ATG is in a more favourable context for translation initiation (Kozak (1987) Nucl. Acids Res., 15, 8125-8148) than the second and third in-frame ATG at nucleotides 316-318 and 325-327. The putative initiation codon is preceded by a 5′ untranslated sequence of 282 nucleotides that is GC-rich (80% GC), which is not uncommon for growth factor receptors (Kozak (1991) J. Cell Biol., 115, 887-903). The 3′ untranslated sequence comprises 193 nucleotides and ends with a poly-A tail. No bona fide poly-A addition signal is found, but there is a sequence (AATACA), 17-22 nucleotides upstream of the poly-A tail, which may serve as a poly-A addition signal.
ALK-2 CDNA was cloned by screening an amplified oligo (dT) primed human placenta cDNA library with a radiolabelled insert derived from the PCR product 11.2. Two clones, termed HP53 and HP64, with insert sizes of 2.7 kb and 2.4 kb respectively, were identified and their sequences were determined. No sequence difference in the overlapping clones was found, suggesting they are both derived from transcripts of the same gene.
Sequence analysis of cDNA clone HP53 (SEQ ID No. 3) revealed a sequence of 2719 nucleotides with a poly-A tail. The longest open reading frame encodes a protein of 509 amino-acids. The first ATG at nucleotides 104-106 agrees favourably with Kozak's consensus sequence with an A at position 3. This ATG is preceded in-frame by a stop codon. There are four ATG codons in close proximity further downstream, which agree with the Kozak's consensus sequence (Kozak, supra), but according to Kozak's scanning model the first ATG is predicted to be the translation start site. The 5′ untranslated sequence is 103 nucleotides. The 3′ untranslated sequence of 1089 nucleotides contains a polyadenylation signal located 9-14 nucleotides upstream from the poly-A tail. The cDNA clone HP64 lacks 498 nucleotides from the 5′ end compared to HP53, but the sequence extended at the 3′ end with 190 nucleotides and poly-A tail is absent. This suggests that different polyadenylation sites occur for ALK-2. In Northern blots, however, only one transcript was detected (see below).
The cDNA for human ALK-3 was cloned by initially screening an oligo (dT) primed human foreskin fibroblast cDNA library with an oligonucleotide (SEQ ID No. 23) derived from the PCR product 5.2. One positive cDNA clone with an insert size of 3 kb, termed ON11, was identified. However, upon partial sequencing, it appeared that this clone was incomplete; it encodes only part of the kinase domain and lacks the extracelluar domain. The most 5′ sequence of ON11, a 540 nucleotide XbaI restriction fragment encoding a truncated kinase domain, was subsequently used to probe a random primed fibroblast cDNA library from which one CDNA clone with an insert size of 3 kb, termed ONF5, was isolated (SEQ ID No. 5). Sequence analysis of ONF5 revealed a sequence of 2932 nucleotides without a poly-A tail, suggesting that this clone was derived by internal priming. The longest open reading frame codes for a protein of 532 amino-acids. The first ATG codon which is compatible with Kozak's consensus sequence (Kozak, supra), is at 310-312 nucleotides and is preceded by an in-frame stop codon. The 5′ and 3′ untranslated sequences are 309 and 1027 nucleotides long, respectively.
ALK-4 cDNA was identified by screening a human oligo (dT) primed human erythroleukemia cDNA library with the radiolabelled insert of the PCR product 11.1 as a probe. One cDNA clone, termed 11H8, was identified with an insert size of 2 kb (SEQ ID No. 7). An open reading frame was found encoding a protein sequence of 383 amino-acids encoding a truncated extracellular domain with high similarity to receptor serine/threonine kinases. The 3′ untranslated sequence is 818 nucleotides and does not contain a poly-A tail, suggesting that the cDNA was internally primed. cDNA encoding the complete extracellular domain (nucleotides 1-366) was obtained from HEL cells by RT-PCR with 5′ primer (SEQ ID No. 24) derived in part from sequence at translation start site of SKR-2 (a cDNA sequence deposited in GenBank data base, accesion number L10125, that is identical in part to ALK-4) and 3′ primer (SEQ ID No. 25) derived from 11H8 cDNA clone.
ALK-5 was identified by screening the random primed HEL cell λgt 10 cDNA library with the PCR product 11.1 as a probe. This yielded one positive clone termed EMBLA (insert size of 5.3 kb with 2 internal EcoRI sites). Nucleotide sequencing revealed an open reading frame of 1509 bp, coding for 503 amino-acids. The open reading frame was flanked by a 5′ untranslated sequence of 76 bp, and a 3′ untranslated sequence of 3.7 kb which was not completely sequenced. The nucleotide and deduced amino-acid sequences of ALK-5 are shown in SEQ ID Nos. 9 and 10. In the 5′ part of the open reading frame, only one ATG codon was found; this codon fulfils the rules of translation initiation (Kozak, supra). An in-frame stop codon was found at nucleotides (−54)-(−52) in the 5′ untranslated region. The predicted ATG start codon is followed by a stretch of hydrophobic amino-acid residues which has characteristics of a cleavable signal sequence. Therefore, the first ATG codon is likely to be used as a translation initiation site. A preferred cleavage site for the signal peptidase, according to von Heijne (1986) Nucl. Acid. Res. 14, 4683-4690, is located between amino-acid residues 24 and 25. The calculated molecular mass of the primary translated product of the ALK-5 without signal sequence is 53,646 Da.
Screening of the mouse embryo λEX Iox cDNA library using PCR, product 11.1 as a probe yielded 20 positive clones. DNAs from the positive clones obtained from this library were digested with EcoRI and HindIII, electrophoretically separated on a 1.3% agarose gel and transferred to nitrocellulose filters according to established procedures as described by Sambrook et al, supra. The filters were then hybridized with specific probes for human ALK-1 (nucleotide 288-670), ALK-2 (nucleotide 1-581), ALK-3 (nucleotide 79-824) or ALK-4 nucleotide 1178-1967). Such analyses revealed that a clone termed ME-7 hybridised with the human ALK-3 probe. However, nucleotide sequencing revealed that this clone was incomplete, and lacked the 5′ part of the translated region. Screening the same cDNA library with a probe corresponding to the extracelluar domain of human ALK-3 (nucleotides 79-824) revealed the clone ME-D. This clone was isolated and the sequence was analyzed. Although this clone was incomplete in the 3′ end of the translated region, ME-7 and ME-D overlapped and together covered the complete sequence of mouse ALK-3. The predicted amino-acid sequence of mouse ALK-3 is very similar to the human sequence; only 8 amino-acid residues differ (98% identity; see SEQ ID No. 14) and the calculated molecular mass of the primary translated product without the putative signal sequence is 57,447 Da.
Of the clones obtained from the initial library screening with PCR product 11.1, four clones hybridized to the probe corresponding to the conserved kinase domain of ALK-4 but not to probes from more divergent parts of ALK-1 to -4. Analysis of these clones revealed that they have an identical sequence which differs from those of ALK-1 to -5 and was termed ALK-6. The longest clone ME6 with a 2.0 kb insert was completely sequenced yielding a 1952 bp fragment consisting of an open reading frame of 1506 bp (502 amino-acids), flanked by a 5′ untranslated sequence of 186 bp, and a 3′ untranslated sequence of 160 bp. The nucleotide and predicted amino-acid sequences of mouse ALK-6 are shown in SEQ ID Nos. 17 and 18. No polyadenylation signal was found in the 3′ untranslated region of ME6, indicating that the cDNA was internally primed in the 3′ end. Only one ATG codon was found in the 5′ part of the open reading frame, which fulfils the rules for translation initiation (Kozak, supra), and was preceded by an in-frame stop codon at nucleotides 163-165. However, a typical hydrophobic leader sequence was not observed at the N terminus of the translated region. Since there is no ATG codon and putative hydrophobic leader sequence, this ATG codon is likely to be used as a translation initiation site. The calculated molecular mass of the primary translated product with the putative signal sequence is 55,576 Da.
Mouse ALK-1 (clone AM6 with 1.9 kb insert) was obtained from the mouse placenta λZAPII cDNA library using human ALK-1 cDNA as a probe (see SEQ ID No. 11). Mouse ALK-4 (clone 8al with 2.3 kb insert) was also obtained from this library using human ALK-4 cDNA library as a probe (SEQ ID No. 15).
To summarise, clones HP22, HP57, ONF1, ONF3, ONF4 and HP29 encode the same gene, ALK-1. Clone AM6 encodes mouse ALK-1. HP53, HP64 and HP84 encode the same gene, ALK-2. ONF5, ONF2 and ON11 encode the same gene ALK-3. ME-7 and ME-D encode the mouse counterpart of human ALK-3. 11H8 encodes a different gene ALK-4, whilst 8aI encodes the mouse equivalent. EMBLA encodes ALK-5, and ME-6 encodes ALK-6.
The sequence alignment between the 6 ALK genes and TβR-II, mActR-II and ActR-IIB is shown in FIG. 3 . These molecules have a similar domain structure; an N-terminal predicted hydrophobic signal sequence (von Heijne (1986) Nucl. Acids Res. 14: 4683-4690) is followed by a relatively small extracellular cysteine-rich ligand binding domain, a single hydrophobic transmembrane region (Kyte & Doolittle (1982) J. Mol. Biol. 157, 105-132) and a C-terminal intracellular portion, which consists almost entirely of a kinase domain ( FIGS. 3 and 4 ).
The extracelluar domains of these receptors have cysteine-rich regions, but they show little sequence similarity; for example, less than 20% sequence identity is found between Daf-1, ActR-II, TBR-II and ALK-5. The ALKs appear to form a subfamily as they show higher sequence similarities (15-47% identity) in their extracellular domains. The extracellular domains of ALK-5 and ALK-4 have about 29% sequence identity. In addition, ALK-3 and ALK-6 share a high degree of sequence similarity in their extracellular domains (46% identity).
The positions of many of the cysteine residues in all receptors can be aligned, suggesting that the extracellular domains may adopt a similar structural configuration. See FIG. 5 for ALKs-1, -2, -3 & -5. Each of the ALKs (except ALK-6) has a potential N-linked glycosylation site, the position of which is conserved between ALK-1 and ALK-2, and between ALK-3, ALK-4 and ALK-5 (see FIG. 4 ).
The sequence similarities in the kinase domains between daf-1, ActR-II, TβR-II and ALK-5 are approximately 40%, whereas the sequence similarity between the ALKs 1 to 6 is higher (between 59% and 90%; see FIG. 6 ). Pairwise comparison using the Jutun-Hein sequence alignment program (Hein (1990) Meth, Enzymol., 183, 626-645), between all family members, identifies the ALKs as a separate subclass among serine/threonine kinases ( FIG. 7 ).
The catalytic domains of kinases can be divided into 12 subdomains with stretches of conserved amino-acid residues. The key motifs are found in serine/threonine kinase receptors suggesting that they are functional kinases. The consensus sequence for the binding of ATP (Gly-X-Gly-X-X-Gly in subdomain I followed by a Lys residue further downstream in subdomain II) is found in all the ALKs.
The kinase domains of daf-1, ActR-II, and ALKs show approximately equal sequence similarity with tyrosine and serine/threonine protein kinases. However analysis of the amino-acid sequences in subdomains VI and VIII, which are the most useful to distinguish a specificity for phosphorylation of tyrosine residues versus serine/threonine residues (Hanks et al (1988) Science 241 42-52) indicates that these kinases are serine/threonine kinases; refer to Table 2.
TABLE 2
SUBDOMAINS
(SEQ ID NOS:)
KINASE
VIB
VIII
Serine/threonine
DLKPEN
G (T/S) XX (Y/F) X
kinase consensus
35
37-40
Tyrosine kinase
DLAARN
XP (I/V)
consensus
36
(K/R) W (T/M)
41-48
Act R-II
DIKSKN
GTRRYM
Amino acids 322-327
Amino acids 361-366
of SEQ ID NO: 30
of SEQ ID NO: 30
Act R-IIB
DFKSKN
GTRRYM
Amino acids 345-350
Amino acids 361-366
of SEQ ID NO: 31
of SEQ ID NO; 31
TβR-II
DLKSSN
GTARYM
Amino acids 379-384
Amino acids 420-425
of SEQ ID N O: 32
of SEQ ID NO: 32
ALK-I
DFKSRN
GTKRYM
Amino acids 330-335
29
of SEQ ID NO: 3
ALK -2, -3, -4, -5,
DLKSKN
GTKRYM
& -6
28
29
The sequence motifs DLKSKN (Subdomain VIB) and GTKRYM (Subdomain VIII), that are found in most of the serine/threonine kinase receptors, agree well with the consensus seguences for all protein serine/threonine kinase receptors in these regions. In addition, these receptors, except for ALK-1, do not have a tyrosine residue surrounded by acidic residues between subdomains VII and VIII, which is common for tyrosine kinases. A unique characteristic of the members of the ALK serine/threonine kinase receptor family is the presence of two short inserts in the kinase domain between subdomains VIA and VIB and between subdomains X and XI. In the intracellular domain, these regions, together with the juxtamembrane part and C-terminal tail, are the most divergent between family members (see FIGS. 3 and 4 ). Based on the sequence similarity with the type II receptors for TGF-β and activin, the C termini of the kinase domains of ALKs-1 to -6 are set at Ser-495, Ser-501, Ser-527, Gln-500, Gln-498 and Ser-497, respectively.
mRNA Expression
The distribution of ALK-1, -2, -3, -4 was determined by Northern blot analysis. A Northern blot filter with mRNAs from different human tissues was obtained from Clontech (Palo Alto, Calif.). The filters were hybridized with 32 P-labelled probes at 42° C. overnight in 50% formaldehyde, 5× standard saline citrate (SSC; 1×SSC is 50 mM sodium citrate, pH 7.0, 150 mM NaCl), 0.1% SDS, 50 mM sodium phosphate, 5× Denhardt's solution and 0.1 mg/ml salmon sperm DNA. In order to minimize cross-hybridization, probes were used that did not encode part of the kinase domains, but corresponded to the highly diverged sequences of either 5′ untranslated and ligand-binding regions (probes for ALK-1, -2 and -3) or 3′ untranslated sequences (probe for ALK-4). The probes were labelled by random priming using the Multiprime (or Mega-prime) DNA labelling system and [α- 32 P] dCTP (Feinberg & Vogelstein (1983) Anal. Biochem. 132: 6-13). Unincorporated label was removed by Sephadex G-25 chromatography. Filters were washed at 65° C., twice for 30 minutes in 2.5×SSC, 0.1% SDS and twice for 30 minutes in 0.3×SSC, 0.1% SDS before being exposed to X-ray film. Stripping of blots was performed by incubation at 90-100° C. in water for 20 minutes.
The ALK-5 mRNA size and distribution were determined by Northern blot analysis as above. An EcoRl fragment of 980 bp of the full length ALK-5 cDNA clone, corresponding to the C-terminal part of the kinase domain and 3′ untranslated region (nucleotides 1259-2232 in SEQ ID No. 9) was used as a probe. The filter was washed twice in 0.5×SSC, 0.1% SDS at 55° C. for 15 minutes.
Using the probe for ALK-1, two transcripts of 2.2 and 4.9 kb were detected. The ALK-1 expression level varied strongly between different tissues, high in placenta and lung, moderate in heart, muscle and kidney, and low (to not detectable) in brain, liver and pancreas. The relative ratios between the two transcripts were similar in most tissues; in kidney, however, there was relatively more of the 4.9 kb transcript. By reprobing the blot with a probe for ALK-2, one transcript of 4.0 kb was detected with a ubiquitous expression pattern. Expression was detected in every tissue investigated and was highest in placenta and skeletal muscle. Subsequently the blot was reprobed for ALK-3. One major transcript of 4.4 kb and a minor transcript of 7.9 kb were detected. Expression was high in skeletal muscle, in which also an additional minor transcript of 10 kb was observed. Moderate levels of ALK-3 mRNA were detected in heart, placenta, kidney and pancreas, and low (to not detectable) expression was found in brain, lung and liver. The relative ratios between the different transcripts were similar in the tested tissues, the 4.4 kb transcript being the predominant one, with the exception for brain where both transcripts were expressed at a similar level. Probing the blot with ALK-4 indicated the presence of a transcript with the estimated size of 5.2 kb and revealed an ubiquitous expression pattern. The results of Northern blot analysis using the probe for ALK-5 showed that a 5.5 kb transcript is expressed in all human tissues tested, being most abundant in placenta and least abundant in brain and heart.
The distribution of mRNA for mouse ALK-3 and -6 in various mouse tissues was also determined by Northern blot analysis. A multiple mouse tissue blot was obtained from Clontech, Palo Alto, Calif., U.S.A. The filter was hybridized as described above with probes for mouse ALK-3 and ALK-6. The EcoRI-PstI restriction fragment, corresponding to nucleotides 79-1100 of ALK-3, and the SacI-HpaI fragment, corresponding to nucleotides 57-720 of ALK-6, were used as probes. The filter was washed at 65° C. twice for 30 minutes in 2.5×SSC, 0.1% SDS and twice for 30 minutes with 0.3×SSC, 0.1% SDS and then subjected to autoradiography.
Using the probe for mouse ALK-3, a 1.1 kb transcript was found only in spleen. By reprobing the blot with the ALK-6 specific probe, a transcript of 7.2 kb was found in brain and a weak signal was also seen in lung. No other signal was seen in the other tissues tested, i.e. heart, liver, skeletal muscle, kidney and testis.
All detected transcript sizes were different, and thus no cross-reaction between mRNAs for the different ALKs was observed when the specific probes were used. This suggests that the multiple transcripts of ALK-1 and ALK-3 are coded from the same gene. The mechanism for generation of the different transcripts is unknown at present; they may be formed by alternative mRNA splicing, differential polyadenylation, use of different promotors, or by a combination of these events. Differences in mRNA splicing in the regions coding for the extracellular domains may lead to the synthesis of receptors with different affinities for ligands, as was shown for mActR-IIB (Attisano et al (1992) Cell 68, 97-108) or to the production of soluble binding protein.
The above experiments describe the isolation of nucleic acid sequences coding for new family of human receptor kinases. The cDNA for ALK-5 was then used to determine the encoded protein size and binding properties.
Properties of the ALKs CDNA Encoded Proteins
To study the properties of the proteins encoded by the different ALK cDNAs, the cDNA for each ALK was subcloned into a eukaryotic expression vector and transfected into various cell types and then subjected to immunoprecipitation using a rabbit antiserum raised against a synthetic peptide corresponding to part of the intracellular juxtamembrane region. This region is divergent in sequence between the various serine/threonine kinase receptors. The following amino-acid residues were used:
ALK-1
145-166
ALK-2
151-172
ALK-3
181-202
ALK-4
153-171
ALK-5
158-179
ALK-6
151-168
The rabbit antiseru against ALK-5 was designated VPN.
The peptides were synthesized with an Applied Biosystems 430A Peptide Synthesizer using t-butoxycarbonyl chemistry and purified by reversed-phase high performance liquid chromatography. The peptides were coupled to keyhole limpet haemocyanin (Calbiochem-Behring) using glutaraldehyde, as described by Guillick et al (1985) EMBO J. 4, 2869-2877. The coupled peptides were mixed with Freunds adjuvant and used to immunize rabbits.
Transient Transfection of the ALK-5 CDNA
COS-1 cells (American Type Culture Collection) and the R mutant of MvlLu cells (for references, see below) were cultured in Dulbecco's modified Eagle's medium containing 10% fetal bovine serum (FBS) and 100 units/ml penicillin and 50 μg 1 ml streptomycin in 5% C0 2 atmosphere at 37° C. The ALK-5 cDNA (nucleotides (-76) -2232), which includes the complete coding region, was cloned in the pSV7d vector (Truett et al, (1985) DNA 4, 333-349), and used for transfection. Transfection into COS-1 cells was performed by the calcium phosphate precipitation method (Wigler et al (1979) Cell 16, 777-785). Briefly, cells were seeded into 6-well cell culture plates at a density of 5×10 5 cells/well, and transfected the following day with 10 μg of recombinant plasmid. After overnight incubation, cells were washed three times with a buffer containing 25 mM Tris-HCl, pH 7.4, 138 mM NaCl, 5 mM KC1, 0.7 mM CaCl 2 , 0.5 mM MgCl 2 and 0.6 mM Na 2 HP0 4 , and then incubated with Dulbecco's modified Eagle's medium containing FBS and antibiotics. Two days after transfection, the cells were metabolically labelled by incubating the cells for 6 hours in methionine and cysteine-free MCDB 104 medium with 150 μCi/ml of [ 35 S]-methionine and [ 35 S]-cysteine (in vivo labelling mix; Amersham). After labelling, the cells were washed with 150 mM NaCI, 25 mM Tris-HCl, pH 7.4, and then solubilized with a buffer containing 20mM Tris-HCl, pH 7.4, 150 mM NaCl, 10 mM EDTA, 1% Triton X-100, 1% deoxycholate, 1.5% Trasylol (Bayer) and 1 mM phenylmethylsulfonylfluoride (PMSF; Sigma). After 15 minutes on ice, the cell lysates were pelleted by centrifugation, and the supernatants were then incubated with 7 μl of preimmune serum for 1.5 hours at 4° C. Samples were then given 50 μl of protein A-Sepharose (Pharmacia-LKB) slurry (50% packed beads in 150 mM NaCl, 20 mM Tris-HCl, pH 7.4, 0.2% Triton X100) and incubated for 45 minutes at 4° C. The beads were spun down by centrifugation, and the supernatants (1 ml) were then incubated with either 7 μl of preimmune serum or the VPN antiserum for 1.5 hours at 4° C. For blocking, 10 μg of peptide was added together with the antiserum. Immune complexes were then given 50 μl of protein A-Sepharose (Pharmacia-LKB) slurry (50% packed beads in 150 mM NaCl, 20 mM Tris-HCl, pH 7.4, 0.2% Triton X-100) and incubated for 45 minutes at 4° C. The beads were spun down and washed four times with a washing buffer (20 mM Tris-HCl, pH 7.4, 500 mM NaCI, 1% Triton X-100, 1% deoxycholate and 0.2% SDS), followed by one wash in distilled water. The immune complexes were eluted by boiling for 5 minutes in the SDS-sample buffer (100 mM Tris-HCl, pH 8.8, 0.01% bromophenol blue, 36% glycerol, 4% SDS) in the presence of 10 mM DTT, and analyzed by SDS-gel electrophoresis using 7-15% polyacrylamide gels (Blobel and Dobberstein, (1975) J.Cell Biol. 67, 835-851). Gels were fixed, incubated with Amplify (Amersham) for 20 minutes, and subjected to fluorography. A component of 53Da was seen. This component was not seen when preimmune serum was used, or when 10 μg blocking peptide was added together with the antiserum. Moreover, it was not detectable in samples derived from untransfected COS-1 cells using either preimmune serum or the antiserum.
Digestion with Endoglycosidase F
Samples immunoprecipitated with the VPN antisera obtained as described above were incubated with 0.5 U of endoglycosidase F (Boehringer Mannheim Biochemica) in a buffer containing 100 mM sodium phosphate, pH 6.1, 50 mM EDTA, 1% Triton X-100, 0.1% SDS and 1% β-mercaptoethanol at 37° C. for 24 hours. Samples were eluted by boiling for 5 minutes in the SDS-sample buffer, and analyzed by SDS-polyacrylamide gel electrophoresis as described above. Hydrolysis of N-linked carbohydrates by endoglycosidase F shifted the 53 kDa band to 51 kDa. The extracelluar domain of ALK-5 contains one potential acceptor site for N-glycosylation and the size of the deglycosylated protein is close to the predicted size of the core protein.
Establishment of PAE Cell Lines Expressing ALK-5
In order to investigate whether the ALK-5 cDNA encodes a receptor for TGF-β, porcine aortic endothelial (PAE) cells were transfected with an expression vector containing the ALK-5 cDNA, and analyzed for the binding of 125 I-TGF-βl.
PAE cells were cultured in Ham's F-12 medium supplemented with 10% FBS and antibiotics (Miyazono et al., (1988) J. Biol. Chem. 263, 6407-6415). The ALK-5 cDNA was cloned into the cytomegalovirus (CMV)-based expression vector pcDNA I/NEO (Invitrogen), and transfected into PAE cells by electroporation. After 48 hours, selection was initiated by adding Geneticin (G418 sulphate; Gibco-BRL) to the culture medium at a final concentration of 0.5 mg/ml (Westermark et al, (1990) Proc. Natl. Acad. Sci. USA 87, 128-132). Several clones were obtained, and after analysis by immunoprecipitation using the VPN antiserum, one clone denoted PAE/TβR-1 was chosen and further analyzed.
Iodination of TGF-βl, Binding and Affinity Crosslinking
Recombinant human TGF-μl was iodinated using the chloramine T method according to Frolik et al., (1984) J. Biol. Chem. 259, 10995-11000. Cross-linking experiments were performed as previously described (Ichijo et al., (1990) Exp. Cell Res. 187, 263-269). Briefly, cells in 6-well plates were washed with binding buffer (phosphate-buffered saline containing 0.9 mM CaCl 2 , 0.49 mM MgCl 2 and 1 mg/ml bovine serum albumin (BSA)), and incubated on ice in the same buffer with 125 I-TGF-βl in the presence or absence of excess unlabelled TGF-βl for 3 hours. Cells were washed and cross-linking was done in the binding buffer without BSA together with 0.28 mM disuccinimidyl suberate (DSS; Pierce Chemical Co.) for 15 minutes on ice. The cells were harvested by the addition of 1 ml of detachment buffer (10 mM Tris-HCl, pH 7.4, 1 mM EDTA, 10% glycerol, 0.3 mM PMSF). The cells were pelleted by centrifugation, then resuspended in 50 μl of solubilization buffer (125 mM NaCl, 10 mM Tris-HCl, pH 7.4, 1 mM EDTA, 1% Triton X-100, 0.3 mM PMSF, 1% Trasylol) and incubated for 40 minutes on ice. Cells were centrifuged again and supernatants were subjected to analysis by SDS-gel electrophoresis using 4-15% polyacrylamide gels, followed by autoradiography. 125I-TGF-βl formed a 70 kDa cross-linked complex in the transfected PAE cells (PAE/TβR-I cells). The size of this complex was very similar to that of the TGF-β type I receptor complex observed at lower amounts in the untransfected cells. A concomitant increase of 94 kDa TGF-β type II receptor complex could also be observed in the PAE/TfiR-I cells. Components of 150-190 kDa, which may represent crosslinked complexes between the type I and type II receptors, were also observed in the PAE/TβR-I cells.
In order to determine whether the cross-linked 70 kDa complex contained the protein encoded by the ALK-5 cDNA, the affinity cross-linking was followed by immunoprecipitation using the VPN antiserum. For this, cells in 25 cm 2 flasks were used. The supernatants obtained after cross-linking were incubated with 7 μl of preimmune serum or VPN antiserum in the presence or absence of 10 μg of peptide for 1.5 h at 4° C. Immune complexes were then added to 50 μl of protein A-Sepharose slurry and incubated for 45 minutes at 4° C. The protein A-Sepharose beads were washed four times with the washing buffer, once with distilled water, and the samples were analyzed by SDS-gel electrophoresis using 4-15% polyacrylamide gradient gels and autoradiography. A 70 kDa cross-linked complex was precipitated by the VPN antiserum in PAE/TβR-1 cells, and a weaker band of the same size was also seen in the untransfected cells, indicating that the untransfected PAE cells contained a low amount of endogenous ALK-5. The 70 kDa complex was not observed when preimmune serum was used, or when immune serum was blocked by 10 μg of peptide. Moreover, a coprecipitated 94 kDa component could also be observed in the PAE/TBR-I cells. The latter component is likely to represent a TGF-β type II receptor complex, since an antiserum, termed DRL, which was raised against a synthetic peptide from the C-terminal part of the TGF-β type II receptor, precipitated a 94 kDa TGF-β type II receptor complex, as well as a 70 kDa type I receptor complex from PAE/TβR-I cells.
The carbohydrate contents of ALK-5 and the TGF-β type II receptor were characterized by deglycosylation using endoglycosidase F as described above and analyzed by SDS-polyacrylamide gel electrophoresis and autoradiography. The ALK-5 cross-linked complex shifted from 70 kDa to 66 kDa, whereas that of the type II receptor shifted from 94 kDa to 82 kDa. The observed larger shift of the type II receptor band compared with that of the ALK-5 band is consistent with the deglycosylation data of the type I and type II receptors on rat liver cells reported previously (Cheifetz et al (1988) J. Biol. Chem. 263, 16984-16991), and fits well with the fact that the porcine TGF-β type II receptor has two N-glycosylation sites (Lin et al (1992) Cell 68, 775-785), whereas ALK-5 has only one (see SEQ ID No. 9).
Binding of TGF-β 1 to the type I receptor is known to be abolished by transient treatment of the cells with dithiothreitol (DTT) (Cheifetz and Massague (1991) J. Biol. Chem. 266, 20767-20772; Wrana et al (1992) Cell 71, 1003-1014). When analyzed by affinity cross-linking, binding of 125 I-TGF-βl to ALK-5, but not to the type II receptor, was completely abolished by DTT treatment of PAE/TβR-1 cells. Affinity cross-linking followed by immunoprecipitation by the VPN antiserum showed that neither the ALK-5 nor the type II receptor complexes was precipitated after DTT treatment, indicating that the VPN antiserum reacts only with ALK-5. The data show that the VPN antiserum recognizes a TGF-β type I receptor, and that the type I and type II receptors form a heteromeric complex.
125 I-TGF-l Bindiing & Affinity Crosslinking of Transfected COS Cells
Transient expression plasmids of ALKs -1 to -6 and TβR-II were generated by subcloning into the pSV7d expression vector or into the pcDNA I expression vector (Invitrogen). Transient transfection of COS-1 cells and iodination of TGF-βl were carried out as described above. Crosslinking and immunoprecipitation were performed as described for PAE cells above.
Transfection of cDNAs for ALKs into COS-1 cells did not show any appreciable binding of 125 I-TGFβ1, consistent with the observation that type I receptors do not bind TGF-β in the absence of type II receptors. When the TβR-II cDNA was co-transfected with cDNAs for the different ALKs, type I receptor-like complexes were seen, at different levels, in each case. COS-1 cells transfected with TβR-II and ALK cDNAs were analyzed by affinity crosslinking followed by immunoprecipitation using the DRL antisera or specific antisera against ALKs. Each one of the ALKs bound 125 I-TGF-βl and was coimmunoprecipitated with the TβR-II complex using the DRL antiserum. Comparison of the efficiency of the different ALKs to form heteromeric complexes with TβR-II, revealed that ALK-5 formed such complexes more efficiently than the other ALKs. The size of the crosslinked complex was larger for ALK-3 than for other ALKs, consistent with its slightly larger size.
Expression of the ALK Protein in Different Cell Types
Two different approaches were used to elucidate which ALK's are physiological type I receptors for TGF-β.
Firstly, several cell lines were tested for the expression of the ALK proteins by cross-linking followed by immunoprecipitation using the specific antiseras against ALKs and the TGF-β type II receptor. The mink lung epithelial cell line, MvlLu, is widely used to provide target cells for TGF-β action and is well characterized regarding TGF-β receptors (Laiho et al (1990) J. Biol. Chem. 265, 18518-18524; Laiho et al (1991) J. Biol. Chem. 266, 9108-9112). Only the VPN antiserum efficiently precipitated both type I and type II TGF-β receptors in the wild type MvlLu cells. The DRL antiserum also precipitated components with the same size as those precipitated by the VPN antiserum. A mutant cell line (R mutant) which lacks the TGF-β type I receptor and does not respond to TGF-β (Laiho et al, supra) was also investigated by cross-linking followed by immunoprecipitation. Consistent with the results obtained by Laiho et al (1990), supra the type III and type II TGF-β receptor complexes, but not the type I receptor complex, were observed by affinity crosslinking. Crosslinking followed by immunoprecipatition using the DRL antiserum revealed only the type II receptor complex, whereas neither the type I nor type II receptor complexes was seen using the VPN antiserum. When the cells were metabolically labelled and subjected to immunoprecipitation using the VPN antiserum, the 53 kDa ALK-5 protein was precipitated in both the wild-type and R mutant MvlLu cells. These results suggest that the type I receptor expressed in the R mutant is ALK-5, which has lost the affinity for binding to TGF-β after mutation.
The type I and type II TGF-β receptor complexes could be precipitated by the VPN and DRL antisera in other cell lines, including human foreskin fibroblasts (AG1518), human lung adenocarcinoma cells (A549), and human oral squamous cell carcinoma cells (HSC-2). Affinity cross-linking studies revealed multiple TGF-β type I receptor-like complexes of 70-77 kDa in these cells. These components were less efficiently competed by excess unlabelled TGF-βl in HSC-2 cells. Moreover, the type II receptor complex was low or not detectable in A549 and HSC-2 cells. Cross-linking followed by immunoprecipitation revealed that the VPN antiserum precipitated only the 70 kDa complex among the 70-77 kDa components. The DRL antiserum precipitated the 94 kDa type II receptor complex as well as the 70 kDa type I receptor complex in these cells, but not the putative type I receptor complexes of slightly larger sizes. These results suggest that multiple type I TGF-β receptors may exist and that the 70 kDa complex containing ALK-5 forms a heteromeric complex with the TGF-β type II receptor cloned by Lin et al (1992) Cell 68, 775-785, more efficiently that the other species. In rat pheochromocytoma cells (PC12) which have been reported to have no TGF-β receptor complexes by affinity cross-linking (Massague et al (1990) Ann. N.Y. Acad. Sci. 593, 59-72), neither VPN nor DRL antisera precipitated the TGF-β receptor complexes. The antisera against ALKs -1 to -4 and ALK6 did not efficiently i munoprecipitate the crosslinked receptor complexes in porcine aortic endothelial (PAE) cells or human foreskin fibroblasts.
Next, it was investigated whether ALKs could restore responsiveness to TGF-β in the R mutant of MvlLu cells, which lack the ligand-binding ability of the TGF-β type I receptor but have intact type II receptor. Wild-type MvlLu cells and mutant cells were transfected with ALK cDNA and were then assayed for the production of plasminogen activator inhibitor-1 (PAI-1) which is produced as a result of TGF-β receptor activation as described previously by Laiho et al (1991) Mol. Cell Biol. 11, 972-978. Briefly, cells were added with or without 10 ng/ml of TGF-βl for 2 hours in serum-free MCDB 104 without methionine. Thereafter, cultures were labelled with [ 35 S] methionine (40 μCi/ml) for 2 hours. The cells were removed by washing on ice once in PBS, twice in 10 mM Tris-HCl (pH 8.0), 0.5% sodium deoxycholate, 1 mM PMSF, twice in 2 mM Tris-HCl (pH 8.0), and once in PBS. Extracellular matrix proteins were extracted by scraping cells into the SDS-sample buffer containing DTT, and analyzed by SDS-gel electrophoresis followed by fluorography using Amplify. PAI-1 can be identified as a characteristic 45 kDa band (Laiho et al (1991) Mol. Cell Biol. 11, 972-978). Wild-type MvlLu cells responded to TGF-β and produced PAI-1, whereas the R mutant clone did not, even after stimulation by TGF-βl. Transient transfection of the ALK-5 cDNA into the R mutant clone led to the production of PAI-1 in response to the stimulation by TGF-βl, indicating that the ALK-5 cDNA encodes a functional TGF-β type I receptor. In contrast, the R mutant cells that were transfected with other ALKs did not produce PAI-1 upon the addition of TGF-βl.
Using similar approaches as those described above for the identification of TGF-β-binding ALKs, the ability of ALKs to bind activin in the presence of ActRII was examined. COS-1 cells were co-transfected as described above. Recombinant human activin A was iodinated using the chloramine T method (Mathews and Vale (1991) Cell 65, 973-982). Transfected COS-1 cells were analysed for binding and crosslinking of I-activin A in the presence or absence of excess unlabelled activin A. The crosslinked complexes were subjected to immunoprecipitation using DRL antisera or specific ALK antisera.
All ALKs appear tc bind activin A in the presence of Act R-II. This is more clearly demonstrated by affinity cross-linking followed by immunopreciptation. ALK-2 and ALK-4 bound 125 I-activin A and were coimmunoprecipitated with ActR-II. Other ALKs also bound 125I-activin A but with a lower efficiency compared to ALK-2 and ALK-4.
In order to investigate whether ALKs are physiological activin type I receptors, activin responsive cells were examined for the expression of endogenous activin type I receptors. MvlLu cells, as well as the R mutant, express both type I and type II receptors for activin, and the R mutant cells produce PAI-1 upon the addition of activin A. MvlLu cells were labeled with 125 I-activin A, cross-linked and immunoprecipitated by the antisera against ActR-II or ALKs as described above.
The type I and type II receptor complexes in MvlLu cells were immunoprecipitated only by the antisera against ALK-2, ALK-4 and ActR-II. Similar results were obtained using the R mutant cells. PAE cells do not bind activin because of the lack of type II receptors for activin, and so cells were transfected with a chimeric receptor, to enable them to bind activin, as described herein. A plasmid (chim A) containing the extracelluar domain and C-terminal tail of Act R-II (amino-acids −19 to 116 and 465 to 494, respectively (Mathews and Vale (1991) Cell, 65., 973-982)) and the kinase domain of TBR-II (amino-acids 160-543) (Lin et al (1992) Cell, 68, 775-785) was constructed and transfected into pcDNA/neo (Invitrogen). PAE cells were stably transfected with the chim A plasmid by electroporation, and cells expressing the chim A protein were established as described previously. PAE/Chim A cells were then subjected to 125 I-activin A labelling crosslinking and immunoprecipitation as described above.
Similar to MvlLu cells, activin type I receptor complexes in PAE/Chim A cells were immunoprecipitated by the ALK-2 and ALK-4 antisera. These results show that both ALK-2 and ALK-4 serve as high affinity type I receptors for activin A in these cells.
ALK-1, ALK-3 and ALK-6 bind TGF-βl and activin A in the presence of their respective type II receptors, but the functional consequences of the binding of the ligands remains to be elucidated.
The invention has been described by way of example only, without restriction of its scope. The invention is defined by the subject matter herein, including the claims that follow the immediately following full Sequence Listings. | A new receptor family has been identified, of activin-like kinases. Novel proteins have activin/TGF-beta-type I receptor functionality, and have consequential diagnostic/therapeutic utility. They may have a serine/threonine kinase domain, a DFKSRN or DLKSKN sequence in subdomain VIB and/or a GTKRYM sequence in subdomain VIII. | 2 |
FIELD
[0001] The present disclosure addresses the improvements introduced in support posts used for vertical signposts where, notably, such support posts present innovated constructive characteristics obtained by the association of a new composition developed as of the reuse of manufactured products through plastic and tire ground rubber, as well as new arrangements of structure hardware incorporated in the body of the support post enabling improvement in the mechanical resistance, mainly support post breakdown, due to its construction.
BACKGROUND
[0002] It is known to use signposts for the purpose of guiding users of a route along their path of travel. Such signpost provide users with the necessary information for directions, as well as, among others, information with regard to the distances covered over their route.
[0003] Such signposts also have the purpose of guiding the users with regard to the existence of services throughout the travel path, such as gas stations, restaurants, hospitals, police stations, among others. In addition, signposts have the purpose of guiding users with regard to the occurrence of geographical reference points such as state and city borders, rest area locations, historic parks and sites and educational messages of traffic safety.
[0004] Such signposts typically encompass graphic images applied to signs of different shapes, such as rectangular, supported above the ground by a support post. The planar surface of the signs can present different colors (e.g., green, red, etc.), where legends, arrows and diagrams in a different color (e.g., white, black, etc.) could be applied. Signs are also provided for highway identification having a particular shape. Likewise supplementary signs identifying services often present a blue background.
[0005] According to the current regulation in DENATRAN (Brazil), the support posts must be sized and fixed in order to withstand the load of the signpost itself and the effects of wind action acting on the sign while ensuring its correct position. The support posts must be fixed in order to keep the signs in their correct position, preventing them from being turned or displaced. For the fixation of the sign to the support post, it must be used proper fixing elements, in order to prevent its loosening of displacement, even after impacts or collusions.
[0006] Currently, the materials primarily used for production of support posts are galvanized steel and immunized wood, especially hardwood. The fact is that the hardwood was replaced by treated eucalyptus wood because of the shortage on the environment. Thus, the eucalyptus wood, according to the provisions of Law No. 97 of Oct. 20, 1965 and decree No. 58016 of Mar. 18, 1955 (Brazil), must receive treatment with water soluble protector in autoclave under vacuum and high pressure in order to receive the black color painting, as well as presenting retention and penetration rate of 6.5 kg of the protecting material per m 3 of wood according to NBR 6232 (Brazil).
[0007] However, despite of eucalyptus wood having its origin from replanting, it presents a difficult process for its treatment, in addition to chemicals used, such as arsenic, Copper Chrome Arsenic or Copper Chrome Boric Acid, which can bring health concerns for postconsumer used of this wood.
[0008] Further drawback lies in the fact of support post made as of wood treated after its useful life for incineration to the formation of coal or other purposes, but without due care in relation to the chemicals that are present in a significant amount as 6.5 kg/m 3 . The allocation of these supports for Class I Landfill would be suggested, which is a very difficult procedure to be inspected.
[0009] On the other hand, the support posts made of steel present susceptibility to corrosion developed by the chemical or electrochemical action, which is commonly used as “rust”, affecting not only the aesthetic appearance of the material, as well as the mechanical resistance and useful life.
[0010] In order to aggregate suitable resistance characteristics there are specific treatments, such as galvanizing obtained by means of application of chemicals in the support post body, such as the galvanizing process by immersion where the zincs with 98.0% of purity, contain more than 1.0% of lead and small amounts of other metals such as cadmium, iron, tin and copper, as well as the aluminum sometimes is added in small amounts, around 0.005% to increase the shine of the part and let its coating smoother.
[0011] It occurs that, during the process of galvanization process by hot immersion, two residues appear and can contaminate the bath, that is, dreg, a slurry consisting of Fe—Zn—5.0%+95% —, heavier than the molten zinc, which is concentrated in the bottom of the tank and grey or zinc oxide slag that is formed in the bath surface, referred to as “earth”.
[0012] It is crucial that the parts are passivated after the galvanization, aiming to preserve them against wet storage stain. Some materials may present growth of the intermediate layers, due to the chemical composition and, therefore, dark Grey staining process. In this case, the speedy of the cooling of the material must be accelerated in a passivating bath.
[0013] Thus, it is verified that the natural resources, such as iron ore are used in the production of support posts of galvanized steel, as well as other natural sources for the obtainment of energy to cast the iron ore, in addition to charcoal, mineral coal and electrical energy, cause harm to the environment.
[0014] Another considerable drawback of current support post due to the necessary resistance to weather consists in the fact that they are deemed true fixed barriers against impacts by collision of vehicles, often causing death, which has being a cause for technological studies, aiming to find troubleshooting for this drawback. Accordingly, support posts must be structured to not be a factor causing injury or death in public roads, according to NBR15486 (Brazil). Thus, it required that the support post have a collapsible property such that, during the collision by a vehicle with the support post, the support post bends away from the colliding vehicle without breaking free and not providing abrupt deceleration of the vehicle and its passengers.
[0015] In a research conducted in specialized database, it was found documents related to supports/rebar/crosspiece obtained as of recycling material.
[0016] The document No. PI 0505428-1 is related to the polymer crosspiece, with natural fibers and structural hardware resulting from extruded or injected origin, thermoformed compound of virgin or recycled plastic mixed with natural fibers in a ratio of 1 to 70% of the composition and structured with metallic rods, giving full play to replace hardwood treated or used as “crosspiece”. As the structural reinforcement, it is presented four rebar in the diameter of six to 12 mm, depending on the diameter, of the structure required from the crosspiece according to structure requirement.
[0017] The document No. PI 0704541-7 is related to the process to reuse and transform packages and toxic and contaminated materials in new products, and products obtained as of the manufacture of crosspiece, among others.
[0018] The document No. C1 0900485-8 consists of the process for obtaining railway sleepers but with the replacement of the core wood for a core made of the mixture of recycled polymer and chopped glass fiber, to be positioned in the region of fixation of tirefonds and support plates, jointly to longitudinal stiffeners rebar.
[0019] The document No. U.S. Pat. No. 4,150,790 is referred to the enhanced railway sleeper made by forming and bonding lignocellulose material in a monolithic triturated beam around a plurality of reinforcing bars, each one of which has a plurality of spaced protrusions fixing attached throughout its length, in specific positions with regard to midpoint of the loop and the rails mounted.
[0020] The document No. U.S. Pat. No. 5,658,519 refers to the elongate element, made of the supply of a plastic core substantially solid within a extrusion die, continuously, and a molten plastic within a framework causing surrounds of the molten plastic and binding for the plastic core and reinforcing bars to feed into the framework, in positions that surround the plastic core.
[0021] Upon performing an analysis of the documents, it is verified that the patents of No. PI 0505428-1, PI 0704541-7, C1 0900485-8, U.S. Pat. No. 4,150,790 and U.S. Pat. No. 5,658,519 use recycling materials, but differently from the material used by the applicant for the obtainment of supports for vertical signposts.
SUMMARY
[0022] Aiming to present improvements in the consumer market, the applicant developed improvements introduced in support for the vertical signposts.
[0023] Such support is developed by the association of new composition obtained through the use of high density polyethylene—HDPE. The HDPE can be purchased new for the support. However, HDPE can also be obtained, but not limited to, through the recycling of detergent bottles, disinfectant, motor oil, softeners, disinfectants, bleach, pesticides, and ground rubber obtained by tire recycling or the like. The HDPE provides structure for the support as well as an aesthetically pleasing finish for the support.
[0024] In the composition of the support cross-linked polyethylene, commonly abbreviated PEX or XLPE is added. The XLPE component is known in the market as Polycure. Though XPLE can be purchased new for the support, one source of XPLE arises from the recycling of electrical cables. The use of XPLE, which is a thermoset resin, promotes fire resistance and ultraviolet resistance. The inclusion of XPLE provides UV protection for the support extending its useful life and also provides a high level of fire resistance for the support.
[0025] In one arrangement, ground rubber, which may be sourced from used tires, is included in the composition. The ground rubber provides viscosity that enables the support to be extruded. Also the ground rubber provides ductility to the support.
[0026] The support resists wind strengths/velocities related to the worst scenario of world historical highs. While withstanding the worst wind situations, the support also presents, as a fundamental feature, breakdown capability. That is, the support is constructed with ability to bend when a vehicle collides with the support. That is, the support folds in response to collision/shock, preferably but not limited to, at a height of about 10-20 cm above the ground in which the lower portion of the support is disposed, so that the vehicle does not suffer serious damage or abrupt deceleration. Further, the support maintains integrity such that the support does not separate where the upper portion is projected back to the highway potentially endangering other users of the route. The material breakdown also prevents the signpost to be protruded above the vehicle, as the post bends away from a vehicle colliding with the support.
[0027] The breakdown occurs in view of the material ductile property. In addition to the ductility, fragility points are included in the bottom part of the support. Preferably, the fragility points are located approximately 20 cm above the ground after installation. This fragility point consist of one or more holes, typically but not limited to, 10 to 15 mm of diameter that runs through the support in at least one direction and preferably both directions, crosswise.
[0028] The section of the support made as of the recycling polymer can present different cross sections with variations of length. For instance:
[0000] i) quadrangular section with diameter of, for instance, 8×8 cm and up to 5.5 m of length; ii) circular cross section with a diameter of, for instance, 6cm and up to 4 m of length; iii) quadrangular section with a diameter of 10×10 cm and up to 6 cm of length; iv) rectangular section with dimension of 7×15 cm and up to 6 m of length; v) quadrangular section with dimension of, for instance, 5.5×5.5 cm and up to 3 m of length.
[0029] To improve the structural properties of the support made of polymer, the support may further include internal reinforcement fittings, which in one arrangement are in the form of steel bars (e.g., rebar). Such rebar is installed within the polymer support and, with the combination of distinct polymer sections and with the diameter variation of rebars, enhances the mechanical properties of the support.
[0030] Such polymer sections may also receive tubular sections, such as conduits, allowing the passage of cables and electric wires in order to facilitate the installation of lights, reflectors, lighted signs and related about the polymeric support.
[0031] One of the main advantages of this support of signposts lies in the fact that the new composition promoting an alternative to reduce the use of natural and energy resources, as well as it allows the reuse of products made from plastic in order to reduce pollution of the environment.
[0032] Another advantage of the reuse of plastic for obtaining signpost support of vertical supports lies in the fact of replacing brackets made from wood, which is scarce in nature or have a high cost of production.
[0033] Another advantage lies in the fact the forecast of ‘Polycure’—XLPE—in support of the composition to promote a high concentration of ‘UV resistance’—ultraviolet and flame-retardant promoting greater resistance to media.
[0034] Another major advantage lies in the fact that the polymer composition associated with the distribution of the steel bars and points of weakness in the bottom of the support, allow the support to acquire desired breakdown characteristics. That is, the support has the necessary resistance dictated by technical standards, while reducing the potential for secondary accidents, since the support and the signpost are folded during collision rather than separating while not offering shock resistance sufficient to be characterized as a fixed barrier, which provides abrupt deceleration of the vehicle and its occupants.
DESCRIPTION OF THE FIGURES
[0035] To complement the present description in order to obtain a better understanding of the characteristics of the present invention and according to a preferred practical embodiment thereof, accompanying description, attached hereto, a set of drawings where, exemplified way, although not limiting, it represented its operation:
[0036] The FIG. 1 represents a view in perspective and vertical support signpost with the indication sectional structural support body;
[0037] The FIG. 1A illustrates a section on the support, as shown in FIG. 1 ;
[0038] The FIG. 1B illustrates the support in side view, in partial section applied in the region of the weak points;
[0039] The FIG. 1C represents, as an example, breakdown movement of the support in case of vehicle collision or the like.
[0040] The FIGS. 2 , 3 and 4 show cross-sectional views of quadrangular sections 8×8 cm illustrating the corresponding rebars arrangement;
[0041] The FIGS. 5 and 6 show views in cross-sections corresponding circular sections illustrating the rebars arrangement;
[0042] The FIGS. 7 , 8 and 9 illustrate cross sectional views of quadrangular sections 10×10 cm illustrating the corresponding rebars arrangement;
[0043] The FIGS. 10 , 11 and 12 represent views of cross sections of rectangular sections 7×15 cm illustrating the corresponding rebars arrangement;
[0044] The FIGS. 13 , 14 , 15 and 16 show cross sectional views of quadrangular sections, circular and rectangular illustrating the arrangement of rebars and associated tube sections.
DETAILED DESCRIPTION
[0045] With reference to the illustrated drawings, the present disclosure refers to “IMPROVEMENTS INTRODUCED IN SUPPORT FOR VERTICAL SIGNPOST”, more precisely it is about a support ( 1 ) for vertical sign (VS), type used for setting directions as well as information about the distances, paths, petrol stations, restaurants, hospitals, police stations, and places of interest as well as guide vehicle drivers and pedestrians about the routes, destinations, access, distances, ancillary services and tourist attractions, and can also have the function of user education.
[0046] According to the invention, the support ( 1 ) is obtained from the composition of association (F) formed recycled high density polyethylene—HDPE—, tire ground rubber obtained by recycling and component ‘XLPE’/ Polycure from the recycling of electrical cables. These elements that can be aggregated in different proportions so long as they are in at least one range that can be defined as follows:
55 to 98% 70% of HDPE—high-density polyethylene recycled; 28 to 35% of XLPE/Polycure recycled; 5 to 15% of tire ground rubber; 1.0 to 3.0% of ultraviolet resistance; and 1.0 to 3.0% of anti-flame.
The ultraviolet resistance and anti-flame materials may be incorporated within the XLPE. That is, the 28-35% of XLPE may include these materials.
[0052] As an example of possible polymer compositions, but not limited to below represented formulations, at least three formulations are exemplified for the practical solution for implementing this support, namely:
a) Formula (A)
[0000]
70% of HDPE—high-density polyethylene recycled;
30% of XLPE—Polycure recycled.
b) Formula (B)
[0000]
60% HDPE—high-density polyethylene recycled;
30% of XLPE/Polycure recycled;
10% of tire ground rubber.
c) Formula (C)
[0000]
95% HDPE—High Density Polyethylene recycled;
2.5% of ultraviolet resistance;
2.5% of anti-flame.
In relation to Formula (C), the ultraviolet resistance and anti-flame properties may originate from additive other than XLPE. For instance, Carbon Black may be utilized as the anti UV material, and Magnesium Hydroxide may be utilized as the flame retardant.
[0061] The section ( 2 ) of the support ( 1 ) made from the composition of recycled polymers may show different cross sections of length variations (X), namely: i) a square section ( 2 A) with dimension (x)/(y) preferably of 8×8 cm and up to 5.5 m in length; ii) a circular section ( 2 B) with a diameter (Z), preferably of 6 cm and up to 4 m long; iii) a square section ( 2 C) with dimensions (x 1 )/(y 1 ) of 10×10 cm and up to 6 m in length; iv) rectangular ( 2 D) with dimension (x 2 )/(y 2 ) of 7×15 cm up to 6 m in length; v) a square section ( 2 E) with a dimension (x 3 )/(y 3 ), preferably of 5.5 cm×5.5 cm and up to 3 m in length.
[0062] All the supports ( 1 ) are provided at least one weak point (P 1 ) (fragility aperture) and preferably two points (P 1 ) prevailing in the lower part of the support which is a height (H) from 10 to 20 cm from the ground after installation. This(these) point(s) of weakness (P 1 ) consist of hole(s) from 10 to 15 mm in diameter which pierces the underside of the support part, in one direction, preferably in cross direction. It will be appreciated that other sections of the supports are substantially identical in shape to the section including the points of weakens with the exception that the points of weakness are absent.
[0063] The support ( 1 ) obtained from the innovative composition of recycled polymers incorporates various structural arrangements hardware or rebars ( 3 ), these arrangements that are specific for combination with the various sections ( 2 A), ( 2 B), ( 2 C), ( 2 D) and ( 2 E) of the section ( 2 ) conferring resistance to variations of the support ( 1 ). This hardware ( 3 ) may be in the form of steel rebars and feature diametric variations. Though illustrated as having circular cross-sections, it will be appreciated that the hardware ( 3 ) may have other cross-sectional shapes as well. In one embodiment, the hardware extends continuously within the support ( 1 ) between a bottom end of the support and a top end of the support.
[0064] In a preferred constructive version, the sections ( 2 A) with quadrangular dimensions (x)/(y) can receive the following arrangements of rebars ( 3 a ):
a) Four rebars ( 3 a 1 ) with a diameter (d 1 ), preferably of 8 mm and two weak points (P 1 ) arranged in a crossway (see FIG. 2 ). That association and arrangement consists resistance as shown below:
[0000]
1. Binding Test:
Width (mm)
81.3
Thickness (mm)
80.2
Load flow (N)
20,600
b) Four rebars ( 3 a 2 ) having a diameter (d 2 ), preferably 6 mm and two weak points (P 1 ) arranged in a cross shape (see FIG. 4 ). That association and arrangement make up the strength as shown below:
[0000]
1. Binding Test:
Width (mm)
82.8
Thickness (mm)
83.0
Load flow (N)
15,600
c) A pair of rebars ( 3 a 3 ) with a diameter (d 3 ), preferably of 6 mm and a pair of rebars ( 3 a 4 ) with a diameter (d 4 ), preferably of 8 mm and two weak points (P 1 ) arranged in a crossway (see FIG. 3 ). That association and arrangement makes up the strength as shown below:
[0000]
1. Binding Test:
Width (mm)
80.2
Thickness (mm)
80.4
Load flow (N)
20,200
[0068] In a second constructive variation, the circular sections ( 2 B) with a diameter (z) can receive the following arrangements rebars ( 3 b ):
[0000] d) Four rebars ( 3 b 1 ) with a diameter (d 5 ), preferably of 6 mm and two weak points (P 1 ) arranged in a crossway (see FIG. 5 );
e) Six rebars ( 3 b 2 ) with a diameter (d 6 ), preferably of 4 mm and two weak points (P 1 ) arranged in a crossway (see FIG. 6 );
That association and arrangement of rebars ( 3 b 1 ) and ( 3 b 2 ) with section ( 2 B) comprises the mechanical strength as shown below:
[0000]
1. Binding Test:
Diameter (mm)
60.5
Load flow (N)
3,600
[0069] In a third constructive variation, the sections ( 2 C) with dimensions (x 1 )/(y 1 ) can receive the following arrangements rebars ( 3 c ):
[0000] f) Four rebars ( 3 c 1 ) with a diameter (d 7 ), preferably of 10 mm and two weak points (P 1 ) arranged in a crossway (see FIG. 7 );
g) Four rebars ( 3 c 2 ) with a diameter (d 8 ), preferably of 8 mm and two weak points (P 1 ) arranged crossway (see FIG. 8 );
h) A pair of rebars ( 3 c 3 ) with a diameter (d 9 ) of 8 mm and preferably a pair of rebars ( 3 c 4 ) with a diameter (d 10 ), preferably of 10 mm, apart from two weak points (P 1 ) arranged crossway (see FIG. 9 ).
[0070] That association and arrangement of rebars ( 3 c 1 ), ( 3 c 2 ), ( 3 c 3 ) and ( 3 c 4 ) with section ( 2 C) comprises the mechanical strength as shown below
[0000]
1. Bending Test:
Width (mm)
102.8
Thickness (mm)
99.7
Load flow (N)
35,000
[0071] In the fourth constructive variation, the sections ( 2 D) with dimension (x 2 )/(y 2 ) can receive the following rebar arrangement ( 3 d ):
[0000] i) Four rebars ( 3 d 1 ) with a diameter (d 11 ), preferably 10 mm and two weak points (P 1 ) arranged in cross form (see FIG. 10 );
j) Four rebars ( 3 d 2 ) with a diameter (d 12 ), preferably of 8 mm and two weak points (P 1 ) arranged crossway (see FIG. 11 );
l) A pair of rebars ( 3 d 3 ) with a diameter (d 13 ), preferably of 8 mm and A pair of rebars ( 3 d 4 ) with a diameter (d 14 ), preferably of 10 mm, apart from two weak points (P 1 ) arranged crossway (see FIG. 12 ).
[0072] The association and arrangement of rebars ( 3 d 1 ), ( 3 d 2 ), ( 3 d 3 ) and ( 3 d 4 ) with section ( 2 D) comprises the mechanical strength as shown below:
[0000]
1. Bending Test:
Width (mm)
72.7
151.8
Thickness (mm)
153.4
72.8
Rated load (N)
11,500
27,500
Load flow (N)
20,000
67,469
[0073] In the fifth constructive variant, the sections ( 2 E) with dimensions (x 3 )/(y 3 ) can receive the following arrangements rebars ( 3 c ):
[0000] m) Four rebars ( 3 c 1 ) with a diameter (d 7 ), preferably of 6 mm and two weak points (P 1 ) arranged in a crossway (see FIG. 7 );
[0074] That association and arrangement of rebars ( 3 c 1 ), section ( 2 E) comprises the mechanical strength as shown below:
[0000]
1. Bending Test:
Width (mm)
55.0
Thickness (mm)
55.0
Load flow (N)
4,000
[0075] In the sixth constructive variation, the sections ( 2 A), ( 2 B), ( 2 C), ( 2 D) and ( 2 E) can receive rebars ( 3 ) and tube sections ( 4 ) as conduits for the passage of electrical cables and wires (f) in order to facilitate the installation of lights, reflectors, luminous plate and the like on the polymeric support plates (see FIGS. 13 to 16 ). In this fifth variation are applied to the two weak points (P 1 ) arranged crossway.
[0076] The description of the polymer composition associated with the distribution of the steel bars, tube sections and points of weakness in the bottom of the support, allows the support to acquire currently desired breakdown characteristics, since the support has the necessary wind resistance dictated by technical standards, while cooperating with the reduction of accidents, since the support and the signpost are folded away from the collision and not offering resistance to shock intensity sufficient to be characterized as a fixed barrier, which can provide abrupt deceleration of the vehicle and its occupants causing risk to physical integrity and health of the same, as usually happens.
[0077] The support is, in one embodiment, produced in an extrusion process. That is, the formula utilized, along with any rebars and/or conduits are forced through a die. Such manufacturing is known to those skilled in the art and not further discussed.
[0078] Modifications may be introduced with regard to certain construction details and form, without this implying depart from the fundamental principles that are clearly substantiated in the set of claims, thus understood that the terminology did not have the limitation of purpose. | Disclosed is a support post for supporting roadway signs. In one embodiment, a polymer support post is formed of a composition of high density polyethylene—HDPE—, ground rubber and ‘XLPE’/Polycure. All these materials may be sourced from recycled materials. Additionally, the support may include ultra-violet materials and flame retardant materials. In one embodiment, the ultra-violet materials and flame retardant material are included in recycled XLPE material. One or more support rods may be disposed within the polymer support post. Additionally, one or more fragility apertures may extend through the support post to allow the support post to collapse upon impact. | 4 |
RELATED APPLICATIONS
[0001] This application is a divisional of, claims the benefit of and priority to U.S. Non-Provisional application Ser. No. 13/811,151, titled, “A Safety Mechanism For A Well, A Well Comprising The Safety Mechanism, And Related Methods,” filed Feb. 26, 2013, which is a National Stage Entry of PCT Application No. PCT/GB2011/051377, titled, “A Safety Mechanism For A Well, A Well Comprising The Safety Mechanism, And Related Methods,” filed Jul. 20, 2011, which is a PCT Application of GB1012175.4, titled, “A Well comprising a Safety Mechanism and Sensors,” filed Jul. 20, 2010 each of which is incorporated herein by reference in its entirety.
FIELD
[0002] This invention relates to a safety mechanism, such as a valve, sleeve, packer or plug, for a well; a well comprising the safety mechanism; and methods to improve the safety of wells; particularly but not exclusively subsea hydrocarbon wells.
BACKGROUND
[0003] In recent years, oil and gas has been recovered from subsea wells in very deep water, of the order of over 1 km. This poses many technical problems in drilling, securing, extracting and abandoning wells in such depths.
[0004] In the event of a failure in the integrity of the well, wellhead apparatus control systems are known to shut the well off to prevent dangerous blow-out, or significant hydrocarbon loss from the well. Blow-out-preventers (BOPs) are situated at the top of subsea wells, at the seabed, and can be activated from a control room to shut the well, or may be adapted to detect a blow-out and shut automatically. Should this fail, a remotely operated vehicle (ROV) can directly activate the BOP at the seabed to shut the well.
[0005] In a completed well, rather than a BOP, a “Christmas” tree is provided at the top of the well and a subsurface safety valve (SSV) is normally added, “downhole” in the well. The SSV is noimally activated to close and shut the well if it loses communication with the controlling platform, rig or vessel.
[0006] Despite these known safety controls, accidents still occur and a recent example is the disastrous blow-out from such a subsea well in the Gulf of Mexico, causing a massive explosion resulting in loss of life, loss of the rig and a significant and sustained escape of oil into the Gulf of Mexico, threatening wildlife and marine industries.
[0007] Whilst the specific causes of the disaster are, at present, unclear, some aspects can be observed: an Emergency Dis-connect System (EDS) controlled from the rig failed to seal and disconnect the vessel from the well; a dead-man/AMF system at the seabed failed to seal the well; subsequent Remotely Operated Vehicle (ROV) intervention also failed to activate the safety mechanisms on the BOP. Clearly the conventional systems focused primarily on the blow-out-preventer did not activate at the time of the blow-out and also failed to stem the tide of oil into the sea after control communication was lost with the rig.
SUMMARY
[0008] Thus there is a need to improve the safety of oil wells especially those situated in deep water regions.
[0009] Given the difficulty in communicating and controlling downhole tools (that is tools in the well), especially where communications are severed, one might consider the provision of a further shut off mechanism with the BOP situated at the seabed. However the inventors of the present invention have noted that the addition of more equipment at this point will be extremely difficult because it will increase the size and height of the components placed at this point, which immediately prior to installation, will be difficult for rigs to accommodate. Moreover, whilst this would add a further protective measure, it is largely the same concept as the existing safety systems. Indeed, increasing the complexity of the control systems to support these additional features may potentially have a detrimental impact on reliability of the over-all system rather than increasing the level of safety provided.
[0010] In the case of adding a further conventional control mechanism for devices, such as a valve, or sensor downhole; the inventors of the present invention also note limitations since, in the event of a blow-out, the ability to function these devices may be lost due to the inability to fluctuate pressure to control pressure activated devices, or due to the loss of control lines.
[0011] Thus it is difficult for a skilled person to design a further safety system which can practically add to the safety systems already provided in oil wells.
[0012] An object of the present invention is to mitigate problems with the prior art, and preferably to improve the safety of wells.
[0013] According to a first aspect of the present invention there is provided a safety mechanism comprising:
[0000] an obstructing member moveable between, normally from, a first position where fluid flow is permitted, and, normally to, a second position where fluid flow is restricted;
a movement mechanism;
and a wireless receiver normally a transceiver, adapted to receive, and normally transmit, a wireless signal;
wherein the movement mechanism is operable to move the obstructing member from one of the first and second positions to the other of the first and second positions in response to a change in the signal being received by the wireless transceiver.
[0014] The obstructing member can in certain embodiments therefore start at either the first or second positions.
[0015] The transceiver, where it provided, is normally a single device with a receiver functionality and a transmitter functionality; but in principle a separate receiver and a separate transmitter device may be provided. These are nonetheless considered to be a transceiver as described herein when they are provided together at one location.
[0016] Relays and repeaters may be provided to facilitate transmission of the wireless signals from one location to another.
[0017] The invention also provides a well comprising at least one safety mechanism according to the first aspect of the invention.
[0018] Typically the well has a wellhead.
[0019] Thus the present invention provides a significant benefit in that it can move, normally shut, an obstructing member, such as a valve, packer, sleeve or plug in response to a wireless signal. Significantly this is independent of the provision of control lines, such as hydraulic or electric lines, between a well and a wellhead apparatus, for example the BOP. Thus in the event of a disastrous blowout or explosion, a wireless signal can be sent to the valve merely by contacting the wellhead apparatus typically at the top of the well with a wireless transmitter, which will send the appropriate signal. For certain embodiments the wireless transmitter may be mounted onto the wellhead apparatus. Indeed this can be achieved even if the wellhead apparatus has suffered extensive damage, and/or the hydraulic, electric and other control lines have been damaged and the conventional safety systems have lost all functionality, since the wireless signal requires no intact control lines in order to shut off the valve. Thus this removes the present dependence on a functioning BOP/wellhead apparatus to prevent the egress of oil, gas or other well fluids into the sea.
[0020] In certain embodiments the transmitter may be provided as part of a wellhead apparatus.
[0021] Wellhead apparatus as used herein includes but is not limited to a wellhead, tubing and/or casing hanger, a BOP, wireline/coiled tubing lubricator, guide base, well tree, tree frame, well cap, dust cap and/or well canopy.
[0022] Typically the wellhead provides a sealing interface at the top of the borehole. Typically any piece of equipment or apparatus at or up to 20-30 m above the wellhead can be considered for the present purposes as wellhead apparatus.
[0023] Said “change in the signal” can be a different signal received, or may be receiving the control signal where no control signal was previously received and may also be loss of a signal where one was previously received. Thus in the latter case the safety mechanism may be adapted to operate when wireless communication is lost which may occur as a consequence of an emergency situation, rather than necessarily requiring a control signal positively sent to operate the safety mechanism.
[0024] Indeed the invention more generally provides a transceiver configured to activate and send signals after an emergency situation has occurred as defined herein.
[0025] In preferred embodiments the transceiver is an acoustic transceiver and the control signal is an acoustic control signal. In alternative embodiments, the transceiver may be an electromagnetic transceiver, and the signal an electromagnetic signal. Combinations may be provided—for example part of the distance may be travelled by an acoustic signal, part by an electromagnetic signal, part by an electric cable, and/or part from a fiber optic cable; all with transceivers as necessary.
[0026] The acoustic signals may be sent through elongate members or through well fluid, or a combination of both. To send acoustic signals through the fluid, a pressure pulser or mud pulser may be used.
[0027] Preferably the obstructing member moves from the first to the second position.
[0028] Preferably the safety mechanism incorporates a battery.
[0029] The safety mechanism is typically deployed subsea.
[0030] The transceiver comprises a transmitter and a receiver. The provision of a transmitter allows signals to be sent from the safety mechanism to a controller, such as acknowledgement of a control signal or confirmation of activation.
[0031] The safety mechanism may be provided on a drill string, completion string, casing string or any other elongate member or on a sub-assembly within a cased or uncased section of the well. The safety mechanism may be used in the same wells as a BOP or a wellhead, tree, or well-cap and may be provided in addition to a conventional subsurface safety valve.
[0032] Typically a plurality of safety mechanisms are provided.
[0033] The transceiver may be spaced apart from the movement mechanism and connected by conventional means such as hydraulic line or electric cable. This allows the wireless signal to be transmitted over a smaller distance. For example the wireless signal can be transmitted from the wellhead apparatus to a transceiver up to 100 m, sometimes less than 50 m, or less than 20 m below the top of the well which is connected though hydraulics or electric cabling to the obstructing member. This allows the safety mechanism in accordance with the present invention to operate even when the wellhead, wellhead apparatus or the top 100 m, 50 m or 20 m of the well is damaged and control lines therein broken. Thus the benefits of embodiments can be focused on a particular areas. Accordingly embodiments of the present invention can be combined with fluid and/or electric control systems.
[0034] Preferably a sensor is provided to detect a parameter in the well, preferably in the vicinity of the safety mechanism.
[0035] Thus such sensors can provide important information on the environment in all parts of the well especially around the safety mechanism and the data from the sensors may provide information to an operator of an emergency situation that may be occurring or about to occur and may need intervention to mitigate the emergency situation.
[0036] Preferably the information is retrieved wirelessly, although other means, such as data cables, may be used. Preferably therefore the safety mechanism comprises a wireless transmitter, and more preferably a wireless transceiver.
[0037] The sensors may sense any parameter and so be any type of sensor including but not necessarily limited to temperature, acceleration, vibration, torque, movement, motion, cement integrity, pressure, direction and inclination, load, various tubular/casing angles, corrosion and erosion, radiation, noise, magnetism, seismic movements, stresses and strains on tubular/casings including twisting, shearing, compressions, expansion, buckling and any form of deformation; chemical or radioactive tracer detection; fluid identification such as hydrate, wax and sand production; and fluid properties such as (but not limited to) flow, density, water cut, pH and viscosity. The sensors may be imaging, mapping and/or scanning devices such as, but not limited to, camera, video, infra-red, magnetic resonance, acoustic, ultra-sound, electrical, optical, impedance and capacitance. Furthermore the sensors may be adapted to induce the signal or parameter detected by the incorporation of suitable transmitters and mechanisms. The sensors may also sense the status of equipment within the well, for example valve position or motor rotation.
[0038] The wireless transceiver may be incorporated within the sensor, valve or safety mechanism or may be independent from it and connected thereto. The sensors may be incorporated directly in the equipment comprising the transmitters or may transfer data to said equipment using cables or short-range wireless (e.g. inductive) communication techniques. Short range is typically less than 5 m apart, often less than 3 m apart and indeed may be less than 1 m apart.
[0039] The sensors need to operate only in an emergency situation but can also provide details on different parameters at any time. The sensors can be useful for cement tests, testing pressures on either side of packers, sleeves, valves or obstructions and wellhead pressure tests and generally for well information and monitoring from any location in the well.
[0040] The wireless signals may be sent retroactively, that is after an emergency situation has occurred, for example after a blow out.
[0041] Typically the sensors can store data for later retrieval and are capable of transmitting it.
[0042] The safety mechanism may be adapted to move the obstructing member to/from the first position from/to the second position automatically in response to a parameter detected by the sensor. Thus at a certain “trip point” the safety mechanism can close the well, if for example, it detects a parameter indicative of unusual data or an emergency situation. Preferably the safety mechanism is adapted to function in such a manner in response to a plurality of different parameters all detecting unusual data, thus suggesting an emergency situation. The parameter may be any parameter detected by the sensor, such as pressure, temperature, flow, noise, or indeed the absence of flow or noise for example.
[0043] Such safety mechanisms are particularly useful during all phases when a BOP is in use and especially during non-drilling phases when a BOP is in use.
[0044] Preferably the trip point can be varied by sending instructions to a receiver coupled to (not necessarily physically connected thereto) or integral with, the sensors and/or safety mechanism. Such embodiments can be of great benefit to the operator, since the different operations downhole can naturally experience different parameters which may be safe in one phase but indicative of an emergency situation in another phase. Rather than setting the trip point at the maximum safety level for all phases, they can be changed by communications including wireless communication for the different phases. For example, during a drilling phase the vibration sensed would be expected to be relatively high compared to other phases. Sensing vibration to the same extent in other phases may be indicative of an emergency situation and the safety mechanism instructed to change their trip point after the drilling phase.
[0045] For certain embodiments, a sensor is provided above and below the safety mechanisms and can thus monitor differential parameters in these positions which can in turn elicit information on the safety of the well. In particular any pressure differential detected across an activated safety mechanism would be of particular use in assessing the safety of the well especially on occasions where a controlling surface vessel moves away for a period of time and then returns.
[0046] Sensors and/or transceivers may also be provided in casing annuli.
[0047] In use, an operator can react to any abnormal and potentially dangerous occurrence which the sensors detect. This can be a variety of different parameters including pressure, temperature and also others like stress and strain on pipes or any other parameters/sensors referred to herein but not limited to those.
[0048] Moreover with a plurality of sensors, the data may provide a profile of the parameters (for example, pressure/temperature) along the casing and so aid identification where the loss of integrity has occurred, e.g. whether the casing, casing cement, float collar or seal assembly have failed to isolate the reservoir or well. Such information can allow the operator to react in a quick, safe and efficient manner; alternatively the safety mechanism can be adapted to activate in response to certain detected parameters or combination of parameters, especially where two or three parameters are showing unusual values.
[0049] Such a system may be activated in response to an emergency situation.
[0050] Thus the invention provides a method of inhibiting fluid flow from a well in an emergency situation, the method comprising:
[0000] in the event of an emergency, sending a wireless signal into the well to a safety mechanism according to the first aspect of the invention.
[0051] Preferred and other optional features of the previous embodiment are preferred and optional features of the method according to the invention immediately above.
[0052] An emergency or emergency situation is where uncontrolled fluid flow occurs or is expected to occur, from a well; where an unintended explosion occurs or there is an unacceptable risk that it may occur, where significant structural damage of the well integrity is occurring or there is an unacceptable risk that it may occur, or where human life, or the environment is in danger, or there is an unacceptable risk that it may be in danger. These dangers and risks may be caused by a number of factors, such as the well conditions, as well as other factors, such as severe weather.
[0053] Thus normally an emergency situation is one where at least one of a BOP and subsurface safety valve would be attempted to be activated, especially before/during or after an uncontrolled event in a well.
[0054] Furthermore, normally an emergency situation according to the present invention is one defined as the least, more or most severe accordingly to the IADAC Deepwater Well Control Guidelines, Third Printing including Supplement 2000, section 4.1.2. Thus events which relate to kick control may be regarded as an emergency situation according to the present invention, and especially events relating to an underground blowout are regarded as an emergency situation according to the present invention, and even more especially events relating to a loss of control of the well at the sea floor (if a subsea well) or the surface is even more especially an emergency according to the present invention.
[0055] Methods in accordance with the present invention may also be conducted after said emergency and so may be performed in response thereto, acting retroactively.
[0056] The method may be provided during all stages of the drilling, cementing, development, completion, operation, suspension and abandonment of the well. Preferably the method is provided during a phase where a BOP is provided on the well.
[0057] Optionally the method is conducted during operations on the well when attempts have been made to activate the BOP.
[0058] During these phases, embodiments of the present invention are particularly useful because the provision of physical control lines during these phases would obstruct the many well operations occurring at this time; and indeed the accepted practice is to avoid as much as possible installing devices which require communication for this reason. Embodiments of the present invention go against this practice and overcome the disadvantages by providing wireless communications. Thus an advantage of embodiments of this invention is that they enable the use of a safety valve or barrier in situations where conventional safety valves or barriers could not, or would not, normally be deployed.
[0059] The safety mechanism may comprise a valve, preferably a ball or flapper valve, preferably the valve may incorporate a mechanical over-ride controlled, for example, by pressure, wireline, or coiled tubing or other intervention methods. The valve may incorporate a ‘pump through’ facility to permit flow in one direction.
[0060] The obstructing member of the safety mechanism may be a sleeve.
[0061] Optionally the safety mechanism may be actuated directly using a motor but alternatively or additionally may be adapted to actuate using stored pressure, or preferably using well pressure acting against an atmospheric chamber, optionally used in conjunction with a spring actuator.
[0062] When the safety mechanism comprises a valve, especially if the valve has a sleeve, it may be provided in a casing sub and adapted to move from one of the first and second positions to the other of the first and second positions, and then back to the first of the first and second positions.
[0063] Thus a well may comprise a casing having a casing sub with the safety mechanism in the form of a valve therein, the valve communicating between an inner and outer side of the casing; wherein the valve is adapted to move from one of the first and second positions to the other of the first and second positions, and then back to the first of the first and second positions.
[0064] The safety mechanism may incorporate components which are replaceable, or incorporate key parts, such as batteries, or valve bodies which are replaceable without removing the whole component from the well. This can be achieved using methods such as side-pockets or replaceable inserts, using conventional methods such as wireline or coiled-tubing.
[0065] In order to retrieve data from the sensors and/or actuate the safety mechanism, one option is to deploy a probe. A variety of means may be used to deploy the probe, such as an electric line, slick line wire, coiled tubing, pipe or any other elongate member. Such a probe could alternatively or additionally be adapted to send signals. Indeed such a probe may be deployed into a casing annulus if required.
[0066] In other embodiments, the wireless signal may be sent from a device provided at the wellhead apparatus or proximate thereto, that is normally within 300 m. In one embodiment wireless signals can be sent from a platform, optionally with wireless repeaters provided on risers and/or downhole. For other embodiments, the wireless signals can be sent from the seabed wellhead apparatus, after receiving sonar signals from the surface or from an ROV. In other embodiments, the wireless signals can be sent from the wellhead apparatus after receiving a satellite signals from another location. Furthermore if the wellhead is a seabed wellhead, the wireless signals can be then sent from the seabed wellhead apparatus, after receiving sonar signals, which had been triggered/activated after receiving a satellite signal from another location.
[0067] The surface or surface facility may be for example a nearby production facility standby or supply vessel or a buoy.
[0068] Thus the device comprises a wireless transmitter, or transceiver and preferably also comprises a sonar receiver, to receive signals from a surface facility and especially a sonar transceiver so that it can communicate two-way with the surface facility. For certain embodiments an electric line may be run into a well and the wireless transceiver attached towards one end of the line. In other embodiments the signal may be sent from an ROV via a hot-stab connection or via a sonar signal from the ROV.
[0069] Therefore the invention also provides a device, in use fitted or retro-fitted to a top of a well, comprising a wireless transmitter and a sonar receiver; especially for use in an emergency situation.
[0070] The device is relatively small, typically being less than 1 m 3 , preferably less than 0.25 m 3 , especially less than 0.10 m 3 and so can be easily landed on the wellhead apparatus. The resulting physical contact between the wellhead apparatus and the device provides a connection to the well for transmission of the wireless signal. In alternative embodiments the device is built into the wellhead apparatus, which is often at the seabed but may be on land for a land well.
[0071] Thus such devices also operate wirelessly and do not require physical communication between the wellhead apparatus and a controlling station, such as a vessel or rig.
[0072] Embodiments of the invention also include a satellite device comprising a sonar transceiver and a satellite communication device. Such embodiments can communicate with the well, such as with said device at the wellhead apparatus in accordance with a previous aspect of the invention, and relay signals onwards via satellite. The satellite device may be provided on a rig or vessel or a buoy.
[0073] Thus according to one aspect of the invention there is provided a well apparatus comprising a well and a satellite device comprising a satellite communication mechanism, and a sonar, the device configured to relay information received from the sonar by satellite.
[0074] Preferably the device is independent of the rig, for example it may be provided on a buoy. Thus in the event that the rig is lost, the buoy may relay a control signal from a satellite to the well to shut down the well.
[0075] In a further embodiment the device at the wellhead apparatus may be wired to a surface or remote facility. Preferably however, the device is provided with further wireless communication options for communication with the surface facility. Typically the device has batteries to permit operation in the event of damage to the cable.
[0076] The safety mechanism may comprise a subsurface safety valve, optionally of known type, along with a wireless transceiver.
[0077] In alternative embodiments, the safety mechanism comprises a packer and an expansion mechanism. The movement mechanism causes the expansion mechanism to activate which expands the packer and so moving the packer from said first position to said second position.
[0078] Thus according to a further aspect of the present invention there is provided a packer apparatus comprising a packer and an activation mechanism, the activation mechanism comprising an expansion mechanism for expanding the packer and a wireless transceiver adapted to receive a wireless control signal and control the activation mechanism.
[0079] The wireless signal is preferably an acoustic signal and may travel through elongate members and/or well fluid.
[0080] Alternatively the wireless signal may be an electromagnetic or any other wireless signal or any combination of that and acoustic.
[0081] References throughout to “expanding” and “expansion mechanisms” etc include expanding a packer by compression of an elastomeric element and/or inflating a packer and inflation mechanisms etc and/or explosive activation with explosive mechanisms, or actuation of a swell mechanism by exposure of a swellable element to an activating fluid, such as water or oil.
[0082] The packer apparatus may be provided downhole in any suitable location, such as on a drill string or production tubing and, surprisingly, in a casing annulus between two different casing strings, or between the casing and formation or on a sub-assembly within a cased or uncased section of the well.
[0083] In use after deployment and wireless activation downhole according to the present invention, the packer may be provided in the expanded state to provide a further barrier against fluid movement therepast, especially those provided on an outer face of an elongate member in a well. Those between said casing and a drill string/production tubing, are preferably reactive to an emergency situation that is unexpanded.
[0084] Thus the invention also provides a well apparatus comprising:
[0000] a plurality of casing strings;
a packer apparatus provided on one of the casing strings;
the packer apparatus comprising a wireless transceiver, and adapted to expand in response to a change in a wireless signal in order to restrict flow of fluid through an annulus between said casing string and an adjacent elongate member.
[0085] As noted above, the packer may be provided in use in the expanded configuration and act as a permanent barrier to resists fluid flow or may be provided in the unexpanded configuration and activated as required, for example in response to an emergency situation. Moreover the packer may be adapted to move from an expanded configuration, corresponding to the second position of the safety mechanism where fluid flow is restricted (normally blocked) and retract to the first position where fluid flow is permitted.
[0086] The adjacent elongate member may be another of the casing strings or may be a drill pipe or may be production tubing.
[0087] The invention also provides a packer as described herein for use on a production string in an emergency situation.
[0088] For example in a gas lift operation the packer may be provided on the production tubing and activated only in the event of an emergency.
[0089] Typically the packer is provided as a permanent barrier when the adjacent member is another casing string, and in the unexpanded configuration when the elongate member is a drill pipe of production tubing that is they remain unexpanded until they expand in response to an emergency situation.
[0090] Whilst the packer of the packer apparatus may expand in an inward or outward direction, preferably it is adapted to expand in an inward direction.
[0091] The annulus may be a casing annulus.
[0092] Thus an advantage of such embodiments is that fluid flow through an annulus can be inhibited, preferably stopped, by provision of such a packer in an annulus. Normally fluid does not flow through the casing annulus of a well and so the skilled person would not consider placing a packer in this position. However the inventors of the present invention have realized that the casing annulus is a flow path through which well fluid may flow in the event of a well failure and blow out. Such an event may be due to failure of the formation, cement and/or seals provided with the casing system and wellhead.
[0093] Preferably a plurality of packer apparatus are provided. Different packer apparatus may be provided in the same or in different annuli.
[0094] Preferably the packer apparatus is/are provided proximate to the top of the well. In this way the packers can typically inhibit fluid flow above the fault or suspected fault, in the casing. Therefore the packer(s) may be provided within 100 m of the wellhead, more preferably within 50 m, especially within 20 m, and ideally within 10 m.
[0095] The packers provided in a casing annulus may be non-weight packers, that is they do not necessarily have engaging teeth for example the packers may be inflatable or swell types.
[0096] The casing packers may be installed above the cemented-in section of the casing and they thus typically provide an additional barrier to flow of fluids above that traditionally provided by a portion of the well being cased in.
[0097] In alternative embodiments the packers may be provided on an inner side of the casing adjacent to a cemented in portion of the casing, thus inhibiting a flow path at this point, whilst the cement inhibits the flow path on the outside portion of the casing.
[0098] The safety mechanism may be a packer-like element without a through bore and so in effect function as a well plug or bridge plug.
[0099] In certain embodiments, the packer may be provided on a drill string.
[0100] Thus the invention provides a method of drilling, comprising during a drilling phase providing a drill string comprising a packer apparatus as defined herein.
[0101] As drill strings typically rotate and move vertically in a well during a drilling phase, a skilled person would not be minded to provide a packer thereon since a packer resists movement. However the inventors of the present invention note that a packer provided thereof can be used in an emergency situation and so provides advantages.
[0102] Thus the packer may be provided on drill string, production string, production sub-assembly and may operate in cased or uncased sections of the well.
[0103] The safety mechanisms and packers described herein may also have additional means of operation such as hydraulic and/or electric lines.
[0104] Thus the present invention also provides a method of deploying a safety mechanism according to the present invention, monitoring the well using data received from sensors as described herein associated with the safety mechanism whilst abandoning the well and/or cementing the well and/or suspending the well.
[0105] Unless otherwise stated methods and mechanisms of various aspects of the present invention may be used in all phases including drilling, suspension, production/injection, completion and/or abandonment of well operations.
[0106] The wireless signal for all embodiments is preferably an acoustic signal although may be an electromagnetic or any other signal or combination of signals.
[0107] Preferably the acoustic communications include Frequency Shift Keying (FSK) and/or Phase Shift Keying (PSK) modulation methods, and/or more advanced derivatives of these methods, such as Quadrature Phase Shift Keying (QPSK) or Quadrature Amplitude Modulation (QAM), and preferably incorporating Spread Spectrum Techniques. Typically they are adapted to automatically tune acoustic signaling frequencies and methods to suit well conditions.
[0108] Embodiments of the present invention may be used for onshore wells as well as offshore wells.
[0109] An advantage of certain embodiments is that the acoustic signals can travel up and down different strings and can move from one string to another. Thus linear travel of the signal is not required. Direct route devices thus can be lost and a signal can still successfully be received indirectly. The signal can also be combined with other wired and wireless communication systems and signals and does not have to travel the whole distance acoustically.
[0110] Any aspect or embodiment of the present invention can be combined with any other aspect of embodiment mutatis mutandis.
BRIEF DESCRIPTION OF THE DRAWINGS
[0111] An embodiment of the present invention will now be described, by way of example only, and with reference to the accompanying figures in which:
[0112] FIG. 1 is a diagrammatic sectional view of a well in accordance with one aspect of the present invention;
[0113] FIG. 2 is a schematic diagram of the electronics which may be used in a transmitting portion of a safety mechanism of the present invention;
[0114] FIG. 3 is a schematic diagram of the electronics which may be used in a receiving portion of a safety mechanism of the present invention; and,
[0115] FIGS. 4 a - 4 c are sectional views of a casing valve sub in various positions.
DETAILED DESCRIPTION
[0116] FIG. 1 shows a well 10 comprising a series of casing strings 12 a , 12 b , 12 c , and 12 d and adjacent annuli A, B, C, D between each casing string and the string inside thereof, with a drill string 20 provided inside the innermost casing 12 a.
[0117] As is conventional in the art, each casing strings extends further into the well than the adjacent casing string on the outside thereof. Moreover, the lowermost portion of each casing string is cemented in place as it extends below the outer adjacent string.
[0118] In accordance with one aspect of the present invention, safety packers 16 are provided on the casing above the cemented as well as on the drill string 20 .
[0119] These can be activated acoustically at any time including retroactively i.e. after the emergency, in order to block fluid flow through the respective annuli. Whilst normal operation will not require the activation of such packers, they will provide a barrier to uncontrolled hydrocarbon flow should the casing or other portion of the well control fail.
[0120] Moreover sensors (not shown), in accordance with one aspect of the present invention, are provided above and below said packers in order to monitor downhole parameters at this point. This can provide information to operators on any unusual parameters and the sealing integrity of the packer(s).
[0121] Acoustic relay stations 22 are provided on the drill pipe as well as various points in the annuli to relay acoustic data retrieved from sensors in the well.
[0122] A safety valve 25 is also provided in the drill string 20 and this can be activated acoustically in order to prevent fluid flow through the drill string.
[0123] In such an instance a device (not shown) comprising a sonar receiver and an acoustic transceiver installed or later landed at a wellhead apparatus such as a BOP structure 30 at the top of the well. The operator sends a sonar signal from a surface facility 32 which is converted to an acoustic signal and transmitted into the well by the device. The subsea valve 25 picks up the acoustic signal and shuts the well downhole (rather than at the surface), even if other communications are entirely severed with the BOP.
[0124] In alternative embodiments a packer picks up the signal rather than the safety valve 25 . The packer can then shut a flowpath e.g. an annulus.
[0125] Thus embodiments of the present invention benefit in that they obviate the sole reliance on seabed/rig floor/bridge BOP control mechanisms. As can be observed by disastrous events in the Gulf of Mexico in 2010, the control of a well where the BOP has failed can be extremely difficult and ensuing environmental damage can occur given the uncontrolled leak of hydrocarbons in the environment. Embodiments of the present invention provide a system which reduce the risk of such disastrous events happening and also provide a secondary control mechanism for controlling subsurface safety mechanisms, such as subsurface valves, sleeves, plugs and/or packers.
[0126] For certain embodiments a control device is provided on a buoy or vessel separate from a rig. The device comprises sonar transmitter and a satellite receiver. The device can therefore receive a signal from a satellite directed from an inland installation, and communicate this to the well in order to shut down the well; all independent of the rig. In such embodiments, the well can be safely closed down even in the disastrous event of losing the rig.
[0127] A casing valve sub 400 is shown FIGS. 4 a - 4 c comprising an outer body 404 having a central bore 406 extending out of the body 404 at an inner side through port 408 and an outer side through port 410 . A moveable member in the form of a piston 412 is provided in the bore 406 and can move to seal the port 408 . Similarly a second moveable member in the form of a piston 414 is provided in the bore 406 and can move to seal the port 410 . Actuators 416 , 418 control the pistons 412 , 414 respectively.
[0128] The casing valve sub 400 is run as part of an overall casing string, such as a casing string 12 shown in FIG. 1 , and positioned such that the port 408 faces an inner annulus and the port 410 faces an outer annulus.
[0129] In use, the pistons 412 , 414 can be moved to different positions, as shown in FIGS. 4 a , 4 b and 4 c , by the actuators 416 , 418 in response to wireless signals which have been received. Thus the pressure between the inner and outer annuli can be sealed from each other by providing at least one of the pistons 412 , 414 over or between the respective ports, 408 , 410 as shown in FIG. 4 a , 4 c.
[0130] In order to equalize the pressure between the inner and outer annuli, the pistons 412 , 414 are moved to a position outside of the ports 408 , 410 so they do not block them nor block the bore 406 therebetween, as shown in FIG. 4 b . The pressures can thus be equalized.
[0131] Thus such embodiments can be useful in that they provide an opportunity to equalize pressure between two adjacent casing annuli if one exceeded a safe pressure and/or if an emergency situation had occurred.
[0132] The port can then be isolated and pressure monitored to see if pressure is going to build-up again. Thus, in contrast to for example a rupture disk, where it cannot return to its original position, embodiments of the present invention can equalize pressure between casing strings, be reset, and then repeat this procedure again, and for certain embodiments, repeat the procedure indefinitely.
[0133] In one scenario the pressure in a casing string may build up due to fluid flow and thermal expansion. A known rupture disk can resolve problems of excessive pressure, and the well can continue to function normally. However a further occurrence of such excess pressure cannot be dealt with. Moreover it is sometimes difficult to ascertain whether the excess pressure was caused by such a manageable event or whether it is indicative of a more serious problem especially if repeated occurrences of the excess pressure cannot be detected nor alleviated in known systems. Embodiments of the present invention mitigate these problems. For some embodiments, a number of different casing subs 401 may be used in one string of casing.
[0134] FIG. 2 shows a transmitting portion 250 of the safety mechanism. The portion 250 comprises a transmitter (not shown) powered by a battery (not shown), a transducer 240 and a thermometer (not shown). An analogue pressure signal generated by the transducer 240 passes to an electronics module 241 in which it is digitized and serially encoded for transmission by a carrier frequency, suitably of 1 Hz-10 kHz, preferably 1 kHz-10 kHz, utilizing an FSK modulation technique. The resulting bursts of carrier are applied to a magnetostrictive transducer 242 comprising a coil formed around a core (not shown) whose ends are rigidly fixed to the well bore casing (not shown) at spaced apart locations. The digitally coded data is thus transformed into a longitudinal sonic wave.
[0135] The transmitter electronics module 241 in the present embodiment comprises a signal conditioning circuit 244 , a digitizing and encoding circuit 245 , and a current driver 246 . The details of these circuits may be varied and other suitable circuitry may be used. The transducer is connected to the current driver 246 and formed round a core 247 . Suitably, the core 247 is a laminated rod of nickel of about 25 mm diameter. The length of the rod is chosen to suit the desired sonic frequency.
[0136] FIG. 3 shows a receiving portion 360 of the safety mechanism. A receiving portion 361 comprises a filter 362 and a transducer 363 connected to an electronics module powered by a battery (not shown). The filter 362 is a mechanical band-pass filter tuned to the data carrier frequencies, and serves to remove some of the acoustic noise which could otherwise swamp the electronics. The transducer 363 is a piezoelectric element. The filter 362 and transducer 363 are mechanically coupled in series, and the combination is rigidly mounted at its ends to one of the elongated members, such as the tubing or casing strings (not shown). Thus, the transducer 363 provides an electrical output representative of the sonic data signal. Electronic filters 364 and 365 are also provided and the signal may be retransmitted or collated by any suitable means 366 , typically of a similar configuration to that shown in FIG. 2 .
[0137] An advantage of certain embodiments is that the acoustic signals can travel up and down different strings and can move from one string to another. Thus linear travel of the signal is not required. Direct route devices thus can be lost and a signal can still successfully be received indirectly. The signal can also be combined with other wires and wireless communication systems and does not have to travel the whole distance acoustically.
[0138] Improvements and modifications may be made without departing from the scope of the invention. Whilst the specific example relates to a subsea well, other embodiments may be used on platform or land based wells. | A safety mechanism ( 401 ) comprising: (i) an obstructing member ( 412,414 ) moveable between a first position where fluid flow is permitted, and a second position where fluid flow is restricted; (ii) a movement mechanism ( 416,418 ); (iii) a wireless receiver ( 360 ), optionally a transceiver, adapted to receive a wireless signal such as electromagnetic or acoustic. The movement mechanism ( 416,418 ) is operable to move the obstructing member ( 412,414 ) from one of the first and second positions to the other of the first and second positions in response to a change in the signal being received by the wireless receiver ( 360 ). The safety mechanism also has (iv) a valve ( 401 ) in a casing sub; the valve ( 401 ) being adapted to move from one of the first and second positions to the other of the first and second positions, and then back to the first of the first and second positions. | 4 |
BACKGROUND OF THE INVENTION
In the conventional filament winding operation, a fibrous strand impregnated with a thermosetting resin is wound in a helical pattern in a number of superimposed layers on a mandrel to form a tubular article.
In one type of filament winding operation, a single band of webs or fibers is applied to the mandrel in a helical pattern, and depending on the width of the band and the winding angle, the turns or convolutions may be spaced apart in each pass along the length of the mandrel, in which case a cross-over pattern is obtained, or the side edges of the convolutions can be in abutting relation, in which case a continuous fibrous layer is obtained in each pass.
In another type of filament winding operation, a 360° delivery of the fibrous strands is utilized, meaning that a multiplicity of strands are simultaneously applied to the mandrel at spaced locations throughout the entire circumference of the mandrel. In this type of delivery, the winding head has a circular configuration and is spaced radially outward of the mandrel and the strands pass through a radial slot in the winding head and are guided onto the outer surface of the mandrel. Rotation of the mandrel in combination with longitudinal advancement of either the mandrel or the winding head will cause the strands to be wound in a helical pattern on the mandrel.
At start-up of the winding operation of this latter type of machine, the multiplicity of fibrous strands are grouped together and wound manually in two or three turns about an end of the mandrel to lock the strands to the mandrel. After the strands are suitably locked to the mandrel, the winding operation can proceed. As the manually applied strands are bunched together, this portion of the wound article must be severed after completion of winding and scrapped. When utilizing a mandrel having a diameter in the range of 8 to 12 inches, about 24 inches of the end of the wound article is normally scrapped, resulting in a substantial waste of material.
As an added problem, the initial attachment of the multiplicity of strands to the mandrel at the start of winding is directly dependent upon the skill of the operator, and if some of the strands are not firmly attached to the mandrel, the entire winding pattern may be defective, with the result that the entire article must be scrapped. As the fibrous strands are normally coated with a thermosetting resin, the manual wrapping of the resin coated strands about the mandrel at the start of the winding operation is a messy and time-consuming task.
After completion of the wound article, the multiplicity of fibrous strands must be cut. Due to the tension on the strands, cutting, in some cases, will cause the strands to snap back through the head before a subsequent article can be wound. As the typical winding operation may contain up to 1500 separate strands, the rethreading of the strands is a very time-consuming operation.
Wind-off rings have been used in the past in filament winding systems, particularly in the winding of yarn on spools or creels. After completion of winding, the yarn is transferred to a wind-off ring, the yarn is severed, and the completed wound article can be removed and a new spool or mandrel inserted. The use of the wind-off ring eliminates the need of reattaching the yarn to the spool at the start of each winding operation.
SUMMARY OF THE INVENTION
The invention relates to a filament winding machine which provides a uniform winding pattern over substantially the entire length of the mandrel and minimizes scrap. In accordance with the invention, one end of the mandrel is provided with a cylindrical extension or sleeve having a smaller diameter than the mandrel and a wind-off ring is disposed longitudinally adjacent the sleeve.
In starting the winding procedure, the fibrous strands are wound on the ring to lock the strands to the ring, and the winding is then transferred to the sleeve. After several turns to lock the strands to the sleeve, the winding is then transferred to the mandrel. The diameter of the sleeve is correlated to the diameter of the mandrel and the winding angle, so that no slippage of the strands occur as they pass from the sleeve onto the mandrel. As there is no slippage of the strands as they are initially wound on the mandrel, the entire length of the wound article has a uniform winding pattern, with the result that scrap at the ends of the wound article is minimized.
The mechanism can also include a second wind-off ring section which is disposed adjacent the first wind-off ring section. At the shut-down of operation, the thermosetting resin is removed from the resin bath and replaced with solvent. The fibrous strands are passed through the solvent bath and wound on the first wind-off ring section until the strands being wound are seen to be substantially free of resin. Thereafter, the winding is transferred to the second wind-off ring section. The resin impregnated strands can then be removed from the first section and the mandrel sleeve. As the strands wound on the section ring section are free of resin, the strands will not fuse together during shut down.
At start up, the strands are initially wound on the second ring section for a few turns, until it is seen that the strands being wound are coated with resin. The winding is then transferred to the first wind-off ring section and continued in the manner previously described.
As it is not necessary for the strands to be reattached to the mandrel, even after periods of shut down of production, a substantial time and labor saving is achieved. Furthermore, it is not necessary for the operator to physically contact the resin impregnated strands.
The apparatus of the invention lends itself to automation and no operator is required for the part-to-part winding of the articles.
While the invention has particular application to filament winding systems utilizing a 360° delivery of the fibrous strands or filaments, it can also be used in connection with winding systems in which a single band of fibrous material is wound on the mandrel.
Other objects and advantages of the invention will appear in the course of the following description.
DESCRIPTION OF THE DRAWINGS
The drawings illustrate the best mode presently contemplated of carrying out the invention.
In the drawings:
FIG. 1 is a schematic side elevation of the filament winding apparatus of the invention;
FIG. 1 is a transverse section showing the mandrel and winding head;
FIG. 3 is an enlarged side elevation showing the start of the winding operation with the strands being wound on the outer section of the wind-off ring;
FIG. 4 is a fragmentary section taken along line 4--4 of FIG. 3;
FIG. 5 is an end view of the wind-off ring;
FIG. 6 is a view similar to FIG. 3, showing the transfer of the winding to the mandrel sleeve;
FIG. 7 is a view similar to FIG. 3 showing the transfer of the winding to the outer surface of the mandrel; and
FIG. 8 is a view similar to FIG. 3 showing the winding being transferred from the mandrel onto the mandrel sleeve and onto the wind-off sleeve.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 illustrates schematically a filament winding machine incorporating the invention. In general, the filament winding machine includes a winding head 1 which acts to wind a multiplicity of fibrous strands 2 impregnated with a thermosetting resin onto the outer surface of a mandrel 3 in a number of superimposed helical layers to form a tubular article.
The winding head comprises a structural frame 4 which supports a pair of rings 5 that are mounted concentrically of the mandrel 3. As best shown in FIG. 3, the rings 5 are spaced apart to provide a slot 6 through which the fibrous strands 2 are delivered onto the outer surface of the mandrel. As illustrated in FIG. 2, the strands are applied to the mandrel at spaced locations throughout 360°. In practice, there may be up to 1500 separate strands or elements delivered to the mandrel.
In the illustrated filament winding machine, the winding head 1 is fixed and the mandrel 3 is adapted to rotate about its axis and reciprocate axially with respect to the winding head to wind the fibrous strands onto the outer surface of the mandrel.
The fibrous strands which can take the form of mineral fibers, such as glass, or asbestos; vegetable fibers, such as cotton or wool; synthetic fibers, such as nylon, polyester, or the like; or metal fibers such as steel. The strands are coated with an uncured thermosetting resin, such as polyester or epoxy resin, by passing the strands through resin baths, not shown, prior to winding the strands on the mandrel.
The ends of the mandrel 3 are supported for rotation in a headstock 7 and a tailstock 8, both of which are mounted for axial movement in a conventional manner on a carriage 9. The axial movement is required in order to insert and lock a mandrel between the headstock and tailstock at the start of winding operations, and to remove the wound mandrel after the winding operation is completed. The mechanism for moving the headstock and tailstock, and locking the headstock to the mandrel to impart rotation to the mandrel is conventional.
To provide relative movement between the fixed winding head 1 and the mandrel, the carriage, which carries the headstock and tailstock 8, is mounted for reciprocating movement on guide rails 10 which are mounted on foundation 11. The drive mechanism for moving the carriage 9 on the rails 10 is also conventional and in itself forms no part of the present invention.
To rotate the mandrel about its axis, a sprocket drive indicated generally by 12, connects the main drive unit, which is mounted on the carriage 9, and a shaft 13 journalled in the headstock 7. Thus, the mandrel is moved in an axial direction and simultaneously rotated about its axis to thereby wind the fibrous strands about the outer surface of the mandrel in a generally helical pattern. While the drawings have illustrated the winding head 1 as being fixed and the mandrel being advanced axially and rotated about its axis, it is contemplated that the mandrel can be fixed and the winding head can be advanced axially of the mandrel, and it is further contemplated that the winding head can be rotated about the axis of a fixed mandrel.
In accordance with the invention, the end of the mandrel adjacent the tailstock is provided with an extension or sleeve 14 which has a reduced diameter, as compared with the outer diameter of the mandrel itself. The outside diameter of the sleeve 14 is equal to the outside diameter of the mandrel times the sine of the angle α, where α is the angle to the horizontal of the first layer of winding on the mandrel. For example, if the mandrel has a diameter of 10 inches and the winding angle is 45°, the sleeve should have a diameter of 7.07 inches. By utilizing a sleeve diameter in accordance with this formula, the strands will not slip as they pass from the sleeve onto the mandrel at the start of winding thereby preventing distortion of the winding pattern.
The sleeve has a length equal to or greater than 1.5 times the width of the fibrous band being wound on the mandrel, and preferably 2.5 times that width.
Located along the outer edge of the mandrel sleeve 14 is a series of pins or pegs 15 which are spaced around the circumference of the extension. As illustrated, the pins are spaced approximately 30° apart.
The sleeve 14 is also provided with a longitudinal cutting groove 16 which can receive a knife or blade to permit an operator or an automatic cutting device to remove wound strands from the sleeve during the period when winding is performed on the mandrel or when winding has been completed.
The tailstock 8 includes a wind-off ring 17 which is located adjacent the outer end of the mandrel sleeve 14. The wind-off ring 17 includes a pair of side-by-side sections 18 and 19 which are separated by a circumferential rib 20. The wind-off ring sections 18 and 19 have a diameter equal to approximately 0.5 to 1.25 times the diameter of the sleeve 14. In addition, the end of the section 18 adjacent the mandrel sleeve 14, can be provided with a series of radially extending pins 21 which are spaced approximately 30° apart.
Several longitudinal cutting grooves 22 are formed at spaced locations around the circumference of the wind-off ring 17 to permit wound strands to be cut from the sections 18 and 19.
A conventional clutch, not shown, connects the wind-off ring 17 with the mandrel shaft. By engaging the clutch the wind-off ring 17 will rotate with the mandrel 3, while disengaging the clutch will enable the mandrel to rotate independently of the wind-off ring.
At the start of machine operation, the multiplicity of dry, non-resin coated strands 2 passing through the winding head 1 are grouped together and manually wound around the outer section 19 of the wind-off ring 17 to lock the strands to the wind-off ring. A beveled or tapered guide collar 23 is positioned adjacent section 19 and aids in guiding the strands on the section 19. The winding head at this time is located in alignment with the tailstock 8.
The mandrel 1 is then clamped between the headstock 7 and tailstock 8.
With the mandrel in position, the resin baths are filled with resin and the mandrel is then rotated about its axis and moved axially to transfer the winding to the section 18 of the wind-off ring, as shown in FIG. 3. The winding is continued on section 18 until the fibers being wound thereon are all well wetted with resin, and this is generally accomplished in about 1/2 to 2 revolutions of the mandrel and wind-off ring.
The fibrous strands are then transferred to the mandrel sleeve 14 by axial movement of the mandrel, as illustrated in FIG. 6. As the strands pass from the section 18 of the wind-off ring to the sleeve 14, groups of strands pass between the pins 15 which serve to properly space the groups around the circumference of the mandrel sleeve. A winding angle of approximately 50° to the horizontal is used from the section 18 of the wind-off ring 17 onto the mandrel sleeve 14, until the strands are at a location adjacent the end of the mandrel 2.
The winding is then transferred to the outer surface of the mandrel 3 by continued axial movement of the mandrel, as shown in FIG. 7, and as previously related, the diameter of the mandrel sleeve 14 is correlated with the diameter of the mandrel 2, along with the angular degree of winding, so that a non-slip pattern is achieved in movement of the multiplicity of strands from the sleeve 14 onto the mandrel 2, thereby preventing distortion of the desired winding angle at the end of the mandrel.
Continued axial movement of the mandrel along with rotation results in the fibrous strands being applied to the outer surface of the mandrel in a helical pattern to provide a layer of the wound article.
After the first layer of windings have been applied to the mandrel, the longitudinal movement of the mandrel is reversed to apply a second fibrous layer and subsequent layers can be applied by continued reciprocation of the mandrel relative to the winding head.
After one complete layer of fibrous strands have been applied to the mandrel, the windings on the sections 18 and 19, as well as the windings on the mandrel sleeve 14 can be removed. By declutching the wind-off ring, while the mandrel continues to rotate, a knife or similar tool can be inserted within the grooves 16 and 22 to sever the windings on the wind-off ring and mandrel sleeve.
After the desired number of layers have been completed, the fibrous strands are delivered onto the mandrel sleeve 14, as shown in FIG. 8, and again, because of the correlation of the diameter of the mandrel sleeve relative to the mandrel and the winding angle, the delivery of the fibers will be on a non-slipping path, so there will be no distortion of the winding pattern at the mandrel end.
After winding several revolutions onto the mandrel sleeve 14, the winding is then transferred to the section 18 of the wind-off ring, can be larger than the mandrel and again several revolutions are made on the section 18 to lock the strands to the wind-off ring. At this stage, the windings on the end of the mandrel can be retained in place by applying a circumferential band of metal wire or fibrous material around to windings on the mandrel sleeve, or alternately, around the windings at the end of the mandrel. With the strands on the mandrel secured, the strands extending between sleeve 14 and wind-off ring section 18 can then be severed, so that the mandrel can then be removed from the head and tail stock.
The mandrel with the wound fibrous material is then placed in an oven to cure the thermosetting resin and after curing, the end of the cured tublar article is trimmed and the article is stripped from the mandrel.
The section 19 of the wind-off ring 17 has particular function when the filament winding operation is to be shut down overnight or for a week-end. In this situation, the resin baths or impregnators are drained and replaced with solvent baths and the strands are wound on section 18 until the strands being wound are seen to be relative free of resin and are impregnated only with the solvent. The winding of the resin-free strands is then transferred to the section 19 and several revolutions are made in order to firmly attach the strands to the section. The resin impregnated windings on the section 18 can then be severed and removed. As the strands wound on the section 19 are not impregnated with resin, there is no resin curing problem when the machine is shut down overnight or for extended periods.
At the start up of the next operation, the solvent is drained from the baths and replaced with the uncured resin. The winding is continued on the ring section 19 until the strands being wound are seen to be fully impregnated with resin, and then the winding is transferred to the ring section 18 and the operation proceeds as described above.
With the use of the invention, the fibrous strands can be delivered onto the mandrel at the start of the winding cycle without distortion and without operator assistance, and similarly, the invention enables the strands to pass from the mandrel without distortion and without operator assistance at the end of the winding pogram. As the entire winding pattern on the mandrel is without distortion, end waste is substantially reduced as opposed to conventional filament winding operations.
All winding angles up to 89° to the horizontal can be accommodated and the invention is applicable to all mandrel diameters from less than 1 inch up to 20 feet or greater.
The invention also substantially eliminates the need for manually re-attaching the strands to each mandrel as it is installed in the machine, and the reattachment can be an extremely tedious and time consuming operation when dealing with systems using a 360° delivery of strands. With the construction of the invention, the strands are locked to the wind-off ring when mandrels are removed and installed and even after periods of downtime, there is no necessity to manually reattach strands at the start-up of operation.
The apparatus of the invention provides a more accurate and uniform winding pattern from piece-to-piece and thereby results in the physical properties of the wound particles being more uniform.
The apparatus of the invention also lends itself to complete automation without an attendant.
While the drawings have shown the mandrel 3 being of a larger diameter than the wind-off ring 17, it is contemplated that the diameter of the wind-off ring and in this latter situation, the pins 21 would function to maintain the fibrous strands in properly spaced relation as they travel from the outer wind-off ring section 18 onto the mandrel sleeve.
While the drawings have illustrated a filament winding apparatus having a winding head that delivers a multiplicity of fibrous strands onto the mandrel throughout 360°, it is contemplated that the winding head can take different forms, as for example, a single relatively wide band of fibrous material can be applied at a single location along the circumference of the mandrel.
Various modes of carrying out the invention are contemplated as being within the scope of the following claims particularly pointing out and distinctly claiming the subject matter which is regarded as the invention. | A filament winding machine for winding fibrous strands coated with a resin binder onto a mandrel in a helical pattern to form a tubular article. One end of the mandrel is provided with an extension or sleeve having a smaller diameter than the mandrel, and a wind-off ring is disposed longitudinally adjacent the sleeve. In operation, the fibrous strands are initially wound on the wind-off ring to lock the strand to the ring, and the winding is then transferred to the sleeve and after several turns on the sleeve, the winding is then transferred to the outer surface of the mandrel. The diameter of the mandrel sleeve is correlated with the diameter of the mandrel and the winding angle so that no slippage of the strands occur as they pass from the sleeve onto the mandrel, thereby resulting in minimum scrappage for the wound article. | 1 |
SUMMARY OF THE INVENTION
The present invention relates to a dye of the general formula I ##STR2## where A is cyano or carbamoyl,
R is hydrogen, alkyl or phenyl,
R 1 is hydrogen, chlorine, bromine, or nitro,
R 2 is hydrogen, chlorine, bromine, nitro, methyl, trifluoromethyl, sulfamoyl, N-monoalkyl- or N,N-dialkylsulfamoyl (where alkyl is of 1 to 4 carbon atoms), or a sulfonic acid phenyl ester, methylphenyl ester, chlorophenyl ester or methoxyphenyl ester group,
R 3 is hydrogen or alkyl of 1 to 8 carbon atoms which may be interrupted by oxygen and may be substituted by hydroxyl, pyrrolidonyl, phthalimidyl, alkoxy of 1 to 8 carbon atoms, allyloxy, benzyloxy, phenylethoxy, phenoxy, methylphenoxy, chlorophenoxy, methoxyphenoxy, or optionally substituted arylsulfonyl, or is benzyl, phenylethyl or cyclohexyl, or is phenyl which is unsubstituted or substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, phenoxy or dialkylamino (where alkyl is of 1 to 4 carbon atoms), or is naphthyl, pyridyl, thienyl or furyl,
the substituents B 1 independently of one another are hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic, heterocyclic or acyl radical and B 2 is hydrogen or an aliphatic radical.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Alkyl R is, for example, methyl, ethyl, propyl, butyl or pentyl.
Radicals B 1 independently of one another are, for example, hydrogen, alkyl of 1 to 18 carbon atoms, alkyl of 2 to 8 carbon atoms which may be interrupted by ether-oxygen and is substituted by hydroxyl, alkoxy of 1 to 8 carbon atoms, benzyloxy, β-phenylethoxy, phenoxy, tolyloxy, cyclohexyloxy or cyano, cycloalkyl of 5 to 8 carbon atoms, hydroxycyclohexyl, β-hydroxyethoxycyclohexyl, polycycloalkyl of 7 to 12 carbon atoms, hydroxynorbornyl, hydroxymethylnorbornyl or hydroxyethylnorbornyl or chloromethylnorbornyl, phenylalkyl or tolylalkyl, where alkyl is of 1 to 4 carbon atoms, phenyl which is unsubstituted or substituted by chlorine, hydroxyl, methoxy, ethoxy, methyl, ethyl or hydroxyethoxy, allyl, pyrrolidonylalkyl, where alkyl is of 2, 3, 4 or 6 carbon atoms, carboxyalkyl, where alkyl is of 2 to 5 carbon atoms, ##STR3##
Examples of B 2 are the same aliphatic radicals as those given for B 1 , and the same remarks apply, within the scope of the general definition, to R 3 . R 3 may in addition be, for example, phenylsulfonylmethyl, tolylsulfonylmethyl, methoxyphenylsulfonylmethyl, chlorophenylsulfonylmethyl or bromophenylsulfonylmethyl.
Examples of individual radicals B 1 , B 2 and R 3 (to the extent that they fall under the general definition) are, in addition to those already mentioned:
1. Unsubstituted or substituted alkyl: CH 3 , C 2 H 5 , n- and i-C 3 H 7 , n- and i-C 4 H 9 , C 6 H 13 , ##STR4## CH 2 CH 2 OH, (CH 2 ) 3 OH, ##STR5## (CH 2 ) 4 OH, (CH 2 ) 6 OH, ##STR6## (CH 2 ) 2 O(CH 2 ) 2 OH, (CH 2 ) 3 O(CH 2 ) 4 OH, (CH 2 ) 3 OC 2 H 4 OH, (CH 2 ) 2 CN, (CH 2 ) 5 CN, (CH 2 ) 6 CN, (CH 2 ) 7 CN, (CH 2 ) 2 O(CH 2 ) 2 CN, (CH 2 ) 3 O(CH 2 ) 2 CN, (CH 2 ) 2 O(CH 2 ) 2 O(CH 2 ) 2 CN, (CH 2 ) 3 OC 2 H 4 OCH 3 , (CH 2 ) 3 OC 2 H 4 OC 2 H 5 , (CH 2 ) 3 O(CH 2 ) 6 OH, (CH 2 ) 3 OC 2 H 4 OCH(CH 3L ) 2 , (CH 2 ) 3 OC 2 H 4 OC 4 H 9 , (CH 2 ) 3 OC 2 H 4 OCH 2 C 6 H 5 , (CH 2 ) 3 OC 2 H 4 OC 2 H 4 C 6 H 5 , ##STR7## (CH 2 ) 3 OC 2 H 4 OC 6 H 5 , ##STR8## the corresponding radicals which contain two or three of the groups --OC 2 H 4 , ##STR9## CH 2 CH 2 OCH 3 , CH 2 CH 2 OC 2 H 5 , CH 2 CH 2 OC 3 H 7 , CH 2 CH 2 OC 4 H 9 , CH 2 CH 2 OC 6 H 5 , (CH 2 ) 3 OCH 3 , (CH 2 ) 3 OC 2 H 5 , (CH 2 ) 3 OC 3 H 7 , (CH 2 ) 3 OC 4 H 9 , ##STR10## (CH 2 ) 3 OC 6 H 13 , (CH 2 ) 3 OC 8 H 17 , (CH 2 ) 3 O--, (CH 2 ) 3 OCH 2 C 6 H 5 , (CH 2 ) 3 OC 2 H 4 C 6 H 5 , (CH 2 ) 3 OC 6 H 5 , ##STR11##
2. Substituted and unsubstituted cycloalkyl and polycycloalkyl: ##STR12##
3. Aralkyl: ##STR13## and corresponding radicals which contain C 6 H 4 CH 3 instead of C 6 H 5 ;
4. Substituted or unsubstituted phenyl: C 6 H 5 , C 6 H 4 CH 3 , C 6 H 3 (CH 3 ) 2 , C 6 H 4 OCH 3 , C 6 H 4 OC 2 H 5 , C 6 H 4 OH, ##STR14## C 6 H 4 OCH 2 CH 2 OH and C 6 H 4 Cl;
5. CH 2 CH--CH 2 , (CH 2 ) 2 COOH, (CH 2 ) 5 COOH and ##STR15## where n is 2, 3, 4 or 6, C 2 H 4 OCOCH 3 , C 2 H 4 OCHO, C 2 H 4 OCOCH 3 , (C 2 H 4 O) 2 COCH 3 , (C 2 H 4 O) 2 CHO, (CH 2 ) 3 OCOCH 3 , (CH 2 ) 3 OCHO and C 2 H 4 OCOC 2 H 4 COOH.
Further examples of R 3 are CH 2 OCH 3 , CH 2 OC 2 H 4 , CH 2 OC 3 H 7 , CH 2 OC 4 H 9 , CH 2 OCH 2 CH═CH 2 , CH 2 OCH 2 C 6 H 5 and CH 2 OC 6 H 5 .
Examples of preferred substituents B 1 and B 2 are hydrogen, CH 3 , C 2 H 5 , n- and i-C 3 H 7 , n- and i-C 4 H 9 , C 6 H 13 , CH 2 CH 2 OH, (CH 2 ) 3 OH, ##STR16## (CH 2 ) 4 OH, (CH 2 ) 6 OH, ##STR17## (CH 2 ) 2 O(CH 2 ) 2 OH, (CH 2 ) 3 O(CH 2 ) 2 OH, (CH 2 ) 3 O(CH 2 ) 4 OH, (CH 2 ) 3 O(CH 2 ) 6 OH, ##STR18## CH 2 CH 2 OCH 3 , CH 2 CH 2 OC 2 H 5 , CH 2 CH 2 OC 4 H 9 , (CH 2 ) 3 OCH 3 , (CH 2 ) 3 OC 2 H 5 , (CH 2 ) 3 OC 3 H 7 , (CH 2 ) 3 OC 4 H 9 , ##STR19## (CH 2 ) 3 OC 2 H 4 OCH 3 , (CH 2 ) 3 OC 2 H 4 OC 4 H 9 , (CH 2 ) 3 OC 2 H 4 OC 6 H 5 , ##STR20## CH 2 C 6 H 5 , C 2 H 4 C 6 H 5 , ##STR21## C 6 H 5 , C 6 H 4 CH 3 , C 6 H 4 OCH 3 and C 6 H 4 OC 2 H 4 OH.
Examples of radicals ##STR22## are pyrrolidino, piperidino, morpholino and N-methylpiperazino.
Examples of some preferred diazo components are: ##STR23##
On cellulose fibers, natural polyamides and synthetic nylons, polyesters and other synthetic fibers the dyes of the formula I give yellow to red dyeings with very good lightfastness, fastness to thermofixing and fastness to wet treatments. The tinctorial strength and the clear hues achievable with many of the dyes deserve particular mention.
Dyes of the formula given in claim 1 which are of particular industrial importance are those where
A is cyano or carbamoyl,
R is hydrogen or alkyl of 1 to 3 carbon atoms,
R 1 is hydrogen, chlorine, bromine or nitro,
R 2 is hydrogen, chlorine, bromine, nitro, methyl, trifluoromethyl, sulfamoyl, N-monosubstituted or N,N-disubstituted alkylsulfamoyl, where alkyl is of 1 to 4 carbon atoms, or a sulfonic acid phenyl ester, methylphenyl ester, chlorophenyl ester or methoxyphenyl ester group,
R 3 is hydrogen or alkyl of 1 to 8 carbon atoms which is unsubstituted or substituted by hydroxyl, alkoxy of 1 to 8 carbon atoms, allyloxy, phenoxy, methylphenoxy, chlorophenoxy or methoxyphenoxy, or is benzyl, phenylethyl or cyclohexyl, or is phenyl which is unsubstituted or substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy or phenoxy, or is naphthyl, pyridyl, thienyl or furyl, or is
--X--(O--Y).sub.n OT
X is alkylene of 1 to 3 carbon atoms,
Y is alkylene of 2 or 3 carbon atoms,
n is 1 or 2,
T is hydrogen, alkyl of 1 to 4 carbon atoms, benzyl, phenylethyl, phenyl or tolyl,
B 1 is hydrogen, alkyl of 1 to 8 carbon atoms, alkyl of 2 to 8 carbon atoms which is substituted by hydroxyl, alkoxy of 1 to 8 carbon atoms, phenoxy, tolyloxy, phenyl, alkanoyloxy of 1 to 8 carbon atoms, alkoxycarbonyl (where alkoxy is 1 to 8 carbon atoms), alkylaminocarbonyloxy. (where alkyl is of 1 to 4 carbon atoms) or phenylaminocarbonyloxy, or cyclohexyl, norbornyl, allyl, phenyl, tolyl or chlorophenyl, or
--Y--(O--Y).sub.n --OT
and
B 2 is hydrogen or alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by hydroxyl or by alkoxy of 1 to 4 carbon atoms.
Preferably, R is hydrogen or methyl and B 2 is hydrogen. A further preferred combination is where R is H and A is CONH 2 .
The preferred meanings of B 1 are those given above.
The dye of the formula I may be prepared by reacting a diazonium compound of an amine of the formula ##STR24## with a coupling component of the formula ##STR25## Diazotization and coupling are carried out in accordance with conventional methods.
In the Examples which follow, parts and percentages are by weight, unless stated otherwise.
EXAMPLE 1
24 parts of the compound of the formula (1) (see above) are dissolved in 250 parts by volume of glacial acetic acid and 50 parts by volume of propionic acid. 32 g of 40% strength nitrosylsulfuric acid are added dropwise at 0°-5° C. and the mixture is then stirred for 2 hours at 0°-5° C. The excess nitrous acid is then destroyed in the conventional manner by adding urea.
The diazotized mixture thus obtained is introduced, at 0°-5° C., into a mixture obtained by dissolving 28 parts of 2-(ω-hydroxy-butoxyamino)-6-amino-3-cyano-4-methylpyridine in 500 parts of water by means of 15 parts of 10 N hydrochloric acid and adding 250 parts of ice.
Sufficient saturated sodium acetate solution is then added dropwise to the coupling mixture to produce complete coupling at a pH of from 4 to 5.
The resulting dye is filtered off, washed with water and dried at 100° C. The powder obtained gives a yellow solution in N-methylpyrrolidone or dimethylformamide and on polyester or nylon fabrics gives yellow dyeings of very good lightfastness and great fastness to thermofixing.
EXAMPLE 2
A solution of 27 parts of 2,6-bis-(methoxyethylamino)-3-cyano-4-methylpyridine in 100 parts by volume of glacial acetic acid is added, at 0°-5° C., to the diazotized mixture obtained as described in Example 1, paragraph 1, and 500 parts by volume of a saturated sodium acetate solution are then added.
The resulting dye is filtered off, washed with water and ethanol and dried at 100° C. The product is a yellow powder which gives a yellow solution in N-methylpyrrolidone. On polyester or cotton fabrics or polyester/cotton union fabrics, yellow prints of very good lightfastness and wetfastness are obtained.
EXAMPLE 3
32 parts of 40 percent strength nitrosylsulfuric acid are added, at 0°-5° C., to a solution of 28 parts of the compound of the formula 2 (see list of diazo components on page 5) in 100 parts by volume of concentrated sulfuric acid. After stirring for 2 hours at 0°-5° C., the excess nitrous acid is destroyed in the conventional manner by adding urea.
The resulting mixture is run gradually, at 0°-5° C., into a mixture of 27 parts of 2,6-bis-(methoxyethylamino)-3-cyano-4-methylpyridine, 3,000 parts by volume of N-methylpyrrolidone and 500 parts of ice.
After completion of coupling, the dye is filtered off, washed with ethanol and dried. The dark red powder gives a red solution in N-methylpyrrolidone and produces fast bluish red prints on polyester and on cotton.
EXAMPLE 4
14.8 parts of the diazo component of the formula ##STR26## are stirred into a mixture of 70 parts of glacial acetic acid, 10 parts of propionic acid and 5 parts by volume of sulfuric acid and after cooling to 5° C., 14 parts of 40% strength nitrosylsulfuric acid are added whilst cooling. The diazotized mixture is then stirred for 70 minutes at 0°-5° C. Thereafter, the diazonium salt solution is run into a solution, cooled to 0°-5° C., of 8.05 parts of 2,6-bis-ethylamino-3-cyano-4-methylpyridine in 600 parts by volume of water and 8 parts by volume of concentrated hydrochloric acid. After raising the pH of the mixture to 2.0-2.2 by means of dilute sodium acetate solution or sodium hydroxide solution, the coupling reaction is soon complete. The mixture is heated to 60°-70° C. and the product is filtered off and washed salt-free with water at 60°-70° C. After drying, 22.5 parts of a dark brown powder, which gives a bluish red solution in N-methylpyrrolidone, are obtained.
The dye has the formula ##STR27## The dye gives fast bluish red prints on polyester and on cotton, and dyes polyester by the HT process, at 125°-140° C., in fast bluish red hues.
EXAMPLE 5
12.7 parts of the compound of the formula ##STR28## are introduced, at 0°-5° C., into a mixture of 26.4 parts of 96-98% strength sulfuric acid, 13.5 parts of 42% strength nitrosylsulfuric acid, 20 parts of propionic acid and 120 parts of glacial acetic acid. The mixture is then stirred for 3.5 hours at 0°-5° C. The finished diazonium salt mixture is run into a solution, cooled to 0°-5° C., of 11.6 parts of 2,6-bis-methoxypropylamino-3-cyano-4-methylpyridine in 600 parts by volume of water and 10 parts by volume of concentrated hydrochloric acid. The coupling reaction is completed rapidly on raising the pH to 2.0-2.2 by means of dilute sodium hydroxide solution. The mixture is stirred for 1 hour and then heated to 70° C., and the dye which has precipitated is filtered off, washed salt-free with water, and dried. 23 parts of a yellowish red powder of the formula ##STR29## are obtained.
The dye gives a red solution in N-methylpyrrolidone and dyes polystyrene in lightfast golden yellow to orange hues.
EXAMPLE 6
14.0 parts of the diazo component of the formula ##STR30## are dissolved in 200 parts by volume of glacial acetic acid at 50°-55° C. 2 parts of an emulsifier and 150 parts of ice are added. The mixture is then acidified with 18 parts by volume of concentrated hydrochloric acid at 0°-5° C., after which 21 parts by volume of a 23% strength aqueous sodium nitrite solution are added dropwise. The diazotization reaction is complete after stirring for 2 hours and a clear solution is obtained, which is combined with a solution, cooled to 5° C., of 17.6 parts of 2,6-bis-methoxypropylamino-3-cyano-4-methylpyridine in 600 parts by volume of water and 13 parts by volume of concentrated hydrochloric acid. After raising the pH to 2, the mixture is stirred for 30 minutes, after which it is heated to 70° C. and the dye which has precipitated is filtered off, washed salt-free with water and dried. 31.5 parts of a dark brown powder of the formula ##STR31## are obtained. This product gives a bluish red solution in dimethylformamide and produces fast bluish red prints on polyester and on cotton. Polyester can be dyed with the dye by the HT process or thermosol process.
The following dyes can be obtained by methods similar to those described in the preceding Examples:
__________________________________________________________________________ Hue on poly- ester orNo. Diazo component Coupling component cotton__________________________________________________________________________7 Diazo component of the formula 2 ##STR32## red8 Diazo component of the formula 2 ##STR33## red9 Diazo component of the formula 2 ##STR34## red10 Diazo component of the formula 4 ##STR35## yellow11 Diazo component of the formula 4 ##STR36## yellow12 Diazo component of the formula 4 ##STR37## yellow13 Diazo component of the formula 1 ##STR38## yellow14 Diazo component of the formula 1 ##STR39## yellow15 Diazo component of the formula 1 ##STR40## yellow16 Diazo component of the formula 3 ##STR41## yellow17 Diazo component of the formula 3 ##STR42## yellow__________________________________________________________________________
TABLE 1__________________________________________________________________________ ##STR43## Hue on poly-No. R.sup.1 R.sup.2 R.sup.3 n ester__________________________________________________________________________18 CH.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub.3 C.sub.6 H.sub.5 0 yellow19 " " " 1 red20 CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5 " 0 yellow21 " " " 1 red22 CH.sub.2 CH.sub.2 OCOOC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCOOC.sub.2 H.sub.5 " 0 yellow23 " " " 1 red24 CH.sub.2 CH.sub.2 OCONHC.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OCONHC.sub.6 H.sub.5 " 0 yellow25 " " " 1 red26 CH.sub.2 CH.sub.2 OCONHC.sub.4 H.sub.9 CH.sub.2 CH.sub.2 OCONHC.sub.4 H.sub.9 " 0 yellow27 " " " 1 red28 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 " 0 yellow29 H " " 0 yellow30 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 ##STR44## 0 yellow31 H (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 CH.sub.3 1 red32 " " C.sub.2 H.sub.5 1 red33 " (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH " 1 red34 " " (CH.sub.2).sub.2 OCH.sub.3 1 red35 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 " 1 red36 CH.sub.2 CH.sub.2 OCH.sub.3 " " 1 red37 " " C.sub.2 H.sub.5 1 red38 CH.sub.2 CH.sub.2 OH " " 1 red39 CH.sub.2 CH.sub.2 OCH.sub.3 " C.sub.6 H.sub.5 1 red40 " C.sub.4 H.sub.9 (n) " 1 red41 " (CH.sub.2).sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 1 red42 " " CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 1 red43 (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 " 1 red44 " " CH.sub.2 CH.sub.2 OCH.sub.3 1 red45 " " CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 1 red46 " " CH hd 3 1 red47 " C.sub.4 H.sub.9 (n) C.sub.6 H.sub.5 1 red48 CH.sub.2 CH.sub.2 OCH.sub.3 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 ##STR45## 1 red49 " CH.sub.2 CH.sub.2 OCH.sub.3 " 1 red50 (CH.sub.2).sub. 3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 " 1 red51 CH.sub.2 CH.sub.2 OCH.sub.3 " " 1 red52 C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) " 1 red53 C.sub.2 H.sub.5 C.sub.3 H.sub.7 (n) (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 1 red54 " C.sub.2 H.sub.5 " 0 yellow55 C.sub.3 H.sub.7 (n) " " 0 yellow56 " " " 1 red57 CH.sub.2 CH.sub.2 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 C.sub.2 H.sub.5 1 red58 " " CH.sub.2 CH.sub.2 CH.sub.3 1 red59 " CH.sub.2 CH.sub.2 OCH.sub.3 " 1 red60 (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 " 1 red61 ##STR46## " " 1 red62 " ##STR47## " 1 red63 ##STR48## ##STR49## C.sub.2 H.sub.5 1 red64 (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 C.sub.4 H.sub.9 (n) 1 red65 " " ##STR50## 1 red66 " " ##STR51## 0 yellow67 " " " 1 red68 C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) " 1 red69 H ##STR52## CH.sub.2 CH.sub.2 OCH.sub.3 0 yellow70 CH.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub.3 (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 1 red71 " " " 0 yellow72 (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 ##STR53## 0 yellow73 " " " 1 red__________________________________________________________________________
TABLE 2__________________________________________________________________________ ##STR54## Hue on cot-No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8 ton__________________________________________________________________________74 Br Br (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 CN CH.sub.3 C.sub.6 H.sub.5 yel- low75 " " " " H " H " yel- low76 H H " " (CH.sub.2).sub.2 OCH.sub.3 " " (CH.sub.2).sub.2 O(CH.sub.2) .sub.2 OC.sub.6 H.sub.5 yel- low77 " " (CH.sub.2).sub.3 OCH.sub.3 H (CH.sub.2).sub.3 OCH.sub.3 " CH.sub.3 ##STR55## yel- low78 O.sub.2 N " " (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 " " C.sub.2 H.sub.5 red79 " Cl " H (CH.sub.2).sub.3 OCH.sub.3 " " C.sub.6 H.sub.5 dull blu- ish red80 " Br " " " " " " dull blu- ish red81 " H " " " CONH.sub.2 H " dull blu- ish red82 NO.sub.2 NO.sub.2 " (CH.sub.2).sub.3 OCH.sub.3 H CN CH.sub.3 " vio- let83 O.sub.2 N H C.sub.2 H.sub.5 H C.sub.2 H.sub.5 CONH.sub.2 H (CH.sub.2).sub.2 O(CH.sub.2) .sub.2 OC.sub.6 H.sub.5 dull blu- ish red84 " " " " " CN CH.sub.3 (CH.sub.2).sub.2 OCH.sub.2 C.sub.6 H.sub.5 red85 " " " " " " " (CH.sub.2).sub.2 OCH.sub.2 CH.sub.2 C.sub.6 H.sub.5 red86 " " " " " " " (CH.sub.2).sub.2 OC.sub.6 H.sub.5 red87 " " (CH.sub.2).sub.3 OCH.sub.3 " (CH.sub.2).sub.3 OCH.sub.3 " " CH.sub.2C.sub.6 H.sub.5 red88 " " (CH.sub.2).sub.2 OCH.sub.3 " (CH.sub.2).sub.2 OCH.sub.3 " " " red89 " " (CH.sub.2).sub.3 OCH.sub.3 " (CH.sub.2).sub.3 OCH.sub.3 " " ##STR56## red90 H H ##STR57## H ##STR58## " " C.sub.6 H.sub.5 red91 CF.sub.3 H (CH.sub.2).sub.2OCH.sub.3 H (CH.sub.2).sub.2OCH.sub.3 " " " gold- en yel- low92 CF.sub.3 H (CH.sub.2).sub.3OCH.sub.3 H (CH.sub.2).sub.3OCH.sub.3 " " " yel- low- ish or- ange93 CF.sub.3 H H H ##STR59## " " " gold- en yel- ow__________________________________________________________________________
TABLE 3__________________________________________________________________________ ##STR60##No. T.sup.2 R.sup.3 R.sup.7 R.sup.1 R.sup.2 Hue__________________________________________________________________________94 CF.sub.3 C.sub.6 H.sub.5 H CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 golden yellow95 (C.sub.2 H.sub.5).sub.2 NO.sub.2 S " CH.sub.3 " " orange96 " " " (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 "97 " " " C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) "98 C.sub.6 H.sub.5 O.sub.3 S CH.sub.3 " " " "99 " C.sub.2 H.sub.5 " (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 "100 O.sub.2 N CH.sub.2 OCH.sub.3 " " " bluish101 " " H " " "102 " " C.sub.2 H.sub.5 " " "103 " " CH.sub.3 C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) "104 " " " C.sub.3 H.sub.7 (n) C.sub.3 H.sub.7 (n) "105 O.sub.2 N CH.sub.2 OCH.sub.3 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 bluish red106 " CH.sub.2 OC.sub.6 H.sub.5 " " " bluish red107 " " " C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) bluish red108 " CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 (n) " " " red109 " " " C.sub.3 H.sub.7 (n) C.sub.3 H.sub.7 (n) "110 " " " C.sub.2 H.sub.5 C.sub.2 H.sub.5 "111 " " " (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 bluish red112 " Ch.sub.2 CH.sub.2 OC.sub.2 H.sub.5 Ch.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 red113 " " " C.sub.3 H.sub.7 (n) C.sub.3 H.sub.7 (n) "114 " " " " (CH.sub.2).sub.3 OCH.sub.3 "115 " " " CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 "116 " " " C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) "117 " " " (CH.sub.2 9.sub.2 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 "118 " " " C.sub.2 H.sub.5 C.sub.6 H.sub.13 (n)119 " " " " C.sub.6 H.sub.13 (i) "120 O.sub.2 N CH.sub.2 OCH.sub.3 CH.sub.3 C.sub.2 H.sub.5 C.sub.6 H.sub.13 (i) red121 " CH.sub.2 OC.sub.2 H.sub.5 " C.sub.3 H.sub.7 (n) C.sub.3 H.sub.7 (n) red122 " " " C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) "123 " " " (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 "124 " ##STR61## " " " "125 " CH.sub.2 Ch.sub.2 OC.sub.4 H.sub.9 (n) " " " "126 " " " C.sub.2 h.sub.5 C.sub.2 H.sub.5 "127 " " " C.sub.2 H.sub.7 (n) C.sub.3 H.sub.7 (n) "128 " CH.sub.2 CH.sub.2 OC.sub.6 H.sub.13 (n) " C.sub.2 H.sub.5 C.sub.2 H.sub.5 "129 " ##STR62## " " " "130 " " " C.sub.3 H.sub.7 (n) C.sub.3 H.sub.7 (n) "131 " " " (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 "132 " H " C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) "133 " " " (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 "134 " CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 (n) CH.sub.3 C.sub.2 H.sub.5/ C.sub.2 h.sub.5 "135 " " " C.sub.3 H.sub.7 (n) C.sub.3 H.sub.7 (n) "__________________________________________________________________________ ##STR63##Ex. X R R.sup.1 R.sup.2 hue__________________________________________________________________________144 SO.sub.2 N(C.sub.2 H.sub.5).sub.2 C.sub.6 H.sub.5 C.sub.2 H.sub.4 C.sub.6 H.sub.5 C.sub.2 H.sub.4 C.sub.6 H.sub.5 orange145 " " C.sub.2 H.sub.4 OCH.sub.3 " "146 " " (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5 H "147 Cl " " H "148 ##STR64## " C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 "149 " " C.sub.3 H.sub.6 OCH.sub.3 C.sub.3 H.sub.6 OCH.sub.3 "150 H ##STR65## " " yellow151 H CH.sub.2 SO.sub.2 C.sub.6 H.sub.5 " " "152 NO.sub.2 " " " red153 " CH.sub.3 C.sub.2 H.sub.4 C.sub.6 H.sub.5 C.sub.2 H.sub.4 C.sub.6 H.sub.5 "154 " C.sub.2 H.sub.5 " " "155 " CH.sub.2 OCH.sub.3 " " "156 " C.sub.2 H.sub.4 OCH.sub.3 " " "157 " C.sub.2 h.sub.4 OC.sub.3 H.sub.7 (n) " " "158 " " C.sub.2 h.sub.4 OCONHC.sub.4 h.sub.9 (n) C.sub.2 h.sub.5 "159 " C.sub.2 h.sub.4 OCH.sub.3 " " "160 " C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n) C.sub.2 h.sub.4 OCONHC.sub.6 h.sub.5 " "__________________________________________________________________________No. T.sup.2 R.sup.3 R.sup.7 R.sup.1 R.sup.2 hue__________________________________________________________________________161 O.sub.2 N CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 (n) CH.sub.3 C.sub.4 h.sub.9 (n) C.sub.4 H.sub.9 (n) red162 " " " (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3) "163 " CH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2).sub.2 OC.sub.4 H.sub.9 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 "164 " " " C.sub.3 H.sub.7 (n) C.sub.3 h.sub.7 (n) "165 " " " C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) "166 " C.sub.6 h.sub.5 " H (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 "167 Cl " " " (CH.sub.2).sub.3 O(CH.sub.2).sub.4 golden yellow168 Br " " (CH.sub.2 9.sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 orange__________________________________________________________________________ | An azo dye of the general formula ##STR1## where A is cyano or carbamoyl,
R is hydrogen, alkyl or phenyl,
R 1 is hydrogen, bromine, chlorine or nitro,
R 2 is hydrogen, chlorine, bromine, nitro, methyl, trifluoromethyl, sulfamoyl, N-monoalkyl- or N,N-dialkylsulfamoyl (where alkyl is of 1 to 4 carbon atoms), or a sulfonic acid phenyl ester, methylphenyl ester, chlorophenyl ester or methoxyphenyl ester group,
R 3 is hydrogen or alkyl of 1 to 8 carbon atoms which may be interrupted by oxygen and may be substituted by hydroxyl, pyrrolidonyl, phthalimidyl, alkoxy of 1 to 8 carbon atoms, allyloxy, benzyloxy, phenylethoxy, phenoxy, methylphenoxy, chlorophenoxy, methoxyphenoxy, or optionally substituted arylsulfonyl, or is benzyl, phenylethyl or cyclohexyl, or is phenyl which is unsubstituted or substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, phenoxy or dialkylamino (where alkyl is of 1 to 4 carbon atoms), or is naphthyl, pyridyl, thienyl or furyl,
the substituents B 1 independently of one another are hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic, heterocyclic or acyl radical and
B 2 is hydrogen or an aliphatic radical.
The dyes may be used for dyeing synthetic fibers, especially polyesters, and cellulose/polyester union fabrics, and give very fast dyeings. | 2 |
FIELD OF THE INVENTION
[0001] The invention relates to electronic circuits, and especially to an assembly of multi-chip circuits operating on microwave, millimeter wave or radio frequency ranges, which assembly is based on a multi-layer flex substrate.
BACKGROUND OF THE INVENTION
[0002] Monolithic microwave integrated circuits (MMIC) are used in microelectronics at high frequency ranges. During assembly, individual semiconductor chips are typically connected to a base structure, i.e. substrate, which is in turn connected to a circuit panel, such as printed circuit board (PCB). In multi-chip modules, several unpackaged semiconductor chips are placed on one substrate. The substrate is then connected to a common circuit panel and enclosed in a common package. This saves space that would be wasted when using individually packaged semiconductor chips. A multi-chip module (MCM) is usually an assembly made of a rigid material, such as ceramic or other material, which comprises a ceramic substrate and several semiconductor chips on the substrate and in which the connections between the semiconductor chips are implemented by multi-layer circuitries insulated from each other by insulating layers and connected to each other by lead-throughs. In conventional multi-chip assemblies, the adjacent chips are placed on the surface of the substrate by means of a planar technique, and non-planar solutions are impossible.
[0003] One reason for the poor microwave performance in conventional assemblies of monolithic microwave integrated circuits comprising ceramic substrates is the connections between the chip surface and the conductive patterns in the different layers of the multi-layer circuit panel. The insertion loss of a coaxial line or stripline on top of the inter-layer connections increases at high frequencies, which in turn causes a weakening in the signal strength. One of the biggest problems in MMIC assemblies comprising ceramic substrates is also the incompatibility caused by the different thermal coefficients of expansion of the substrate and the semiconductor circuits.
BRIEF DESCRIPTION OF THE INVENTION
[0004] It is thus an object of the invention to implement an integrated circuit assembly and a method for making one in such a manner that the above-mentioned problems are solved. This is achieved by a method of making an integrated circuit assembly, the method of the invention comprising providing a flex substrate having one or more dielectric layers, assembling one or more semiconductor chips to said flex substrate, said semiconductor chips having an active surface and a plurality of contact pads on said active surface, providing one or more conductive layers on said flex substrate, said conductive layers forming the electrical connections required for the assembly and electrically connecting the contact pads to the conductive layers.
[0005] The invention also relates to an integrated circuit assembly, the integrated circuit assembly of the invention comprising a flex substrate that comprises one or more dielectric tape layers, one or more semiconductor chips on said flex substrate, said semiconductor chips comprising an active surface having several contact pads, one or more conductive layers on said flex substrate, said conductive layers forming the electric connections required in the assembly, and means for connecting said contact pads directly to the conductive layer of the flex substrate.
[0006] Preferred embodiments of the invention are set forth in the dependent claims.
[0007] The assembly of the invention provides several advantages. One advantage of the invention is that it is possible to have very high component densities on assemblies operating at high frequency ranges. A further advantage is that inexpensive organic materials can be used as the substrates without the material selection impeding the operation of the assembly. The flex substrate used in the solution of the invention receives the stress caused by the different thermal coefficients of expansion of the materials, thus reducing the stress directed to the joint between the circuit and substrate and improving the reliability of the device and saving costs. A yet further advantage of the invention is that the assembly of the invention comprising a flex substrate is suited for use for three-dimensional, non-planar mounting of said components.
BRIEF DESCRIPTION OF THE FIGURES
[0008] The invention will now be described in more detail using as examples the attached drawings showing the preferred embodiments of the invention, in which
[0009] [0009]FIG. 1 shows a top plan view of an assembly of the presented solution comprising flex substrate,
[0010] [0010]FIGS. 2A and 2B show a cross-profile of an embodiment of the presented solution,
[0011] [0011]FIG. 2C shows a top plan view of the embodiment of FIGS. 2A and 2B,
[0012] [0012]FIGS. 3A and 3B show a cross-profile of an embodiment of the presented solution,
[0013] [0013]FIG. 3C shows a top plan view of the embodiment of FIGS. 3A and 3B,
[0014] [0014]FIGS. 4A and 4B show a cross-profile of an embodiment of the presented solution,
[0015] [0015]FIG. 4C shows a top plan view of the embodiment of FIGS. 4A and 4B,
[0016] [0016]FIG. 5A shows a cross-profile of an embodiment of the presented solution,
[0017] [0017]FIG. 5B shows a top plan view of the embodiment of FIG. 5A.
DETAILED DESCRIPTION OF THE INVENTION
[0018] [0018]FIG. 1 shows a top view of an assembly 101 according to one embodiment of the presented solution. The assembly 101 comprises a flex substrate 102 that comprises one or more dielectric tape layers. In the embodiment of FIG. 1, said dielectric tape layers are made of a flexible, organic material, such as polyimide, LCP (Liquid Crystal Polymer) or other suitable flex substrates. Several electronic components, such as semiconductor chips 90 , 91 , 92 , are connected to the flex substrate 102 . On top of the flex substrate 102 , there are conductive layers 104 made of an electrically conductive material, such as copper. Vias 106 are formed through the flex substrate layers 102 , and at least some of the vias form an electrical contact between the semiconductor chips 90 , 91 , 92 and the conductive layers 104 . The vias 106 are at least partly filled with a conductive material 105 , such as metal. In FIG. 1, the locations of the vias 106 are marked, even though when seen from the top, at least a part of them remain under the conductive layers 104 . Some of the conductive layers 104 run between vias 106 and some of them run from the vias 106 at the semiconductor chips 90 , 91 , 92 to the edge of the flex substrate 102 . Thus, some of the conductive layers 104 form an electrical contact between one or more semiconductor chips 90 , 91 , 92 , whereas some of them form an electrical contact from the semiconductor chips 90 , 91 , 92 to the edges of the flex substrate 102 . The conductive layers 104 extending to the outer edges of the flex substrate 102 are used in connecting the assembly 101 electrically to a motherboard, for instance. The conductive layers 104 thus form the necessary electrical connections in the assembly. The conductive layers 104 can for instance form a microstrip, stripline or coplanar wave-guide configuration.
[0019] In FIG. 1 according to the embodiment of the presented solution the semiconductor chips 90 , 91 , 92 are also connected to a mechanical part 114 , such as a mechanical base, a frame or a heatsink.
[0020] In FIG. 1, the visible part of the semiconductor chips 90 91 , 92 is shown by a continuous line. The parts of the semiconductor chips 90 , 91 , 92 that remain under the flex substrate 102 in a top view of the assembly 101 and at which vias 106 are formed in the flex substrate 102 , are marked with a dashed line.
[0021] The unpackaged semiconductor chips 90 , 91 , 92 can be electrically connected to the flex substrate 102 in several different ways. The semiconductor chips 90 , 91 , 92 can be connected in manners known per se, for instance by reflow soldering, microwelding, by using flip chip techniques or large BGA (ball grid array) balls.
[0022] The semiconductor chips 90 , 91 , 92 can, according to the presented solution, be microwave chips (MW), for instance. In addition to microwave chips, RF (radio frequency) and DC signals and a ground layer can be integrated to one and the same flex substrate 102 .
[0023] Due to the flexible nature of the flex substrate 102 , the flex substrate 102 according to one embodiment of the presented solution can receive mechanical stress in the semiconductor chip 90 , 91 , 92 interconnects. The assembly 101 can also be made three-dimensional depending on the requirements of each assembly, such as thermal solutions and in-out signaling.
[0024] [0024]FIGS. 2A, 2B and 2 C show one embodiment of the invention, in which the conductive layers 104 form a microstrip line configuration. Typically, a microstrip line is made up of a strip line and ground layer having a dielectric substrate between them. FIG. 2A shows an enlarged cross-profile of the embodiment of the presented solution. The active surface 103 of the semiconductor chip 90 has contact pads 108 . Alternatively, the contact pads 108 can also be solder balls or bumps. Vias 106 are formed in the flex substrate 102 , through which the semiconductor chip 90 is electrically connected directly to the conductive layers 104 on top of the vias 106 . The conductive layers 104 are on top of the flex substrate 102 in such a manner that some of the conductive layers 104 come above the vias 106 .
[0025] The flip chip technique used in electrically connecting the semiconductor chips 90 , 91 , 92 is a useful alternative in GaAs devices that operate at microwave and RF ranges. In the solder-bump flip chip technique, unpackaged semiconductor chips are directly connected to the flex substrate. A direct connection to the flex substrate is formed through contact bumps made on the active surface of the semiconductor chips. Due to the flexibility of the flex substrate, no underfill is needed. The bumpless universal contact unit (UCU) technique is another flip chip technique. No balls, contact bumps or underfill are needed in connections in the UCU technique. In the UCU technique, contact pads 108 are formed of aluminum or copper, for instance, on the active surface 103 of the semiconductor chips 90 , 91 , 92 , and on top of the pads, electrical contacts are formed for instance by means of the conductive material 105 in the vias 106 .
[0026] In the embodiment of FIG. 1, the semiconductor chip 90 is typically reflow soldered to the conductive material 105 in the vias 106 and the conductive layers 104 . Instead of soldering, microwelding or UCU methods known per se can also be used.
[0027] In one embodiment of the invention, a space 110 free of the substrate material, such as an air window, is formed in the flex substrate 102 above the active surface 103 of the semiconductor chip 90 . The purpose of the space 110 free of the substrate material is to minimize the effect of the flex substrate 102 on the performance of the semiconductor chip 90 . The space 110 free of the substrate material is of equal height to one or more flex substrate layers in the presented solution. The height of the space 110 free of the substrate material can be adjusted as required to ensure that the operation of the semiconductor chip 90 is as trouble-free as possible.
[0028] The ground layer 112 is connected to the flex substrate 102 opposite the conductive layers 104 in such a manner that the flex substrate 102 is between the conductive layers 104 and the ground layer 112 .
[0029] In FIGS. 2A and 2B according to one embodiment of the presented solution the semiconductor chip 90 is also connected to a mechanical part 114 , such as a mechanical base, a frame or a heatsink.
[0030] [0030]FIG. 2B shows the embodiment of FIG. 2A from the side. The figure shows that some of the contact pads 108 are connected to the ground layers 112 below the flex substrate 102 . FIG. 2C shows the embodiment of FIGS. 2A and 2B from the top. The part of the semiconductor chip 90 that is visible when seen from the top is marked with a continuous line, and a dashed line shows the part of the semiconductor chip 90 that remains below the flex substrate 102 when seen from the top. The conductive layers 104 run on top of the vias 106 at the location of the semiconductor chip 90 to the edges of the flex substrate 102 .
[0031] As described in FIGS. 2A, 2B and 2 C, the microwave performance of the assembly can be improved considerably by using air windows 110 next to the active surface 103 of the semiconductor chip 90 .
[0032] [0032]FIGS. 3A, 3B and 3 C disclose a solution according to one embodiment of the invention, in which the conductive layers 104 form a stripline configuration. In a stripline configuration, the stripline is typically between two ground layers. In FIGS. 3A, 3B and 3 C, the flex substrate comprises layers 102 a and 102 b. FIG. 3A is an enlarged cross-profile of the embodiment of the presented solution. The semiconductor chip 90 is reflow soldered to the conductive material 105 in the conductive vias 106 and to the conductive layers 104 . Instead of reflow soldering, the semiconductor chip 90 can be electrically connected to the conductive layers 104 by brazing or by using flip chip techniques known per se.
[0033] Conductive vias 106 are formed in the lower flex substrate layer 102 a above the active surface 103 of the semiconductor chip 90 . The conductive layers 104 are above the conductive vias 106 , and thus between the flex substrate layers 102 a and 102 b. The space 110 free of the flex substrate material, such as an air window, at the location of the active surface 103 of the semiconductor chip 90 is formed by making an opening through both flex substrate layers 102 a and 102 b or just through the flex substrate layer 102 a. The upper ground-layer 112 b is on top of the upper flex substrate layer 102 b located above the conductive layers 104 and the lower ground-layer 112 a is below the lower flex substrate layer 102 a.
[0034] [0034]FIG. 3B shows the embodiment of FIG. 3A from one side. As can be seen in the figure, at least some of the contact pads 108 of the semiconductor chip 90 are electrically connected to the conductive layer 104 and some of the contact pads 108 are connected to the lower ground-layer 112 a. The upper ground-layer 112 b is electrically connected to the lower ground-layer 112 a through the conductive vias 106 formed through the flex substrate layers 102 a, 102 b. FIG. 3C shows a top view of the embodiment of FIGS. 3A and 3B. The upper ground-layer 112 b covers most of the figure. In a top view, a part of the active surface of the semiconductor chip 90 and a part of the upper flex substrate layer 102 b are visible. The figure also shows the locations of the vias 106 formed through the upper flex substrate layer 102 b, which remain under the upper ground-layer 112 b.
[0035] [0035]FIGS. 4A, 4B, 4 C show a solution according to one embodiment of the invention, in which the conductive layers 104 form a coplanar transmission line, such as a coplanar waveguide line, configuration. In a coplanar line, there are typically ground layer halves on both sides of a stripline. FIG. 4A shows an enlarged cross-profile of the flex substrate 102 . There are contact pads 108 on top of the active surface 103 of the semiconductor chip 90 . The flex substrate 102 comprises conductive vias 106 , through which the semiconductor chip 90 is electrically connected directly to the conductive layers 104 on top of the conductive vias 106 . The semiconductor chip 90 is reflow soldered to the conductive material 105 in the conductive vias 106 and to the conductive layers 104 . Instead of reflow soldering, the semiconductor chip 90 can be electrically connected to the conductive layers 104 by brazing or by using flip chip techniques known per se. The conductive layers 104 are on top of the flex substrate in such a manner that some of the conductive layers 104 are above the conductive vias 106 . In a preferred embodiment of the invention, a space 110 free of the flex substrate material, such as an air window, is formed at the location of the active surface 103 of the semiconductor chip 90 in the flex substrate 102 .
[0036] [0036]FIG. 4B shows the embodiment of FIG. 4A from one side. As can be seen in the figure, some of the contact pads 108 are connected to the ground layers 112 a and 112 b located on top of the flex substrate 102 through the conductive vias 106 formed through the flex substrate 102 in such a manner that the ground layers 112 a and 112 b are on both sides of the conductive layer 104 . FIG. 4C shows a top view of the embodiment of FIGS. 4A and 4B. The section of the semiconductor chip 90 that is visible as seen from above is marked with a continuous line and the sections marked with a dashed line show the sections of the semiconductor chip 90 that remain under the ground layer 112 when seen from above. The ground layers 112 a and 112 b are on both sides of the conductive layers 104 . The vias 106 formed through the flex substrate layer 102 remain under the ground layers 112 a, 112 b and the conductive layers 104 when seen from above. A part of the flex substrate layer 102 is visible when seen from above.
[0037] [0037]FIGS. 5A and 5B show one embodiment, in which the semiconductor chip is replaced by surface mount device (SMD) packages 196 , 197 , 198 which comprise a semiconductor chip or other components. In FIG. 5A, an active SMD package 198 is directly connected to the conductive layers 104 on top of the flex substrate 102 by means of large contact material components 109 , such as pads, leads, BGA (Ball Grid Array) balls or similar. Alternatively a QFP (Quad Flat Package) package technique can be used. In FIG. 5A, two passive SMD packages 196 , 197 , such as chip capacitors, are also on top of the flex substrate 102 . The two passive SMD packages 196 , 197 in FIGS. 5A and 5B are identical, but in respect of each other they are positioned in different directions. The SMD packages 196 , 197 are typically reflow soldered to the conductive layers 104 . FIGS. 5A and 5B also show the solder joints 194 of the passive SMD packages 196 , 197 . For simplicity, not all the conductive layers and ground layers on top of the flex substrate 102 are shown in FIGS. 5A and 5B.
[0038] In FIGS. 5A and 5B a passive component 195 is integrated in the flex substrate 102 . In FIGS. 5A and 5B the passive component 195 is a coil, made up from some of the conductive layers 104 on the flex substrate 102 . It is also possible to integrate directly to the flex substrate 102 other passive components, such as capacitances, resistors, filters, and couplers, using metal tracks, dielectrics, vias, air, and other materials.
[0039] [0039]FIGS. 5A and 5B also show a patch matrix antenna 199 integrated to the flex substrate 102 . In FIGS. 5A and 5B the patch matrix antenna 199 is on the other side of the flex substrate 102 than the SMD packages 196 , 197 , 108 and the passive component 195 . The patch matrix antenna 199 is made up of some of the conductive layers 104 on the flex substrate 102 .
[0040] [0040]FIG. 5B shows a top view of the embodiment of FIG. 5A. The locations of the BGA balls 109 of the active SMD package 198 are marked in FIG. 5B even though in reality they remain under the SMD package 198 when seen from above. In a top view, the location of the patch matrix antenna 199 , which remains under the flex substrate 102 , is also marked. The FIG. 5B also shows the passive SMD packages 196 , 197 and the passive component 195 , such as a coil.
[0041] In FIG. 5B some of the conductive layers 104 , forming for example metal tracks, on top of the flex substrate layer 102 run from the SMD packages 196 , 197 , 198 to the edges of the flex substrate 102 forming the required connections in the assembly. Some of the conductive layers 104 run from the active SMD package 198 to the solder joint 194 of the passive SMD package 196 and some to the patch matrix antenna 199 through the flex substrate 102 . One of the conductive layers 104 also runs from one passive SMD package 196 to the other passive SMD package 197 and from there to the edge of the flex substrate 102 . In FIG. 5B the spiral shaped coil 195 can be seen. The conductive layers 104 connect the coil 195 to the other passive SMD package 197 and to the edges of the flex substrate 102 . The inner part 180 of the spiral shaped coil 195 is connected to the assembly for example by using a connective via 106 .
[0042] In the embodiments according to FIGS. 5A and 5B both active and passive components are integrated to one flex substrate 102 , whereby it is possible to have very high component densities on assemblies operating at high frequency ranges. The passive components, such as inductors or capacitors, to be integrated to the flex substrate 102 can be made up of conductive layers 104 and/or dielectric tape layers of the flex substrate 102 . In addition, resistive layers or patches can also be added to form resistors, which passive components can comprise RF elements made without active components.
[0043] In the solutions according to the embodiments described above, patch-type and/or area-matrix-built-type antennas, for instance, can be integrated to one and the same flex substrate 102 , where it is also possible to have for example spaces 110 free of the substrate material, such as air windows, to minimize the effect of the flex substrate 102 on the performance of the assembly.
[0044] In the solutions according to the embodiments described above, the flex substrate 102 forms a flexible protection for electric connections and receives the stress caused by the different thermal coefficients of expansion of the used materials, thus improving reliability and saving costs. Due to the flexibility of the flex substrate material 102 , it can also be bent three-dimensionally around a bending point, and the components can also be located in arbitrary (3D) positions with respect to each other. Non-planar configurations are thus possible. By means of the presented solutions, it is possible to have very high component densities for microwave circuits.
[0045] Even though the invention has been explained in the above with reference to examples in accordance with the accompanying drawings, it is obvious that the invention is not restricted to them but can be modified in many ways within the scope of the inventive idea disclosed in the attached claims. | The invention relates to an integrated circuit assembly and a method of making same. The method according to the invention comprising providing a flex substrate having one or more dielectric tape layers, assembling one or more semiconductor chips to said flex substrate, said semiconductor chips having an active surface and a plurality of contact pads on said active surface, providing one or more conductive layers on said flex substrate, said conductive layers forming the electrical connections required for the assembly, electrically connecting the contact pads to the conductive layers. | 8 |
BACKGROUND OF THE INVENTION
This invention relates to locks and, more particularly, to apparatus for retaining the shell in working relationship with its housing in sliding door or plunger locks.
Plunger locks are often used to provide security in conjunction with sliding doors. The locks are generally cylindrical in shape and retained in a bore in the door and oriented substantially perpendicularly to the door panel. A lock housing is attached directly to the door and a shell, or insert, in the housing is responsive to a key and slides perpendicularly to the door between a locked position and an unlocked position. Often a portion of the housing projects from the front of the door panel. The length of the projection depends upon the relative length of the housing and the panel thickness.
In conventional plunger locks, a longitudinal slot is defined by the housing. A tapped hole in the side of the shell retains a screw with a fillister head. The screw head slides in the slot as the shell is moved between the locked and unlocked positions. Thus, the shell and slot combination limits rotational motion of the shell within the housing. Furthermore, when the lock is in the unlocked state, a bias spring urges the shell away from the locked position until the screw head abuts the end of the slot. Thus, the screw and slot combination also establishes the unlocked position.
As mentioned previously, a portion of the housing often projects from the panels retaining the locks. This projection is sometimes great enough that an end of the slot is exposed. When a conventional plunger lock is mounted with an end of the slot exposed and left in the unlocked position, the screw head is exposed. Therefore, persons can remove the screw and thus remove the shell from the housing, surreptiously determine the combination of the locking apparatus and reassemble the lock without detection. Such surreptious action can be avoided by the application of the lock to panels of a thickness sufficient to conceal the screw even when the lock is in the unlocked position. Obviously the range of panel thicknesses to which the locks can be applied with full security is substantially narrowed by the solution. An alternative suggestion is to provide a number of locks with various housing lengths and utilize shorter housings with the thinner panels. This, however, entails increased cost. Furthermore, a complete solution is not provided because extremely thin panels, such as metal doors, still cannot be accommodated. This is because a reduction in housing length also reduces the length of travel of the shell. Thus, insufficient locking action becomes a problem.
It is an object of this invention, therefore, to provide a plunger lock that can be utilized on thin panels with full security.
SUMMARY OF THE INVENTION
This invention is characterized by a lock, such as a sliding door or plunger lock. A lock housing retains a shell that is movable between a locked position and an unlocked position. Locking apparatus within the shell is responsive to a key and releasably restrains the shell in the locked position. A restraining system is also responsive to the same key and selectively prevents the removal of the shell from the housing. Prior lock construction methods often involved removable screws with the disadvantages discussed above. The subject lock overcomes those disadvantages inasmuch as removal of the shell can only be achieved by a person in possession of the proper key. However, as will be explained below, disassembly is a fast and easy process and is quickly performed by the holder of the proper key. Furthermore, it should be stressed that the key utilized for disassembly is the conventional key used for normal lock operation. No special "dismantling" key is required. Consequently, a plunger lock is provided that affords full security even in thin panels and yet can quickly and easily be disassembled by the possessor of the proper key.
A feature of the invention is the inclusion of a limit system in the lock to limit the longitudinal motion of the shell within the housing. The housing defines a longitudinal slot and a permanently mounted stud which mates with the slot is affixed to the shell. Thus, the unlocked position of the subject lock is established in a manner similar to the prior art locks by the abutment of the stud against the end of the slot. However, the above cited disadvantage of the prior art locks, that of the possibility of surreptious disassembly, is prevented inasmuch as the stud is an integral part of the shell and thus cannot be removed and replaced without detection. Integral is intended to mean permanently affixed. For example, the stud can be a rivet headed over.
Another feature of the invention is the provision of an access groove for facilitating the insertion of the stud into the slot during lock assembly. An entry groove, substantially parallel to the slot, is defined by the inner wall of the housing. The entry groove is connected to the slot by a connecting slot. The entry groove extends to the end of the housing and the stud is inserted directly therein during assembly. Consequently, assembly of the lock entails the insertion of the shell into the housing with the stud entering the entry groove and sliding therein to the intersection of the connecting slot and the entry groove. Rotation of the shell within the housing then moves the stud through the connecting slot into the longitudinal slot.
A further feature of the invention is the inclusion of a rotational restraining system to restrain rotational motion of the shell within the housing. When the shell is rotationally restrained, the lock cannot be disassembled by a reversal of the above described assembly procedure. The rotational restraining system works in conjunction with the locking apparatus which comprises a locking wafer that projects from the periphery of the shell and is received by a locking slot defined by the housing. The wafer is biased to project from the periphery of the shell. Thus, when the shell is pushed to the locked position and the wafer becomes aligned with the locking slot, the wafer snaps into the slot thus establishing the locked condition. The wafer can then be withdrawn from the slot in response to proper manipulation of the key. A rotational restraining groove, substantially parallel to the longitudinal slot, is defined by the interior wall of the housing and intersects the locking slot. As the shell moves between the locked and unlocked positions, the locking wafer slides within the rotational restraining groove. Thus, the wafer is not brought to shear with the surface of the shell and consequently rotational motion of the shell within the housing is restricted. Thus, as mentioned previously, the lock cannot be disassembled merely by positioning the stud near the connecting slot and rotating the shell so that the stud moves to the entry groove. Disassembly of the lock requires positioning the stud near the connecting slot and actuating the proper key to withdraw the locking wafer from the rotational restraining groove. Only when the locking wafer is withdrawn to the point of shear with respect to the shell can the shell be rotated so as to disassemble the lock. Thus, disassembly is possible only with the aid of the correct key. Consequently, a lock is provided that can be manufactured inexpensively and yet provides full security when utilized with panels that cover only the locking slot.
DESCRIPTION OF THE DRAWINGS
These and other objects and features of the present invention will become more apparent upon a perusal of the following description taken in conjunction with the accompanying drawings wherein:
FIG. 1 is an elevation view of one side of the subject lock in the unlocked position;
FIG. 2 is an elevation view of an end of the subject lock;
FIG. 3 is an elevation view of the side of the subject lock opposite the side depicted in FIG. 1;
FIG. 4 is an elevation view of the side of the lock shown in FIG. 3 with the lock in the locked position;
FIG. 5 is a sectional plan view taken along the lines 5--5 in FIGS. 1 and 2;
FIG. 6 is a plan view of the shell;
FIG. 7 is an elevation view of the shell;
FIG. 8 is a sectional view of the shell taken along line 8--8 of FIG. 6;
FIG. 9 is a sectional elevation view of the shell taken along the line 9--9 in FIG. 6; and
FIG. 10 is a sectional elevation view of the shell taken along the line 10--10 in FIG. 6.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring first to FIGS. 1 and 2 there is shown a plunger lock 21 including a housing 22 with a mounting flange 23. The lock 21 is generally mounted on a sliding door in the conventional manner. The housing 22 projects through a bore in the door and the flange 23 abuts against the inner portion of the door. The lock 21 is secured to the door by screws passing through screw holes 24 in the flange 23.
A shell 25 is longitudinally slidable within the housing 22. As the shell 25 slides, a stud 26, permanently mounted thereon, slides in a longitudinal slot 27. A bias spring (not shown) urges the shell 25 toward the right hand position shown in FIG. 1. Consequently, the stud abuts against an unlock limit wall 28 of the slot 27 to establish the unlocked position of the lock 21. The mating slot 27 and stud 26 also permanently stop rotation of the shell 25 in all longitudinal positions thereof except where the stud 26 is aligned with an entry groove 29, defined by the inner wall of the housing 22. The entry groove 29 extends to the outer end of the housing and is substantially parallel to the slot 27. Coupling the entry groove 29 and the slot 27 is a connecting slot 31.
Referring now to FIGS. 2, 3 and 4 there is shown a locking slot 32 defined by the housing 22. A rotational restraining groove 33 is defined by the inner wall of the housing 22 and intersects the locking slot 32. A locking wafer 34 is biased to project from the periphery of the shell 25 and, when the lock 21 is in the locked position (FIG. 4), the locking wafer 34 is received in the locking slot 32. When the lock 21 is in any position other than the locked position, the locking wafer 34 is slidably received in the rotational restraining groove 33. Thus as the shell reciprocates between the locked position shown in FIG. 4 and the unlocked position shown in FIGS. 1 and 3 the shell 25 cannot turn with respect to the housing 22. In the locked position, a locking member 35 that is affixed to one end of the shell 25, projects beyond the mounting flange 23.
Referring now to FIG. 5 there is shown a sectional plan view of the lock taken along the lines 5--5 in FIGS. 1 and 2. Shown more clearly in FIG. 5 is the spacial relationship between the stud 26 and the latching wafer 34. Also shown is an opening 36 in the mounting flange 23 through which the latching member 35 passes when the lock 21 is in the locked position. Furthermore, the bias spring 37 is visible in FIG. 5. It is this spring that urges the shell 25 toward the unlocked position and holds the stud 26 against the unlock limit wall 28 (FIG. 1).
Referring now to FIGS. 6-8 there is shown the shell 25. A small bias spring 41 urges the locking wafer 34 to project from the periphery of the shell 25. As shown, the shell 25 in the vicinity of the locking wafer 34 is shaped so as to prevent rotation of the wafer within the shell.
A movable stud 42 is shown within an opening 43 in the wafer 34. It will be appreciated that, due to the juxtaposition of the stud 42 and the opening 43 and the shape of the opening, when the stud is moved in a circular path about the center of the shell 25, as shown by an arrow 44, the wafer 34 is drawn into the shell. Furthermore, the wafer 34 can be pressed into the shell 25 without corresponding motion of the stud 42 if the small force of the bias spring 41 is overcome.
Referring now to FIGS. 9 and 10 it is seen that the shell 25 defines an upper spline 45 and a lower spline 46 that do not extend to the area of the locking wafer 34. A collar 47 around the inner wall of the shell 25 marks the termination of the splines 45 and 46 and also (as seen in FIG. 9) restricts the locking wafer 34 to one dimensional motion in and out of the shell. A key responsive plug 48 is rotatably mounted within the shell 25 by conventional apparatus. It is seen that a plurality of key actuated wafers 49 are normally projecting into the upper spline 45. When the proper key is inserted in a keyway 51 (FIGS. 2 and 7) the wafers 49 are brought to shear with the plug 48 and thus the plug can be rotated within the shell 25. Furthermore, it will be appreciated that stud 42 is an extension of the plug 48.
During assembly of the lock 21, the plug 48 is inserted in the shell 25 with care being taken that the stud 42 enters the opening 43. The lock 21 then comprises three pieces: the housing 22, the shell 25 and the bias spring 37. After the bias spring 37 is placed around the latch member 35, the shell 25 is inserted into the housing 22. The shell 25 must be inserted so that the stud 26 enters the entry groove 29. It will be observed from FIG. 7 that the stud 26 and the locking wafer 34 are diametrically opposed about the shell 25. However, it will be observed from FIG. 2 that the entry groove 29 and the rotational restraining groove 33 are not diametrically opposed. Thus, to insert the shell 25, the wafer 34 is drawn into the shell 25 to shear. The wafer 34 may be drawn in by proper manipulation of a key in the keyway 51 or by external pressure on the wafer 34 itself. When the wafer 34 is at shear the shell 25 will slide into the housing 22 to the end of the entry groove 29 at which time the stud 26 will be in the connecting slot 31. Rotating the shell 25 clockwise (as viewed in FIG. 2) causes the stud 26 to move to the slot 27. As the stud 26 enters the slot 27, the locking wafer 34 enters the rotational restraining groove 33 and snaps thereinto thus preventing further rotation of the shell 25 within the housing 22. Also at that time, the shell 25 is free to slide longitudinally within the housing 22 and the bias spring 37 urges the shell toward the unlocked position.
The lock 21 is then fully assembled. It is mounted in a door or panel in the conventional manner. To move the lock 21 to the locked position, the shell 25 is pushed forward until the position shown in FIG. 4 is achieved. At that time, the small bias spring 41 pushes the locking wafer 34 into the latching slot 32. In order to unlock the lock 21 the proper key is inserted in the keyway 51 and rotated clockwise (as viewed in FIG. 2). Clockwise rotation of the key causes the stud 42 to move in the direction of the arrow 44 (FIG. 8). Consequently, the locking wafer 34 is withdrawn from the latching slot 32 and the bias spring 37 urges the lock 21 to the unlocked position.
To disassemble the lock 21, the key is inserted in the keyway 51 and the shell 25 is pushed toward the locked position until the stud 26 is aligned with the connecting slot 31. The key is then rotated in a clockwise direction (as viewed in FIG. 2) sufficiently far to withdraw the latching wafer 34 out of its latched position within the restraining groove 33 and into a shell removal position at shear with the shell 25. When the latching wafer 34 is at shear, the shell 25 can rotate with respect to the housing 22. Holding the latching wafer 34 at shear the shell 25 is rotated in a counterclockwise direction (as seen in FIG. 2) until the stud 26 reaches the end of the connecting slot 31 and can pass into the entry groove 29. Then the shell 25 is withdrawn from the housing 22 with the stud 26 passing through the entry groove 29.
Obviously, many modifications and variations of the present invention are possible in light of the above teachings. For example, it will be appreciated that the technique of making disassembly of the lock depend upon proper manipulation of the regular lock actuating key can be applied to locks other than plunger locks. It is to be understood, therefore, that the invention can be practiced otherwise than as specifically described. | Disclosed is a lock comprising a housing and a shell movable therein between a locked position and an unlocked position. Locking apparatus is responsive to a key and releasably restrains the shell in the locked position. Restraining apparatus is responsive to the same key and selectively prevents the removal of the shell from the housing. | 4 |
CROSS-REFERENCE TO A RELATED APPLICATION
This application is a continuation-in-part application of the previous application No. 20,050, filed Mar. 16, 1970 for "Production of Carbon Shaped Articles Having High Anisotropy" now abandoned.
BACKGROUND OF THE INVENTION
a. Field of the Invention
This invention relates to an improved method of producing carbonaceous or graphitic articles in fibrous or film form having high anisotropy by selecting a substance having particular chemical structure and properties as a carbon precursor. (The carbonaceous or graphitic shaped articles will hereinafter be called in general term "carbon shaped articles".)
B. Discussion of Prior Arts
There have been known several methods of producing carbon shaped articles, particularly carbon fibers, representative methods of which are as follows:
1. A method, in which the fibers made of natural of synthetic high polymer materials such as polyacrylonitrile, polybenzimidasole, cellulose, etc. are baked.
2. A method, in which pitch as a raw material is formed into a fibrous shape by melt-spinning, thereafter subjecting the fibers to infusibilization treatment and then to carbonization.
The abovementioned second method has been invented by one of the present inventors, and is suited for obtaining products of uniform quality and high strength, as taught in U.S. Pat. No. Re. 27,794 (Otani) and No. 3,629,379 (Otani).
The characteristic feature of producing the carbon fibers from pitch as taught in the abovementioned patents is such that natural or synthetic organic compounds are baked at a temperature of from 300° to 500° C (heat-treatment in an inert gas atmosphere) to obtain a pitch substance in a molten state, then the molten pitch substance is subjected to melt-spinning, and the thus spun filaments are oxidized to infusibilize so that the individual filament may not be fused together by further heat-treatment, after which the infusibilized filaments are subjected to carbonization. In this case, the melt-spinning is carried out by using the raw material pitch of a particular class having mean molecular weight of 400 and above. The thus spun filaments are then subjected to the infusibilization treatment and carbonization, followed by, if necessary, the graphitization treatment, thereby obtaining the carbonaceous or graphitic fibers.
However, no precise study has ever been made as to the molecular orientation of the carbonaceous or graphitic fibers obtained by the patented methods, and the relationship between the crystal growth and the physical properties or structure of the raw material pitch as well.
The present inventors have connected further studies and experiments on the abovementioned problems, and have finally found out that carbonaceous or graphitic shaped articles having high modulus of elasticity and excellent crystal orientation, particularly high anisotropy, can be obtained by the use of carbon precursors with particularly orientable molecular class as the principal constituent.
The present invention is directed to a more limited definition of the pitch in its physical properties to suit the purpose of obtaining carbon shaped articles having the modulus of elasticity of 1,400 tons/cm 2 and above, which is at the present moment made the object of practical use as the carbonaceous or graphitic fibers for reinforcement purpose. This value of the modulus of elasticity is twice or more as high as that of carbon fibers obtained heretofore with usual pitch as the raw material.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a method for producing carbon shaped articles having high anisotropy and high modulus of elasticity from raw material pitch.
It is another object of the present invention to provide a method for obtaining the abovementioned pitch suited for the raw material to produce carbon fibers having such excellent properties.
The foregoing objects, other objects as well as the principle of the present invention will become more apparent from the following detailed description of the invention together with preferred embodiments thereof.
DETAILED DESCRIPTION OF THE INVENTION
For the purpose of the present invention, the term "anisotropy" is meant by the optical anisotropy, and the term "anisotropy of the raw material pitch" is meant by the anisotropic portions to be recognizable from observation through a polarization microscope on the polished surface of the raw material pitch in its cross-section, which has been cooled to solidify from its molten state having a melt-viscosity thereof of lower than 700 poises. Also, the term "anisotropy of the carbon shaped body" is meant by the orientation in the axial direction bo be recognized from observation through the polarization microscope on the polished surface of the carbon shaped body in its cross-section, which is parallel to the axial direction of such carbon shaped article, and the orientation in the axial direction of the planar molecules by the X-ray analyses.
The most suitable raw material pitch to obtain the carbon shaped body according to the present invention has the carbon content in the range of from 95 to 96.5% by weight, a mean molecular weight of more than 400, and is capable of assuming a uniform molten state at a temperature range of from 320 to 480° C, and showing the melt viscosity of higher than 0.4 poise but not exceeding 700 poises, and is anisotropic to the extent that an isotropic portion thereof can hardly be recognized with a polarization microscope examination on a polished surface thereof.
Such raw material pitch of high anisotropy is obtained by subjecting organic compounds of highly aromatic structure as the principal constituent to heat treatment or chemical treatments.
In the following, detailed explanations will be given as to the method of obtaining the pitch exhibiting such high anisotropy.
Generally speaking, according to the present inventors, it has been found out that the abovementioned pitch of high anisotropy can be obtained by subjecting an organic substance to heat-treatment under specific conditions which vary with the chemical composition of the organic substance. For example, when the organic substance is a highly condensed polycyclic compound having seven rings or more and having large flatness in the molecular structure as a main component, it is heated at a temperation of 380° to 600° C for 30 to 600 minutes, preferably at a temperature of 450° to 600° C for 30 to 90 minutes, in a non-oxidizing atmosphere. On the other hand, when the organic substance is a condensed polycyclic compound having less than seven rings as a main component, it is heattreated with two steps, namely it is heated to 300° to 500° C as is described in U.S. Pat. No. Re 27794 as the first step and then heated to 380° to 450° C for 60 - 300 minutes as the second step, the both steps being carried out in a non-oxidizing atmosphere. These condensed polycyclic compounds are not necessarily pure products, but they may be a mixture of two or more such compounds, or those such as pitches.
In practice, when a compound containing therein, as the basic compound and skeleton, a condensed polycyclic structure having not less than seven rings, and, in some cases, substituent groups such as methyl group, amino group, and so forth in certain numbers, and quinone-type oxygen as well is heated to a temperature immediately before coking, the compound generally exhibits a state, in which the molecular structures become planar and parallel each other due to the condensed polycyclic structures of the compoundand the polycondensation having taken place among the condensed polycyclic structures.
According to the present inventors, 1,2,3,4,5,6,7,8-tetrabenzanthracene belonging to this kind of condensed polycyclic compounds posess the melting point of 428° C and can be made a spinnable anisotropic pitch substance by the heat-treatment at a temperature range of from 460° C to 470° C. Also, other substances such as phenanthrene, crysene, pyrene, coronene, perylene, benzoperylene, or a mixture thereof have been found to be converted to the pitch substances showing low viscosity by subjecting the same to the two-step heat-treatment. In this case, addition to the mixture compounds of the Lewis acid catalyst such as AlCl 3 , FeCl 3 , and so on, which is capable of forming π-type complex compound with such compounds, would, in some occasion, effectively function even at a temperature of lower than 300° C at the first step and then at a temperature of 380° to 450° C at the second step.
Also, black pitch obtained by heating a polycyclic compound such as dibenzo-triptycene (hereinafter abbreviated as "DBT") having high aromaticity, but not having the planar molecular structure, at a temperature of 350° C for 3 hours in a nitrogen atmosphere, thereafter, further heating the same to a temperature of 450° C for 1 hour has also been clearly observed to have anisotropy under a polarization microscope. ##STR1## The pitch exhibited a viscosity of 30 poises at the elevated temperature of 480° C, had the carbon content of 95.2%, hence the pitch is sufficiently useful as the raw material pitch for the purpose of the present invention.
Further, the substance having fluidity even at a temperature of 400° C and above obtained by subjecting resinous pitch or tar obtained by heat-treating crude petroleum oil or its tractionated components at a temperature of from 700° C to 2,000° C for a cracking time of from 1/1,000 to 1/10 second to heating at a temperature of 250 to 550° C for 1 to 300 minutes and distilling off rather volatile matters during the heating, and then by subjecting the material to the second heating at a temperature of 380° to 450° C for 60 to 300 minutes in which a procedure of removing fine solid particles by filtration is included, has also been verified to be the anisotropic pitch.
In the case of heating tetrabenzo (a,c,h,j)-phenazine, a pitch which is mixture of the dimer and the trimer is produced. Yet, the pitch has sufficient fusibility and melt-viscosity that enable shaping of the articles, and has been observed to have anisotropy under a polarization microscope. Examples of such substance can be recognized in some sorts of dyestuff such as "Threne Yellow 3RT", "Threne Gold Orange 3G", "Indanthrene Brown BR", and "Threne Red RK", all of which are the manufacture of Mitsui Kagaku Kabushiki Kaisha, Japan, and can be identified by the principal constituent of: ##STR2##
When any one or a mixture of the afore-described anisotropic pitch substances is used for shaping carbon articles, those which have been cooled to solidify from its molten state with the melt viscosity of less than 700 poises scarcely show isotropic portion, when observed by a polarization microscope. Further, when these substances are shaped, for instance, into fibers, and then the fibers are observed through the polarization microscope and X-ray diffraction along the polished surface of the fibers in parallel with the axial direction of the fibers, there can be recognized orientation of the planar molecules in the axial direction of the fibers. When the substance is shaped into a film, the same orientation can also be recognized on the polished surface along the plane.
The fibers made from aforementioned anisotropic pitch, when subjected to carbonization or graphitization, whether or not they are infusibilized, have been verified by X-ray observation to have orientation as high as that of the so-called high modulus carbon fibers which were subjected to the orientation-elongation at a graphitization stage.
The modulus of elasticity of the shaped articles from these substances is also improved in comparison with the shaped articles obtained from the conventional pitch material. That is, with the substances of the present invention, the carbon shaped articles having the Young's modulus of more than 1,400 tons/cm 2 are found producible. It is now clear that extremely unique effect can be obtained by the use of this kind of pitch exhibiting the anisotropy.
In summary of the foregoing explanations, there can be present carbon precursors having stable fluidity with the viscosity of from 0.4 to 700 poises at a temperature below the thermal decomposition temperature as seen in a few instances as already stated in the foregoing, and, at the same time, exhibiting anisotropy, which can be recognized by observation through the polarization microscope after cooling of the substance. Use of such substances as the raw material is the fundamental concept of the present invention. Such raw material is shaped into fibers or film by the ordinary methods. When manufacturing the carbon fibers, melt-spinning method is advantageous, and other methods such as extrusion, compression, centrifugal method, spray, and the like methods can all be used effectively. In the case of the film forming, the casting process which is generally practiced is employed.
The infusibilization treatment after shaping as is the case with the pitch fibers is carried out in an oxidizing atmosphere such as ozone, oxygen, oxides of nitrogen, halogens, and sulfur trioxides (SO 3 ), or an atmosphere containing therein one or more kinds of these gases, or in sulfur vapor. Contact-treatment of the pitch fibers after the oxidation treatment with ammonia gas not only accelerates the infusibilization, but also improves the carbonization yield and the mechanical strength of the resulting carbon fibers. It is also recognized that, by this treatment, the molecular orientation of the fibers at the temperature of from 700° to 1,500° C, for example, or at the stage of carbonaceous structure from the crystallographic standpoint, is strengthened. Such strengthening effect can also be clearly recognized at the stage of the heat-treatment higher than 1,500° C, wherein the impairment in the crystallinity and molecular orientation of the shaped products subjected to the oxidation-treatment alone can be safeguarded by this ammonia treatment. Since the raw material used in the present invention is generally of a high softening point and large heat stability, the infusibilization treatment can be done under a stronger conditions than in the case of the conventional pitch fibers. It is generally practiced within a few hours at a temperature between a normal temperature and a temperature at which the object to be treated causes no softening and deforming. The shaped body which has completed the infusibilization is calcined in a non-oxidizing atmosphere to be carbonized or graphitized.
The raw material of the present invention, as has been described in the foregoing, not only is desirable for manufacturing carbon fibers of high anisotropy and improved modulus of elasticity, but also enables production of carbonaceous or graphitic films having high flexibility. When films are formed from the heretofore known isotropic pitch material and subjected to carbonization or graphitization treatment, only carbonaceous film similar to thin glass film and having poor flexibility could only be obtained. However, according to the present invention, highly flexible carbonaceous or graphitic films could be produced by thinly pouring the abovementioned raw material in molten state onto a polished surface of a metal plate, silica plate, and silicon or ceramic plate, and then calcining the same under heat in a non-oxidizing atmosphere without applying any tension thereto. In this case, the infusibilization treatment prior to the calcination in the non-oxidizing atmosphere is not always necessary. The reasons for this is that the shaped body is held on the substrate and is protected from deformation or fusion due to heating. High flexibility of the film thus obtained is due to the fact that the planes of the condensed rings of the substance orientate along the plane direction at the time of film forming, the basic structure thereof is succeeded by carbonaceous or graphitic films after the calcination.
PREFERRED EMBODIMENTS
In order to enable those skilled in the art to reduce the present invention into practice, the following actual examples are presented. It should, however, be noted that these examples are merely illustrative, and that changes and modifications may be made within the spirit and scope of the present invention as set forth in the appended claims.
EXAMPLE 1
1 g of phenanthrene was added to 10 g of crysene, and the mixture was sealed in an glass ampoule under a nitrogen atmosphere and was placed in an autoclave. The autoclave was held in an electric furnace for 3 hours which temperature had been maintained at 500 at 530° C, so as to keep the mixture at a temperature of around 480° C for 75 to 90 minutes. The resulting mixture was filtered with stainless steel net at a temperature of 420° C and the filterate was further kept at the same temperature for 90 minutes, both procedures being conducted under a nitrogen atmosphere. The total time for keeping the mixture at 420° C was around 2 hours. This substance, when observed its polished surface after cooling through a polarization microscope, showed orientation to such an extent that isotropic portion could hardly be recognized. As the result of the elementary analyses, ultra-violet ray spectrum, infrared ray spectrum, and X-ray analyses, it was verified to be a pitch having condensed polycyclic aromatic structure containing 10 to 11 aromatic rings. The pitch also indicated its carbon content of 96.5%, means molecular weight of 450, viscosity of 100 poises at 350° C, and high anisotropy.
This substance was melt-spun at 350° C through nozzles of 0.5 mm in diameter in accordance with the extrusion spinning method, whereby fibers of about 17 microns in diameter were formed. By the abovementioned observation methods, the fibers were verified to have high molecular orientation in the axial direction of the fibers. The fibers thus formed were made about 50 cm long and hung within a heating furnace without applying any external load thereto for the oxidation treatment in air containing 10% by volume of NO 2 at a temperature of 150 to 200° C for 5 hours, and subsequently in air alone of an elevated temperature of 300° C for 2 hours, thereby to infusibilize the fibers. Next, when the article was heat-treated in a nitrogen atmosphere first to a temperature of 1,000° C at the rise rate of 5° C/min., and then to a temperature of 2,800° C at the rise rate of 10°-20° C/min., there was finally obtained graphite fibers which exhibited as the result of the X-ray observation molecular orientation to such an extent that 80% of the plane of the condensed rings within the range of ± 10° from the axial direction of the fibers. The carbonization yield of the fibers after the above heat-treatment was 95%, which was found to be a value higher by 80 by 90% than in the case of carbon fibers obtained from the ordinary pitch containing as its principal constituent the condensed polycyclic structure of about 3 to 5 rings.
The modulus of elasticity of the fibers was approximately 2,200 tons/cm 2 . In contrast thereto, the pitch fibers formed from ordinary pitch material in the same manner exhibited no orientation as the result of observation through a polarization microscope, and the elasticity modulus of the finally obtained graphite fibers was only approximately 450 tons/cm 2 .
EXAMPLE 2
5 g. of phenanthrene and 1 g. of aluminum chloride (AlCl 3 ) were added to 20 g. of benzopyrene, and the mixture was heated at 250° C to 270° C for 3 hours in an autoclave of nitrogen atmosphere, thereafter the batch was washed with hydrochloric acid and then rinsed with water to remove AlCl 3 , and the resulting pitch was then heated at 400° to 420° C for 3 hours, whereby a pitch substance exhibiting a uniform molten state of 340° C to 350° C and the melt viscosity of approximately 150 poises was obtained. This pitch was found to have the carbon content of 96.0% and the molecular weight of 480. This pitch substance, when observed its polished surface after cooling through a polarization microscope, showed orientation to such an extent that isotropic portion could hardly be recognized. As the result of the elementary analyses, ultra-violet ray spectrum, infrared ray spectrum, and X-ray analyses, it was found to be a pitch having the condensed polycyclic structure of 9 to 12 rings in average and compounds in which average two units of the abovementioned condensed polycyclic structure were linked together with a single number of bridge.
This substance was melt-spun in the same manner as in Example 1 above to form fibers of about 19 microns in diameter. The fibrous article was verified to have high molecular orientation in the axial direction of the fiber. The fibers were subjected to infusibilization treatment in the same manner as in Example 1, thereafter they were heat-treated at 2,800° C to graphitize. The graphite fibers thus obtained exhibited molecular orientation to such an extent that about 83% of the plane of the condensed rings within ± 10° from the axial direction of the fibers. The carbonization yield of the fiber was 96% and its elasticity modulus was approximately 2,300 tons/cm 2 .
EXAMPLE 3
A pitch obtained by removing distillable components at 380° C/10 mm Hg or below by the distillation under reduced pressure of a tar substance produced by thermal cracking of crude petroleum oil (Seria origin) at 1,800° C for 4/1,000 second was melted to eliminate fine particles of non-melting components therein at 410° C, whereby pitch substance showing a uniform molten state at 350° C to 420° C and the melt-viscosity of about 350 poises. The pitch indicated the desired anisotropy, and had the carbon content of 96.5% and the mean molecular weight of 650. According to observation through a polarization microscope, this pitch was found to have perfect orientation, and, as the result of the elementary anaylses, X-ray analyses, infrared ray spectrum, and other measurements, it was further found to be an aromatic hydrocarbon compound containing 2.7% sulfur, in which two units of condensed polycyclic structure containing 7 to 9 rings are linked together by a single number of bridge, and less than one in average of methyl group along is contained in the unit structure.
This pitch was melt-spun at 400° C to 420° by using a rotary cylindrical spinning machine of 100 mm dia., 20 mm deep, and having 30 tiny holes of 0.3 mm each, at a rotational speed of about 800 rpm, whereby pitch fibers of about 15 microns in diameter was obtained. This pitch fiber was also recognized to have high molecular orientation in the axial direction through the polarization microscope. The X-ray observation also revealed high orientation. The carbonization yield of the fiber after the infusibilization and carbonization was 92% and its elasticity modulus was measured at 2,800 tons/cm 2 . The degree of orientation due to the X-ray analyses was 85% with L c 600A, L a 3/4 1,000A, and d 002 3.368A, measured by Gakushin method.
EXAMPLE 4
By heat-treating the crystals of tetrabenzo(a,c,h,j)-phenazine having the melting point of 485° C at 580° C to 590° C for 1 hour, a glossy, black substance was obtained. This substance showed the melting temperature of 300° C to 310° C, and the melt thereof exhibited good fluidity, the viscosity of which at 350° C was approximately 50 poises. The carbon content of this substance was 96.0%, and its mean molecular weight was 410. The polished surface of the substance after cooling, when observed through a polarization microscope, indicated high orientation to such an extent that not a trace of isotropic portion could be recognized therein. As the result of the elementary analyses, ultra-violet ray spectrum, infrared ray spectrum, and molecular weight measurement, it was verified that the substance was a new kind of high aromatic compound of the following formula. ##STR3##
This substance was melt-spun at 350° C to 370° C in the same manner as in Example 2, whereby long fibers of about 15 microns in diameter was obtained. Further, when the fibers were subjected to the infusibilization, carbonization and graphitization same as in Examples 1 and 2, high molecular orientation could be observed by X-ray. Also, the modulus of elasticity was as high as 3,200 tons/cm 2 .
This substance was also cast on a clean silica disc of 30 mm in diameter to form a thin film of 5 to 15 microns. The film was also recognized by the polarization microscope to have perfect anisotropy in the direction of the place as is the case with the fibers. When this film was heat-treated in an argon gas atmosphere upto a temperature of 1,000° C at the rise rate of 1° to 2° C/min., and then upto a temperature of 2,800° C at the rise rate of 5 to 20° C/min., it turned into a highly flexible film. The carbonization yield at that time was 91%.
When the film was measured by X-ray, it was verified that the distance between the strata was 3.370 A, the length of the ab planes was 350 A, and the lapping in the direction of the C axis was 330 A. In comparison with the film obtained from the ordinary pitch, the values of which are respectively 3.385 A, 180 to 200 A, and 140 to 160 A, measured by Gakushin method, the film of the present invention possesses high orientation. | In the production of carbon shaped articles such as fibers, films, etc. having high molecular orientation, anisotropy, strength, and modulus of elasticity through the steps of forming raw material pitch into desired shapes, infusibilization of the same followed by carbonization optionally graphitization, a raw material pitch having particular physical properties such as melt viscosity of 0.4 to 700 poises at a temperature range of 320° to 480° C, eminent structural anisotropy, and fluidity is used to produce such desired shaped product. | 3 |
FIELD OF THE INVENTION
[0001] The present invention relates to an acceleration sensor having a mass situated over a plane of a substrate.
BACKGROUND INFORMATION
[0002] Triaxial acceleration sensors, in particular triaxial micromechanical acceleration sensors, are needed for applications in entertainment and automotive electronics. A maximally compact design of the acceleration sensors is desired in those cases.
[0003] The basic principle of micromechanical acceleration sensors is that a seismic mass is movably supported with respect to stationary electrodes on a substrate with the aid of a suspension. The seismic mass and the stationary electrodes form one or more capacitors. A deflection of the seismic mass caused by an acceleration acting on the micromechanical acceleration sensor results in a change in the capacitances of these capacitors, which may be detected and represents a measure of the magnitude of the effective acceleration. To avoid zero deviations, capacitance changes are preferably evaluated differentially.
[0004] In the related art, triaxial acceleration sensors are implemented using three sensor cores which are independent of each other and have separate seismic masses, which are situated next to each other on a shared chip. This results in large space requirements and comparatively large acceleration sensors.
SUMMARY OF THE INVENTION
[0005] According to the present invention, an acceleration sensor includes a substrate and a first mass element, which is connected to the substrate in such a way that the first mass element is rotatable about an axis, the first mass element being connected to a second mass element in such a way that the second mass element is movable along a first direction parallel to the axis, and the first mass element being connected to a third mass element in such a way that the third mass element is movable along a second direction perpendicular to the axis. This acceleration sensor may be advantageously designed to be extremely compact.
[0006] The first mass element is preferably designed asymmetrically with respect to the axis. An acceleration acting perpendicularly to the substrate's plane thus causes the mass element to tilt about the axis, which improves its detectability.
[0007] In a preferred specific embodiment of the acceleration sensor, the substrate is a silicon substrate. A method compatible with conventional silicon processing may thus be used for manufacturing the acceleration sensor.
[0008] One embodiment of the acceleration sensor provides that at least one detection electrode, which is fixedly connected to the substrate and allows a rotation of the first mass element about the axis to be detected, is situated opposite to the first mass element. In a refinement of this specific embodiment, at least two detection electrodes are provided, the detection electrodes allowing a differential evaluation of a rotation of the first mass element about the axis. Zero deviations of the acceleration sensor may be suppressed due to the differential evaluation.
[0009] A detection electrode is preferably provided on each side of the axis, both detection electrodes being designed to be symmetrical to each other with respect to the axis. This symmetry provides advantages regarding the linearity and offset stability of the acceleration sensor.
[0010] In one embodiment of the acceleration sensor, the first mass element has a frame, the second mass element being connected to the frame via at least one bending spring which is extensible in the first direction. In another embodiment, the third mass element is connected to the frame via at least one bending spring which is extensible in the second direction. These embodiments make a very compact design of the acceleration sensor possible.
[0011] In a preferred specific embodiment, the second mass element has first finger electrodes, opposite to which first substrate electrodes fixedly connected to the substrate are situated, the first finger electrodes and substrate electrodes allowing a deflection of the second mass element in the first direction to be detected.
[0012] In another preferred specific embodiment, the third mass element has second finger electrodes, opposite to which second substrate electrodes fixedly connected to the substrate are situated, the second finger electrodes and substrate electrodes allowing a deflection of the third mass element in the second direction to be detected.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 shows a first specific embodiment of a triaxial acceleration sensor.
[0014] FIG. 2 shows a second specific embodiment of a triaxial acceleration sensor.
DETAILED DESCRIPTION
[0015] FIG. 1 shows a schematic representation of a first specific embodiment of an acceleration sensor 300 , which is situated in the z direction above a surface of a substrate 322 , lying in the x-y plane. Acceleration sensor 300 is suitable for detecting accelerations in all three spatial directions x, y, z. Acceleration sensor 300 is manufactured, for example, from a silicon substrate, as a micromechanical component.
[0016] Acceleration sensor 300 includes an external frame 313 , which is situated in the x-y plane. External frame 313 has a rectangular basic shape. The outer edges of external frame 313 are formed by a first frame part 316 , a second frame part 317 , a third frame part 318 , and a fourth frame part 319 . First frame part 316 and third frame part 318 are oriented parallel to the y axis. Second frame part 317 and fourth frame part 319 are oriented parallel to the x axis. The area enclosed by first, second, third, and fourth frame parts 316 , 317 , 318 , 319 is subdivided into three sections, adjacent in the x direction, by a fifth frame part 320 and a sixth frame part 321 , which are oriented parallel to the y axis. First frame part 316 is wider compared to third frame part 318 and forms an additional mass 303 .
[0017] A fixing point 301 , connected to the substrate, is situated in the central area section of the three area sections enclosed by external frame 313 , which runs between fifth frame part 320 , second frame part 317 , sixth frame part 321 , and fourth frame part 319 . Fixing point 301 is connected to external frame 313 via two z springs 308 oriented in the y direction. z springs 308 are designed as torsion springs. A first z spring 308 connects fixing point 301 to second frame part 307 . A second z spring 308 connects fixing point 301 to fourth frame part 319 . z springs 308 form an axis of rotation oriented in the y direction, about which external frame 313 may be tilted.
[0018] The second area section enclosed by external frame 313 has an essentially rectangular shape and is situated between first frame part 316 , second frame part 317 , fifth frame part 320 , and fourth frame part 319 . A first internal frame 304 , which represents a mass element and has an essentially rectangular basic shape, is situated within this area section. First internal frame 304 is connected to external frame 313 via two y springs 307 . The edge of first internal frame 304 , adjacent to second frame part 317 of external frame 313 , is connected to second frame part 317 via first y spring 307 . The edge of first internal frame 304 adjacent to fourth frame part 319 of external frame 313 is connected to fourth frame part 319 via second y spring 307 . Both y springs 307 have a meandering or S shape. y springs 307 are designed to be elastic in the y direction, but rigid in the x and z directions.
[0019] The third area section enclosed by external frame 313 has an essentially rectangular shape and is delimited by sixth frame part 321 , second frame part 317 , third frame part 318 , and fourth frame part 319 . This area section is essentially filled by a second internal frame 305 , which represents a mass element. Second internal frame 305 is connected to external frame 313 via two x springs 306 . The external edge of second internal frame 305 , adjacent to sixth frame part 321 of external frame 313 , is connected to sixth frame part 321 via first x spring 306 . The external edge of second internal frame 305 , adjacent to third frame part 318 of external frame 313 , is connected to third frame part 318 via second x spring 306 . x springs 306 are designed as meandering or S-shaped bar springs and are elastic in the x direction, but rigid in the y and z directions.
[0020] First internal frame 304 is subdivided into three rectangular area sections adjacent to each other in the x direction. The central area section of first internal frame 304 has a flat design and is situated in the z direction above a first z electrode 311 , fixedly connected to the substrate. First z electrode 311 has essentially the same dimension in the x and y directions as the central area section of first internal frame 304 . The central area section of first internal frame 304 and first z electrode 311 form a capacitor, whose capacitance is a function of the distance between the central area section of first internal frame 304 and first z electrode 311 .
[0021] The area elements of first internal frame 304 situated on both sides of the central area section of first internal frame 304 are designed as a grid having grid bars running in the x direction and forming a plurality of y electrode fingers 315 . y electrode fingers 315 are situated in the z direction above y substrate electrodes 310 , fixedly connected to the substrate. y electrode fingers 315 and y substrate electrodes 310 form a capacitor, whose capacitance is a function of the distance between y electrode fingers 315 and y substrate electrodes 310 .
[0022] The area covered by second internal frame 305 is subdivided into three rectangular area sections having approximately the same size, adjacent to each other in the y direction. The central area section of second internal frame 305 has a flat design and is situated in the z direction above a second z electrode 312 , fixedly connected to the substrate. Second z electrode 312 has essentially the same dimension in the x and y directions as the central area section of second internal frame 305 . The central area section of second internal frame 305 and second z electrode 312 form a capacitor, whose capacitance is a function of the distance between the central area section of second internal frame 305 and second z electrode 312 .
[0023] The area sections of second internal frame 305 , situated on both sides of the central area section of second internal frame 305 , are designed as a grid having grid bars running in the y direction and forming a plurality of x electrode fingers 314 . x electrode fingers 314 are situated in the z direction above x substrate electrodes 309 , which are fixedly connected to the substrate. x electrode fingers 314 and x substrate electrodes 309 form capacitors, whose capacitance is a function of the distance between x electrode fingers 314 and x substrate electrodes 309 .
[0024] External frame 313 , y springs 307 , first internal frame 304 , x springs 306 , and second internal frame 305 together form a rocker mass 302 , or a mass element. Due to the additional mass 303 formed by first frame part 316 of external frame 313 , rocker mass 302 has an asymmetric design with respect to the axis of rotation formed by z springs 308 . On one side of the axis of rotation formed by z springs 308 , rocker mass 302 has a mass which is greater than that on the other side of the axis of rotation by additional mass 303 .
[0025] An acceleration acting on acceleration sensor 300 in the x direction exerts a force acting on second internal frame 305 in the x direction. It results in an elastic deformation of x springs 306 and in a deflection of second internal frame 305 relative to external frame 313 . The distance between x electrode fingers 314 and x substrate electrodes 309 changes due to the deflection of second internal frame 305 , which changes the capacitance of the capacitor formed thereby. This may be detected by an electronic evaluation system connected to acceleration sensor 300 . The capacitance change represents a measure of the magnitude of the acceleration acting on acceleration sensor 300 .
[0026] An acceleration acting in the x direction also generates forces acting on external frame 313 and first internal frame 304 in the x direction. However, since y springs 307 and z springs 308 have a rigid design in the x direction, these forces do not cause external frame 313 or first internal frame 304 to deflect.
[0027] An acceleration acting on acceleration sensor 300 in the y direction results in a force acting on first internal frame 304 in the y direction and deflects it by an elastic deformation of y springs 307 against external frame 313 . The distance thus changed between y electrode fingers 315 and y substrate electrodes 310 changes the capacitance of the capacitor formed thereby, which may be detected and quantified by an electronic evaluation system connected to acceleration sensor 300 . The capacitance change is a measure of the magnitude of the acceleration acting in the y direction. Since x springs 306 and z springs 308 are not deformable in the y direction, second internal frame 305 and external frame 313 are not deflected.
[0028] An acceleration acting on acceleration sensor 300 in the z direction generates a force acting on rocker mass 302 in the z direction, which, due to additional mass 303 on one side of the axis of rotation formed by z springs 308 , results in a torque acting on rocker mass 302 and in a tilt of rocker mass 302 about the axis of rotation formed by z springs 308 . The greater the acceleration acting on rocker mass 302 , the greater the tilt angle. Due to the tilting of rocker mass 302 , the distances between first internal frame 304 and first z electrode 311 , and between second internal frame 305 and second z electrode 312 , are changed. Depending on the direction of tilt of rocker mass 302 , one of the distances increases, while the other one decreases. This changes the capacitances of the capacitors formed by first internal frame 304 and first z electrode 311 , or second internal frame 305 and second z electrode 312 . This is detected with the aid of an electronic evaluation system. The changes in opposite directions of the two capacitances allow a differential evaluation of the capacitance changes, which provides a linearized relationship between output signal and input acceleration.
[0029] Since y springs 307 and x springs 306 are not deformable in the z direction, first internal frame 304 and second internal frame 305 are not deflected with respect to external frame 313 .
[0030] FIG. 2 shows a second specific embodiment of the present invention based on an acceleration sensor 400 . Acceleration sensor 400 is situated in a z direction above a substrate 422 , situated in an x-y plane. Substrate 422 may be a silicon substrate, for example. Acceleration sensor 400 may be manufactured, for example, using semiconductor microstructuring methods.
[0031] Acceleration sensor 400 has an external frame 413 having a first frame part 416 , a second frame part 417 , a third frame part 418 , and a fourth frame part 419 , which are situated as lateral edges of a rectangle. First frame part 416 and third frame part 418 are oriented parallel to the y axis. Second frame part 417 and fourth frame part 419 are oriented parallel to the x axis. First frame part 416 is designed to be wider than third frame part 418 and thus represents an additional mass 403 .
[0032] The area enclosed by external frame 413 is subdivided into three area sections adjacent in the x direction by a fifth frame part 420 and a sixth frame part 421 , which run parallel to the y axis and are situated between second frame part 417 and fourth frame part 419 . A fixing point 401 , fixedly connected to the substrate, is situated in the central area section delimited by fifth frame part 420 , second frame part 417 , sixth frame part 421 , and fourth frame part 419 . External frame 413 is connected to fixing point 401 via two z springs 408 oriented in the y direction. First z spring 408 extends from fixing point 401 to second frame part 413 . Second z spring 408 extends from fixing point 401 to fourth frame part 419 . z springs 408 are designed as bar-shaped torsion springs and form an axis of rotation which is parallel to the y axis, and about which external frame 413 may be tilted against the substrate situated in the x-y plane.
[0033] The area section enclosed by first frame part 416 , second frame part 417 , fifth frame part 420 , and fourth frame part 419 is essentially filled by a rectangular first internal frame 404 , which represents a mass element. A lateral edge of first internal frame 404 , parallel to second frame part 417 , is connected to second frame part 417 via a first y spring 407 . The lateral edge of first internal frame 404 adjacent to fourth frame part 419 is connected to fourth frame part 419 via a second y spring 407 . y springs 407 are elastically deformable in the y direction, but are rigid in the x and z directions. y springs 407 are designed as meandering or S-shaped bar springs. y springs 407 allow first internal frame 404 to deflect against external frame 413 .
[0034] The area section delimited by sixth frame part 421 , second frame part 417 , third frame part 418 , and fourth frame part 419 is essentially filled by a second internal frame 405 , which represents a mass element and has a basic rectangular shape. The external edge of second internal frame 405 , adjacent to sixth frame part 421 , is connected to sixth frame part 421 via a first x spring 406 . The external edge of second internal frame 405 , adjacent to third frame part 418 , is connected to third frame part 418 via a second x spring 406 . x springs 406 are designed as meandering or S-shaped bar springs and are elastically deformable in the x direction, but are rigid in the y and z directions. x springs 406 allow second internal frame 405 to deflect against external frame 413 .
[0035] First internal frame 404 has a central rectangular area which has a flat design and is situated in the z direction above a first z electrode 411 , fixedly connected to the substrate. The flat area of first internal frame 404 and first z electrode 411 together form a capacitor, whose capacitance is a function of the distance between first internal frame 404 and first z electrode 411 . The area of first internal frame 404 surrounding the central area of first internal frame 404 is formed by two grid sections which are adjacent in the x direction. The grid sections of first internal frame 404 have grid bars oriented in the x direction and forming y electrode fingers 415 , which are situated in the z direction above a plurality of y substrate electrodes 410 , fixedly connected to the substrate. y electrode fingers 415 , oriented in the x direction, extend from the edge of frame 404 to the central, flat area of first internal frame 404 , i.e., to a bar of frame 404 , separating the two grid sections. y electrode fingers 415 , adjacent to the central, flat area of first internal frame 404 , are thus shorter than the two y electrode fingers 415 , adjacent to the bar of frame 404 separating the two grid sections. y electrode fingers 415 and y substrate electrodes 410 form capacitors, whose capacitances are a function of the distance between y electrode fingers 415 and y substrate electrodes 410 .
[0036] Second internal frame 405 has a central, flat, rectangular section which is situated in the z direction above a z electrode 412 , fixedly connected to the substrate. The flat section of second internal frame 405 and second z electrode 412 form a capacitor, whose capacitance is a function of the distance between the flat section of second internal frame 405 and second z electrode 412 . The flat section of second internal frame 405 is enclosed by two grid sections of second internal frame 405 , which are adjacent in the y direction and have a plurality of grid bars oriented in the y direction, forming a plurality of x electrode fingers 414 . x electrode fingers 414 , oriented in the y direction, extend from the edge of frame 405 to the central, flat area of second internal frame 405 , i.e., to a bar of frame 405 , separating the two grid sections. x electrode fingers 414 , which are adjacent to the central, flat area of second internal frame 405 , are thus shorter than x electrode fingers 414 , adjacent to the bar of frame 405 , separating the two grid sections. x electrode fingers 414 are situated in the z direction above a plurality of x substrate electrodes 409 , fixedly connected to the substrate and, together with these, form capacitors, whose capacitance is a function of the distance between x electrode fingers 414 and x substrate electrodes 409 .
[0037] External frame 413 , y springs 407 , first internal frame 404 , x springs 406 and second internal frame 405 together form a rocker mass 402 , or a mass element. Rocker mass 402 is asymmetrical with respect to the axis formed by z springs 408 . The part of rocker mass 402 enclosing first frame part 416 has additional mass 403 with respect to the other part of rocker mass 402 .
[0038] An acceleration acting on acceleration sensor 400 in the x direction results in a force acting on second internal frame 405 in the x direction and deflects it against external frame 413 while x springs 406 are elastically deformed. This changes the distance between x electrode fingers 414 and x substrate electrodes 409 , which changes the capacitance of the capacitors formed thereby. The greater the acceleration acting on acceleration sensor 400 , the greater the deflection and thus the capacitance changes. The capacitance changes may be detected with the aid of an electronic evaluation system. y springs 407 and z springs 408 are rigid in the x direction; therefore, an acceleration acting in the x direction does not cause external frame 413 or first internal frame 404 to deflect.
[0039] An acceleration acting on acceleration sensor 400 in the y direction results in a force acting on first internal frame 404 in the y direction and deflects it against external frame 413 while y springs 407 are elastically deformed. This changes the distance between y electrode fingers 415 and y substrate electrodes 410 , which results in a capacitance change of the capacitors formed by y electrode fingers 415 and y substrate electrodes 410 , which may be detected by an electronic evaluation system. The greater the deflection and thus the capacitance changes are, the greater the acceleration acting on the acceleration sensor. x springs 406 and z springs 408 are rigid in the y direction; therefore, there is no deflection of second internal frame 405 or of external frame 413 .
[0040] An acceleration acting on acceleration sensor 400 in the z direction generates a force acting on rocker mass 402 in the z direction and, due to additional mass 403 , in a torque causing rocker mass 402 to tilt about the axis of rotation formed by z springs 408 . The greater the force acting on acceleration sensor 400 , the greater the angle of tilt. Due to the tilting of rocker mass 402 , the distances between first internal frame 404 and first z electrode 411 , and between second internal frame 405 and second z electrode 412 are changed, which results in a capacitance change, detectable by an electronic evaluation system, of the capacitors formed by first internal frame 404 and first z electrode 411 , and second internal frame 405 and second z electrode 412 . Since the capacitance changes have opposite signs, a differential evaluation is possible, thereby suppressing the zero deviations. Because x springs 406 and y springs 407 are rigid in the z direction, no deflection of first internal frame 404 or of second internal frame 405 occurs against external frame 413 .
[0041] Acceleration sensor 400 shown in FIG. 2 has the advantage over acceleration sensor 300 shown in FIG. 1 that the flat central sections of first internal frame 404 and of second internal frame 405 , and first z electrode 411 and second z electrode 412 are symmetrical with respect to each other, which offers advantages regarding linearity and offset stability. On the other hand, in acceleration sensor 300 , the surface area of first internal frame 304 and second internal frame 305 is made better use of, which increases the basic capacitance and thus the sensitivity of the capacitors provided for detecting z accelerations.
[0042] x substrate electrodes 309 and 409 and y substrate electrodes 310 and 410 of acceleration sensors 300 , 400 shown in FIGS. 1 and 2 may also be optionally designed in such a way that deflections of first internal frames 304 , 404 and second internal frames 305 , 405 caused by accelerations result in capacitance changes, which may be evaluated differentially. The technical details are known to those skilled in the art from the related art. | An acceleration sensor includes a substrate and a first mass element, which is connected to the substrate in such a way that the first mass element is rotatable about an axis, the first mass element being connected to a second mass element in such a way that the second mass element is movable along a first direction parallel to the axis, and the first mass element being connected to a third mass element in such a way that the third mass element is movable along a second direction perpendicular to the axis. | 6 |
STATUS OF RELATED APPLICATIONS
This application is a continuation-in-part of U.S. Ser. No. 14/336,036, filed on Jul. 21, 2014, the contents hereby incorporated by reference as if set forth in its entirety.
FIELD OF THE INVENTION
The present invention relates to new chemical entities and the incorporation and use of the new chemical entities as fragrance materials.
BACKGROUND OF THE INVENTION
There is an ongoing need in the fragrance industry to provide new chemicals to give perfumers and other persons the ability to create new fragrances for perfumes, colognes and personal care products. Those with skill in the art appreciate how small differences in chemical structures can result in unexpected and significant differences in odor, notes and characteristics of molecules. These variations allow perfumers and other persons to apply new compounds in creating new fragrances.
SUMMARY OF THE INVENTION
The present invention provides novel chemicals and their unexpected advantageous use in improving, enhancing or modifying the fragrance of perfumes, colognes, toilet waters, cosmetic products, personal care products, fabric care products, cleaning products, air fresheners, and the like.
One embodiment of the present invention is directed to novel cyclohexanol compounds represented by the following formula:
isomers or mixtures of isomers thereof,
wherein one of R and R′ represents hydrogen with the other representing a C 1 -C 6 linear, branched, or cyclic alkyl, alkenyl, alkynyl or aromatic group; and
one of the dashed lines represents a carbon-carbon single bond with the other representing a carbon-carbon double bond.
Another embodiment of the present invention is directed to the use of the compounds provided above as fragrance materials in perfumes, colognes, toilet waters, personal products, fabric care products, and the like.
Another embodiment of the present invention is directed to a fragrance composition comprising the compounds provided above.
Another embodiment of the present invention is directed to a fragrance product comprising the compounds provided above.
Another embodiment of the present invention is directed to a method of improving, enhancing or modifying a fragrance formulation by incorporating an olfactory acceptable amount of the compounds provided above.
These and other embodiments of the present invention will be apparent by reading the following specification.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of the present invention may also be represented by ethylidene-substituted cyclohexanols of Formula II and vinyl-substituted cyclohexanols of Formula III in the following:
isomers or mixtures of isomers thereof,
wherein R and R′ are defined as above.
The compounds of the present invention may be further represented by cyclohexanols of Formula IV in the following:
isomers or mixtures of isomers thereof,
wherein one of R 1 and R 2 represents hydrogen with the other representing a C 1 -C 6 linear, branched or cyclic alkyl group; and
one of the dashed lines represents a carbon-carbon single bond with the other representing a carbon-carbon double bond.
The cyclohexanol compounds of Formula II, III and IV may be further represented by Formula V and Formula VI in the following:
isomers or mixtures of isomers thereof,
wherein one of R 1 and R 2 are defined as above.
The novel cyclohexanols of the present invention are illustrated, for example, by following examples.
The compounds of the present invention were prepared with 3-vinyl-7-oxa-bicyclo[4.1.0]heptane according to the following reaction scheme, the details of which are specified in the Examples. Materials and catalysts were purchased from Aldrich Chemical Company unless noted otherwise.
wherein RhCl 3 represents Rhodium(III) chloride; and
R and R′ are defined as above.
Those with skill in the art will recognize that some of the compounds of the present invention have a number of chiral centers, thereby providing numerous isomers of the claimed compounds. It is intended herein that the compounds described herein include isomeric mixtures of such compounds, as well as those isomers that may be separated using techniques known to those having skill in the art. Suitable techniques include chromatography such as high performance liquid chromatography, referred to as HPLC, particularly silica gel chromatograph, and gas chromatography trapping known as GC trapping. Yet, commercial versions of such products are mostly offered as mixtures.
The compounds of the present invention, for example, possess strong and complex sweet, spicy, woody and vanilla notes.
The use of the compounds of the present invention is widely applicable in current perfumery products, including the preparation of perfumes and colognes, the perfuming of personal care products such as soaps, shower gels, and hair care products, fabric care products as well as air fresheners and cosmetic preparations. These compounds can also be used to perfume cleaning agents, such as, but not limited to detergents, dishwashing materials, scrubbing compositions, window cleaners and the like. In these preparations, the compounds of the present invention can be used alone or in combination with other perfuming compositions, solvents, adjuvants and the like. The nature and variety of the other ingredients that can also be employed are known to those with skill in the art.
Many types of fragrances can be employed in the present invention, the only limitation being the compatibility with the other components being employed. Suitable fragrances include but are not limited to fruits such as almond, apple, cherry, grape, pear, pineapple, orange, strawberry, raspberry; musk; and flower scents such as lavender-like, rose-like, iris-like, carnation-like. Other pleasant scents include herbal and woodland scents derived from pine, spruce and other forest smells. Fragrances may also be derived from various oils, such as essential oils, or from plant materials such as peppermint, spearmint and the like.
A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891, the contents of which are incorporated by reference as if set forth in its entirety. Another source of suitable fragrances is found in Perfumes, Cosmetics and Soaps , Second Edition, edited by W. A. Poucher, 1959. Among the fragrances provided in this treatise are acacia, cassie, chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle, hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cut hay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose, vanilla, violet, wallflower, and the like.
The term “improving” in the phrase “improving, enhancing or modifying a fragrance formulation” is understood to mean raising the fragrance formulation to a more desirable character. The term “enhancing” is understood to mean making the fragrance formulation greater in effectiveness or providing the fragrance formulation with an improved character. The term “modifying” is understood to mean providing the fragrance formulation with a change in character.
The terms “fragrance formulation”, “fragrance composition”, and “perfume composition” are understood to mean the same and refer to a formulation that is intended for providing a fragrance character to a perfume, a cologne, toilet water, a personal product, a fabric care product, and the like. The fragrance formulation of the present invention is a composition comprising a compound of the present invention.
Olfactory acceptable amount is understood to mean the amount of a compound in a perfume composition. The compound will contribute its particular olfactory characteristics, but the olfactory effect of the perfume composition will be the sum of the effects of each of the perfumes or fragrance ingredients. Thus the compounds of the invention can be used to alter the aroma characteristics of a perfume composition, or by modifying the olfactory reaction contributed by another ingredient in the composition. The amount will vary depending on many factors including other ingredients, their relative amounts and the effect that is desired.
The amount of the compounds of the present invention employed in a fragrance formulation varies from about 0.005 to about 70 weight percent, preferably from 0.005 to about 50 weight percent, more preferably from about 0.5 to about 25 weight percent, and even more preferably from about 1 to about 10 weight percent. Those with skill in the art will be able to employ the desired amount to provide desired fragrance effect and intensity. In addition to the compounds of the present invention, other materials can also be used in conjunction with the fragrance formulation. Well known materials such as surfactants, emulsifiers, polymers to encapsulate the fragrance can also be employed without departing from the scope of the present invention.
In addition, the compounds of the present invention are also surprisingly found to provide superior ingredient performance and possess unexpected advantages in malodor counteracting applications such as body perspiration, environmental odor such as mold and mildew, bathroom, and etc. The compounds of the present invention substantially eliminate the perception of malodors and/or prevent the formation of such malodors, thus, can be utilized with a vast number of functional products.
Examples of the functional products are provided herein to illustrate the various aspects of the present invention. However, they do not intend to limit the scope of the present invention. The functional products may include, for example, a conventional room freshener (or deodorant) composition such as room freshener sprays, an aerosol or other spray, fragrance diffusers, a wick or other liquid system, or a solid, for instance candles or a wax base as in pomanders and plastics, powders as in sachets or dry sprays or gels, as in solid gel sticks, clothes deodorants as applied by washing machine applications such as in detergents, powders, liquids, whiteners or fabric softeners, fabric refreshers, linen sprays, closet blocks, closet aerosol sprays, or clothes storage areas or in dry cleaning to overcome residual solvent notes on clothes, bathroom accessories such as paper towels, bathroom tissues, sanitary napkins, towellets, disposable wash cloths, disposable diapers, and diaper pail deodorants, cleansers such as disinfectants and toilet bowl cleaners, cosmetic products such as antiperspirant and deodorants, general body deodorants in the form of powders, aerosols, liquids or solid, or hair care products such as hair sprays, conditioners, rinses, hair colors and dyes, permanent waves, depilatories, hair straighteners, hair groom applications such as pomade, creams and lotions, medicated hair care products containing such ingredients as selenium sulphide, coal tar or salicylates, or shampoos, or foot care products such as foot powders, liquids or colognes, after shaves and body lotions, or soaps and synthetic detergents such as bars, liquids, foams or powders, odor control such as during manufacturing processes, such as in the textile finishing industry and the printing industry (inks and paper), effluent control such as in processes involved in pulping, stock yard and meat processings, sewage treatment, garbage bags, or garbage disposal, or in product odor control as in textile finished goods, rubber finished goods or car fresheners, agricultural and pet care products such as dog and hen house effluents and domestic animal and pet care products such as deodorants, shampoo or cleaning agents, or animal litter material and in large scale closed air systems such as auditoria, and subways and transport systems.
Thus, it will be seen that the composition of the invention is usually one in which the malodor counteractant is present together with a carrier by means of which or from which the malodor counteractant can be introduced into air space wherein the malodor is present, or a substrate on which the malodor has deposited. For example, the carrier can be an aerosol propellant such as a chlorofluoro-methane, or a solid such as a wax, plastics material, rubber, inert powder or gel. In a wick-type air freshener, the carrier is a substantially odorless liquid of low volatility. In several applications, a composition of the invention contains a surface active agent or a disinfectant, while in others, the malodor counteractant is present on a fibrous substrate. In many compositions of the invention there is also present a fragrance component which imparts a fragrance to the composition. The fragrances stated above can all be employed.
Malodor counteracting effective amount is understood to mean the amount of the inventive malodor counteractant employed in an air space or a substrate such as a functional product that is organoleptically effective to abate a given malodor while reducing the combined intensity of the odor level, wherein the given malodor is present in air space or has deposited on a substrate. The exact amount of malodor counteractant agent employed may vary depending upon the type of malodor counteractant, the type of the carrier employed, and the level of malodor counteractancy desired. In general, the amount of malodor counteractant agent present is the ordinary dosage required to obtain the desired result. Such dosage is known to the skilled practitioner in the art. In a preferred embodiment, when used in conjunction with malodorous solid or liquid functional products, e.g., soap and detergent, the compounds of the present invention may be present in an amount ranging from about 0.005 to about 50 weight percent, preferably from about 0.01 to about 20 weight percent, more preferably from about 0.05 to about 10 weight percent and even more preferably from about 0.1 to about 5 weight percent. When used in an air space that is in conjunction with malodorous gaseous functional products, the compounds of the present invention may be present in an amount ranging from about 0.2 mg to about 2 g per cubic meter of air, more preferably from about 0.4 mg to about 0.8 g per cubic meter of air, more preferably from about 2 mg to about 0.4 g per cubic meter of air and even more preferably from about 4 mg to about 0.2 g per cubic meter of air.
The following are provided as specific embodiments of the present invention. Other modifications of this invention will be readily apparent to those skilled in the art. Such modifications are understood to be within the scope of this invention. The chemical materials used in the preparation of the compounds of the present invention are commercially available from Aldrich Chemical Company. As used herein all percentages are weight percent unless otherwise noted, ppm is understood to stand for parts per million, mol is understood to be mole, mmol is understood to be millimole, L is understood to be liter, mL is understood to be milliliter, Kg is understood to be kilogram and g be gram, psi is understood to be pound-force per square inch, and mmHg is understood to be millimeters (mm) of mercury (Hg). IFF as used in the examples is understood to mean International Flavors & Fragrances Inc., New York, N.Y., USA.
Example I
Preparation of 2-Propoxy-4-vinyl-cyclohexanol (Structure 29) and 2-Propoxy-5-vinyl-cyclohexanol (Structure 30)
A 5-L, 4-neck round bottom flask was fitted with a temperature probe, a glass stir shaft, a water condenser and an addition funnel Propanol (CH3CH2CH2OH) (1.4 Kg) and Amberlyst® 15 (15 g) were charged into the flask and brought to reflux. 3-Vinyl-7-oxa-bicyclo[4.1.0]heptane (476 g, 3.8 mol) was fed in over 1 hour. The reaction was aged for additional 6 hours and then cooled to room temperature. The reaction mixture was decanted to provide a mixture of 2-propoxy-4-vinyl-cyclohexanol (Structure 29) and 2-propoxy-5-vinyl-cyclohexanol (Structure 30) (1:1) (699 g).
1 H NMR (CDCl 3 , 400 MHz): 5.78-5.90 (m, 1H), 4.94-5.15 (m, 2H), 3.06-3.79 (m, 4H), 2.46-2.58 (m, 1H), 2.34-2.45 (m, 1H), 1.80-2.05 (m, 2H), 1.42-1.72 (m, 6H), 0.93 (t, J=7.4 Hz, 3H)
The isomeric mixture Structure 29 and 30 was described as having sweet, spicy and vanilla notes.
Example II
Preparation of (E)-4-Ethylidene-2-propoxy-cyclohexanol (Structure 17), (Z)-4-Ethylidene-2-propoxy-cyclohexanol (Structure 18), (E)-5-Ethylidene-2-propoxy-cyclohexanol (Structure 19) and (Z)-5-Ethylidene-2-propoxy-cyclohexanol (Structure 20)
The mixture of 2-propoxy-4-vinyl-cyclohexanol (Structure 29) and 2-propoxy-5-vinyl-cyclohexanol (Structure 30) (699 g) (prepared as above in Example I) and RhCl 3 (2.0 g, 9.6 mmol) were combined in a fresh 5-L, 4-neck round bottom flask fitted with a temperature probe, a glass stir shaft and a Dean-Stark trap. The reaction mixture was heated to reflux. About 600 mL propanol was removed via the Dean-Stark trap during the reaction. The reaction mixture was aged at reflux for additional 5 hours. Gas chromatography (GC) analysis was used to monitor the completion of the reaction. The reaction mixture was then cooled. Further distillation at a vapor temperature of 123° C. with a pressure of 2 mmHg provided the mixture of (E)-4-ethylidene-2-propoxy-cyclohexanol (Structure 17), (Z)-4-ethylidene-2-propoxy-cyclohexanol (Structure 18), (E)-5-ethylidene-2-propoxy-cyclohexanol (Structure 19) and (Z)-5-ethylidene-2-propoxy-cyclohexanol (Structure 20) (Structure 17:Structure 18:Structure 19:Structure 20=about 0.74:0.83:0.95:1.0) (575 g, 79% yield).
The mixture of (E)-4-ethylidene-2-propoxy-cyclohexanol (Structure 17), (Z)-4-ethylidene-2-propoxy-cyclohexanol (Structure 18), (E)-5-ethylidene-2-propoxy-cyclohexanol (Structure 19) and (Z)-5-ethylidene-2-propoxy-cyclohexanol has the following NMR spectral characteristics:
1 H NMR (CDCl 3 , 500 MHz): 5.14-5.34 ppm (m, 1H), 1.66-3.68 ppm (m, 10H), 1.52-1.66 ppm (m, 5H), 1.09-1.34 ppm (m, 1H), 0.88-1.02 ppm (m, 3H)
The isomeric mixture Structure 17, 18, 19 and 20 was described as having particularly desirable, strong and complex sweet, spicy, woody and vanilla notes.
(E)-4-Ethylidene-2-propoxy-cyclohexanol (Structure 17) has the following NMR spectral characteristics:
1 H NMR (CDCl3, 500 MHz): 5.22-5.30 ppm (m, 1H), 3.57-3.64 ppm (m, 1H), 3.51-3.57 ppm (m, 1H), 3.30-3.40 ppm (m, 2H), 2.92-3.03 ppm (m, 1H), 2.67 ppm (br, 1H), 2.47-2.64 ppm (m, 2H), 2.02-2.10 ppm (m, 1H), 1.86-1.94 ppm (m, 1H), 1.66-1.78 ppm (m, 1H), 1.56-1.66 ppm (m, 5H), 1.19-1.29 (m, 1H), 0.94 (t, 3H, J=7.41 Hz)
(E)-4-Ethylidene-2-propoxy-cyclohexanol was described as having spicy, clove-leaf, floral and medicinal notes.
(Z)-4-Ethylidene-2-propoxy-cyclohexanol (Structure 18) has the following NMR spectral characteristics:
1 H NMR (CDCl 3 , 500 MHz): 5.25-5.32 ppm (m, 1H), 3.62-3.70 ppm (m, 1H), 3.50-3.62 ppm (m, 1H), 3.31-3.43 ppm (m, 1H), 2.95-3.03 ppm (m, 2H), 2.66 ppm (br, 1H), 2.13-2.20 ppm (m, 1H), 1.98-2.08 ppm (m, 2H), 1.55-1.66 ppm (m, 6H), 1.23-1.34 ppm (m, 1H), 0.96 ppm (t, 3H, J=7.41 Hz)
(Z)-4-Ethylidene-2-propoxy-cyclohexanol was described as having spicy, clove-leaf and medicinal notes.
(E)-5-Ethylidene-2-propoxy-cyclohexanol (Structure 19) has the following NMR spectral characteristics:
1 H NMR (CDCl 3 , 500 MHz): 5.23-5.30 ppm (m, 1H), 3.56-3.64 ppm (m, 1H), 3.41-3.47 ppm (m, 1H), 3.33-3.39 ppm (m, 1H), 3.13-3.20 ppm (m, 1H), 2.58 ppm (br, 1H), 2.48-2.60 ppm (m, 2H), 2.02-2.10 ppm (m, 2H), 1.67-1.78 ppm (m, 1H), 1.55-1.67 ppm (m, 5H), 1.11-1.21 ppm (m, 1H), 0.94 ppm (t, 3H, J=7.41 Hz)
(E)-5-Ethylidene-2-propoxy-cyclohexanol was described as having balsamic, sweet, spicy and vanilla notes.
(Z)-5-Ethylidene-2-propoxy-cyclohexanol (Structure 20) has the following NMR spectral characteristics:
1 H NMR (CDCl 3 , 500 MHz): 5.25-5.36 ppm (m, 1H), 3.57-3.64 ppm (m, 1H), 3.32-3.43 ppm (m, 2H), 3.13-3.20 ppm (m, 1H), 2.86-2.93 ppm (m, 1H), 2.66 ppm (br, 1H), 2.17-2.23 ppm (m, 1H), 1.96-2.10 ppm (m, 2H), 1.76-1.84 ppm (m, 1H), 1.56-1.67 (m, 5H), 1.13-1.24 ppm (m, 1H), 0.94 ppm (t, 3H, J=7.41 Hz)
(Z)-5-Ethylidene-2-propoxy-cyclohexanol was described as having spicy, clove-leaf, medicinal and slight cooling herbal notes.
Example III
Following cyclohexanols were similarly prepared.
(E)-4-Ethylidene-2-methoxy-cyclohexanol (Structure 1), (Z)-4-Ethylidene-2-methoxy-cyclohexanol (Structure 2), (E)-5-Ethylidene-2-methoxy-cyclohexanol (Structure 3) and (Z)-5-Ethylidene-2-methoxy-cyclohexanol (Structure 4)
1 H NMR (CDCl 3 , 400 MHz): 5.15-5.43 (m, 1H), 3.32-3.62 (m, 4H), 1.94-3.14 (m, 6H), 1.67-1.94 (m, 1H), 1.48-1.67 (m, 3H), 1.08-1.37 (m, 1H)
The isomeric mixture of Structure 1, 2, 3 and 4 was described as having balsamic, sweet, spicy, fruity, fresh and minty notes.
(E)-4-Ethylidene-2-ethoxy-cyclohexanol (Structure 5), (Z)-4-Ethylidene-2-ethoxy-cyclohexanol (Structure 6), (E)-5-Ethylidene-2-ethoxy-cyclohexanol (Structure 7) and (Z)-5-Ethylidene-2-ethoxy-cyclohexanol (Structure 8)
1 H NMR (CDCl 3 , 400 MHz): 5.16-5.38 (m, 1H), 3.32-3.85 (m, 3H), 2.12-3.25 (m, 4H), 1.84-2.11 (m, 2H), 1.64-1.84 (m, 1H), 1.48-1.64 (m, 3H), 1.04-1.34 (m, 4H)
The isomeric mixture of Structure 5, 6, 7 and 8 was described as having strong and complex sweet, spicy, fruity, woody, clove-leaf, floral, green, smoky and leathery notes.
(E)-4-Ethylidene-2-isopropoxy-cyclohexanol (Structure 21), (Z)-4-Ethylidene-2-isopropoxy-cyclohexanol (Structure 22), (E)-5-Ethylidene-2-isopropoxy-cyclohexanol (Structure 23) and (Z)-5-Ethylidene-2-isopropoxy-cyclohexanol (Structure 24)
1 H NMR (CDCl 3 , 400 MHz): 5.18-5.33 (m, 1H), 3.65-3.85 (m, 1H), 2.96-3.57 (m, 2H), 1.87-2.95 (m, 5H), 1.63-1.87 (m, 1H), 1.50-1.63 (m, 3H), 1.07-1.36 (m, 7H)
The isomeric mixture of Structure 21, 22, 23 and 24 was described as having sweet, spicy, woody and vanilla notes.
2-Methoxy-4-vinyl-cyclohexanol (Structure 25) and 2-Methoxy-5-vinyl-cyclohexanol (Structure 26)
1 H NMR (CDCl 3 , 500 MHz): 5.73-5.92 (m, 1H), 4.94-5.14 (m, 2H), 3.67-3.83 (m, 1H), 3.38 (s, 3H), 3.01-3.29 (m, 1H), 2.37-2.60 (m, 2H), 1.79-2.03 (m, 2H), 1.44-1.68 (m, 4H)
The isomeric mixture of Structure 25 and 26 was described as having fruity, vanilla and green notes.
2-Ethoxy-4-vinyl-cyclohexanol (Structure 27) and 2-Ethoxy-5-vinyl-cyclohexanol (Structure 28)
1 H NMR (CDCl 3 , 500 MHz): 5.74-5.96 (m, 1H), 4.95-5.17 (m, 2H), 3.07-3.77 (m, 4H), 2.47-2.57 (m, 1H), 2.18-2.45 (br, 1H), 1.78-2.06 (m, 2H), 1.42-1.72 (m, 4H), 1.20 (t, J=6.9 Hz, 3H)
The isomeric mixture of Structure 27 and 28 was described as having spicy and vanilla notes.
2-Isopropoxy-4-vinyl-cyclohexanol (Structure 35) and 2-Isopropoxy-5-vinyl-cyclohexanol (Structure 36)
1 H NMR (CDCl 3 , 400 MHz): 5.68-5.95 (m, 1H), 4.89-5.16 (m, 2H), 3.16-3.83 (m, 3H), 2.70-2.86 (m, 1H), 2.41-2.61 (m, 1H), 1.73-1.98 (m, 2H), 1.43-1.73 (m, 4H), 1.10-1.22 (m, 6H)
The isomeric mixture of Structure 35 and 36 was described as having a spicy note.
2-Butoxy-4-vinyl-cyclohexanol (Structure 37) 2-Butoxy-5-vinyl-cyclohexanol (Structure 38)
1 H NMR (CDCl 3 , 400 MHz): 5.68-5.95 (m, 1H), 4.91-5.14 (m, 2H), 3.04-3.80 (m, 4H), 2.41-2.66 (m, 2H), 1.79-2.05 (m, 2H), 1.44-1.73 (m, 6H), 1.31-1.44 (m, 2H), 0.92 (t, J=7.3 Hz, 3H)
The isomeric mixture of Structure 37 and 38 was described as having sweet and spicy notes.
2-Isobutoxy-4-vinyl-cyclohexanol (Structure 39) and 2-Isobutoxy-5-vinyl-cyclohexanol (Structure 40)
1 H NMR (CDCl 3 , 400 MHz): 5.72-5.98 (m, 1H), 4.86-5.14 (m, 2H), 3.56-3.83 (m, 1H), 3.06-3.40 (m, 3H), 2.41-2.63 (m, 2H), 1.74-2.00 (m, 3H), 1.44-1.73 (m, 4H), 0.85-0.95 (m, 6H)
The isomeric mixture of Structure 39 and 40 was described as having onion- and garlic-like notes.
Example IV
Additional hydrogenated cyclohexanols were prepared via the hydrogenation of the corresponding cyclohexanols prepared in the above.
4-Ethyl-2-methoxy-cyclohexanol (Structure 41) and 5-Ethyl-2-methoxy-cyclohexanol (Structure 42)
1 H NMR (CDCl 3 , 500 MHz): 3.57-3.74 (m, 1H), 3.38 (s, 3H), 3.02-3.21 (m, 1H), 2.32 (br, s, 1H), 1.74-1.89 (m, 2H), 1.59-1.68 (m, 1H), 1.39-1.55 (m, 4H), 1.26-1.35 (m, 2H), 0.87-0.92 (m, 3H)
The isomeric mixture of Structure 41 and 42 was described as having spicy and vanilla but phenolic notes.
4-Ethyl-2-ethoxy-cyclohexanol (Structure 43) and 5-Ethyl-2-Ethoxy-cyclohexanol (Structure 44)
1 H NMR (CDCl 3 , 500 MHz): 2.96-3.78 (m, 4H), 2.50 (br, s, 1H), 1.96-2.13 (m, 1H), 1.57-1.88 (m, 2H), 1.36-1.57 (m, 2H), 1.08-1.36 (m, 6H), 0.77-1.04 (m, 4H)
The isomeric mixture of Structure 43 and 44 was described as having earthy, woody and green but phenolic notes.
4-Ethyl-2-propoxy-cyclohexanol (Structure 45) and 5-Ethyl-2-propoxy-cyclohexanol (Structure 46)
1 H NMR (CDCl 3 , 400 MHz): 2.91-3.92 (m, 5H), 1.06-2.16 (m, 11H), 0.72-1.03 (m, 6H)
The isomeric mixture of Structure 45 and 46 was described as having spicy and vanilla but phenolic notes.
4-Ethyl-2-isobutoxy-cyclohexanol (Structure 47) and 5-Ethyl-2-isobutoxy-cyclohexanol (Structure 48)
1 H NMR (CDCl 3 , 400 MHz): 2.58-3.76 (m, 5H), 1.00-2.14 (m, 10H), 0.77-1.00 (m, 9H)
The isomeric mixture of Structure 47 and 48 was described as having spicy and woody notes with bacon character.
Accordingly, the novel cyclohexanols represented by Formula I-VI possess unexpected superior and desirable effect when compared to their corresponding hydrogenated compounds.
Example V
Establishment of Malodor Models
The sweat, mold/mildew, bathroom and smoke malodor models were prepared based on Applicants' proprietary formulations for assessing the effectiveness of various malodor counteractants.
Preparation of Test Samples:
Two aluminum dishes were placed in an 8 oz glass jar. A malodor material was pipetted into one aluminum dish, and a compound of the present invention diluted in a solvent (1%) or a solvent alone control was pipetted into the other aluminum dish. The jar was then capped and the samples were allowed to equilibrate for one hour before the testing.
Testing Procedure:
Test samples were presented in a blind and random order to 15-18 internal panelists (consisting of men/women with an age range of 25 to 55). However, different odor samples were arranged in an alternative order (for example, sweat, mold/mildew, sweat, mold/mildew, and etc.).
The panelists were instructed to take the steps of i) sniff jars containing only the malodor materials for familiarization prior to the testing; ii) uncap a jar; iii) place their noses at a distance of about 3-4 inches above the opening; iv) take short sniffs for 3 seconds; and v) enter a rating of overall intensity and malodor intensity on a handheld computer.
The overall and malodor intensity was rated using the Labeled Magnitude Scale (LMS) [Green, et al., Chemical Senses, 21(3), June 1996, 323-334]. Percent malodor reduction (“% MOR”) represents the perceived reduction in mean malodor intensity of the sample containing the malodor in the presence of a malodor counteractant relative to the negative control (Malodor Alone).
Results and Discussion:
The mean ranks of the malodor coverage for the above test were as follows:
Compound (1%)
Malodor
% MOR
A Mixture of Structures 5, 6, 7 and 8
Sweat
87.23
Mold/Mildew
74.63
Bathroom
84.78
Smoke
48.81
A Mixture of Structures 17, 18, 19 and 20
Sweat
81.49
Mold/Mildew
66.50
Bathroom
83.81
Smoke
51.31
Compounds of the present invention were demonstrated effective in counteracting various types of malodors. | The present invention pertains to a method of counteracting malodor by introducing a malodor counteracting effective amount of novel cyclohexanol compounds, wherein the compounds are represented by the following formula:
an isomer or a mixture of isomers thereof,
wherein one of R and R′ represents hydrogen with the other representing a C 1 -C 6 linear, branched or cyclic alkyl, alkenyl, alkynyl or aromatic group; and
one of the dashed lines represents a carbon-carbon single bond with the other representing a carbon-carbon double bond. | 3 |
RELATED APPLICATIONS
Not Applicable
FIELD AND BACKGROUND
1. Field
The present field relates generally to a display device for mounting on doors, and more specifically to a secure display device suitable for mounting on an existing door, providing protection to the door and against tampering with the device.
2. Background
Businesses are susceptible to various forms of vandalism, particularly those businesses located where people are likely to be found after business hours. Vandalism may take the form of physical destruction of property, such as signs or displays affixed to the exterior of the business' door. In other instances, particularly with respect to businesses located near bar and restaurants, the vandalism may take the form of public urination at or near the door to the business. This is a particular problem for businesses having doors set away from the sidewalk or otherwise offering some protection against observation. Inebriated patrons of a bar may, for example, use the relative seclusion of the doorway as a safe place for urination. Not only does this cause a problem for the exterior of the business, but with many businesses the urine is able to penetrate the area between the door and the doorjamb to the interior of the business.
SUMMARY
Provided is a secure door display suitable for mounting on a standard metal or wooden door, the door display having a shield to discourage public urination in the vicinity of the door and to protect the door and business from the same.
The door display holder and protector is preferably made from lightweight material and adapted for easy installation on an existing door. The device can be used on any external door of a commercial business, and is designed for easy cleaning when necessary. The device protects metal doors against corrosion caused by urination at or near the door, as well as from the elements.
The present device also provides a secure display holder suitable for displays of various sizes. The device is made secure by an interior fastening mechanism not accessible from the exterior of the door. The secure nature of the device makes tampering with or removing the device from the door difficult, providing advantages over traditional signage or other notices affixed to the exterior of a door.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front perspective view of a door having one embodiment of a door protector device affixed thereto.
FIG. 2 is a rear perspective view of the door and device of FIG. 1 .
FIG. 3 is a front view of a door having one alternative embodiment of a door protector device affixed thereto.
FIG. 4 is a front and side perspective view of the door and device of FIG. 3 .
FIG. 5 is a perspective view of the door protector device of FIGS. 3 and 4 .
FIG. 5A is a cross-section view of the door protector device of FIGS. 3 through 5 showing a channel formed by the device and having a sign held therein.
FIG. 6 is a close view of a rod and nut attachment embodiment suitable for use with various embodiments of the present device.
FIG. 7 is a perspective view of one alternative embodiment of a door protector device.
FIG. 8 is a rear view of the door protector device of FIG. 7 .
FIG. 9 is a rear view of an embodiment of the present device wherein the display holder is positioned on a door and held in place via a nut and screw with a spacer and insert.
FIG. 9A is a close view of a screw, nut, and insert combination of the embodiment of the present device shown in FIG. 9 .
FIG. 9B is a close top view of an embodiment of the present device shown in FIG. 9 with the screw, nut, and insert combination displaced toward the interior of the door.
FIG. 10 is a top view of an embodiment of the present device shown in FIG. 9 .
DETAILED DESCRIPTION
The present secure display holder and protector (referred to hereinafter as the “device” or the “door protector,” for example) is suitable for use with a variety of doors, including metal doors, glass doors, metal screen doors, and wooden doors. The device may, in fact, be used with any suitable door. The device is preferably constructed of a light-weight material such as aluminum or a strong, hard synthetic polymer. Any suitable materials may, however, be used for the present device and any of its component parts.
One embodiment of the device is constructed of a thin, flat portion of metal that covers the lower part of the outside of a door, from the door knob and deadbolt area to the bottom of the door, and from one side of the door to the other. The lower portion of the device is preferably curved outward, away from the door, to form a ramp-like structure that prevents fluids from seeping under the door and also tends to repel urine, for example, back toward a person urinating near the door, thereby discouraging urination at or near the door.
The protector may be secured to the door using four inserts that go between the door and the door frame. The inserts are preferably formed integrally with the door protector and extend therefrom, though the inserts may also be mechanically fastened to the door protector or, in the case of a metal door protector, welded thereto. The end of the inserts that extend into the interior of the business include openings defined therein suitable for receiving a long screw or rod having a threaded portion at at least one end thereof. The door protector may also be held in place by a screw extending through the opening in the insert, the screw securing an L-shaped spacer to the insert, the L-shaped spacer contacting the back of the door securely.
In some embodiments of the device, the inserts may wrap around the door rather than only extending from the front of the door past the rear thereof. Such inserts may be held in place with one or more small screws and a nut.
The front portion of the door protector preferably includes a frame holder with three sides that are channeled, such as in a C or U shape, and that includes a brace along the rear of the door. The channel formed by the three sides of the frame holder is configured to hold signage, any be made of a variety of suitable materials, including plexiglass or other synthetic polymers, wood, chipboard, metals, and the like. In one embodiment of the device, the channels are approximately ½ inch in width and ½ inch in depth.
Some embodiments of the present device may include the frame holder as well as the curved door protector at the lower portion thereof, and some embodiments may include only the door protector or only the secure frame holder. In each embodiments, the various ways in which the device may be secured to the door are the same. Each of the various embodiments has the advantage of fitting tight against the door, covering a large area of the door and providing protection thereto, providing a professional appearance whether used with or without signage or other displays, and can be modified to fit the dimensions of any given door.
Turning to the drawings, wherein like numerals indicate like parts, FIG. 1 is a perspective view of a conventional door 10 with one embodiment of a door protector 12 associated therewith. As shown in the figure, door protector 12 includes a curved or ramp bottom portion 14 designed to repel water, urine, or other fluids. First insert 16 and second insert 18 are visible, extending from the door protector along the edge of the door and projecting beyond the rear thereof.
FIG. 2 is a perspective view of the rear of door 10 in FIG. 1 , with door protector 12 attached thereto. As can be seen in the figure, third insert 20 and fourth insert 22 also extend from door protector 12 beyond the rear of the door. The various door protectors includes openings in the ends thereof that extend beyond the rear of the door. In the embodiment of the door protector shown in FIG. 2 , a first rod 24 extends between first insert 16 and third insert 20 , and a second rod 26 extends between second insert 18 and fourth insert 22 . The thin rods may include a flattened portion at one end, to prevent the end of the rod passing through the opening in the respective insert, and may include a threaded portion at the other end such that the rod can be secured in place with a butterfly nut or other fastener made up to the threads of the rod and secured firmly against the respective insert.
FIG. 3 provides front view of a conventional door 100 having a door protector 112 affixed thereto, the door protector 112 formed as a frame holder for displaying signage or other materials. The embodiment of door protector 112 shown in FIG. 3 does not include a curved or ramped portion to repel fluid, though it is contemplated that such a curved or ramped portion may be provided. As shown in FIG. 4 , door protector 112 affixes to door 100 in the same manner as door protector 12 , above, with first and second inserts 116 and 118 shown. Dashed lines in FIG. 3 indicate the position of first rod 124 and second rod 126 , which extend behind door 100 .
FIG. 5 depicts door protector 112 detached from a door, rendering the various inserts, as well as the nature of the frame, more visible. FIG. 5A is a cross-section view of a sign 128 positioned within a C channel created by door protector 112 .
FIG. 6 is a closer rear view of door protector 112 attached to a door 100 . The view shows more clearly inserts 116 , 118 , 120 , and 122 . First rod 124 extends from first insert 116 to third insert 120 , and second rod 126 extends from second insert 118 to fourth insert 122 . Both rods include a threaded portion 132 to which butterfly nut 130 is made up, securing the respective rod in place. The end of the rod not having the threaded portion is preferably flattened or otherwise sized or shaped so as to be incapable of passing through the opening in the insert.
FIG. 7 depicts an alternative arrangement of the present device wherein the door protector includes a frame holder for holding signage, for example, and is secured to a door using a screw/spacer/nut combination rather than the mechanisms described above.
FIG. 8 is a rear view of the embodiment shown in FIG. 7 , and provides a detailed view of the screw/spacer/nut arrangement, as well as the relation of the insert to the door.
FIG. 9 depicts an embodiment of the present device wherein the display holder is positioned on an interior surface of the door. A nut and screw with a space and insert hold the device firm against the door. FIG. 9A shows a close view of nut 344 , screw 340 , insert 316 , and spacer 346 , altogether an assembly 348 . FIG. 9B shows an embodiment of the present device utilizing assembly 348 , with insert 316 elongated to move assembly 348 toward the interior of door 300 .
As shown in FIGS. 9 through 9B , portions of the device extend between the door and jamb to secure the device to a conventional or existing door. These portions are minimal and do not allow for tampering with the device or any display contained therein.
FIG. 10 is a top view of a door having the embodiment of the present device of FIG. 9 installed thereon. The mechanism by which the device is secured to the door is shown, as is the display holder portion for inserting a sign or other display or indicia therein.
It is contemplated that while the various embodiments shown and described herein depicts a device that extends from the door knob to the lower portion of the door, any desired portion of the door may be covered, including the portion extending from the door know to the upper portion of the door. | A device for protecting a door includes a body extending over at least a portion of the door and two inserts, extending from opposing edges of the body between the door and the door frame. A rod attached to the two inserts and extending therebetween contacts a surface of the door and secures the device thereto. | 4 |
BACKGROUND OF THE INVENTION
Electric heat pumps have become common means for heating and cooling indoor spaces. Such units typically employ direct expansion of refrigerants such as CFCs and HCFCs. They typically position a compressor and condensor coil in the ambient environment, where the condensor may be exposed to ambient air, usually by use of a fan. The other component of the system comprises an evaporator coil which is positioned in the indoor space, and which transfers heat to and from the indoor air circulated over the coil. As is well known in the art of heating and refrigeration, the heat pump heats indoor spaces by transfering sensible heat from the ambient atmosphere to the indoor air, while when desired, it cools indoor spaces by transfering heat from the indoor air to the ambient (in the same manner as a conventional air conditioner. Typical heat pumps also employ a resistive heating coil for supplementation of the heating function when ambient temperatures are too low to permit the desired heating.
Regenerative type periodic flow devices are conventionally employed for the transfer of heat or a material from one fluid stream to another, and thereby from one area or zone in space to another. Typically, a sorptive mass is used to collect heat or a particular mass component from one fluid stream which flows over or through that mass. The flowing fluid is rendered either cooler (in the case of heat sorption) or less concentrated (in the case of, for instance, adsorption of particular gases). The sorptive mass is then taken "off-stream" and regenerated by exposure to a second fluid stream which is capable of accepting the heat or material desorbed with favorable energetics.
In some applications continuous flow systems are used, where the sorptive media itself is moved between two or more flowing fluid streams. The most common construction employed for such systems is a porous disk, often referred to as a wheel or rotor. In its simplest form, such a wheel is divided into two flow zones, and fluid is passed over the sorptive surface of the wheel (typically flowing through the thickness of the disc parallel to the rotational axis of the cylinder) as the wheel is rotated to carry the sorptive material from one zone, into the other, and back again to complete a revolution. In a heat exchanger wheel, for instance, one zone of warm fluid and one zone of cooler fluid are present. Heat is adsorbed by the material of the wheel in the warm flow zone, and is carried away from the wheel as the sorptive material passes through the cool flow zone.
BRIEF DESCRIPTION OF THE INVENTION
The system and method of the present invention comprises a space conditioning system based upon an integrated direct expansion heat pump with desiccant wheel and heat exchange (thermal) wheel. The system is controlled to have four distinct modes of operation: Heating, Cooling/Regneration, Coil Defrost, and Regeneration. Three evaporator/condensor coils are employed, and these are controlled with pairs of solenoid operated diverter valves capable of directing refrigerant flows.
In the preferred embodiment of the present invention, an integrated heat pump desiccant/water vapor exchange system for providing temperature conditioned air to an enclosed space (the "conditioned space" ) such as a supermarket or shopping mall is comprised of desiccant/water vapor exchangers (which are preferably multi-wheel systems), coupled with direct expansion heat pump apparatus which provides both cooling, as well as a source of heat energy for use in regeneration of the desiccant medium. A mixed-component refrigerant is employed which provides larger ranges of operating conditions in the heat pump part of the system.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 depicts a schematic representation of an integrated heat pump desiccant/water vapor exchange space conditioning system of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIG. 1 there is shown in schematic form a multi wheel desiccant/water vapor exchange system integrated into a heat pump, which may be controlled according to the present invention. Two air flow paths are defined through the system, one of which is air taken from an enclosed conditioned space. This air stream will typically contain large amounts of water vapor and will be warmer than the desired temperature at which the conditioned space is to be maintained. In a supermarket, for instance, evaoporation of water from goods, and exhaled and perspired moisture contribute to high humidity. Operation of refrigeration equipment, lights, and other machinery, as well as heat given off by humans and heating from insolation raise the temperature as well.
Typical direct expansion types of space conditioning systems use evaporator coils to both condense moisture from the air stream (the latent load), and to cool the airstream (the sensible load). Such systems typically use chlorofluorocarbon (CFC) refrigerants which are now known to be harmful to the environment. There have also been employed desiccant systems which first adsorb water vapor from the air stream using an inorganic material with a high K value for more hydrated states. After adsorption of water vapor (an exothermic process which yields dry, but extremely hot air), a cooling step is required which may be carried out using a heat exchanger to recover the thermal energy and recycle it for us in regenerating the desiccant by heating to drive off adsorbed water. The present invention combines these two approaches to yield a highly efficient system which is capable of heating, cooling, and dehumidifying an enclosed space.
Compressor 50 which is typically driven by an electric motor (not shown), serves to compress gaseous refrigerant which has absorbed heat from an air stream. Coils 10, 20, and 30 may either be evaporation coils in which a liquid refrigerant is allowed to expand (thereby absorbing heat from the ambient surrounding the coil), or in which a compressed stream of high temperature refrigerant is allowed to condense to a liquid (thus liberating heat which is transferred to the ambient surrounding the coil).
The coil 20, through which regeneration, or ambient air, is passed, will be denoted herein as the outdoor coil. The coil 30, through which process air passes before being delivered into the conditioned space, will be denoted herein as the indoor coil. The coil 10, which serves to reclaim heat, will be denoted as the reclaim coil. The state of coils 10, 20 and 30 is controlled by a first diverter valve D2 and a second diverter valve D3, where both the first and second diverter valves are solenoid operated, and a first valve S1, a second valve S2 and a third valve S3, where the first, second and third valves are solenoid operated. The reclaim coil 10 has a first side 10a in fluid communication with suction header 60, and a second side 10b in fluid communication with receiver 80. The outdoor coil 20 has a first side 20a in fluid communication with suction header 60 and discharge header 70, and a second side 20b in fluid communication with receiver 80. The indoor coil 30 has a first side 30a in fluid communication with suction header 60 and discharge header 70, and a second side 30b in fluid communication with receiver 80. Each diverter valve is interposed between a coil and flow lines in communication with suction header 60 and discharge header 70.
In operation, suction header 60 contains relatively cool (40° F. SST) gaseous R-22 refrigerant under low pressure (70 PSIG) which has absorbed heat from the ambient surrounding one or more coils. Discharge header 70 contains relatively hot (130° F. SST) gaseous refrigerant under high pressure (296 PSIG). Receiver 80, which is connected to each coil through an associated solenoid operated valve, typically contains relatively cool liquid refrigerant at high pressure.
In the cooling and dehumidification mode of the present invention, process air (that taken from the indoor space to be conditioned, and which contains both sensible heat and relatively high levels of water vapor) is first directed to a desiccant wheel 100, from which it exits at a temperature of approximately 110° F. and a moisture content of 20 gr/lb. This air stream is then directed to a heat exchange wheel 200, from which it exits at a relatively cool 85° F. This cool, dry air stream is then directed to a direct expansion coil 30, which further cools the air stream to the desired level (typically 65° F.). This air is then returned to the indoor space, or it may be directed to rehumidification means 32 to add moisture to be supplied to the conditioned space.
Regeneration air (from the ambient and typically at 100° F.) is optionally cooled by exposure to a water vapor phase-change cooling means to approximately 78° F. It is then exposed to thermal wheel 200 which carries heat, and the regeneration air absorbs this heat and is raised to approximately 105° F. The air stream is then exposed to coil 20, which heats the air still further (coil 20 functions as a condensor coil by allowing discharge refrigerant to liberate heat, thereby changing state to a liquid). This 140° F. air is then directed through desiccant wheel 100 to heat the desiccant, thereby regenerating the desiccant by driving off adsorbed water. The heat remaining in this air stream (which typically exits the desiccant wheel at 110° F.) may then be reclaimed by use of coil 10 as an evaporator, if desired, leaving the exhaust air stream at 90° F.
The states of the valves which control refrigerant flow in the system of the present invention are summarized in Table I.
TABLE I______________________________________Diverter Valve Position Settings DehumidifyDehumidify /Cool Heat Defrost______________________________________D2 On On Off OnD3 Off Off On OnS1 Modulated Modulated Off ModulatedS2 On On Modulated OnS3 Off Modulated On Off______________________________________
Optionally, the system and method of the present invention may also control other ancillary systems such as post-conditioning systems, cogeneration systems, air flow controllers, and the like to provide an optimum solution for a multivariable system such as optimization of total energy consumption, within predetermined limits of conditioned space temperature and humidity, or the optimization of conditioned space "humiture" (the physiologically perceived temperature) within predetermined limits of energy consumption.
The system of the present invention may be implemented as a software/hardware system employing a general purpose digital microprocessor such as a Motorola 68030 (optionally used as part of a general purpose computer system, or with such peripheral circuits and interfaces as may be necessary to provide the required signals and storage.) Of course, those skilled in the art will recognize that while the present invention has been described with reference to specific embodiments and applications, the scope of the invention is to be determined solely with reference to the appended claims.
STATEMENT OF INDUSTRIAL UTILITY
The system and method of the present invention may be used in the operation and control of a space conditioning system. | An energy-efficient space conditioning system comprising an integrated direct expansion heat pump with desiccant and thermal exchange wheels. A method is disclosed for controlling the system to have four distinct modes of operation: Heating, Cooling/Regneration, Coil Defrost, and Regeneration. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the field of design and construction of shoes. More particularly, the present invention relates to the field of shoe designs which includes at least one compartment for concealing items
2. Description of the Prior Art
Many types of shoes are known in the prior art. However, while shoes have been developed for unique stylized designs and for comfort and wearablity including shoes for special purposes such as walking, hiking and fashion, shoes have not been used as a device to carry valuable items in a concealed way.
Many women fear carrying valuable items such as credit cards and cash in their purse where it can be snatched. There is a significant need for a unique wearing item which enables valuables such as credit cards, cash and keys to be retained in a safe and concealed manner.
SUMMARY OF THE INVENTION
The present invention is a shoe having the unique feature of a concealed compartment within the shoe to enable valuables such as cash, keys, coins, jewelry and credit cards to be concealed in a safe and secure manner so that they are concealed while at the same time not interfering with the wearability of the shoe.
It has been discovered, according to the present invention, that if a portion of the shoe such as the inner sole is divided into two longitudinal sections, then a compartment for retaining items can be formed into one of the sections and concealed by the overlay of the mating second inner sole section.
It has further been discovered, according to the present invention, that if the first and second inner sole sections are at least partially removably affixed to each other by attachment means such as mating hook and loop fasteners, then the compartment remains concealed and obscured from view so that the items retained therein are kept in a safe and secure manner and still can be readily accessed to insert and remove items from the compartment.
It has further been discovered, according to the present invention, that if the upper section of the inner sole is covered by an insole which may also contain padding between the insole and the upper section of the inner sole or have an insole which is padded, then the wearer can comfortably wear the shoe without any discomfort received from the items retained in the compartment.
It has additionally been discovered, according to the present invention, that if the compartment extends for a portion of the length of the shoe, then flat items such as bills and cash, spa keys, home keys, gym keys, coins, lucky charms, jewelry, business cards, phone cards, credit cards, identification cards such as driver's licenses and ATM cards can be safely concealed and stored within the pocket.
It has also been discovered that in an alternative embodiment, instead of having the inner sole divided into two longitudinal sections, a separate compartment layer may be affixed between the interior surface of the outer sole of the shoe and the one-piece inner sole, with the separate compartment layer having the compartment for retaining items. The separate compartment layer is itself affixed to the interior surface of the outer sole of the shoe and has the means for removably attaching a portion of the separate compartment layer to the lower surface of the one-piece inner sole.
It is therefore an object of the present invention to provide a concealed pocket for safely retaining flat items such as keys, bills, coins, jewelry and various cards such as business cards, driver's licenses, credit cards etc. in a safe and secure manner so that they are hidden within the shoe while at the same time enabling the wearer to comfortably wear the shoe in a normal manner.
It is another object of the present invention to provide means for removably opening a section of the shoe such as mating sections of an inner sole or the location between a separate compartment layer and the one-piece inner sole so that the items contained within the compartment concealed within a portion of the inner sole or compartment layer can be readily accessible by simply removing the shoe and lifting up one portion of the shoe from the other.
It is an additional object of the present invention to have the mating sections of the shoe which conceal the pocket having the items therein removably attached to each other by means such as hook and loop fasteners, snap fasteners, etc.
It is another object of the present invention to form a pocket into any type of shoe whether it be a fashion shoe, wearing shoe, hiking shoe, or any other shoe wherein a portion of the inner sole or separate compartment layer can be easily accessed to reach a concealed pocket within the inner sole or separate compartment layer to place the items within the concealed compartment and thereafter remove the items when needed.
Further novel features and other objects of the present invention will become apparent from the following detailed description, discussion and the appended claims, taken in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Referring particularly to the drawings for the purpose of illustration only and not limitation, there is illustrated:
FIG. 1 is a perspective view of the present invention shoe in the wearing condition where the concealed compartment retaining items is concealed within the shoe and obscured from view;
FIG. 2 is a side elevational view of the present invention shoe with a portion of the second section of inner sole and its affixed insole extended from the lower section of inner sole to expose the concealed compartment within the lower section of the inner sole and expose its contents;
FIG. 3 is a cross-sectional view taken along Line 3 — 3 of FIG. 2 ;
FIG. 4 is a top plan view of a portion of the lower section of inner sole;
FIG. 5 is a bottom plan view of a portion of the upper section of inner sole;
FIG. 6 is a perspective view of an alternative embodiment of the present invention shoe in the wearing condition where the concealed compartment retaining items is in a separate compartment layer concealed within the shoe and obscured from view;
FIG. 7 is a side elevational view of the alternative embodiment of the present invention shoe illustrated in FIG. 6 , with a portion of the one-piece inner sole and its affixed insole extended from the separate compartment layer to expose the concealed compartment within the separate compartment layer and expose its contents;
FIG. 8 is a cross-sectional view taken along Line 8 — 8 of FIG. 7 ;
FIG. 9 is a top plan view of a portion of the separate compartment layer; and
FIG. 10 is a bottom plan view of a portion of the one-piece inner sole.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Although specific embodiments of the present invention will now be described with reference to the drawings, it should be understood that such embodiments are by way of example only and merely illustrative of but a small number of the many possible specific embodiments which can represent applications of the principles of the present invention. Various changes and modifications obvious to one skilled in the art to which the present invention pertains are deemed to be within the spirit, scope and contemplation of the present invention as further defined in the appended claims.
Referring to FIGS. 1 through 5 , there is shown at 10 one embodiment of the present invention shoe. The present invention shoe 10 comprises an outer sole of the shoe 12 . The outer sole includes an exterior surface 14 of the outer sole and an interior surface 16 of the outer sole of the shoe 10 . The heel 18 of the shoe is attached to the rear portion of the exterior surface 14 of the outer sole of the shoe 12 .
Affixed to the outer sole of the shoe is the inner sole 20 of the shoe 10 . A unique feature of the present invention is to divide the inner sole 20 into two separate sections, a first lower section 22 and a second upper section 26 . The inner sole 20 extends for the entire length of the shoe as illustrated in FIGS. 2 and 3 . The first lower section 22 of the inner sole 20 further comprises a concealed compartment 30 which is located adjacent the heel area as shown in FIGS. 2 and 3 formed into the lower section 22 of the inner sole 20 of the shoe 10 . The concealed compartment 30 comprises a first edge 32 , a second edge 34 ,a front edge 36 and a rear edge 38 . As illustrated in the figures, the first and second lengthwise edges 32 and 34 and the front edge 36 are stitched together to form a closed portion of the compartment. The rear edge 38 contains an opening 40 located adjacent the heel 18 by which access can be gained to the concealed compartment 30 .
The second upper section of the inner sole 26 contains a lower surface 28 which abuts and mates with the upper surface 24 of the first lower section 22 of the inner sole 20 . The lower surface 28 of the second section 26 of the two portion inner sole 20 forms a completely concealed package so that when the lower surface 28 of the second section 26 of the inner sole 20 is formed against the upper surface 24 of the first lower section 22 of the inner sole 20 , the compartment 30 is completely concealed.
Attached to the rear portion of the upper surface 24 of first lower section 22 of inner sole 20 is a first fastener means 50 . Attached to the rear portion of the lower surface 28 of the second upper section 26 of inner sole 20 is a second mating fastener means 52 . By way of example, the fastener means can be hook and loop fasteners 50 and 52 respectively as illustrated in the figures. It will be appreciated that other fastener means which, by way of example, can be mating snap fasteners, can also be utilized and are within the spirit and scope of the present invention.
As illustrated in the figures, the lower surface 23 of the first lower section of the inner sole is affixed to the interior surface 16 of the outer sole of the shoe.
Attached above the upper surface 58 of the second upper section 26 of the inner sole 20 is the insole 60 . The insole 60 has a lower surface 62 which is aligned with and abuts and is attached to the upper surface 58 of the upper second section 26 of the inner sole 20 . The upper surface 64 of the insole 60 is exposed and the foot rests on top of the upper surface 64 of the insole 60 . Also as illustrated in the cross-sectional view of FIG. 3 , there is an optional padding 66 which may be contained between the insole 60 and the inner sole 20 . Alternatively, the insole 60 itself can be made of padded material. The purpose of the padding or the padded insole 60 is to provide sufficient cushioning so that the wearer will not have any discomfort by the objects contained within the compartment 30 while wearing the shoe.
The body of the shoe 70 is attached to the front portion of the shoe as illustrated in the figures and can be affixed between the interior surface 16 of the outer sole 12 of the shoe 10 and the lower surface 23 of first lower section 22 of inner sole 20 .
Items 100 such as hotel room keys, spa keys, home keys, gym keys, lucky charms, cash and bills, coins, jewelry, and cards such as driver's licenses, identification cards, ATM cards, credit cards, phone cards and business cards, can be retained within the concealed compartment 30 . As illustrated in FIG. 1 , when the mating fasteners 50 and 52 are brought together, the compartment 30 is completely concealed within the shoe and therefore, is obscured from view. Therefore, the wearer can safely wear the shoe without fear that the valuable items 100 contained within the compartment 30 may be lost or exposed. When access is desired to be gained to the compartment, the wearer simply removes the shoe from the wearer's foot, and raises the second upper section 22 of the inner sole 20 from the first lower section 22 of the inner sole 20 so that the concealed compartment 30 is exposed and the items retained therein can be accessed by means of opening 40 .
Referring to FIGS. 6 through 10 , there is shown at 110 an alternative embodiment of the present invention shoe. The alternative embodiment of the present invention shoe 110 comprises an outer sole of the shoe 112 . The outer sole includes an exterior surface 114 of the outer sole and an interior surface 116 of the outer sole of the shoe 110 . The heel 118 of the shoe is attached to the rear portion of the exterior surface 114 of the outer sole of the shoe 112 .
In the alternative embodiment of the present invention, affixed to the interior surface 116 of the outer sole of the shoe is a separate compartment layer 90 which extends for the entire length of the shoe as illustrated in FIGS. 7 and 8 . The separate compartment layer further comprises a concealed compartment 130 which is located adjacent the heel area as illustrated in FIGS. 7 and 8 formed into the separate compartment section 90 of the shoe 110 . The concealed compartment 130 comprises a first edge 132 , a second edge 134 , a front edge 136 , and a rear edge 138 . As illustrated in the figures, the first and second lengthwise edges 132 and 134 and the front edge 136 are stitched together to form a closed portion of the compartment. The rear edge 138 contains an opening 140 located adjacent the heel area by which access can be gained to the concealed compartment 130 .
Set above the separate compartment layer 90 is the inner sole 120 which contains a lower surface 128 which abuts and mates with the upper surface 124 of the separate compartment section 90 . The lower surface 128 of the inner sole 120 when it abuts against the upper surface 124 of the separate compartment section 90 forms a completely concealed package so that the compartment 130 is completely concealed.
Attached to the rear portion of the upper surface 124 of the separate compartment section 90 is a first fastener means 150 . Attached to the rear portion of the lower surface 128 of the inner sole 120 is a second mating fastener means 152 . By way of example, the fastener means can be hook and loop fasteners 150 and 152 respectively as illustrated in the figures. It will be appreciated that other fastener means which, by way of example, can be mating snap fasteners, can also be utilized and are within the spirit and scope of the present invention.
As illustrated in the figures, the lower surface 123 of the separate compartment section 90 is affixed to the interior surface 116 of the outer sole of the shoe 110 .
Attached above the upper surface 158 of the inner sole 120 is the insole 160 . The insole 160 has a lower surface 162 which is aligned with and abuts and is attached to the upper surface 158 of the inner sole 120 . The upper surface 164 of the insole 160 is exposed and the foot rests on top of the upper surface 164 of the insole 160 . Also as illustrated in the cross-sectional view of FIG. 3 , there is an optional padding 166 which may be contained between the insole 160 and the inner sole 120 . Alternatively, the insole 160 itself can be made of padded material. The purpose of the padding or the padded insole 160 is to provide sufficient cushioning so that the wearer will not have any discomfort by the objects contained within the compartment 130 while wearing the shoe.
The body of the shoe 170 is attached to the front portion of the shoe as illustrated in FIGS. 6 through 10 and can be affixed between the interior surface 116 of the outer sole 112 of the shoe 110 and the lower surface 123 of separate compartment section 90 or alternatively, between the interior surface 116 of the outer sole 112 of the shoe 110 and the lower surface 128 of the inner sole 20 .
Items 200 such as hotel room keys, spa keys, home keys, gym keys, lucky charms, cash and bills, coins, jewelry, and cards such as driver's licenses, identification cards, ATM cards, credit cards, phone cards and business cards, can be retained within the concealed compartment 130 . As illustrated in FIG. 6 , when the mating fasteners 150 and 152 are brought together, the compartment 130 is completely concealed within the shoe and therefore, is obscured from view. Therefore, the wearer can safely wear the shoe without fear that the valuable items 200 contained within the compartment 130 may be lost or exposed. When access is desired to be gained to the compartment, the wearer simply removes the shoe from the wearer's foot, and raises the second inner sole 20 from the separate compartment section 90 so that the concealed compartment 130 is exposed and the items retained therein can be accessed by means of opening 140 .
The alternative embodiment of the shoe can also be made of any type of desired material and any style. The separate compartment layer 90 can be made of fabric material. It can be a walking shoe, running shoe, hiking shoe, fashion shoe etc., and can be a flat shoe as illustrated in the figures or can be a shoe with a higher heel. The concept of the present invention enables the wearer to safely wear the shoe while retaining valuable items within the concealed compartment.
Defined in detail, the present invention is a shoe comprising: (a) an outer sole having an exterior surface, an interior surface, a front portion and a rear portion; (b) a heel attached to the exterior surface of the rear portion of the outer sole; (c) an inner sole having an aligned first lower section and second upper section, the first lower section having a lower surface aligned with the upper surface of the outer sole, the lower section of the inner sole affixed to the outer sole; (d) the first lower section of the inner sole further comprising an upper surface into which is formed adjacent the heel a compartment to retain objects, the compartment having a first lengthwise edge, a second lengthwise edge, a front edge all of which are affixed to the upper surface to form a closed portion of the compartment and a rear edge containing an opening adjacent the location of the heel through which access can be gained to the compartment; (e) the second upper section of the inner sole matching the shape of the first lower section, the second upper section having a lower surface which abuts and mates with the upper surface of the first lower section, the second upper section being partially attached to the first lower section along their respective first halves, the two sections being aligned but separated along their respective rear halves; (f) a first fastener means attached to the rear portion of the upper surface of the first lower section and a second mating fastener means attached to the rear lower surface of the second upper section, so that when the two fastener means are brought together, the two sections of the inner sole are aligned and the compartment is concealed and when the fastener means are separated and the rear half of the second upper section is moved away from the rear half of the first lower section, the compartment is exposed; (g) an insole aligned with and affixed to an upper surface of the second section of the inner sole; and (h) a body attached to the front portion of the shoe; (i) whereby money, credit cards and other items may be safely retained within the compartment.
Defined broadly, the present invention is a shoe including a heel, comprising: (a) an inner sole sandwiched between an outer sole and an insole; (b) the inner sole having two aligned sections which are a lower section and an upper section, the lower section affixed to the outer sole and the upper section affixed to the insole; (c) the lower section of the inner sole further comprising an upper surface which faces and is aligned with a lower surface of the second section, a compartment adjacent the heel for retaining objects formed into the lower section of the inner sole, the compartment having an opening adjacent the location of the heel aligned with the upper surface of the lower section of the inner sole so that objects can be inserted into and removed from the compartment when the upper surface at the location of the opening is exposed; (d) the upper section of the inner sole being affixed to a portion of the lower section of the inner sole and removably aligned with another portion of the lower section of the inner sole at the location of the opening to the compartment; and (e) mating fastener means attached at opposing surfaces of the lower section and the upper section such that when the fastener means are closed, the compartment and opening are concealed within the inner sole and when the fastener means are opened and a portion of the upper section is moved away from the lower section, the opening to the compartment is exposed.
Defined more broadly, the present invention is a shoe including a heel, comprising: (a) an inner sole sandwiched between an outer sole and an insole; and (b) the inner sole being formed in two opposing sections wherein a portion of one section is removable from an opposing portion of the other section, the inner sole having a concealed compartment for retaining objects formed into the inner sole, the compartment having an opening adjacent the location of the heel which is exposed when one portion of the inner sole is moved away from the opposing portion of the inner sole.
In an alternative embodiment, the present invention defined in detail is a shoe including a heel, comprising: (a) an outer sole having an exterior surface, an interior surface, a front portion and a rear portion; (b) a heel attached to the exterior surface at the rear portion of the outer sole; (c) a compartment layer which extends for at least a portion of the length of the shoe, a concealed compartment located adjacent the heel formed into the compartment layer, the compartment layer having an upper surface through which an access opening adjacent the location of the heel is formed to gain access to the concealed compartment, the compartment layer having a lower surface adjacent the interior surface of the outer sole, the compartment layer affixed to the outer sole; (d) an inner sole having a lower surface aligned with an positioned above the compartment layer, the inner sole affixed to a portion of the compartment layer and removably aligned above the compartment layer at the location of the opening to the compartment; (e) a first fastener means attached to a rear portion of the upper surface of the compartment layer and a second mating fastener means attached to a rear portion of the lower surface of the inner sole, so that when the two fastener means are brought together, the compartment layer and the inner sole are aligned and attached and the compartment is concealed and when the fastener means are separated and a portion of the inner sole is moved away from a portion of the compartment layer, the opening to the compartment is exposed; (f) an insole aligned with and affixed to an upper surface of the inner sole; and (g) a body attached to the front portion of the shoe; (h) whereby money, credit cards and other items may be safely retained within the compartment.
Defined more broadly, the alternative embodiment of the present invention is a shoe including a heel, comprising: (a) an outer sole, a separate compartment layer aligned with and positioned above the outer sole, an inner sole aligned with and positioned above the separate compartment layer, and an insole aligned with and positioned above the inner sole; (b) the separate compartment layer affixed to the outer sole, the separate compartment layer having a compartment located adjacent the heel for retaining objects formed into the separate compartment layer, the compartment having an opening adjacent the location of the heel aligned with an upper surface of the separate compartment layer so that objects can be inserted into and removed from the compartment when the upper surface at the location of the opening is exposed; and (c) the inner sole having a lower surface aligned with and positioned above the separate compartment layer, the inner sole affixed to a portion of the separate compartment layer and removably aligned above the separate compartment layer at the location of the opening to the compartment.
Of course the present invention is not intended to be restricted to any particular form or arrangement, or any specific embodiment, or any specific use, disclosed herein, since the same may be modified in various particulars or relations without departing from the spirit or scope of the claimed invention hereinabove shown and described of which the apparatus or method shown is intended only for illustration and disclosure of an operative embodiment and not to show all of the various forms or modifications in which this invention might be embodied or operated.
The present invention has been described in considerable detail in order to comply with the patent laws by providing full public disclosure of at least one of its forms. However, such detailed description is not intended in any way to limit the broad features or principles of the present invention, or the scope of the patent to be granted. Therefore, the invention is to be limited only by the scope of the appended claims. | A shoe having the unique feature of a concealed compartment within the shoe to enable valuables to be concealed in a safe and secure manner so that they are concealed while at the same time not interfering with the wearability of the shoe. The concealed compartment is either formed within a two-piece inner sole so that the compartment is formed within the lower portion of the inner sole and the upper portion of the inner sole is removably attached to the lower portion of the inner sole through fastener means so that when the fastener means are closed, the compartment is concealed and when the fastener means are opened, the upper portion of the inner sole can be moved away from the lower portion of the inner sole to expose the compartment. Alternatively, the compartment is formed into a separate compartment layer which is positioned above the outer sole and below the inner sole. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
The present application claims the benefit of U.S. Provisional Patent Application No. 61/444,240 filed on Feb. 18, 2011. The entirety of U.S. Provisional Patent Application No. 61/444,240 is incorporated herein by reference.
BACKGROUND OF THE INVENTION
Metals and alloys will undergo an expansion in size when subjected to elevated temperatures. The degree of this expansion is characterized by the material property known as the coefficient of thermal expansion (COTE). The COTE is a function of both material properties (composition, thermal history, etc.) and external variables (most notably the temperature). The COTE of an alloy is a key property considered in the design of components in most types of mechanical systems operating at elevated temperatures.
Low thermal expansion alloys have been employed in gas turbine engines to provide a high level of dimensional control in critical components such as seal and containment rings, cases, and fasteners. In such applications, other important properties can include mechanical strength, containment capabilities, and oxidation resistance. One alloy which possesses such properties is HAYNES® 242® alloy, developed, manufactured, and sold by Haynes International. This is a Ni—Mo—Cr alloy with a nominal composition of Ni-25Mo-8Cr (all compositions in this document are given in wt. % unless otherwise noted). This alloy was covered by U.S. Pat. No. 4,818,486 of Michael F. Rothman and Hani M. Tawancy which was assigned to Haynes International Inc. The 242 alloy is currently employed in numerous gas turbine applications in both the aero and land-based gas turbine industries.
HAYNES 242 alloy is a high strength, low COTE alloy designed for use in gas turbine engines. It is strengthened by an age-hardening heat treatment which results in the formation of long range ordered domains of the Ni 2 (Mo, Cr) phase. These domains provide high tensile and creep strength at temperatures up to around 1300° F. (704° C.). The COTE of 242 alloy is low compared to other Ni-base alloys. This can be attributed to the presence of a high molybdenum (Mo) content in the alloy (25 wt. %). Mo is well known to lower the COTE of nickel-base alloys. Another key feature of 242 alloy is the good oxidation resistance. The presence of 8 wt. % Cr provides sufficient oxidation resistance for use without a protective coating being necessary or in applications where some measure of oxidation resistance is desirable in the event of spallation of the protective coating. Yet another key feature of 242 alloy is its excellent fabricability (formability, hot/cold workability, and weldability) with respect to other age-hardenable nickel-base alloys. Ni-base alloys which are age-hardenable by the gamma-prime phase, for example, are well known to be susceptible to fabrication issues, arising from the fast precipitation kinetics of the gamma-prime phase. In contrast, the Ni 2 (Mo, Cr) phase responsible for age-hardening in 242 alloy has slow precipitation kinetics and therefore 242 alloy does not suffer from the fabricability problems described above.
However, the maximum use temperature of age-hardened 242 alloy (around 1200 to 1300° F./(649 to 704° C.)) can limit the use of the alloy in certain applications. As designers are pushing the operating temperatures to higher and higher levels, the need for a low COTE alloy capable of operating at higher temperatures is becoming necessary. A low COTE alloy which can maintain its high mechanical strength to temperatures of 1400° F. (760° C.) or more would represent a significant advantage to the gas turbine industry.
SUMMARY OF THE INVENTION
The principal object of this invention is to provide alloys which possess a low coefficient of thermal expansion, good oxidation resistance, and excellent strength up to at least 1400° F. (760° C.). These highly desirable properties have been found in alloys with elemental compositions in certain ranges, and defined by quantitative relationships which could not have been expected from the prior art. The composition of these alloys are nickel base, contain molybdenum from 21 to 24 wt. %, chromium from 7 to 9 wt. %, and greater than 5 wt. % tungsten. Furthermore, the overall composition of these alloys must have an “R value” ranging between 31.95 and 33.45 where the R value is defined by the following relationship (where elemental quantities are in wt. %):
R= 2.66Al+0.19Co+0.84Cr−0.16Cu+0.39Fe+0.60Mn+Mo+0.69Nb+2.16Si+0.47Ta+1.36Ti+1.07V+0.40W
Boron may be present in these alloys in a small, but effective trace content up to 0.015 wt. % to obtain certain benefits known in the art. To enable the removal of oxygen and sulfur during the melting process, these alloys typically contain small quantities of aluminum and manganese (up to about 0.5 and 1 wt. %, respectively), and possibly traces of magnesium, calcium, and rare earth elements (up to about 0.05 wt. %). Furthermore, iron, copper, carbon, and cobalt are likely impurities in such materials, since they may be carried over from other nickel alloys melted in the same furnaces. Iron is the most likely impurity, and levels up to 2 wt. % are tolerated in materials such as B-2 and 242 alloys. In 242 alloy, copper is allowed up to 0.5 wt. %, carbon is allowed up to 0.03 wt. %, and cobalt is allowed up to 1 wt. %. It is anticipated that similar impurity contents can be tolerated in the alloys of this invention. Other elements which could be present include, but are not limited to, niobium, silicon, tantalum, titanium, and vanadium. It is anticipated that the levels of these impurities would not exceed around 0.2% each, and that these levels could be tolerated by alloys of this invention. To ensure excellent fabricability, the gamma-prime forming elements (Al, Ti, Nb, and Ta) must be kept at sufficiently low levels to ensure that the gamma-prime phase does not occur in appreciable quantities.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph in which RT yield strength of several Ni—Mo—Cr and Ni—Mo—Cr—W alloys is plotted against the R value.
FIG. 2 is a graph in which RT yield strength of the same several Ni—Mo—Cr and Ni—Mo—Cr—W alloys is plotted against the R value.
FIG. 3 is a graph which shows the hardness of several alloys both before and after the application of an aging heat treatment at 1400° F. (760° C.).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
We provide Ni—Mo—Cr—W based alloys which typically contain 21 to 24% molybdenum, 7 to 9% chromium, and greater than 5 wt. % tungsten, along with typical impurities and minor element additions, which have a low coefficient of thermal expansion and which have excellent strength and ductility at temperatures ranging from room to temperature to as high as 1400° F. (760° C.). These alloys are also expected to have good oxidation resistance. This combination of properties is a desirable one for many gas turbine applications including, but not limited to, seal and containment rings, cases, and fasteners. We have further found that it is required to maintain the R value within the range of 31.95 to 33.45 where R is defined by the following equation:
R= 2.66Al+0.19Co+0.84Cr−0.16Cu+0.39Fe+0.60Mn+Mo+0.69 Nb+2.16Si+0.47Ta+1.36Ti+1.07V+0.40W
and the elemental compositions are given in wt. %.
A total of 36 alloys were tested and presented here to describe the invention. Of these, 35 were experimental alloys (labeled A through Y and AA through JJ) and the other was the commercial 242 alloy. The compositions of all 36 alloys are given in Table 1 along with the calculated R value for each composition.
TABLE 1
Composition of Alloys Tested in the Present Study
Alloy
Cr
Mo
W
Al
B
C
Co
Cu
Fe
Mn
Si
Ni
R value
A
7.88
22.24
6.27
0.18
0.003
0.004
0.07
0.02
1.08
0.34
0.08
Bal.
32.65
B
6.82
22.04
6.21
0.17
0.003
0.003
0.07
0.02
1.08
0.34
0.07
Bal.
31.49
C
8.86
22.35
6.28
0.18
0.003
<0.002
0.07
0.02
1.07
0.34
0.10
Bal.
33.63
D
7.66
22.16
5.12
0.15
0.003
0.002
0.07
0.02
1.05
0.34
0.08
Bal.
31.84
E
8.32
21.91
7.96
0.16
0.003
0.003
0.07
0.02
1.07
0.33
0.09
Bal.
33.33
F
7.74
21.29
6.24
0.18
0.003
0.004
0.09
0.02
1.07
0.31
0.08
Bal.
31.56
G
7.86
20.10
6.14
0.18
0.002
0.003
0.09
0.02
1.06
0.31
0.06
Bal.
30.38
H
7.95
23.02
4.15
0.18
0.003
0.002
0.08
0.02
1.01
0.32
0.05
Bal.
32.54
I
7.49
21.47
6.16
0.14
0.002
0.004
0.06
0.02
0.99
0.32
0.06
Bal.
31.31
J
8.01
23.01
3.09
0.13
0.002
0.002
0.06
0.04
1.14
0.36
0.02
Bal.
32.03
K
7.95
21.34
6.31
0.13
0.002
<0.002
0.06
0.03
0.98
0.30
0.06
Bal.
31.59
L
7.91
22.01
6.11
0.13
0.002
0.003
0.06
0.03
0.95
0.30
0.06
Bal.
32.13
M
7.88
21.59
5.70
0.14
0.002
0.002
0.05
0.02
0.98
0.30
0.05
Bal.
31.54
N
8.00
21.61
6.54
0.14
0.002
0.002
0.07
0.03
0.96
0.30
0.06
Bal.
32.01
O
7.92
22.60
6.16
0.17
0.002
0.002
0.06
0.02
1.08
0.35
0.06
Bal.
32.94
P
7.88
22.29
5.89
0.16
0.004
0.003
0.06
n.m.
1.11
0.33
0.14
Bal.
32.64
Q
8.15
22.51
6.07
0.38
0.003
0.003
0.06
0.02
1.08
0.38
0.08
Bal.
33.63
R
7.81
22.71
6.01
0.21
0.002
0.002
0.09
0.02
1.05
0.32
0.06
Bal.
32.98
S
7.92
23.36
5.96
0.30
0.003
0.002
0.06
0.02
1.07
0.31
0.06
Bal.
33.94
T
7.90
23.21
5.47
0.22
0.002
<0.002
0.06
0.02
1.05
0.31
0.05
Bal.
33.33
U
7.84
23.04
6.37
0.25
0.002
0.002
0.07
0.02
1.08
0.30
0.06
Bal.
33.58
V
8.10
21.08
9.82
0.11
0.002
0.002
0.05
n.m.
1.09
0.31
0.03
Bal.
32.79
W
7.66
23.32
2.97
0.12
0.002
0.003
0.06
0.02
1.04
0.33
0.03
Bal.
31.94
X
7.88
24.68
6.29
0.21
0.003
0.002
0.08
0.02
1.03
0.30
0.06
Bal.
35.10
Y
8.00
19.61
9.84
0.12
0.002
0.001
0.05
n.m.
1.07
0.32
0.03
Bal.
31.27
242
7.70
24.93
0.18
0.19
0.003
0.003
<0.05
0.02
1.10
0.35
0.08
Bal.
32.78
AA
9.26
19.61
2.89
<0.01
<0.002
0.002
0.01
0.06
1.01
<0.01
<0.01
Bal.
28.93
BB*
6.01
18.11
0.04
0.46
0.003
0.004
0.01
0.06
9.11
0.31
0.03
Bal.
30.22
CC
7.81
22.93
5.25
0.13
0.002
0.003
0.06
0.05
1.02
0.33
0.05
Bal.
32.64
DD
7.04
23.59
5.68
0.13
0.002
0.002
0.06
0.04
1.02
0.32
0.05
Bal.
32.82
EE
8.61
21.84
6.27
0.13
0.002
0.002
0.07
0.01
1.01
0.33
0.06
Bal.
32.66
FF
7.87
22.34
6.24
0.11
0.002
0.002
2.07
0.05
1.02
0.33
0.05
Bal.
32.56
GG
7.73
21.96
6.20
0.12
0.002
0.005
5.17
0.03
1.02
0.32
0.05
Bal.
32.93
HH
7.88
22.28
6.21
0.12
0.002
0.003
0.19
0.04
2.51
0.32
0.05
Bal.
33.01
II
7.89
21.26
6.15
0.12
<0.002
0.006
0.06
<0.01
4.97
0.32
0.05
Bal.
32.92
JJ
7.88
22.54
6.30
0.14
0.002
0.002
0.06
0.01
1.01
0.33
0.07
Bal.
32.80
n.m. = not measured
*Other elements—Ti: 1.49 wt. %
To produce material for testing, ingots of the experimental alloys were produced by vacuum induction melting followed by electroslag remelting. The ingots were then forged and hot rolled to produce ½″ thick plate. One of the alloys (alloy X) badly cracked during the rolling operation and was considered to have too poor fabricability for use as a commercial product. No further testing was done on alloy X and it is not considered an alloy of the present invention. The remaining as-rolled plates were then annealed at temperatures ranging from 1950° F. to 2100° F. (1066 to 1149° C.) to produce a uniform microstructure with an ASTM grain size typically between 3½ and 4½. The commercial 242 alloy was obtained from the manufacturer in the form of ½″ plate in the as-annealed condition. The alloys were subjected to several tests to determine their suitability for low-COTE, high strength gas turbine parts for use at temperatures up to 1400° F. (760° C.). This program involved tests to determine the strength and ductility (the combination of which describe a material's containment capability) of the alloys both at room temperature (RT) and 1400° F. (760° C.), the stability/hardening response at 1400° F. (760° C.), and the COTE of the alloys.
As described above, a key property of alloys of this type is the tensile strength at temperatures ranging from room temperature (RT) up to the highest expected service temperature. Of particular interest in this test are two properties: yield strength and ductility (elongation). For gas turbine applications for which the present alloy would be a candidate, a candidate alloy would have high values for both of these two properties. In our experience, gas turbine parts, such as seal and containment rings and cases, made from alloys with a RT yield strength greater than 116 ksi (800 MPa) and a RT elongation greater than 20% should have acceptable containment capability and toughness. The RT tensile properties (including both yield strength and elongation) of several alloys are shown in Table 2. Prior to testing, the samples were given a two-step age-hardening heat treatment of 1400° F. (760° C.)/24 h/furnace cool to 1200° F. (649° C.)/48 h/air cool. Of the 32 alloys tested, 22 alloys were found to have an acceptable RT yield strength of greater than 116 ksi (800 MPa), and 28 were found to have an acceptable RT elongation of 20% or greater. A total of 18 alloys (A, E, H, L, N, O, P, R, T, V, CC, DD, EE, FF, GG, HH, JJ, and 242 alloy) were found to have acceptable values for both RT yield strength and RT elongation.
TABLE 2
Room Temperature Tensile Properties
0.2% Offset
Ultimate
%
%
Al-
Yield Strength
Tensile Strength
Elonga-
Reduction
loy
ksi
MPa
ksi
MPa
tion
in Area
A
124.5
858
196.7
1356
26.2
25.4
B
113.4
782
186.1
1283
39.6
47.2
C
128.4
885
194.2
1339
18.6
18.4
D
113.4
782
184.6
1273
37.1
37.7
E
130.9
903
201.0
1386
29.0
27.7
F
111.6
769
183.4
1265
38.5
39.8
G
102.1
704
173.8
1198
42.5
45.8
H
117.1
807
188.3
1298
38.2
41.2
I
111.6
769
183.0
1262
39.0
39.4
K
113.9
785
185.9
1282
37.7
38.2
L
118.6
818
189.9
1309
34.2
33.0
M
112.4
775
183.7
1267
37.6
37.9
N
119.4
823
190.8
1316
36.1
38.1
O
119.6
825
194.7
1342
30.2
32.4
P
130.4
899
206.1
1421
24.7
27.0
Q
139.0
958
205.8
1419
15.0
15.1
R
127.9
882
198.2
1367
27.4
27.0
S
147.7
1018
209.2
1442
14.0
15.5
T
125.2
863
197.7
1363
30.2
28.3
U
140.7
970
203.2
1401
12.2
12.7
V
133.3
919
202.7
1398
26.7
27.9
242
121.8
840
192.6
1328
36.1
49.9
AA
52.7
363
119.4
823
63.9
66.0
BB
65.6
452
124.9
861
56.4
52.4
CC
120.4
830
193.2
1332
27.6
25.6
DD
128.1
883
201.7
1391
30.1
31.9
EE
125.6
866
197.8
1364
27.6
26.3
FF
125.2
863
198.6
1369
28.8
29.8
GG
120.3
829
196.0
1351
30.9
32.9
HH
119.2
822
186.3
1285
20.1
19.9
II
110.3
761
178.4
1230
20.4
19.6
JJ
126.3
871
198.6
1369
26.2
26.4
It was discovered by the present inventors that the capability of a given alloy to pass the two RT tensile property requirements could be associated with the composition of the alloy using the alloy's “R value” as described by the following equation:
R= 2.66Al+0.19Co+0.84Cr−0.16Cu+0.39Fe+0.60Mn+Mo+0.69Nb+2.16Si+0.47Ta+1.36Ti+1.07V+0.40W [1]
where the elemental compositions are given in wt. %.
In FIG. 1 , the RT yield strength of the tested Ni—Mo—Cr and Ni—Mo—Cr—W alloys is plotted against the R value. As shown in FIG. 1 , the RT yield strength of the alloys tended to increase with increasing R value. It can be seen that alloys with an R value greater than 31.95 achieve a yield strength greater than the minimum target of 116 ksi (800 MPa). Alloys with an R value greater than 31.95 were found to pass the 116 ksi (800 MPa) minimum, while alloys with an R value less than 31.95 had a RT yield strength which fell below the minimum. The only exception to this was alloy II (not shown in FIG. 1 ) which had a yield strength of only 110.3 ksi (761 MPa) while having an R value of 32.92. However, this alloy had a very high Fe level of 4.97 wt. %. That level of iron is unacceptable for reasons set forth below. Thus, alloys of the present invention are required to have an R value of greater than 31.95 (while also having an Fe level of 3 wt. % or less).
Conversely, the RT elongation of the tested alloys tended to decrease with increasing R value. As shown in FIG. 2 the RT elongation of these same alloys are plotted against the R value. Alloys with an R value less than 33.45 have RT elongations greater than the minimum target of 20%. Alloys with an R value greater than 33.45 were found to fail the RT tensile elongation requirement of 20% or greater, while alloys with an R value less than 33.45 were found to have acceptable RT tensile elongation. Thus, alloys of the present invention are required to have an R value of less than 33.45. Combining the two requirements, we have the following requirement for alloys of this invention:
31.95 <R< 33.45 [2]
For age-hardenable alloys, such as those of the present invention, it is of great importance that the strengthening precipitates responsible for the age-hardening response remain stable across the full range of temperatures to which the alloy would be exposed in service. For alloys which would be suitable for use up to 1400° F. (760° C.) (as demanded for alloys of the present invention), it would therefore be necessary that the strengthening precipitates be stable up to that temperature. In this study, it was determined that a simple method of determining whether the age-hardening response is indeed stable for a given alloy at 1400° F. (760° C.), is to give the alloy (in the annealed condition) a 48-hour heat treatment at 1400° F. (760° C.) and then measuring the RT hardness. Alloys which were observed to increase significantly in hardness after the 1400° F. (760° C.) heat treatment were considered to have sufficient stability at that temperature. In the annealed condition, all of the alloys tested in this study had hardness values below the minimum of the Rockwell C range. That is, they had Rc values less than 20. After the 48-hour heat treatment some of the alloys were found to significantly harden, as shown in Table 3.
TABLE 3
Hardness (Rc)
Before 1400° F. (760° C.)
After 1400° F. (760° C.)
Alloy
Heat Treatment
Heat Treatment
A
<20
29
B
<20
<20
D
<20
<20
E
<20
32
F
<20
<20
G
<20
<20
H
<20
<20
J
<20
<20
L
<20
25
N
<20
23
O
<20
33
P
<20
32
R
<20
32
T
<20
32
V
<20
37
W
<20
<20
Y
<20
<20
242
<20
<20
AA
<20
<20
BB
<20
<20
CC
<20
32
DD
<20
36
EE
<20
25
FF
<20
23
GG
<20
23
HH
<20
30
II
<20
<20
JJ
<20
33
The most unique and useful aspect of the alloys of the present invention is illustrated in FIG. 3 where the hardness of several alloys is plotted both before and after the application of an aging heat treatment at 1400° F. (760° C.). It is seen in the figure that only alloys with greater than 5 wt. % tungsten were found to undergo hardening as a result of the heat treatment. This age-hardening response is necessary to provide the alloy with high strength at temperatures up to and including the heat treatment temperature of 1400° F. (760° C.). This is a significantly higher use temperature than had been achieved in previously existing alloys of the same general class (characterized by low thermal expansion, high strength, and good oxidation resistance).
This data demonstrates the unexpected result that tungsten is critical to the success of the alloy. Only alloys with greater than 5 wt. % tungsten have the desired age-hardening response following the 1400° F. (760° C.) heat treatment (and thus, the potential for use in the specified gas turbine applications up to 1400° F. (760° C.)). In FIG. 3 , the hardness before and after the 48-hour heat treatment at 1400° F. (760° C.) is shown for a number of alloys. Only alloys with greater than 5 wt. % tungsten exhibited a hardening response. Thus, for alloys of the present invention:
W>5 [3]
where W is the elemental symbol for tungsten, and the elemental content is given in wt. %.
Despite the necessity of having greater than 5 wt. % tungsten, this quality alone was not sufficient to ensure that a given alloy would age-harden at 1400° F. (760° C.). In addition to the presence of greater than 5 wt. % tungsten, it was found that the R value of the alloy must also be greater than the critical 31.95 value derived from the RT tensile properties of the two-step aged samples described previously. This can be seen in Table 4 where the hardness before and after the 48-hour treatment at 1400° F. (760° C.) is shown alongside the R value for a number of alloys (all of which had a tungsten content of greater than 5 wt. %). For alloys with an R value of less than 31.95, the hardness was found to not increase after receiving the 48-hour 1400° F. (760° C.) treatment. On the other hand, alloys with an R value greater than 31.95 were found to increase in hardness to values of 23 Rc or higher. Thus, the criticality of the minimum R value is reinforced. Yet another characteristic was found to be critical to ensure that a given alloy would age-harden at 1400° F. (760° C.). This characteristic was the Fe level. All of the alloys which satisfied both Eqn. [2] and [3] above were found to age-harden at 1400° F. (760° C.), with the notable exception of alloy II. This alloy had 4.97 wt. % Fe—higher than any of the other alloys. The alloy with the highest Fe level which did age-harden at 1400° F. (760° C.) was alloy HH with an Fe content of 2.51 wt. %. These observations were consistent with the previously described fact that alloy HH satisfied the RT tensile yield strength requirement, while alloy II did not. Therefore, alloys of this invention should have an Fe limit of up to only 3 wt. %:
Fe≦3 [4]
It should be noted that the element Fe is not required in the alloys of the present invention, but is normally present in most nickel-base alloys. The presence of Fe allows economic use of revert materials, most of which contain residual amounts of Fe. An acceptable, essentially Fe-free alloy might be possible using new furnace linings and high purity charge materials (with an accompanying significant increase in production cost). Therefore, it is expected the alloys of this invention will normally contain small amounts of Fe which must be carefully controlled to not exceed the level stipulated in Eq. [4].
A closer look at the importance of tungsten is given in Table 5. Here, the hardness before and after the 48-hour heat treatment at 1400° F. (760° C.) is shown along with the tungsten content. For this table, only alloys with an R value in the acceptable range (between 31.95 and 33.45) are included. From the table it is seen that for all alloys with a tungsten content of less than 5 wt. %, no hardening response was observed. However, for all alloys with greater than 5 wt. % tungsten a distinct hardening response was found. Thus, the criticality of the minimum tungsten content is clearly demonstrated.
Another interesting observation in Table 5, is that increasing the tungsten beyond the critical 5 wt. % threshold did not necessarily result in further hardening. For example, alloy T (with an tungsten content of 5.47 wt. %) had a hardness of 32.3 Rc after the 48-hour heat treatment at 1400° F. (760° C.), while alloy E (with a tungsten content of 7.96 wt. %) had a hardness of only 31.9 Rc after the same heat treatment. Of course, both these values had considerably age-hardened relative to their as-annealed hardness value of <20 Rc.
The four alloys in Table 5 with less than 5 wt. % tungsten (H, J, W, and 242 alloy) are not considered part of the present invention as they satisfy Eqn. [2] and Eqn. [4], but not Eqn. [3]. However, the 16 alloys in Table 5 with greater than 5 wt.% tungsten (A, E, L, N, O, P, R, T, V, CC, DD, EE, FF, GG, HH, and JJ alloys) are considered alloys of the present invention as they satisfy Eqns. [2], [3], and [4].
TABLE 4
All alloys have: W > 5 wt. % (& Fe ≦ 3 wt. %)
Hardness (Rc)
Before 1400° F.
After 1400° F.
(760° C.) Heat
(760° C.) Heat
Alloy
R value
Treatment
Treatment
G
30.38
<20
<20
Y
31.27
<20
<20
B
31.51
<20
<20
F
31.56
<20
<20
D
31.85
<20
<20
N
32.01
<20
23
L
32.13
<20
25
FF
32.56
<20
23
P
32.64
<20
32
CC
32.64
<20
32
EE
32.66
<20
25
A
32.67
<20
29
V
32.79
<20
37
JJ
32.80
<20
33
DD
32.82
<20
36
GG
32.93
<20
23
O
32.94
<20
33
R
32.98
<20
32
HH
33.01
<20
30
T
33.33
<20
32
E
33.34
<20
32
TABLE 5
All alloys have: 31.95 < R value < 33.45 (& Fe ≦ 3 wt. %)
Hardness (Rc)
Before 1400° F.
After 1400° F.
Tungsten
(760° C.) Heat
(760° C.) Heat
Alloy
(wt. %)
Treatment
Treatment
242
0.18
<20
<20
W
2.97
<20
<20
J
3.09
<20
<20
H
4.15
<20
<20
CC
5.25
<20
32
T
5.47
<20
32
DD
5.68
<20
36
P
5.89
<20
32
R
6.01
<20
32
L
6.11
<20
25
O
6.16
<20
33
GG
6.20
<20
23
HH
6.21
<20
30
FF
6.24
<20
23
A
6.27
<20
29
EE
6.27
<20
25
JJ
6.30
<20
33
N
6.54
<20
23
E
7.96
<20
32
V
9.82
<20
37
As discussed above, alloys of this invention must satisfy Eqns. [2], [3], and [4]. In Eqn. [3] the tungsten is required to be greater than 5 wt. %. That is, no upper limit for tungsten was given in this equation. However, it should be recognized that the further imposition of Eq. [2] would necessarily require certain limits of the various elements (including tungsten) present in these alloys when considered in terms of the overall composition (including, especially, the required elements chromium and molybdenum). Given these restraints there is an effective tungsten upper limit. Considering the 16 example alloys (A, E, L, N, O, P, R, T, V, CC, DD, EE, FF, GG, HH, and, JJ) which are considered part of the present invention, the tungsten levels ranged from greater than 5 up to 10 wt. % (see Table 1). However, this invention is not necessarily limited to 10 wt. % tungsten since it is possible to satisfy both Eqn. [2] and Eqn. [3], at even higher levels of tungsten, while maintaining the required levels of both chromium and molybdenum.
Increasing the amount of tungsten in the alloy increases the density of the alloy causing the same volume of material to weigh more. Because less weight is desired in jet engines, where the present alloy is expected to be used, we prefer to keep tungsten within the range of greater than 5 up to 7% of the alloy.
Another property critical to alloys of this invention is the strength of the alloy at 1400° F. (760° C.) as determined by a tensile test at that temperature. Such testing was performed on five of the experimental alloys. The tests were performed on samples in the same two-step age-hardened condition used to measure the RT tensile properties (described earlier). The compositions of all five alloys satisfied Eq. [2] and Eq. [4]. That is, they all had an R value and an Fe level in the acceptable range. However, two of the alloys (H alloy and 242 alloy) had a tungsten content below 5 wt. % (and thus did not satisfy Eqn. [3]), while three of the alloys (E, P, and V) had greater than 5 wt. % tungsten (thus satisfying Eqn. [3]) and were alloys of the present invention. The results are given in Table 6 along with the tungsten content. It is clear from Table 6 that both H alloy and 242 alloy had a much lower 1400° F. (760° C.) yield strength (around 50 ksi/345 MPa), while that of alloys E, P, and V were much higher, ranging from 73 to 80 ksi (503 to 552 MPa). All five alloys were observed to have excellent ductility (elongation) at this temperature. These findings provide further evidence that the alloys of this invention are very well suited for operation at temperatures up to 1400° F. (760° C.).
TABLE 6
1400° F. (760° C.) Tensile Properties
31.95 < R value < 33.45 (& Fe ≦ 3 wt. %)
Tung-
0.2% Offset
Ultimate
%
%
Al-
sten
Yield Strength
Tensile Strength
Elonga-
Reduction
loy
(wt. %)
ksi
MPa
ksi
MPa
tion
in Area
242
0.18
50.5
348
96.1
663
111.7
89.5
H
4.15
49.6
342
95.2
656
93.9
62.7
P
5.89
73.0
503
107.0
738
64.3
64.6
E
7.96
76.1
525
110.9
765
75.2
64.4
V
9.82
80.4
554
117.4
809
51.5
54.0
As mentioned previously, one of the best features of alloys age-hardened by only the Ni 2 (Mo,Cr) phase is their excellent fabricability (including formability, hot workability, and weldability). This is a result of the slow precipitation kinetics of the Ni 2 (Mo,Cr) phase. This contrasts with alloys containing intentional additions of one or more of the gamma-prime forming elements Al, Ti, Nb, and Ta. The resulting gamma-prime phase, while providing an age-hardening response, has fast precipitation kinetics which lead to reduced fabricability. The alloys of this invention are intentionally kept low in the amount of the gamma-prime forming elements. Specifically, the levels of Al, Ti, Nb, and Ta should be kept below 0.7, 0.5, 0.5, and 0.5 wt. %, respectively. In fact, even lower levels of these elements are more preferred. These levels will be described further later in this specification.
As discussed earlier, another key property of this class of alloys is a low coefficient of thermal expansion (COTE). The COTE of P, V, and 242 alloys are shown in Table 7. Note that P and V alloys are alloys of the present invention, while 242 alloy is not. All three alloys had R values in the acceptable range of 31.95<R<33.45. Among these three alloys, the COTE was found to decrease with decreasing tungsten content. As described in the Background section, the 242 alloy is considered a low COTE alloy. It stands to reason that since the COTE of alloys P and V are even lower than for 242 alloy, that the presence of tungsten in the former two alloys represents an improvement in terms of this critical material property.
The contrast between the commercial 242 alloy and the alloys of this invention is deserving of further discussion. As discussed in the Background section, 242 alloy is a commercial product derived from the invention described in U.S. Pat. No. 4,818,486. The 242 alloy is a Ni-25Mo-8Cr alloy with no intentional tungsten addition. However, the U.S. Pat. No. 4,818,486 describes Mo and W as being “interchangeable” and allows for W levels as high as 30 wt. %. There were no example alloys in U.S. Pat. No. 4,818,486 containing tungsten, and no data provided to support the claim that the elements Mo and W were interchangeable. In contrast, some qualities which tungsten was expected to impart were expected to be less desirable (cost, weight, metal working characteristics) although no evidence was provided to support those expectations, either. In comparison to U.S. Pat. No. 4,818,486, a stark contrast is seen when considering the findings of the present invention. The results reported in this application explicitly show that the elements Mo and W are indeed not interchangeable. In fact, it was clearly demonstrated that the presence of a sufficient amount of tungsten in the Ni—Mo—Cr alloys containing nickel, molybdenum and chromium within the ranges set forth in U.S. Pat. No. 4,818,486 was a necessity to achieve the desired qualities of RT tensile yield strength and elongation, and stability of the age-hardening effect to temperatures as high as 1400° F. (760° C.). Without the tungsten addition, these properties could not be achieved. It was further found that tungsten has the desirable effect of lowering the coefficient of thermal expansion. Neither of these findings could have been expected based on the teachings of U.S. Pat. No. 4,818,486.
TABLE 7
Coefficient of Thermal Expansion
All alloys have: 31.95 < R value < 33.45 (& Fe ≦ 3 wt. %)
Mean CTE,
Mean CTE,
RT to 1200° F.
RT to 1400° F.
(RT to 649° C.)
(RT to 760° C.)
micro
micro
Tungsten
inches/
inches/
Alloy
(wt. %)
inch-° F.
μm/m-° C.
inch-° F.
μm/m-° C.
242
0.18
6.93
12.5
7.77
14.0
P
5.89
6.74
12.1
7.48
13.5
V
9.82
6.58
11.8
7.24
13.0
One patent found in the prior art was Magoshi et al. (U.S. Pat. No. 7,160,400). That invention describes alloys which are hardened by both the gamma-prime phase (Ni 3 Al, Ni 3 (Al,Ti), Ni 3 (Al,Ti,Nb,Ta)) and the Ni 2 (Cr,Mo) phase. These alloys are distinct from the alloys of the present invention which intentionally only contain the latter of these two phases. As described previously in this specification, this is because the gamma-prime phase can lead to undesirable properties such as poor formability, workability, and weldability. In the alloys of the present invention the gamma-prime forming elements (Al, Ti, Nb, and Ta) are intentionally kept to low levels to avoid gamma-prime formation. In contrast, the Magoshi et al. patent requires a minimum Al+Ti content of 2.5 at. %, which is higher than allowed in the present invention. Furthermore, the Magoshi et al. patent does not describe the methods of controlling the composition described herein (Eqns. [2], [3], and [4]) which are necessary to reach the desired properties of the present invention. Moreover, the claimed ranges in Magoshi et al. contain compositions which do not meet the requirements of the present invention. Indeed, alloy AA of the present description falls within the Magoshi et al. claims, but does not meet the minimum RT yield strength requirement (Table 2) and does not respond to age-hardening at 1400° F. (760° C.) (Table 3).
Another patent found in the prior art was Kiser et al. (U.S. Pat. No. 5,312,697). That patent describes low thermal expansion alloys for use overlaying on steel substrates. However, the alloys disclosed by Kiser et al. differ significantly from the present invention in that they do not require age-hardenability at 1400° F. (760° C.) (an indicator of high strength for use temperatures as high as 1400° F. (760° C.)). The Mo range in the Kiser et al. patent is 19 to 20 wt. % Mo, well below the 21-24 wt. % required by the present invention. The tungsten levels are also below those of the present invention. Furthermore, there is no teaching in the Kiser et al. patent about controlling the elemental relationships (Eqns. [2], [3], and [4]) to ensure the age-hardening/strength requirements of the present invention. In fact, the compositional ranges described by the Kiser et al. invention cannot be expected to meet the requirements of the present invention, as evidenced by alloy BB described herein in Table 1. This alloy falls in the Kiser et al. range, but not that of the present invention. It was shown in Tables 2 and 3 that alloy BB has neither the required RT tensile strength nor the age-hardenability at 1400° F. (760° C.) required by alloys of the present invention.
For convenience, a table is provided (Table 8) that details which alloys described in this specification are considered part of the present invention, and which are not. Also included in Table 8 is a description of whether each alloy satisfied the R value and tungsten level requirements for the invention as described by Eqn. [2] and Eqn. [3], respectively.
TABLE 8
Alloy Summary
Tungsten
Alloy of this
Alloy
“R value”
level
invention
A
OK
OK
YES
B
LOW
OK
NO
C
HIGH
OK
NO
D
LOW
OK
NO
E
OK
OK
YES
F
LOW
OK
NO
G
LOW
OK
NO
H
OK
LOW
NO
I
LOW
OK
NO
J
OK
LOW
NO
K
LOW
OK
NO
L
OK
OK
YES
M
LOW
OK
NO
N
OK
OK
YES
O
OK
OK
YES
P
OK
OK
YES
Q
HIGH
OK
NO
R
OK
OK
YES
S
HIGH
OK
NO
T
OK
OK
YES
U
HIGH
OK
NO
V
OK
OK
YES
W
OK
LOW
NO
X*
HIGH
OK
NO
Y
LOW
OK
NO
242
OK
LOW
NO
AA
LOW
LOW
NO
BB
LOW
LOW
NO
CC
OK
OK
YES
DD
OK
OK
YES
EE
OK
OK
YES
FF
OK
OK
YES
GG
OK
OK
YES
HH
OK
OK
YES
II
OK
OK
NO**
JJ
OK
OK
YES
*Badly cracked during hot rolling.
**Fe was too high (>3 wt. %)
From the data presented we can expect that the alloy compositions set forth in Table 9 will also have the desired properties.
TABLE 9
Other Alloy Compositions
Alloy
Cr
Mo
W
Al
B
C
Co
Cu
Fe
Mn
Si
Other
R value
1
8
22
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
—
32.37
2
7
22.5
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
—
32.03
3
9
22
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
—
33.21
4
8.5
21
7
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
—
32.19
5
7.2
24
5.2
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
—
33.38
6
8
22
5.1
0.18
0.003
0.003
0.08
0.02
1
0.25
0.08
—
31.96
7
8
22
7
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
—
32.77
8
8
21.5
9
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
—
33.07
9
8
21
10
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
—
32.97
10
7
21
13
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
—
33.33
11
7
21
16.4
—
—
—
—
—
—
—
—
—
33.44
12
8.5
22.5
6
—
—
—
—
—
—
—
—
—
32.04
13
8
22
6
0.18
0.006
0.003
0.08
0.02
1
0.33
0.08
—
32.37
14
8
22
6
0.18
0.003
0.03
0.08
0.02
1
0.33
0.08
—
32.37
15
8
22
6
0.18
0.003
0.003
1
0.02
0.5
0.33
0.08
—
32.35
16
8
22
6
0.5
0.003
0.003
0.08
0.02
1
0.33
0.08
—
33.22
17
8
22
6
0.18
0.003
0.003
0.08
0.02
1
0.8
0.08
—
32.65
18
8
22
6
0.18
0.003
0.003
—
—
1
0.33
—
—
32.19
19
8
22
6
0.18
0.003
0.003
0.08
0.5
1
0.33
0.08
—
32.29
20
8
22
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.2
—
32.63
21
8
22
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
0.05
Ca
32.37
22
8
22
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
0.05
Mg
32.37
23
8
22
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
0.05
Y
32.37
24
8
22
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
0.05
Hf
32.37
25
8
22
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
0.05
Ce
32.37
26
8
22
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
0.05
La
32.37
27
8
22
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
0.2
Nb
32.51
28
8
22
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
0.2
Ta
32.47
29
8
22
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
0.2
Ti
32.64
30
8
22
6
0.18
0.003
0.003
0.08
0.02
1
0.33
0.08
0.2
V
32.59
The alloy of the present invention must contain, by weight, 7% to 9% chromium, 21 to 24% molybdenum, greater than 5% tungsten and the balance nickel plus impurities and may contain aluminum, boron, carbon, calcium, cobalt, copper, iron, magnesium, manganese, niobium, silicon, tantalum, titanium, vanadium, and rare earth metals within the ranges set forth in Table 10.
TABLE 10
Optional Elements in Weight Percent
Element
Broad range
Narrow range
Typical
Al
less than 0.7
up to 0.5
About 0.2
B
Trace to 0.015
0.002-0.006
About 0.003
C
up to 0.1
0.002-0.03
About 0.003
Ca
up to 0.1
up to 0.05
Co
up to 5
up to 1
About 0.08
Cu
up to 0.8
up to 0.5
About 0.02
Fe
up to 3
up to 2
About 1.0
Mg
up to 0.1
up to 0.05
Mn
up to 2
up to 1
About 0.5
Nb
less than 0.5
up to 0.2
Si
up to 0.5
up to 0.2
About 0.05
RE*
up to 0.1
up to 0.05
Ta
less than 0.5
up to 0.2
Ti
less than 0.5
up to 0.2
V
up to 0.5
up to 0.2
*Rare earth metals (RE) may include hafnium, yttrium, cerium, and lanthanum,
While we prefer that cobalt content not exceed 5%, it is likely that higher amounts could be present without sacrifice of the desired properties.
From the compositions of the alloys identified in Table 8 as an alloy of this invention and from the other acceptable alloy compositions in Table 9 we see that an alloy having the desired properties may contain in weight percent 7% to 9% chromium, 21% to 24% molybdenum, greater than 5% tungsten, up to 3% iron, with a balance being nickel and impurities. And the alloy must further satisfy the following compositional relationship:
31.95 <R< 33.45
Where the R value is defined by the equation:
R= 2.66Al+0.19Co+0.84Cr−0.16Cu+0.39Fe+0.60Mn+Mo+0.69Nb+2.16Si+0.47Ta+1.36Ti+1.07V+0.40W
The alloy has better hardness after being age-hardened at 1400° F. (760° C.) if tungsten is present from greater than 5% up to 10% as indicated by FIG. 3 . Optional elements may be present in amounts set forth in Table 10.
From the specific amounts of the elements in the alloys tested that were considered to be within the invention we see that an alloy having the desired properties may contain in weight percent 7.04% to 8.61% chromium, 21.08% to 23.59% molybdenum. 5.25% to 9.82% tungsten, up to 2.51% iron, with a balance being nickel and impurities. The alloy must further satisfy the following compositional relationship:
32.01 <R< 33.33
Where the R value is defined by the equation:
R= 2.66Al+0.19Co+0.84Cr−0.16Cu+0.39Fe+0.60Mn+Mo+0.69Nb+2.16Si+0.47Ta+1.36Ti+1.07V+0.40W
Although we have described certain present preferred embodiments of our alloy it should be distinctly understood that our invention is not limited thereto but may be variously embodied within the following claims; | An alloy designed for use in gas turbine engines which has high strength and a low coefficient of thermal expansion is disclosed. The alloy may contain in weight percent 7% to 9% chromium, 21% to 24% molybdenum, greater than 5% tungsten, up to 3% iron, with a balance being nickel and impurities. The alloy must further satisfy the following compositional relationship: 31.95<R<33.45, where the R value is defined by the equation:
R =2.66Al+0.19Co+0.84Cr−0.16Cu+0.39Fe+0.60Mn+Mo+0.69Nb+2.16Si+0.47Ta+1.36Ti+1.07V+0.40W
The alloy has better hardness after being age-hardened at 1400° F. (760° C.) if tungsten is present from greater than 5% up to 10% and a preferred density if the alloy contains greater than 5% up to 7% tungsten. | 2 |
This application is a continuation of application Ser. No. 09/176,021, filed Oct. 21, 1998.
FIELD OF THE INVENTION
The present invention relates to a lock-up control of a torque converter, used in the automatic transmission system of a vehicle.
BACKGROUND OF THE INVENTION
Torque converters carry out the functions of absorbing torque fluctuations or increasing torque in order to transmit the motive force between the input/output elements through a fluid.
Since their transmission efficiency is lower than the conventional friction clutch, during running conditions where absorbing torque fluctuations or increasing torque are not necessary, the input/output elements of the torque converter are directly connected and put in a lock-up state.
In vehicles provided with an automatic transmission and a torque converter equipped with such a lock-up clutch, the torque converter is generally put in the lock-up state during coast running in order to increase the fuel cut period.
However when shifting from coast running to power running by depressing the accelerator pedal while the torque converter is maintained in the lock-up state, the torque converter may experience a torque shock due to sudden increase of input torque.
In order to suppress this torque shock, Tokkai Hei, 8-233098 published in 1996 by the Japanese Patent Office discloses the unlocking of the torque converter when shifting from coast running to power running is performed.
However in this conventional technique, if shifting between coast running and power running is frequently repeated during driving, the torque converter will be repeatedly locked up and unlocked. Thus the clutch facing of the lock-up clutch will soon wear out and this will adversely affect to the durability of the torque converter.
SUMMARY OF THE INVENTION
It is therefore an object of this invention to avoid frequent lock-up and unlock of the torque converter, while also avoiding torque shock when shifting from coast running to power running.
In order to achieve the above object, this invention provides a lock-up control device for a torque converter in a vehicle. The torque converter comprises an input element connected to an engine which rotates according to a depression of an accelerator and an output element connected to an automatic transmission. The lock-up control device comprises a sensor for detecting a depression degree of the accelerator, a sensor for detecting a vehicle speed, and a microprocessor programmed to determine whether or not the vehicle is coasting based on the depression degree of the accelerator, determine whether or not the torque converter is in a lock-up state wherein the input and output elements are directly combined, calculate an accelerator depression speed from the depression degree of the accelerator, shift the torque converter to an unlock state in which the input and output elements are indirectly combined when the vehicle is coasting, the torque converter is in the lock-up state, and the accelerator depression speed is larger than a predetermined speed, determine whether or not the vehicle speed is within a predetermined re-lock-up prevention speed range, and prevent the torque converter from shifting to the lock-up state when the torque converter has been shifted to the unlock state and the vehicle speed is within the predetermined re-lock-up prevention speed range.
When the engine comprises a throttle which operates according to the depression of the accelerator, it is preferable that the accelerator depression degree sensor comprises a sensor for detecting an opening of the throttle.
It is also preferable that the microprocessor is further programmed not to shift the torque converter to the lock-up state when the vehicle speed is less then the predetermined re-lock-up prevention speed range irrespective of the accelerator depression speed.
It is also preferable that the microprocessor is further programmed to learn an average speed of the accelerator depression from coasting of the vehicle, and modify the re-lock-up prevention speed range to a larger range when the average speed is larger than a standard value.
In this case, it is further preferable that the microprocessor is further programmed to set the larger range by modifying an upper limit of the re-lock-up prevention speed range to a larger value.
It is also preferable that the microprocessor is further programmed to set the larger range by modifying a lower limit of the re-lock-up prevention speed range to a smaller value.
It is also preferable that the microprocessor is further programmed to calculate a time elapsed from when the torque converter was shifted from the lock-up state to the unlock state, and allow the torque converter to shift to the lock-up state when the elapsed time has reached a set time even when the vehicle speed is within the predetermined re-lock-up prevention speed range.
In this case, it is further preferable that the microprocessor is further programmed to learn an average speed of the accelerator depression from coasting of the vehicle, and modify the set time to a longer time when the average speed is larger than a standard value.
The details as well as other features and advantages of this invention are set forth in the remainder of the specification and are shown in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of a torque converter and a control device therefor according to this invention.
FIG. 2 is an enlarged view of essential parts of FIG. 1 .
FIG. 3 is a flow chart describing a lock-up control process performed by a controller according to this invention.
FIG. 4 is similar to FIG. 3, but showing a second embodiment of this invention.
FIG. 5 is similar to FIG. 3, but showing a third embodiment of this invention.
FIG. 6 is a diagram showing a lock up region of the torque converter and a vehicle speed region for preventing re-lock-up of the converter according to this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1 of the drawings, an engine 1 is connected to an automatic transmission 3 via a torque converter 2 . An output torque of the transmission 3 is transmitted to vehicle wheels 5 via a differential gear 4 .
The a torque converter 2 comprises a pump impeller 2 A connected to a rotating axis of the engine 1 , a turbine runner 2 B connected to an input axis of the transmission 3 and a lock-up clutch 2 C which combines the pump impeller 2 A and the turbine runner 2 B in a lock-up state. In this state, the torque is directly transmitted from the pump impeller 2 A to the turbine runner 2 B. When the lock-up clutch 2 C is in an unlock state, the torque is transmitted by fluid sealed in a space between the pump impeller 2 A and the turbine runner 2 B. In this state the pump impeller 2 A and the turbine runner 2 B can slip with respect to each other.
The force for locking up the lock-up clutch 2 C is determined by the differential pressure of the applied pressure P A and the release pressure P R . If the applied pressure P A is lower than the release pressure P R , the lock-up clutch 2 C is in the unlock state. If the applied pressure P A is greater than the release pressure P R and the resultant differential pressure is greater than a predetermined value, the lock-up clutch 2 is in the lock-up state. The applied pressure P A and the release pressure P R are controlled by a control system described below.
A lock-up control valve 11 provides the applied pressure P A and the release pressure P R on the basis of the signal pressure P S from a lock-up solenoid 13 . The lock-up solenoid 13 generates the signal pressure P S according to a signal D output from a controller 12 , this signal changing over between ON and OFF. The construction of the lock-up control valve 11 and the lock-up solenoid 13 is shown in FIG. 2, which is known in the art.
The lock-up solenoid 13 uses a fixed pilot pressure P P as a base pressure and generates the signal pressure P S according to the signal D from the controller 12 .
The lock-up control valve 11 comprises a spool which receives the release pressure P R and the above signal pressure P S in one direction and the applied pressure P A and force of the spring 11 A in the other direction. When the signal pressure P S is high, the applied pressure P A is also high and if the differential pressure (P A −P R ) is greater than the force required for the lock-up of the lock-up clutch 2 C, the torque converter is placed in the lock-up state.
On the other hand, when the signal pressure P S is low, the differential pressure (P A −P R ) is less than the force required for the lock-up, the lock-up control valve 11 releases the lock-up clutch 2 C.
As shown in FIGS. 1 and 2, a signal from a throttle opening sensor 21 which detects a throttle opening TVO of the engine 1 and a signal from a vehicle speed sensor 22 which detects the vehicle speed VSP are inputted into the controller 12 .
The controller 12 comprises a microcomputer which has a central computing unit (CPU), a read only memory (ROM), a random access memory (RAM) and an input/output inter face (I/O interface).
The controller 12 conducts a lock-up control process shown in FIG. 3 on the basis of the above input signals. This process is performed at a fixed interval.
First, in a step the throttle opening TVO and the vehicle speed VSP are read. Then it is determined in a step S 32 if the lock-up clutch 2 C is in the lock-up state used while the vehicle is in the coast running. When the result is negative, normal lock-up control is carried out in a step S 33 . Normal lock-up control is explained as follows.
On the basis of the throttle opening TVO and the vehicle speed VSP, it is determined whether the vehicle running condition is in a lock-up region or unlock region by referring to a map shown in FIG. 6 . When in the unlock region, the signal D is OFF and as a result the lock-up clutch 2 C is unlocked. When in the lock-up region, the signal D is ON, and as a result the lock-up clutch 2 C is locked up.
The state in which the lock-up clutch 2 C is locked up while the vehicle is in the coast running is distinguished by the fact that the throttle opening TVO is 0 while the vehicle speed VSP is not 0.
When the above lock-up/coast running condition has been detected in the step S 32 , the process proceeds to a step S 34 .
In the step S 34 , the difference of the current throttle opening TVO and that of the immediately preceding occasion when the process was performed TVO 31 is computed. The result is then divided by the interval of the process execution so as to obtain a throttle operating speed, which corresponds to an accelerator pedal depression speed.
In a next step S 35 , it is determined whether or not the accelerator pedal depression speed above is higher than a fixed value. If the accelerator pedal depression speed is higher than the fixed value, it is determined that the lock-up clutch 2 C should be unlocked and the process proceeds to a step S 37 . If on the other hand the accelerator pedal depression speed is equal to or less than the fixed value, the lock-up clutch 2 C is maintained in the lock-up state in a step S 36 and the process terminates without performing further steps.
In the step S 37 , the command signal D is turned to be OFF, the lock-up clutch 2 C is unlocked, and at the same time a timer TM which measures time elapsed from this unlock operation is activated.
In a step S 38 , as shown in FIG. 6, preset vehicle speeds VSPL and VSPH as well as set time TS are read.
The preset vehicle speeds are used to determine the vehicle speed range in which re-lock-up should be prevented until the elapsed time from the unlock operation reaches the set time TS.
The upper limit of vehicle speed VSPH corresponds to the lower limit of a vehicle speed range which does not cause torque shock problems due to shifts from coast running to power running.
The lower limit of vehicle speed VSPL corresponds to the upper limit of a vehicle speed range in which the lock-up clutch 2 C is not locked-up in coast running.
As far as the vehicle is driven in the vehicle speed range between VSPL and VSPH, re-lock-up is prevented until the time elapsed after the unlock operation of the lock-up clutch 2 C reaches the set time TS. The set time TS is determined beforehand as an allowable period of time during which fuel consumption and noise will not become problems, even if re-lock-up is not performed after the shift to power running which has accompanied the unlock operation of the lock-up clutch 2 C.
In a step S 39 , it is determined whether or not to allow re-lock-up on the basis of the following conditions: whether or not the vehicle speed VSP is in the vehicle speed range between the vehicle speeds VSPL, VSPH, or whether the timer TM, which measures the elapsed time from the release of lock-up due to the shift to power running, has exceeded set time TS.
The speed range below the lower limit vehicle speed VSPL is the range where lock-up of the torque converter is not performed, so re-lock-up is not allowed in this range irrespective of the accelerator pedal depression speed.
If re-lock-up is not allowed, the process repeats the steps S 38 and S 39 until re-lock-up is allowed. When the conditions allowing re-lock-up are satisfied, the process proceeds to step S 40 and outputs a lock-up ON command so as to place the torque converter in the lock-up position.
In this embodiment, for example when the shift is made by quickly depressing the accelerator pedal from coast running in the lock-up state at point X in FIG. 6 to power running at point Y in the same figure, the torque converter is released from the lock-up, and the generation of torque shock due to sudden increase of the input torque to the torque converter 2 is thereby prevented.
When this input torque increase is stopped, re-lock-up of the torque converter 2 is not performed until the vehicle speed VSP moves out of the speed range between VSPL and VSPH, or the elapsed time from the release of lock-up reaches the set time TS. Therefore, even if coast running and power running are alternated at short intervals, the torque converter 2 is maintained in the unlock state.
Therefore problems with respect to the durability of the clutch facing of the lock-up clutch 2 C suffering early wear due to being turned ON and OFF frequently is avoided.
On the other hand, when the vehicle speed VSP has moved out of the above speed range or when the elapsed time has reached the set time TS, the prevention of re-lock-up is released and the torque converter may be locked up again. Hence, increase of fuel consumption due to the continuation of the unlock state over a long period is also avoided.
FIG. 4 shows a second embodiment of this invention.
In this embodiment, the upper and lower limits of vehicle speed VSPH and VSPL, which determine the vehicle speed range for preventing re-lock-up, are set by learning the habits of the driver in accelerator pedal operation. That is to say, it is based on whether the driver has a tendency to repeat coasting and power running which leads to problems of wear and tear.
In FIG. 4, steps S 41 and S 42 are added between steps S 37 and S 38 in the flowchart of FIG. 3 .
In the step S 41 , the pattern of the driver's operation when depressing the accelerator pedal from coast running to power running is learned. This includes the learning of the average degree of depression of the accelerator pedal during a shift period from coast running to power running. If this value is large, it is determined that the driver has a tendency to repeat coasting and power running and hence the clutch facing of the torque converter will soon wear out.
In the next step 42 , the learnt value is compared with a predetermined standard range. When the learnt value is larger than the predetermined standard range, the lower limit of vehicle speed VSPL is lowered by ΔVSP, and the upper limit of vehicle speed VSPH is raised by ΔVSP. When the learnt value is within the standard range, the lower limit VSPL and upper limit VSPH are unchanged.
As a result, on the basis of the pattern of the driver's operation of depressing the accelerator pedal, the vehicle speed range for preventing re-lock-up is enlarged depending on the speed with which the driver depresses the accelerator pedal. Hence the frequency with which the vehicle speed VSP moves out of that range decreases. Therefore even for drivers with a tendency to often repeat shifts between coasting and power running, durability problems of the clutch facing can be avoided.
FIG. 5 shows a third embodiment of this invention.
In this embodiment, the set time TS is determined according to the learnt value corresponding to the habits of the driver in depressing the accelerator pedal. In this context, a step S 43 is substituted for step S 42 of FIG. 4 .
Step S 41 which is the prior step to the step S 43 is identical to that of FIG. 4 .
In the step S 43 , once it is determined that the learnt value is larger than the predetermined standard range, the set time TS is lengthened by ΔT, and in the subsequent step S 38 , the lengthened set time TS is read.
According also to this embodiment, even when the driver has a tendency to frequently repeat shifts between coast running and power running, durability problems of the clutch facing can be avoided.
In the second and third embodiments, either of set vehicle speeds VSPL, VSPH or set time TS was varied on the basis of learnt value. It is needless to say, however, that these arrangements may be applied simultaneously.
In the above embodiments, the throttle opening sensor 21 is used for detecting the accelerator operation speed. However, it is also possible to directly measure the degree of the accelerator pedal depression to obtain the accelerator pedal depression speed.
The corresponding structures, materials, acts, and equivalents of all means plus function elements in the claims below are intended to include any structure, material, or acts for performing the functions in combination with other claimed elements as specifically claimed. | A lock-up controller is provided for shifting a torque converter of a vehicle from the lock-up state to the unlock state when the accelerator pedal is depressed at a speed larger than a predetermined speed when the vehicle is coasting. The controller is further functioning to prevent the torque converter from shifting to the lock-up state when the torque converter has been shifted to the unlock state and the vehicle speed is within the predetermined re-lock-up prevention speed range so as to avoid frequent lock-up/unlock operation of the torque converter. | 5 |
BACKGROUND
1. Technical Field
The present disclosure relates to mounting apparatuses and, more particularly, to a mounting apparatus for a slide rail.
2. Description of the Related Art
A rackable server system includes a rack and a plurality of servers slidably mounted to the rack with a plurality of slide rail assemblies. Each of the slide rail assemblies includes two mounting apparatus at opposite ends of the slide rail assembly for fixing the slide rail assembly to opposite supporting posts of the rack. However, each of the mounting apparatuses is designed for a kind of particular-sized supporting posts. Therefore, the slide rail assembly cannot be fixed to differently-sized supporting posts.
BRIEF DESCRIPTION OF THE DRAWINGS
Many aspects of the present embodiments can be better understood with reference to the following drawings. The components in the drawings are not necessarily drawn to scale, the emphasis instead being placed upon clearly illustrating the principles of the present embodiments. Moreover, in the drawings, all the views are schematic, and like reference numerals designate corresponding parts throughout the several views.
FIG. 1 is an exploded, isometric view of an embodiment of a mounting apparatus, a slide rail, and a supporting post of a rack, the mounting apparatus including a supporting bracket, a latch member, a holding member, a button, and a resilient member.
FIG. 2 is an assembled, isometric view of the mounting apparatus and the slide rail of FIG. 1 .
FIGS. 3 and 4A are side plan views of FIG. 2 , respectively showing the latch member in unlocked and locked positions.
FIG. 4B is similar to FIG. 4A , but showing the mounting apparatus locked to another rack post.
DETAILED DESCRIPTION
The disclosure, including the accompanying drawings, is illustrated by way of example and not by way of limitation. It should be noted that references to “an” or “one” embodiment in this disclosure are not necessarily to the same embodiment, and such references mean at least one.
Referring to FIG. 1 , an embodiment of a mounting apparatus is provided for mounting a slide rail 80 to a rack post 90 defining a plurality of through holes 92 . The mounting apparatus includes a supporting bracket 1 , a latch member 3 , a holding member 5 , a button 6 , and a resilient member 7 .
The slide rail 80 defines a substantially C-shaped cross section, and includes a web 82 with two flanges 84 extending from upper and lower sides of the web 82 , respectively. The web 82 forms a plurality of fixing pins 842 extending from an outer surface of the web 82 .
The supporting bracket 1 includes a sidewall 12 , two flanges 14 perpendicularly extending from upper and lower sides of the sidewall 12 , an end plate 16 perpendicularly extending from a front end of the sidewall 12 , and an engaging tab 18 perpendicularly extending from a rear end of the sidewall 12 . The sidewall 12 defines two parallel first slide slots 122 extending in a longitudinal direction of the sidewall 12 , adjacent to the end plate 16 , and a second slide slot 123 (shown in FIG. 3 ) extending substantially parallel to the first slide slots 122 , and arranged at a top side of the first slide slots 122 . A through hole 124 is defined in the sidewall 122 , between the first slide slots 122 . A plurality of fixing holes 128 is defined in the sidewall 12 , adjacent to the engaging tab 18 . A plurality of fixing pins 126 protrudes from an outer surface of the sidewall 12 , and arranged in an area bounded by the plurality of fixing holes 128 . Two inserting pins 162 extend forward from the end plate 16 of the supporting bracket 10 . Each of the inserting pins 162 includes a first inserting segment extending from the end plate 16 , and a second inserting segment extending from the first inserting segment. A shoulder 1625 is formed at a distal end of the first inserting segment, facing the second inserting segment. An engaging hole 181 is defined in the engaging tab 18 .
The latch member 3 includes a slide bracket 20 and two positioning pins 40 . The slide bracket 20 includes a side panel 22 , two flanges 23 extending outwards from upper and lower sides of the side panel 22 , a blocking plate 24 perpendicularly extending from a front end of the side panel 22 , and an engaging tab 26 extending from a rear end of the side panel 22 . A substantially arc-shaped opening 221 is defined in the rear end of the side panel 22 . Two positioning holes 223 are defined in the side panel 22 , near upper and lower sides of the opening 221 , respectively. The blocking plate 24 defines two through holes 242 therein. A handle 248 extends forward from the blocking plate 24 . Each of the positioning pins 40 includes an abutting portion 44 , and a mounting portion 42 . The abutting portion 44 includes a first abutting block 441 , a second abutting block 442 , and a third abutting block 443 stacked up one by one. The first, second, and third abutting blocks 441 , 442 , and 443 are disc-shaped. A diameter of the second abutting block 442 is smaller than a diameter of the first abutting block 441 , and greater than a diameter of the third abutting block 443 .
The holding member 5 is a metal sheet, which is bent to form a holding plate 51 and a pressing tab 54 . The holding plate 51 includes a mounting portion 511 , an elongated portion 513 extending from a front end of the mounting portion 511 , and two substantially L-shaped retaining portions 515 extending from a front end of the elongated portion 513 . A plurality of securing holes 5113 is defined in the mounting portion 511 . A connecting hole 5151 is defined in the elongated portion 513 , between the retaining portions 515 . Each of the retaining portions 515 forms a forward side 5152 , and a rearward side 5153 opposite to the forward side 5152 and facing the mounting portion 511 . The pressing tab 54 extends forward from a rear end of the mounting portion 511 , and includes two spaced pressing portions 542 elastically resisting against the retaining portions 515 , respectively.
The button 6 includes a cylindrical main body 61 with a diameter smaller than the through hole 124 of the supporting bracket 1 , and a fixing portion 62 extending from an end of the main body 61 .
In one embodiment, the resilient member 7 is a coil spring, with two hooks 72 correspondingly formed at opposite ends of the resilient member 7 .
Referring to FIGS. 2 to 4A , in assembly, the button 6 is mounted to a side of the holding plate 51 opposite to the pressing tab 54 , with the fixing portion 62 of the button 6 fixed in the connecting hole 5151 of the holding plate 51 . The holding member 5 is mounted to the supporting bracket 1 , with the fixing pins 126 of the supporting bracket 1 fixed in the securing holes 5113 of the holding member 30 . The main body 61 of the button 6 extends through the through hole 124 of the sidewall 12 of the supporting bracket 1 . The slide bracket 20 of the latch member 3 is slidably coupled to the supporting bracket 1 , with the engaging tab 26 slidably engaged in the second slide slot 123 . The mounting portions 42 of the positioning pins 40 extend through the corresponding first slide slots 122 of the supporting bracket 1 and are retained in the corresponding positioning holes 223 of the slide bracket 20 . Therefore, the positioning pins 40 are fixed to the slide bracket 20 , and slidably engaged with the supporting bracket 1 . One of the hooks 72 of the resilient member 7 is engaged in the engaging hole 181 of the engaging tab 18 of the supporting bracket 1 , and the other hook 72 is engaged with the engaging tab 26 of the slide bracket 20 . In an initial status, the slide bracket 20 is located in a position to make the fixing pins 126 extend into the through holes 242 of the blocking plate 24 of the slide bracket 20 . The positioning pins 40 are located behind the retaining portions 515 of the holding member 5 .
The mounting apparatus is installed to the slide rail 80 , with the protrusions 842 of the slide rail 80 correspondingly fixed in the fixing holes 128 of the supporting bracket 1 .
Referring to FIG. 3 , to mount the slide rail 80 to the rack post 90 , the main body 61 of the button 6 is pushed to move the retaining portions 515 of the holding member 5 away from the sidewall 12 of the supporting bracket 1 , until the retaining portions 515 disengage from the corresponding positioning pins 40 . Therefore, the positioning pins 40 are capable of sliding forward along the corresponding first slide slots 122 . The handle 248 is operated to pull the slide bracket 20 forward, the positioning pins 40 move with the slide bracket 20 toward the front end of the corresponding first slide slots 122 of the supporting bracket 1 . The resilient member 7 is deformed. The blocking plate 24 of the slide bracket 20 moves away from the end plate 16 of the supporting bracket 1 to make the inserting pins 162 disengage from the corresponding through holes 242 of the blocking plate 24 . The button 6 is released, the holding member 5 is restored to make the holding plate 51 tightly abut against the sidewall 12 of the supporting bracket 1 . The handle 248 is released. The resilient member 7 is restored to pull the slide bracket 20 backwards until the positioning pins 40 abut against the forward sides 5152 of the corresponding retaining portions 515 of the holding plate 51 . Therefore, the latch member 3 is kept in an unlocked position, ready for engaging with the rack post 90 .
Referring to FIG. 4A , the slide rail 80 is handled to make the inserting pins 162 insert into the corresponding through holes 92 of the rack post 90 , until the shoulders 1625 of the inserting pins 162 abut against, a rear surface of the rack post 90 . The button 6 is pushed to move the retaining portions 515 of the holding plate 51 away from the sidewall 12 of the supporting bracket 1 to disengage the holding member 5 from the positioning pins 40 . The resilient member 7 is restored to slide the slide bracket 20 backwards, until the blocking plate 24 abuts against a front surface of the rack post 90 to tightly sandwich the rack post 90 between the blocking plate 24 and the shoulders 1625 of the inserting pins 162 . At the same time, the positioning pins 40 slide with the slide bracket 20 along the corresponding first slide slots 122 of the supporting bracket 1 to approach to the rear ends of the first slide slots 122 . The button 6 is released, the holding member 5 is restored. The retaining portions 515 of the holding plate 51 move towards the sidewall 12 of the supporting bracket 1 . in one embodiment, the rearward sides 5153 of the retaining portions 515 abut against the third abutting blocks 441 of the corresponding positioning pins 40 to keep the slide bracket 20 in a locked position where the slide rail 80 is retained to the rack post 90 by the mounting apparatus.
Referring to FIG. 4B , when the slide rail 80 is mounted to another rack post 90 ′ having a thickness greater than that of the rack post 90 of FIG. 4A , the rearward sides 5153 of the retaining portions 515 will abut against the first abutting blocks 442 or the second abutting blocks 443 of the corresponding positioning pins 40 to keep the slide bracket 20 in the locked position and increase the distance between the blocking plate 24 and the end plate 16 corresponding to thickness of the another rack post 90 ′. Therefore, the mounting apparatus can fix the slide rail 80 to different-sized rack posts.
When the slide rail 80 is mounted to another rack post greater than the rack post 90 , the rearward sides 5153 of the retaining portions 515 will abut against the first abutting blocks 442 or the second abutting blocks 443 of the corresponding positioning pins 40 to keep the slide bracket 20 in the locked position. Therefore, the mounting apparatus can fix the slide rail 80 to different-sized supporting posts.
It is believed that the present embodiment and its advantages will be understood from the foregoing description, and it will be apparent that various changes may be made thereto without departing from the spirit and scope of the description or sacrificing all of its material advantages, the examples hereinbefore described merely being exemplary embodiments. | A fixing apparatus includes a mounting bracket secured to a slide rail, a latch member, and a holding member. The mounting bracket includes an inserting pin extending into a through hole of a rack post. The latch member includes a slide bracket, and a positioning pin forming a plurality of abutting blocks stacked up one by one. A rear end of the holding member is secured to the mounting bracket, and includes a retaining portion extending forwards. The latch member is slidable between a locking position to prevent the inserting pin from being disengaged from the through hole of the rack post, and an unlocking position to enable the insert pin to slide out of the through hole of the rack post. the retaining portion of the holding member is selectively abuts against one of the abutting blocks of positioning pin to prevent the latch member from sliding towards the unlocking position. | 7 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/592,220, filed Jul. 30, 2004.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates generally to organizing devices. More specifically, the invention is a static clinging vinyl sheet having special indicia adapted for placement over a white board, the vinyl sheet clinging to the white board due to the inherent electrostatic nature of the material. A colored erasable marker pen, for example, is used to place indicia on the vinyl sheet.
[0004] 2. Description of the Related Art
[0005] The related art of interest describes various training aid devices, but none discloses the present invention. There is a need for a device that permits adding temporary indicia on a transparent plastic overlay sheet as a teaching or scheduling aid. The related art of interest will be distinguished in the order of perceived relevance to the present invention.
[0006] U.S. Pat. No. 6,324,777 B1 issued on Dec. 4, 2001, to Chi L. Ngan describes a static cling calendar having an electrostatic swingable cover which will attract a sheet underlying the cover so that when the cover is swung, the underlying sheet will be picked by the cover to expose the underside of the sheet as well as the next succeeding sheet. The calendar is distinguishable for requiring multiple electrostatic sheets.
[0007] U.S. Pat. No. 3,797,134 issued on Mar. 19, 1974, to Eldon S. Wingerd describes an arithmetic concepts display board having a grid portion defined by ridges for equal squares with pegs rising from every other gridline intersection on every other grid line. The board is distinguishable for requiring pegs.
[0008] U.S. Pat. No. 3,638,332 issued on Feb. 1, 1972, to Ann M. Jones describes a writing readiness paper for teaching children to print on the proper lines consisting of a paper sheet having a plurality of a series of different colored horizontal parallel lines thereon. The writing paper is distinguishable for requiring a series of different colored horizontal and parallel lines.
[0009] U.S. Design Pat. No. 39,492 issued on Sep. 1, 1908, to William J. Guy describes a shorthand note sheet having a parallel series of bold wavy lines separated by a dotted line and a line. The shorthand note sheet is distinguishable for requiring a specific series of three line types in parallel.
[0010] U.S. Pat. No. 3,191,318 issued on Jun. 29, 1965, to Robert G. Hoffmann describes a mathematic teaching aid comprising a rectangular board of wood, metal or plastic partially perforated with a plurality of holes provided in a pattern of a rectangular grid representing a two-dimensional space. A horizontal groove for the X-axis and a vertical groove for the Y-axis are formed on the board. The board is distinguishable for requiring a board having the XY graph, but not the graph on a flexible sheet above the board.
[0011] U.S. Pat. No. 3,461,573 issued on Aug. 19, 1969, to Willard O. Stibal describes a modern mathematics demonstration unit board comprising a coordinate graph with equal unit areas and X and Y axes dividing the board into quadrants. One quadrant has trigonometric indicia along the top and side, and angle indicia corresponding to the trigonometry. Another quadrant has numerical base indicia adjacent an upper edge. Volumetric unit members increasing in size from one to several units, and mathematical symbol elements are attachable to the board. The volumetric unit is equal to the cube of a unit area of the coordinate graph. The unit board is distinguishable for requiring mathematical units.
[0012] U.S. Pat. No. 3,514,874 issued on Jun. 2, 1970, to Raymond A. Strohl describes a longhand-writing guide comprising a rectangular board or platen having a one-piece frame and an insertion slot on one side. The platen has horizontal and vertical guide lines and other indicia which show through the sheet to help the writer keep straight lines and vertical alignment of the paragraph and other indentations. The inner edge of the frame has notches for locating page numbers. The longhand-writing guide board is distinguishable for requiring a frame with guide lines.
[0013] U.S. Pat. No. 4,028,826 issued on Jun. 14, 1977, to Angelo Brandifino et al. describes a perpetual memory bank calendar comprising a framed window behind which different month cards including a memorandum space being erasable, different colored stickers being mounted adjacent each memorandum entry with matching stickers over the specific date on the calendar. An endless movable belt is positioned over the month card and imprinted with the days of the week. The device is distinguishable for requiring a calendar.
[0014] U.S. Pat. No. 4,114,298 issued on Sep. 19, 1978, to Robert L. Sandelman describes a perpetual calendar comprising a rectangular board has transparent letters and numbers positioned in a predetermined matrix arrangement on a transparent sheet. Within the matrix arrangement are abbreviation for each day, each month and numerals from one to thirty-one. Small pieces of opaque material which will adhere to the sheet are sized to overly any day, month and numeral so that any calendar date can be indicated by adhering the pieces of opaque material to the rear of the transparent letters and numerals to define the month, day and the numerical date. The calendar is distinguishable for being limited to a calendar.
[0015] U.S. Pat. No. 4,173,082 issued on Nov. 6, 1979, to Joan Niquette describes paper sheets for teaching writing skills containing three module staffs of contiguous, distinctly shaded bands of equal width printed with non-photographically reproducible ink on a sheet. The bands of each module are spaced from a similar module by a non-colored band, and an uncolored area is provided about the periphery of the sheet. Letters are printed or written commencing in the space of the middle one of shaded bands of each module to teach writing in an area rather than on a line. The ascending and descending portions of the letters are formed on the upper and lower bands to teach proper proportioning of the letters and the words formed on any one staff are spaced from words on an adjacent staff and the periphery of the paper by the non-colored areas to stimulate proper spacing and margination. The paper is distinguishable for requiring shaded bands printed with non-photographically reproducible ink.
[0016] U.S. Pat. No. 4,250,642 issued on Feb. 17, 1981, to Harald Riehle describes a rectangular planar planning aid device comprising a transparent flexible foil sheet having adhesive on its top surface for adhesion of planning elements and/or symbols having smooth surfaces. The foil is applied to another sheet containing a pictorial representation. The device is distinguishable for requiring an adhesive coated foil sheet.
[0017] U.S. Pat. No. 4,652,239 issued on Mar. 24, 1987, to Barnett J. Brimberg describes a space planning system comprising a flexible cast-colored paper substrate with a smooth, flexible sheet of static cling vinyl electrostatically adhered to the coated surface. The vinyl sheet is die cut into a plurality of graphic symbol elements in the shapes of plan or axonometric views of wall sections, windows, furniture, appliances, plants, and the like to be arranged in a floor space to be planned. In use, the graphic symbol elements are peeled from the substrate and electrostatically adhered to the work surface of a flexible work sheet to design a space and arrangement of articles on the space. A first type of work sheet of clear transparent polyester is reverse printed with a square or axonometric grid. A second type of work sheet can be secured ton one or both sides of a rigid board. The devices are distinguishable for requiring a plastic sheet cut into a plurality of graphic symbol elements such as wall sections, windows, furniture, appliances, and plants to be mounted on a flexible work sheet.
[0018] U.S. Pat. No. 4,741,119 filed on May 3, 1988, to Stanley J. Baryla describes an electrostatic display board comprising a transparent display window over a paper sheet document clinging electrostatically on a dielectric plastic backing board having an easel-type support leg. The display board is distinguishable for requiring a transparent display window sheet over a paper sheet.
[0019] U.S. Pat. No. 5,370,538 issued on Dec. 6, 1994, to Fahim R. Sidray describes instructive devices for transforming pictorial images in orthogonal dimensions comprising the optional use of overhead projectors. A composition of translations or a combination of rotation and translations in two orthogonal dimensions are obtained to locate superimposed picture images to any selective location with respect to stationary pictures. Another embodiment provides animated motion of pictures, diagrams or graphs as a mathematics teaching aid. The devices are distinguishable for requiring projectors.
[0020] U.S. Pat. No. 5,954,512 issued on Sep. 21, 1999, to David M. Fruge describes a behavior tracking board providing recording and monitoring of one or more individuals' general behavior. The board comprises one or more horizontal rows, with each row corresponding to a child. Each row includes a movable marker captured in a track and moved from one side to the opposite left side. Alternatively, markers could initially be centrally located, and moved to the right for exemplary behavior and to the left for less than desirable behavior. The behavior tracking board is distinguishable for requiring tracks and markers.
[0021] U.S. Pat. No. 6,159,329 issued on Dec. 12, 2000, to Charles M. Tschanz describes self-adhesive graph appliqués used on small graphs, text pages or calculations using small adhesive-backed appliqués or labels which have been preprinted with a graphical coordinate grid. The appliqués are distinguishable for being required to be preprinted with a graphical coordinate grid.
[0022] U.K. Patent Specification No. 627,881 published on Aug. 17, 1949, for Ralph W. Furness et al. describes a sign comprising a sheet having a highly glazed surface, and letters, numerals or the like characters in the form of flexible pieces of thin sheet polyvinyl chloride having a highly glazed surface being mounted by pressing. The device is distinguishable for requiring the pressure-mounting of letter, numerals and the like on a sheet.
[0023] U.K. Patent Specification No. 842,480 published on Jul. 27, 1960, for Hermann Holtz describes a ferromagnetic chart for statistical purposes comprising an assortment of magnetic stick-on articles such as blocks, circles, musical notes, chain links, and the like posted on a flexible geographical chart. The device is distinguishable for requiring magnetic articles to be posted on a flexible ferromagnetic chart.
[0024] None of the above inventions and patents, taken either singly or in combination, is seen to describe the instant invention as claimed. Thus, graphic organizers solving the aforementioned problems is desired.
SUMMARY OF THE INVENTION
[0025] The graphic organizer is a sheet of vinyl material having an electrostatic property whereby the sheet will cling on contact to a surface such as the surface of a white board. The graphic organizer is pre-printed with any of several indicia of a form commonly used, for example, in a classroom. In a first embodiment, the graphic organizer bears the indicia of a monthly calendar. A second embodiment is a weekly calendar. A third embodiment is a lined sheet having regularly spaced lines or, alternatively, a lined sheet having doubled lines alternating with dashed lines. A fourth embodiment is a coordinate graph layout with numbered positive and negative X and Y axes. A fifth embodiment is a coordinate graph layout having X and Y axes defining a single quadrant. The single quadrant coordinate graph may be oriented to illustrate any of the four quadrants of a Cartesian coordinate system. Separate overlay strips are numbered to label the axes.
[0026] The vinyl sheet material may be transparent or opaque, as various advantages of either will be apparent. In use, a graphic organizer is applied to a surface, and particularly to the surface of a white board. An erasable dry marker pen may be used to write or mark on the graphic organizer. Thus, for example, when during the course of teaching mathematics it is desirable to perform an exercise on the white board that requires an X-Y coordinate grid, a graphic organizer bearing the coordinate graph layout is applied to the white board surface. Graphs or equations, or other markings, which are relevant to the exercise, may be marked on the graphic organizer to illustrate the exercise, and the graphic organizer may be quickly removed and replaced to illustrate another exercise or to move on to another topic without destroying the markings applied to the graphic organizer.
[0027] In addition to the various indicia that may be printed on the surface of the graphic organizer, additional, smaller pieces of the vinyl material may be provided with particular indicia printed thereon. For example, small overlay pieces of the vinyl material imprinted with the days of a week, or numbers indicating the days of the month, may be provided with a graphic organizer having the indicia of a grid for a monthly or weekly calendar. The small overlay pieces may be rearranged on the graphic organizer to accommodate different calendar formats or different calendar months.
[0028] Additionally, small removable adhesive labels or magnetic overlay pieces may be used over the corners of the graphic organizer, to help stabilize the graphic organizer and prevent the corners from peeling away from the white board during use. When magnetic overlay pieces are used, the white board may contain small permanent magnets to which the magnetic overlay pieces may be attracted, or the entire board may be made from a permanent magnetic material. Optionally, the graphic organizer may be made from flexible, permanent magnetic sheets that will secure to the magnetic board.
[0029] It is an object of the invention to provide improved elements and arrangements thereof for the purposes described which is inexpensive, dependable and fully effective in accomplishing its intended purposes.
[0030] These and other objects of the present invention will become readily apparent upon further review of the following specification and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] FIG. 1 is a top perspective view of a first embodiment of a graphic organizer according to the present invention, the graphic organizer bearing indicia of a monthly calendar sheet.
[0032] FIG. 2 is a top perspective view of a second embodiment of a graphic organizer according to the present invention, the graphic organizer bearing indicia of a calendar grid, along with separate overlay pieces bearing indicia of days of the week and numeric indicia.
[0033] FIG. 3A is a top perspective view of a first species of a third embodiment of a graphic organizer according to the present invention, the graphic organizer bearing indicia of parallel ruled lines.
[0034] FIG. 3B is a top perspective view of a second species of a third embodiment of a graphic organizer according to the present invention, the graphic organizer bearing indicia of parallel double-ruled lines alternating with dashed lines.
[0035] FIG. 4 is a top perspective view of a fourth embodiment of a graphic organizer according to the present invention, the graphic organizer bearing indicia of a Cartesian graph design with numbered positive and negative X-Y axes.
[0036] FIG. 5 is a top perspective view of a fifth embodiment of a graphic organizer according to the present invention, the graphic organizer bearing indicia of a Cartesian graph design and X and Y axes, along with numeric overlays bearing numeric indicia for the X-Y axes.
[0037] FIG. 6 is a plan view of the numeric overlays as shown in FIG. 5 .
[0038] Similar reference characters denote corresponding features consistently throughout the attached drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0039] The present invention is directed to five embodiments of a graphic organizer having the purpose of increasing the efficiency of teaching or planning meetings with a visual aid. Teachers and students no longer have to stare into a bright overhead display shown on a screen in a dark room. These educational tools facilitate the teaching of a lesson by saving the time required to draw the specific grids and to enable the insertion and erasures of indicia. Made from vinyl sheeting having an inherent electrostatic property that causes the sheeting to adhere to a surface such as a white board, a graphic organizer according to this invention may be removably placed on such surface, marked on with a dry erase type of marker, and removed without destroying the markings. Thus, a classroom exercise illustrated on one graphic organizer may be removed for another lesson, and replaced for later review.
[0040] Turning now to FIG. 1 , a first embodiment of a graphic organizer 10 is shown overlying a rectangular white board 100 . The graphic organizer 10 comprises a flexible substrate 12 having visual indicia of a calendar, including gridlines 14 defining seven columns 16 titled with the days of the week and five rows 18 for the weeks in a month. A blank margin 60 along the top of the graphic organizer 10 provides space for a removable title overlay 62 . The flexible substrate 12 is made of a sheet material having an inherent electrostatic property that causes the material to adhere to a surface such as a white board 100 , such as a thin vinyl sheeting. The title overlay 62 is made from the same material as the flexible substrate 12 , and so will cling to the flexible substrate 12 when placed on the flexible substrate 12 . It can be recognized that additional overlays may be provided, allowing various functional and decorative indicia to be added to the graphic organizer 10 , such as a decorative overlay 64 , showing seasonal and other images such as a Christmas tree in December, a turkey for Thanksgiving, snowflakes during winter months, and various other images. The visual indicia is painted, silk-screened, or otherwise printed on the surface of the flexible substrate 12 , or on overlay pieces, preferably in a dark color, such as black, cranberry, dark green, dark blue, or dark violet, to contrast with an underlying white board 100 . The graphic organizer 10 may be marked with a dry erasable marker (not shown). The graphic organizer 10 is rectangular, and can range in horizontal and vertical dimensions from several inches to several feet. It can be recognized that a graphic organizer 10 of large dimensions is suited for use, for example, in a classroom situation, overlaid on a white board 100 or the like to be viewed by students in a classroom. Alternatively, a graphic organizer 10 of small dimensions may be stored in a notebook and individually by individual students in the classroom. The graphic organizer 10 can be used on a variety of surfaces, including a white board 100 surface, a glass surface such as a window, and others.
[0041] Additionally, small removable adhesive labels or magnetic overlay pieces 70 may be used over the corners of the graphic organizer 10 , to help stabilize the graphic organizer and prevent the corners from peeling away from the white board 100 during use. When magnetic overlay pieces 70 are used, the white board 100 may contain small permanent magnets to which the magnetic overlay pieces 70 may be attracted, or the entire board may be made from a permanent magnetic material. Optionally, the graphic organizer 10 may be made from flexible, permanent magnetic sheets that will secure to the magnetic board. The small removable adhesive labels or magnetic overlay pieces 70 may be formed in any shape, such as geometric shapes and shapes of objects relating to the subjects of the graphic organizer 10 , and may have functional and decorative indicia painted, silk-screened, or otherwise printed on the surface of the adhesive labels or magnetic overlay pieces 70 . The adhesive labels or magnetic overlay pieces 70 may also be used with any of the graphic organizer embodiments enumerated hereforth.
[0042] Turning now to FIG. 2 , a second embodiment of a graphic organizer 20 is illustrated. The second embodiment of the graphic organizer 20 bears the visual indicia of a week or planning calendar, including gridlines 14 defining several rows 18 and a column 16 for each of the seven weekdays, and an additional column 26 for scheduling, the additional column 26 being demarked by line 24 having greater thickness than the gridlines 14 . The visual indicia are printed on the flexible substrate 12 . Above the columns 16 , 26 is a row of heading overlays 28 indicating the scheduling column or indicating a day of the week. The heading overlays 28 are separate, small pieces made from the same material as the flexible substrate 12 , having appropriate indicia printed thereon to identify the days of a week, and to identify a scheduling column. The heading overlays 28 are overlaid on the flexible substrate 12 , removably adhering by virtue of their electrostatic property, allowing the week or planning calendar to be rearranged. Numeric overlays 22 are additional separate, small pieces made from the same material as the flexible substrate 12 , and have numeric indicia printed thereon. The numeric overlays 22 may be overlaid on the flexible substrate 12 , for example to identify dates. Additionally, the graphic organizer 20 may be used, with all of the overlays removed, as a blank grid for a variety of purposes.
[0043] Turning now to FIGS. 3A and 3B , a third embodiment of a graphic organizer 30 is illustrated, bearing visual indicia of parallel ruled lines printed on the flexible substrate 12 . In a first species of the third embodiment, seen in FIG. 3A , the visual indicia of parallel ruled lines consists of solid, evenly spaced, and parallel ruled lines 32 , each of the parallel ruled lines 32 being horizontal and extending substantially across the width of the flexible substrate 12 . A title line 36 is centered at the top of the graphic organizer 10 , separated above the ruled lines 32 .
[0044] In a second species of the third embodiment, seen in FIG. 3A , graphic organizer 30 bears visual indicia of parallel lines comprising six line groups 34 , each line group 34 having an upper 35 and a lower 37 solid ruled line, and a single dashed line 36 between the upper 35 and lower 37 solid ruled lines. All of the lines 35 , 36 , 37 are horizontal and extend substantially across the width of the flexible substrate 12 . This arrangement of parallel lines is useful for teachers to demonstrate, and for younger students to practice, writing skills such as writing upper and lower case printed and cursive letters in a straight line. In each of the line groups 34 , the upper 35 solid ruled line is an upper margin for practicing capital printed or cursive letters; the dashed lines 36 are guidelines for the height of the lower case printed or cursive letter, and the lower 37 solid ruled line is a baseline for the letters. Both species of the graphic organizer 30 may be used as a white board 100 overlay, or, in a smaller size, may be used individually by students at the student's desk to practice the student's individual penmanship. The graphic organizers 30 help students learn to write paragraphs with titles in evenly spaced and parallel lines, and help the students with basic handwriting skills.
[0045] Turning now to FIG. 4 , a fourth embodiment of a graphic organizer 40 is illustrated. The fourth embodiment of the graphic organizer 40 bears the visual indicia of a Cartesian grid graph 42 , printed on the flexible substrate 12 , along with a positive and negative numbered horizontal X axis 44 and a similar numbered vertical Y axis 46 defining four quadrants. Alternatively, the X axis 44 and the Y axis 46 may be located to define a single quadrant. It can be recognized that the numbering of the axes 44 and 46 may be omitted from the flexible substrate 12 , and replaced with separate numeric overlay strips bearing appropriate numbering indicia for numbering the axes 44 and 46 . Similar numeric overlay strips are discussed below, and illustrated with the embodiment of FIG. 5 . This embodiment can be used in student classes from grade school through college to teach coordinate number pairs, linear equations, slope, quadratic equations, and other lessons.
[0046] Turning now to FIG. 5 , a fifth embodiment of a graphic organizer 50 is illustrated. The fifth embodiment of the graphic organizer 50 bears the visual indicia of a Cartesian grid graph 42 printed on the flexible substrate 12 , similar to the graphic organizer 40 discussed above. Additional indicia include a bold X axis 59 , printed near the bottom edge of the Cartesian grid graph 42 , and a bold X axis 58 , printed near the left hand edge of the Cartesian grid graph 42 . Separate numeric overlay pieces are provided for numbering of each of the X axis 54 and the Y axis 56 .
[0047] Referring also to FIG. 6 , an X axis numeric overlay 59 has numeric indicia printed thereon oriented to be read with the X axis numeric overlay 59 oriented in a horizontal position along the X axis 54 , while a Y axis numeric overlay 58 has numeric indicia printed thereon oriented to be read with the Y axis numeric overlay 58 oriented in a horizontal position along the Y axis 56 . With the numeric overlays 58 , 59 positioned on the graphic organizer 50 over the X and Y axes 54 , 55 , the numeric indicia of the numeric overlays 58 , 59 are in alignment with the Cartesian grid graph 42 , the numeric indicia correctly numbering the axes. It can be recognized that the graphic organizer 50 may be placed onto a white board in any orientation, depicting any of the four Cartesian quadrants. Thus, it can further be recognized that the X axis numeric overlay 59 and the Y axis numeric overlay 58 may be imprinted with numeric indicia according to any quadrant, or any numbering system. The X axis numeric overlay 59 and the Y axis numeric overlay 58 are made from the same material as the flexible substrate 12 and will cling to the flexible substrate 12 when placed on the flexible substrate 12 .
[0048] Thus, a variety of educational tools for use on a white board or the like comprising a transparent or opaque plastic overlay sheet with printed indicia has been shown to aid students in penmanship, grammar and understanding mathematics.
[0049] It is to be understood that the present invention is not limited to the embodiments described above, but encompasses any and all embodiments within the scope of the following claims. | The graphic organizer is a flexible sheet of material having a property whereby the sheet will cling on contact to a white board surface or the like. Various visual indicia are printed on the material surface, such as a monthly calendar, a weekly calendar, a lined sheet having regularly spaced lines or, alternatively, a lined sheet having doubled lines alternating with dashed lines, and a coordinate graph layout with numbered positive and negative X and Y axes. The sheet material may be transparent or opaque. In use, a graphic organizer is applied to a surface, such as a white board surface. A dry erase marker is used to mark on the graphic organizer. Additional, smaller pieces of the sheet material may be provided with particular indicia printed thereon, such as days of a week, or numbers, the small overlay pieces being rearrangable on the graphic organizer surface. | 6 |
FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0001] Not applicable.
TECHNICAL FIELD OF THE INVENTION
[0002] The present invention is directed in general to power converters, and, more specifically, to an active clamp power converter with improved zero-voltage switching of the primary power transistor to reduce turn-on switching losses.
BACKGROUND OF THE INVENTION
[0003] The active clamp switching topology for DC/DC converters is well known in the field of electronic power conversion, and its advantages and operation are described by Leu, et al. Further explanation of its operation and circuit variations are described by Vinciarelli (RE-36,098), Boylan (U.S. Pat. No. 5,327,333), Jacobs (U.S. Pat. No. 6,288,920), Fraidlin (U.S. Pat. No. 6,377,476), and Boylan (U.S. Pat. No. 6,445,598), which are each included herein by reference in their entirety. Numerous switching circuit topologies are known that provide practical means of DC/DC conversion, for example, variations of the full and half bridge, the flyback, the SEPIC and others. But an outstanding characteristic of the active clamp topology is its ability to provide the minimum sustained voltage stress on the output rectifying diodes when the power supply is required to operate over a range of input voltages. This characteristic may allow the use of lower voltage-rated parts for the output diodes, providing both performance improvement and lower cost.
[0004] The active clamp topology utilizes two active switches on the primary side of the power transformer that alternately conduct during substantially non-overlapping/contiguous periods during a switching cycle. One switch, the primary switch, closes for a duty cycle D to couple the primary of the power transformer to an input power source, and then a second switch, the reset switch, coupled to a clamp capacitor and the primary of the power transformer, closes for a complementary period 1-D to reset the flux in the power transformer to substantially its value at the beginning of a switching cycle. A characteristic of the active clamp topology in many practical applications is the ability to close the reset switch at any rated load with insignificant turn-on loss, i.e., with zero-voltage switching (ZVS). This requires a brief delay between turn-off of the primary switch and turn-on of the reset switch, and this timing is generally not critical because the body diode in a MOSFET transistor, which is the common but not required implementation of these active switches, automatically conducts at the required turn-on time. If a switch technology different from a MOSFET is used, a diode is assumed effectively to be in parallel with the controlled terminals of the switch to reduce the switch turn-on timing uncertainty.
[0005] However, the switching transition from the reset switch conducting to the primary switch conducting often does not result in ZVS at higher rated load currents for the active clamp power converter. This occurs because the current in the magnetizing inductance of the power transformer, which is a principal energy source to enable ZVS for this switching transition, is often insufficient to counteract the output current reflected to the primary winding of the power transformer at higher load currents. The reflected output current flows in the primary winding in a direction opposite to the direction of the magnetizing current at this time. Reducing the magnetizing inductance of the power transformer to increase the magnetizing current is usually not practical because reducing the magnetizing inductance generally increases power loss due to a resulting higher level of recirculating current. The result is only a partial reduction in the voltage across the primary switch when the reset switch is opened at higher output currents. The switch voltage rings with parasitic circuit capacitance and inductance until the primary switch is enabled to conduct. Thus the primary switch is turned on sustaining substantial voltage across its controlled terminals, resulting in loss of energy stored in parasitic capacitance. Turning on the primary switch without ZVS may also cause additional losses elsewhere in the circuit.
[0006] Thus while the active clamp topology has benefits such as a low voltage rating for the rectifying diodes and ZVS for the reset switch, it suffers from inability to provide ZVS during the transition from the reset switch conducting to the primary switch conducting at higher load currents. Accordingly, what is needed in the art is a way to preserve the benefits of the active clamp circuit topology while providing a way to achieve ZVS or substantially reduced switch voltage during the reset-to-primary switching transition at higher load currents, thereby providing reduced switching losses for the converter.
SUMMARY OF THE INVENTION
[0007] To address the above-discussed deficiencies of the prior art, the present invention provides an active clamp resonant transition system and method of operating the same for use with an active clamp power converter having a power transformer with a primary and a secondary winding, a primary switch coupling the primary of the power transformer to an input power source, and a reset switch coupled to a clamp capacitor and the primary of the power transformer to reset the flux in the power transformer to substantially its value at the beginning of a switching cycle. In one embodiment, an active clamp resonant transition system includes an inductor coupled between the primary winding of the power transformer and the primary switch, and a diode coupled between the inductor and the clamp capacitor. In another embodiment, the active clamp resonant transition system includes a second diode coupled between the inductor and ground. In another embodiment, the active clamp resonant transition system includes a snubber capacitor coupled between the inductor and the diode. In another embodiment, the active clamp resonant transition system includes a resistor coupled between the clamp capacitor and the snubber capacitor.
[0008] The foregoing has broadly outlined preferred and alternative features of the present invention so that those skilled in the art may understand the detailed description of the invention that follows. Additional features of the invention will be described hereinafter that form the subject of the claims of the invention. Those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiment as a basis for designing or modifying other structures for carrying out the same purposes of the present invention. Those skilled in the art should also realize that such equivalent constructions do not depart from the spirit and scope of the invention in its broadest form.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] For a more complete understanding of the present invention, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
[0010] [0010]FIG. 1 illustrates a schematic diagram of an active clamp power converter from the prior art.
[0011] [0011]FIG. 2 illustrates a schematic diagram of an embodiment of an active clamp power converter utilizing an n-channel MOSFET for the primary switch, an n-channel MOSFET for the reset switch, and an active clamp resonant transition system, constructed according to the principles of the present invention.
[0012] [0012]FIG. 3 illustrates a schematic diagram of an embodiment of an active clamp power converter utilizing an n-channel MOSFET for the primary switch, a p-channel MOSFET for the reset switch, and an active clamp resonant transition system, constructed according to the principles of the present invention.
[0013] [0013]FIG. 4 illustrates waveforms for the circuit in FIG. 3 representing the drain-to-source voltage of the primary switch and the voltage at the node coupling the active clamp resonant transition system to the primary of the power transformer, illustrating both transitions of a switching cycle. FIG. 4 includes a waveform representing the voltage across the resistor coupled between the clamp capacitor and the snubber capacitor.
DETAILED DESCRIPTION
[0014] [0014]FIG. 1 illustrates an active clamp power converter 100 of the prior art. The DC input power source, Vin, which typically ranges, for example, between 36 and 75 volts for typical telecommunications systems, supplies input power to the power transformer T 1 . The transformer T 1 has Np primary turns and Ns secondary turns that are selected to provide a required output voltage with consideration of the resulting duty cycle and stress on power train components. The primary switch Qpri, shown on FIG. 1 as an n-channel MOSFET, is controlled by a pulse-width controller (not shown) that controls Qpri to be conducting for a duty cycle D. The reset switch Qreset, also shown on FIG. 1 as an n-channel MOSFET, is coupled to the clamp capacitor Cclamp and the primary switch Qpri. The switch Qreset is controlled to conduct for a substantially complementary period 1-D. The duty cycle D is adjusted by the pulse-width controller to regulate a characteristic of the output, such as output voltage, output current, or a combination of the two. The AC voltage appearing on the secondary of the power transformer is rectified by the forward diode DS 1 and the freewheeling diode DS 2 , and the DC component of the resulting waveform is coupled to the output through the low-pass filter consisting of the inductor Lout and the capacitor Cout producing an output voltage Vout. Active switches such as MOSFETs may be substituted for either or both of the diodes DS 1 and DS 2 to improve power conversion efficiency. The secondary winding of the transformer T 1 may be tapped, as is well understood in the art, to increase the DC component of the voltage presented to the low-pass filter in relation to the AC components of that voltage. The sense of the secondary winding, Ns, of the power transformer may also be reversed to operate the converter in a flyback mode. Various other secondary-side rectification arrangements may be used, for example a current doubler, as described in Blair, et al., U.S. Pat. No. 6,483,724. The active clamp power converter is a familiar design choice for switching power converters, and further details of its operation and design are described in the previously cited references.
[0015] During the switching transition from the primary switch Qpri conducting to the reset switch Qreset conducting, a ZVS transition is usually easily obtained. This occurs because the power transformer magnetizing current referenced to its primary, and the output current, also referenced to the primary, both flow in the same direction. This direction is such that opening the reset switch usually causes its parasitic capacitance to be charged and the parasitic capacitance of the primary switch to be discharged by these currents, enabling the body diode of the primary switch automatically to conduct after a brief delay, providing a substantially lossless/ZVS transition.
[0016] However, during the switching transition from the reset switch Qreset conducting to the primary switch Qpri conducting, a ZVS transition is usually difficult to obtain at high load currents. This occurs because the power transformer magnetizing current referenced to its primary, and the output current, also referenced to the primary, flow in opposite directions. If the output current is low, then the power transformer magnetizing current may be sufficient to obtain a ZVS transition; modest gapping of the power transformer core may be employed to reduce the magnetizing inductance so that sufficient energy is provided to obtain ZVS. However, particularly at higher output currents, the direction of the reflected output current flow to the primary of the power transformer subtracts from the energy that would otherwise be available to obtain ZVS for this transition. Gapping the transformer sufficiently to retain ZVS at high output currents is usually not practical because the required level of recirculating magnetizing current would create substantial additional losses.
[0017] Other switching topologies exhibit corresponding switching characteristics. The phase-shifted full bridge exhibits two “easy” ZVS transitions and two that are difficult. Redl and Balogh in U.S. Pat. No. 5,198,969 take advantage of pairs of primary power switches coupled in series between two input power rails in a four-state phase-shifted bridge and provide an inductor and two clamp diodes to achieve ZVS for the more difficult transition. Blair, et al., in U.S. Pat. No. 6,483,724 B1 provide an inductor and two clamp diodes between two input power rails to achieve ZVS for the more difficult transition in a three-state bridge. However, in the active clamp power converter, the two primary power switches are not coupled between two input power rails, obviating that choice to recirculate power with minimal loss back to an input power source.
[0018] In FIG. 2 is shown a schematic diagram of an embodiment of the invention for an active clamp power converter 200 utilizing an n-channel MOSFET for the primary switch Qpri and an n-channel MOSFET for the reset switch Qreset, including an active clamp resonant transition system 210 . The inductor L ZVS provides an energy source to achieve ZVS or reduced turn-on voltage for the reset-to-primary switching transition. The diode Dp 2 clamps the node coupling the inductor L ZVS and the primary of the power transformer T 1 to the clamp capacitor Cclamp. Excess energy stored in L ZVS during the switching transition is resonantly transferred to the clamp capacitor through the diode Dp 2 . It is desirable to return the excess energy stored in the clamp capacitor to the input power source. This circuit arrangement allows the return of excess energy transferred to the clamp capacitor Cclamp to the input power source in a substantially lossless manner during the on time of the reset switch. The inductor Lzvs also provides an energy source to assist in reducing voltage associated with turn-on of the reset switch. The diode Dp 1 clamps the node to ground and also allows transfer to the clamp capacitor of the excess energy in L ZVS associated with the primary-to-reset transition; in this transition the body diode of Qreset resonantly couples energy from L ZVS to the clamp capacitor. The essential operation of the circuit is retained if active switches are substituted for one or both of the diodes Dp 1 and Dp 2 . The remaining circuit elements in FIG. 2 correspond functionally to similarly identified elements in FIG. 1.
[0019] In FIG. 3 is shown a schematic diagram of an embodiment of the invention for an active clamp power converter 300 utilizing an n-channel MOSFET for the primary switch Qpri and a p-channel MOSFET for the reset switch Qreset, including an active clamp resonant transition system 310 . Using a p-channel MOSFET for the reset switch allows its source to be grounded, simplifying its gate drive arrangement in a practical circuit. The inductor L ZVS provides an energy source to achieve ZVS for the reset-to-primary switching transition or reduced turn-on voltage. The diode Dp 2 clamps the node coupling the inductor Lzvs and the primary of the power transformer T 1 utilizing a capacitor Csnubber. A circuit element, shown on FIG. 3 as a resistor Rbalance, removes excess charge accumulated in the capacitor Csnubber during the reset-to-primary transition and transfers this charge to the clamp capacitor with only modest power loss. Other circuit elements can be substituted for the resistor Rbalance to remove excess charge accumulated in the capacitor Csnubber such as an active switch. The reset switch Qreset transfers excess charge in the clamp capacitor Cclamp back to the input power source in a substantially lossless manner. The diode Dp 1 operates in a manner similar to its operation in the circuit shown on FIG. 2. The remaining circuit elements in FIG. 3 correspond functionally to similarly identified elements in FIG. 1 and FIG. 2.
[0020] The capacitor Csnubber sustains a voltage comparable to the voltage of the clamp capacitor Cclamp. Accordingly the power loss in the resistor Rbalance is not substantial, and does not significantly detract from the relatively lossless energy transfers associated with the switching transitions. Thus a practical circuit arrangement to recover excess energy associated with the switching transitions is provided.
[0021] Exemplary component values for an active clamp power converter represented on FIG. 3, powered from a 48-volt input, switching at 330 kHz with 15 μH of power transformer magnetizing inductance and 0.1 μH of leakage inductance referenced to the primary winding, with equal primary and secondary turns, are listed below:
[0022] L ZVS =0.2 μH
[0023] C clamp =0.22 μF
[0024] R balance =1000 Ω
[0025] C snubber =0.05 μF
[0026] L out =20 μH
[0027] C out =20 μF
[0028] [0028]FIG. 4 shows voltages for the circuit in FIG. 3 for both switching transitions from a circuit simulation that includes representative component parasitic resistance and capacitance, with the component values above and a 3-ohm load. In FIG. 4 are shown the drain-to-source voltage Vpri across the primary switch and the voltage Vnode at the node coupling the active clamp resonant transition system to the primary of the power transformer. The reset switch is disabled to conduct at approximately 21.1 μs, and the primary switch is enabled to conduct at approximately 21.25 μs. The primary switch is disabled to conduct at approximately 22.45 μs, and the reset switch is enabled to conduct at approximately 22.55 μs.
[0029] In FIG. 4 is also shown the voltage V Rbalance across a 1000-ohm resistor R balance coupled between the clamp capacitor and the snubber capacitor. The dissipation in the 1000-ohm resistor is about 80 mW, and the power delivered to the load is approximately 130 W, illustrating the insubstantial level of power dissipation in the resistor R balance .
[0030] Although the present invention has been described in detail and with reference to specific embodiments, those skilled in the art should understand that various changes, substitutions and alterations can be made as well as alterative embodiments of the invention without departing from the spirit and scope of the invention in its broadest form. | A DC-DC converter is disclosed comprising an active clamp topology, including an active clamp resonant transition system to provide substantially zero or reduced voltage for turn-on of the primary switch. The resonant transition system includes an inductor in series with the primary winding of the power transformer and a clamp diode that operate cooperatively to turn on the primary switch with reduced voltage. The addition of these circuit components provides lower switching losses and lower component stresses in the overall design. | 7 |
BACKGROUND OF THE INVENTION
1. Filed of the Invention
The invention, in general, relates to a novel tub for washing fluid and, more particularly to a tub of the kind referred to for rotatably accommodating a washing machine drum and provided at its exterior wall with rib structures.
2. The Prior Art
A washing fluid tubs made of non-metallic materials for washing machines is well known in the art. The tub is made of a synthetic material and is mounted as a molded part in the interior of a washing machine. The structure of the tub is such as to accommodate components or aggregates cooperating with the tub thereon. The tub is characterized by an opening in its axis of rotation for receiving the drive shaft of the rotatable drum disposed in the tub. Moreover, brackets may be arranged below the tub for receiving a drive motor, for instance connected to the drum by a fan belt or the like. The tub is also provided with at least one connecting pipe for feeding and removing the washing fluid.
In order to impart to the rear wall of the tub the rigidity or strength required rotatably to support the drum thereon, the tub, as disclosed, for instance, by German patent specification DE 199 60 501 A1, is provided with rib structures which lend stiffness or structural strength to the rear area of the tub in particular. Such a washing fluid tub, in a washing machine which is loaded through the sidewall of the drum, is mounted within the housing of the machine with the loading opening being disposed at the upper side of the cylindrical wall. Since in such an arrangement requires opening of the tub for placing laundry into the drum, it is possible that when loading wet laundry or adding water through the opening water may drip or swill between housing and the outer wall of the tub. However, for reasons of electrical safety, it is absolutely necessary that neither water nor humidity reach the electrical components mounted within the machine.
In a front-loading washing machine the loading opening is disposed in the front wall of the washing fluid tub and the opening is sealed with respect to the housing of the machine by a folding bellows seal. In a normal operation it may be assumed that the tub in the housing is protected from water leakage. However, with a leaking feed hose above the tub it is nevertheless possible in a front-loading washing machine that water leaks to the outer surface, particularly in the area of its cylindrical surface, of the washing fluid tub. Here, too, it is absolutely necessary that neither water nor humidity reach any electrical components.
While according to the state of the art the integral rib structures are capable of preventing this, they nevertheless leave room for improvement. A further known possibility is to protect electrical components from penetrating water and humidity by housings, covers or encapsulations. Such measures would, however, not only be relatively complex and, therefore, expensive, but they would also impede heat dissipation. Another known construction proposes an elastic folding bellows between the loading opening of the washing fluid tub and the opening of the housing for preventing the penetration of water in this area. However, since the loading opening is of rectangular configuration a lasting and reliable seal between the surrounding margin of the loading opening and the housing cover cannot be ensured because of possible leakage of the folding bellows.
JP 02305596 A of “Patent Abstracts of Japan” discloses a tub washing machine having a vertical rotational axis. In this case, the drive motor is arranged beneath the bottom of the tub. To prevent condensation water from running along the wall of the tub to the bottom of the tub and in this area from dripping onto the motor, an outwardly directed collar-shaped rib is arranged on the wall of the tub. However, the rib acts rather like a cover in the vicinity of the motor. Water sprays and splashes may easily get below this cover and drip onto the motor. Another disadvantage is that water dripping off the cover precipitates and splashes on the bottom of the housing immediately adjacent the motor.
OBJECTS OF THE INVENTION
It is therefore a primary object of the invention to provide a washing fluid tub capable of withstanding problems caused by leaking or splashing water.
Another object of the invention is to provide a washing fluid tub provided with means for diverting undesired water from critical areas of the washing machine.
Other object will in part be obvious and will in part appear hereinafter.
SUMMARY OF THE INVENTION
In the accomplishment of these and other objects, the invention, in a preferred embodiment thereof, provides a washing fluid tub having at its exterior wall integrally formed stiffening rib structures and, adjacent thereto, water deflection ribs for protecting aggregates cooperating with the tub from leaking water and humidity and for collecting and diverting water, and in the upper area of its external wall a plurality of ribs affecting an advance channeling of water and humidity.
Advantageously, further ribs are surrounding the lower area of the external wall for catching the water in a controlled manner and for diverting it. The surrounding rib is provided with defined drip-off sites for diverting the water from exactly defined sites so that it will be either directly or indirectly guided to areas where it cannot cause any damage. In this manner it is possible to prevent water from flowing over the deflection rib to critical areas, for instance those, where electrical components are present.
An advance channeling of water running along the outside of the tub ensures early on that water is kept away from critical areas. In accordance with the invention water is caused to drip off exactly defined sites. In case a deflection rib is flowed over by a wave of water, it is deflected by an additional rib at sites, for instance over the drive motor. The major purpose of the advance channeling is to keep water away from areas where it could drip off from a large height and thus splash directly or indirectly to critical areas. Moreover, larger quantities of water are divided to prevent subsequent spilling from water diverting ribs. The advance channeling ribs are pointed at their lower end sections. Accordingly, water running along the outer edge of the rib is returned to the washing fluid tub. The surrounding rib then serves to keep advance channeled water running long the outside of the washing fluid tub away from the lower range of the tub where the motor is mounted and to direct it to defined drip-off sites. The drip-off sites are selected such that water can neither directly or indirectly reach electrical contact areas. In case water is returned to the washing fluid tub because of overflow from a water diverting rib or undefined dripping or flowing off, a third redundant stage is provided. Remaining water which has not been detained by prior means is diverted in a defined manner by the pointedly converging ribs.
All brackets, tabs, etc. mounted at the lower range are provided with points from which water may drip off. The angles of the points are selected such that water running along the extended edge cannot flow to critical areas.
The defined drip-off sites are advantageously characterized by being of V-shaped configuration. In this connection, a first embodiment provides for a drip-off nose below a V-shaped drip-off site for ensuring a defined dripping-off of water without allowing it to flow back in the direction of the tub.
In another embodiment the V-shaped ribs converge, or are formed such, that they impart a defined direction of flow to the water. There may be provided a forward directed recess in the tip of the V-shape with a downwardly pointing lug being provided on one of the two ribs. Water thus initially moved to the lowest point of the V-shape, with the water, because of the recess, assuming a direction of flow along the downwardly pointed lug and parallel to the wall of the tub at some distance therefrom. In a practical embodiment the lower edge of the lug is of a large radius so that the water no longer drips vertically downwardly but, because of forces of adhesion, is diverted laterally.
In accordance with a particularly advantageous embodiment of a defined drip-off site a notch open in a forward direction is provided at the top of ribs converging in a V-shaped configuration which also results in a defined flow direction. Advantageously, the notch may be provided in a lug provided below the line of intersection of the ribs.
DETAILED DESCRIPTION OF THE SEVERAL DRAWINGS
The novel features which are considered to be characteristic of the invention are set forth with particularity in the appended claims. The invention itself, however, in respect of its structure, construction and lay-out as well as its manufacturing techniques, together with other advantages and objects thereof, will be best understood from the following description of preferred embodiments when read in connection with the appended drawings, in which:
FIG. 1 is a perspective view of a washing fluid tub from the rear wall thereof;
FIG. 2 is a further perspective view of the washing fluid tub from the front side thereof;
FIG. 3 is a detailed view of a defined drip-off site;
FIG. 4 is a further embodiment according to FIG. 3 ;
FIG. 5 is a further embodiment of a drip-off site according to FIG. 3 ;
FIG. 6 is a further embodiment of a defined drip-off site according to FIG. 3 ; and
FIG. 7 a washing fluid tub arranged within a washing machine.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 7 schematically depicts a washing machine 21 provided with a washing fluid tub 1 with a drum 22 rotatably disposed therein. Aggregates 23 , for instance the motor for rotating the drum 22 , are disposed at the lower section of the washing fluid tub 1 .
FIG. 1 is a perspective view of a washing fluid tub 1 for a washing machine with a drum being mounted for rotation therein. The washing fluid tub 1 is preferably made of a synthetic material with rib structures 3 being integrally joined with the exterior wall 2 of the washing fluid tub 1 . As may be seen in the rear wall view of the washing fluid tub 1 the rib structures 3 extend concentrically in the direction of a bearing sleeve 4 which serves to seat and bear the drive shaft (not shown in detail) of the drum rotatably mounted in the washing fluid tub 1 . Brackets 5 are provided beneath the washing fluid tub 1 for supporting a motor (not shown in detail) for driving the drum.
In a lower portion of the cylindrical wall of the washing fluid tub 1 there is provided an opening 6 through which the washing fluid may be removed.
FIG. 2 depicts the washing fluid container 1 from its closed front side, with a closure device 7 being provided above the washing fluid tub 1 as is customary in top-loading machines. As may be seen from looking at FIGS. 1 and 2 , water run-off ribs 8 are formed at the outer wall 2 of the tub 2 which on the one hand protect aggregates (not shown in any detail) cooperating with the tub 1 from leaking water and/or humidity and which on the other hand collect and divert the leaked water and humidity. For instance, ribs 9 are formed at the upper region of the outer wall of the tub 1 which affect an advance channeling of the water. The ribs 9 are shaped such that in the direction of flow they extend to a tip or convergent so that this advance channeling provides for an effective diversion. For instance, at the rear surface, FIG. 1 , ribs 9 are connected in the manner of wings to the receiving sleeve 4 of the bearing, on both sides thereof, so that water occurring at the upper section is initially caught while the section below the receiving sleeve 4 remains free of any water. FIG. 2 , which depicts the front side of the washing fluid tub 1 , also depicts a wing-like arrangement of ribs 10 which point angularly away from the center and also maintain the lower section free of water.
As may be seen further from FIGS. 1 and 2 , axially extending ribs 11 embracing the outer wall of tub 1 are integrally formed to the lower area of the tub 1 which serve to catch water in a controlled manner. Such a rib 11 may be seen in FIG. 1 in particular with the shape of the rib extending at the rear surface and on the surface of the cylindrical wall. A separate rib 13 is integrally formed with the front surface at the lower portion thereof which serves to catch water from the upper ribs 10 to divert it to the lower area of the washing fluid tub 1 . As may be particularly seen in the perspective view of FIG. 1 , defined drip-off sites 14 are formed into the embracing ribs 11 which affect a controlled diversion of the occurring water. It will be understood by those skilled in the art that additional drip-off ribs 15 are provided on the brackets 5 for the motor, dampeners or shock-absorbers for particularly critical sections at the exterior wall 2 of the tub 1 .
The drip-off site 14 may be differently shapes as shown in FIGS. 3 , 4 and 5 . Thus, FIG. 3 depicts a defined drip-off site 14 which preferably is V-shaped. The perspective presentation of FIG. 3 reveals a drip-off nose 16 integrally formed below the V-shaped drip-off site 14 . It will be apparent that if water occurs between the two branches of the V-shape it will collect at the deepest part thereof and that it will want to flow out of the V-shape. To prevent a return flow to the wall 17 of the tub, the collected water will be diverted by way of the drip-off nose 16 parallel to the wall of the tub 17 , at some distance therefrom.
Another embodiment of a defined drip-off site 14 is also shown in perspective FIG. 4 . The ribs 18 and 19 forming the V-shape are converging or are shaped such that a recess 21 is formed at the tip of the V-shape. However, the recess 21 extends over only part of the width of the ribs at their side opposite from the wall 17 of the tub. A lug is formed at one of the two ribs 18 , 19 , at rib 19 , converging in the V-shape which extends beyond the deepest point of the drip-off site 14 . As a consequence of the flow path thus formed is direction of flow is attained which extends parallel to the wall 17 of the tub at some spacing therefrom. The flow pattern of the water is also improved by the recess 21 at the tip of the converging ribs 18 , 19 always directing the water to one of the vertically downwardly pointing ribs. A large radius at the lower edge of the lug the water, because of adhesion forces, experiences a large lateral component of movement, pointing from the lower edge parallel to the wall 12 of the tub as indicated by the flow arrows.
A further variant of a drip-off site 14 in accordance with the invention is shown in FIGS. 5 and 6 . FIG. 5 depicts a notch 20 opened in a forward direction at the tip of the ribs 18 , 19 converging in a V-shape. The opening angle of the notch 20 results in a direction of flow of the water away from the wall 17 of the tub. The notch 20 is sunk in a lug below the intersecting line of the ribs 18 , 19 .
As a result of the forward-pointing notch, FIG. 5 , the flowing-off water attains a stronger component of movement. The mass inertia of the water results in the water dripping or running off in a forward direction. Moreover, because of the pointedly converging notch 20 the water is progressively further separated from the ribs 18 , 19 since the contact surfaces become increasingly smaller.
The adhesion force causes drops of water initially to be retained in the forward notch 20 , FIG. 6 , until further water causes drops to fall off in a vertical direction. In this manner, the tendency of the water under the ribs 18 , 19 to flow to the area to be protected is effectively counteracted. | A washing fluid tub of a washing machine for accommodating a rotatably driven laundry drum and provided with electrical components in its vicinity, the tub being provided at its outer surface with a plurality of rib structures for diverting any leaking water from the electrical components, at least some of the rib structures being provided with V-shaped drip-off sites for controlling the direction of flow of the water. | 3 |
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation of pending U.S. patent application Ser. No. 14/347,631 filed Mar. 26, 2014, which is the U.S. National Phase under 35 U.S.C. §371 of International Application No. PCT/EP2012/068787, filed on Sep. 24, 2012, which claims the benefit of EP 11182771.3, filed Sep. 26, 2011. The entire contents of these applications are incorporated by reference herein.
BACKGROUND
Step conveyors and methods of the type stated initially are known, for example, from the documents DE 10 2004 012 133 A1 and EP 1 652 799 A1.
The known step conveyors have the disadvantage, on the basis of the low step height, that they are not able to convey piece goods upward, and if they are lying on the contact surface, no edge projecting at least approximately perpendicular from the contact surface can lie against the conveying step. This particularly applies to cylindrical piece goods, such as bottles or cylindrical cans, for example.
SUMMARY
The disclosure relates to an apparatus for separation of piece goods to be placed in storage in an automated storage unit, having a step conveyor for conveying piece goods out of a supply, beyond a top edge of the step conveyor, onto a collection device, wherein the step conveyor comprises an inclined contact surface and a first step that can be moved parallel to the contact surface, having a conveying edge parallel above the contact surface, wherein the distance between the contact surface and the conveying edge corresponds to a minimal step height, which suffices for pushing block-shaped piece goods upward, and a control device for controlling the step conveyor, which device is coupled with a sensor, which detects whether an article of piece goods has been conveyed beyond the upper edge. Furthermore, the disclosure relates to a method for separation of piece goods to be placed in storage in an automated storage unit, using a step conveyor having an inclined contact surface having an upper edge, a supply disposed at the lower end of the contact surface, for accommodating piece goods, and a first step that can be moved parallel above the contact surface, from the supply to the upper edge, having a conveying edge parallel to the contact surface, wherein the distance between the contact surface and the conveying edge corresponds to a minimal step height, which suffices for pushing block-shaped piece goods upward, wherein the supply is filled with piece goods, and the first step is repeatedly moved from the supply to the upper edge, until conveying of a further article of piece goods over the upper edge is no longer detected.
In order to achieve the most effective separation possible, or in other words, in order to ensure that as few piece goods as possible pass over the upper edge of the contact surface at the same time, a low height of the conveying step is aimed at. The height of the conveying step, that is, the distance between the contact surface and the conveying edge (usually the upper edge of a conveying plate, facing forward), should merely be so high that the step suffices for pushing piece goods, usually block-shaped piece goods, upward. In this connection, unevenness and rounded edges of the block-shaped piece goods to be transported, on the one hand, as well as movement speeds of the conveying step and the mass of the piece goods and the resulting inertia and friction forces, on the other hand, may be taken into consideration. If the step height is selected too low, the case can occur, for example, that the conveying step moving upward pushes itself under the article of piece goods.
It is therefore the task of the subject technology to create an apparatus and a method for separation, which permit not only separation of block-shaped piece goods but also separation of cylindrical piece goods that are mixed with the block-shaped piece goods in a supply.
This task is accomplished, according to the disclosure, by means of an apparatus and methods having the characteristics described herein.
According to the disclosure, an apparatus for separation, of the type indicated initially, is characterized in that the step conveyor has a second step that can be moved parallel above the first step and the contact surface, having a step height that is at least so high that the second step is suitable for conveying cylindrical piece goods having the greatest expected diameter, and that the control device is configured in such a manner that it controls the step conveyor in such a manner that after the supply has been filled, the first step is repeatedly activated until the sensor no longer detects conveying of a further article of piece goods, and thereupon the second step is activated.
The method stated initially, for separation, is characterized, according to the disclosure, in that a step conveyor is used that has a second step that can be moved parallel above the first step and the contact surface, having a step height that is at least so high that the second step is suitable for conveying cylindrical piece goods having the greatest expected diameter, wherein after repeatedly moving the first step, until conveying of a further article of piece goods beyond the upper edge is no longer detected, the second step is moved from the supply to the upper edge. Preferably, the second step is subsequently repeatedly moved from the supply to the upper edge, until conveying of a further article of piece goods beyond the upper edge is no longer detected.
The minimum height of the second step depends, at first, on the maximal expected diameter of the cylindrical piece goods, and on the inclination of the contact surface, and is greater, in every case, than the radius of the cylindrical piece goods, minus the product of the radius and the cosine of inclination. The minimum step height calculated in this manner is furthermore increased on the basis of the friction and inertia forces that occur during pushing up, where this increase grows with the ratio of the friction and inertia forces to the weight of the article of piece goods, but does not become greater than the maximal expected radius. The minimum step height may be determined experimentally.
The conveying edge of the first step can be formed not just by an edge of a plate, but also by a tensed wire or cable. Preferably, however, it is formed by the front upper edge of a step plate. In a preferred apparatus, the first step comprises a level plate having a conveying surface that follows the conveying edge, perpendicular to the plate plane. Preferably, the second step also comprises a level plate having a conveying surface perpendicular to the plate plane. The plate of the first and/or of the second step can also be formed from a plurality of parallel strip segments coupled so as to pivot, which are connected with one another in the manner of a roller blind and guided by way of the contact surface. Furthermore, the plate or the segments of the second step can be of a lesser thickness than would correspond to the step height, for example just as thick as the plate or the segments of the first step. In this case, the second step, at the upper edge, has a plate that is angled away from the plate or the uppermost segment, perpendicular to the contact surface, the front surface of which plate forms the conveying surface that determines the step height.
The provision of the second step having a step height suitable for transporting cylindrical piece goods, in combination with the sequence of the use of the first and second steps, according to the disclosure, not only permits separation of any desired shape of articles of piece goods; it furthermore ensures that first the block-shaped piece goods are sorted out of the supply, before the cylindrical piece goods are placed in storage.
In preferred embodiments, the control device is configured so that it controls the step conveyor in such a manner that the first step is either moved back or moved along with the second step, while the second step is being activated. It is preferred that the first step moves along with the second. This prevents the formation of a gap below the second conveying step, in which small piece goods could become jammed.
A further development of the disclosure is characterized in that the sensor detects arrival of piece goods on the collection device, where the control device, when arrival of an article of piece goods or multiple piece goods on the collection device is detected, interrupts conveying of further piece goods to the collection device until the article of piece goods or the piece goods have been removed from the collection device and transported further. Interruption of further conveying of piece goods to the collection device makes undisturbed detection and undisturbed picking up of the piece goods lying on the collection device possible, for further transport to an automated storage unit.
Preferably, the collection device has a plate that can pivot about an axis parallel and adjacent to the upper edge, where a pivot drive is coupled with the control device, where the plate is inclined before an article of piece goods is conveyed beyond the upper edge, in such a manner that it drops away from the upper edge, so that arriving piece goods can slide down on the plate, and where the control device, when arrival of an article of piece goods or multiple piece goods on the collection device is detected, moves the plate into the horizontal position, by way of the pivot drive, so that sliding of the piece goods is braked (either completely or in such a manner that the sliding article of piece goods slides sufficiently slowly against a stop). The plate is preferably inclined at least 30° relative to the horizontal, in order to ensure that the packages slide down.
Advantageous and/or preferred further developments of the disclosure are characterized in the dependent claims.
BRIEF DESCRIPTION OF THE DRAWINGS
In the following, the subject technology will be described in greater detail, using a preferred exemplary embodiment shown in the drawings. The drawings show:
FIG. 1 , a schematic sectional view of the separation apparatus according to the disclosure, with a supply filled with block-shaped and cylindrical piece goods, during conveying of a block-shaped article of piece goods by the first conveying step;
FIG. 2 , the apparatus according to FIG. 1 during further conveying upward of the block-shaped article of piece goods, just before it passes over the upper edge;
FIG. 3 , the apparatus shown in FIGS. 1 and 2 , during passage of the block-shaped article of piece goods over the upper edge of the step conveyor;
FIG. 4 , the apparatus shown in FIGS. 1 to 3 , after the block-shaped article of piece goods arrives on the collection device and during retraction of the first conveying step;
FIG. 5 , the apparatus shown in FIGS. 1 to 4 , after all the block-shaped piece goods have been conveyed onto the collection device and transported further by the latter, where the apparatus is shown at the start of the renewed upward movement of the first conveying step;
FIG. 6 , the apparatus shown in FIG. 5 , during upward movement of the first conveying step;
FIG. 7 , the apparatus shown in FIGS. 5 and 6 , at the beginning of upward movement of the second conveying step;
FIG. 8 , the apparatus shown in FIG. 7 , during upward movement of the second conveying step, which is moving a cylindrical article of piece goods;
FIG. 9 , a schematic sectional side view of the step conveyors with the two conveying steps;
FIG. 10 , a sketch that illustrates the forces that occur when pushing up a cylindrical article of piece goods, and their influence on the minimum step height that is provided; and
FIG. 11 , a schematic sectional side view of the step conveyor, in which the plates of the two conveying steps are configured as roller blinds.
DETAILED DESCRIPTION
FIG. 1 shows a schematic sectional side view of the apparatus 1 for separation of piece goods 2 , which are to be placed in storage in an automated storage unit. The piece goods 2 to be placed in storage are first supposed to be separated, subsequently identified and measured, and then transferred in a predetermined position (orientation) at a predetermined location of a storage apparatus (gripper) of an automated storage unit.
The separation apparatus 1 comprises a step conveyor 3 that is configured with a contact surface 8 , by way of a slanted plane. A first conveying step 9 moves above the contact surface 8 ; this step has a plate that is guided parallel above the contact surface 8 , having a face surface, where piece goods 2 A that lie on the contact surface 8 and against the face surface of the first conveying step 9 are pushed upward by the conveying step 9 , beyond an upper edge 13 of the contact surface 8 , when the conveying step 9 is moved upward in the direction of the arrow 10 and driven by a drive 14 .
In place of the first conveying step 9 , multiple first conveying steps can also be provided, which are disposed one on top of the other and parallel to the contact surface 8 . Furthermore, the conveying edge, that is, the upper edge of the face surface of the conveying plate, can assume not only a horizontal position, in other words a position perpendicular to the movement direction of the plate, but also can be disposed at a slant to this orientation, as is described in the document EP 1 652 799 A1 that has already been mentioned. In the preferred embodiment that is shown in FIG. 1 , the first conveying step 9 merely comprises a conveying plate having a face surface and conveying edge perpendicular to the movement direction (arrow 10 ).
In the lower section of the inclined plane, a supply bunker 4 is formed above the contact surface 8 and the plates of the conveying steps, by placement of lateral delimitation walls 12 , which bunker can accommodate a plurality of block-shaped and/or cylindrical piece goods 2 . The piece goods are preferably containers or packages of medications, such as block-shaped boxes or bottles and cans.
Adjacent to the upper edge 13 of the contact surface 8 , beyond which the piece goods 2 are conveyed by the step conveyor 3 , a collection device in the form of a collection surface 5 is disposed. The piece goods 2 pushed beyond the upper edge 13 fall onto this collection surface 5 . Furthermore, a sensor 7 is schematically shown in FIG. 1 , which detects when an article of piece goods or multiple piece goods are being conveyed beyond the upper edge 13 and are arriving on the surface 5 of the collection device. The collection surface 5 is inclined, where it drops away from the side adjacent to the upper edge 13 , so that arriving piece goods move (slide) away from the upper edge 13 . The collection device has a drive 23 assigned to it, which can move the collection surface 5 into a horizontal position.
Both the sensor 7 and the drive 14 of the step conveyor 3 and the drive 23 of the collection device are coupled with a control device 6 . The control device 6 is furthermore coupled with a gripping apparatus (not shown). The gripping apparatus is disposed above the collection surface 5 and serves to grasp the piece goods 2 that lie on it, if applicable to bring them into the detection range of a scanner for detection of imprinted identification information or a sensor for detection of dimensions of the article of piece goods, and to transfer them to a storage placement apparatus of the automated storage unit. Furthermore, an optical scanner or an image recording device coupled with the control device 6 can be disposed above and/or below the collection surface 5 , which can detect the location and position (orientation) of the piece goods 2 lying on the collection surface 4 , so that the control device 6 , using this information, can activate the gripping device in such a manner that it grasps one of the arriving piece goods, in targeted manner, and transports it further.
FIGS. 1 to 4 illustrate the function of the first conveying step 9 for conveying block-shaped piece goods 2 A out of the supply 4 onto the collection surface 5 . FIG. 1 shows how the front surface with the conveying edge of the conveying plate of the first conveying step 9 , which edge faces upward, makes contact with a side surface of a block-shaped article of piece goods 2 A that is lying on the contact surface 8 . The conveying step 9 then moves in the direction of the arrow 10 , so that the block-shaped article of piece goods 2 A is taken along and pushed upward. FIG. 2 shows the moment when the article of piece goods approaches the upper edge of the contact surface 8 . In a preferred embodiment, a sensor (not shown in the drawing), for example a photo eye, is disposed just ahead of the upper end of the contact surface 8 , in such a manner that it detects the approach of one or more piece goods 2 A being pushed by the conveying step to the upper edge 13 . As soon as such an approach has been detected, the conveying speed is reduced. This has the result that when multiple piece goods 2 A are pushed simultaneously, the likelihood decreases that two or more piece goods 2 A pass beyond the upper edge 13 before the conveying step can be stopped and then moved back. FIG. 3 shows the moment when the article of piece goods 2 A tips over the upper edge 13 of the contact surface 8 and thereby gets into the detection region of the sensor 7 . Immediately after detection of the passage of the article of piece goods 2 A over the conveying edge 13 and the arrival on the collection surface 5 , the drive 23 brings the collection surface 5 into a horizontal position, so that the downward sliding movement of the article of piece goods 2 A is stopped. FIG. 4 shows the state after the article of piece goods 2 A has assumed a rest position on the collection surface 5 . In FIG. 4 , it is furthermore shown how the first conveying step 9 is moved back in the direction of the arrow 10 , into the starting position. The collection surface 5 is situated in the horizontal position and remains in it until the article of piece goods 2 A has been removed. As soon as the article of piece goods 2 A has been removed from the collection surface 5 by the gripper device, the control device 6 can instruct the drive 14 of the step conveyor 3 to move the first conveying step 9 upward again, where the conveying step grasps a further article of piece goods 2 or multiple further piece goods 2 and pushes them upward on the contact surface 8 .
The first conveying step 9 is subsequently moved up and back until all the block-shaped piece goods 2 have been conveyed beyond the upper edge 13 onto the collection surface 5 , and removed from there by means of the gripper device. Because of the low height of the conveying step 9 , first only the block-shaped piece goods that come to lie on the contact surface 8 in front of the conveying step 9 are conveyed upward and further onto the collection surface 5 .
FIG. 5 schematically shows the state that occurs after all the block-shaped piece goods have been conveyed. In the example shown, two cylindrical piece goods 2 B remain in the supply chamber 4 . In FIGS. 5 and 6 , it is shown how the control device 6 again controls the drive 14 of the step conveyor 13 , in such a manner that the latter moves the first conveying step 9 upward. In this connection, however, no further article of piece goods can be conveyed beyond the upper edge 13 , so that the control device 6 recognizes, on the basis of the signal of the sensor 7 , that no further piece goods 2 can be conveyed using the first conveying step 9 .
In an alternative embodiment, it is also possible that activation of the first conveying step 9 is repeated several (a few) times after no arrival of an article of piece goods 2 on the collection surface 5 has been detected by the sensor 7 . For example, this can be repeated twice or three times. This serves to ensure that a last block-shaped article of piece goods that might not yet have been detected is conveyed during one of the further conveying attempts, for example if it first had to be tilted into a suitable position within the supply (for example, a first conveying attempt could lead to tilting of the last block-shaped article of piece goods, so that upward conveying of the block-shaped article of piece goods only succeeds during the second attempt).
After the control device 6 has now detected that no further (block-shaped) piece goods 2 can be transported any longer, using the first conveying step 9 , the control device 6 at first assumes that there might still be cylindrical piece goods in the supply 4 . It thereupon activates a second conveying step 11 , using the drive 14 , as illustrated in FIGS. 7 and 8 . FIG. 7 shows the moment when the movement of the second conveying step 11 along the arrow 15 starts. The front surface of the second conveying step 11 lies against a cylindrical article of piece goods 2 B. FIG. 8 shows the time point when the cylindrical article of piece goods 2 B has been moved upward (rolled and/or pushed) on the contact surface 8 , by means of the upward movement of the second conveying step 11 , just before the upper edge 13 has been reached. By means of further upward movement of the second conveying step 11 , finally the cylindrical article of piece goods 2 B is transported beyond the upper edge 13 onto the collection surface 5 . There the article of piece goods 2 B can be grasped and transported further by the gripping device, controlled by the control device 6 .
In the preferred exemplary embodiment shown in FIGS. 7 and 8 , the first conveying step 9 is moved upward parallel with the second conveying step 11 . In an alternative embodiment, not shown here, the first conveying step 9 could remain in the retracted position while the second conveying step 11 is moved upward.
FIG. 9 illustrates once again the elements of the step conveyor 3 (without piece goods 2 lying on it), in greater detail. In the exemplary embodiment shown, two conveying steps, namely a first conveying step 9 and a second conveying step 11 , are disposed above a contact surface 8 . Both conveying steps 9 and 11 are moved by a drive 14 , shown only schematically here. The first conveying step 9 , with its conveying edge 16 that faces upward, has the step height 18 , which preferably amounts to 8-20 mm, for example 15 mm, and is composed of a plate thickness of 10 mm and an air gap of 5 mm under the plate, for example. The conveying edge 16 can (as shown in the example) be formed by a right-angle outer edge. However, it is also possible that the edge is configured to have an acute angle, so that only the edge itself, but not the front surface, lies against the side wall of the article of piece goods that lies on the contact surface 8 and is to be transported upward. The second conveying step 11 is shown in the retracted position and has the step height 19 shown, which amounts, for example, to 45 mm. The second conveying step has a conveying front surface 17 with which it pushes the (cylindrical) piece goods to be transported upward. Furthermore, in FIG. 9 a delimitation wall 12 of the supply bunker 4 is shown, as is the sensor 7 that detects passage of the piece goods over the upper edge 13 of the contact surface 8 .
FIG. 10 illustrates the dimensioning of the minimum height hmin of the second conveying step as a function of the expected maximal radius r of cylindrical piece goods to be conveyed, and of the inclination angle α of the contact surface 8 . If one were to ignore the inertia forces and friction that occur, particularly adhesion friction when starting to push the piece goods, this would result in a minimum height hmin of the second step that would correspond to the radius r of the cylindrical piece goods minus the product of the radius r and the cosine of the inclination (cos α), in other words
h min =r−r* cos α =r* (1−cos α) (1)
The minimum step height hmin determined in this manner is furthermore increased on the basis of the friction and inertia forces that occur during upward pushing, which are indicated in FIG. 10 with FR, where in FIG. 10 , the combination of a weight force vector with the (displaced) friction force vector is shown. The upper edge of the step having the height hmin is not allowed to engage below the intersection point at which the extended vector of the composite force (shown as a dotted line) intersects the mantle of the cylindrical article of piece goods, because otherwise, tipping over the step is threatened. The stated increase in the minimum step height hmin grows with the ratio of friction and inertia forces FR to the weight FG of the article of piece goods, but does not become greater than the maximal expected radius r. In particular, light cylindrical piece goods (having a low weight force) and great friction force require a higher step, which comes closer to the maximal value of the minimum step height Max(hmin)=r, the radius. The minimum step height may be determined experimentally.
FIG. 11 schematically shows a preferred configuration of the plates of the two steps 9 and 11 in the form of roller blinds. The plates of the first step 9 and of the second step 11 are formed, in each instance, from a plurality of parallel strip segments that are coupled so as to pivot, and are guided above the contact surface 8 in parallel lateral guides (not shown), and guided in arc-shaped lateral guides at the lower end of the contact surface 8 . In this way, the construction space required in the plane of the contact surface 8 is shortened. Furthermore, the segments of the second step are selected to be just as thick as the segments of the first step, which simplifies production. The second step 11 , at the upper edge, has a plate 22 that is angled away perpendicular to the contact surface 8 , from the uppermost segment, the front surface 17 of which forms the conveying surface that determines the step height. | An apparatus for separating piece goods which are to be stored in an automated store comprises a stepped conveyor for conveying piece goods from a stockpile beyond an upper edge of the stepped conveyor to a collecting device, wherein the stepped conveyor comprises an inclined bearing surface and a first step which can be moved in parallel over the bearing surface with a conveying edge which is parallel to the bearing surface, wherein the spacing between the bearing surface and the conveying edge corresponds to a minimum step height which suffices to push parallelepiped-shaped piece goods upwards, and a control device for actuating the stepped conveyor, which control device is coupled to a sensor which detects whether a piece goods item has been conveyed beyond the upper edge. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application claims priority under 35 U.S.C. §119 of German Patent Application No. 10 2012 024 104.6, filed Dec. 10, 2012, the disclosure of which is hereby incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
The present invention relates to a compacting machine comprising a shaft, an unbalanced mass and a drum, wherein the shaft is connected both to the unbalanced mass and to the drum and is adapted to transfer imbalance forces from the unbalanced mass to the drum.
BACKGROUND OF THE INVENTION
A compacting machine can take the form of a vibrating compactor. Vibrating compactors are dynamic compacting machines that are adapted to transfer energy, in addition to their own weight, into a volume to be compacted, for example, the ground. For this purpose, use is usually made of vibration produced by unbalanced masses. Vibrating compactors can be used, for example, for the purpose of compacting the subsurface of roads, runways, or dams. They take the form of, for example, agitator plates, vibrating rollers, single-drum compactors, vibratory plates, duplex rollers, or trench compactors. They can be used in the construction of roads and paths and wherever the ground or pavings have to be compacted. By this means, it is possible to improve the load bearing strength of a subsurface and to reduce subsidence.
Such vibrating compactors have at least one drum or plate, to which the vibration produced by the unbalanced mass can be transferred. The unbalanced mass is usually provided on a shaft, as, for example, an imbalance shaft mounted on roller bearings. In some cases, a plurality of adjustable unbalanced masses is provided so that various types of vibration can be produced.
Known vibration generators comprising an unbalanced mass or a plurality of unbalanced masses take up much room. The construction, thereof, is complicated and expensive. In operation, the degree of noise generated is high and a limit has been reached as regards the permissible stresses, more particularly, the centrifugal forces and rotational speeds.
SUMMARY OF THE INVENTION
The essential elements of a compacting device according to one embodiment of the present invention comprise at least one shaft, an unbalanced mass, and a drum, wherein the at least one shaft is connected to both the unbalanced mass and the drum, and is adapted to transfer the imbalance force from the unbalanced mass to the drum. According to one aspect of the present invention, the shaft has at least one exciter bearing, in which the unbalanced mass will rotate during vibration operation, wherein the exciter bearing comprises one or a plurality of plain bearings, and, in particular, exclusively plain bearings. A plain bearing comprises just a bearing surface and no additional rolling elements such as, for example, in roller bearings. A plain bearing is, thus, basically a shaft rotating in a hole. Plain bearings can comprise bushings or other bearing elements. Plain bearings are sometimes alternatively called journal bearings, slide bearings or friction bearings. It will be readily understood that any statements made hereinafter with respect to one shaft apply to compacting devices comprising a plurality of shafts as well.
The shaft is preferably one that is capable of generating vibration when rotated. Preferably, the vibration is generated on account of the fact that the shaft comprises, or is connected to, an unbalanced mass. In a particularly preferred embodiment, a shaft is adapted to rotate not only about its own axis, but also about another shaft. In one embodiment, a second shaft plus a housing forms an unbalanced mass and the second shaft and the unbalanced mass rotate about the shaft. Preferably, the shaft is adapted to be stationary during this process. The vibration produced is preferably transmitted to the drum via a driving shaft. A shaft may of course also consist of multiple components.
Thus, the exciter bearing is the bearing which is arranged between the component forming the unbalanced mass and the component supporting the unbalanced mass. In other words, by means of the exciter bearing, the component forming the unbalanced mass and the component of the compaction machine supporting the unbalanced mass are mounted and connected to each other so as to be able to move relative to one another about the axis of rotation of the unbalanced mass. According to one embodiment of the present invention, said exciter bearing is at least partially and, in particular, completely configured as a plain bearing.
A drum is the tubular wall of a rolling body. Preferably, the drum used is a smooth drum. The drum is rotatably mounted, for example, on a machine frame of the compacting machine by means of what will hereinafter be referred to as drum bearing. As opposed to the exciter bearing, the drum bearing is preferably a roller bearing. The speeds generated by the drum bearing are comparatively low and essentially depend on the respective travel speed of the compacting machine. Compared to the drum bearing, the speeds generated by the exciter bearing are relatively high and have a high frequency. As regards the shaft, in particular, the driving shaft of the drum, it can, thus, comprise a drum bearing as far as the manner in which the drum is mounted on the machine frame is concerned, for example, and, spatially separated therefrom, simultaneously an exciter bearing having an unbalanced mass which rotates during vibration operation. The present invention according to one embodiment is directed to said exciter bearing being at least partially and, in particular, completely configured as a plain bearing.
The plain bearings used are preferably hydrodynamic fluid bearings. Preferably, hydrodynamic lubrication is provided. Preferably, 0.5 liter of oil per minute are provided for lubrication.
Advantageously, the shaft, unbalanced mass, and plain bearing form a vibration generator. The vibration generator is preferably mounted at one end, but more preferably at both ends. In the case of the shaft being mounted at one end only, it is preferably connected to a driving shaft in such a manner that the vibration generator is mounted. In the case of the shaft being mounted at both ends, it is preferably additionally prolonged such that it extends axially symmetrically to the driving shaft and away therefrom on that side of the vibration generator that is opposite to the driving shaft. This portion of the shaft is bearing-mounted, so that the vibration generator is bearing-mounted at both of its opposite ends.
In one embodiment, a substantially L-shaped bracket is provided on an extension of the shaft, which bracket extends around the vibration generator and is fixed to the driving shaft side of the vibration generator. Preferably, the center of gravity of the L-shaped bracket lies in a plain bearing or adjacent to a plain bearing, so that the load thereon is small. The vibration generator is preferably driven by a commercial-type drive engine, as, for example, a geared engine.
Preference is given to the provision of a bolt-on plate for the purpose of fixing the vibration generator. Preferably, this bolt-on plate comprises a plane bolt-on face and a linear overflow oil connector.
Advantageously, the plain bearing is adapted to absorb imbalance forces and driving forces. By this means, imbalance forces and driving forces can be efficiently absorbed. In this way, it is possible to arrange the bearings in a particularly space-saving manner.
Driving forces are preferably those forces to be understood that act on the shaft as a result of pressure differences.
In one embodiment, a gear wheel is adapted to absorb small axial forces at a lateral surface.
Preferably, the plain bearing is designed such that it is particularly resistant both to wear due to rotary movements and to wear caused by imbalance forces. In one embodiment, the compacting machine is adapted to discharge hydraulic oil to a point on the plain bearing at which the components of the plain bearing are liable to be subjected to compressive imbalance forces to a particularly high extent.
In one embodiment, the compacting machine comprises a drive that complies with the principal of a hydraulic geared engine, which drive comprises a housing and a driving shaft that is adapted to transfer the vibration to the drum, and the unbalanced mass forms part of the drive, more particularly of the housing and/or the driving shaft. In this way, the unbalanced mass can be integrated in the compacting machine in a very space-saving manner. In the case of systems already equipped with hydraulic means, such as mobile machines for ground compaction, the hydraulic system can be implemented for the production of vibration and for the lubrication of the plain bearing. These objectives can, thus, be very efficiently satisfied. In such a configuration, the plain bearing is preferably arranged between the driving shaft and, for example, a part of the housing or a bearing element fixed to the housing. Additionally, the gear wheel which is arranged on the shaft rotating about the drive shaft may preferably also be accommodated in a plain bearing.
Preferably, the compacting machine comprises a drive complying with the principal of a hydraulic geared engine, which drive comprises a housing and a driving shaft that is adapted to transfer vibration to the drum, and the unbalanced mass is indirectly or directly connected to the drive, more particularly, to the housing and/or the driving shaft.
In a preferred embodiment, the hydraulic geared engine comprises two gear wheels capable of being driven by a flow of oil. Preferably, one of the gear wheels is coupled to the unbalanced mass and the other to the drum, the shafts of both gear wheels ideally being arranged in a plain bearing.
Preferably, the mass of a shaft is not axially symmetrical to the axis of rotation of the driving shaft. In a particularly preferred embodiment, a shaft rotates about the axis of rotation of the driving shaft. Preferably, the housing is adapted to rotate at least partially about a shaft, wherein the mass of the housing is not axially symmetrically distributed.
In one embodiment, the machine is powered by a distinctly overlarge hydraulic geared engine, which is adapted to run at reduced pressure. Preferably, a hydraulic geared engine being able to run at a permissible pressure of approximately 200 bar in continuous operation is operated at approximately 50 bar. By this means, the bearings have leeway for additional radial loads so that they can absorb imbalance forces in addition to the driving forces.
In a preferred embodiment, the drive comprises a first gear wheel, a second gear wheel, a first shaft and a second shaft, wherein the first gear wheel is connected to the first shaft and the second gear wheel to the second shaft, and the first gear wheel engages the second gear wheel, the first shaft being connected to the driving shaft and the axis of the second shaft not being in alignment with the axis of the driving shaft. In the case of such a construction, the unbalanced mass can be provided in a very simple manner. Preferably, the unbalanced mass comprises the second shaft with the second gear wheel. The second shaft comprising the second gear wheel preferably rotates about the axis of rotation of the driving shaft. In a particularly preferred embodiment, the unbalanced mass comprises that portion of the housing of the drive that encloses the second shaft and the second gear wheel. This portion of the housing is preferably adapted to rotate about the axis of rotation of the driving shaft. Advantageously, the unbalanced mass of this portion of the housing is not axially symmetrical to the axis of rotation of the driving shaft. The first and the second shaft are preferably each mounted in a respective plain bearing. Thus, in addition to these plain bearings in which the first and the second shaft are mounted, the overall configuration further comprises at least one drum bearing which is arranged separately from said plain bearings and by means of which the drum is rotatably mounted on the machine frame.
In particular, compact constructions can be realized by combining the drive, the shaft and the plain bearing to form a subassembly. In this way, a very simple construction can be realized.
Advantageously, the subassembly is adapted such that it can be connected as a whole to other components for the purpose of producing vibration therein.
Preferably, there is communication between a toothed gear system of the drive and the plain bearing, so that the oil that can be used for driving the hydraulic geared engine can be passed on to the plain bearing, where it may be implemented for lubrication of the bearings. By this means, the lubrication of the plain bearing can be carried out in a very simple manner. There is no need to provide an oil pump and an oil filter for the express purpose of lubrication and maintenance of these portions or to provide a clean space.
The oil used is preferably hydraulic oil. The pressure at which the oil is transported to the hydraulic geared engine can also be implemented for passing the oil to the plain bearing. In a preferred embodiment, oil is passed to the plain bearing by means of centrifugal forces, which are formed due to rotation of a shaft about a driving shaft.
It is advantageous to adapt the space in which the plain bearing is disposed such that it is capable of being completely filled with oil. This is a very simple way of ensuring adequate lubrication of the plain bearing. Preferably, the amount of oil used for lubrication of the bearings is very small and is kept in the order of magnitude of one liter per minute.
Preferably, the construction space surrounds the plain bearing almost completely.
It is advantageous when the space in which the plain bearing is disposed comprises both an influent duct and an effluent duct, such that the plain bearing is adapted to be located in a flow of oil and the heat from the plain bearing is capable of being dissipated via the flow of oil. Overheating of the plain bearing can, thus, be prevented in a simple manner.
The size of the space in which the plain bearing is disposed is advantageously restricted such that the oil that surrounds the plain bearing can be replaced quickly enough for the dissipation of an adequate quantity of heat.
In one embodiment, the compacting machine is adapted to achieve heat dissipation via the preferably high flow of driving oil. For this purpose, the heat from the plain bearing is preferably transferred to a toothed gear system of the hydraulic geared engine so that it can be dissipated with the driving oil.
In a preferred embodiment, the compacting machine comprises two or more shafts, of which the rotational speed and/or position are controllable, so that a direction of vibration can be set. The energy of compaction can, thus, be selectively used and adapted to requirements. Preferably, this makes it possible to achieve directional vibration and/or a modifiable direction thereof, more particularly, a directional and/or modifiable amplitude.
In a particularly preferred embodiment, the shafts are adapted to be capable of rotating independently of each other such that they can be caused to rotate at different rotational speeds and/or phase positions relatively to each other. By this means, different types of vibration can be provided, which are continuously repeated.
Preferably, a detector and an indicator are provided, wherein the detector is adapted to detect the position and/or rotational speed of a shaft and to forward the relevant data to the indicator. Thus, an operator of the compacting machine will obtain information concerning the position and/or rotational speed of a shaft and can vary the same as required. By this means, the selective adjustment of a directional vibration, more particularly, of a directional amplitude and/or a modifiable direction is simplified.
The detector used is preferably an electrical detector, more preferably, a Hall effect sensor having a magnetic ring or an inductive detector.
The indicator used is preferably a display or a number of light signaling units standing for various settings.
Advantageously, a controlling or regulating device is provided, by means of which the operator can adjust the position and/or rotational speed of a shaft. Preferably, a hydraulic valve is provided, by means of which the flow of oil can be influenced so as to modify the position and/or rotational speed of a shaft. In the case of the provision of a hydraulic geared engine, it is preferred that the hydraulic valve can be opened by various amounts for the purpose of varying the rate of the volumetric flow to the toothed gear system so that, in this way, the rotational speed of the gear wheels can be influenced.
In a particularly preferred embodiment, software is provided, which is adapted to process the position and/or rotational speed registered by the detector and to control the drives in an appropriate manner. The software can make it possible to adjust the position and/or rotational speed of a shaft as required. By this means, the operator is relieved of this task. Preferably, the software is adapted such that it carries out adjustments continuously during operation. In this way, adjustments can be carried out very frequently.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is further described below with reference to exemplary embodiments illustrated in the drawings. In the diagrammatical drawings:
FIG. 1 shows a compacting machine;
FIG. 2 shows a vibration generator;
FIG. 3 shows a vibration generator, which is mounted in bearings at both ends;
FIG. 4 shows a conventional vibration generator fixed by means of a bolt-on plate and a bracket; and
FIG. 5 shows imbalance masses in the shafts of a geared engine.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 illustrates a compacting machine 30 in the form of a vibratory roller, as used for compacting a subsurface in areas constructed for traffic. It comprises a frame 31 , an operator's cabin 32 and one or two drums 33 . Within at least one drum there is situated a vibration generator for the purpose of producing vibration for transference by the respective drum 33 to the subsurface.
FIG. 2 shows a vibration generator 1 comprising a housing 2 , in which a first shaft 4 is mounted by means of a first plain bearing 3 . The first shaft 4 is provided with a first gear wheel 5 that comprises a first toothed gear system 6 . A second shaft 8 is mounted in the housing 2 by means of a second plain bearing 7 . The second shaft 8 is provided with a second gear wheel 9 , which comprises a second toothed gear system 10 . The first shaft 4 and the second shaft 8 and, also, the first gear wheel 5 and the second gear wheel 9 are disposed such that the first toothed gear system 6 and the second toothed gear system 10 engage each other and the first gear wheel 5 meshes with the second gear wheel 9 . The first shaft 4 transitions into the driving shaft 11 . Thus, the shaft 4 is not formed integrally with the driving shaft 11 as one piece. The first shaft 4 is mounted axially symmetrical to the driving shaft 11 . The second shaft 8 is mounted such that its rotation axis is not in alignment with the rotation axis of the driving shaft 11 and the first shaft 4 .
Between the housing 2 and the driving shaft 11 there is provided a packing ring 12 . By means of a press fit joint 13 , the driving shaft 11 is connected to a drum holding fixture 14 which is mounted in the drum 33 by means of the drum bearing 15 . The drum bearing 15 and the exciter bearing 23 are, thus, separated spatially and functionally. The drum holding fixture 14 has an influent duct 16 , which continues within the driving shaft 11 and extends to the first toothed gear system 61 the second toothed gear system 10 , to the first plain bearing 3 and the second plain bearing 7 . There is, also, provided an effluent duct 17 , which extends from the first toothed gear system 6 , the second toothed gear system 10 , the first plain bearing 3 , and the second plain bearing 7 through the driving shaft 11 and the drum holding fixture 14 . The influent duct 16 and effluent duct 17 are in each case connected to a hydraulic oil supply device (not shown).
In operation, hydraulic oil is passed through the influent duct 16 to the first gear wheel 5 and to the second gear wheel 9 . By this means, the first gear wheel 5 and the second gear wheel 9 rotate together with the first shaft 4 and the second shaft 8 , as powered by the hydraulic geared engine.
Oil is fed through the influent duct 16 also to the first plain bearing 3 and to the second plain bearing 7 . In this case, approximately 0 . 5 I/min of oil or more is fed to the first plain bearing 3 and to the second plain bearing 7 . This ensures that hydrodynamic lubrication takes place in the plain bearings 3 , 7 .
The substantially closed, rotating housing 2 requires a seal only at one location. On account of the low internal pressure present at that location, a cheap gasket is sufficient.
During the operation of the vibration generator 1 , the first gear wheel 5 meshes with the second gear wheel 9 . On account of the fact that the first shaft 4 is mounted axially symmetrical to the driving shaft 11 in axis R and that the second shaft 8 is mounted such that its rotation axis R′ runs parallel to the rotation axis R of the driving shaft 11 , as in the illustrated example, there is formed an unbalanced mass. This unbalanced mass comprises the weight of the second shaft 8 comprising the second gear wheel 9 and the region of the housing 2 enclosing the second shaft 8 comprising the second gear wheel 9 . This unbalanced mass, when rotating about the rotation axis R of the first shaft in vibration operation, produces vibration, which is transferred by the driving shaft 11 and the drum holding fixture 14 to a drum which is not shown but indicated by arrows 33 . Thus, the first plain bearing 3 forms an exciter bearing since it is the bearing in which the unbalanced mass of the vibration generator 1 rotates during vibration operation. In addition thereto, and separate therefrom, a drum bearing 25 is provided between the driving shaft 11 and the drum 33 , which drum bearing, as in the present embodiment, preferably is a roller bearing of known type, in which the drum 33 of the compacting machine 30 rotates about the drum holding fixture 14 during travel operation.
Due to the fact that only the plain bearings 3 , 7 are used for the purpose of mounting the shafts 4 , 8 , the vibration generator 1 can withstand high stresses, and high rotational speeds can be employed. The vibration generator 1 is quiet compared with the use of conventional mounts in roller bearings. The construction can be effected in a space-saving manner. The plain bearings 3 , 7 absorb both driving forces and centrifugal forces.
Due to the fact that the plain bearings 3 , 7 are supplied with the same oil as the gear wheels 5 , 9 , the vibration generator 1 can have very space-saving dimensions. This type of oil supply is particularly efficient in systems already equipped with hydraulic means.
FIG. 3 shows a vibration generator 1 with bearings at both ends. This vibration generator 1 is not only mounted such that the first shaft 4 transitions into the driving shaft 11 , but also that the first shaft 4 passes through that side of the housing 2 that is opposite to the driving shaft 11 and is rigidly fixed outside the housing 2 by a bolt 18 , with a further drum bearing 15 being provided at this end of the driving shaft 11 in extension thereof. In terms of further construction, the vibration generator 1 is comparable to the embodiment shown in FIG. 2 , so that in this respect reference is made to the aforesaid. Here too the exciter bearing 23 is configured as a plain bearing 3 , by means of which the housing 2 rotates about the axis R in vibration operation. Consequently, the drum bearings 15 and the exciter bearing 23 are spatially separated here too.
Due to this double-ended mounting method, the vibration generator 1 is mounted in a particularly reliable manner.
FIG. 4 shows a vibration generator 1 , which is fixed to the drum holding fixture 14 by means of a bolt-on plate 19 . This bolt-on plate 19 has a plane bolt-on face 20 and a linear overflow oil connector 21 .
On that side of the vibration generator 1 that is situated opposite to the bolt-on plate 19 , there is provided a bracket 22 , in which a prolonged portion of the first shaft 4 is accommodated. This bracket 22 extends towards the bolt-on plate 19 in such a manner that the center of gravity lies in the region of the bearing.
By this means, the vibration generator 1 can, on the one hand, be securely mounted without placing an additional load on the driving shaft 11 , while, on the other hand, the bracket 22 makes it possible to position the vibration generator 1 on one side, so that the space available for construction can be better exploited.
During vibration operation, the bracket and the first shaft 4 rotate about the axis R in the manner described above, with the bracket acting as the unbalanced weight, comparable to the housing 2 . The exciter bearing 23 is configured as plain bearing 3 .
The engine used is one that is distinctly overlarge for driving purposes and that runs at reduced pressure. In this case, an engine being able to run at a permissible oil pressure of 200 bar in continuous operation is used at a distinctly lower pressure of, say, 50 bar. By this means, the bearings have leeway for additional radial stresses and can absorb the forces resulting from the unbalanced mass.
Alternatively, two vibration generators 1 can be coupled to each other such that they rotate in opposite directions. By means of appropriate regulating means, the two vibration generators can be controlled so as to make a directional amplitude and a change in direction, thereof, possible similarly to that known in vibrating plates and certain rollers, as, for example, the Asphalt Manager.
In order to make it possible to control of the two vibration generators, a hydraulic valve (not shown) is provided, by means of which the oil supply can be regulated in a specific manner.
Furthermore, a Hall effect sensor comprising a magnetic ring can be provided for the acquisition of the rotational speed and the position of a shaft 4 , 8 . By the acquisition of the current rotational speed and the position of a shaft 4 , 8 , the vibration can be controlled more specifically.
The Hall effect sensor can be used for the purpose of feeding the registered data to an indicator and/or to software. The operator or the software can then adjust the oil supply according to the data registered.
FIG. 5 shows unbalanced masses in the shafts 25 of a geared engine 24 (cover removed). These shafts 25 are solid or provided with an unbalanced mass 26 at one end and are hollow at the other end. In operation, these shafts 25 produce vibration due to the fact that their masses are not axially symmetrically distributed.
By varying the alignment of the shafts 25 relatively to each other, it is possible to influence the vibration in a specific manner. A directional amplitude can be produced.
Here again, the shafts 25 are mounted in plain bearings 27 in a housing 28 . In this way, high rotational speeds can be achieved, large unbalanced masses 26 can be provided, and the construction is space-saving. Thus, according to this embodiment, the unbalanced masses 26 form a respective part of the shafts 25 . Each shaft is equipped with a respective exciter bearing 23 , which is configured as a plain bearing 3 , between the shaft and the housing 28 . During vibration operation, the shafts 25 rotate about the shafts R 1 and R 2 . Parallel thereto and spatially separated from the exciter bearings 23 , the rotation axis R 3 of the drum 33 extends through the drum bearing 15 .
In summary, the essential feature of the present invention is the fact that in the various embodiments the exciter bearing 23 is configured as a plain bearing.
While the present invention has been illustrated by description of various embodiments and while those embodiments have been described in considerable detail, it is not the intention of Applicants to restrict or in any way limit the scope of the appended claims to such details. Additional advantages and modifications will readily appear to those skilled in the art. The present invention in its broader aspects is therefore not limited to the specific details and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of Applicants' invention. | The present invention relates to a compacting machine comprising a shaft, an unbalanced mass and a drum, wherein the shaft is connected both to the unbalanced mass and to the drum and is adapted to transfer imbalance forces from the unbalanced mass to the drum, and further wherein the shaft is mounted in a plain bearing. | 4 |
BACKGROUND OF THE INVENTION
1. Field of Invention
This invention relates to a system and method for re-directing incoming calls. More specifically, the invention relates to re-directing incoming calls to a provider originating switch to support Intelligent Network (IN) services in public switched telephone networks (PSTN) and Internet protocol (IP) domains.
2. Description of Related Art
As use of the Internet has grown, subscribers have become interested in receiving the same telephone services over the Internet that they presently enjoy over the PSTN. This has pushed telecommunication providers to provide services to their subscribers which make telecommunication contact easier and better in the Internet realm.
As telecommunication service providers seek to provide these new services, new techniques are being developed. For example, a commonly-owned patent, assigned to AT&T Corporation, U.S. Pat. No. 5,473,677, issued on Dec. 5, 1995 to D'Amato et al., which is hereby incorporated herein in its entirety, relates to providing real-time call control within a telecommunications network. Real-time call control is provided using a call selection processor which is separate from the switches that relay the call. The call selection processor responds to in-coming calls and uses information carried in the associated signaling messages to determine what application processor, if any, should be involved on the call. This permits selected calls to be differentiated from other calls so as to allow the selected calls to receive special treatment.
In enabling selected calls to be differentiated for special treatment, such features as call waiting have been implemented over the Internet. See, for instance, another commonly-owned patent, assigned to AT&T Corporation, U.S. Pat. No. 5,805,587 (incorporated herein in its entirety), issued on Sep. 8, 1998 to Norris et al., which relates to alerting a service subscriber whose telephone is connected to the Internet of a waiting call via that Internet connection. A waiting call to a subscriber may be forwarded via the PSTN to a services platform, which in turn establishes a connection to the subscriber using the Internet. The platform then notifies the subscriber of the waiting call via the Internet connection. The platform may then forward the telephone call to the subscriber via the Internet responsive to a subscriber request to do so without interrupting the subscriber's Internet connection.
Many subscribers of telecommunication service providers want Caller-ID as well. This is especially true in regard to the use of the service over the Internet. An attempt at providing this type of service was made in U.S. Pat. No. 5,724,412, issued on Mar. 2, 1998, to Srinivasan, which relates to providing a telephone service subscriber with Internet information related to a caller attempting to call the subscriber. Identification information relating to a caller attempting to call the subscriber is provided to the called party via the Internet after a caller has attempted to reach the called party.
Thus, Internet enabled IN services such as Internet call waiting, Caller-ID delivery, local number portability, CNAME, etc., have now become commonly available to service subscribers. These are IN services in that the incoming calls receive intelligent routing/treatment. Commonly, telecommunication service providers provide these Internet-enabled intelligent services. Implementing these services often requires access to a telecommunication service provider's service control point (SCP). This access is provided via a “database dip”.
SUMMARY OF THE INVENTION
However, when the telecommunication service provider for the subscriber is different than the telecommunication service provider of the caller, who initiated the incoming call that is not a call to an 800 number, providing IN services, e.g., call-waiting, call-forwarding, or caller ID, some degree of access is required to information in the SCP, that is managed by the called party's telecommunication service provider. Access to such information by other telecommunication service providers is detrimental to the telecommunication service provider because such information is proprietary. Nevertheless, performance of certain IN services require use of that information. Therefore, the telecommunication service provider is faced with a difficult problem of protecting information while having to utilize that information to provide IN services for IP related uses.
The present invention provides a solution to such a problem. By providing a system and method that performs re-routing of an incoming call based on proprietary data within the control of the telecommunication service provider's equipment without having to provide access by other telecommunication service providers, the subscriber's telecommunication provider can effectively provide service without risking dissemination of that proprietary data.
In accordance with an illustrative embodiment of the present invention, an incoming call that requires IN services, such as call-routing or call-waiting, is re-routed to a service provider originating switch (POS) following receipt of the incoming call at the local exchange carrier (LEC) servicing the called subscriber. For example, if a LEC determines that the destination phone number for the incoming call is busy, the LEC reroutes the incoming call to the POS via a specific exchange number. In aPage: 4 more general sense, the service subscriber's LEC will implement a termination attempt trigger (TAT). This exchange number includes a real exchange number with dummy digits, meaning that there is not a telephone station with such a number, for the rest of the phone number. The POS recognizes that the exchange and dummy digits indicate a re-routed call coming from a LEC to the POS for rerouting using IN services.
As a result of this recognition, the POS parks the call and interacts with an SCP that performs a query regarding the called party's service information. This service information is stored in a database that stores information about the telecommunication subscriber's service information. As a result of that query, the SCP provides information to the POS on how to re-route the incoming call. Thus for systems that provide Internet Caller-ID Delivery Plus Service, such information may include an alternate phone number or alternate phone numbers which may receive the re-routed call. The SCP information may also include the priority of each of those alternative phone numbers.
As a result, the SCP query may not identify an alternative telephone-station to which the incoming call can be completed because, for example, there are no alternative telephone-stations listed in the database or none of the alternative telephone-stations are available to complete the call. In such a case, the SCP may analyze the information in the database to determine whether there is a universal resource locator (URL) where an additional alternative telephone-station or stations may be listed. The SCP then accesses the URL information using a web service control point (WSCP). Such a URL may be updated by the called party at his/her convenience. Such an updatable URL provides the opportunity for the called party to alter his/her information more easily so as to facilitate providing more effective IN services over the IP domain.
These and other features and advantages of this invention are described in, or are apparent from, the following description of the apparatus/systems and methods according to this invention.
BRIEF DESCRIPTION OF THE DRAWINGS
Various embodiments of this invention will be described in detail, with reference to the following figures, wherein:
FIG. 1 shows a diagram of a communication system that provides IN services to a subscriber according to an exemplary embodiment of the invention;
FIG. 2 shows a diagram of a data packet format used in conjunction with the exemplary embodiment of the present invention;
FIGS. 3 and 4 show flowcharts of the steps in a telecommunication method that provide IN services to a subscriber according to the exemplary embodiment of the invention; and
FIG. 5 shows a diagram of a telecommunication system that provides IN services to a subscriber according to an exemplary embodiment of the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention is useful in connection with a method and system for Internet Caller-ID Delivery Plus Service. In such a system, an incoming telephone call is received by a telecommunication service provider's POS, the telephone call having been routed to the POS by a local exchange carrier (LEC) in the area from which the telephone call was placed. The LEC can route the call to the POS if, for example: 1) the calling party is a subscriber of the telecommunication service provider; 2) the telephone station number called was an 800 number; or 3) the telecommunication service provider has a special arrangement with the LEC.
The POS attempts to contact the called party, i.e., the subscriber, via a primary telephone-station and any alternative telephone-station associated with the service subscriber. If attempts to reach the service subscriber via the telephone fail, the POS provides the option of leaving voice-mail for the called party at the primary telephone-station.
FIG. 1 illustrates a telecommunication system 100 that provides IN services to a subscriber according to an exemplary embodiment of the invention. FIG. 1 depicts the interrelationship between two different telecommunication service providers 101 and 103 in delivering a call to a called party at any one of a number of telephone-stations 135 or alternative telephone-stations (ATN) 185 or 190 served by the first telecommunication service provider 103 , from a calling party's telephone-station 105 , served by a second telecommunication service provider 101 . The calling party's telephone-station 105 is coupled to a LEC 110 , operated by the second telecommunication service provider 101 , via a transmission line 107 . The LEC 110 is also coupled to a switch SW 1 120 via a transmission line 115 . The switch SW 1 120 is owned by a telecommunication service provider other than the first telecommunication service provider 103 .
The switch SW 1 120 is also coupled to a LEC 130 , operated by the first telecommunication service provider 103 , via a transmission line 125 . LEC 130 is coupled to the called party's primary telephone-station (PTN) 135 via a transmission line 137 and coupled to a POS 140 via a transmission line 139 . This primary telephone-station 135 may be any type of telephone-station, e.g., landline telephone-station, cellular telephone-station, beeper, Internet telephone, etc. When the PTN 135 is not available for completion of the telephone call, the LEC 130 re-routes incoming calls to the POS 140 via the transmission line 139 . The LEC 130 may either be operated by the first telecommunication service provider 103 or have some arrangement with the first provider 103 to perform this rerouting.
The POS 140 is operated by the first telecommunication service provider 103 . The POS 140 is coupled to an alternate LEC 180 via a transmission line 147 . The alternate LEC 180 is also either operated by the first telecommunication service provider 103 or has some agreement with the first provider 103 . The alternate LEC 180 is coupled to the called party's alternate telephone-station (ATN) 185 via a transmission line 187 and the ATN 190 via transmission line 189 . The ATNs 185 and 190 may be any type of telephone-station, e.g., landline telephone-station, cellular telephone-station, beeper, Internet telephone, etc.
The LEC 130 includes a router (not shown in FIG. 1) which is a software instrument that, under specified conditions, forwards, i.e., triggers, a call to the POS 140 . For example, an incoming call is triggered to the POS 140 if the called party has subscribed to IN services provided by the first telecommunication service provider 103 and the called party's telephone-station is busy or not answering. The router routes the incoming call to the POS 140 with a dummy exchange number or the like, e.g., 836-0000, to indicate that the call being routed to the POS 140 is subject to IN servicing.
The POS 140 is also coupled to an SCP 150 via a transmission line 145 that is an SS 7 signaling path. The SCP 150 contains a database that includes information about the IN services subscribed to by the called party. The POS 140 queries the database of the SCP 150 to determine any alternative telephone numbers for the called party based on the telephone number of the PTN 135 called for the incoming call. The database of the SCP 150 contains the PTN, i.e., the primary telephone-station number dialed by the calling party, and ATNs for the called party. Thus, for example, if the calling party is attempting to reach the called party at the PTN 135 , the POS 140 will find that the service subscriber may have ATNs 185 , 190 at which he/she may be reached.
Further, the database may also contain further information relating to the service subscriber including Internet based routing information, for example, an IP address of a URL that may be accessed using WSCP 160 . The SCP 150 is coupled to the WSCP 160 via a transmission line 157 , which is a signaling path. The WSCP 160 is also coupled to a URL 170 via a transmission line 165 , which is also a signaling path. The URL 170 contains information about additional ATN 190 , besides the ATN 185 , to which an incoming call may be routed through transmission lines 189 or 187 , respectively.
When the PTN 135 is dialed, the list of ATNs is retrieved from the SCP 150 . Each of the PTN 135 and the ATN 185 are dialed beginning with the PTN. A line is considered to be unavailable for connection if the call is not answered after a specified number of rings or the telephone station is busy. The incoming call is connected to the first available line. Subsequent to attempting call completion using the PTN 135 and ATN 185 listed in the database of the SCP 150 , any URL 170 information is retrieved from the SCP 150 . The URL information is then retrieved using the WSCP 160 and any resulting additional ATN 190 is used to attempt to complete the call. If the call cannot be completed, the call may be rerouted back to the PTN 135 to leave a voice mail or answering machine message.
The primary function of the system 100 is to support the incoming calls to the service subscriber. If a voice connection is available along the transmission line 137 , the LEC 130 will route the call to the PTN 135 on the transmission line 137 . Otherwise, the LEC 130 routes the incoming call to the POS 140 via the transmission line 139 . The POS 140 then routes the incoming call to the SCP 150 which provides instructions to the POS 140 to connect the incoming call to the service subscriber, using one of the provided ATN 185 listed in the database in the SCP 150 . Should subsequent attempts to connect the incoming call using one of the provided ATN 185 fail, the SCP 150 commands the POS 140 to disconnect the caller from the SCP 150 and connect to its Web counter-part WSCP 160 .
To accomplish this, the SCP database is populated with a database with records for service subscribers. Each record in the database must have the service subscriber's PTN as a key column, and may include a list of ATNs 185 in the order desired, such as an office number, to be used to reach the service subscriber. The database record may also include the URL that lists additional information about the service subscriber's present location.
An exemplary embodiment of the invention is preferably used in conjunction with Signaling System Number 7 (SS7) networks. In the SS7 network, a message is sent in the forward direction as part of an ISUP (ISDN user Part) call to set-up protocol. FIG. 2 illustrates the initial address message (IAM) 200 for an incoming telephone call. The IAM 200 is a mandatory message which initiates capture of an outgoing circuit and which transmits address and other information relating to the routing and handling of the incoming call.
As shown in FIG. 2, the IAM 200 contains information about the incoming call including the dialed number 210 , the dialing number 220 and a special bit 230 . The dialed number 210 is the called party's PTN or 135 in FIG. 1 . The dialing number 220 is the calling number information (CNI), also known as calling line identification (CLI). The CNI is the telephone-station number of the calling party 105 , which is sent to the called party for identification purposes. Many service providers also support Caller Name, which transmits the name of the calling party along with the originating telephone number. A special bit 230 is also included that is used in the exemplary embodiment of the invention to indicate that the re-routed incoming call is a re-routed call that has already traversed a POS 140 operated by the telecommunication service provider 103 . When the incoming call traverses the LEC 130 , the special bit 230 is set to indicate that the call is an incoming call that is being sent to a POS operated by the telecommunication service provider 103 . This set special bit 230 also indicates subsequently that the incoming call has already been routed to the POS operated by the telecommunication service provider 103 .
FIGS. 3 and 4 illustrate a method for routing an incoming telephone call in accordance with an exemplary embodiment of the invention.
The method begins in step 300 and control proceeds to step 305 for receiving a call at a LEC. In step 305 , the incoming call is received at a terminating LEC that is to connect the incoming call to the called party's PTN and control proceeds to step 310 . In step 310 , the LEC connects the incoming call to the called party's PTN and control proceeds to step 315 . In step 315 , the LEC determines whether the PTN is available for call completion. If the PTN is available for completion of the incoming call, control proceeds to step 320 in which the LEC completes the incoming call with the PTN and control proceeds to step 415 in FIG. 4, where the method ends. The operation of completing a call is the act of receiving an answer at the telephone-station, thereby eliminating the need for re-routing.
Otherwise, control proceeds to step 325 in which the LEC disconnects the incoming call from the PTN, parks the incoming call and sets the special bit 230 in the IAM to indicate that the call is subject to call forwarding. Control then proceeds to step 330 in which the LEC reroutes the incoming call to the POS with a fictitious number using an exchange code of a desired POS (Local Routing Number (LRN)).
This routing to the POS is performed by the terminating LEC forwarding the incoming call using a virtual telephone-station number with an exchange code of the desired POS (Local Routing Number (LRN)), e.g., 836, followed by a series of dummy characters, e.g., 0000. Thus, the LEC routes the incoming call to the POS using the virtual telephone number, e.g., 836-0000.
Control then proceeds to step 335 . In step 335 , the POS determines whether the IAM relates to an incoming call that has been rerouted from the LEC by analyzing the forwarding number, e.g., 836-6400, used by the LEC to route the incoming call to the POS. If the forwarding number indicates a rerouted incoming call, control proceeds to step 340 . Otherwise control proceeds to step 345 in which non-rerouted calls are processed in a conventional manner and to step 415 in FIG. 4 in which the method ends.
In step 340 , the POS then queries the SCP using the PTN information stored in the called party's information 210 of the IAM 200 as the key and control proceeds to step 350 (of FIG. 4 ). In step 350 , the SCP looks up the alternative routing information in the SCP database and control proceeds to step 355 . For example, the information within the database indicates any services to which the subscriber has subscribed and any ATNs to which incoming calls may be routed, listed in order of priority. In step 355 , the incoming call is connected in accordance with the highest priority ATN information stored in the SCP and control proceeds to step 360 . For example, in step 355 , the incoming call may be connected through a LEC to an ATN.
In step 360 , it is determined whether the call can be completed in accordance with the highest priority ATN, e.g., based on the availability of the first alternate telephone-station. If the first ATN is available, control proceeds to step 365 where the call is completed at the first ATN and control proceeds to step 415 where the method ends. Otherwise, control proceeds to step 370 where the incoming call is disconnected from the first ATN and the incoming call is parked. Control then proceeds to step 375 .
Step 375 determines whether additional ATNs are listed in the SCP database and may be used to forward the incoming call. If additional ATNs are available, control proceeds to step 330 in FIG. 3 for routing based on the remaining ATN information. Steps 330 - 375 are performed for the ATNs listed in the SCP database in order of priority. If during the call-forwarding of steps 330 - 375 , the incoming call is completed, control proceeds to step 415 where the method ends.
Otherwise, control proceeds to step 380 in which it is determined whether a URL field in the database identifies a URL that contains information about the present location of the subscriber, such as further alternative telephone numbers. If the field fails to indicate a URL, control proceeds to step 410 where the incoming call is routed to the PTN so that the calling party may leave an answering machine message or voice-mail, if those are options or services offered by the called party. Control then proceeds to step 415 where the method ends.
If the field indicates a URL, control proceeds to step 385 , in which the ATN information at the URL are returned for use in call-forwarding. Control then proceeds to step 390 . In step 390 , the incoming call is routed to a LEC and connected to the highest priority ATN based on the information at the URL, e.g., information about the subscriber's present location. Control then proceeds to step 395 in which it is determined whether the highest priority ATN is available. If the ATN is available, control proceeds to step 400 where the call is completed at the ATN and control proceeds to step 415 where the method ends. Otherwise, control proceeds to step 405 where the incoming call is disconnected from the ATN and the incoming call is parked. Control then proceeds to step 410 where the POS routes the incoming call to the PTN so that the calling party may leave an answering machine message or voice-mail, if those are options or services offered by the called party. Control then proceeds to step 415 where the method ends.
FIG. 5 shows a telecommunication system 500 that provides IN services to a subscriber according to another exemplary embodiment of the invention. Unlike FIG. 1, FIG. 5 actually depicts the telecommunication system structure operated by a single telecommunication service provider 503 . Thus, in FIG. 5, an incoming call is delivered from a calling party's telephone-station 505 to a called party served by the same telecommunication service provider 503 . The calling party's telephone-station 505 is coupled to a LEC 510 via a transmission line 507 .
The LEC 510 is also coupled to a POS 540 via a transmission line 517 . The POS 540 is also coupled to a LEC 530 via a transmission line 527 and a LEC 580 via a transmission line 577 . Each of LEC 530 and LEC 580 is either operated by the telecommunication service provider 503 or has some agreement with the service provider 503 to perform rerouting for IN services. LEC 530 is coupled to the called party's telephone-station 535 via a transmission line 537 . LEC 580 is coupled to the called party's ATN 585 via a transmission line 587 . These telephone-stations 535 and 585 may be any type of telephone-station, e.g., landline telephone-station, cellular telephone-station, beeper, Internet telephone, etc.
The POS 540 is operated by the telecommunication service provider 503 that provides services to which the incoming call is directed. The POS 540 is coupled to an SCP 550 via a transmission line 547 . The SCP 550 is also coupled to a WSCP 560 via a transmission line 557 . The WSCP 560 is also coupled to a URL 570 via a transmission line 567 . The URL 570 contains information about additional ATNs 590 , besides the telephone-station 585 , to which an incoming call may be routed through transmission lines 589 .
IN services are provided to a subscriber in the architecture illustrated in FIG. 5 in a method very similar to how IN services are provided in the architecture of FIG. 1 . However, one significant difference is that the LEC 530 does not set the special bit 230 in the IAM of FIG. 2 . This is because the incoming call has already traversed the POS 540 before the incoming call reaches the LEC 530 . Therefore, before the LEC 510 routes the incoming call through the POS 540 , the LEC 510 sets the special bit 230 in the IAM 200 to indicate that the incoming call has been routed through the POS 540 and the POS 540 in turn routes the incoming call to the terminating LEC 530 of the PTN 535 . The remaining methodology for forwarding the incoming call using the system 500 is similar to that illustrated in FIG. 1 and described in conjunction with FIGS. 3 and 4.
While the present invention has been described with reference to specific embodiments, it is not confined to the specific details set forth but is intended to cover such modifications or changes as may come within the scope of this invention.
While this invention has been described in conjunction with the specific embodiments outlined above, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art. Accordingly, the preferred embodiments of the invention, as set forth above, are intended to be illustrative, not limiting. Various changes may be made without departing from the spirit and scope of the invention.
For example, the relationship between the alternative telephone-station 185 and the POS 140 may be altered. Specifically, it is foreseeable that the ATNs 185 or 190 may be coupled to the first LEC 130 rather than the second LEC 180 .
Additionally, the SCP or URL may include IP address information for the subscriber so that an electronic mail message may be left at the address indicating information about the call that was not completed. Such information may include an electronic message from the called party.
Also, Page: 15 although the operation of the present invention has been explained using the application of providing Caller-ID delivery, it is foreseeable that other triggers besides termination attempt trigger (TAT) may be used to cause re-routing, for example, when providing call-forwarding on receipt of a busy signal.
Accordingly, the exemplary embodiments set forth herein are intended to be illustrative, not limiting. Various alterations may be made without departing from the spirit and scope of the invention. | A system and method performs rerouting of an incoming call to a telecommunication services subscriber to provide intelligent network services based on proprietary data about the subscriber's services. This proprietary data is within the control of the telecommunication service provider's equipment. Rerouting is performed without providing access to the proprietary data by other telecommunication service providers. Using such a system and method the subscriber's telecommunication provider can effectively provide intelligent network services without risking dissemination of that proprietary data. | 8 |
This application is a divisional of Ser. No. 07/527,740 filed May, 23, 1990 now U.S. Pat. No. 5,051,520.
BACKGROUND OF THE INVENTION
The present invention relates to a new class of stiff, fluorinated, polycyclic xanthene monomers and polymers prepared therefrom.
The ever more stringent performance requirements of the electronic packaging industry mandate the development of polymers with lower dielectric constant and lower moisture absorption. Improvement in these properties has in the past been effected by the introduction of fluorine into the polymer. Unfortunately, this was always accompanied by deterioration of other properties, such as lowering of the glass transition temperature, increasing the coefficient of thermal expansion and increasing solvent sensitivity.
SUMMARY OF THE INVENTION
Accordingly, the present invention relates to a new class of stiff, fluorinated monomers, based on two novel tricyclic xanthene core systems, 9,9-bis(perfluoroalkyl)xanthene (I) and 9-phenyl-9-perfluoroalkylxanthene (II) ##STR1## The monomers have utility in the preparation of advanced high-performance polymers, particularly polyimides. The rigid core decreases the coefficient of thermal expansion of the polymers while the fluorine substituents improve the dielectric constant and water absorption properties.
The novel invention compositions contain both a --CR f R' f -- or --C(phenyl)R f -- bridge and a --O-- bridge.
According to the present invention there is provided a composition of matter, and the preparation thereof, of the formula ##STR2## wherein R is selected from the group consisting of phenyl, substituted phenyl and perfluoroalkyl of 1 to 16 carbon atoms and Rf is perfluoroalkyl of 1 to 16 carbon atoms.
In a further embodiment of the invention there is provided a composition of matter, and the preparation thereof, of the formula ##STR3## wherein R is selected from the group consisting of phenyl, substituted phenyI and perfluoroalkyI of 1 to 16 carbon atoms, 16 carbon atoms: R f is perfluoroalkyl of 1 to 16 carbon atoms; X is selected from the group consisting of H, CH 3 , CO 2 H, COCl, NH 2 and NCO; Y is the same as X; and X and Y together are --CO--O--CO--. Another embodiment of the invention comprises a novel composition of the formula ##STR4##
The invention further relates to a polyimide polymer having the following recurring structural unit ##STR5## wherein R is selected from the group consisting of phenyl, substituted phenyl and perfluoroalkyl of 1 to 16 carbon atoms; R f is perfluoralkyl of 1 to 16 carbon atoms; A is a divalent radical containing at least two carbon atoms, the two amino groups of said diamine each being attached to separate carbon atoms of said divalent radical; and n is a positive integer.
In the above definitions of R and R f as perfluoroalkyl, a more preferred number of carbon atoms is I to 18.
DETAILED DESCRIPTION OF THE INVENTION
The core ring systems (I) of the compositions of the invention can be prepared by using either a singlebridging or a double-bridging process. Scheme I depicts the preparation of 9,9-bis(trifluoromethyl)-2,3,6,7-tetramethylxanthene (III) using both processes.
In the double-bridging process both the ether bridge and the --C(CF 3 ) 2 -bridge are introduced in a single step. This involves reaction of hexafluoroacetone (HFA) with two molar equivalents of 3,4dimethylphenol to form the bridging --C(CF 3 ) 2 - linkage concurrent with intramolecular dehydration of the two hydroxyl groups ortho to the -C(CF3)2- bridge to form the xanthene ether link of (III). The reaction is run in hydrofluoric acid (HF) at temperatures ranging from 180° to 220° C. using a molar ratio of HF/HFA of 10 or more.
Other substrates such as resorcinol and 3-aminophenol may be used in the simultaneous HFA bridging and cyclodehydration process. Reaction of resorcinol with two molar equivalents of HFA at 220° C. (Scheme II) provided 9,9-bis(trifluoromethyl)-3,6-dihydroxy xanthene (VII).
Reaction of (VII) with two equivalents of p-nitrochlorobenzene in dimethylacetamide solvent in the presence of potassium carbonate followed by hydrogenation of the dinitro precursor, provided 9,9-bis-(trifluoromethyl)-3,6-bis(4-aminophenoxy)xanthene (VIII), a new diamine monomer for use in polymer synthesis. A polyester (IX) derived from reaction of (VII) with a mixture of isophthaloyl and terephthaloyl chIorides was also found to have utility as a high flux membrane film for O 2 /N 2 separation.
The parent monomer, 9,9-bis(trifluoromethyl)xanthene (I, R f =R' f =CF 3 ) was prepared by reaction of (VlI) with sodium hydride and 5-chloro-1-phenyl-lH-tetrazole to form 9,9-bis(trifluoromethyl)-3,6-bis(1- phenyl-1H-tetrazolyl-5-oxy)xanthene which was catalytically reduced to (I) (Scheme IV). ##STR6##
In the single-bridging process for preparing the core ring systems (Scheme I), the ether linkage is first preformed separately followed by formation of the --C(CF 3 ) 2 -- bridge. Thus, (III) was prepared by reacting HFA in HF with 3,3'-di-o-xylyl ether (DXE), which already contained the xanthese ether linkage, at temperatures ranging from 110° to 140° C. and an HF/DXE ratio of 8-20, perferably 10-15.
The single-bridging process is preferred to the double-bridging process for preparing the core ring systems (I), since it requires lower reaction temperatures, gives higher yeilds despite being a two-step process, and generates fewer by-products.
Other aromatic ethers terminated by 3,4- dimethylphenoxy gropus can also be used in the single-bridging process. For example, p-tolylether (Scheme III, X) reacts with HFA in HF to provide 9,9- bis-(trifluoromethyl)-2,7- mimethylxanthene (XI). ##STR7##
Once produced, (III) (Scheme I) was readily oxidized to 9,9-bis(trifluoromethyl)-2,3,67- xanthenetetracarboxylic aicd (IV), dehydrated to 9,9-bis(trifluoromethyl)xanthene tetracarboxylic dianhydride (V) and subsequently polymerized with 4,4'-diaminodiphenylether to form polyimide (VI) (V-ODA). Analogous polyimides were obtained using 3,4'-diaminodiphenylether, (I)-ODA and paraphenylenediamine. Oxidation of (III) to the tetraacid (IV) was performed using potassium permanganate in aqueous pyridine. Other methods, such as Mn/Co catalyzed oxidation with oxygen or air, or oxidation with nitric acid can also be used.
Conversion of (IV) to the dianhydride (V) can be effected thermally, by boiling in acetic anhydride, or by heating a slurry of (IV) in chloroform with excess thionyl chloride. Thermal conversion by heating at 20° C overnight is preferred. The polyimide (VI) was prepared by reacting the dianhydride (V) with a substantially equimolar amount of 4,4'-diaminodiphenylether in dimethylacetamide to form a polyamide acid and then thermally converting the polyamide acid to the polyimide.
In similar fashion (XI) (Scheme III) was oxidized with permanganate to 9,9-bis(trifluoromethyl)xanthene2,7-dicarboxylic acid (XII) and then reacted with thionyl chloride to provide 9,9-bis(trifluoromethyl)-xanthene-2,7-dicarbonyl chloride (XIII). The diacid chloride was subsequently reacted with sodium azide by the Curtius Reaction to provide 9,9-bis(trifluoromethyl)xanthene-2,7-diisocyanate (XIV) which was hydrolyzed to 9,9-bis(trifluoromethyl)xanthene-2,7-diamine (XV). ##STR8##
The core ring system (II) was prepared in similar fashion using the single-bridging process and RCOR f insteand of HFA to provide analogous compounds containing a --CRR f -- bridge instead of a --C(CF 3 ) 2 -- bridge. Compounds of the structure RCOR f include those wherein R is phenyl or substituted phenyl and R f is CF 3 , C 2 F 5 , C 3 F 7 and C 8 F 17 .
For example, the reaction of 3,3'-di-o-xylyl ether (DXE) with trifluoroacetylbenzene (R=phenyl, R f =CF 3 ) in HF at 140° C. provided 9-phenyl-9-trifluoromethyl-2,3,6,7-tetramethylxanthene (XVI) (Scheme V). Oxidation of (XVI) with potassium permanganate gave 9-phenyl-9-(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic acid (XVII) which was thermally converted to 9-phenyl-9-trifluoromethyl)xanthene- 2,3,6,7-tetracarboxylic dianhydride (XVIII) by heating under vacuum at 250° C.
The parent monomer (II, R f =CF 3 ) was prepared (Scheme VI) using the single-bridging process by reaction of p-tolyl ether (X) and trifluoromethylphenyl ketone in HF at 130° C. to provide 9-phenyl-9-trifluoromethyl-2,7-dimethylxanthene (XIX), followed by oxidation to the dicarboxylic acid (XX) and catalytic decarboxylation to (II). The diacid (XX) could also be converted to the diacyl chloride (XXI), then to the diacyl azide and, finally, to the diisocyanate (XXII) as previously described.
Polyimides encompassed by the present invention include those having the recurring structural unit ##STR9## wherein R is selected from the group consisting of phenyl, subtituted phenyl and perfluoroalkyl of 1 to 16 carbon atoms; R f is perfluoroalkyl of 1 to 16 carbon atoms (and more preferably 1 to 8 carbon atoms); A is a divalent radical containing at least two carbon atoms, the two amino groups of said diamine each being attached to separate carbon atoms of said divalent radical and n is a positive integer.
The polyimides display outstanding physical properties making them useful as shaped structures such as self-supporting films, fibers and filaments. The structures are characterized by high tensile properties, desirable electrical properties, stability to heat and water and very low coefficient of thermal expansion. The polyimides are generally prepared by reacting dianhydrides (V) or (XVIII) with an aromatic diamine in an inert organic solvent to form a polyamide acid solution and subsquently converting the polyamide-acid to polyimide essentially as described in U.S. Pat. No. 3,179,614; U.S. Pat. No. 3,179,630 and U.S. Pat. No. 3,179,634, the disclosures of which are incorporated herein by reference.
If desired, dianhydrides (V) or (XVIII) can also be blended with from 15 to 85 mole % of other dianhydrides, such as pyromellitic dianhydride; 2,3,6,7-naphthalene tetracarboxylic dianhydride; 3,3',4,4'-biphenyl tetracarboxylic dianhydride; 1,2,5,6-naphthalene tetracarboxylic dianhydride; 2,2',3,3'-biphenyl tetracarboxylic dianhydride; 3,3',4,4'-benzophenone tetracarboxylic dianhydride; 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride; bis(3,4-dicarboxyphenyl) sulfone dianhydride; 3,4,9,10-perylene tetracarboxylic dianhydride; bis(3,4-dicarboxyphenyl) propane dianhydride; 1,1-bis-(2,3-dicarboxyphenyl) ethane dianhydride; 1,1-bis-(3,4-dicarboxyphenyl) ethane dianhydride; bis-(2,3-dicarboxyphenyl) methane dianhydride; bis-(3,4-dicarboxyphenyl) methane dianhydride; oxydiphthalic dianhydride; bis (3,4-dicarboxyphenyl) sulfone dianhydride; and the like.
Suitable diamines for use in the polyimide compositions of the invention include:
meta-phenylenediamine;
paraphenylene diamine;
4,4'-diamino-diphenyl propane;
4,4'-diamino-diphenyl methane;
benzidine;
4,4'-diamino-diphenyl sulfide;
4,4'-diamino-diphenyl sulfone;
3,3'-diamino-diphenyl sulfone;
4,4'-diamino-diphenyl ether;
2,6-diamino-pyridine;
bis-(4-amino-phenyl)diethyl silane;
bis-(4-amino-phenyl)phosphine oxide;
bis-(4-amino-phenyl)-N-methylamine;
1,5-diamino-naphthalene;
3,3'-dimethyl-4,4'-diamino-biphenyl;
3,3'-dimethoxy benzidine;
2,4-bis(beta-amino-t-butyl)toluene;
bis-(para-beta-amino-t-butyl-phenyl)ether;
para-bis(2-methyl-4-amino-pentyl)benzene;
para-bis-(1,1-dimethyl-5-amino-pentyl)benzene;
m-xylylene diamine;
p-xylylene diamine;
bis(para-amino-cyclohexyl)methane;
hexamethylene diamine;
heptamethylene diamine;
octamethylene diamine;
nonamethylene diamine;
decamethylene diamine;
3-methylheptamethylene diamine;
4,4-dimethylheptamethylene diamine;
2,11-diamino-dodecane;
1,2-bis-(3-amino-propoxy)ethane;
2,2-dimethyl propylene diamine;
3-methoxy-hexamethylene diamine;
2,5-dimethylhexamethylene diamine;
2,5-dimethylheptamethylene diamine;
5-methylnonamethylene diamine;
1,4-diamino-cyclohexane;
1,12-diamino octadecane;
H 2 N(CH 2 ) 3 O(CH 2 ) 3 NH 2 ;
H 2 N(CH 2 ) 3 S(CH 2 ) 3 NH 2 ;
H 2 N(CH 2 ) 3 N(CH 3 )(CH 2 ) 3 NH 2 ;
and mixtures thereof.
Useful solvents include normally liquid N,N-dialkylcarboxylamides, generally. Preferred solvents include the lower molecular weight members of such carboxylamides, particularly N,N-dimethylformamide and N,N-dimethylacetamide. Other useful compounds of this class of solvents are N,N-diethylformamide and N,N-diethylacetamide. Other solvents which may be used are dimethylsulfoxide, N-methyl-2-pyrrolidone, tetramethyl urea, dimethylsulfone, hexamethylphosphoramide, tetramethylene sulfone, and the like. The solvents can be used alone, in combinations with one another or in combinations with poor solvents such as benzene, benzonitrile, dioxane, etc. The amount of solvent used preferably ranges from 75 to 90 weight % of the polyamic acid, since this concentration has been found to give optimum molecular weight.
Conversion of the polyamic acid to polyimide can be accomplished by either a thermal conversion or a chemical conversion process. According to the thermal conversion process, the polyamic acid solution is cast on a heated conversion surface, such as a metal drum or belt, and heated at a temperature of above about 50° C. to partially convert the polyamic acid to polyimide. The extent of polyamic acid conversion depends on the temperature employed and the time of exposure, but, generally about 25 to 95% of amic acid groups are converted to imide groups. The partially converted polyamic acid is then heated at or above 220° C. to obtain complete conversion to the polyimide.
In the chemical conversion process, the polyamic acid solution is first chilled to about 10° C. to -10° C. and polyamic acid conversion chemicals are added. The polyamic acid conversion chemicals are tertiary amine catalysts and anhydride dehydrating materials. The preferred anhydride dehydrating material is acetic anhydride and is used in slight molar excess of the amount of amic acid groups in the polyamic acid, typically about 2-2.5 moles per equivalent of polyamic acid. A comparable amount of tertiary amine catalyst is used. Besides acetic anhydride, other operable lower fatty acid anhydrides include propionic, butyric, valeric, mixed anhydrides of these with one another and with anhydrides of aromatic monocarboxylic acids, for example, benzoic acid, naphthoic acid, and the like, and with anhydrides of carbonic and formic acids, as well as aliphatic ketenes (ketene and dimethyl ketene). Ketenes may be regarded as anhydrides of carboxylic acids 5 derived from drastic dehydration of the acids.
The preferred tertiary amine catalysts are pyridine and beta-picoline and they are used in an amount of about one mole per mole of anhydride dehydrating material. Tertiary amines having approximately the same activity as the preferred pyridine and beta-picoline may also be used. These include 3,4-lutidine; 3,5-lutidine; 4-methylpyridine; 4-isopropyl pyridine; N-dimethylbenzylamine; isoquinoline; 4-benzylpyridine, and N-dimethyldodecylamine. Trimethylamine and triethyl amine are more active than those amines listed above and can be used in smaller amounts.
The polyamic acid conversion chemicals react at about room temperature or above to convert polyamic acid to polyimide. The chemical conversion reaction occurs at temperatures from 10° to 120° C., with the reaction being very rapid at the higher temperatures and very slow at the lower temperatures. Below a certain temperature, polyamic acid chemical conversion comes to a practical halt. This temperature is generally about 10° C. It is important, therefore, that the polyamic acid solution be chilled below this temperature before adding the polyamic acid conversion chemicals and that the temperature of the solution, with conversion chemicals, be maintained below this temperature during extrusion or casting.
The treated, chilled, polyamic acid solution is cast or extruded onto a heated conversion surface whereupon some of the solvent is evaporated from the solution, the polyamic acid is partially chemically converted to polyimide, and the solution takes the form of a polyamic acid-polyimide gel. Conversion of amic acid groups to imide groups depends on contact time and temperature but is usually about 25 to 95% complete.
The gel is subsequently dried to remove the water, residual solvent, and remaining conversion chemicals, and the polyamic acid is completely converted to polyimide. The drying can be conducted at relatively mild conditions without complete conversion of polyamic acid to polyimide at that time, or the drying and conversion can be conducted at the same time using higher temperatures. Preferably, high temperatures are used for short times to dry the film and convert it to polyimide in the same step. It is preferred to heat the film to a temperature of 200°-450° C. for 15 to 400 seconds.
The xanthene core monomers (I) and (II) are particularly useful for the preparation of polyimide polymers. The diacid chlorides, diacids, diisocyanates and diamine monomers of the present invention can also be used to prepare polyamides, polyesters, polycarbonates and polyurethanes by techniques which are well-known in the art.
The advantageous properties of this invention can be observed by reference to the following examples which illustrate, but do not limit, the invention. All parts and percentages are by weight unless otherwise indicated.
All reagents used were commercial materials, unless otherwise indicated. IR spectra were measured as Nujol mulls, or as polyimide films, on a Perkin-Elmer Grating IR Spectrophotometer Model 457. NMR spectra were determined on the GE QE-300 instrument, using deuterochloroform as solvent and tetramethylsilane as internal standard.
Aromatic Ether Precursors
All aryl ethers were prepared by the reaction of the appropriate potassium aryloxide with a mono- or dibromoaryl precursor, using NMP as solvent. The method is illustrated by the preparation of 3,3'-di-o-xylyl ether (DXE).
3.3'-di-o-xylyl Ether (DXE)
In a 3-L four-neck flask was placed 1.2L toluene, 500 g (4.1 mole) of 3,4-dimethylphenol, and 227 g (4.1 mole) KOH pellets. The mixture was stirred with an efficient mechanical stirrer and refluxed, water being removed via a Dean-Stark trap. When all the water was removed, at which point the potassium phenolate salt started to crystallize out, about 500 ml toluene was distilled out (leaving enough toluene, so that the slurry was still stirrable). About 500 ml N-methylpyrrolidone (NMP) was added, along with 750 g (4.1 mole) -bromo-o-xylene, and 100 g copper powder. The reaction mixture was heated again, and remaining toluene was distilled out through a tall Vigreux column. When all the toluene had been distiIled out, and the temperature in the flask reached about 200° C., the distillation column was replaced with a condenser, and the vigorously stirred mixture was refluxed overnight. The mixture was filtered through a bed of Celite, and the flask was rinsed with some DMF, which was used to wash the filter cake. The filtrate was concentrated at atmospheric pressure, until DMF and most of the NMP was distilled out, then distillation was continued at reduced pressure, collecting the product boiling at 140°-145° C./ 1.4-1.7 Torr. The still warm fraction was poured into 500 ml stirred methanol; this resulted in precipitation of a crystalline product, which was filtered off and washed with methanol. A second crop was obtained from the filtrate for a total yield in the 360-420 g (55-65%) range, taking into consideration that the starting -bromo-o-xylene was only 70% pure. NMR of the title material: d 7.03, d 6.80, dd 6.73, s 2.19 in the correct 1:1:1:6 ratio; the two non-identical methyl groups show up as a singlet. From the filtrates one could distill a fraction boiling where the main product boiled. This oil could not be crystallized, and by NMR consisted of an approximately 50/50 mixture of DXE and the mixed ether arising from the isomeric 3-bromo-oxylene, which comprised almost 30% of the starting material.
Di-p-tolyl Ether (X)
Obtained in 56% yield; NMR: d 7.10, d 6.87, s 2.30 ppm in 2:2:3 ratio.
EXAMPLE 1
9,9-Bis(trifluoromethyl)xanthene (I, R f =R' f =CF 3 )
A. 9,9-bis(trifluoromethyl)-3,6-bis(1-phenyl1H-tetrazolyl-5-oxy)xanthene
In 250 ml of dry diglyme was stirred at room temperature 5 g of 50% sodium hydride in mineral oil, plus 17.5 g (0.05 mole) 9,9-bis(trifluoromethyl)-3,6dihydroxyxanthene (VII). The hydrogen evolved was measured by a wet-test meter. When hydrogen evolution stopped, 18.1 g (0.1 mole) of 5-chlorophenyl-lHtetrazole was added in one portion, and the mixture was stirred and gently heated until the second evolution of hydrogen stopped. The flask contents were drowned with stirring in 2.5L ice water. A solid separated, which was filtered off, dissolved in methylene chloride, and filtered through a bed of alumina. The filtrate was stripped to dryness, and the residue was stirred with methanol, and was filtered. There was obtained a total of 27.1 g (86%) of a solid with a sharp IR spectrum, which contained no OH or CO peaks. The NMR spectrum was consistent with the assigned structure: d 7.97, dd 7.78, m 7.6, d 7.45, dd 7.34 in 1:2:3:1:1: ratio, assigned to the 1H, phenyl ortho H's, phenyl m and p H's, 4H, and 2H, respectively.
B. 9,9-bis(trifluoromethyl)xanthene (I)
A mixture of 25 g 9,9-bis(trifluoromethyl)-3,6-bis-(1-phenyl-1H-tetrazolyl-5-oxy)xanthene and 6 g of 5% palladium on carbon in 250 ml THF was heated in a shaker tube at 400 psi of hydrogen for 16 hrs at 100° . The pressure dropped by 42 psi which occurred within the first 9 hrs, and did not change thereafter. The reaction mixture was filtered, and the residue was fractionally distilled. The product distilled at 105°/1.2 Torr and was obtained in 5.0 g (39%) yield. It was recrystallized from methanol and purified further by vacuum sublimation. M.p. 74°-75° C. NMR: dd 7.88; td 7.44 plus overlapping td and dd 7.3-7.4 in 1:1:1:1 ratio; C 13 NMR: m 52.5 (bridgehead C), 110.0 (C next to the bridge), 117.6 (4C), 123.3 (2C), quartet (J =287 Hz) 124.3 (CF 3 ), 130.2 (lC), 131.5 (3C) and 151.0 (C next to 0) ppm, in agreement with the assigned structure. The mass spectrum of (I) showed the molecular formula to be C 15 H 8 F 6 O, and had a parent peak at 318, plus prominent peaks at 249 (parent minus CF 3 ), 199 (parent minus C 2 H 5 ), 100 (C 2 F 4 ) and 69 (CF 3 ). Elemental analysis: Calc. for C 15 H 8 F 6 O: C 56.5; H 2.52; Found: C 56.6; H 2.91.
EXAMPLE 2
9-Phenyl-9-trifluoromethylxanthene (II, R f =CF 3 )
A 6 g sample of 9-phenyl-9-trifluOrOmethylxanthene2,7-dicarboxylic acid (XX) was stirred and refluxed in ml quinoline along with 11 g of copper powder, the emanating gas being measured by a wet-test meter. The theoretical amount of CO 2 was evolved in two hours. The reaction mixture was cooled, filtered through a bed of Celite into 800 ml of water, acidified with 100 ml of concentrated hydrochloric acid, and left standing overnight. The supernantant liquid was decanted, and the residue was taken up in methylene chloride, and filtered through a bed of alumina. The solvent was stripped, the residue was stirred with methanol, and was filtered, yielding 3.1 g (66%) of a white solid. It was recrystallized from methanol; m.p. 89°-90°. The IR spectrum was sharp with no OH or CO bands. The NMR spectrum was confirmatory, with the following peaks: d 7.42; m 7.3-7.4; d 7.19, td 6.96, d 6.87 in 2:5:2:2:2 ratio. The compound was analyzed by mass spectrometry which showed the parent ion at 326, along with other Peaks, the strongest being at 257 (parent minus trifluoromethyl), and also at 249 (parent minus phenyl), and 199 (parent minus phenyl and minus difluorocarbene). The mass spectrum confirmed the molecular formula as C 20 H 13 F 3 O.
EXAMPLE 3
9,9-Bis(trifluoromethyl)-2,3,6,7-tetramethylxanthene (III)
Double Bridging Process
A mixture of 330 g (2.7 moles) 3,4-dime:hylphenol, 225 g (1.35 moles) HFA and 300 g (15 moles) HF was shaken in an autoclave for 15 hrs at 220°. The reaction mixture was poured into a one-gallon polyethylene jar, half-filled with ice-water and containing excess sodium hydroxide. The product was extracted with methylene chloride, the extracts were filtered through alumina, and stripped. Distillation of the residue in vacuo gave several fractions. The fraction, boiling at 190°-210°/1 Torr was chromatographed on alumina, packing and eluting with methylene chloride. The orange band was collected, and the fraction was stripped. Stirring of the residue with excess methanol, filtration, washing of the solid with more methanol, and air-drying gave 86 g (17%) of (III) which melts at 214°-215°, and sublimes readily in vacuo at 180° /1 Torr; it can be recrystallized from toluene or heptane, but is sparingly soluble in methanol. Analysis: Calc. for C 19 H 16 F 6 O: C, 61.0; H, 4.28; F, 30.5; Found: C, 61.3, H, 4.40; F, 30.7% NMR: s 7.57, s, 6.95, s, 2.26 ppm in 1:1:6 ratio
Single-Bridging Process
A mixture of 200 g (0.88 mole) DXE, 150 g (0 88 mole) HFA, and 236 g (11.8 moles) HF was heated at 120° for 8 hrs in a shaker tube. After venting excess HF, the tube contents were drowned in a one-gallon polyethylene jar containing 2L ice-water, and 500 ml of 50% NaOH. The shaker tube was rinsed out with methylene chloride, and the washings were added to the jar. Most of the aqueous layer was decanted, and the product was 5 extracted wth 3-4L of methylene chloride. The slurry was filtered once through a bed of Celite to remove a pasty sludge and the layers were separated. The organic layer was filtered through a layer of alumina, and then stripped to dryness. The reddish crystalline residue 30 was dissolved in 150-200 ml of boiling toluene, partially cooled and diluted with 500 ml methanol, which resulted in rapid crystallization. The solid was filtered, washed with methanol until the washings were no longer red, and was air-dried, yielding 95-105 g (29-32%) of pale creamy solid. The filtrates were stripped to dryness, and the residue was distilled over a short-path column. Pale orange material boiling at 200-210°/1 Torr was collected, dissolved in minimum quantity of boiling toluene and diluted with methanol, yielding another 15-20 g of product, for a total yield in the 33-41% range.
EXAMPLE 4
9.9-Bis(trifluoromethyl)-2,3,6,7-xanthene-tetracarbosylic acid (IV)
9,9-Bis(trifluoromethyl-2,3,6,7-tetramethylxanthene (III) (20 g, 0.053 mole) was reluxed in a mixture of 40 ml pyridine and 200 ml water with rapid mechanical stirring, and 50 g (0.316 mole) potassium permanganate was added in portions through the top of the condenser. After addition was complete, the slurry was refluxed for hr. The mixture was filtered hot through Celite, and concentrated down to about 50 ml. A mixture of 35 g NaOH and 535 ml water was added, and the oxidation was repeated, using 45 g (0.28 mole) KMnO 4 . After the second oxidation, excess permanganate was destroyed with isopropyl alcohol. The mixture was filtered through Celite, and the filtrate was acidified with sulfuric acid. This produced a white precipitate, which was filtered, and washed thoroughly with water. The tetraacid (IV) was dried in a convection oven overnight at 150° and was obtained in 16 g yield (61%). It was used for conversion to the anhydride, without further purification.
EXAMPLE 5
9,9-Bis(trifluoromethyl)- 2,3,6,7-xanthenetetracarboxylic Dianhydride (V)
9,9- Bis(trifluoromethyl)-2,3,6,7-xanthenetetracarboxylic acid (IV) was converted to dianhydride (V) by drying overnight in a convection oven at 220°. Even during drying at 150°-180° some conversion to the anhydride took place. The dehydration could be followed by means of changes in the carbonyl region from those of tetraacid (IV) (descending pattern at 1860, 1780, 1740 and 1710 cm -1 ) to those of dianhydride (V) (1860, 1775 vs). Both, TGA and DSC data for (IV) indicate dehydration occurring around 240°, and the second event (melting/sublimation of (V)) taking place around 355°-360°.
Tetraacid (IV) could also be dehydrated by acetic anhydride; refluxing with excess acetic anhydride for one hour usually sufficed to dehydrate (IV). Dianhydride (V) was essentially insoluble in acetic anhydride, and could be isolated by simple filtration and drying of the slurry.
Another method, used for dehydrating tetraacid (IV) involved refluxing a slurry of (IV) in chloroform with excess thionyl chloride for two hours. Again, since dianhydride (V) was essentially insoluble in chloroform, simple filtration and washing with chloroform yielded the product.
Purification of dianhydride (V) could not be achieved by recrystallization since it has very low solubility in acetic acid/acetic anhydride mixtures. It could, however, be sublimed at 250° /1 Torr. This was done conveniently in small sublimer tubes, where fairly large crystals with a slight yellowish cast could be grown. Pure dianhydride (V) melts in a capillary at 355-356°. IR (Nujol mull): 1860, 17775 (vs) cm -1 . It was too insoluble for determining its NMR spectrum. Analysis: Calc. for C 19 H 4 F 6 O 7 : C, 49.8; H, 0.87; F,
24.9; Found: C, 50.1; H. 1.11; F, 24.9%.
EXAMPLE 6
Polyimide films derived from 9.9-bis(trifluoromethyl)xanthene tetracarboxylic dianhydride (V)
In a flame-dried and nitrogen-flushed 500 ml roundbottom flask was placed 5.00 g (0.025 mole) of 4,4'-diaminodiphenylether (ODA) which was dissolved in 200 ml dry NMP. To the stirred solution was added in portions 1.45 g (0 025 mole) of 9,9-bis(trifluoromethyl)xanthenetetracarboxylic dianhydride (V). Most of the I0 dianhydride (V) dissolved within one hour, but the rest only upon stirring overnight. Dianhydride (V) was doubly sublimed, but still not very pure, as it contained sublimation residue particles which adhered to the sublimate electrostatically. The 8% by weight solution of polyamic acid was converted into a film by [either casting or spin coating, and cured at 350°-400° C. in air. The (V)-ODA film was very thin, but did have a sharp IR, and was characterized by imide peaks at 1785 and 1730 (vs) cm - 1.
More concentrated solutions, up to 27% solids, were prepared as above, and produced thicker (V)-ODA films with the properties listed in Table I.
In similar fashion, polyimide films were prepared from 9,9-bis(trifluoromethyl)xanthenetetracarboxylic ianhydride (V) and paraphenylenediamine (PPD), 3,4-diaminodiphenyl ether (3,4'-ODA), resorcinol oxydianiline (RODA) and (I)-ODA. Physical properties of the films are given in Table I.
TABLE I__________________________________________________________________________PHYSICAL PROPERTIES OF POLYIMIDE FILMS FROM9,9-BIS (TRIFLUOROMETHYL) XANTHENE TETRACARBOXYLIC DIANHYDRIDE (V) Spin or Final Temp. Cure Time Thickness* Tensile Strength Elastic Modulus ElongationFilm Cast (°C.) (min.) (um) (MPa) (GPa) (%)__________________________________________________________________________(V)-ODA Spin 350 60 10 115 ± 8 1.6 ± 0.1 20 ± 6 Spin 350 60 23 ± 2 110 ± 6 1.5 ± 0.2 20 ± 6 Cast 350 60 6 ± 1 115 ± 9 1.3 ± 0.1 21 ± 6 Cast 350 60 18 ± 2 97 ± 5 1.2 ± 0.1 15 ± 2 Cast 350 60 27 ± 1 82 ± 18 1.8 ± 0.1 6 ± 3(V)-3,4'-ODA Spin 350 60 10 83 ± 6 1.4 ± 0.1 8 ± 1(V)-PPD Spin 350 60 8 147 ± 10 4.3 ± 0.2 4 Spin 350 60 47 ± 7 208 ± 21 4.0 ± 0.2 10 ± 1 Spin 400 60 8.3 ± 0.3 280 ± 21 7.1 ± 0.3 7 ± 2(V)-RODA Spin 400 60 6.5 ± 0.7 110 ± 19 2.3 ± 0.2 7 ± 3(V)-(I)ODA Spin 40 60 8.2 ± 0.3 126 ± 15 2.2 ± 0.2 16 ± 8__________________________________________________________________________ *Typical thickness deviations for cast films were ± 8 to 12%; for spin coated films ± 0.5 to 2%
EXAMPLE 7
9,9-Bis(trifluoromethyl)-2,7-dimethylxanthene (XI)
A mixture of 200 g (1 mole) p-tolyl ether, 166 g (1 mole) HFA and 220 g (11 moles) HF was heated at 140° for 8 hrs in a shaker tube. After distilling out residual HF, the tube contents were poured into excess ice-cold dilute NaOH. The product was extracted with methylene chloride, the extracts were passed through a short alumina column, and stripped to dryness. The residue was distilled in vacuo, collecting the cut boiling around 110° /1.7 Torr, which partly solidified on standing. It was stirred with methanol, filtered, washed with more methanol, and dried, yielding a total of 24.3 g (7%) of (XI) as white crystals in two crops (14.5 and 9.8 g). 9,9-Bis(trifluoromethyl)-2,7-dimethylxanthene (XI) is quite volatile, and sublimes in vacuo below 100° , and melts at 136-137° . Analysis: Calc. for C 17 H 12 F 6 O: C, 59.0; H, 3.47; F, 33.0; Found: C, 59.3; H, 3.56; F, 33.5%. The NMR spectrum was confirmatory: s 7.65, dd 7.23, d 7.06, s 2.35 ppm in 1:1:3 ratio.
EXAMPLE 8
9,9-Bis(trifluoromethyl)xanthene-2,7-dicarboxylic acid (XII)
To a refluxing solution of 34.6 g (0.1 mole) of 9,9-bis(trifluoromethyl)-2,7-dimethylxanthene (XI) in ml pyridine and 100 ml water was added in portions g (0.35 mole) potassium permanganate. After 90 min reflux (as the permanganate color was discharged, and Mn02 precipitated) the mixture was filtered, and the filtrate was boiled down to about 100 ml. The residue was diluted with 70 g of 50% NaOH and 400 ml water, and oxidized with an additional 55 g KMnO 4 as above. Filtration of the mixture, and acidification with sulfuric acid yielded a white precipitate, which was filtered, and washed well with water. The material melts at 344°-347° in capillary (DSC shows a peak at 53°) and is sublimable in vacuo. Analysis: Calc. for C 17 H 8 F 6 O 5 : C, 50.3; H, 1.97; F, 28.1; Found: C, 51.2; H, 1.75; F, 25.8. IR: 1700 00 (vs), 1620, 1560 cm -1 .
EXAMPLE 9
9,9Bis(trifluoromethyl)xanthene-2,7-dicarbonyl chloride (XIII)
A mixture of 20 g 9,9-bis(trifluoromethyl)xanthene-2,7-dicarboxylic acid (XII), 250 ml chloroform and 20 ml (excess) thionyl chloride was stirred and refluxed until the slurry became a pale yellow solution (4 hrs). The volatiles were distilled out, ultimately at house vacuum, and the residue (16 g, 73%) was purified by sublimation. The product (XIII) can also be recrystallized from toluene/heptane. M.p. 216°-218° IR: 1750 (vs) cm -1 . NMR: s 8.76, dd 8.31, d 7.44 in 1:1:1 ratio. Analysis: Calc. for C 17 H 6 C1 2 F 6 O 3 : 1.35; Cl 16.0; F 25.7; Found: C 46.1; H 1.22; Cl 15.9; F 26.3.
EXAMPLE 10
9,9-Bis(trifluoromethyl)xanthene-2.7-diisocyanate (XIV)
A mixture of 4.43 g (0.01 mole) of 9,9-bis(trifluoromethyl)xanthene-2,7-dicarbonyl chloride (XIII), 4.43 g (0.07 mole) technical sodium azide and 100 ml toluene was refluxed overnight, the emanating nitrogen being measured by a wet-test meter. A total of 0.42L (84% theory) was evolved. The mixture was filtered, and the filtrate evaporated, yielding 2.4 g (60%) of waxy solid, with a strong NCO band at 2270 cm -1 . lt was sublimed in vacuo; m.p. 105°-107°.
EXAMPLE 11
9,9-Bis(trifluoromethyl)xanthene-2,7-diamine (XV)
A mixture of 10 g crude 9,9-bis(trifluoromethyl)-xanthene-2,7-dicarbonyl chloride (XIII) and 10 g sodium azide was stirred and refluxed overnight in 150 ml toluene. The mixture was filtered, and stripped to dryness, and the residue was refluxed for 3 hrs in 100 ml 20% hydrochloric acid. The slurry was filtered, and the filtrate was basified yielding some solid. The initial solid from the acid solution was stirred in excess aquomethanolic sodium hydroxide, and filtered. After drying, and combining the two solids, there was obtained 4.1 g (52%) of the diamine (XV). It can be distilled in a sublimation tube, and solidifies on cooling. After recrystallization from heptane, the product melted at 137°-138° , and had amine bands at 3470, 3400, 3370, 3350 and 3230 cm -1 . NMR:d (small J) 7.13, d (large J) 6.98, dd 6.80 and broad peak around 3.5 ppm in 1:1:1:2 ratio, corresponding to the 1, 3, 4, and amino protons, respectively.
EXAMPLE 12
9,9-Bis(trifluoromethyl)-3,6-dihydorxyxanthene (VII)
A mixture of 300 g (2.7 moles) resorcinol, 225 g (1.35 moles) HFA and 300 g (15 moles) HF was heated in a shaker tube to 220° and kept there for 15 hrs. After distilling out excess HF, the reaction mixture was poured into a one-gallon polyethylene jar, half-filled with ice-water, and containing 200 g potassium acetate. The lumpy, and sometimes sticky, reddish-brown solid was isolat®d by filtration, washed with water, and air dried (yield of this crude solid averaged about 450 g). 1t was placed in a 4L beaker, and the product was extracted with 2L of boiling toluene, stirring well with a large metal spatula. The extracts were decanted hot from the red tar insoluble in toluene (but very soluble in acetone), and filtered through a 2-cm bed of Celite. On cooling, amber crystals of (VII) grew from the solution. They were filtered off, and a second crop was obtained by concentrating the mother liquors, and cooling. Total yield for a number of runs averaged about 100 g (20%). After repeated recrystallization from toluene, using Darco, pale yellowish platelets were obtained, m.p. 209°-210°. Analysis: Calc. for C 15 H 8 F 6 O 3 : C, 51.4; H, 2.29; F, 32.6; Found: C, 51.3; H, 2.45; F, 32.9%. The IR spectrum of (VII) has strong phenolic OH at 3100-3500 cm -1 , which disappears on acetylation (see below). NMR (in (CD3)2CO, since CDC13 solubility was very low): d 7.70; dd 6.65; OH singlet 5.42 ppm in 1:2:1 ratio.
Since neither chromatography, nor repeated recrystallization, using Darco, succeeded in removing the yellowish color, the diol was purified by conversion to the diacetate, which was purified by short-path
distillation (main cut b.p. 195°-204°/1.4 Torr.). The diacetate was recrystallized from toluene/heptane yielding snow white crystals, and was then hydrolyzed by heating overnight in methanol with an equivalent amount of NaOH. The pale amber solution was stripped, the residue was stirred with 300 ml hot water, filtered, the solid was washed repeatedly with hot water and was then air-dried. Yield was quantitative.
EXAMPLE 13
9,9-Bis(trifluoromethyl)-3.6-bis(4-amino-phenoxy)xanthene (VIII)
A mixture of 51.4 g of 9,9-bis(trifluoromethyl)-3,6-dihydroxyxanthene (VII) (0.147 mole), 46.3 g p-nitrochlorobenene (0.294 mole), 120 ml DMAC and 44.7 g anhydrous potassium carbonate (0.32 mole) was refluxed 4.5 hrs. The mixture was filtered, and the solid was washed with copious amounts of water, and then with methanol. After drying there was obtained a total of 83.7 g (96%) of crude product. The NMR spectrum of the dinitro compound was in agreement with the structure: the A 2 B 2 pattern of the p-nitrophenoxy group as doublets at 8.28 and 7.18, d (b, large J) 7.92 (1-H), dd 6.94 (2-H) and d (small J) 6.87 (4-H ppm, in the correct 1:2:1:1 ratio.
The crude dinitro compound (75 g) was hydrogenated at 50° in 400 ml ethanol, using 3 g of 10% Pd/C catalyst at 500 psi hydrogen pressure, until there was no further pressure drop. The reduction mixture was filtered, the filtrate was concentrated down to 300 ml, cooled, and acidified with 280 ml of concentrated hydrochloric acid. The amine hydrochloride was filtered, washed with 20% hydrochloric acid, and dried under a nitrogen blanket. After drying in a vacuum oven, there was obtained 68 g of the dihydrochloride. It was dissolved in aqueous methanol, and the solution was made basic with sodium hydroxide, which liberated the diamine (XIII). It was isolated by filtration, and washed with much water. After drying under nitrogen, there was obtained 58 g of white solid. The material softens around 89°, and melts at 124° turning dark.
It was purified by distillation in vacuo, and boiled at 305°-307°/1.5 Torr. The NMR spectrum was confirmatory: A 2 B 2 pattern as doublets at 8.27 and 7.18, the 4-H as broad d (large J) 7.92, 3-H as dd 6.94, 1-H as d (small J) 6.87, and NH 2 as broad (about 1.0 ppm) singlet, centered at 3.46 ppm, in the correct ratio: 2:2:1:1:1:2. Analysis: Calc. for C 27 H 18 F 6 O 3 N 2 : C 60.9; H 3.38; F 2I.4; N 5.26; Found: C 61.3; H 3.19; F 21.2; N 5.01%.
EXAMPLE 14
9-Phenyl-9-trifluormethyl-2,3,6,7-tetramethylxanthene (XVI)
A mixture of 32 g (0.14 mole) of 3,3'-di-o-xylyl ether (DXE), 25 g (0.14 mole) trifluoroacetylbenzene, and 40 g (2 moles) HF was heated in a shaker tube at 140° for 8 hrs. After distilling off most of the HF, the residue was transferred to a polyethylene jar containing excess cold 20% NaOH. The product was extracted with methylene chloride, the extracts were run through a short column packed with alumina, and stripped to dryness. The pasty residue was stirred with methanol, and filtered. The resulting solid was washed with methanol, and air-dried. It was purified further by sublimation at 200° /1 Torr, and then by recrystallization from toluene. The product (XVI), obtained in 31 g (58%) yield, melted at 214°-215°. Analysis: Calc. for C 24 H 21 F 3 O: C, 75.4; H, 5.50; F, 14.9; Found: C, 75.6; H, 5.52; F, 14.8%. NMR: d 7.40; quartet 7.30; s 6.96, s 6.58, s 2.23, s 2.07 ppm in the correct 2:3:2:2:6:6 ratio. Repeating this run on larger scale (200 g trifluoroacetylbenzene) and lower temperature (130°), improved the yield to 92%.
EXAMPLES 15 AND 16
9-Phenyl-9-(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic Acid (XVII) and 9-Phenyl-9-(trifluoromethyl)xanthene-2,3,6,7-dianhydride (XVII)
A 75 g sample (0.196 mole) of 9-phenyl-9-trifluoromethyl-2,3,6,7-tetramethylxanthene (XVI) was oxidized with potassium permanganate in two stages, as was done before with (III). This yield of air-dried crude tetraacid (XVII) was 75 g (76%). The crude tetraacid (XVII) was converted to the dianhydride (XVII) by heating under vacuum at 250°. The crude dianhydride (XVIII) can be sublimed in vacuo, and it also can be recrystallized from anisole, as a bis-solvate (by NMR: the PX peaks are at 7.89 and 7.60 ppm, in addition to anisole peaks). Purification of dianhydride (XVIII) was effected by high-precision sublimation in a McCarter sublimer. After a lower-melting foreshot, the main fraction was collected. It contained two different crystalline types: one consisted of clear light yellow crystals of dianhydride (XVIII) of 99.9% purity, m.p. 276°, the other component crystallized as opaque white clusters of needles. Purity of dianhydride (XVIII) was in the 98.1-99.0% range. Analysis: Calc. for C 24 H 9 F.sub. O 7 : C: 61.8; H 1.93; F 12.2; Found: C 61.9, H 2.03, F 11.8.
EXAMPLE 17
9-Phenyl-9pentafluoroethyl-2,3,6,7-tetramethylxanthene
A mixture of 101 g DXE and 100 g phenyl pentafluoroethyl ketone (both 0.45 mole) was heated with 112 g (5.6 mole) HF in a shaker tube at 130° for 8 hrs. After venting off excess HF, the reaction mixture was poured into excess cold aqueous sodium hydroxide. The product was extracted with a 50/50 mixture of methylene chloride and chloroform, the extracts were filtered through a 5-cm layer of alumina, and stripped. The residue was stirred with methanol, and was filtered. There was obtained 173 g (89.6%) of crude 9-phenyl-9-pentafluoroethyl-2,3,6,7-tetramethylxanthene. It was recrystallized from a 80/20 heptane/toluene mixture; m.p. 178°-179°. The IR spectrum was sharp, and the NMR spectrum consisted of: d 7.43, asym. m 7.23, s 6.91, s(b) 6.66, s 2.20 and s 2.04 in the correct 2:3:2:2:6:6 ratio. Analysis: Calc. C 25 H 21 F 5 O: C 69.4; H 4.86; F 22.0 ; Found: C 69.5; H 4.92; F 22.5%.
EXAMPLE 18
9-Phenyl-9-perfluorooctyl-2,3,6,7-tetramethylxanthene
A mixture of 8.7 g of DXE and 20 g phenyl perfluorooctyl ketone (both 0.038 mole) was heated with 0 g (0.5 mole) HF in a shaker tube at 130° for 8 hrs. After venting excess HF, the product mixture was poured into excess cold aqueous alkali, and was extracted with a 50/50 mixture of methylene chloride and chloroform. The extracts were filtered through alumina, stripped and the residue was stirred with methanol. Filtration yielded 9-phenyl-9-perfluorooctyl-2,3,6,7-tetramethylxanthene in two crops, 6.9 and 1.1 g, for a total of 8.0 g (29% yield). The product was recrystallized from heptane; m.p. 177°-178°. NMR: d 7.41, m 7.28, s 6.94, s(b) 6.67, s 2.24, s 2.07, in the correct 2:3:2:2:6:6 ratio. Analysis: Calc. for C 31 H 21 F 17 O: C 50.8; H 2.87; F 44.1; Found: C 50 8; H 2.94; F 44.1%.
EXAMPLE 19
9-Phenyl-9-Perluoropropyl-2.3.6.7-tetramethylxanthene
A mixture of 31.6 g phenyl perfluoropropyl ketone and 26 g DXE (both 0.115 mole) was heated with 30 g (1.5 moles) HF for 8 hrs at 135°. The reaction mixture was drowned in excess cold aqueous sodium hydroxide, extracted with a 50/50 methylene chloride and chloroform mixture; the extracts were filtered through alumina, stripped, and the residue was stirred with excess methanol. The white solid was filtered, and was obtained after drying in 24.9 g (44.9%) yield. After recrystallization from toluene/heptane, the product melted at 189°-190°. NMR: d 7.43, m 7.2-7.3, s 6.91, s(b) 6.66, s 2.23, s 2.07 in 2:3:2:2:6:6 ratio. Analysis: Calc. for C 26 H 21 F 7 O: C 64.7; H 4.36; F 27.6; Found: C 64.7; H 4.55; F 25.0, 25.1.
EXAMPLE 20
9-Trifluoromethyl-9-pentafluoroethyl-2,3,6,7-tetramethylxanthene
A mixture of 45.2 g DXE, 41 g trifluoromethyl pentafluoroethyl ketone (both 0.2 mole) and 50 g HF (2.5 moles) was heated in a shaker tube at 140° for 8 hrs. After venting residual HF, the reaction mixture was transferred to a polyethylene jar, containing icewater, plus excess sodium hydroxide. The product was extracted with methyIene chloride, the extracts were run through a bed of alumina, stripped, and the residue was stirred with methanol, and filtered. There was obtained a total of 18 g (21%) of white 9-trifluoromethyl-9-pentafluoroethyl-2,3,6,7-tetramethylxanthene. It is very soluble in toluene, chloroform, but insoluble in methanol. It was purified by sublimation, and then recrystallized from heptane; m.p. 139-140° . The NMR spectrum was confirmatory: s (b) 7.57; s 6.93 and s 2.27 ppm in the correct 1:1:6 ratio. Analysis: Calc. for C 20 H 16 F 8 O: C 56.6; H 3.77; F 35.85; Found: C.56.8; H 3.77; F 33.0, 33.1.
EXAMPLE 21
9-Phenyl-9-trifluoromethyl-2,7-dimenthylxanthene (XIX)
A mixture of 114 g (0.54 mole) p-tolyl ether (X), g (0.54 mole) trifluoromethyl phenyl ketone, and g (8 moles) HF was heated in an autoclave for 8 hrs at 130°. After venting excess HF, the reaction mixture was quenched in 2L ice water, containing 500 ml 50% NaOH. The product was extracted with methylene chloride, the extracts were filtered through a layer of alumina, stripped and distilled in vacuo. There was obtained 140 g (73%) of distillate boiling at 186°-210°/2 Torr. The solid was recrystallized from methanol or isopropyl alcohol. M.p. 150°-151°. NMR: d 7.40, m 7.30, s 7.07, s(b) 6.64, s 2.16 ppm in 2:3:4:2:6 ratio. AnaIysis: Calc. for C 22 H 17 F 3 O: C 74.6; H 4.80; F 16.1; Found: C 74 7; H 4.90; F I5.g%.
EXAMPLE 22
9-Phenyl-9trifluoromethylxanthene-2,7-dicarboxvlic Acid (XX)
A 100 g batch of 9-phenyl-9-trifluoromethyl-2,7-dimethylxanthene (XIX) was oxidized in the same manner as a 75 g batch of (III). At the final filtration stage there was some granular white solid present in the MnO 2 filter cake. It was extracted with methylene chloride, and identified as unreacted starting material. Yield of recovered (XIX) was 16 g. From the filtrate, upon acidification with sulfuric acid there was obtained, after filtering, washing, and drying, 74 g (75%) of the dicarboxylic acid (XX). In another, larger scale preparation, the yield was 89%.
EXAMPLE 23
9- Phenyl-9-trifluoromethylxanthene-2,7-dicarbonyl Dichloride (XXI)
A slurry of 82 g (0.2 mole) of dried, crude -phenyl-9-trifluoromethylxanthene-2,7-dicarboxylic acid (XX) and 50 ml (large excess) of thionyl chloride in 500 ml chloroform was stirred and heated to gentle reflux in an oil bath. After 3 hrs of refluxing, the solution became clear. It was stirred overnight, and allowed to cool. Volatiles were stripped at atmospheric pressure, 0 ml heptane plus some Darco was added to the residue, the mixture was heated to reflux, and filtered through Celite. On cooling, crystals were obtained, which were filtered off and washed with hexane. 9-phenyl-9-trifluoromethylxanthene-2,7-dicarbonyl dichloride (XXI) was obtained in 64.7 g (71.7%) yield. Another 10.7 g I2%) of the dichloride was obtained by stripping the filtrate, and short-path distillation at about 200°/0.8 Torr, and stirring the syrupy distillate with heptane. After two recrystallizations from heptane the product melted at 128°-130°. IR: very strong carbonyl at 1750 cm -1 . NMR: dd 8.15, "s" 7.74, m 7.3-7.5 ppm in 2:7(5+2) ratio.
EXAMPLE 24
9-Phenyl-9-trifluoromethylxanthene-2 7-dicarbonyl azide
To a stirred solution of 5.0 9 9-phenyl-9-trifluoromethylxanthene-dicarbonyl dichloride (XXI) in ml methylene chloride was added an aqueous solution of 5 g (large excess) sodium azide plus 0.05 g tetrabutylammonium bromide (as phase transfer agent). The two-phase mixture was stirred vigorously for 2 hrs, then the organic layer was separated, and filtered through a small bed of alumina. On evaporation, there was obtained 4.5 g of a white solid, which showed a strong azide band at 2140 cm -1 and a strong carbonyl band at 1685 cm -1 . NMR: d 8.04, "s" 7.62, m 7.37, d 7.30 ppm in the correct 2:2:5:2 ratio. The compound melts with vigorous bubbling at 126°-127°.
EXAMPLE 25
9-Phenyl-9-trifluoromethylxanthene-2,7- diisocyanate (XXII)
A two phase system, consisting of 45 g (0.1 mole) of 9-phenyl-9-trifluoromethylxanthenedicarbonyl dichloride (XXI) in 300 ml methylene chloride, and 22 g sodium azide plus 0.5 g Bu 4 NBr in 100 ml water was stirred vigorously at room temperature for 1.5 hr. The orange organic layer was separated, stirred with Darco, and filtered through a Celite/alumina layer. The colorIess fiIrrate was added dropwise to boiling toluene in a closed system, so that the solvent distilled out, and the nitrogen evolved could be measured by a wet-test meter. After all methylene chloride had distilled out and the toluene was refluxing, the theoretical amount of nitrogen was evolved. Toluene was distilled out at reduced pressure. The residue was extracted with 200 ml of boiling heptane. On cooling the solution, crystals were obtained in two crops 27.4 g and 7.8 g, for a total of 35.2 g (86.3%) of 9-phenyl-9-trifluoromethylxanthene2,7-diisocYanate (XXII). The compound melts at 133°-134°, and contains a very strong NCO band at 2260 cm -1 . NMR: m 7.37, d 7.15, dd 7.06, "s" 6.56 (10 in 5:2:2:2 ratio. Analysis: Calc. for C 22 H 11 F 3 N 2 O 3 : C 64.7; H 2.70; F 14.0; Found: C 64.9; H 2.91; F 13.8%.
EXAMPLE 26
9-(4-Perfluorohexylphenyl)-9-heptafluoropropyl-2,3,6,7-tetramethylxanthene
A mixture of 25.1 g dixylyl ether (0 11 mole) and g 4-perfluorohexylphenyl heptafluoropropyl ketone (0.11 mole) was heated with 35 g (1.75 moles) HF in an autoclave at 140° C. for 8 hrs. After removal of excess HF the clave contents were transfered into a jar containing excess ice and sodium hydroxide. The product was extracted with methylene chloride, and the extracts were filtered through a bed of alumina, and stripped to dryness. The residue was stirred with methanol, and filtered yielding 60 g (68%) of the product in two crops (56.4 g, and 3.6 g). The material can be recrystallized from heptane or from isopropyl alcohol; M.p. 121°-122° C. It can also be distilled in vacuo. NMR: A 2 B 2 doublet 7.55, s 6.95, s 6.58, s 2.23 and s 2.07 ppm in the correct 4:1:1:3:3 ratio.
EXAMPLE 27
9,9-Bis(trifluoromethyll)-3,6-dihydroxyxanthene polyester (IX)
A solution of 7.020 g of 9,9-bis(trifluoromethyl)3,6-dihydroxyxanthene (VII) and 6.5 ml of triethylamine in 50 ml of methylene chloride was stirred at room temperature as 4.070 g of a 70:30 mixture of isophthaloyl chloride and terephthaloyl chloride in 20 ml of methylene chloride was added over 5 min. The mixture became cloudy and was stirred at reflux for one hour, and then at room temperature overnight. The solution was added to 500 ml of methanol in a blender; the precipitated polymer was filtered, reblended with 500 ml of fresh methanol, and filtered again. The polymer was then blended with warm tap water, filtered, washed with methanol and dried to yield 9.2 g of polyester; u inh =0.37 (0.4% in NMP). Film was cast from a 15% solution of polymer in THF and the solvent was removed in a vacuum oven at 130° . The film was tested for oxygen and nitrogen separation at 500 psig (feed gas: 21% O 2 /79% N 2 ): the O 2 /N 2 separation factor was 4.50 and the oxygen permeability was 7.0 Barrers. The film was fairly strong even at this low molecular weight. | Disclosed are rigid fluorinated monomers, their preparation, and polymers derived therefrom based on two novel tricyclic xanthene core systems, 9,9-bis-(perfluoroalkyl)xanthene (I) and 9-phenyl-9-perfluoro-alkylxanthene (II). The monomers have utility in the preparation of advanced high-performance polymers, particularly polyimides. | 2 |
BACKGROUND OF THE INVENTION
This invention relates to a circuit arrangement with a load connected to the output of an amplifier and a voltage generator having a d.c. output that delivers the supply voltage for at least the output stage of the amplifier.
Such circuit arrangements are used, for example, in an NMR tomography unit for the generation of magnetic gradient fields by means of a gradient coil arrangement which in this case forms the load on the amplifier. FIG. 1a shows the typical time curve of the magnetic flux for such a gradient coil arrangement. If the eddy current effects are disregarded, then the current through this coil arrangement has the same curve. Its amplitude in this case is typically 200 A.
FIG. 1b shows the time curve of the voltage at the gradient coil arrangement which is necessary for the current curve shown in FIG. 1a. During the rise and fall of the current two voltage pulses of relatively high amplitude (of the order of 70 V) have to be produced. Between these pulses there has to be a voltage which is just sufficient to compensate the active resistance loss of the coil arrangement.
The supply voltage for the amplifier feeding the coil arrangement must be slightly higher than the peak voltage at the gradient coil arrangement. The power loss in the amplifier is given by the integral of the product of the current as shown in FIG. 1a and the difference between the supply voltage and the voltage as in FIG. 1b. It is particularly large if the current through the coil arrangement is large and the voltage at the coil arrangement is small.
SUMMARY OF THE INVENTION
It is an object of the invention to design a circuit arrangement of the type mentioned in the preamble such that the power loss, which is converted into heat in the amplifier is smaller than in the above-described case.
The invention achieves this object in that the voltage generator contains several d.c. voltage sources with d.c. voltage of varying magnitude and a switch arrangement which connects one of the d.c. voltage sources or the series arrangement of several d.c. voltage sources to the d.c. voltage output, a control circuit is provided which derives a control voltage for controlling the switch arrangement from the input signal of the amplifier in such a way that the voltage at the d.c. output follows the input voltage in steps, but always remains a certain amount larger than the amount of the input voltage multiplied by the gain of the amplifier.
In this case, therefore, the circuit arrangement which determines the voltage at the d.c. voltage output is switched in such a way that this voltage is always somewhat larger than the inherently required voltage at the load. The difference between the supply voltage and the voltage at the load is relatively small therefore so that the power loss converted into heat in the amplifier is also considerably smaller than in the case of a system with a constant supply voltage. The supply voltage required for the amplifier results from its input voltage which is converted by the control circuit into a control signal for the control circuit. Because the rate of change of the supply voltage is determined only by the switching time of the switches, and not by capacitors or the like, it can respond very rapidly to changes of the input voltage.
The number of different supply voltages which the voltage generator as configured in claim 1 can deliver is greater than the number of the d.c. voltage sources because several of the sources can also be connected in series to produce the supply voltage. In principle it should be possible to obtain any combination of the d.c. voltage sources by connecting a switch in series with each d.c. voltage source and by connecting a switch in parallel each time with this series arrangement. However, this requires two switches in push-pull connection and suitable measures to prevent the two switches from inadvertently being closed at the same time, which would result in short-circuiting of the d.c. voltage source in question. This expense can be reduced by a further development in which the switch arrangement for each d.c. voltage source has a series-connected switch for this purpose and each of these series arrangements is connected in parallel with a diode which is driven in the reverse direction for the d.c. voltage in question. Then every time a switch is opened, the supply voltage of the d.c. voltage generator flows through the parallel-connected diode element.
A further development of the invention has provision for a capacitor to be connected in parallel to at least one d.c. voltage source. This development is useful in all cases in which the relevant d.c. voltage source is switched on only for a relatively short time. When feeding gradient coils, for example, the d.c. voltage source is switched on for the maximum d.c. voltage only during the current rise and fall. If the capacitor connected in parallel with it is dimensioned in such a way that it is discharged only negligibly by the current flowing during these periods, the d.c. voltage source does not have to produce this peak output and need only be designed for the mean output required.
In a further development of the invention the d.c. voltage of each source is in each case twice as big or twice as small as the next smallest or next largest d.c. voltage respectively of another d.c. voltage source i.e. the voltages of the DC voltage sources are in a binary weighted sequence (1, 2, 4, etc.). The control circuit then contains an analog-digital converter which converts a signal derived from the amplifier input signal into a binary coded data word of which the most significant bits form the control signal and the high-order bit in each case activates the d.c. voltage source with the higher d.c. voltage. In this way a relatively simple construction of the control circuit is obtained by means of an analog-digital converter. The only additional measures which need to be taken are to ensure that the voltage at the d.c. voltage output of the voltage generator follows the input voltage in steps, but by an amount which always remains a certain amount larger than the desired amplifier output voltage. This can be achieved, for example, by adding a constant value to the analog voltage proportional to the amplifier input voltage or by the appropriate selection beforehand of the characteristic curve of the analog-digital converter.
BRIEF DESCRIPTION OF THE DRAWING
The invention will be explained in greater detail below with the aid of the accompanying drawings in which:
FIG. 1a and 1b show the time slopes of current and voltage at a gradient coil arrangement,
FIG. 2 shows an embodiment of the invention,
FIG. 3 shows the circuit of the voltage generator,
FIG. 4 shows the output stage of an amplifier for the gradient coil arrangement and
FIG. 5 shows the characteristic curves of the amplifier and the control circuit.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 2, an input stage generates an output voltage the time curve of which largely corresponds to that in FIG. 1b. The circuit can contain a digital memory which stores the time curve of the magnetic flux as in FIG. 1a at a sequence of support points. This sequence is converted by means of a digital-analog converter into an analog signal as per FIG. 1a, from which the voltage curve in FIG. 1b can then be generated by an analog network. This voltage can be tapped at the output terminals of circuit 1, the voltage at the outputs being in push-pull connection and connected symmetrically to ground. This voltage is fed to an amplifier 2 having output terminals 3 which are connected to a gradient coil 4 having a central tapping which is grounded. The supply voltage is taken from the d.c. output 5+, 5- of the voltage generator 6, the d.c. output voltage of which follows the voltage at the input of the amplifier in such a way that it is always a certain amount larger than the output voltage assigned to the input voltage at the amplifier output.
The voltage generator 6 is shown in detail in FIG. 3. It comprises four d.c. voltage sources U 1 , U 2 , U 3 , U 4 which deliver voltages of 5 V, 10 V, 20 V, 40 V which means that their d.c. voltages are in the ratio 1:2:4:8. Each of the voltage sources U 1 . . . U 4 is connected in parallel with a capacitor C 1 . . . C 4 the capacitance of which is dimensioned in such a way that it can supply the peak power (during the voltage pulses at the beginning and at the end). The voltage sources U 1 . . . U 4 need to be designed only for the mean power when they are only active in these phases for the supply voltage. For the rest, the capacitors provide smoothing.
An electronically controllable switch S 1 . . . S 4 is connected in series with each of the d.c. voltage sources. An output terminal 5+ is connected to switch S 4 , while the d.c. voltage output terminal 5- is connected to the voltage source U 1 . If several switches are closed, then the d.c. voltages of the associated voltage sources are added together. Connected between the d.c. voltage output terminals 5+, 5- is the series arrangement of four diodes D 1 . . . D 4 , the connection points of which are each connected to the like pole of the voltage sources U 1 . . . U 4 . If, therefore, more than one switch is open (switches S 2 and S 4 in FIG. 3), then the direct current generated by d.c. voltage sources U 1 and U 3 , whose switches (S 1 and S 3 ) are closed, flows via the diodes (D 2 and D 4 ) which are allocated to the inactive voltage sources (U 2 and U 4 ). The result of this is that the diodes D 1 . . . D 4 with the same forward direction have to be connected in series so that, on the one hand, they can conduct the current delivered by the other d.c. voltage sources and, on the other, they do not short-circuit the allocated voltage source. The resulting current flow is indicated by the solid continuous line in FIG. 3.
The switch arrangement S 1 . . . S 4 is controlled by a control circuit which can comprise a circuit 7 (FIG. 2) for the absolute value formation, an adding stage 8 and an analog-digital converter 9. The circuit 7 for the absolute value formation converts the signal fed to the amplifier 2 into a voltage which is proportional to the amount of this signal. The output voltage of this circuit is fed to one input of an analog adding stage 8 at the other adding input of which there is a constant voltage which has the same polarity as the output signal of circuit 7. The output signal of the adding stage is fed to an analog-digital converter 9 which converts the analog input voltage into a digital data word and thereby controls the switch arrangement. The most significant bit of this data word controls switch S 4 which switches on or off the d.c. voltage source U 4 with the highest d.c. voltage, the second most significant bit controls switch S 3 for the d.c. voltage source U 3 with the second highest d.c. voltage etc. If the analog-digital converter 9 delivers a control signal with more than four bits, only the four most significant bits are used for the control of switches S 1 . . . S 4 .
The layout of the control circuits 7, 8, 9, in particular the magnitude of the d.c. voltage to be added, follows from FIG. 5 in which the dependences of the output voltage of the amplifier (straight line 10) and of the output voltage of the d.c. voltage generator (curve 11) are represented as a function of the amplifier input voltage u. It can be seen that the curve 11 is always positioned above the straight line 10, and in such a way that the difference never falls below a minimum value. This minimum value is dimensioned in such a way that for every input voltage u the amplifier is in a position to generate at terminals 3 the output voltage resulting from the characteristic 10. It is also possible, however, to omit the adding stage 8 and to make the analog-digital converter non-linear from the outset so that a characteristic curve like that in FIG. 5 is obtained.
As FIG. 1b shows, the polarity of the voltage at the gradient coil 4 varies. Consequently, the amplifier must be designed in such a way that it can deliver positive and negative output voltages. A suitable embodiment of the output stage of such an amplifier is shown in FIG. 4. This is a transistor bridge amplifier which in each of its two branches connected between the 5+ and 5- output terminals of the voltage generator 6 contains the series arrangement of two npn-transistors 12 and 13 and 14 and 15, respectively. The transistor bridges are controlled in such a way that the voltage between the bases of two series-connected transistors remains largely constant and that the potentials at the bases of transistors 12 and 13 and 14 and 15, on the other hand, are varied in push-pull action. The driver and, where appropriate, preamplifier stages required for this can be connected to the supply voltage delivered by voltage generator 6. However, connection is also possible to a separate d.c. voltage generator.
The starting point of the above description was a circuit arrangement with a gradient coil such as may form part of an NMR tomography unit. However, the invention can also be applied--in all cases where the concern is to reduce the power loss of an amplifier, particularly in the case of an inductive or capacitive load.
As a rule, the supply voltage cannot follow a change of the input voltage as quickly as the output voltage of the amplifier can. Therefore distortion can occur at the output of the amplifier when the input voltage increases. In an NMR tomography unit such short-lived distortions usually are not a disturbing factor. In applications in which these distortions are not acceptable the input voltage could be fed to the amplifier via a delay element so that the supply voltage is already increased, where necessary, if the amplifier input voltage requires a larger supply voltage. To prevent the supply voltge from falling before the input signal has decreased accordingly, the control circuit or the d.c. voltage generator could be operated in such a way that a small time constant is obtained in the case of voltage rises and a large time constant in the case of voltage drops. | A circuit in which a load connected to the output of an amplifier, and in particular for the gradient coil arrangement in a nuclear magnetic resonance tomography unit. To reduce the power loss in the amplifier, especially where, as in NMR tomography, high currents must be switched in relatively short time intervals, the supply voltage for the amplifier is delivered by a d.c. voltage generator the output voltage of which follows the input voltage in steps, but always remains a certain amount larger than the output voltage of the amplifier assigned to the respective input voltage. | 6 |
CROSS-REFERENCE TO RELATED PATENT APPLICATION
[0001] This application claims priority to provisional application No. 60/989,831 filed Nov. 22, 2007, the entirety of which is incorporated herein by reference.
[0002] Some references, which may include patents, patent applications and various publications, are cited and discussed in the description of this invention. The citation and/or discussion of such references is provided merely to clarify the description of the present invention and is not an admission that any such reference is “prior art” to the invention described herein. All references cited and discussed in this specification are incorporated herein by reference in their entireties and to the same extent as if each reference was individually incorporated by reference.
FIELD OF THE INVENTION
[0003] The present application relates generally to the methods and pharmaceutical compositions for regulating the expression of a nucleic acid. More specifically, the present application relates to the methods and pharmaceutical compositions for regulating the expression of Guanosine- (G-) and/or Guanosine-cytosine-rich (GC-rich) nucleic acid.
BACKGROUND OF THE INVENTION
[0004] Thalidomide is a racemic compound and chemically named 2-(2,6-dioxo-3-piperidinyl)-1H-iso-indole-1,3(2H)-dione. Despite the high risk of teratogenicity, thalidomide is emerging as a drug for treating cancer and inflammatory disease (Franks et al., 2004). Furthermore, with its anti-angiogenic and immunomodulatory activities, thalidomide is also considered as an effective drug for treating refractory multiple myeloma (Singhal et al., 1999). Actually, in addition to the myeloma, thalidomide has been widely tested on various types of cancer such as colorectal cancer (Franks et al., 2004), myelodysplastic syndrome, Waldenstrom's macroglobulinemia, myelofibrosis with myeloid metaplasia, brain tumor (Elcuthcrakis-Papaiakovou et al., 2004), acute myeloid leukemia, non-Hodgkin's lymphoma, lung cancer, breast cancer, neuroendocrine tumors, hepatocellular carcinoma (Kumar et al., 2004), mantle cell lymphoma, pancreatic cancer (Teo et al., 2005), renal cell carcinoma, prostate cancer, Kaposis's sarcoma, melanoma (Richardson et al., 2002) and prolactinoma (Mukdsi et al., 2006). Clinical studies in some immunological disorders, including rheumatoid arthritis, erythema nodosum leprosum, Behcet's syndrome, sarcoidosis, Crohn's disease (Franks et al., 2004), aphthous ulcers (Teo et al., 2005), aphthous stomatitis, lupus erythematosus, prurigo nodularis (Wu et al., 2005), ankylosing spondylitis (Scalapino et al., 2003), chronic heart failure (Gullestad et al., 2005) and graft-versus-host disease (GVHD) after allogeneic bone marrow transplantation and renal transplantation (Richardson et al., 2002; Matthews et al., 2005), further support thalidomide's immunomodulatory properties. The anti-angiogenic activity of thalidomide is also be confirmed in angiogenesis-associated diabetic diseases, such as diabetes retinophathy (Bosco et al., 2003). Although these data hold promise in the treatment of the mentioned diseases and/or disorders, the mechanism of action for thalidomide is still not completely understood. Some reports showed thalidomide treatment could reduce plasma basic fibroblast growth factor (bFGF) level, and a positive response for thalidomide treatment in glioma and multiple myeloma (Fine et al., 2000; Neben et al., 2001; Sato et al., 2002). The changes of bFGF level in serum and/or plasma during therapy imply that bFGF might be the target for thalidomide.
[0005] bFGF belongs to the FGF gene family and is a potent autocrine and/or paracrine mitogen that is expressed ubiquitously. bFGF participates in many biological activities including stimulation of mesodermal formation, angiogenesis, smooth muscle cell proliferation and regulation of development of nervous system and eye (Bikfalvi et al., 1997). bFGF is known to be overexpressed in various types of tumors, such as brain tumor, prostate cancer (Elcuthcrakis-Papaiakovou et al., 2004), prolactinoma (Mukdsi et al., 2006), breast cancer (Fuhrmann-Benzakein et al., 2000), head and neck cancer, soft tissue sarcoma, renal cell carcinoma, colorectal carcinoma, hepatocellular carcinoma, ovarian carcinoma, endometrial carcinoma (Poon et al., 2001), melanoma (Ugurel et al., 2001), lung cancer (Ueno et al., 2001; Iwasaki et al., 2004), Kaposis's sarcoma (Samaniego et al., 1998), pancreatic cancer (Yamanaka et al., 1993), multiple myeloma (Sezer et al., 2001), myelodysplastic syndrome, leukemia (Aguayo et al., 2000), non-Hodgkin's lymphoma (Giles et al., 2004) and bladder cancer (Nguyen et al., 1994). bFGF is also associated with sleep disorder (Okumura et al., 1996), immunological disorders and angiogenesis-associated diseases, such as rheumatoid arthritis, osteoarthritis (Nakashima et al., 1994), Crohn's disease (Di Sabatino et al., 2004), Behcet's disease (Erdem et al., 2005), systemic sclerosis (Lawrence et al., 2006), polyarteritis nodosa (Kikuchi et al., 2005), vernal keratoconjunctivitis (Leonardi et al., 2000), psoriasis (Andrys et al., 2007), proliferative diabetic retinopathy (Boulton et al., 1997), age-related macular degeneration (Frank, 1997), asthma (Hoshino et al., 2001) and pulmonary arterial hypertension (Benisty et al., 2004). It is also reported that neoangiogenesis is also an integral part of the immunopathogenesis of chronic inflammatory diseases such as rheumatoid arthritis, psoriasis and retinopathy (Andrys et al., 2007). The secretion of bFGF is independent of the traditional endoplasmic reticulum (ER)—Golgi pathway (Mignatti et al., 1992). In addition to the secreted form, there existed four nuclear-target-forms of bFGF, which are translated alternatively from upstream inframe CUG codons of an internal ribosome entry site (IRES)-dependent mechanism. The structure of IRES is formed by the G-rich N-terminal of bFGF transcripts (Florkiewicz et al., 1989; Vagner et al., 1995). The low molecular weight bFGF (LMW bFGF) is translated by using the first AUG codon of bFGF transcript, and the high molecular weight bFGFs (HMW bFGFs) translated by using the upstream CUG codons. Although the C-terminal part of LMW and HMW bFGFs are the same, the functions are believed to differ from each other due to the different intracellular distributions and the N-terminal extension of HMW bFGFs (Quarto et al., 2005). It has been shown that nuclear accumulation of bFGFs or an increased ratio of high HMW bFGFs to LMW bFGF is an indicator for tumor progression (Fukui et al., 2003). Overexpression of bFGF in cancer cells were also correlated to the advanced tumor stage and poor prognosis of pancreatic cancer (Yamanaka et al., 1993).
[0006] The expression of bFGF transcript is under the control of G-rich promoter, which might be capable of forming secondary structure, such as G-quadruplexes, which could be targeted by some deoxyribonucleic acid (DNA) binding drugs to interact with and subsequently alter the promoter activity (Hurley et al., 2000). It is reported that kinds of genes have G- and/or GC-rich region, such as vascular endothelial growth factor (VEGF), platelet-derived growth factor-A (PDGF-A), hypoxia-inducible factor-1α (HIF-1α), B-cell CLL/lymphoma 2 (Bcl-2), v-myb myeloblastosis viral oncogene homolog (avian) (c-Myb), v-kit Hardy-Zuckerman 4 feline sarcoma viral oncogene homolog (c-Kit), retinoblastoma (Rb), ret proto-oncogene (Ret), avian myelocytomatosis viral oncogene homolog (c-MYC), Kirsten rat sarcoma-2 viral (v-Ki-ras2) oncogene homolog (KRAS) (Qin et al., 2008), type II tumor necrosis factor (TNF) receptor (Bethea et al., 1997), insulin-like growth factor (IGF-1), IGF-1 receptor, integrin, tetraspains and human telomerase reverse transcriptase (hTERT) (Drucker et al., 2003). Besides the transcriptional regulation by the G-rich promoter, the N-terminal extension of bFGF transcript is also G-rich, which could be functioning to regulate the translation of different isoforms. The G-rich region of ribonucleic acid (RNA) transcript can serve as the targets for some DNA binding drugs, and consequently modulation of expression of isoforms.
[0007] The teratogenic activity of thalidomide was proposed to be its binding to both DNA and RNA of fetus whether administrated orally or parenterally, and the binding of the thalidomide glutarimide moiety to DNA might alter the secondary structure of DNA (Bakay et al., 1968; Huang et al., 1990; Huang et al., 1999; Nicholls, 1966). Drucker et al. reported that thalidomide could down-regulate transcripts levels for genes with GC-rich promoter in a relative high concentration over 12.5 μg/ml (Drucker et al., 2003).
[0008] In addition, some U.S. patents also disclosed the thalidomide could be used in treating immunological disease and cancer and inhibition of angiogenesis, such as U.S. Pat. No. 6,124,322, U.S. Pat. No. 6,235,756, U.S. Pat. No. 6,617,354, U.S. Pat. No. 6,914,067, U.S. Pat. No. 7,230,012 and U.S. Pat. No. 7,435,726.
[0009] U.S. Pat. No. 6,124,322 entitled “Intravenous form of thalidomide for treating immunological diseases” relates to an aqueous thalidomide solution which is suitable as a parenteral form of application of thalidomide, particularly as an intravenous form of application. U.S. Pat. No. 6,235,756 entitled “Methods and compositions for inhibition of angiogenesis by thalidomide” relates to a method for preventing unwanted angiogenesis, particularly in angiogenesis dependent or associated diseases, by administration of compounds such as thalidomide and related compounds. U.S. Pat. No. 6,423,321 entitled “Cytokine antagonists for the treatment of sensorineural hearing loss” relates to the method for inhibiting the action of TNF and/or IL-1 antagonists for treating hearing loss in a human by administering a TNF antagonist and/or an IL-1 antagonist for reducing the inflammation affecting the auditory apparatus of said human, or for modulating the immune response affecting the auditory apparatus of said human, by administering a therapeutically effective dosage level to said human of a TNF antagonist and/or an IL-1 antagonist. U.S. Pat. No. 6,617,354 entitled “Method of stabilizing and potentiating the action of anti-angiogenic substances” relates to die use of anti-angiogenic agents in the cure of cell proliferative disorders including cancer and other disorders caused by uncontrolled angiogenic activity in the body. U.S. Pat. No. 6,914,067 entitled “Compositions and methods for the treatment of colorectal cancer” relates to pharmaceutical compositions comprising thalidomide and irinotecan, to methods of treating colorectal cancer, and to methods of reducing or avoiding adverse effects of irinotecan. U.S. Pat. No. 7,230,012 entitled “Pharmaceutical compositions and dosage forms of thalidomide” relates to the pharmaceutical compositions and dosage forms comprising thalidomide and pharmaceutically acceptable prodrugs, salts, solvates, hydrates, and clathrates thereof. And, U.S. Pat. No. 7,435,726 entitled “Compositions and methods for the treatment of cancer” relates to the pharmaceutical compositions including thalidomide and an anti-cancer agent, particularly a topoisomerase inhibitor, to methods of treating cancer, and to methods of reducing or avoiding adverse effects associated with anti-cancer agents such as topoisomerase inhibitors.
[0010] Even though the thalidomide has been used in treating cancer and immunological disease, and inhibition of angiogenesis, the relevant mechanism of action for thalidomide is still not so clear. Therefore, elucidation of the mechanism of action for thalidomide will be beneficial in the methods and/or pharmaceutical compositions for cancer, immunological disorder, angiogenesis-associated disease.
BRIEF SUMMARY OF THE INVENTION
[0011] In one aspect, the present application relates to a method for regulating bFGF expression. The method includes a step of interacting the G- and/or GC-rich region of the bFGF with thalidomide.
[0012] Preferably, the thalidomide has a concentration between 100 μg/ml and 0.01 μg/ml.
[0013] Preferably, the thalidomide has a concentration between 10 μg/ml and 0.1 μg/ml.
[0014] Preferably, the G- and/or GC-rich region has more than 50% GC content therein.
[0015] Preferably, the thalidomide is sustainedly released by a drug delivery technology.
[0016] Preferably, the thalidomide is encapsulated.
[0017] In another aspect, the present application relates to a pharmaceutical composition for regulating bFGF expression. The pharmaceutical composition includes thalidomide.
[0018] In a further aspect, the present application relates to a method for treating a disease associated with an expression of bFGF. The method includes a step of interacting the G- and/or GC-rich region of the bFGF with thalidomide.
[0019] Preferably, the disease is a bFGF overexpression-associated disease.
[0020] Preferably, the bFGF overexpression-associated disease is one selected from the group consisting of cancer, immunological disorder, angiogenesis-associated disease and sleep disorder
[0021] Preferably, the cancer is one selected from the group consisting of brain tumor, prostate cancer, pancreatic cancer, breast cancer, lung cancer, head and neck cancer, bladder cancer, renal cell carcinoma, colorectal carcinoma, hepatocellular carcinoma, ovarian carcinoma, endometrial carcinoma, prolactinoma, melanoma, Kaposis's sarcoma, soft tissue sarcoma, multiple myeloma, myelodysplastic syndrome, non-Hodgkin's lymphoma and leukemia.
[0022] Preferably, the immunological disorder is one selected from the group consisting of rheumatoid arthritis, osteoarthritis, Behcet's disease, systemic sclerosis, polyarteritis nodosa, psoriasis, asthma, vernal keratoconjunctivitis and Crohn's disease.
[0023] Preferably, the angiogenesis-associated disease is one selected from the group consisting of pulmonary arterial hypertension, rheumatoid arthritis, asthma, psoriasis, proliferative diabetic retinopathy and age-related macular degeneration.
[0024] In a further aspect, the present application relates to a pharmaceutical composition for treating a disease associated with an expression of bFGF with G- and/or GC-rich region thereof. The pharmaceutical composition includes thalidomide.
[0025] In yet another aspect, the present application relates to a method for regulating expression of a DNA and/or RNA having G- and/or GC-rich region. The method includes a step of interacting the G- and/or GC-rich region of the bFGF with thalidomide having a concentration between 100 μg/ml and 0.01 μg/ml.
[0026] Preferably, the DNA and/or RNA having G- and/or GC-rich region is one selected from the group consisting of bFGF, VEGF, PDGF-A, HIF-1α, Bcl-2, c-Myb, c-Kit, Rb, Ret, c-MYC, KRAS, type II TNF receptor, IGF-1, IGF-1 receptor, integrin, tetraspains and hTERT.
[0027] Preferably, the thalidomide is sustainedly released by a drug delivery technology.
[0028] Preferably, the thalidomide is sustained by an encapsulation.
[0029] In yet another aspect, the present application relates to a pharmaceutical composition for regulating expression of a DNA and/or RNA having G- and/or GC-rich region. The pharmaceutical composition includes thalidomide between 100 μg/ml and 0.01 μg/ml.
[0030] In yet another aspect, the present application relates to a method for treating a disease associated with an expression of a DNA and/or RNA having G- and/or GC-rich region. The method includes a step of interacting the G- and/or GC-rich region with thalidomide having a concentration between 10 μg/ml and 0.1 μg/ml.
[0031] Preferably, the disease is one selected from the group consisting of cancer, immunological disorder, angiogenesis-associated disease and sleep disorder.
[0032] In a further aspect, the present application relates to a pharmaceutical composition for treating a disease associated with an expression of a DNA and/or RNA having G- and/or GC-rich region. The pharmaceutical composition includes thalidomide between 100 μg/ml and 0.01 μg/ml.
[0033] In yet another aspect, the present application relates to a method for increasing bio-availability of thalidomide to bFGF. The method includes a step of retaining a concentration of the thalidomide by a slow-release technology.
[0034] Preferably, the concentration of the thalidomide is retained between 10 μg/ml and 0.1 μg/ml.
[0035] In yet another aspect, the present application relates to a pharmaceutical composition for increasing bio-availability of thalidomide to bFGF. The pharmaceutical composition has thalidomide in a slow-release vehicle.
[0036] These and other aspects will become apparent from the following description of the preferred embodiment taken in conjunction with the following drawings, although variations and modifications therein may be affected without departing from the spirit and scope of the novel concepts of the disclosure.
[0037] The accompanying drawings illustrate one or more embodiments of the invention and, together with the written description, serve to explain the principles of the invention. Wherever possible, the same reference numbers are used throughout the drawings to refer to the same or like elements of an embodiment.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0038] FIG. 1A shows the effect of thalidomide on bFGF transcript levels of U-87 MG cells. Thalidomide (0˜10 μg/ml) was freshly prepared from the stock solution before being added to the cells for treatment of 3 hr.
[0039] FIG. 1B shows the effect of thalidomide on bFGF transcript levels of U-87 MG cells. Thalidomide (0˜10 μg/ml) was freshly prepared from die stock solution before being added to the cells for treatment of 12 hr.
[0040] FIG. 1C shows the effect of pre-incubation of thalidomide in culture medium alone on bFGF transcript levels of U-87 MG cells. Thalidomide (0˜10 μg/ml) was incubated with culture medium alone for 9 hr before being added to the cells for treatment of 3 hr.
[0041] FIG. 1D shows the effect of thalidomide on bFGF transcript levels of U-87 MG cells. Liposomal thalidomide (0˜10 μg/ml) was added to the cells for treatment of 12 or 24 hr.
[0042] FIG. 2A shows the effect of thalidomide on bFGF protein expression levels of U-87 MG cells. Liposomal thalidomide (0˜10 μg/ml) was added to the cells for treatment of 12 hr, and bFGF protein expression levels were determined by FACS analysis.
[0043] FIG. 2B shows the effect of thalidomide on the intracellular distribution of bFGF protein. Free-form or liposomal thalidomide (0.1˜10 μg/ml) was added to the U-87 MG cells for treatment of 12 hr, and bFGF protein distribution was examined by fluorescence microscopy. DNAs were stained with Hoechst 33258 as a nuclear marker. The magnification was 400.
[0044] FIG. 2C shows the effect of thalidomide on multiple isoforms of bFGF protein expression. Free-form or liposomal thalidomide (0.1˜10 μg/ml) was added to the U-87 MG cells for treatment of 12 hr, and cellular bFGF content was analyzed by Western blot.
[0045] FIG. 3A shows the effect of thalidomide on cell proliferation. Free-form or liposomal thalidomide (0˜100 μg/ml) was added to the U-87 MG cells for treatment of 72 hr, and the relative cell growth was determined by resazurin assay.
[0046] FIG. 3B shows inhibition of anchorage-independent growth of U-87 MG cell by thalidomide. Cells were cultured in soft agar containing free-form or liposomal thalidomide (0˜10 μg/ml). Colonies were photographed 14 days after the start of the relevant experiment.
[0047] FIG. 3C shows inhibition of anchorage-independent growth of U-87 MG cell by thalidomide. Cells were cultured in soft agar containing free-form or liposomal thalidomide (0˜10 μg/ml). Colonies were counted 14 days after the start of the relevant experiment.
[0048] FIG. 3D shows disaggregation of spheroids by thalidomide, and reversal of thalidomide disaggregation effect by bFGF. Cells were suspended in culture medium containing 0˜10 μg/ml of thalidomide with or without exogenous bFGF. Spheroids were photographed by phase-contrast microscopy. The magnification was 100.
[0049] FIG. 3E shows inhibition of three-dimension growth of U-87 MG cells by thalidomide. Cells were suspended in culture medium containing 0˜10 μg/ml of thalidomide. The percentage of aggregation was analyzed.
[0050] FIG. 4A shows inhibition of bFGF promoter-controlled EGFP reporter gene expression by thalidomide in U-87 MG cells. The cells were stably transfected with plasmid pbFGF-EGFP. After 0˜10 μg/ml thalidomide treatment for 3 hr, EGFP transcript expression levels were determined by flow cytometry.
[0051] FIG. 4B shows inhibition of bFGF promoter-controlled EGFP reporter gene expression by thalidomide in U-87 MG cells. The cells were stably transfected with plasmid pbFGF-EGFP. After 0˜10 μg/ml thalidomide treatment for 3 hr, EGFP transcript expression levels were determined by real-time PCR analysis.
[0052] FIG. 5A is a schematic representation of the plasmid pLMW-IRES and pHMW-IRES.
[0053] FIG. 5B shows inhibition of LMW-IRES-dependent translation by thalidomide in U-87 MG cells. Cells were stably transfected with the bicistronic vector pLMW-IRES from FIG. 5A and treated with 0˜10 μg/ml thalidomide for 12 hr. The IRES activity was determined by calculating the LucR/LucF ratio.
[0054] FIG. 5C shows inhibition of HMW-IRES-dependent translation by thalidomide in U-87 MG cells. Cells were stably transfected with the bicistronic vector p KM W-IRES from FIG. 5A and treated with 0˜10 μg/ml thalidomide for 12 hr. The IRES activity was determined by calculating the LucR/LucF ratio.
[0055] FIG. 6A shows partial bFGF cDNA sequence. The G-rich fragment is marked by a solid line box and non-G-rich control DNA fragment marked by a dotted line box.
[0056] FIG. 6B shows a UV-VIS absorbance spectrum of thalidomide after incubation with G-rich bFGF DNA fragment.
[0057] FIG. 6C shows a UV-VIS absorbance spectrum of thalidomide after incubation with non-G-rich bFGF control DNA fragment.
[0058] FIG. 7A is a western blot showing in bFGF knock-down clones and control clone, the expression levels of bFGF protein were dramatically reduced compared with those of the internal control GAPDH. Clone Nos. 1˜3 represent those clones which were derived from U-87 MG cells expressing bFGF shRNA Nos. 1˜3, respectively.
[0059] FIG. 7B shows cell proliferation ability of bFGF knock-down clones and control clone.
[0060] FIG. 7C shows inhibition of anchorage-independent growth of bFGF knock-down clones by thalidomide and recovery by exogenous bFGF treatment. Cells were cultured in soft agar containing free-form or liposomal thalidomide (0˜10 μg/ml) with or without exogenous bFGF. Colonies were photographed 14 days later.
[0061] FIG. 7D shows inhibition of anchorage-independent growth of bFGF knock-down clones by thalidomide and recovery by exogenous bFGF treatment. Cells were cultured in soft agar containing free-form or liposomal thalidomide (0˜10 μg/ml) with or without exogenous bFGF. Colonies were counted 14 days later.
[0062] FIG. 8A shows morphology of spheroids from bFGF knock-down clones and control clone. Spheroids were photographed by phase-contrast microscopy.
[0063] FIG. 8B shows the diameters of spheroids from bFGF knock-down clones and control clone.
[0064] FIG. 8C shows the number of cells in the spheroids from bFGF knock-down clones and control clone.
[0065] FIG. 9 is a schematic drawing showing bFGF expression would be regulated by thalidomide on at least two levels.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
[0066] The terms used in this specification generally have their ordinary meanings in the art, within the context of the invention, and in the specific context where each term is used. Certain terms that are used to describe the invention are discussed below, or elsewhere in the specification, to provide additional guidance to the practitioner regarding the description of the invention. For convenience, certain terms may be highlighted, for example using italics and/or quotation marks. The use of highlighting has no influence on the scope and meaning of a term; the scope and meaning of a term is the same, in the same context, whether or not it is highlighted. It will be appreciated that same thing can be said in more than one way. Consequently, alternative language and synonyms may be used for any one or more of the terms discussed herein, nor is any special significance to be placed upon whether or not a term is elaborated or discussed herein. Synonyms for certain terms are provided. A recital of one or more synonyms does not exclude the use of other synonyms. The use of examples anywhere in this specification including examples of any terms discussed herein is illustrative only, and in no way limits the scope and meaning of the invention or of any exemplified term. Likewise, the invention is not limited to various embodiments given in this specification.
[0067] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In the case of conflict, the present document, including definitions will control.
[0068] As used herein, “around”, “about” or “approximately” shall generally mean within 20 percent, preferably within 10 percent, and more preferably within 5 percent of a given value or range. Numerical quantities given herein are approximate, meaning that the term “around”, “about” or “approximately” can be inferred if not expressly stated.
Overview of the Invention
[0069] In a preferred embodiment of the present application, it is showed that thalidomide down-regulated the expression of bFGF RNA transcripts by targeting its G- and/or GC-rich promoter in U-87 MG human glioma cells at the relatively low concentration of 0.1 μg/ml even lower than the prior clinical therapeutic scrum concentrations of 1.8-10 μg/ml (Elcuthcrakis-Papaiakovou et al., 2004). A preferred embodiment also shows that thalidomide down-regulated the expression of different bFGF isoforms in a dose-dependent manner (0.1, 1, 10 μg/ml), which is resulting from the change of the G- and/or GC-rich IRES activity. Because thalidomide had been reported to be highly susceptible to hydrolysis in solution (Eriksson et al., 1998), the present application further provides a method for increasing the bio-availability of thalidomide at the concentration between 0.1 to 10 μg/ml by a slow-release technology, such as encapsulated by liposome.
[0070] A preferred embodiment implicated the G- and/or GC-rich promoter and/or G- and/or GC-rich coding sequence of bFGF are the major targets of thalidomide. By applying thalidomide as a research tool, it is also possible to find out that bFGF may play a very important role in tumor anchorage-independent growth, which is a hallmark of tumorigenicity. The molecular mechanism of thalidomide provided in the preferred embodiment of die present application offers a new way for the arrest of cancers, angiogenesis-associated diseases, immunological disorders and sleep disorders in a relative lower therapeutic dose using drug delivery technologies, such as those performed by liposome, N-trimethyl chitosan and pH-dependent sustained release, and especially provides the useful indicator for treating diseases with high bFGF expression level instead of random clinical trials.
EXAMPLES
[0071] Without intent to limit the scope of the invention, exemplary instruments, apparatus, methods and their related results according to the embodiments of the present invention are given below. Note that titles or subtitles may be used in the examples for convenience of a reader, which in no way should limit the scope of the invention. Moreover, certain theories are proposed and disclosed herein; however, in no way they, whether they are right or wrong, should limit the scope of the invention so long as the invention is practiced according to the invention without regard for any particular theory or scheme of action.
Example 1
Thalidomide Down-Regulates bFGF RNA Levels in U-87 MG Cells
[0072] To examine whether the anti-tumor effect of thalidomide is via down-regulating the expression of bFGF, a high grade human glioma U-87 MG cell line was used due to its highly basal level of bFGF (Ke et al., 2000). The U-87 MG cells were purchased from American Type Culture Collection (ATCC, Rockville, Md.) and maintained in Dulbecco's modified Eagle's medium (DMEM; Gibco) containing 10% heat inactivated fetal bovine serum (FBS; Gibco) and antibiotics, such as penicillin G (Sigma-Aldrich) and streptomycin (Sigma-Aldrich), at 37° C. in a humidified incubator of 5% CO 2 -95% air. Thalidomide (TYY Biopharm, Taiwan) was dissolved in dimethyl sulfoxide (DMSO; Sigma-Aldrich) first to make a stock solution of 50 mg/ml, and then diluted to various, desired concentrations with medium. The maximum of the final concentration of DMSO in the medium was 0.02%.
[0073] Real-time RT-PCR analysis was used to assess the RNA levels of bFGF in U-87 MG cells. After being treated with indicated concentrations (0, 0.1, 1 and 10 μg/ml) of thalidomide for 3 hr and 12 hr, U-87 MG cells were washed twice with ice-cold phosphate buffered saline (PBS) and RNA was extracted by using RNA-Bee™ RNA isolation solvent (Tel-test). Total RNA (5 μg) was used to prepare cDNA by using AMV reverse transcriptase (Promega). The reverse-transcribed cDNA samples were analyzed by real-time PCR using ABI Prism 7700 Sequence Detection System (Applied Biosystems) and the SYBR Green Master Mix kit (Applied Biosystems). Real-time PCR primers targeting human glyceraldehyde 3-phosphate dehydrogenase (GAPDH) primers (SEQ ID NO. 1 and SEQ ID NO. 2), bFGF primers (SEQ ID NO. 3 and SEQ ID NO. 4) were designed using Primer Express software (Applied Biosystems), and primers' sequences are shown in Table 1.
[0074] The PCR condition is as follows: 95° C. denaturation for 10 min followed by 40 cycles of 95° C. for 15 sec, 55° C. for 20 sec, and 72° C. for 40 sec. The expression level of human GAPDH was used as an internal reference. Relative gene expression levels were calculated with the 2 −ΔΔCT . bFGF RNA levels in U-87 MG cells were markedly reduced after being treated with 0.1˜10 μg/ml thalidomide for 3 hr ( FIG. 1A ) even at concentrations lower than the reported therapeutic dose (3-6 μg/ml) (Vacca et al., 2005). However, when cells were treated with thalidomide for longer periods (12 hr), its inhibitory effect on bFGF expression disappeared ( FIG. 1B ).
[0000]
TABLE 1
Name
Sequence
SEQ ID NO.
GAPDH-F
5′-AATGTCACCGTTGTCCAGTTG-3′
1
GAPDH-R
5′-GTGGCTGGGGCTCTACTTC-3′
2
bFGF-F
5′-ATCAAAGGAGTGTGTGCTAACC-3′
3
bFGF-R
5′-ACTGCCCAGTTCGTTTCAGTG-3′
4
bFGF promoter-F
5′-GTGGCACCTGGTATATCCTAGTG-3′
5
bFGF promoter-R
5′-AGCCTCGAGCCGCTCGG-3′
6
EGFP-F
5′-CCATGGTGAGCAAGGGCGAG-3′
8
EGFP-R
5′-TGAGGGTCAGCTTGCCGTAGG-3′
9
LMW-IRES-F
5′-CTCCTGACGCGGGGCCGTGCCCCGGAGCGG-3′
10
LMW-IRES-R
5′-CTCACAACGGGTTGTGAGGGTCGCTCTTCT G-3′
11
HMW-IRES-F
5′-CTCCTGACGCGTGAGGAGGGAGGAGGACTG G-3′
13
HMW-IRES-R
5′-CTCACAACGGGTTGTGAGGGTCGCTCTTCT C-3′
14
[0075] In order to test the stability of thalidomide in the culture medium alone, the thalidomide stock solution was diluted with fresh culture medium to 0.1˜10 μg/ml and incubated at 37° C. in a humidified incubator of 5% CO 2 -95% air for 9 hr before being added to the U-87 MG cells for 3 hr. As shown in FIG. 1C , thalidomide completely lost its activity even after a short (9 hr) incubation in culture media. In order to increase the stability of thalidomide in aqueous solution, thalidomide could be encapsulated by a vehicle or pharmaceutical acceptable carriers, such as liposome and N-trimethyl chitosan. Thalidomide was encapsulated by liposome to form liposomal thalidomide according to the method described previously (Fang et al., 2005) with modifications. Briefly, egg phosphatidylcholine (120 mg; Fluka) and cholesterol (30 mg; Sigma) in the ratio of 4 to 1 by weight and 12 mg thalidomide were mixed together, dissolved in 5 ml of a chloroform-methanol solution (2:1, v/v), and then evaporated in a rotary evaporator at 40° C. Solvent traces were removed by maintaining lipid films under a vacuum for overnight. The films were first hydrated with 10 ml distilled water in a bath-type sonicator at 4° C. for 1 hr. The aqueous dispersion of liposome was further homogenized with a probe-type sonicator to give a smaller size of liposome, followed by filtration through a series of nylon meshes of 74, 53, 30 and 10 μm pore size, and then centrifuged at 26,000×g to collect the liposome pellet. The liposomal thalidomide was dissolved in methanol and its UV absorbance measured at 230 nm so as to determine the concentration of the liposomal thalidomide. Interestingly, significant inhibition of bFGF transcripts in U-87 MG cells by liposomal thalidomide was detectable even after treating for 24 hr ( FIG. 1D ), but the dose response observed earlier ( FIG. 1A ) was no longer seen.
Example 2
Thalidomide is Sustained Release Via N-Trimethyl Chitosan Encapsulation
[0076] N-trimethyl chitosan (TMC) was synthesized as previously described (Thanou et al., 2000). Briefly, chitosan (2 g; Sigma-Aldrich) was sieved through nylon meshes of 300 μm pore size and mixed with sodium iodide (4.8 g; Sigma-Aldrich) in 15% (w/v) sodium hydroxide (11 ml; NaOH, Sigma-Aldrich), iodomethane (11.5 ml; Sigma-Aldrich) and 1-methyl-2-pyrrolidinone (80 ml; Sigma-Aldrich) at 60° C. for 75 min. The product was precipitated by 4 volume 95% (v/v) ethanol, isolated by centrifugation at 1670×g and thoroughly washed with ether to remove ethanol. Then the obtained product was dissolved in 1-methyl-2-pyrrolidinone (80 ml; Sigma-Aldrich) at 60° C. to remove ether and then mixed with sodium iodide (4.8 g; Sigma-Aldrich) in 15% (w/v) (11 ml; NaOH, Sigma-Aldrich) and iodomethane (11.5 ml; Sigma-Aldrich) at 60° C. for the secondary step of reductive methylation. The product was precipitated by addition of 4 volume 95% (v/v) ethanol, isolated by centrifugation at 1670×g and thoroughly washed with ether. The purification steps included that each product was dissolved in 10% (w/v) sodium chloride (20 ml; NaCl, J. T. Baker) to exchange the iodide with chloride, precipitated by 4 volume 95% (v/v) ethanol, isolated by centrifugation at 1670×g, thoroughly washed with ether and dialyzed against deionized water overnight. The TMC was dried in vacuo and measured its characterization in D 2 O by a 500-MHz spectrometer (Bruker Avance 500 MHz NMR). The nanoparticles of thalidomide encapsulated by TMC were prepared using a ionic-gelation method under magnetic stirring at room temperature as previously described (Mi et al., 2008). In brief, thalidomide (18.16 mg/31.91 mL (deionized H 2 O/ethanol=2/3, v/v)) was premixed with an aqueous poly(γ-glutamic acid) (18.26 mg/1.97 ml deionized H 2 O; Vedan, Taiwan). Subsequently, magnesium sulfate (36.54 mg/4.12 mL deionized H 2 O; MgSO 4 , Sigma-Aldrich) was blended into the mixture and thoroughly stirred for 1 hr. An aqueous TMC (114.6 mg/20 mL deionized H 2 O) was added into the mixed solution under magnetic stirring at room temperature for 1 hr. In order to determine the loading content and loading efficiency, nanoparticles of thalidomide encapsulated by TMC were collected by centrifugation at 45,000 rpm (227480×g) in a Beckman 55.2 Ti rotor (Beckman Coulter) and assayed by liquid chromatography Mass (LC/MS/MS; Bruker). Compared with rapid hydrolysis of thalidomide as previous report (Eriksson et al., 1998), thalidomide encapsulated by TMC could be released sustainedly.
Example 3
Thalidomide Down-Regulates bFGF Protein Levels and its Nuclear Distribution
[0077] U-87 MG cells were treated with indicated concentrations (0, 0.1, 1 and 10 μg/ml) of free-form and liposomal thalidomide and fixed in 4% (w/v) paraformaldehyde (Sigma-Aldrich) in PBS for 15 min, permeabilized with 0.01% (v/v) Triton X-100 (Sigma-Aldrich) or 0.5% (v/v) saponin (Sigma-Aldrich) in PBS for 30 min at room temperature. The cells were subsequently treated with 0.5 μg polyclonal rabbit anti human bFGF antibody (ab16828, Abeam) for 30 min at room temperature, washed, followed by staining with FITC-conjugated goat anti-rabbit IgG (Jackson ImmunoResearch) at 1:200 dilution for 30 min. Hoechst 33258 (Sigma-Aldrich) was used as a nuclear marker. The cells were then washed and visualized using a fluorescence microscope (Olympus Optical Co, Tokyo, Japan) or analyzed using the BD FACSCalibur™ flow cytometer (BD Biosciences). The relative expression level of cellular bFGFs was calculated by normalized the mean fluorescence value of each treatment with the empty liposome treated control. The Immunofluorescence stainings showed that thalidomide down-regulated not only total ( FIG. 2A ) but also nuclear ( FIG. 2B ) level of bFGF proteins. Because HMW bFGFs were the major isoforms localized in nucleus (Renko et al., 1990), a decrease of its signal intensity in this compartment might reflect a reduced expression of HMW bFGFs.
[0078] Immunoblot (or western blot) analysis was therefore performed to analyze the amount of different bFGF isoforms and GAPDH was used as die internal control, which level would not be affected by thalidomide. After being treated with indicated concentrations (0, 0.1, 1 and 10 μg/ml) of free-form and liposomal thalidomide, U-87 MG cell lysate was prepared using lysis buffer (50 mM Tris [hydroxymethyl] aminomethane (Tris; USB), 1% (v/v) TritonX-100 (Sigma-Aldrich), 150 mM sodium chloride (NaCl; J. T. Baker), 1 mM ethylenediaminetetraacetic acid (EDTA; Sigma-Aldrich), 1 mM phenylmethylsulphonyl fluoride (PMSF; Sigma-Aldrich). Cell lysates (2 μg) containing proteins were separated with using 15% polyacrylamide gel electrophoresis and transferred to a polyvinylidene fluoride (PVDF) membrane (PerkinElmer). The membrane was incubated with polyclonal rabbit anti human bFGF antibody (ab16828, Abeam) at 1:200 dilution or anti-GAPDH antibody (ab9482, Abeam) at 1:10000 dilution, which was used as an internal control, followed by horseradish peroxidase-conjugated anti-IgG secondary antibody (Jackson ImmunoResearch) at 1:5000 dilution. The enhanced chemiluminescent (ECL; PerkinElmer) detection method (Amersham) was used for blotting analysis. Without treatment of thalidomide, U-87 MG expressed all bFGF isoforms, but the 24-kilodalton (kDa) one was lower than the other forms ( FIG. 3C ). Even though both HMW and LMW bFGFs were translated from the same transcript, a decrease of the HMW bFGFs induced by thalidomide was more dramatic than that of LMW ones (1 and 10 μg/ml), while liposomal thalidomide could down-regulate not only the level of HMW bFGF but also the level of LMW bFGF dose-dependently ( FIG. 3C ).
Example 4
Effects of Thalidomide on Cell Proliferation and Anchorage-Independent Growth
[0079] Since thalidomide could down-regulate bFGF expression in U-87 MG cells, we next evaluated its effects on their growth because overexpression of this growth factor in glioma cells was reported to stimulate their proliferation in an autocrine manner, and the introduction of bFGF antisense oligonucleotides in these cells could block their growth and colony formation in soft agar (Murphy et al., 1992). Cell proliferation ability was assayed using a resazurin assay (Nociari et al., 1998), in which resazurin dye was used as a redox indicator to detect cell growth, not cell death. Resazurin sodium (Sigma-Aldrich) stock solution in PBS (5 mM) was prepared, and the working solution (50 μM) was diluted from the stock using DMEM (Gibco) without FBS. Approximately 3000 U-87 MG cells were seeded onto 96-well plates (Costar, Corning), allowed to attach at 37° C. in a humidified incubator of 5% CO 2 -95% air for 16 hr, and treated with indicated concentrations (0, 0.1, 1, 10, and 100 μg/ml) of free-form and liposomal thalidomide for 72 h. For resazurin assay, the culture medium was removed and freshly diluted resazurin working solution (100 μl) was added into each well. Following incubation at 37° C. in a humidified incubator of 5% CO 2 -95% air for 2 hr, the resazurin dye was reduced by the activity of living cells, and the reduced form of resazurin was determined at a fluorescence excitation wavelength 530 nm and emission wavelength 590 nm by a Victor 2 1420 Multilable Counter (Wallac, PerkinElmer). As shown in FIG. 3A , only high concentration (100 μg/ml) of liposomal thalidomide could slightly reduce the proliferation of U-87 MG cells.
[0080] Because bFGF was known to promote cell transformation (Vagner et al., 1996), the soft agar colony formation assay (Murphy et al., 1992) and hanging drop method (Kelm et al., 2003) were used to assess the effects of thalidomide on anchorage-independent and three-dimensional growth abilities of U-87 MG cells, respectively. The colony forming assay was performed according to a two-layer agar technique (Murphy et al., 1992). The bottom layer consisted of 0.3 ml of DMEM with 10% FBS and 0.5% (w/v) agarose (Amresco). Approximately 1000 U-87 MG cells were added to the same medium containing 10% FBS and 0.3%) (w/v) low-melting agarose (Amresco) plus indicated concentrations (0, 0.1, 1 and 10 μg/ml) of free-form thalidomide, and plated in 24-well plates (Costar, Corning) onto the base layer. After 2 weeks of incubation at 37° C. in a humidified incubator of 5% CO 2 -95% air, cells were stained with 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT; Sigma-Aldrich) dye solution and plates were photographed and colonies numbers counted. Colony-forming ability (size, >0.1 mm) was measured. As shown in FIG. 3B and FIG. 3C , free-form and the lyposomal thalidomide were effective at low concentration (0.1 μg/ml) and clearly exhibited a dose-dependent response.
[0081] For hanging drop assay, approximately 1000 U-87 MG cells per 20 μl of cell suspension in culture medium (DMEM with 10% FBS) with indicated concentrations (0, 0.1, 1 and 10 μg/ml) of free-form thalidomide were spotted on the cover of a 6-cm culture dish (Falcon). The cover was returned to its top position with the cell suspension droplet facing down toward the bottom dish, which contained 5 ml of DMEM for maintenance of moisture during incubation. The spheroids were formed for 48 hr after the incubation at 37° C. in a humidified incubator of 5% CO 2 -95% air. Each spheroid was photographed by using phase-contrast microscopy. The aggregation percentage was assayed by calculating the aggregation ability from 20 spheroids for each assay condition. The cell aggregates formed in spheroid culture was abolished by free-form thalidomide dose-dependently ( FIG. 3D and FIG. 3E ).
Example 5
Thalidomide Down Regulates bFGF Transcription by Regulating its G- and/or GC-Rich Promoter
[0082] To evaluate the effect of thalidomide on the transcription driven by bFGF promoter, pbFGF-EGFP plasmid, containing bFGF promoter to drive the expression of enhanced green fluorescence protein (EGFP), was stably transfected into U-87 MG to get U87-bFGF-EGFP cell. Briefly, genomic DNA was purified from U-87 MG cells. About 500 ng genomic DNA was used as template and amplification of PCR fragments were performed on ABI 2700 thermocycler by using Taq polymerase (GENET BIO). The primers (SEQ ID NO. 5 and SEQ ID NO. 6) used for amplifying bFGF promoter was showed in Table 1. The PCR condition was 96° C. for 10 min followed by 35 cycles of 95° C. for 40 sec, 58° C. for 40 sec, and 72° C. for 1 min, and thereafter 72° C. for 7 min and then kept at 4° C. The bFGF promoter fragments (SEQ ID NO. 7) were cloned into pGEMT-easy vector (Promega) and subcloned into pEGFP-N2 vector (BD Biosciences Clontech) to generate plasmid pbFGF-EGFP. Approximately 2×10 5 U-87 MG cells were plated in 6-well plates (Falcon) 24 hr before transfection and exposed to 3 μg total DNA (plasmid pbFGF-EGFP) and 3 μl Lipofectamine 2000 (Invitrogen Corp.) in DMEM without FBS according to the manufacture's brochure of Lipofectamine 2000. After cultured at 37° C. in a humidified incubator of 5% CO 2 -95% air for 48 hr, cells were trypsinized and passaged into DMEM with 10% FBS (20× dilutions). Stable transfectants (U87-bFGF-EGFP cells) were selected by using geneticin (800 μg/ml; Merck Biosciences) for 1 month.
[0083] U87-bFGF-EGFP cells were treated with indicated concentrations (0, 0.1, 1 and 10 μg/ml) of free-form thalidomide for 3 hr. The fluorescence of EGFP was measured by flow cytometry (FACS Calibur, BD Biosciences). The relative fluorescence indexes were measured to evaluate the effect of thalidomide on the expression of EGFP controlled by bFGF promoter. The RNA levels of EGFP were analyzed by real-time RT-PCR and GAPDH was used as an internal control. The EGFP primers (SEQ ID NO. 8 and SEQ ID NO. 9) are shown in Table 1. Thalidomide was shown to diminish EGFP transcripts and the fluorescence in a dose-dependent pattern after 3 hr treatment ( FIG. 4A and FIG. 4B ).
Example 6
Thalidomide Down Regulates bFGF Translation by Modulating its IRES Activity
[0084] To examine whether the G- and/or GC-rich region in IRES of N-terminal extension of bFGF transcript could also be regulated by thalidomide, plasmids pHMW-IRES and pLMW-IRES ( FIG. 5A ) were designed using bicistronic vector as previous described (Creancier et al., 2000). There were two luciferase genes, Renilla luciferase (LucR) and firefly luciferase (LucF), which were controlled by the cytomegalovirus (CMV) promoter and separated by the LMW-IRES fragment (SEQ ID NO. 12) and HMW-IRES fragment (SEQ ID NO. 15) in plasmids pLMW-IRES or pHMW-IRES ( FIG. 5A ), respectively. The LMW-IRES fragment (SEQ ID NO. 12) and HMW-IRES fragment (SEQ ID NO. 15) were amplified from U-87 MG genomic DNA by PCR with the primers (SEQ ID NO. 10, SEQ ID NO. 11, SEQ ID NO. 13 and SEQ ID NO. 14) showed in Table 1, then cloned into pGEMT-easy vector (Promega) and subcloned into a bicistronic vector system (Promega) to generate plasmids pLMW-IRES and pHMW-IRES, respectively. Approximately 2×10 5 U-87 MG cells were plated in 6-well plates (Falcon) 24 hr before transfection and exposed to 3 μg total DNA (plasmid pLMW-IRES or pHMW-IRES) and 3 μl Lipofectamine 2000 (Invitrogen, Carlsbad, USA) in DMEM without FBS according to the manufacture's brochure of Lipofectamine 2000. After cultured at 37° C. in a humidified incubator of 5% CO 2 -95% air for 48 hr, cells were trypsinized and passaged into DMEM with 10% FBS (20× dilutions). Stable transfectants (U87-HMW-IRES and U87-LMW-IRES cells) were selected by using geneticin (800 μg/ml; Merck Biosciences) for 1 month.
[0085] U87-LMW-IRES and U87-HMW-IRES cells were treated with indicated concentrations (0, 0.1, 1 and 10 μg/ml) of liposomal thalidomide for 12 hr, and the two luciferase activities were measured in each cell extracts by scintillation counting in a Victor 2 1420 Multilabel Counter (Wallac, PerkinElmer). The IRES activity was determined by calculating the LucR/LucF ratios (the ratio of renilla to firefly luciferase activity) normalized by the untreated control. Thalidomide did alter the IRES activity in a dose-dependent manner for both LMW-IRES and HMW-IRES ( FIG. 5B and FIG. 5C ).
Example 7
The UV-VIS Absorbance of Thalidomide is More Effectively Quenched by a G-Rich DNA Fragmen
[0086] The GC content of large genomic DNA (>100 kb) ranges from 30% to 65% and the average is about 40% (Venter et al., 2001; Lander et al., 2001). Nucleic acid with GC content more than 50% would be G- and/or GC-rich. The G-rich fragment with 91% GC content and non-G-rich control fragment with 44% GC content were designed from the promoter region of bFGF ( FIG. 6A ). To examine whether thalidomide could interact preferentially with the G- and/or GC-rich region of bFGF, the ultraviolet-visible (UV-VIS) absorbance of thalidomide was assayed using a Hitachi U2000 Spectrophotometer with the scanning range from 330 to 190 nm. The absorbance of thalidomide would be diminished by bound tightly with the secondary structure of a DNA (Usha et al., 2005). As shown in FIG. 6B and FIG. 6C , a more severe quench of the absorbance at 230 nm of thalidomide was detected when it was incubated with a G-rich fragment than with non-G-rich control fragment, and this result suggested that thalidomide might bind preferentially with nucleic acids that have a high content of GC.
Example 8
Anchorage-Independent Growth of U-87 MG Cells is Suppressed by Knocking Down its bFGF Expression
[0087] It has been demonstrated that thalidomide not only down-regulated bFGF expression in U-87 MG cells but also inhibited their colony formation in soft agar, then the tumorigenicity of these cells was examined to determine whether it was reduced by knocking down its bFGF expression.
[0088] Recombinant lentiviruses were produced by transient transfection of human embryonic kidney cell line 293T cells (ATCC, Rockville, Md.) using the ecalcium-phosphate method according to the guideline provide by the National RNAi Core Facility (Institute of Molecular Biology/Genomic Research Center, Academia Sinica, supported by the National Research Program for Genomic Medicine Grants of NSC, Taiwan). Briefly, 293 T cells were cotransfected with 20 μg pLKO.1-puro lentiviral vector (National RNAi Core Facility, Academia Sinica, Taipei, Taiwan) expressing non-target control shRNA (shGFP control, as shown in Table 2) (SEQ ID NO. 19) or bFGF shRNA (bFGF shRNA No. 1, No. 2, or No. 3, Table 2) (SEQ ID NO. 16, SEQ ID NO. 17 and SEQ ID NO. 18) along with 6 μg envelope plasmid pMD.G (National RNAi Core Facility, Academia Sinica, Taipei, Taiwan) and 15 μg packaging plasmid pCMVΔR8.91 (National RNAi Core Facility, Academia Sinica, Taipei, Taiwan). Fresh culture medium (DMEM with 10% FBS) was replaced after 6 hr of the transfection. Infectious lentviruses were harvested at 40 and 64 hr post-transfection and filtered through 0.45 μm low protein binding filter (Millipore). The viral particles were spun down by ultracentrifugation (Beckman SW28 swingle bucket, 4° C., 2 h at 26,000 rpm). After centrifugation, the supernatants were discarded, and the viral pellets were suspended in 200 μl of FBS-free DMEM and stored at −70□.
[0089] To prepare bFGF knock-down cells, approximately 10 6 U-87 MG cells in 5 ml DMEM with 10% FBS were plated into 6-cm culture dish (Falcon) and incubated at 37° C. in a humidified incubator of 5% CO 2 -95%) air for 16 hr to allow cell attachment. The cells were then infected with lentivirus suspension (100 μl) for 24 hr. Because the recombinant lentivirus had puromycin resistant gene, fresh medium (DMEM with 10% FBS) containing 1 μg/ml puromycin (Sigma-Aldrich) for knock-down cells selection was replaced every 3 days for 2 weeks. After selection, three bFGF knock-down clones from the respective shRNAs were selected and named as clone#1, clone#2 and clone#3.
[0000]
TABLE 2
Name
Sequence
SEQ ID NOs.
bFGF shRNA #1
GCA GTC ATA AAC AGA AGA
16
ATA
bFGF shRNA #2
GAC CCT CAC ATC AAG CTA
17
CAA
bFGF shRNA #3
CTA TCA AAG GAG TGT GTG
18
CTA
shGFP control
ACG TCT ATA TCA ATG GCC
19
GAC A
[0090] The western blot result shown that these three knock-down clones had different efficacies in down-regulating the expression of endogenous bFGF ( FIG. 7A ). The cell proliferation activity of each clones showed no significant difference from that of the control clone except clone #3 ( FIG. 7B ). The anchorage-independent growth of these bFGF down-regulating cells was significant inhibited, especially the clone#3 ( FIG. 7C ). To distinguish between the contribution of LMW and HMW bFGF to the anchorage-independent growth of U-87 MG cells, aforementioned clones were incubated with recombinant LMW bFGF (0, 10, 50 and 250 ng/ml) before colonies formed in soft agar, which were then counted. Although the number of colonies formed from the bFGF down-regulating cells was increased significantly by LMW bFGF supplementation, the anchorage-independent growth abilities were only partially restored by this treatment ( FIG. 7D and Table 3). The relevant results showed that nuclear bFGF (HMW ones) also plays an important role in cell transformation.
[0000]
TABLE 3
recombinant human bFGF (ng/ml)
0
10
50
250
control
46.8 ± 6.3
52.0 ± 7.0
57.8 ± 5.2**
58.8 ±
7.0*
clone#1
16.0 ± 6.7***
38.5 ± 4.4*
23.5 ± 3.2***
21.0 ±
7.3***
clone#2
14.8 ± 1.6***
25.8 ± 3.4***
23.3 ± 2.8***
27.2 ±
7.6***
clone#3
10.2 ± 3.2***
20.8 ± 2.1***
21.0 ± 3.6***
21.7 ±
4.4***
Results were expressed as the mean ± S.E. (n = 6 per group).
*p < 0.05,
**p < 0.01,
***p < 0.001 vs. 0 ng/ml bFGF control cells (Student's t test).
Example 9
The Three-Dimensional Growth of U-87 MG was Diminished After Knock Down Cellular bFGF Level
[0091] By using the hanging drop method to force tumor cells growing into spheroid, the time bFGF knock-down clones needed to aggregate was longer than control (date not shown), and the size of spheroids was shown to be significantly smaller ( FIG. 8A and FIG. 8B ). For further analysis, the spheroids were transferred into 96-well plates (Costar, Corning) containing 100 μl DMEM without FBS in each well. After allowed to attach at 37° C. in a humidified incubator of 5% CO 2 -95% air for about 12 hr and removal of the culture medium, the spheroids were stained with methylene blue (200 μl of 5 g/l in methanol; Sigma-Aldrich) for 30 min. The wells were washed for 5 times with tap water to remove the excess of dye and then the plates were allowed to dry overnight at 25° C. The stained spheroids were solved with 2% (w/v) SDS (200 μl/well; J. T. Baker) at 25° C. for 24 hr. The viable cells in spheroid were expressed as a percentage of the methylene blue absorbance (at 650 nm) of spheroid lysates measured by PowerWave™ HT 340 (BioTek). The results showed that the cell number is also correlated with the cellular level of bFGF ( FIG. 8C ) and exogenous bFGF can accelerate cell proliferation ability and recovered the spheroid size in a dose-dependent manner (Table 4). It indicated that the ability of U-87 MG cells to grow into a three-dimensional spheroid is likely dependent on the endocrine machinery of bFGF.
[0000]
TABLE 4
recombinant human bFGF (ng/ml)
0
10
50
250
Control
1.00 ± 0.14
1.02 ± 0.10
1.08 ± 0.20
1.49 ± 0.20**
clone#1
0.83 ± 0.04*
0.99 ± 0.14
0.99 ± 0.18
1.08 ± 0.30
clone#2
0.51 ± 0.25**
0.69 ± 0.24*
0.89 ± 0.4
1.10 ± 0.18
clone#3
0.36 ± 0.11**
0.42 ± 0.14**
0.73 ± 0.21*
0.85 ± 0.15
Results were expressed as relative index of untreated control ± S.E. (n = 8 per group).
*p < 0.05,
**p < 0.01 vs. 0 ng/ml bFGF control cells (Student's t test).
[0092] Thalidomide has been used and studied for more than 50 years, but its mechanisms of action are not fully understood. Many clinical trials of thalidomide were conducted based on its anti-angiogenic and immunomodulatory activities (Elcuthcrakis-Papaiakovou et al., 2004). Interestingly, positive responses of some cancer patients to thalidomide have been shown to correlate with the changes in serum concentration of angiogenic factors such as VEGF, bFGF and HGF (Fine et al., 2000; Neben et al., 2001; Vacca et al., 2005; Kakimoto et al., 2002). In the present application, it is found that low concentration thalidomide was sufficient to down-regulate bFGF in U-87 MG cell dose-dependently and the bio-availability of thalidomide could be increased by a slow-release technology, such, as being encapsulated with liposome, N-trimethyl chitosan and pH-dependent sustained release. In addition, the expression ( FIG. 4A and FIG. 4B ) and DNA binding analyses ( FIG. 6B ) of the present application suggested that the down-regulation of bFGF transcript levels by thalidomide is mediated by its direct interaction with the G-rich promoter of this gene. The effective concentrations of thalidomide were much lower (0.1 and 1 μg/ml) than those (12.5 and 25 μg/ml) used by others to suppress the G-rich hTERT promoter (Drucker et al., 2003). In the meantime, a decrease in bFGF protein levels was also found in these cells after thalidomide treatment which was associated with a change of nuclear localization of high molecular weight (HMW) bFGFs ( FIG. 2B ). The IRES activities present in both HMW and LMW bFGF transcripts (Bonnal et al., 2003) were shown to be down regulated by thalidomide in a dose-dependent manner ( FIG. 5B and FIG. 5C ). It has been suggested that cellular IRESs may have evolved to support low level of expression in normal conditions and an inducible expression in response to different stimuli which can contribute to the development of several pathological condition in human like diabetes, cardiovascular disease and the development and progression of cancer (Komar et al., 2005). bFGF IRES is specifically activated in the aorta wall in streptozotocin-induced diabetic mice, in correlation with increased expression of endogenous bFGF, which is one of the key of diabetes-linked atherosclerosis aggravation (Gonzalez-Herrera et al., 2006). Angiotensin II plays a central role not only in the etiology of hypertension but also in the pathophysiology of cardiac hypertrophy, heart failure, vascular thickening, atherosclerosis and glomerulosclerosis in humans. The biological responses of Angiotention II are mediated by its interaction with angiotensin II type 1 receptor (AT1R), which is closely involved in the pathogenesis of cardiovascular disease. It was demonstrated that AT1R harbors an IRES, and activation of ATR1 play a pivotal role in the pathogenic process (Martin et al., 2003).
[0093] It is well known that solid tumors grow in vivo as multicellular masses in which a proportion of cells is deprived of normal contacts with the basement membrane and is anoikis-resistant. Cell lines derived from such solid rumors are capable of growing in an anchorage-independent manner as colonies in soft agar or suspension culture (Freedman et al., 1974). The acquisition of anchorage-independence is an important hallmark of cancer cells and is thought to be one of the critical factors in the growth and metastasis of cancer. Although certain signaling pathways to abrogate the requirement for intergrin-extracellular matrix-mediated signaling function for anchorage-independent growth of cancer cells has been proposed, die precise molecular mechanism is not fully understood (Grossmann, 2002; Wang, 2004). Contrasted to its ineffectiveness in suppressing the proliferation of U-87 MG cells ( FIG. 3A ), thalidomide efficiently inhibited the anchorage-independent growth and aggregation of these cells at low dose ( FIGS. 3B-3E ). Therefore, a novel tumor-suppressing mechanism of thalidomide it is realized. In this respect, positive correlations between the expression levels of bFGF and anchorage-independent growth of human fibroblast, prostatic epithelial cells and melanocytes have been reported. (Bikfalvi et al., 1995; Quarto et al., 1991; Nesbit et al., 1999; Ropiquet et al., 1997). Hence, down-regulation of colony formation in soft agar of U-87 MG cells by thalidomide attributed to a decreased bFGF expression it induced. This speculation was supported by the shRNA-mediated bFGF knock-down study which clearly showed a positive correlation between cellular bFGF levels and colony forming ability of these cells in soft agar ( FIG. 7A , FIG. 7C and FIG. 7D ). On the other hand, since the addition of recombinant human bFGF only partially rescued the loss of soft agar colony forming ability of U-87 MG cells (Table 3), the contribution of an intracrine signaling of this growth factor to cell transformation was postulated.
[0094] Even though the precise role of nuclear bFGF in U-87 MG cells is unclear, a stimulation of fibroblast growth in low serum by nuclear bFGF has been reported (Arese et al., 1999). Moreover, the nuclear accumulation of bFGF in human astrocytic tumors has been shown as a useful predictor of patients' survival (Fukui et al., 2003). Recent reports showed that cell-cell adhesion was important for anchorage-independent growth but might inhibit anchorage-dependent growth (Hokari et al., 2007). On the other hand, bFGF could regulate the expression of some adhesion molecules such as integrin in endothelial cells (Klein et al., 1993) and glioma periphery (Bello et al., 2001), which contain the G-rich promoter regions and may involve in anchorage-independent growth of embryonic developing tissue (Stephens et al., 2000) and cancer cells (Bikfalvi et al., 1995). Based on the present application, it is realized that thalidomide therefore offers an evolutional insight into a new strategy for the development of novel anticancer drugs based on the mechanisms of anchorage-independence instead of conventional anchorage-dependent, and effectively to suppression of tumorigenicity involving growth and metastasis.
[0095] Many studies focus on the immunomodulatory activities of thalidomide for it could potentially inhibit LPS induced TNF-α secretion by monocytes lower as at 0.3 μg/ml (Sampaio et al., 1991), which is very close the effective concentration throughout the present application. It is said that thalidomide could down-regulate the activity of NF-κB, which is a transcription factor controls huge downstream pathways such as immune response and adhesion molecular expression (Li et al., 2002), through inhibition of IκB kinase activity (Keifer et al., 2001). However, it has been shown that bFGF could regulate IκB kinase activity by binding to the FGFR2 and activating of the downstream signaling pathway (Tang et al., 2007). Beside this, bFGF had also been proved enhancing monocyte and neutrophil recruitment to inflammation, which might result in the amplification of the immunological signaling (Zittermann et al., 2006). Therefore, the present application also highlights a unified molecular mechanism of thalidomide on down-regulation of bFGF expression and signaling, and consequently controls the downstream immune response for its immunomodulatory activity.
[0096] As mentioned above, the present application showed that the G- and/or GC-rich sequence contained in the promoter and the transcripts of bFGF is the target for thalidomide to interact with, which causes the down-regulation of cellular bFGF expression level. The decrease of bFGF would lead to a down-shift of U-87 MG tumorigenicity mediated by anchorage-independent growth, which was confirmed by down-regulate the bFGF level by RNAi. The clinical daily application dose of thalidomide is between 200 to 800 mg in multiple myeloma and to a maximum of 1200 mg in glioma and renal cancer, and the administration would give the serum concentration about 1.8 to 10 μg/ml (Elcuthcrakis-Papaiakovou et al., 2004). According to the present application, however, the effective concentration to inhibit the anchorage independent growth in U-87 MG cells, which is a kind of tumor with high bFGF basal level, was below the therapeutic one. Thus the dose needed for patients with higher bFGF serum level should be much lower than it is applied now, which might reduce the side effects. Besides this, it is realized that using some drug delivery system such as liposome enhances the bioactivity of thalidomide and reduces the side effects thereof. bFGF is not only one of the potent pro-angiogenic factors to endothelial cells, and it also acts as an upstream regulator to control the initiation of angiogenesis (Tsunoda et al., 2007; Seghezzi et al., 1998). Thus the activity of thalidomide in cancer patients might not only for it down-regulate the growth of tumor cells with high pre-treat bFGF expression level, but also for it suppressed the bFGF regulated angiogenesis.
[0097] Combining with the previous finding that bFGF could regulate the NF-kB signaling and functioned to amplify the inflammatory response by enhancing monocyte and neutrophil recruitment, a model for how thalidomide regulates angiogenesis, tumor growth and immune response was showed in FIG. 9 , which offers a reasonable molecular mechanism of thalidomide based on the primary effect on the G- and/or GC-rich promoter and G- and/or GC-rich coding sequence of bFGF. The first level is on the G- and/or GC-rich promoter region of bFGF gene. A drug such as thalidomide may bind to the G- and/or GC-rich promoter region of bFGF gene and thus down regulate the activity of the promoter. The second level is on the IRES of bFGF mRNA. A drug like thalidomide may bind to the IRES and thus down regulate the translation of bFGF transcript. A decrease in bFGF protein levels would lower tumorigenecity and down regulate bFGF-induced angiogenecis. In addition, a decrease in bFGF protein level might also diminish FGFR2-mediated signaling pathway, which would negatively impact nuclear NF-k B site activity and result in a decrease in cellular immune response.
[0098] Based on the embodiments, it is realized that thalidomide down-regulates the expression of bFGF RNA transcripts by targeting its G- and/or GC-rich promoter at the relatively low concentration. A preferred embodiment also shows that thalidomide down-regulates the expression of different bFGF isoforms in a dose-dependent manner, which is resulting from the change of the G- and/or GC-rich IRES activity. Thalidomide had been reported to be highly susceptible to hydrolysis in solution (Eriksson et al., 1998), and the present application further provides a method for increasing the bio-availability of thalidomide by a slow-release technology, such as encapsulated by liposome and TMC. Since the embodiments of the present invention show that the bio-availability of thalidomide would be increased by a relative slow-release technology, those applications based on the present invention and the relevant technologies disclosed in the literatures (such as Gomez-Orellana I. 2005; Lambkin I. et al. 2002; Lamprecht A, 2004; Li C. L. 2005; Mustata G. et al. 2006; Ranade V V. 1991; Rogers J A. et al. 1998; Taira M C. et al. 2004; Tiwari S B. et al. 2008; Zheng A P. et al. 2006) should all be under the spirits of the present invention.
[0099] All of the references cited herein are incorporated by reference in their entirety.
[0100] The foregoing description of the exemplary embodiments of the invention has been presented only for the purposes of illustration and description and is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations are possible in light of the above teaching.
[0101] The embodiments and examples were chosen and described in order to explain the principles of the invention and their practical application so as to enable others skilled in the art to utilize the invention and various embodiments and with various modifications as are suited to the particular use contemplated. Alternative embodiments will become apparent to those skilled in the art to which the present invention pertains without departing from its spirit and scope. Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing description and the exemplary embodiments described therein.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the right of priority based on Taiwan application Ser. No. 092200152, filed on Jan. 6, 2003, which is herein incorporated in its entirety by reference.
BACKGROUND
1. Field of the Invention
The invention relates to locking systems for securing personal computers.
2. Background of the Invention
Locks have a long history of application in securing personal property against theft and other unauthorized use. Reflecting their diverse applications, locks of varying styles have been designed for various applications. One such application is to secure personal computers and the components and information stored within them from theft and vandalism.
Existing locks for personal computers are generally designed to safeguard the valuable item as a whole, instead of the components inside. But the internal components of a computer are often far more valuable than the computer chassis, and because of their relative size, the internal components may be more likely to be stripped from a computer and stolen rather than the entire computer stolen. For example, personal computers often have a removable panel fixed in a closed position by screws, allowing maintenance and servicing of the computer inside. By simply removing these screws, a thief can gain access to the inside of the computer and take valuable components from it—even if the motherboard were fastened to a chassis that is securely locked to a stationary object, such as a desk. The owner can sustain a huge loss in assets due to this oversight. Accordingly, locks designed to safeguard the computer as a whole, instead of the components inside the computer, are insufficient to protect the valuable property of computer owners.
SUMMARY OF THE INVENTION
Accordingly, the invention provides a way to secure the internal components of computer equipment, for example, by preventing the opening of a computer chassis. To prevent access to inside a computer, a locking mechanism is installed over a screw that is used to secure a moveable panel of the computer chassis in a closed position. When installed, the locking mechanism prevents access to the screw, thereby preventing an unauthorized person from opening the panel of the chassis and having access to the contents therein. An authorized user, however, can open the chassis by unlocking the locking mechanism and removing it from the screw.
In one embodiment, the locking mechanism is used to lock a personal computer that has a movable panel secured by a screw that allows access to inside the computer. The locking mechanism includes a lock base and a lock head. The lock base includes a rear panel with a opening for accommodating the screw and two opposing wing panels each with an opening, the lock base configured to receive the screw through the opening of the rear panel when the screw is secured to the panel of the personal computer. Configured to attach to the lock base, the lock head includes a latch that is moveable between a closed position and an open position. When the screw is secured to the panel of the personal computer through the lock base and the latch of the lock head is in the open position, the lock head can be positioned over the lock base to cover and prevent access to the screw. Once positioned in this way, the latch of the lock head can be moved into the closed position to prevent the lock head from being removed from the lock base, thereby preventing access to the screw and the computer from being opened.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded view of a portion of a locking mechanism for a computer chassis, in accordance with an embodiment of the invention.
FIG. 2 is a view of a potion of a locking mechanism for a computer chassis, in accordance with an embodiment of the invention.
FIG. 3 is a view of a lock head for securing a computer chassis, in accordance with an embodiment of the invention.
FIG. 4 is a view of a locking mechanism installed on a computer chassis, in accordance with an embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 and 2 show a disassembled and an assembled view, respectively, of part of a locking mechanism for a computer chassis in accordance with an embodiment of the invention. The locking mechanism is for securing a computer chassis having a cover or panel 4 , which a user can open to gain access to any components inside the computer. In one embodiment, the panel 4 is the rear panel of a computer chassis. The panel 4 includes a screw hole 41 , through which a screw 2 is attached to the computer chassis to secure the panel 4 in a closed position, denying access to the insides of the computer. To open the panel 4 and gain access to any components inside the computer, therefore, a user must first remove the one or more screws 2 from the hole 41 .
In accordance with an embodiment of the invention, a locking mechanism comprises a lock base 1 , a screw 2 , and a lock head 3 . Although the lock base 1 can take many forms, in one design the lock base 1 includes two wing panels 11 , an upper panel 12 , a bottom panel 13 , and a rear panel 14 . The two wing panels 11 each have a hole 111 for accommodating a latch. The upper panel 12 and the bottom panel 13 may be shorter (i.e., extend from the rear panel 14 a shorter distance) than the wing panels 11 and do not reach the holes 111 in the wing panels 11 . The rear panel 14 of the lock base 1 has an opening 141 , preferably not tapped for a screw, through which the screw 2 can be passed to reach the screw hole 41 in the panel 4 .
The wing panels 11 , the upper panel 12 , the bottom panel 13 , and the rear panel 14 form a chamber 15 for holding the screw head 22 of the screw 2 . In one embodiment, these parts of the lock base 1 form a chamber 15 that is closed from the side, thereby preventing access to the screw head 22 —and thus turning of the screw 2 —from the side. The lock base 1 can be formed, for example, by folding a metal sheet as a whole, or by die-casting.
For convenience of use, the lock base 1 can be attached to the panel 4 over the hole 41 , for example, by soldering, welding, or a suitable adhesive. In this way, the lock base 1 stays in place during installation and removal of the lock. In an alternative embodiment, the lock base 1 is not attached to any panel or any computer chassis. This allows the lock base 1 to be used with a number of different types of computer equipment, so the locking mechanism described herein can be compatible with existing computer equipment not specifically designed therefor.
In one embodiment, the screw 2 comprises a screw head 22 and a threaded bolt 21 and is made from metal. As described above, the bolt 21 is smaller than the opening 141 in the lock base rear panel 14 so that it can be passed through the opening 141 , and the screw head 22 is larger than the opening 141 so the screw 2 will secure the lock base 1 in place. The screw 2 is designed to screw into the hole 41 of the panel 4 to lock the panel 4 in a closed position, thereby denying access to the inside of the computer. A slot, cross, hexagon, or other suitable socket 221 is grooved on top of the screw head 22 to facilitate turning and installation of the screw 2 using a tool, such as a screwdriver. The screw 2 may also include a washer 23 to keep the screw 2 in place when installed.
FIG. 3 shows a lock head 3 in accordance with one embodiment of the invention. The lock head 3 is designed to attach to the lock base 1 to prevent access to the screw 2 and thus opening of the panel 4 . In one embodiment, the lock head 3 comprises knob-shaped body that has a slot 31 formed therein, a movable latch 36 , and a key hole 35 . The movable latch 36 is activated through application of a matching key 34 in the key hole 35 . The slot 31 is wider than the distance between the two wing panels 11 of the lock base 1 to allow the lock head 3 to fit over the lock base 1 . The lock head further comprises a baffle plate 32 sized to match the chamber 15 of the lock base 1 and cover the screw head 22 when installed. Accordingly, in combination with the lock base 1 , this baffle plate 32 covers the chamber 15 and prevents any access to the screw 2 . Two gaps 33 between the baffle plate 32 and the inner wall of the slot 31 allow the two wing panels to be located in the gaps 33 when the locking mechanism is installed. FIG. 4 shows the lock head 3 installed on the lock base 1 to prevent access to the screw 2 and prevent opening of the panel 2 . In one embodiment, the lock head 3 includes a locking cable 37 for fixing the entire device, for example, to a desk or other stationary object.
To install the locking mechanism, the opening 141 of the lock base 1 is aligned with the screw hole 41 of the panel 4 . The bolt 21 of the screw 2 is then passed through the through the opening 141 in the lock base 1 and screwed into the screw hole 41 of the panel 4 . These steps are illustrated in FIGS. 1 and 2 . The screw 2 can be screwed into the hole 41 using a screwdriver turning the socket 221 . In this way, the lock base 1 is attached to the panel 4 , which is fixed in the closed position. When installed as described above, the screw head 22 is located in the chamber 15 , as shown in FIG. 2 .
To prevent access to and removal of the screw 2 , the lock head 3 is then installed over the lock base 1 and screw head 22 . Before installation, the latch 36 is placed in an open position to allow the lock head 3 to be placed over the lock plate 1 . To open or close the latch 36 , a key 34 is inserted into the key hole 35 and turned. When the lock head 3 is mounted on the lock base 1 , the wing panels 11 slide in the gaps 33 , and the baffle plate 32 block the front opening of the chamber 15 . To secure the lock head 3 in this position, the latch 36 is activated so that it passes through the holes 111 in the wing panels 11 . In this way, the lock head 3 cannot be removed from the lock base 1 . When the latch 36 in the lock head 3 is positioned through the holes 111 in the wing panels 11 , it is impossible to remover the screw 2 from the screw hole 41 until the lock head 3 is again removed. For example, the baffle plate 32 and lock base 1 together prevent access to the screw 2 , even by using a tool such as a screwdriver or by turning the lock base 1 . This effectively prevents thieves from opening the computer chassis and taking the components therein.
The foregoing description of the embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Persons skilled in the relevant art can appreciate that many modifications and variations are possible in light of the above teaching. It is therefore intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto. | A locking mechanism for a personal computer is installed over a screw that is used to secure a moveable panel of the computer's chassis in a closed position. When installed, the locking mechanism prevents access to the screw, thereby preventing an unauthorized person from opening the panel of the chassis and having access to the contents therein. In one embodiment, the locking mechanism includes a lock base for receiving the screw and a lock head for being positioned over the lock base to cover and prevent access to the screw. | 4 |
FIELD OF THE INVENTION
This Application is based on U.S. provisional application No. 60/006,243 filed Nov. 3, 1995.
The present invention relates to a mobile drilling unit and more particularly to a unit mounted on a single mobile platform capable of both coiled tubing and conventional drilling and servicing of bore holes.
BACKGROUND OF THE INVENTION
Increasingly, the drilling of oil and gas wells is no longer a matter of drilling a vertically straight bore hole from the surface to the zone of hydrocarbon recovery using a traditional drilling platform surmounted by a derrick, the derrick supporting a string of jointed drill pipe with a bit connected to the lower end of the string. Rather, technology and techniques have been developed to deviate the bore's trajectory at angles of up to and sometimes exceeding 90° from the vertical. Directional drilling offers numerous advantages including new approaches to oil and gas traps having non-conventional geometries, economic zone enhancement as can occur for example if the bore hole actually follows an oil or gas bearing strata, improved economics particularly in an over-pressured environment (when formation pressure is sufficient to force hydrocarbons to the surface at potentially explosive rates) and reduced environmental degradation.
After deviating a bore hole from the vertical, it's obviously no longer completely practical to sustain continuous drilling operations by rotating the drill string and the connected bit. Preferably, only the bit, but not the string, is rotated by a downhole motor attached to the lower end of the string, the motor typically consisting of a rotor-stator to generate torque as drilling fluid passes therethrough, a bent housing to deviate the hole by the required amount and which also encloses a drive shaft therethrough to transmit the rotor/stator's torque to a bearing assembly, and a bit rotatably supported at the downhole end of the bearing assembly for cutting the bore hole. This equipment all forms part of a bottom hole assembly (BHA).
Electronic means supported by a mule shoe in the bottom hole assembly and connected to the surface by a wire line passing through the interior of the drill string transmits information with respect to the degree and azimuth of the bore hole's trajectory so that it can be plotted and necessary adjustments made. Sometimes these adjustments require changing of the BHA, in which event the drill string must be tripped out and then back into the well. Each time the motor requires service, or a change in the hole's trajectory is required, this process must be repeated. This results in substantial costs and down time largely due to the time required to make and break all of the joints as the drill string is tripped in and out of the hole.
SUMMARY OF THE INVENTION
To overcome this problem, discrete lengths of jointed drill pipe are replaced whenever feasible with coiled tubing which is a single length of continuous, unjointed tubing spooled onto a reel for storage in sufficient quantity to exceed the maximum length of the bore hole being drilled. The injection and withdrawal of the tubing can be accomplished more rapidly in comparison with conventional drill pipe due in large part to the elimination of joints. However, as with conventional pipe, drilling mud and wire lines for downhole instrumentation pass through the tubing's interior.
Coiled tubing has been extensively used for well servicing as well as for workovers within previously drilled holes.
More recently, tools and methods have been developed for the actual drilling of bore holes using coiled tubing and reference is made in this regard to U.S. Pat. No. 5,215,151 describing one such system.
Nevertheless, and even though the results of coiled tubing drilling to date indicate that this method might eventually replace conventional jointed pipe technology, coiled tubing drilling technology is still being perfected and remains virtually in its infancy. Conventional and coiled tubing drilling continue therefore to co-exist and will for some time. Because coiled tubing drilling technology is still nascent, there have been until now no significant advances in providing equipment capable of performing both conventional and coiled tubing drilling in a combination unit for a complete drilling and pipe handling service.
It is therefore an object of the present invention to provide a self-contained unit that facilitates the safe handling of both flexible coiled tubing and conventional jointed pipe. In a preferred embodiment, the present invention provides a drilling unit for coiled tubing drilling including a mobile collapsible sub-structure and a derrick mounted on a single mobile platform such as a wheeled or tracked trailer. The unit is therefore fully functional for coiled tubing drilling in an underbalanced (over-pressured) or balanced condition and will also handle conventional jointed pipe for drilling with a mud motor or power swivel.
When the coiled tubing drilling system is not in use, the unit can be used for pulling and running jointed pipe such as tubing and casing by using the main draw works as in a conventional operation. The present unit can be mounted on a tridem trailer and is adapted to mechanically fold down to legal transport dimensions. Preferred features include the rear of the trailer being designed to encompass the wellhead and blowout preventers with the mast situated directly overhead, a two-legged mast, a collapsible sub-floor to hold the tubing injector on a hydraulically controlled, telescopically adjustable injector frame with the collapsible sub-floor being movable into place using the mast's main draw works, the sub-floor also acting as a work platform for the operating personnel, and a pin arrangement that can be used to removably mount the tubing injector to the injector frame. The pin arrangement is telescopically associated with the frame and can be raised or lowered by the blocks in the mast when the car is positioned over the wellhead and underneath the injector. Power tongs are suspended from the mast by a cable operated from a jib crane.
Having a mast block for raising and lowering equipment can eliminate the need for a separate crane at the well site.
In another preferred embodiment, the telescopic frame for the tubing injector is supported on rails where it can be controlled and moved hydraulically which allows for remote control as well as quicker and easier positioning of the injector than is currently possible on existing systems. Since all functions can be controlled hydraulically, the present unit is capable of operating with reduced manpower compared to conventional rigs. The ability to operate the equipment remotely eliminates the need to have personnel on the floor during drilling operations.
Thus, the present unit with its flexibility of handling heights and weights of all required equipment including both types of tubing can substantially reduce the amount of equipment on location, reduce drilling time and facilitate a safe way to drill in underbalanced conditions. As well, rigging in and out times are substantially reduced. The mast is also capable of handling BHA's, a lubricator for pressure deployment, the running of jointed pipe and it can also support the tubing string weight in the sub-floor itself.
According to the present invention then, there is provided apparatus for the drilling and servicing of bore holes in the earth, comprising a first sub-assembly adapted for the drilling and servicing of bore holes using jointed and coiled tubing, a second sub-assembly adapted for the drilling and servicing of bore holes using a continuous length of coiled tubing, and platform means adapted to support said first and second sub-assemblies thereon.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the present invention will now be described in greater detail and will be better understood when read in conjunction with the following drawings, in which:
FIG. 1 is a side elevational partially schematic view of the present hybrid unit with the derrick in a raised position;
FIG. 2 is a schematical rear elevational view of the unit of FIG. 1;
FIG. 3 is a plan view of the hybrid unit of FIG. 1;
FIG. 4 is a side elevational view of the hybrid drilling unit of FIG. 1 in a collapsed transport mode;
FIG. 5 is a plan view of the hybrid drilling unit of FIG. 4 in the transport mode;
FIG. 6 is a side elevational, partially exploded view of a telescopic injector frame forming part of the present unit;
FIG. 7 is an end elevational view of the base frame of the frame assembly of FIG. 6;
FIG. 8 is a plan view of the frame of FIG. 6; and
FIG. 9 is an end elevational view of the teleframe portion of the frame of FIG. 6.
DETAILED DESCRIPTION
With reference to the drawings, FIGS. 1, 2 and 3 show the present unit 1 deployed for drilling. The unit comprises, generally, a trailer 40, which may be wheeled, tracked or skidded which supports a first sub-assembly 25 for conventional jointed pipe drilling and a second sub-assembly 75 for coiled tubing drilling.
First sub-assembly 25 includes a pivotable derrick or mast 2 having the usual crown and sheaves 3, block hook 13 and a mast raising hydraulic ram 7. Ram 7 pivots mast 2 about a hinge 8 on lower mast frame 9 between the raised position of the mast shown in FIG. 1 and the lowered, transport position shown in FIG. 4. The mast additionally includes a wire rope 23 for raising and lowering hook 13, some cat line blocks 28 and a jib crane 39 with its own wire rope 47 for suspending power tongs and a backup 35 from the rear of the mast. Hook 13 is raised and lowered by wire rope 23 actuated by a main winch or draw works 14. The unit also includes a separate cat line winch 10 (FIG. 5). A spool 16 (FIG. 5) is provided for wire rope storage and adjacent the spool is a slick line winch 22. A fast line sheave 18 is provided at the base of lower mast frame 9. As best seen in FIG. 5, trailer 40 also supports a wire rope anchor 21 and a catline sheave 23.
Sub-assembly 75 for coil tubing drilling is supported on a collapsible sub-floor 11 which sits atop front pivot legs 6, back pivot legs 15 and back legs 19. With sub-floor 11 in the position shown in FIG. 1, the sub-floor is anchored to the tops of non-pivoting back legs 19 such as by means of pins and is additionally supported in the upright position by removable diagonal braces 41. A telescopic injector frame 5 is movably supported in floor 11 forwardly of mast 2 by means of rails 43 in the sub-floor and cooperating trolley-type wheels 44 on the frame. The frame therefore becomes an adjustable trolley car that supports a coiled tubing drilling injector 30 thereon, the injector including a guide arch 31 that guides the coiled tubing from a coiled tubing storage reel (not shown) into the injector. Injector 30 and frame 5 can be connected to one another by a pin arrangement. The injector can be raised and lowered relative to the frame using hook 13 suspended from mast 2.
Frame 5 is telescopic for adjustments to the height of injector 30 above sub-floor 11. Reference is made to FIGS. 6 to 9 showing frame 5 in greater detail, the frame comprising two main sub-assemblies, a base frame 50 and a telescopically associated teleframe 70. As seen particularly from FIGS. 6 and 7, base frame 50 is generally an open rectangular frame work including four hollow uprights 51, fixed upper and lower cross members 52, fixed cross members 54 spanning the width of the frame and removable lower cross bars 55, the ends of which connect to brackets 57 on the uprights by means of retractable pins 58. Wheels 44 are located at the lower ends of the uprights and are rotatably mounted within protective housings 46.
Upper cross members 52 are set down from the tops of the uprights to provide clearance for brackets 64 that support horizontally aligned hydraulic cylinders 66. The piston rods 67 of each cylinder support a locking pin 68 oriented to pass through holes 69 in the uprights. As will be described below, these pins also pass through holes in the uprights of the teleframe so that its position relative to the base frame can be adjusted.
With reference once again to FIG. 6, teleframe 70 includes four uprights 76 each of which is sized to be telescopically and slidably received into respective ones of uprights 51 on base frame 50. Each upright is formed with a plurality of holes 73 spaced apart at predetermined intervals to selectively align with the holes 69 in uprights 51 for insertion of pins 68. The top of each upright 76 is "boxed" in by a rectangular metal box sleeve 77 connected to the tops of the uprights such as by means of nuts and bolts 78. The sleeves act as stops to limit the insertion of the teleframe uprights into the base frame uprights and also as points of connection for the ends of cylinders 85, seen best in FIGS. 8 and 9, extending across the width of the teleframe adjacent each of its ends. Each of the cylinders 85 slidably supports an annular sleeve 87, the length of which is less than the distance between adjacent bracketing box sleeves 77. These annular sleeves can therefore move from side to side along respective cylinders 85. This movement can be controlled hydraulically by co-acting hydraulic cylinders 90 connected between a box sleeve 77 and a respective annular sleeve 87 as shown most clearly in FIG. 9.
A longitudinally extending ladder frame 95 is rigidly connected to and between annular sleeves 87 for movement in tandem with these sleeves. Welded or otherwise rigidly connected to the ladder frame adjacent its corners are extensions 100, each of which supports one or more vertically oriented tubular sleeves 101. Each sleeve is adapted to receive a flanged and chamfered pin 105 which is connected to the sleeve for example by means of a retractable pin 106. Injector 30 is adapted to engage these pins when lowered onto frame 5. The position of the injector relative to mast 2 can therefore be adjusted both in the back-and-forth directions by movement of frame 5 along rails 43, and from side-to-side by movement of sleeves 87 along cylinders 85. These adjustments are useful to more precisely align the injector with the wellhead. Adjustments to the height of the injector are made by suspending the injector from hook 13, activating cylinders 66 to withdraw locking pins 68, using mast 2 to raise or lower the injector the required amount to align selected holes 73 with holes 69 in the base frame's uprights and reactivating the cylinders to reinsert the locking pins. Obviously, the height of the teleframe can be adjusted before or after installation of the injector.
As mentioned previously, the rear of trailer 40 is designed to encompass a wellhead and/or blowout preventers. This will be seen most clearly from FIG. 5 showing the trailer from above with the mast collapsed into its transport position. As will be seen, the end of the trailer defines a bay 110 that is positioned about the wellhead/blowout preventers. A removable gate 111 is opened when positioning the trailer, and is closed after positioning of the unit. With reference to FIG. 4, the unit is provided with levelling jacks 120 and hydraulic controls 125 can be conveniently located in the sides of the trailer. The units' hydraulics are conventional and will be apparent to those skilled in the art without the need for further detailed description. Trailer 40 will also include all of the usual equipment and hookups for electrical power, well logging, controls, safety equipment and so forth. These systems are known in the art, and a detailed description is therefore being omitted.
A remotely controlled tubing pulling winch 29 located directly underneath collapsible floor 11 within trailer frame 40 is used for pulling the coil tubing over the guide arch 31 into injector 30.
Collapsible floor 11 incorporates a working platform 25 including foldable platform extensions 24 provided about each of sub-assemblies 25 and 75 for operating personnel. Collapsible sub-floor 11, including frame 5, is slung or pivoted into the position shown in FIG. 1 using the main draw works of mast 2. The floor can be similarly lowered into the collapsed transport position shown in FIG. 4 using the draw works after the floor is disconnected from back legs 19 and braces 41 removed. As will be seen from FIG. 4, in this collapsed position, front pivot legs 6 and back pivot legs 15 are folded over about their respective pivot points to lie atop the trailer's flat bed. Platform extensions 24 are folded up to be out of the way for transport purposes. Injector 30 and guide arch 31 are removed from the unit prior to collapse into the transport mode. Mast supports 27 support the upper end of mast 2 when lowered into the transport position again shown in FIG. 4.
The above-described embodiments of the present invention are meant to be illustrative of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications, which would be readily apparent to one skilled in the art, are intended to be within the scope of the present invention. The only limitations to the scope of the present invention are set out in the following appended claims. | There is described an apparatus for the drilling and servicing of bore holes in the earth, comprising a first sub-assembly adapted for the drilling and servicing of bore holes using jointed and coiled tubing, a second sub-assembly adapted for the drilling and servicing of bore holes using a continuous length of coiled tubing, and a platform adapted to support the first and second sub-assemblies thereon. | 4 |
[0001] This application is a divisional of co-pending U.S. application Ser. No. 11/049,058, filed on Feb. 3, 2005, which claims the benefit of the Korean Patent Application Nos. P2004-07244, P2004-07247, P2004-07248, and P2004-07249 filed on Feb. 4, 2004. All of these applications are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to an electro-luminescence display, and more particularly to an electro-luminescence display that is adaptive for reducing its manufacturing cost as well as reducing its process time.
[0004] 2. Description of the Related Art
[0005] Recently, there have been highlighted various flat panel display devices reduced in weight and bulk that is capable of eliminating disadvantages of a cathode ray tube (CRT). Such flat panel display devices include a liquid crystal display (LCD), a field emission display (FED), a plasma display panel (PDP) and an electro-luminescence (EL) display, etc.
[0006] The EL display in such display devices is a self-luminous device capable of light-emitting a phosphorous material by a re-combination of electrons with holes. The EL display device is generally classified into an inorganic EL device using the phosphorous material as an inorganic compound and an organic using it as an organic compound. Such an EL display device has an advantage the its response speed is as fast as the cathode ray tube CRT when compared with a passive luminous device that requires a separate light source like that liquid crystal display. The EL display device also has many advantages of a low voltage driving, a self-luminescence, a thin-thickness, a wide viewing angle, a fast response speed and a high contrast, etc. such that it can be highlighted into a post-generation display device.
[0007] FIG. 1 is a sectional diagram illustrating a general organic EL structure for explanation of light emission principle of an EL display device. The organic EL includes an electron injection layer 4 , an electron carrier layer 6 , a light-emitting layer 8 , a hole carrier layer 10 , a hole injection layer 12 between a cathode 2 and an anode 14 .
[0008] When a voltage is applied between the anode 14 of a transparent electrode and the cathode 2 of a metal electrode, an electron generated from the cathode 2 moves to the light-emitting layer 8 through the electron injection layer 4 and the electron carrier layer 6 . Also, a hole generated from the anode 14 moves to the light-emitting layer 8 through the hole injection layer 12 and the hole carrier layer 10 . Accordingly, the electrons are collided with the holes at the light-emitting layer 8 , wherein the electrons and the holes are supplied from the electron carrier layer 6 and the hole carrier layer 10 , and the electrons and the holes are recombined to generate light. The generated light is emitted through the anode 14 to display a picture. The light-emission brightness of the EL organic device is not proportional to the voltage flowing in both ends of the device, but it is proportional to a supply current, thus the anode 14 is usually connected to a static current source.
[0009] FIG. 2A is a diagram illustrating a general EL display device.
[0010] Referring to FIG. 2A , an EL display device includes an EL display panel 20 having EL cells 28 arranged at each intersection of scan electrode lines SL and data electrode lines DL, a scan driver 22 to drive the scan electrode lines SL, a data driver 24 to drive the data electrode lines DL, and a gamma voltage supplier 26 to supply reference gamma voltages to the data driver 24 .
[0011] Each of the EL cells 28 is selected when a scan pulse is applied to the scan electrode line SL, which is a cathode, to generate a light corresponding to a pixel signal, i.e., data signal or current signal, supplied to the data electrode line DL, which is an anode. Each of the EL cells 28 operates substantially in the same manner as a diode connected between the data electrode line DL and the scan electrode line SL to be equivalent. Accordingly, each of the EL cells 28 supplies a negative scan pulse to the scan electrode line SL, and at the same time applies a positive current according to a data signal to the data electrode line DL, thereby emitting light when a forward voltage is applied. Differently from this, the EL cells 28 included in the unselected scan line do not emit light due to a reverse bias voltage.
[0012] The scan driver 22 sequentially supplies the negative scan pulse to a plurality of scan electrode lines SL.
[0013] The data driver 24 includes more than one data integrated circuit 30 . As the EL display panel 20 becomes bigger, the number of data integrated circuits 30 , which form the data driver 24 , is larger. On the other hand, the data driver 24 might be composed of one data integrated circuit 30 as in FIG. 2B when the EL display panel 20 is made in a small panel like the display panel of a mobile phone.
[0014] In this way, the conventional EL display device supplies the current signal, which is proportional to an input data, to each of the EL cells 28 to make the EL cells 28 emit light, thereby displaying a picture. EL cells 28 is composed of an R cell having a red (hereinafter, “R”) phosphorus, a G cell having a green (hereinafter, “G”) phosphorus, and a B cell having a blue (hereinafter, “B”) phosphorus, for materializing color.
[0015] Each of R, G, B phosphorus's has different efficiency from each other. In other words, the brightness level of R, G, B cells are different from each other in case that data signals of same level to R, G, B cells. Accordingly, the gamma voltages are set differently from each other by R, G, B in comparison with the same brightness in order to meet white balance. The gamma voltage supplier 26 generates a different reference gamma voltage by R, G, B.
[0016] FIG. 3 is a circuit diagram illustrating in detail a gamma voltage supplier 26 shown in FIGS. 2A and 2B .
[0017] Referring to FIG. 3 , the prior art gamma voltage supplier 26 includes an R gamma voltage supplier 32 , a G gamma voltage supplier 34 , a B gamma voltage supplier 36 for supplying each of the different reference gamma voltages by R, G, B.
[0018] The R gamma voltage supplier 32 includes a divided voltage resistors r_R 1 , r_R 2 , r_R 3 connected in series between a supply voltage source VDD and a ground voltage source GND. A divided voltage generated at nodes n 1 , n 2 between the divided voltage resistors r_R 1 , r_R 2 , r_R 3 is supplied to the data driver 24 as a reference gamma voltage. The voltage of the first node n 1 is used as an R reference gamma voltage VH_R of low gray level, and the voltage of the second node n 2 is used as an R reference gamma voltage VL_R of high gray level.
[0019] The G gamma voltage supplier 34 includes a divided voltage resistors r_G 1 , r_G 2 , r_G 3 connected in series between a supply voltage source VDD and a ground voltage source GND. A divided voltage generated at nodes n 3 , n 4 between the divided voltage resistors r_G 1 , r_G 2 , r_G 3 is supplied to the data driver 24 as a reference gamma voltage. The voltage of the third noden 3 is used as a G reference gamma voltage VH_G of low gray level, and the voltage of the fourth node n 4 is used as a G reference gamma voltage VL_G of high gray level.
[0020] The B gamma voltage supplier 36 includes a divided voltage resistors r_B 1 , r_B 2 , r_B 3 connected in series between a supply voltage source VDD and a ground voltage source GND. A divided voltage generated at nodes n 5 , n 6 between the divided voltage resistors r_B 1 , r_B 2 , r_B 3 is supplied to the data driver 24 as a reference gamma voltage. The voltage of the fifth noden 5 is used as a G reference gamma voltage VH_B of low gray level, and the voltage of the sixth node n 6 is used as a G reference gamma voltage VL_B of high gray level.
[0021] In other words, the prior art gamma voltage supplier differently supplies the reference gamma voltage, which corresponds to each of the R cell, the G cell and the B cell, to the data driver 24 . On the other hand, the gamma voltage supplier includes a plurality of the R gamma voltage supplier 32 , the G gamma voltage supplier 34 , and the B gamma voltage supplier 36 , as in FIG. 3 , so that a light of different brightness could be generated in correspondence to an external environment. For example, the gamma voltage supplier 26 can includes three each of the R gamma voltage supplier 32 , the G gamma voltage supplier 34 , and the B gamma voltage supplier 36 so that three modes of reference gamma voltage could be supplied in correspondence to night, day and the external environment. In this case, the number of total resistors included in the gamma voltage supplier 26 has to increase to 27 .
[0022] The data integrated circuit 30 divides voltage as much as the gray levels, which are capable of expressing the reference gamma voltage supplied from the gamma voltage supplier 26 , to generate an analog data which corresponds to each gray level. For this, the data integrated circuit 30 includes a shift register 40 , a first latch array 42 , a second latch array 44 , a digital analog converter (hereinafter, referred to as “DAC”), and an output array 48 .
[0023] The shift register 40 generates a sampling signal to sample data while shifting a start pulse in accordance with a shift clock.
[0024] The first latch array 42 includes a first R latch part 42 a , a first G latch part 42 b and a first B latch part 42 C. The first R latch part 42 a samples an R data in accordance with the sampling signal supplied from the shift register 40 and temporarily stores the R data. The first G latch part 42 b samples a G data in accordance with the sampling signal supplied from the shift register 40 and temporarily stores the G data. The first B latch part 42 C samples a B data in accordance with the sampling signal supplied from the shift register 40 and temporarily stores the B data.
[0025] The second latch array 44 supplies the data from the first latch array 42 to the DAC 46 in response to an output enable signal. For this, the second latch array 44 includes a second R latch part 44 a , a second G latch part 44 b and a second B latch part 44 C. The second R latch part 44 a supplies the data from the first R latch part 42 a to the DAC 46 in response to the output enable signal. The second G latch part 44 b supplies the data from the first G latch part 42 b to the DAC 46 in response to the output enable signal. The second B latch part 44 c supplies the data from the first B latch part 42 c to the DAC 46 in response to the output enable signal.
[0026] The DAC 46 converts the data from the second latch array 44 into the analog data and outputs the converted data to the output array 48 in use of the reference gamma voltage VH_R, VL_R, VH_G, VL_G, VH_B, VL_B. For this, the DAC 46 includes an R DAC 46 a , a G DAC 46 b and a B DAC 46 c.
[0027] The R DAC 46 a receives the R reference gamma voltage VH_R of low gray level and the R reference gamma voltage VL_R of high gray level from the gamma voltage supplier 26 . And the R DAC 46 a generates a plurality of gamma voltages in use of the R reference gamma voltage VH_R of low gray level and the R reference gamma voltage VL_R of high gray level. For example, the R DAC 46 a generates sixty four analog gamma voltages assuming that there is a six bit input data. And the R DAC 46 a selects the analog gamma voltage corresponding to the digital data from the second R latch part 44 a as the analog data which is to be supplied to the data line DL.
[0028] The G DAC 46 b receives the G reference gamma voltage VH_G of low gray level and the G reference gamma voltage VL_G of high gray level from the gamma voltage supplier 26 . And the G DAC 46 b generates a plurality of gamma voltages in use of the G reference gamma voltage VH_G of low gray level and the G reference gamma voltage VL_G of high gray level. For example, the G DAC 46 b generates sixty four analog gamma voltages assuming that there is a six bit input data. And the G DAC 46 b selects the analog gamma voltage corresponding to the digital data from the second G latch part 44 b as the analog data which is to be supplied to the data line DL.
[0029] The B DAC 46 c receives the B reference gamma voltage VH_B of low gray level and the B reference gamma voltage VL_B of high gray level from the gamma voltage supplier 26 . And the B DAC 46 C generates a plurality of gamma voltages in use of the B reference gamma voltage VH_B of low gray level and the B reference gamma voltage VL_B of high gray level. For example, the B DAC 46 c generates sixty four analog gamma voltages assuming that there is a six bit input data. And the B DAC 46 c selects the analog gamma voltage corresponding to the digital data from the second B latch part 44 c as the analog data which is to be supplied to the data line DL.
[0030] The output array 48 supplies the analog data supplied from the DAC 46 to the data electrode lines DL. For this, the output array 48 includes a first output part 48 a , a second output part 48 b , a third output part 48 c . A first output part 48 a supplies the analog data from the R DAC 46 a to the data electrode lines DL which is for supplying data to the R cells. The second output part 48 b supplies the analog data from the G DAC 46 b to the data electrode lines DL which is for supplying data to the G cells. The third output part 48 c supplies the analog data from the B DAC 46 c to the data electrode lines DL which is for supplying data to the B cells.
[0031] As a result, the gamma voltage supplier 26 supplies the reference gamma voltages, which corresponds to the R cell, the G cell and the B cell and are different from each other, to the data driver 24 , and the data driver 24 generates the data signal, which is to be supplied to the R cell, the G cell and the B cell in use of the different reference gamma voltage.
[0032] And yet, the related art EL display device might have the brightness deviation generated between the EL display panels 20 by the deviation of manufacturing process. In other words, the brightness might be different in the same data in accordance with the EL display panel 20 . In order to reduce such a brightness deviation, in the prior art, the resistance value of the resistors included in the gamma voltage supplier 26 is controlled to reduce the brightness deviation between the EL display panels 20 . However, if the brightness deviation is compensated with the resistance value of the resistors, its process time is lengthened due to the adjustment time required for optimization of the resistance value or the replacement time of the resist, thus it is impossible to compensate the exact brightness deviation only by the adjustment of the resistance value.
[0033] The data integrated circuit 30 is mounted on a chip on film COF 50 as in FIG. 5 , the resistors of the gamma voltage supplier 26 are mounted on a flexible printed circuit FPC 52 due to many resistors, which is difficult to be mounted on the COF 50 . Because of many resistors of the gamma voltage supplier 26 like this, it is difficult to secure a margin in designing the FPC. Terminals of one side of the FPC 52 are connected to the COF 50 and terminals of the other side are connected to a printed circuit board PCB (not shown). Due to such FPC 52 and COF 50 , there is a problem that the prior art EL display device has high manufacturing cost due to the FPC 52 , and time is required for aligning the FPC 52 with the COF 50 .
SUMMARY OF THE INVENTION
[0034] Accordingly, it is an object of the present invention to provide an electro-luminescence display that is adaptive for reducing its manufacturing cost as well as reducing its process time.
[0035] In order to achieve these and other objects of the invention, an electro-luminescence display device according to an aspect of the present invention includes a gamma generator to output a reference gamma voltage corresponding to a control data supplied from the outside; and at least one data integrated circuit to receive a data from the outside and to generate a data signal corresponding to the bit number of the data in use of the reference gamma voltage.
[0036] The gamma generator may include: a red gamma part to generate a red reference gamma voltage so that the data signal to be supplied to a red cell can be generated; a green gamma part to generate a green reference gamma voltage so that the data signal to be supplied to a green cell can be generated; and a blue gamma part to generate a blue reference gamma voltage so that the data signal to be supplied to a blue cell can be generated.
[0037] Each of the red gamma part, the green gamma part and the blue gamma part may include: a first resist part and a second resist part to divide the voltage of a supply voltage source; a first analog digital converter to divide the divided voltage supplied from the first resist part into a plurality of voltage levels; a second analog digital converter to divide the divided voltage supplied from the second resist part into a plurality of voltage levels; and a register to supply a first control data so that any one voltage can be outputted in the first analog digital converter, as well as to supply a second control data to that any one voltage can be outputted in the second analog digital converter.
[0038] Each of the first and second resist parts may include three resistors so that the voltage of the supply voltage source can be divided into two voltage values.
[0039] Bit values of the first and second control data may be set to enable the electro-luminescence display device to display uniform brightness.
[0040] The gamma generator and the data integrated circuits may be mounted on a chip-on-film COF.
[0041] The red reference gamma voltage, the green reference gamma voltage, the red reference gamma voltage may be set for a white balance to be balanced in red, green and blue cells.
[0042] The gamma generator may be integrated in the inside of the data integrated circuit.
[0043] An electro-luminescence display device according to another aspect of the present invention includes a gamma generation voltage supplier to generate a plurality of gamma generation voltages; a reference gamma generator to generate a plurality of reference gamma voltages in use of the gamma generation voltages; and at least one data integrated circuit to divide the reference gamma voltage into a plurality of voltage levels and to generate a data signal by selecting any one voltage level among the voltage levels in correspondence to a data from the outside.
[0044] The gamma generation voltage supplier may include: a red gamma generation voltage part to generate a red gamma generation voltage of high gray level and a red gamma generation voltage of low gray level; a green gamma generation voltage part to generate a green gamma generation voltage of high gray level and a green gamma generation voltage of low gray level; and a blue gamma generation voltage part to generate a blue gamma generation voltage of high gray level and a blue gamma generation voltage of low gray level.
[0045] Each of the red, green and blue gamma generation voltage parts may include: a first divided voltage resistor and a second divided voltage resistor installed between a supply voltage source and a ground voltage source in order to generate the gamma generation voltage of high gray level; and a third divided voltage resistor and a fourth divided voltage resistor installed between the supply voltage source and the ground voltage source in order to generate the gamma generation voltage of low gray level.
[0046] The reference gamma generator may include: a red reference gamma generator to generate a red reference gamma voltage of high gray level and a red reference gamma voltage of low gray level in use of the red gamma generation voltage of high gray level and the red gamma generation voltage of low gray level; a green reference gamma generator to generate a green reference gamma voltage of high gray level and a green reference gamma voltage of low gray level in use of the green gamma generation voltage of high gray level and the green gamma generation voltage of low gray level; and a blue reference gamma generator to generate a blue reference gamma voltage of high gray level and a blue reference gamma voltage of low gray level in use of the blue gamma generation voltage of high gray level and the blue gamma generation voltage of low gray level.
[0047] Each of the red, green and blue reference gamma generator may include: a first analog digital converter to receive a first reference voltage that has a higher voltage value than the gamma generation voltage of low gray level and the gamma generation voltage of low gray level, and to divide the received voltage into a plurality of first voltage levels; a second analog digital converter to receive a second reference voltage that has a lower voltage value than the gamma generation voltage of high gray level and the first reference voltage, and to divide the received voltage into a plurality of second voltage levels; and a register to supply a first control data so that any one voltage among the first voltage levels can be outputted in the first analog digital converter, as well as to supply a second control data to that any one voltage among the second voltage levels can be outputted in the second analog digital converter.
[0048] The number of the second voltage levels voltage-divided at the second analog digital converter may be set to be higher than the number of the first voltage levels voltage-divided at the first analog digital converter.
[0049] The first and second control data may be set to enable the electro-luminescence display devices to display uniform brightness.
[0050] The gamma generation voltage supplier may include: a red gamma generation voltage part to generate a red first reference voltage, a red gamma generation voltage of low gray level that has a lower voltage value than the red first reference voltage, a red second reference voltage that has a lower voltage value than the red first reference voltage, and a red gamma generation voltage of high gray level that has a lower voltage value than the red second reference voltage; a green gamma generation voltage part to generate a green first reference voltage, a green gamma generation voltage of low gray level that has a lower voltage value than the green first reference voltage, a green second reference voltage that has a lower voltage value than the green first reference voltage, and a green gamma generation voltage of high gray level that has a lower voltage value than the green second reference voltage; and a blue gamma generation voltage part to generate a blue first reference voltage, a blue gamma generation voltage of low gray level that has a lower voltage value than the blue first reference voltage, a blue second reference voltage that has a lower voltage value than the blue first reference voltage, and a blue gamma generation voltage of high gray level that has a lower voltage value than the blue second reference voltage.
[0051] Each of the red, green and blue gamma generation voltage parts may include: three first divided voltage resistors installed between a supply voltage source and a ground voltage source in order to generate the first reference voltage and the gamma generation voltage of low gray level; and three second divided voltage resistors installed between the supply voltage source and the ground voltage source in order to generate the second reference voltage and the gamma generation voltage of high gray level.
[0052] The reference gamma generator may include: a red reference gamma generator to generate a red reference gamma voltage of high gray level and a red reference gamma voltage of low gray level in use of the red first reference voltage, the red gamma generation voltage of low gray level, the red second reference voltage and the red gamma generation voltage of high gray level; a green reference gamma generator to generate a green reference gamma voltage of high gray level and a green reference gamma voltage of low gray level in use of the green first reference voltage, the green gamma generation voltage of low gray level, the green second reference voltage and the green gamma generation voltage of high gray level; and a blue reference gamma generator to generate a blue reference gamma voltage of high gray level and a blue reference gamma voltage of low gray level in use of the blue first reference voltage, the blue gamma generation voltage of low gray level, the blue second reference voltage and the blue gamma generation voltage of high gray level.
[0053] Each of the red, green and blue reference gamma generators may include: a first analog digital converter to divide the first reference voltage and the gamma generation voltage of low gray level into a plurality of first voltage levels; a second analog digital converter to divide the second reference voltage and the gamma generation voltage of high gray level into a plurality of second voltage levels; and a register to supply a first control data so that any one voltage among the first voltage levels can be outputted in the first analog digital converter, as well as to supply a second control data to that any one voltage among the second voltage levels can be outputted in the second analog digital converter.
[0054] The number of the second voltage levels voltage-divided at the second analog digital converter may be set to be higher than the number of the first voltage levels voltage-divided at the first analog digital converter.
[0055] The first and second control data may be set to enable the electro-luminescence display devices to display uniform brightness.
[0056] The reference gamma generator is integrated in the inside of the data integrated circuit.
[0057] An electro-luminescence display device according to still another aspect of the present invention may include: a red reference gamma generator, a green reference gamma generator and a blue reference gamma generator each having three digital analog converters or more in order to generate a reference gamma voltage of low gray level and a reference gamma voltage of high gray level; and at least one integrated circuit to generate a data signal in use of the reference gamma voltage of low gray level and the reference gamma voltage of high gray level.
[0058] Each of the red, green and blue reference gamma generators may include: a first digital analog converter to divide a voltage supplied to itself in order to generate i (i is a natural number) numbers of voltage levels; a second digital analog converter to divide a voltage supplied to itself in order to generate j (j is a smaller natural number than i) numbers of voltage levels; and a third digital analog converter to receive two voltage levels from the second digital analog converter and to divides the two received voltage levels into j numbers of voltage levels.
[0059] The first digital analog converter may select any one voltage among the i numbers of voltage levels, as the reference gamma voltage of low gray level, to supply the selected voltage to the integrated circuit.
[0060] The third digital analog converter may select any one voltage among the j numbers of voltage levels generated by itself, as the reference gamma voltage of high gray level, and to supply the selected voltage to the integrated circuit.
[0061] The second digital analog converter may supply two voltage levels adjacent to each other among the j numbers of voltage levels generated by itself, to the third digital analog converter.
[0062] Each of the red, green and blue reference gamma generation parts further may include a register storing control data's that control the output of the first digital analog converter, the second digital analog converter and the third digital analog converter.
[0063] The control data's stored at the register may be set to enable the electro-luminescence display devices to display uniform brightness.
[0064] The red reference gamma generator, the green reference gamma generator and the blue reference gamma generator may be mounted in the inside of the integrated circuit.
[0065] An electro-luminescence display device according to still another aspect of the present invention may include: a gamma generation voltage supplier to generate a reference gamma voltage of low gray level and a plurality of gamma generation voltages; a reference gamma generator to generate a reference gamma voltage of high gray level in use of the gamma generation voltages; and a data integrated circuit to generate a data signal in use of the reference gamma voltage of low gray level and the reference gamma voltage of high gray level.
[0066] The gamma generation voltage supplier may include: a red gamma generation voltage supplier to generate a red reference gamma voltage of low gray level so that the data signal to be supplied to a red cell can be generated; a green gamma generation voltage supplier to generate a green reference gamma voltage of low gray level so that the data signal to be supplied to a green cell can be generated; and a blue gamma generation voltage supplier to generate a blue reference gamma voltage of low gray level so that the data signal to be supplied to a blue cell can be generated.
[0067] Each of the red, green and blue gamma generation voltage supplier may include: a variable resistor to divide a voltage value of a common voltage source to generate the reference gamma voltage of low gray level; and a plurality of divided voltage resistors to divide the reference gamma voltage of low gray level into two different voltage levels from each other to generate the gamma generation voltages.
[0068] A resistance value of the variable resistor included in each of the red, green and blue gamma generation voltage supplier may be set to be differently.
[0069] The reference gamma generator may include: a red reference gamma generator to generate a red reference gamma voltage of high gray level so that the data signal to be supplied to a red cell can be generated; a green reference gamma generator to generate a green reference gamma voltage of high gray level so that the data signal to be supplied to a green cell can be generated; and a blue reference gamma generator to generate a blue reference gamma voltage of high gray level so that the data signal to be supplied to a blue cell can be generated.
[0070] Each of the red, green and blue reference gamma generators may include: a digital analog converter to divide the voltages supplied from the gamma generation voltage supplier into a plurality of voltage levels; and a register storing a control data that enables to output any one voltage among the voltage levels voltage-divided at the digital analog converter.
[0071] The control data stored at the register may be set to enable the electro-luminescence display device to display uniform brightness.
[0072] The reference gamma generator may be mounted in the inside of the data integrated circuit.
BRIEF DESCRIPTION OF THE DRAWINGS
[0073] These and other objects of the invention will be apparent from the following detailed description of the embodiments of the present invention with reference to the accompanying drawings, in which:
[0074] FIG. 1 is a sectional diagram illustrating the structure of a general organic electro-luminescence;
[0075] FIGS. 2A and 2B are diagrams representing an electro-luminescence display device of the prior art;
[0076] FIG. 3 is a circuit diagram representing the structure of a gamma voltage supplier shown in FIGS. 2A and 2B ;
[0077] FIG. 4 is a diagram representing in detail a data integrated circuit shown in FIGS. 2A and 2B ;
[0078] FIG. 5 is a diagram illustrating how to install the gamma voltage supplier and the data integrated circuit shown in FIGS. 2 A and 2 B;
[0079] FIG. 6 is a diagram representing an electro-luminescence display device according to a first embodiment of the present invention;
[0080] FIGS. 7A to 7C are diagrams illustrating the structure of a gamma generator shown in FIG. 6 ;
[0081] FIG. 8 is a diagram illustrating how to install the gamma generator and a data integrated circuit shown in FIG. 6 ;
[0082] FIG. 9 is a diagram representing an electro-luminescence display device according to a second embodiment of the present invention;
[0083] FIG. 10 is a diagram representing an electro-luminescence display device according to a third embodiment of the present invention;
[0084] FIG. 11 is a circuit diagram illustrating in detail a gamma generation voltage supplier shown in FIG. 10 ;
[0085] FIG. 12 is a diagram illustrating in detail a reference gamma generator shown in FIG. 10 ;
[0086] FIG. 13 is a graph illustrating in brief a brightness change corresponding to a voltage value;
[0087] FIG. 14 is a circuit diagram illustrating another embodiment of the gamma generation voltage supplier;
[0088] FIG. 15 is a diagram illustrating an embodiment that the reference gamma generator is integrated in the inside of the data integrated circuit;
[0089] FIG. 16 is a circuit diagram illustrating still another embodiment of the gamma generation voltage supplier;
[0090] FIGS. 17A to 17C are circuit diagrams illustrating still another embodiment of the reference gamma generator;
[0091] FIG. 18 is a circuit diagram illustrating in detail a second DAC of FIGS. 17A to 17C ;
[0092] FIGS. 19A to 19C are circuit diagrams illustrating another embodiment of the second DAC;
[0093] FIG. 20 is a diagram for explaining the operation of the second and third DAC's;
[0094] FIG. 21 is a diagram illustrating an example that the gamma generation voltage supplier together with the reference gamma generator is built in the data integrated circuit;
[0095] FIG. 22 is a diagram illustrating an electro-luminescence display device according to a fourth embodiment of the present invention;
[0096] FIG. 23 is a circuit diagram illustrating in detail a gamma generation voltage supplier shown in FIG. 22 ;
[0097] FIGS. 24A to 24C are diagrams illustrating in detail a reference gamma generator shown in FIG. 22 ; and
[0098] FIG. 25 is a diagram illustrating a circuit where the reference gamma generator shown in FIG. 22 is built in an integrated circuit.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0099] Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings.
[0100] Hereinafter, the preferred embodiments of the present invention will be described in detail with reference to FIGS. 6 to 25 .
[0101] FIG. 6 is a diagram illustrating an EL display device according to a first embodiment of the present invention. In the embodiment, it is assumed that at least two data integrated circuits 66 are mounted on a data driver 64 .
[0102] Referring to FIG. 6 , an EL display device according to a first embodiment of the present invention includes an EL display panel 60 having EL cells 70 arranged at each intersection of scan electrode lines SL and data electrode lines DL, a scan driver 62 to drive the scan electrode lines SL, and a data driver 64 to drive the data electrode lines DL.
[0103] Each of the EL cells 70 is selected when a scan pulse is applied to the scan electrode line SL to generate the light corresponding to a data signal supplied to the data electrode line DL. In other words, a designated picture is displayed at the EL display panel 60 because the light corresponding to the data signal is generated in each of the EL cells 70 .
[0104] The scan driver 62 sequentially supplies a scan pulse to a plurality of scan electrode lines SL.
[0105] The data driver 64 includes a plurality of data integrated circuits 66 and a gamma generator 100 .
[0106] The data integrated circuits 66 , which is composed as in FIG. 4 , divides a reference gamma voltage supplied from the gamma generator 100 into a plurality of voltage levels to generate a data signal, and the generated data signal is supplied to the data electrode lines DL. In other words, the data integrated circuits 66 selects the voltage level corresponding to the bit number of data to generate the data signal, and supplies the generated data signal so that the data signal to be synchronized with the scan pulse.
[0107] The gamma generator 100 supplies the reference gamma voltage to the data integrated circuits 66 . For this, the gamma generator 100 includes an R reference gamma generator 68 R, a G reference gamma generator 68 G, and a B reference gamma generator 68 B.
[0108] The R reference gamma generator 68 R generates an R reference gamma voltage VH_R of low gray level and an R reference gamma voltage VL_R of high gray level, and supplies them to the data integrated circuits 66 . The G reference gamma generator 68 G generates an G reference gamma voltage VH_G of low gray level and an G reference gamma voltage VL_G of high gray level, and supplies them to the data integrated circuits 66 . The B reference gamma generator 68 B generates an B reference gamma voltage VH_B of low gray level and an B reference gamma voltage VL_B of high gray level, and supplies them to the data integrated circuits 66 .
[0109] For this, the R reference gamma generator 68 R includes resistance parts 80 , 82 , DAC's 84 , 86 , and registers 88 , as in FIG. 7A .
[0110] The resistance parts 80 , 82 include the first resistance part 80 and the second resistance part 82 . The first resistance part 80 includes divided voltages r_R 1 _H, r_R 2 _H, r_R 3 _H installed between a supply voltage source and a ground voltage source GND. First and second voltages divided by the divided voltage resistors r_R 1 _H, r_R 2 _H, r_R 3 _H are supplied to the DAC 84 . The second resistance part 82 includes divided voltages r_R 1 _L, r_R 2 _L, r_R 3 _L installed between a supply voltage source and a ground voltage source GND. Third and fourth voltages divided by the divided voltage resistors r_R 1 _L, r_R 2 _L, r_R 3 _L are supplied to the DAC 86 .
[0111] The DAC's 84 , 86 include a first DAC 84 and a second DAC 86 . The first DAC 84 divides the first voltage and the second voltage into a plurality of voltage levels. For example, the first and second voltages are divided into 2 i number of voltage level, if an i (i is a natural number) bit is inputted from a register 88 . And, the first DAC 84 supplies any one voltage of a plurality of voltage levels, which are divided from in correspondence to the bit number of the control data supplied from the register 88 , to the data integrated circuits 66 as the R reference gamma voltage VH_R of low gray level.
[0112] The second DAC 86 divides the third voltage and the fourth voltage into a plurality of voltage levels. For example, i bit is inputted from the register 88 , the third and fourth voltage is divided into 2 i numbers of voltage levels. And, the second DAC 86 supplies any one voltage of the voltage levels divided in correspondence to the bit number of the control data supplied from the register 88 , to the data integrated circuits 66 as the R reference gamma voltage VL_R of high gray level.
[0113] In the register 88 , the control data of i bit is stored to control the output voltage value of each of the first DAC 84 and the second DAC 86 . In other words, the first control data of the register 88 is supplied to the first DAC 84 to control the first DAC 84 . And, the second control data of the register 88 is supplied to the second DAC 86 to control the second DAC 86 . Herein, the bit value of the first and second control data inputted to the register 88 is determined by a user. For example, in the register 88 , it is possible to store the control data value that can compensate the brightness deviation generated between the EL display panels 60 .
[0114] To described this in detail, when a brightness deviation exists between the EL display panels 60 , a user controls the first and second data value, which are to be stored in the register 88 , to compensate the brightness deviation between the EL display panels 60 .
[0115] A mode controller (not shown) is installed in an input terminal of the register 88 , and the register 88 receives the first and second control data from the mode controller to control the output values of the first and second DAC's 84 , 86 , thus it is possible to control to display a picture of an appropriate brightness that corresponds to an external environment, i.e., day, night, rain, snow and etc.
[0116] On the other hand, the G gamma generator 68 G and the B gamma generator 68 B are composed as in FIGS. 7B and 7C in this invention. The value stored at the register 88 included in the G gamma generator 68 G and the B gamma generator 68 B are set to have the white balance of the R cell, G cell and B cell balanced. The operation process is substantially the same as the foregoing R gamma generator 68 R, thus a detailed description is to be omitted.
[0117] The gamma generator 100 includes a fewer number of resistors than the gamma voltage supplier 26 of the prior art shown in FIG. 3 . Accordingly, the gamma generator 100 of the present invention can be mounted on a COF 102 along with the data integrated circuit 66 as shown in FIG. 8 . In this way, if the gamma generator 100 on the COF 102 , its manufacturing cost can be reduced.
[0118] FIG. 9 is a diagram illustrating an EL display device according to a second embodiment of the present invention. In the embodiment, it is assumed that one data integrated circuit 200 is mounted on the data driver 64 . In FIG. 9 , the same composition as FIG. 6 is to be given the same reference numerals and of which the further description is to be omitted.
[0119] Referring to FIG. 9 , the EL display device according to the second embodiment of the present invention includes an EL display panel 60 having EL cells 70 arranged at each intersection of scan electrode lines SL and data electrode lines DL, a scan driver 62 to drive the scan electrode lines SL, and a data driver 64 to drive the data electrode lines DL.
[0120] Each of the EL cells 70 is selected when a scan pulse is applied to the scan electrode line SL, to generate the light corresponding to a data signal supplied to the data electrode line DL. In other words, because a designated light corresponding to the data signal is generated in each of the EL cells 70 , a designated picture is displayed in the EL display panel 60 .
[0121] The scan driver 62 sequentially supplies the scan pulse to a plurality of scan electrode lines SL.
[0122] The data driver 64 includes one data integrated circuit 200 . A reference gamma generator 100 is built in the data integrated circuit 200 . And, the other configuration is made as in FIG. 4 .
[0123] The reference gamma generator 100 includes an R reference gamma generator 68 R, a G reference gamma generator 68 G and a B reference gamma generator 68 B. The R reference gamma generator 68 R generates an R reference gamma voltage VH_R of low gray level and an R reference gamma voltage VL_R of high gray level to supply it to an R DAC 200 A. And, the G reference gamma generator 68 G generates a G reference gamma voltage VH_G of low gray level and a G reference gamma voltage VL_G of high gray level to supply it to a G DAC 200 B. And, the B reference gamma generator 68 B generates a B reference gamma voltage VH_B of low gray level and a B reference gamma voltage VL_B of high gray level to supply it to a B DAC 200 C.
[0124] Herein, the composition of each of the R reference gamma generator 68 R, the G reference gamma generator 68 G and the B reference gamma generator 68 B is the same as in FIGS. 7A to 7C , thus their further detail description will be omitted.
[0125] A gamma generator 100 is integrated in the inside of the data integrated circuit 200 in the second embodiment, differently from the first embodiment. If the gamma generator 100 is integrated in the inside of the data integrated circuit 200 in this way, their mounting time is shortened when compared with the case that the data integrated circuit and the gamma generator are separated.
[0126] FIG. 10 is a diagram illustrating an EL display device according to a third embodiment of the present invention.
[0127] Referring to FIG. 10 , an EL display device according to the embodiment of the present invention includes an EL display panel 160 having EL cells 170 arranged at each intersection of scan electrode lines SL and data electrode lines DL, a scan driver 162 to drive the scan electrode lines SL, a data driver 164 to drive the data electrode lines DL, and a gamma generation voltage supplier 172 to supply a gamma generation voltage to the data driver 164 so that a reference gamma voltage is generated.
[0128] Each of the EL cells 170 is selected when a scan pulse is applied to the scan electrode line SL, to generate the light corresponding to a data signal supplied to the data electrode line DL. In other words, when a designated light corresponding to the data signal is generated in each of the EL cells 170 , a designated picture is displayed in the EL display panel 160 .
[0129] The scan driver 162 sequentially supplies the scan pulse to a plurality of scan electrode lines SL.
[0130] The gamma generation voltage supplier 172 supplies a plurality of gamma generation voltages to the data driver 164 so that the reference gamma voltage is generated in the data driver 164 . Herein, the gamma generation voltage supplier 172 includes an R gamma generation voltage part 110 , a G gamma generation voltage part 112 and a B gamma generation voltage part 114 as in FIG. 11 so that the reference gamma voltage is generated differently by R cell, G cell and B cell. Each of the gamma generation voltage part 110 , 112 , 114 is composed of divided voltage resistors to divide the voltage of a supply voltage source VDD.
[0131] The R gamma generation voltage part 110 includes two first divided voltage resistors r_R 1 _H, r_R 2 _H installed in series between the supply voltage source VDD and a ground voltage source GND to generate an R gamma generation voltage VHL_R of low gray level, and two second divided voltage resistors r_R 1 _L, r_R 2 _L installed in series between the supply voltage source VDD and the ground voltage source GND to generate an R gamma generation voltage VLL_R of high gray level.
[0132] Likewise, the G gamma generation voltage part 112 is composed of first divided voltage resistors r_G 1 _H, r_G 2 _H and second divided voltage resistors r_G 1 _L, r_G 2 _L to generate a G gamma generation voltage VHL_G of low gray level and a G gamma generation voltage VLL_G of high gray level. And, the B gamma generation voltage part 114 is composed of first divided voltage resistors r_B 1 _H, r_B 2 _H and second divided voltage resistors r_B 1 _L, r_B 2 _L to generate a B gamma generation voltage VHL_B of low gray level and a B gamma generation voltage VLL_B of high gray level.
[0133] The data driver 164 includes a reference gamma generator 1100 and a plurality of data integrated circuits 166 . The data integrated circuits 166 is composed as in FIG. 4 , generates a data signal by dividing the reference gamma voltage supplied from the reference gamma generator 1100 into a plurality voltage levels, and supplies the generated data signal to the data electrode lines DL.
[0134] The reference gamma generator 1100 generates the reference gamma voltage in use of the gamma generation voltage supplied from the gamma generation voltage supplier 172 . For this, the reference gamma generator 1100 includes R reference gamma generators 168 R, 268 R, G reference gamma generators 168 G, 268 G, B reference gamma generators 168 B, 268 B.
[0135] A first embodiment of the reference gamma generator 1100 shown in FIG. 10 is as follows.
[0136] The R reference gamma generator 168 R generates the R reference gamma voltage VH_R of low gray level and the R reference gamma voltage VL_R of high gray level in use of the R gamma generation voltage VHL_R of low gray level and the R gamma generation voltage VLL_R of high gray level.
[0137] The G reference gamma generator 168 G generates the G reference gamma voltage VH_G of low gray level and the G reference gamma voltage VL_G of high gray level in use of the G gamma generation voltage VHL_G of low gray level and the G gamma generation voltage VLL_G of high gray level.
[0138] The B reference gamma generator 168 B generates the B reference gamma voltage VH_B of low gray level and the B reference gamma voltage VL_B of high gray level in use of the B gamma generation voltage VHL_B of low gray level and the B gamma generation voltage VLL_B of high gray level.
[0139] The R reference gamma generation 168 R, the G reference gamma generation 168 G and the B reference gamma generation 168 B have different resistance value and control data value within the register, and have the same circuit composition. Putting focus on the R reference gamma generator 168 R, the operation of the reference gamma generators 168 R, 168 G and 168 B is described.
[0140] The R reference gamma generator 168 R includes a first DAC 184 , a second DAC 186 and a register 188 as in FIG. 12 .
[0141] The first DAC 184 receives a first reference voltage VH from the external, and receives the R gamma generation voltage VHL_R of low gray voltage from the R gamma generation voltage part 110 . Herein, the first reference voltage is higher than the R gamma generation voltage VHL_R of low gray level. The first DAC 184 is composed of i (i is a natural number) bits, and divides the first reference voltage VH and the R gamma voltage into 2 i numbers of voltage levels. And, the first DAC 184 supplies any one voltage among the voltages to the data integrated circuits 66 , as the R reference gamma voltage VH_R of low gray level, in correspondence to the bit of the first control data supplied from the register 188 .
[0142] The second DAC 186 receives a second reference voltage VL from the external, and receives the R gamma generation voltage VLL_R of high gray voltage from the R gamma generation voltage part 100 . Herein, the second reference voltage is a voltage between the first reference voltage VH and the R gamma generation voltage VLL_R of high gray level. The second DAC 186 is composed of j (j is a natural number) bits, and divides the second reference voltage VL and the R gamma voltage into 2 i numbers of voltage levels. And, the second DAC 186 supplies any one voltage among the voltages to the data integrated circuits 166 , as the R reference gamma voltage VL_R of high gray level, in correspondence to the bit of the second control data supplied from the register 188 .
[0143] On the other hand, the second DAC 186 is composed to have more voltage levels than the first DAC 184 in this invention. In other words, the second DAC 186 outputs any one of the reference gamma voltage of 2 i numbers of voltage levels when compared with that the first DAC 184 outputs any one among the reference gamma voltages of the 2 i numbers of voltage levels, which is smaller than this. In this way, because the second DAC 186 selects the reference gamma voltage among the reference gamma voltages of the larger voltage levels, the present invention might control the R reference gamma voltage VL_R of high gray level more precisely than the prior art, thus the brightness deviation between the display panels 160 might be minimized. To describe this more precisely, the brightness of the display panel 160 might be expressed as in FIG. 13 . In other words, black is displayed when the R reference gamma voltage VH_R of low gray level is supplied, and white is displayed when the R reference gamma voltage VL_R of high gray level is supplied. Herein, the brightness difference between low gray levels might not be easily distinctive with bare eyes, thus the gamma reference voltage is controlled by designated values so that it is relatively easy to similarly control the black brightness between the display panels 160 . On the contrary, the brightness difference between high gray levels is easily distinctive with bare eyes, thus the gamma reference voltage is divided into many voltage levels and one of them is selected, so that the white brightness between the display panels 160 might be set similarly.
[0144] According to an experiment result, in order to similarly set the brightness of low gray level between the display panels 160 , the gamma voltage is to be controlled at the range of approximate 3V. For example, when the first reference voltage VH: 14V, the R gamma generation voltage VHL_R: 11V are each set and when the voltage between the first reference voltage VH and the R gamma generation voltage VHL_R is subdivided to be about 0.2V, the brightness difference of the low gray level can be similarly set between the display panels 160 . Herein, when the first DAC 184 is set to be 4 bits, the 3V voltage is subdivided to have a voltage difference of about 0.1875V, thus the brightness of the low gray level might be similarly or identically set between the display panels 160 .
[0145] Further, the voltage value is to be controlled at the rage of about 5V in order that the brightness of the gray level is similarly set between the display panels 160 . For example, when the second reference voltage VL: 6V, the R gamma generation voltage VLL_R: 1V are each set and when the voltage between the second reference voltage VL and the R gamma generation voltage VLL_R is subdivided to be about 0.1 V, the brightness difference of the high gray level can be similarly set between the display panels 160 . Herein, when the second DAC 186 is set to be 6 bits, the 5V voltage is subdivided to have a voltage difference of about 0.078125V, thus the brightness of the high gray level might be similarly or identically set between the display panels 160 .
[0146] The first control data of i bit is stored at the register 188 to control the output value of the first DAC 184 . And the second control data of j bit is stored at the register 188 to control the output value of the second DAC 186 . Herein, the bit value of the first and second control data inputted into the register 188 is determined by a user. For example, the first and second control data, which can compensate the brightness deviation generated between the EL display panels 60 , is stored at the register 188 . When the brightness deviation is generated between the EL display panel 160 , the user controls the first and second control data values inputted to the register 188 thus the brightness deviation between the EL display panels 60 can be compensated. Further, a mode controller (not shown) is installed at the input terminal of the register 188 , and the register 188 receives the first and second control data from the mode controller to control the output of the first and second DAC 184 , 186 , thus it is possible to control to display a picture of an appropriate brightness that corresponds to an external environment, i.e., day, night, rain, snow and etc.
[0147] The value stored at the register 188 included in the G reference gamma generator 168 G and the B reference gamma generator 168 B is set to make the white balance of the R cell, G cell and B cell balanced.
[0148] On the other hand, the gamma generation voltage supplier 172 of the present invention might be realized in many ways. For example, the gamma generation voltage supplier 172 might be composed as in FIG. 14 . The R gamma generation voltage part 110 , the G gamma generation voltage part 112 and the B gamma generation voltage part 114 have substantially the same circuit composition except that the generated voltage value is different.
[0149] Referring to FIG. 14 , the R gamma generation voltage part 190 includes first divided voltage resistors r_R 1 _H, r_R 2 _H, r_R 2 _H, and second divided voltage resistors r_R 1 _L, r_R 2 _L, r_R 2 _L installed in series between the supply voltage source VDD and the ground voltage source GND. Each of the first and second divided resistors includes three resistors. When comparing the R gamma generation voltage part 190 with the R gamma generation voltage part 110 of FIG. 12 , the R gamma generation voltage part 110 shown in FIG. 12 has three resistors in each of the first and second divided voltage resistors and generates the first reference voltage VH, the R gamma generation voltage VHL_R of low gray level, the second reference voltage VL and the R gamma generation voltage VLL_R of high gray level.
[0150] In other words, the R gamma generation voltage part 190 of FIG. 14 additionally generates the first reference voltage VH to supply it to the first DAC 184 as well as additionally generating the second reference voltage VL to supply it to the second DAC 186 . In this way, when the first reference voltage and the second reference voltage VL are additionally generated in the R gamma generation voltage part 190 , there is an advantage that the brightness of the display panel 160 might be more easily controlled.
[0151] And, in the present invention, the data driver 164 as in FIG. 15 includes one data integrated circuit 1200 . The reference gamma generator 1100 is integrated in the inside of the data integrated circuit 1200 . Herein, the R reference gamma generator 168 R generates the R gamma voltage VH_R of low gray level and the R gamma voltage VL_R of high gray level to supply them to an R DAC 1200 A. The G reference gamma generator 168 G generates the G gamma voltage VH_G of low gray level and the G gamma voltage VL_G of high gray level to supply them to an G DAC 1200 B. The B reference gamma generator 168 B generates the B gamma voltage VH_B of low gray level and the B gamma voltage VL_B of high gray level to supply them to an B DAC 1200 C.
[0152] The composition of each of the R reference gamma generator 168 R, the G reference gamma generator 168 G and the B reference gamma generator 168 B is substantially the same as the embodiment of FIG. 12 .
[0153] In this way, when the gamma generator 1100 is integrated in the inside of the data integrated circuit 1200 , it is possible to obtain an additional effect that its mounting time is shortened.
[0154] FIG. 16 shows still another embodiment of a gamma generation voltage supplier 172 .
[0155] Referring to FIG. 16 , the gamma generation voltage supplier 172 supplies a plurality of gamma generation voltages to the data driver 164 in order that the reference gamma voltage is generated in the data driver 164 . The gamma generation voltage supplier 172 includes the R gamma generation voltage part 2110 , the G gamma generation voltage part 2112 and the B gamma generation voltage part 2114 in order that a different reference gamma voltage is generated by R cell, G cell, B cell. Herein, each of the gamma generation voltage part 2110 , 2112 , 2114 is composed of a plurality of divided voltage resistors to divide the voltage of the supply voltage source VDD.
[0156] The R gamma generation voltage part 2110 supplies a first gamma generation voltage V 1 and a second gamma generation voltage V 2 to the data driver 164 for the R reference gamma voltage VH_R of low gray level to be generated, and in addition supplies a third gamma generation voltage V 3 and a fourth gamma generation voltage V 4 to the data driver 164 for the R reference gamma voltage VL_R of high gray level to be generated. Herein, the third gamma generation voltage V 3 and the fourth gamma generation voltage V 4 have a lower voltage value than the first gamma generation voltage V 1 .
[0157] The G gamma generation voltage part 2112 supplies a fifth gamma generation voltage V 5 and a sixth gamma generation voltage V 6 to the data driver 164 for the G reference gamma voltage VH_G of low gray level to be generated, and in addition supplies a seventh gamma generation voltage V 7 and a eighth gamma generation voltage V 8 to the data driver 164 for the G reference gamma voltage VL_G of high gray level to be generated. Herein, the seventh gamma generation voltage V 7 and the eighth gamma generation voltage V 8 have a lower voltage value than the fifth gamma generation voltage V 5 .
[0158] The B gamma generation voltage part 2114 supplies a ninth gamma generation voltage V 9 and a tenth gamma generation voltage V 10 to the data driver 164 for the B reference gamma voltage VH_B of low gray level to be generated, and in addition supplies a eleventh gamma generation voltage V 11 and a twelfth gamma generation voltage V 12 to the data driver 164 for the B reference gamma voltage VL_B of high gray level to be generated. Herein, the eleventh gamma generation voltage V 11 and the twelfth gamma generation voltage V 12 have a lower voltage value than the ninth gamma generation voltage V 9 .
[0159] A second embodiment of a reference gamma generator 1100 shown in FIG. 10 is the same as in FIGS. 17A to 17C .
[0160] The reference gamma generator 1100 includes an R reference gamma generator 268 R, a G reference gamma generator 268 G and a B reference gamma generator 268 B.
[0161] The R reference gamma generator 268 R generates the R reference gamma voltage VH_R of low gray level in use of the first gamma generation voltage V 1 and the second gamma generation voltage V 2 , and generates the R reference gamma voltage VL_R of high gray level in use of the third gamma generation voltage V 3 and the fourth gamma generation voltage V 4 .
[0162] The G reference gamma generator 268 G generates the G reference gamma voltage VH_G of low gray level in use of the fifth gamma generation voltage V 5 and the sixth gamma generation voltage V 6 , and generates the G reference gamma voltage VL_G of high gray level in use of the seventh gamma generation voltage V 7 and the eight gamma generation voltage V 8 .
[0163] The B reference gamma generator 268 B generates the B reference gamma voltage VH_B of low gray level in use of the ninth gamma generation voltage V 9 and the tenth gamma generation voltage V 10 , and generates the B reference gamma voltage VL_B of high gray level in use of the eleventh gamma generation voltage V 11 and the twelfth gamma generation voltage V 12 .
[0164] The R reference gamma generator 268 R, the G reference gamma generator 268 G and the B reference gamma generator 268 B substantially the same circuit composition, thus putting focus on the R reference gamma generator 268 R, the operation of the reference gamma generators 268 R, 268 G and 268 B is described.
[0165] The R reference gamma generator 268 R includes a first DAC 284 R, a second DAC 286 R and a register 288 R as in FIG. 17A . The first DAC 284 R divides the first gamma generation voltage V 1 and the second gamma generation voltage V 2 supplied from the gamma generation voltage supplier 172 , into a plurality of voltage levels.
[0166] The first DAC 284 R divides the first gamma generation voltage V 1 and the second gamma generation voltage V 2 into 2 i (i is a natural number) numbers of voltage levels. And, the first DAC 284 R supplies any one voltage among the 2 i numbers of voltages to the data integrated circuits 166 , as the R reference gamma voltage VH_R of low gray level, in correspondence to the first control data of i bit supplied from the register 288 .
[0167] The second DAC 286 R divides the third gamma generation voltage V 3 and the fourth gamma generation voltage V 4 supplied from the gamma generation voltage supplier 272 , into 2 j (j>i, j is a natural number) of voltage levels. And the second DAC 268 R supplies any one voltage among the 2 j numbers of voltages to the data integrated circuits 166 , as the R reference gamma voltage VL_R of high gray level, in correspondence to the first control data of j bit supplied from the register 288 .
[0168] Likewise, the second DAC 286 R divides the gamma reference voltage into the voltage levels that are more than those of the first DAC 284 R. In other words, the second DAC 286 R has the 2 j numbers of voltage levels and the first DAC 284 R has the 2 i numbers of voltage levels which is smaller than that. In this way, if the second DAC 286 R has more voltage levels, the R reference gamma voltage VL_R of high gray level can be controlled precisely, thus the brightness deviation between the display panels 60 can be precisely controlled in the high gray level where the gray level difference is easily perceived with bare eyes.
[0169] The first control data of i bit is stored at the register 288 R to control the output of the first DAC 284 R. And the second control data of j bit is stored at the register 288 R to control the output of the second DAC 286 R. Herein, the bit value of the first and second control data inputted to the register 288 R is determined by a user. For example, the first and second control data, which can compensate the brightness deviation generated between the EL display panels 160 , is stored at the register 288 R.
[0170] The G reference gamma generator 268 G of FIG. 7B generates the G reference gamma voltage VH_G of low gray level and the G reference gamma voltage VL_G of high gray level in use of the fifth to eighth gamma generation voltage (V 5 to V 8 ). And, the B reference gamma generator 268 B as in FIG. 7C generates the B reference gamma voltage VH_B of low gray level and the B reference gamma voltage VL_B of high gray level in use of the ninth to twelfth gamma generation voltage V 9 to V 12 .
[0171] This invention might control the reference gamma voltage precisely in use of the control data stored at the registers 288 R, 288 G, 288 B, thus the brightness of the display panel 60 might be controlled minutely. Accordingly, this invention can deal with the brightness deviation between the display panels actively, thus its process time might be shortened.
[0172] On the other hand, if the bit number of the control data stored at the second DAC's 286 R, 286 G, 286 B is big, there is a problem that the size of the second DAC's 286 R, 286 G, 286 B is big. For example, the second DAC's 286 R, 286 G, 286 B includes 64 numbers of resistors R 1 to R 64 as in FIG. 18 to generate sixty four different voltages, as well as includes a selector 71 to output any one voltage among the sixty four voltage levels in correspondence to the second control data.
[0173] If each of the second DAC's 286 R, 286 G, 286 B includes the sixty four resistors R 1 to R 64 and the selector 71 which is to output any one voltage among the sixty four voltages, the size of the second DAC 286 R, 286 G, 286 B becomes bigger, thus its circuit cost gets bigger as much and it becomes difficult to secure the degree of freedom for design. Especially, such problems are to be shown in a bigger scale when the second DAC's 286 R, 286 G, 286 B are integrated in the inside of the data integrated circuit 266 .
[0174] In order to overcome such problems, the reference gamma generator 1100 includes the R reference gamma generator 268 R, the G reference gamma generator 268 G and the B reference gamma generator 268 B, which are composed as in FIGS. 19A to 19C . The R reference gamma generator 268 R, the G reference gamma generator 268 G and the B reference gamma generator 268 B substantially have the same circuit composition, thus putting focus on the R reference gamma generator 268 R, the operation of the reference gamma generators 268 R, 268 G and 268 B is described.
[0175] The R reference gamma generator 268 R includes a first DAC 290 R, a second DAC 292 R and a register 294 R as in FIG. 19A .
[0176] The first DAC 290 R divides the first gamma generation voltage V 1 and the second gamma generation voltage V 2 supplied from the gamma generation voltage supplier 172 , into a plurality of voltage levels. For example, the first DAC 290 R divides the first gamma generation voltage V 1 and the second gamma generation voltage V 2 into 2 i numbers of voltage levels. And the first DAC 290 R supplies any one voltage among a number of voltages to the data integrated circuits 166 , as the R reference gamma voltage VH_R of low gray level, in correspondence to the bit of the first control data supplied from the register 296 R.
[0177] The second DAC 292 R divides the third gamma generation voltage V 3 and the fourth gamma generation voltage V 4 supplied from the gamma generation voltage supplier 172 , into a plurality of voltage levels. For example, the second DAC 292 R divides the third gamma generation voltage V 3 and the fourth gamma generation voltage V 4 into 2 j /2 numbers of voltage levels so that it can be selected by the control data of j/2 (j>i, j/2<i: e.g., j/2 is set to be ‘3’) And the second DAC 292 R supplies the adjacent first divided voltage VL 1 and second divided voltage VL 2 among a plurality of voltages to the third DAC 294 R, in correspondence to the bit of the second control data supplied from the register 296 R. For example, the second DAC 292 R divides the third gamma generation voltage V 3 and the fourth gamma generation voltage V 4 into voltages of eight steps as in FIG. 20 , and the adjacent voltages among the divided voltages, as the first divided voltage VL 1 and the second divided voltage VL 2 , are supplied to the third DAC 294 R, in correspondence to the second control data. And then, the third DAC 294 R divides the first divided voltage VL 1 and the second divided voltage VL 2 supplied from the second DAC 292 R to 2 j /2 numbers of voltage level (8 voltage levels). And, the third DAC 294 R supplies any one voltage among the voltages, as the R reference gamma voltage VL_R of high gray level, to the data integrated circuits, in correspondence to the bit of the third control data.
[0178] In this way, the present invention has its size reduced by more than ½ and secures more degree of freedom for design, when compared with the embodiment of FIGS. 17A to 17C , in use of the second and third DAC 92 , 94 where the output voltage can be selected by the j/2 bit. For example, assuming that j is 6 bit, each of the second DAC 292 R and the third DAC 294 R includes eight resistors. Accordingly, the number of resistors thereof is reduced greatly than that of the sixty four resistors included in the second DAC 286 R shown in FIG. 17A , and accordingly the size gets smaller.
[0179] The first control data of i bit is stored in the register 296 R to control the output value of the first DAC 290 R. And the second and third control data of j/2 bit are stored at the register 296 R to control the output of the second DAC 292 R and the third DAC 294 R. Herein, the bit value of the first to third control data having been inputted in the register 296 R is set to compensate the brightness deviation generated between the EL display panel 160 .
[0180] The G reference gamma generator 268 G of FIG. 19B generates the G reference gamma voltage VH_G of low gray level and the G reference gamma voltage VL_G of high gray level in use of the fifth to eighth gamma generation voltage V 5 to V 8 . And, the B reference gamma generator 268 B of FIG. 19C generates the B reference gamma voltage VH_B of low gray level and the B reference gamma voltage VL_B of high gray level in use of the ninth to twelfth gamma generation voltage V 9 to V 12 .
[0181] The reference gamma generator 1100 included in the reference gamma generators 268 R, 268 G, 268 B might be integrated in the inside of the data integrated circuit 1200 as in FIG. 15 . Further, the gamma generation voltage supplier 172 along with the reference gamma generator 1100 might be integrated in the inside of the data integrated circuit 1200 as in FIG. 21 . In FIG. 21 , the reference numerals “ 1200 A”, “ 1200 B”, “ 1200 B” represent the R DAC, the G DAC and the B DAC, respectively.
[0182] FIG. 22 represents an EL display device according to still another embodiment of the present invention.
[0183] Referring to FIG. 22 , the EL display device according to the embodiment of the present invention includes an EL display panel 360 having EL cells 370 arranged at each intersection of scan electrode lines SL and data electrode lines DL, a scan driver 362 to drive the scan electrode lines SL, a data driver 364 to drive the data electrode lines DL, and a gamma generation voltage supplier 372 to generate gamma generation voltages.
[0184] The gamma generation voltage supplier 372 generates the reference gamma voltages VH_R, VH_G, VH_B of low gray level to supply them to the data integrated circuits 366 . And, the gamma generation voltage supplier 372 supplies a plurality of gamma generation voltages to a reference gamma generator 3100 included in the data driver 364 so that the reference gamma voltages VL_R, VL_G, VL_B of high gray level are generated. The gamma generation voltage supplier 372 includes an R gamma generation voltage part 3110 , a G gamma generation voltage part 3112 , a B gamma generation voltage part 3114 as in FIG. 23 , so that different reference gamma voltages VH_R, VH_G, VH_B and the gamma generation voltage can be generated by R cell, G cell, B cell.
[0185] The R gamma generation voltage part 3110 includes a first variable resistor VR 1 to generate the reference gamma voltage VH_R of low gray level, and divided voltage resistors r_R 1 , r_R 2 , r_R 3 to generate the first and second gamma generation voltages V 1 and V 2 by dividing the reference gamma voltage VH_R of low gray level. Herein, the reference gamma voltage VH_R of low gray level is supplied to the data integrated circuit 366 and the first and second gamma generation voltage V 1 , V 2 are supplied to the reference gamma generator 3100 .
[0186] The G gamma generation voltage part 3112 includes a second variable resistor VR 2 to generate the reference gamma voltage VH_G of low gray level, and divided voltage resistors r_G 1 , r_, r_G 3 to generate the third and fourth gamma generation voltages V 3 and V 4 by dividing the reference gamma voltage VH_G of low gray level. Herein, the reference gamma voltage VH_G of low gray level is supplied to the data integrated circuit 366 and the third and fourth gamma generation voltage V 3 , V 4 are supplied to the reference gamma generator 3100 .
[0187] The B gamma generation voltage part 3114 includes a third variable resistor VR 3 to generate the reference gamma voltage VH_B of low gray level, and divided voltage resistors r_B 1 , r_B 2 , r_B 3 to generate the fifth and sixth gamma generation voltages V 5 and V 6 by dividing the reference gamma voltage VH_B of low gray level. Herein, the reference gamma voltage VH_B of low gray level is supplied to the data integrated circuit 366 and the fifth and sixth gamma generation voltage V 5 , V 6 are supplied to the reference gamma generator 3100 .
[0188] The data driver 364 includes the reference gamma generator 3100 and at least one data integrated circuit 366 . The data integrated circuit 366 is composed as in FIG. 4 , and divides the reference gamma voltages supplied from the gamma generation voltage supplier 372 and the reference gamma generator 3100 into a plurality of voltage levels to generate a data signal, thereby supplying the data signal to the data electrode lines DL.
[0189] The reference gamma generator 3100 generates the reference gamma voltages of high gray level in use of the gamma generation voltages supplied from the gamma generation voltage supplier 372 . For this, the reference gamma generator 3100 includes the R reference gamma generator 368 R, the G reference gamma generator 368 G, the B reference gamma generator 368 B.
[0190] The R reference gamma generator 368 R generates the reference gamma voltage VL_R of high gray level in use of the first gamma generation voltage V 1 and the second gamma generation voltage V 2 . The G reference gamma generator 368 G generates the reference gamma voltage VL_G of high gray level in use of the third gamma generation voltage V 3 and the fourth gamma generation voltage V 4 . The B reference gamma generator 368 B generates the reference gamma voltage VL_B of high gray level in use of the fifth gamma generation voltage V 5 and the sixth gamma generation voltage V 6 . Herein, the R reference gamma generator 368 R, the G reference gamma generator 368 G and the B reference gamma generator 368 B substantially have the same circuit composition, thus putting focus on the R reference gamma generator 368 R, the operation of the reference gamma generators 368 R, 368 G and 368 B is described.
[0191] The R reference gamma generator 368 R includes a DAC 386 R and a register 388 R as in FIG. 24A . The DAC 386 R divides the first gamma generation voltage V 1 and the second gamma generation voltage V 2 supplied from the gamma generation voltage supplier 372 into a plurality of voltage levels. For example, the DAC 386 R is composed of i bit (i is a natural number), and divides the first gamma generation voltage V 1 and the second gamma generation voltage V 2 into 2 i numbers of voltage levels. And the DAC 386 R supplies any one voltage among the 2 i numbers of voltage levels, as the reference gamma voltage VL_R of high gray level, to the data integrated circuits 366 , in correspondence to the control data supplied from the register 388 R.
[0192] In this embodiment, the reference gamma voltage VH controls the voltage value in use of the variable resistors VR 1 , VR 2 and VR 3 , and controls the voltage value in use of the reference gamma voltage VL of high gray level. If the reference gamma voltage VL of high gray level in this way is precisely adjusted by the DAC 386 R, then the brightness deviation between the display panels 360 is minimized.
[0193] The control data of i bit is stored at the register 388 R to control the output value of the DAC 386 R. Herein, the bit value of the control data inputted into the register 388 R is determined by a user. For example, the register 388 R might store the control data where a bit value is set to compensate the brightness deviation generated between the display panels 360 . When there is a brightness deviation between the EL display panels 60 , the user controls the brightness of low gray level in use of the variable resistance value of the first to third variable resistors VR 1 to VR 3 , and controls the bit value of the control data, thereby enabling to compensate the brightness deviation between the display panels 360 . Further, the input terminal of the register 388 R has a mode controller (not shown) installed, and the register 388 R controls the output value of the DAC 386 R by receiving the control data from the mode controller, thus it is possible to control to display a picture of an appropriate brightness that corresponds to an external environment, i.e., day, night, rain, snow and etc.
[0194] In this invention, the G reference gamma generator 368 G and the B reference gamma generator 368 B are composed as in FIGS. 24B and 24C . The G reference gamma generator 368 G generates the reference gamma voltage VL_G of high gray level in use of the third and fourth gamma generation voltage V 3 , V 4 . And the B reference gamma generator 368 B generates the reference gamma voltage VL_B of high gray level in use of the fifth and sixth gamma generation voltage V 5 , V 6 . In FIGS. 24B and 24C , the reference numerals “ 386 G” and “ 386 B” represent the DAC, and “ 388 G” and “ 388 B” represent the register.
[0195] In this invention, the circuits of the reference gamma generator might be integrated in the inside of the data integrated circuit 366 as in FIG. 25 . In FIG. 25 , the reference numerals “ 3200 A”, “ 3200 B” and “ 3200 C” represent the DAC.
[0196] As described above, according to the electro-luminescence display device of the present invention, the reference gamma voltage can be adjusted in use of the control data stored at the register, thus the expression capability of gray level is improved, the brightness deviation between the display panels might be compensated in a short time, and the gamma adjustment time and the process time might be reduced. In addition, the present invention might compensate the brightness deviation exactly because the reference gamma voltage is selected as any one of voltage levels. Further, the gamma voltage generator in this invention is mounted on the COF, thus FPC might be removed, and the number of resistors mounted on the FPC is reduced to decrease the area of the FPC, thereby enabling to secure its design margin broadly. In addition, the invention has the align time of the COF and FPC shortened so that it is possible to obtain an additional effect that its process time might be reduced.
[0197] Although the present invention has been explained by the embodiments shown in the drawings described above, it should be understood to the ordinary skilled person in the art that the invention is not limited to the embodiments, but rather that various changes or modifications thereof are possible without departing from the spirit of the invention. Accordingly, the scope of the invention shall be determined only by the appended claims and their equivalents. | An electro-luminescence display device including red, green and blue reference gamma generators each having three digital analog converters or more in order to generate a reference gamma voltage of low gray level and a reference gamma voltage of high gray level, and at least one integrated circuit to generate a data signal in use of the reference gamma voltage of low gray level and the reference gamma voltage of high gray level. Each reference gamma generator includes a first digital analog converter to divide a voltage supplied to itself in order to generate i numbers of voltage levels, a second digital analog converter to divide a voltage supplied to itself in order to generate j numbers of voltage levels, and a third digital analog converter to receive two voltage levels from the second digital analog converter and to divides the two received voltage levels into j numbers of voltage levels. | 6 |
RELATED APPLICATION DATA
This application claims priority to and is a continuation-in-part of application Ser. No. 14/498,654, filed on Sep. 26, 2014, and entitled “Propulsion System,” which is a continuation-in-part of application Ser. No. 11/514,405 filed on Aug. 30, 2006, and entitled “Stardrive Propulsion System,” now U.S. Pat. No. 8,863,597, issued Oct. 21, 2014, the contents of which are fully incorporated herein for all purposes.
BACKGROUND OF THE INVENTION
Field of Invention
The present invention relates to an impulse device and more particularly pertains to mounting freely movable masses about the periphery of counter rotating circular capture plates which are in turn mounted onto a main rotational axis drive shaft, whereby energy is provided to cause the circular capture plates to counter rotate, while having the ability to move the freely movable masses radially toward and away from the axis of rotation. The invention further relates to a new method of converting rotational energy, as generated by an engine or motor, into linear motion.
Description of the Related Art
Current terrestrial transportation technologies use a variety of mechanisms to convert the rotational energy generated by the engine or motor contained within the vehicle into the linear motion of the vehicle. In the automotive world there are three basic forms of the mechanical device generally known as a transmission that is connected to the motor/engine and in turn itself is connected to a drive shaft and gear assembly that ultimately attaches to the drive wheel(s) (the drive train) to produce the motion of the vehicle. The three basic varieties of an automotive transmission are manual, automatic and continuously variable, with the manual transmission generally being the most efficient form for transmitting the motor/engine power to the drive wheel(s).
In aircraft the choices for converting engine power output into vehicle motion are propellers and jet engine thrust from jet engines such as turbofan engines or turbojet engines. Aircraft propeller efficiency varies according to the shape of the propeller and the angle of incidence of the propeller. In every case the amount of energy used to spin the propeller is significantly greater than the amount of thrust produced. Jet engine efficiency similarly suffers losses between the input of the fuel's energy and the output of the thrust energy. Moreover, propeller aircraft suffer significant efficiency losses as altitude increases.
Marine propellers have thrust to input power ratios similar to aircraft propellers with the additional problem of corrosion and encrustation thrust losses not suffered by aircraft propellers.
Accordingly, there existed a need for a highly efficient device that would solve the problems of fuel inefficiency, excess energy consumption and reduce friction wear of operable parts. In this regard, the present invention substantially fulfills this need.
Prior patented devices have exploited the relationship between the radius of the gyration of movable weights, the centripetal force required to maintain a constant radius of the gyration of movable weights and the effect that varying the radius has on the overall energy balance of the system. By way of example, the prior art includes U.S. Pat. No. 3,968,700. In U.S. Pat. No. 3,968,700 the inventor in his abstract stated that his device “ . . . relates to new and useful improvements in devices that convert the centrifugal forces produced by rotating masses into a propulsive force acting in one direction and which is comprised of a movable supporting structure in which identical sets of masses rotate in opposite directions about an axis which is perpendicular to the desired direction of travel and a mechanism for continuously varying the radius of gyration of each mass during its cycle of revolution.” The method employed in the device of the '700 patent to create and exploit differential centripetal accelerations and convert that difference into a linear force was to have two circular aspects of that device which had their respective centers offset slightly, one circular aspect being comprised of a bearing race and the other circular aspect consisting of an assembly having an axis that has radial arms extending from it and onto which radial arms are mounted masses that can move radially toward and away from the axis along the radial arms. Since in that device the bearing race center is offset from the radial arm center of rotation, when the movable masses gyrated about the offset circular bearing race, the angular velocity, and hence the centripetal acceleration, varied with the difference in those two values, resulting in a produced linear thrust vector. Further, the device in U.S. Pat. No. 3,584,515 similarly exploited the forces generated by varying the radius of a circle around which rotating masses were constrained to take. In U.S. Pat. No. 3,998,107 the same concept of varying the radius of the circle about which masses are rotated to produce a difference from one point to another of the amount of centripetal force generated is also exploited. In the device of the '107 patent, the entire inner housing which contained the movable thrust masses, the cylinders in which the movable masses were contained and the associated connecting rods were caused to rotate about a stationary, crank like shaft that itself could be moved to vary the direction of the resulting centripetal acceleration difference that was induced by varying the radius of gyration. It could not change the magnitude of the resulting thrust vector other than by changing the velocity of gyration. In these cases the direction of the desired thrust vector is fixed by the particular design of the device, or the thrust vector magnitude is limited, or both.
U.S. Pat. No. 3,807,244 and U.S. Pat. No. 2,009,780 are other examples of such devices. In the patents discussed above the direction of the desired thrust vector is fixed by the particular design of the device, or the thrust vector magnitude is limited, or both.
Therefore, it can be appreciated that there exists a continuing need for a new and improved device which can be used to exploit the relationship between the radius of the gyration of movable weights, the centripetal force required to maintain a constant radius of the gyration of movable weights and the effect that varying the radius has on the overall energy balance of the system, without limiting or fixing the directional movement of the thrust vector to the design of the device.
BRIEF SUMMARY OF THE INVENTION
After extensive study of various inertial systems, the present inventor discovered that conventional means of converting the input energy of an engine or motor into thrust that propelled a vehicle could be eliminated. Specifically, it is the object of the present invention to provide a more useful alternative to automotive transmissions and drive trains, aeronautical and marine propellers and for on orbit uses, a more useful alternative to reaction wheels, ion and chemical thrusters.
Accordingly, a primary purpose of the propulsion drive is to use a movable ramp to sequentially and in a continuous sequence accelerate the gyrating inertial thrust masses towards the axis of the counter-rotating disks and thereby translate kinetic energy to the device. Basically, the device exploits the inertial mass and rotational energy of the radially freely movable masses and generates linear motion of the entire device and any object to which the device is affixed. As such, the general purpose of the present invention is to make things move in any desired direction via the reaction force applied to the acceleration ramps and translated to the impulse drive plate, which is attached to a vehicle, with the direction of movement determined by the direction of the impulse body control arm which is under the control of the vehicle's operator.
To attain the linear motion of the device, the present invention essentially comprises an arrangement of freely movable inertial thrust masses that are constrained to move in a circle at high speeds but which also have the ability to freely move radially toward and away from the axis of rotation. The movement of these masses toward the rotational axis is induced mechanically through ramps that increase the inertial thrust mass's centripetal acceleration at sites about the circumference of the circle about which the movable inertial thrust masses are spun. This induced asymmetrical additional centripetal acceleration, by the operation of Newton's Third Law of motion, produces an oppositely directed reaction force in the device, which is the source of the desired thrust. The counter-rotating capture plates and inertia thrust masses negate imparting any angular momentum to the device. The number of the movable masses, elsewhere referred to herein as inertial thrust masses, and the number of impulse ramps or other similarly functioning devices, as well as the size of the circle about which the inertial thrust masses move and the speed of rotation, can be varied to fit the specific application under contemplation. As the invention is mechanical in nature, a conventional oiling system is required, as well as an enclosing shell that protects the moving parts from contamination and collects and reuses the oil.
Energy to rotate the movable inertial thrust masses and actuate the impulse ramps is externally supplied, thus complying with the conservation of energy laws. The bi-directional impulse ramps are powered externally or internally by motors or engines. In the version described herein it is contemplated that a single, external source us used to provide all needed power to the invention's counter rotating drive discs. The mass impulse ramps can be controlled to fit the performance needs of the operator. Since the inertial thrust mass impulse ramps may be positioned anywhere to intercept the motion of the thrust masses about the periphery of their circular motion, the thrust vector produced can be varied at the direction of the operator. Since there are few moving parts that move against other component parts, friction is minimized. As the thrust that is produced by the invention can cause any device to which the invention is attached to move, and the inherent inefficiencies of automotive drive trains and propellers are avoided. Since the inertial thrust masses are continuously reused, the device does not run out of propellant as is the case with ion or chemical thrusters.
There has thus been outlined, rather broadly, the more important features of the invention in order that the detailed description thereof that follows may be better understood, and in order that the present contribution to the art may be better appreciated. There are, of course, additional features of the invention that will be described hereinafter and which will form the subject matter of the claims appended hereto.
In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the Figures. The invention is capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting.
As such, those skilled in the art will appreciate that the conception, upon which this disclosure is based, may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is therefore an object of the present invention to reduce power loss and increase energy efficiency when converting the energy generated by the engine/motor into linear motion.
It is an object of the present invention to provide an impulse drive that may be easily and efficiently manufactured and marketed.
A further object of the present invention to provide environmental benefits resulting from increased energy efficiency in the transportation industry.
Another object of the present invention is to provide economic benefits resulting from the reduced cost of production of the invention as compared to the cost of the production of automotive drive trains.
A further object of the invention is operator control of the device for control of the direction and magnitude of the induced linear thrust vector.
Still another object of the invention is to use movable bi-directional acceleration ramps to change the length of the radius of the circle followed by the inertial thrust masses at one or more locations around the circumference of the circular path followed by the inertial thrust masses, such that when the acceleration ramps are moved into the paths of the gyrating inertial thrust masses, the length of the radius of the circle being followed by the inertial thrust masses is shortened.
A further object of the invention is to increase the centripetal force generated in the device as the speed of gyration of the thrust masses is decreased in proportion to the amount of radial acceleration and the change in the length of the radius of the circle being followed by the inertial thrust masses when the movable bi-directional acceleration ramps are moved into the path of the gyrating inertial thrust masses.
Another application of the device is in space. Current space craft, including commercial satellites, use chemical rockets for propulsion or ion propulsion (one U.S.A. ion propulsion craft has been successful as of the date hereof, the Deep Space One). Since the fuel of the rocket is also the reaction mass which is consumed by the process of generating thrust, once the fuel is exhausted the useful life of the satellite or space craft is ended. The present invention has no such limitation as the reaction mass of the invention consists of the freely movable thrust masses which are retained and reused. So long as a power supply such as solar panels or radioisotope thermoelectric generators (RTGs) can provide electrical energy to a motor to power the invention, thrust is available to stabilize satellites in orbit or to propel space craft as needed or desired.
These together with other objects of the invention, along with the various features of novelty which characterize the invention, are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and the specific objects attained by its uses, reference should be had to the accompanying Figure and descriptive matter in which there is illustrated one of the embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein:
FIG. 1 is an upper perspective illustration of the preferred embodiment of the stardrive propulsion system constructed in accordance with the principles of the present invention.
FIG. 2 is a lower perspective illustration of the preferred embodiment of the stardrive propulsion system constructed in accordance with the principles of the present invention.
FIG. 3 . is a plan view of the lower side of the present invention.
FIG. 4 is a cross-sectional view taken along lines 4 - 4 of FIG. 3 .
FIG. 5 is a right side view of the present invention of FIG. 1 .
FIG. 5A is a secondary right side view of the present invention.
FIG. 6 is a sectional view taken along lines 6 - 6 of FIG. 5 .
FIG. 7 is a sectional view taken along lines 7 - 7 of FIG. 5A to show the area below upper capture plate 5 .
FIG. 8 is a sectional view taken along lines 8 - 8 of FIG. 5A to show the area below the upper clockwise capture plate 10 .
FIG. 9 is an elevational view of the present invention showing the lower side.
FIG. 10 is a perspective view illustration the vectors of motion of the present invention.
FIG. 11 is an alternative embodiment of the present invention.
FIG. 12 is an alternative embodiment of the present invention.
FIG. 13 is a detailed view of the alternative thrust mass of the present invention.
FIG. 14 is a view of the thrust mass taken along line A-A of FIG. 11 .
FIG. 15 is a detailed view of an alternative spring arrangement.
FIG. 16 is a view of the device mounted upon a buoyant vehicle.
FIG. 17 is a view of the device mounted upon a wheeled vehicle.
Similar reference characters refer to similar parts through the several views of the drawings.
DETAILED DESCRIPTION OF THE INVENTION
With reference now to the drawings, and in particular to FIGS. 1 and 2 thereof, a stardrive propulsion system embodying the principles and concepts of the present invention and generally designated by the reference numeral 65 will be described.
The present invention, stardrive propulsion system, is comprised of a plurality of components. Such components in their broadest context include an impulse body, acceleration ramps, a ramp position motor, an upper and lower counter-clockwise capture discs, an upper and lower clockwise capture discs, inertial thrust masses and a motor. The use of effective mass multiplication apparatuses is also disclosed. Such components are individually configured and correlated with respect to each other so as to attain the desired objective.
More specifically, the present invention includes a propulsion device for creating linear motion by applying a fixed mechanical interference, the impulse ramps, to absorb a portion of the kinetic energy as the momentum of rotating inertial thrust masses is diverted by the fixed mechanical interference, within the system. The device includes a plurality of capture plates 9 , 10 , 14 and 15 . The capture plates have a plurality of capture slots 19 that are equidistantly spaced about the periphery of each of respective the capture plates. The plurality of capture plates includes a pair of counter-clockwise rotating capture plates and a pair of clockwise rotating capture plates. The pair of counter-clockwise capture plates are made by a lower counter-clockwise capture plate 4 and an upper counter-clockwise capture plate 5 . The pair of clockwise capture plates are made by a lower clockwise capture plate 10 and an upper clockwise capture plate 9 .
Also, a plurality of capture plate gears is included. The plurality of capture plate gears includes a motor drive gear 20 , a tandem intermediate drive gear 11 , a tandem reversing gear 24 , a clockwise capture plate gear 16 , and counter-clockwise capture plate gear 15 . The tandem intermediate drive gear has an upper gear part 11 a and a lower gear part 11 b . The upper gear part meshes with the tandem reversing gear which meshes with the counter-clockwise capture plate gear which is connected to one of the pair of capture plate shafts for rotation of the lower counter-clockwise capture plate and the upper counter-clockwise capture plate. The lower gear part meshes with clockwise capture plate gear which is connected to another of the pair of capture plate shafts for rotation of the lower clockwise capture plate and the upper clockwise capture plate.
The plurality of capture plates and the plurality of capture plate gears are mounted to an impulse drive plate 1 . The impulse drive plate has a first side 1 a and a second side 1 b , with the plurality of capture plates being mounted on the first side of the impulse drive plate and the plurality of capture plate gears being mounted to the second side of the impulse drive plate. The plurality of capture plates are in rotational communication with the plurality of capture plate gears by way of a pair of co-axial capture plate shafts. The pair of capture plate shafts includes a counter-clockwise capture plate shaft 14 and a clockwise capture plate shaft 13 .
Further, a plurality of inertial thrust masses are positioned within corresponding capture slots of the plurality of capture plates. In this embodiment of the device the upper and lower counter-clockwise capture plates have at least three inertial thrust masses 2 positioned with capture slots. The upper and lower clockwise capture have at least three inertial thrust masses 3 positioned with capture slots. The inertial thrust masses move freely within the capture slots.
An impulse body 7 is mounted to the first side of the impulse drive plate and is spaced from the plurality of capture plates. The impulse body has a plurality of acceleration ramps 17 and 30 . The acceleration ramps are sized to be placed between the plurality of capture plates for engagement of the plurality of inertia thrust masses positioned within the capture slots of the capture plates. Additionally, the impulse body includes two pulleys 43 . One of the pulleys is connected to a ramp position motor drive shaft 45 a and the other pulley is connected to a ramp position screw shaft 46 . A drive belt 44 is used to transfer rotational motion from the one pulley connected to the ramp position motor drive shaft to the other pulley connected to the ramp position screw shaft. A ramp position motor 45 is connected to the ramp position motor drive shaft and mounted on the impulse body. The rotational motion generated by the ramp position motor will cause the ramp position screw 50 to be driven fore and aft for movement of the impulse body and thereby changing the position of the impulse ramps between the plurality of capture plates.
In this embodiment of the device a motor 22 is mounted to the impulse drive plate. The motor receives its power from the vehicle in which the impulse drive plate is mounted thereon. Once the motor is activated, the plurality of capture plate gears is rotated and will in turn rotate the plurality of capture plate shafts. The rotation of the two capture plate shafts causes rotation of the capture plates for clockwise and counter-clockwise rotation of the plurality of inertial thrust masses within the capture slots with the rotating plurality of inertial thrust masses making contact with the impulse ramps. The force that is transmitted to the impulse drive plate is caused by the radial acceleration of the inertial thrust masses by the impulse ramps and causes movement in the direction determined by the movement of an impulse body control arm which is under the control of the vehicle's operator. Simply stated, energy is transferred to the impulse body 7 from the acceleration of the inertial thrust masses 2 and 3 when they pass over and are radially accelerated by their respective acceleration ramp, and is transferred to impulse drive plate 1 .
For the purposes of this application vehicle is defined as any man made means of transportation that is mechanized.
Referring to FIGS. 1 and 2 , impulse drive plate 1 is the mechanism mounting substrate. Motor 22 is connected to impulse drive plate 1 and provides rotation power (referring to FIGS. 3 and 4 ) through motor drive shaft 21 , resulting in the clockwise rotation of motor drive gear 20 . Motor drive gear 20 meshes with tandem intermediate drive gear 11 . The tandem intermediate drive gear 11 is a single part that has a upper gear part 11 a and a lower gear part 11 b . The upper gear part 11 a of tandem intermediate drive gear 11 meshes with tandem reversing gear 24 . The lower gear part 11 b of tandem intermediate drive gear 11 meshes with clockwise capture plate gear 16 . Tandem reversing gear 24 meshes with counter-clockwise capture plate gear 15 . Counter-clockwise capture plate gear 15 is an all in one piece gear and hub that is either built as a one piece or pressed together by glue or other means to be one piece. The rotation of lower counter-clockwise capture plate 4 and upper counter-clockwise capture plate 5 is driven by means of counter-clockwise capture plate shaft 14 connected to counter-clockwise capture plate gear 15 . The rotation of lower clockwise capture plate 9 and upper clockwise capture plate 10 is driven by means of clockwise capture plate shaft 13 , connected to clockwise capture plate gear 16 . Clockwise capture plate shaft 13 is coaxial to counter-clockwise capture plate shaft 14 . As motor 22 applies rotational power to the system, inertia thrust masses 3 move in opposite centrifugal orbits relative to inertia thrust masses 2 .
Referring to FIG. 7 , a plurality of inertia thrust masses 3 is captured in capture slot 19 formed by lower counter-clockwise capture plate 4 and upper counter-clockwise capture plate 5 as shown on FIG. 6 . This plurality of inertia thrust masses 3 are equally spaced along centrifugal path 41 as shown on FIG. 10 , at a velocity and counter-clockwise rotation that causes these masses to be thrown to the outside limits of capture slot 19 by centrifugal force. Inertia thrust mass 3 centrifugal diversion is limited by mass retainer surface 6 , located on the distal end of capture slot 19 . A portion of inertia thrust mass 3 is allowed by mass retainer surface 6 to extend into upper impulse ramp slot 8 .
Referring to FIG. 8 , a plurality of inertia thrust masses 2 is captured in capture slot 19 formed by lower clockwise capture plate 9 and upper clockwise capture plate 10 , as shown on FIG. 6 . This plurality of inertia thrust masses 2 are equally spaced along centrifugal path 41 as shown on FIG. 10 , at a velocity and clockwise rotation that causes these masses to be thrown to the outside limits of capture slot 29 by centrifugal force. In one embodiment, the masses are maintained at the outer limits via mass multiplication apparatuses. Inertia thrust mass 2 centrifugal diversion is limited by mass retainer surface 28 , located on the distal end of capture slot 29 . A portion of inertia thrust mass 2 is allowed by mass retainer surface 28 to extend into lower impulse ramp slot 23 .
Referring to FIG. 10 , as inertia thrust mass 2 and inertia thrust mass 3 contacts the acceleration ramps attached to impulse body 7 , the direction of the masses is diverted by acceleration ramps 17 and 30 , inducing forces by causing resultant vector 32 and resultant vector 33 in vector convergence zone 31 to converge. The impulse vector is collinear as inertia thrust mass 2 and inertia thrust mass 3 reach impulse apex 18 . This creates the maximum force to impulse drive plate 1 , by means of impulse translation from impulse apex 18 into the impulse body 7 as shown in FIG. 4 , and through impulse body bushing 25 , through impulse drive plate 1 , causing an induced motion vector 42 .
Referring to FIG. 10 , as inertia thrust mass 2 and inertial thrust mass 3 pass impulse apex 18 , the force of the masses continues as two opposing and divergent vectors 34 and 35 in vector divergent zone 36 on an Inertial thrust mass path 39 and 40 , as defined by the angle of inertial thrust mass 2 and inertial thrust mass 3 . Referring to FIG. 6 , inertial thrust mass 2 and inertial thrust mass 3 is recaptured by capture slot 29 and capture slot 19 . The recapture vector 37 and 38 forces cancel, and do not cause any reactive force to be applied to induced motion vector 42 .
Referring to FIG. 4 , the force can be regulated by the contact of inertial thrust mass 2 and inertial thrust mass 3 relative to the position of acceleration ramps 17 and 30 , by increasing or decreasing the diverted path of these inertial thrust masses. The acceleration ramps 17 and 30 act as fixed mechanical interferences that translate energy to impulse drive plate 1 by absorbing a portion of the kinetic energy as the momentum of the inertial thrust masses 2 and 3 is diverted by the impulse ramps. This is done by moving the position of Impulse body 7 , thereby positioning the impulse ramp 17 and 30 in lower impulse ramp slot 23 and upper impulse ramp slot 8 , relative to the center or rotation of the inertial thrust masses. Ramp position motor 45 drives and power transmission assembly composed of two pulleys 43 and drive belt 44 to transfer rotational motion to ramp position screw shaft 46 . The ramp position motor is connected to a control system within the vehicle that can be manually or remotely operated. Specifically, one of the pulleys is connected to a ramp position motor drive shaft 45 a and the other pulley is connected to ramp position screw shaft 46 . The drive belt 44 is used to transfer rotational motion from the one pulley connected to the ramp position motor drive shaft to the other pulley connected to the ramp position screw shaft 46 . This motion allows ramp position screw 50 to be driven fore and aft, relative to the center or rotation of the inertial thrust masses, by means of impulse body bushing 25 .
Referring to FIG. 3 , ramp position screw shaft 46 is retained in impulse body 7 by ramp shaft retainer 47 , captured in ramp shaft retainer slot 48 . Referring to FIG. 6 , impulse body 7 is held in place and slides fore and aft relative to the center or rotation of the inertial thrust masses, by means of impulse body forks 49 captured by impulse body retaining slot 51 , located in impulse body bushing 25 .
Referring to FIG. 9 , impulse body control arm 12 is keyed to impulse body 7 and pivots in the impulse driven plate aperture 26 as shown on FIG. 6 . Impulse body control arm is connected to the steering mechanism of the vehicle. Movement of the impulse body control arm 12 changes the impulse vector angle 52 of the impulse body 7 relative to impulse drive plate 1 . This angular movement changes the induced motion vector 42 relative to impulse drive plate 1 , allowing directional control of forces.
Alternative Embodiments
An alternative embodiment of the present invention is disclosed in FIGS. 11-15 . This embodiment is the same in most respects to the primary embodiment discussed above. However, as noted below, the thrust masses are not spherical. Rather, the masses are formed from weighted plates that travel on opposing rollers. Additionally, springs are included to urge each of the thrust masses into an extended orientation relative to the capture discs. This ensures that the thrust masses are exposed and contact the impulse ramp upon rotation. This has the effect of increasing the linear thrust generated by the device. This embodiment is more fully described hereinafter.
As with the primary embodiment, device 110 includes a drive plate 112 upon which a number of the device components are mounted. Drive plate 112 includes both forward and rearward ends. Drive plate 112 supports both an electric motor 114 and an impulse ramp 116 . Impulse ramp 116 is preferably formed adjacent the forward end of drive plate 112 . Additionally, acceleration ramp 116 preferably has an upper extent adjacent the upper capture plates and a lower extent adjacent the lower capture plates. As more fully explained above, ramp 116 may be adjustable to selectively alter both the magnitude and orientation of the forces generated by device 110 .
With specific reference to FIG. 11 , device 110 includes a pair of upper capture plates 118 . Each plate of the pair is identical so only one is shown for clarity. As noted in the cross sectional view of FIG. 4 , upper plates 118 are placed in facing relation with one another, with a series of equally spaced radial slots 122 formed there between. Each slot 122 houses an associated thrust mass 124 . Any of a variety of configurations can be used for thrust masses 124 . In the preferred embodiment, however, each thrust mass 124 takes the form of a plate or body that is supported at either end by a roller 126 . Rollers 126 allow the associated thrust mass 124 to travel within a slot 122 . More specifically, thrusts masses 124 travel between a retracted position at the innermost extent of slot 122 and an extended position. In the extended position, the distal end of thrust mass 124 extends to the end of slot 122 .
The respective thrust masses 124 are urged, or biased, into the extended orientation by way of a series of springs 128 , which extend into the capture disc slots. The springs extend into the slots further than the maximum radial travel of the thrust masses so that each thrust mass is continuously constrained by the spring throughout its radial motion. Any of a variety of spring types can be used. FIG. 13 illustrates the use of a lever arm 128 and an associated coil spring. FIG. 15 illustrates the use of a leaf spring 132 with a first end that is mounted into the wall of the slot 122 . Still yet other spring arrangements can be used. Regardless of the spring type, a spring is positioned within each of the radial slots 122 . As illustrated in FIG. 13 , spring 128 biases the corresponding thrust mass 124 into the second extended position. In use, a motor 114 , functions to rotate the upper capture plates 118 and the associated thrust masses 124 in a first sense “a.”
FIG. 12 illustrates a pair of lower capture plates 142 . A series of equally spaced radial slots 144 is likewise formed between lower capture plates 142 . Each of the radial slots 144 houses a thrust mass 146 , with each thrust mass 146 including opposing rollers 148 to allow the thrust mass 146 to move between the retracted and extended positions. A spring 152 (which is the same construction as spring 128 ) is positioned within each of the radial slots 144 . Spring 152 biases the corresponding thrust mass 146 into the second extended position. Again, motor 114 functions to rotate the lower capture plates 142 and the associated thrust masses 146 in a second sense “b” that is counter to first sense “a.” In the preferred embodiment, three slots and three thrust masses are included in both the upper and lower sets of plates.
The counter rotation (“a” vs. “b”) of the upper and lower capture plates ( 118 and 142 ) causes the thrust masses ( 124 and 146 ) to sequentially encounter impulse ramp 116 . In this regard, the upper masses 124 contact the upper extent of ramp 116 , while the lower masses 146 contact the lower extent of ramp 116 . Each of these encounters forces the corresponding thrust mass ( 124 and 146 ) into the retracted position. Notably, the encounter with ramp 116 forces the thrust masses ( 124 and 146 ) into the retracted position over the bias of the corresponding springs ( 128 and 152 ). As a result, an impulsive force is transferred to ramp 116 and plate 112 and a corresponding forward motion is generated. Finally, FIG. 16 shows the device of the present invention installed upon an inflatable or buoyant device 162 . FIG. 17 shows the device mounted to a wheel based vehicle 164 .
The particular embodiment of the invention herein described, which is but one of several ways that the counter rotating circular capture plates in which the inertial thrust masses are contained and are radially accelerated by a ramp to produce the desired thrust can be configured. | A device that produces linear motion by sequentially and in a continuous sequence accelerating inertial thrust masses at well-defined times towards the axis of counter-rotating disks. The inertial thrust masses are contained in cavities placed equidistantly about the periphery of counter rotating capture disks mounted on a common axle. They are radially accelerated by a bi-directional impulse ramps that can be moved to any position around the periphery of the counter rotating capture plates and into and out of the paths of the gyrating thrust masses to any desired depth within the mechanical range of the impulse ramps which simultaneously engage and radially accelerate the inertial thrust masses of each counter-rotating capture plate. The counter-rotating capture plates are each separately driven by a gear assembly powered by an external engine or motor that powers the rotation of the disks. Each radial acceleration of the inertial thrust masses produces an impulse of force that pushes against the mass accelerator with a force equal to the force used to radially accelerate each thrust mass. Each impulse is a vector force and imparts motion along the chosen vector to any object to which the device is attached. | 5 |
BACKGROUND OF THE INVENTION
The present invention relates to a method of control, and more particularly, to a method of real-time control of a plurality of power output apparatus for providing a predetermined power output at an optimal efficiency of the combined plurality of the power output apparatus.
In systems which have a plurality of apparatus for supplying output power, it is oftentimes necessary to make an allocation between each apparatus in terms of how much power is to be supplied by each apparatus to obtain a desired total power output. The choice of power output from each apparatus can be a simple division of the total power output desired divided by the number of apparatus. However, such a simple and straight forward approach will oftentimes result in a high inefficiency, or put another way, the cost per unit of output power will most likely not be minimal. (The unit of output power can be pounds of steam, watts, BTUs, . . . .) For example, one of the major challenges in the pulp and paper industries is the optimization of steam production rates for plant boilers. Significant cost savings result when plants are switched from a manual allocation system to a computerized allocation system. In present systems, automated solutions have been implemented on mini-computers and have been expensive to implement and provided slow and incomplete service when implemented. The present invention provides a solution to the problems of these present day systems. Thus it is desired to make an allocation of power output to be supplied by each power output apparatus such that the overall cost of the power supplied is minimal, i.e., an economic load allocation of the power output apparatus, and on a real-time basis.
In the preferred embodiment of the present invention, a method for allocating an output load between a plurality of boilers to supply steam most economically will be described; however, the method will be equally applicable to cooling towers, chillers, air conditioners, turbines, . . . .
Some present systems can only perform an economic load allocation for systems which have efficiency curves characterized by linear equations. The method of the present invention can be utilized for any algebraic efficiency characterization equation and yield a complete solution in substantially fewer iterations than previous techniques.
SUMMARY OF THE INVENTION
Therefore, there is provided by the present invention, a method for making a real-time economic load allocation. The method allocates a demanded amount of power to a plurality of power output apparatus, each power output apparatus having a cost curve associated therewith, such that each of the power output apparatus supplies portion of the demanded power. The total of the power outputted from the plurality of power output apparatus equals the amount of the demanded power. Further, the total power outputted from the plurality of power output apparatus is optimally cost efficient. The method comprises the steps of entering data for each of the power output apparatus into a controller, the data providing information about each of the power output apparatus. Solutions are generated for all possible output power demands, within output power bounds of each of the power output apparatus. The solutions indicate the portion of power each power output apparatus is to supply to provide the total power demanded at optimal cost efficiency. The solutions are stored in tables within a storage unit of the controller. Upon receipt of a demand for power, a search is performed of the solution tables to obtain the amount of power each power output apparatus is to supply, the total of the amounts of power from each power output apparatus being equal to the amount of power demanded at optimal cost efficiency. Control signals are then outputted to each of the power output apparatus, the control signals being indicative of the amount of power to be supplied.
In the preferred embodiment, the controller is a process control system which provides the control signals to a plurality of boilers for indicating the quantity of steam each boiler is to supply to the process. The solution of the present invention is performed by optimization by parts. A first and second boiler characteristics are combined to give an optimal cost curve. The combined optimal cost curve of the first and second boiler are combined with a third boiler to yield an optimal cost curve for the first, second and third boiler. The combining continues until the plurality of boilers have been optimally combined to yield the optimal solution for the plurality. This solution method results in many times fewer iterations than present techniques.
Accordingly, it is an object of the present invention to provide a method for making a real-time economic load allocation of power output apparatus.
It is another object of the present invention to provide a method for making a real-time economic load allocation of power output apparatus whereby each power output apparatus efficiency curve can have any algebraic equation characterization.
It is still another object of the present invention to provide a method for making real-time economic load allocation of power output apparatus whereby the number of iterations to provide a complete solution is relatively small.
These and other objects of the present invention will become more apparent when taken in conjunction with the following description and attached drawings, wherein like characters indicate like parts, and which drawings form a part of the present application.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a block diagram of the preferred embodiment of a process control system in which the present invention is utilized;
FIG. 2 shows typical efficiency curves for three boilers;
FIG. 3 shows a flow diagram outlining the setup and overall implementation of the method of the present invention;
FIG. 4, which comprises FIGS. 4A-4C, shows cost examples of cost curves for boilers 5 and 6 of an example, and an optimal cost curve for the combination; and
FIG. 5 shows an example of the generation of the boiler 5/6 optimal cost combination solution table, which is depicted in the optimal cost curve of FIG. 4C.
DETAILED DESCRIPTION
Before describing the method of the present invention, it will be helpful in understanding a process control system, and in particular, the process control system of the preferred embodiment in which the method of the present invention can be utilized. Referring to FIG. 1, there is shown a block diagram of a process control system 10. The process control system 10 includes a plant control network 11, and connected thereto is a data highway 12, which permits a process controller 20' to be connected thereto. In the present day process control system 10, additional process controller 20' can be operatively connected to the plant control network 11 via a corresponding highway gateway 601 and a corresponding data highway 12. A process controller 20, is operatively connected to the plant control network 11 via a universal control network (UCN) 14 to a network interface module (NIM) 602. In the preferred embodiment of the process control system 10, additional process controllers 20 can be operatively connected to the plant control network 11 via a corresponding UCN 14 and a corresponding NIM 602. The process controllers 20, 20' interface the analog input and output signals, and digital input and output signals (A/I, A/0, D/I, and D/0, respectively) to the process control system 10 from the variety of field devices (not shown) which include valves, pressure switches, pressure gauges, thermocouples, . . . .
The plant control network 11 provides the overall supervision of the controlled process, in conjunction with the plant operator, and obtains all the information needed to perform the supervisory function, and includes an interface with the operator. The plant control network 11 includes a plurality of physical modules, which include a universal operator station (US) 122, an application module (AM) 124, a history module (HM) 126, a computer module (CM) 128, and duplicates of these modules (and additional types of modules, not shown) as necessary to perform the required control/supervisory function of the process being controlled. Each of these physical modules includes a microprocessor and is operatively connected to a local control network (LCN) 120 which permits each of these modules to communicate with each other as necessary in accordance with a predetermined protocol. The NIM 602 and HG 601 provide an interface between the LCN 120 and the UCN 14, and the LCN 120 and the data highway 12, respectively. A more complete description of the plant control network 11, and the physical modules can be had by reference to U.S. Pat. No. 4,607,256, and a more complete description of the process controller 20' can be had by reference to U.S. Pat. No. 4,296,464. The process controller 20, provides similar functions to that of process controller 20' but contains many improvements and enhancements.
In the preferred embodiment of the present invention, it is desired to control a plurality of boilers (not shown) which outputs steam for the process being controlled, and more specifically, it is desired to allocate the amount of steam each boiler is to supply such that the total cost of the total steam from all the boilers is minimized. The function of allocating (i.e., the real-time economic load allocator) of the preferred embodiment of the present invention is performed by the application module (AM) 124, although it will be understood by those skilled in the art that the function can be performed by other modules of the process control system 10, including the process controller 20.
The method of the present invention will now be described. For purposes of example, the process includes six (6) boilers which are to be included in supplying steam to the process. All boilers have different cost curves due to the variety of fuels available and different operating efficiency curves. Referring to FIG. 2, there is show typical efficiency curves for three (3) boilers. These curves are typically represented as a third order polynomial equation, but the method of the present invention is not limited to such typical representations.
Referring to FIG. 3, there is shown a flow diagram outlining the setup and overall implementation of the method of the present invention. In the preferred embodiment of the present invention, a user enters the fuel cost, boiler range, and efficiency parameters into the application module 124 as numeric points (block 101). This information essentially makes up the efficiency (or costs) curves referred to above. After the parameters are entered the present invention performs a setup procedure and solves for all possible steam loads, and for the special cases such as offline boilers (block 105). These solutions are stored in solution tables which are used to provide instant recommendations for any steam load solution (block 110). If any of the critical parameters such as the operating efficiency curves or fuel costs are changed, a new setup is performed and new tables created. Typically the setup procedure is completed within one minute of processing time in the preferred embodiment of the present invention. The application module, i.e., the process control system 10, is ready for the process control function. Upon receiving a demand for a steam load, the present invention searches the solution tables and provides instantaneous recommendations to load each boiler for the current steam demand (block 115). When the operator input is received enabling the optimal loading solutions (or indicating other loading desired) the information is outputted directly by the process control system or ramped over a period of time in response to the operator command. The output of the present invention interfaces directly into traditional controller schemes so that bias loads necessary are provided to minimize boiler costs or directly provide each boiler steam demand set point as is well known by those skilled in the art (block 120). As steam demands change (block 125) new control signals are outputted or if the system is in a nonautomatic mode the recommendations are provided (block 115) and an operator input awaited.
Although not shown, as the steam demand changes, the method of the present invention can provide current solutions on a real-time basis to provide the optimal load distribution for the current set of boilers, or a second "global solution"is provided which considers boilers that are to be taken off line, or placed on line. The method of the present invention determines the effects of shutting down boilers during periods of minimum demand while maintaining the required excess capacity to meet changes in the steam demand. This provides a tremendous cost savings during partial plant shutdowns. In addition the method of the present invention can determine the optimum steam load for maintenance for plant shutdowns. When a boiler is shutdown, a partial setup procedure is executed and the solution tables modified to reflect a loss of the boiler and the effects of losing an additional boiler. When the steam demand increases above the excess capacity set point, the method of the present invention will automatically recommend that the offline boiler be restarted to meet the new demand. The setup procedure is then executed and a new set of solution tables is calculated. The local optimization is calculated solutions where the same number of boilers is maintained. The global solution examines all possible distributions of the steam rate across all available boilers (except those designated as being offline for maintenance) and determines the best set of boilers to use for steam production.
The method of the present invention high speed optimization technique utilizes a Method of Optimization by Parts which guarantees that the least cost loading is always determined. Since the performance curve representing boilers are not limited to straight lines (as in the case with some types of optimization, the results of the present invention are extremely accurate). The performance curves can be of any type of algebraic equation including high order polynomials.
The determination of optimal loading of the boilers to meet a predetermined total steam load of the method of the present invention will now be described. For purposes of example only, a system having six (6) boiler will be discussed. As mentioned above, each boiler has its own characteristics resulting in a unique efficiency curve, or cost curve, the cost curve being directly related to the efficiency curve. The method of the present invention combines the cost curves of each of the boilers to obtain an optimal cost curve for the combination of all the boilers. The method uses an optimization by parts technique which combines two (2) boilers in this example, then combines that combination with another boiler, then combines that combination with yet another combination . . . . The total boilers can be expressed as a function of the total steam or f(T) where
f(T)=G(X1, X2, X3, X4, X5, X6)=G.sub.1 (X1)+G.sub.2 (X2)+G.sub.3 (X3)+G.sub.4 (X4)+G.sub.5 (X5)+G.sub.6 (X6)
where
T=total steam,
Xn=steam for the boiler n, and
N.sub.1 ≦X1≦M.sub.1
N.sub.2 ≦X2≦M.sub.2
N.sub.3 ≦X3≦M.sub.3
N.sub.4 ≦X4≦M.sub.4
N.sub.5 ≦X5≦M.sub.5
N.sub.6 ≦X6≦M.sub.6
N 1 , . . . N 6 are known, M 1 . . . M 6 are known, and T (the total steam) equals X1+X2+X3+X4+X5+X6. In addition,
T.sub.min =N.sub.1 +N.sub.2 +N.sub.3 +N.sub.4 +N.sub.5 +N.sub.6
T.sub.max =M.sub.1 +M.sub.2 +M.sub.3 +M.sub.4 +M.sub.5 +M.sub.6.
The functions G 1 . . . G 6 are of any algebraic order or form. Typically boilers are expressed as
G.sub.n (X.sub.n)=A.sub.n X.sup.3.sub.n -B.sub.n X.sup.2.sub.n +C.sub.n X.sub.n -D.sub.n
T.sub.min (the minimum total steam)
T.sub.max (the maximum total steam)
The optimization used in the Method of Optimization by Parts optimizes the f(T) in accordance with the expression
OPT [f(T)]=OPT [G.sub.1 (X1)+OPT [G.sub.2 (X2)+OPT [G.sub.3 (X3)+OPT [G.sub.4 (X4)+OPT [G.sub.5 (X5)+G.sub.6 (X6)]]]]].
OPT=optimize
The technique (or algorithm) of the present invention defines a new variable S 56 =X 5 +X 6
S.sub.56m =M.sub.5 +M.sub.6 and
S.sub.56n =N.sub.5 +N.sub.6.
It is now desired to combine or optimize the boilers 5 and 6 in accordance with the following expression. All combinations are iterated for S 56 from S 56n to S 56m to obtain a new function f 56 (S 56 ). That results in an optimal cost curve for the combination of 56. Next, G 4 (X 4 ) is optimized with the 56 combination
S.sub.456 =X.sub.4 +S.sub.56
S.sub.456m =M.sub.4 +M.sub.56m
S.sub.456n =N.sub.4 +M.sub.56n
This results in combining boiler 4 with the combination of the 56 boilers to obtain a new optimal curve. This continues until all the boilers have been combined as follows
f.sub.456 (S.sub.456)=OPT [G.sub.4 (X.sub.4)+f.sub.56 (S.sub.56)];
f.sub.3456 (S.sub.3456)=OPT [G.sub.3 (X.sub.3)+f.sub.456 (S.sub.456)];
f.sub.23456 (S.sub.23456)=OPT [G.sub.2 (X.sub.2)+f.sub.3456 (S.sub.3456)]; and
f.sub.123456 (S.sub.123456)=OPT [G.sub.1 (X.sub.1)+f.sub.23456 (S.sub.23456)];
and results in five (5) solution tables which are
T 123456
T 23456
T 3456
T 456
T 56
Referring to FIG. 4 which comprises FIGS. 4A, 4B, and 4C, there is shown a cost curve for boiler 5, a cost curve for boiler 6, and a cost curve for the combination of boilers 56 in accordance with the algorithm described above. The abscissa of the curve is the output steam from boiler 5 (S 5 ) in pounds of steam. The ordinate axis is the efficiency or cost. Boiler 5 in this example can output no lower that two (2) lbs of steam and no more than 40 lbs of steam, N 5 and M 5 , respectively. A cost of operating the boiler 5 having an output of 2 lbs of steam is C 5a . Similarly, for outputting 3 lbs of steam the cost of operating boiler 5 is C 5b , . . . . FIG. 4B shows the cost with respect to the output steam production from boiler 6. In this example boiler 6 can output no less than 3 lbs of steam and no more than 50 lbs of steam (N 6 and M 6 , respectively). When boiler 6 operates to output 3 lbs of steam the cost associated with operating boiler 6 is C 6a . The optimization by parts method combines the cost curves of boiler 5 and boiler 6 to arrive at a combined cost curve T 56 shown in FIG. 4C.
The curve is derived by a combination shown in FIG. 5. Referring to FIG. 5, the points of the combination curve is shown. The minimum that the combination can output is 5 lbs of steam, thus, the column S 56 outputs 5 lbs of steam, and the only combination available is S 5 outputting 2 lbs of steam and boiler 6 outputting 3 lbs of steam. The cost associated with the respective boilers are added to derive a total cost, i.e., C 5a +C 6a =C 56a . That results in a single point on the T 56 cost curve and is shown in the T 56 table, or solution table T 56 . To output 6 lbs of steam from the combination, boiler 5 can output 2 lbs of steam in which case boiler 6 outputs 4 lbs of steam or boiler 6 outputs 3 lbs of steam and boiler 5 outputs 3 lbs of steam. No other combination is realizable given the minimum output of both boilers and the desired output, that is 6 lbs of steam. The costs associated with boiler 5 running at 2 lbs of steam is C 5a and the cost associated with running boiler 6 at 4 lbs of steam is C 6b , the sum being the total cost which is C 56b . The other alternative is when boiler 5 and boiler 6 are each outputting 3 lbs resulting in the desired output total of 6 lbs of steam. The cost associated with running boiler 5 with this specified output is C 5b and the cost associated with operating boiler 6 at 3 lbs of steam is C 6a , resulting in a total cost of C 56c . The total costs for 6 lbs output of steam are examined, i.e., C 56b is compared with C 56c and the lowest value selected. In this example the total costs marked with an asterisk are assumed to be the lowest cost and thus form the next point in the T 56 table. Thus the second line contains the point S 56 at 6 lbs of total steam output from the boiler 5 and 6 combination and the total cost being C 56c . The individual values of steam between S 5 and S 6 are also kept in the T 56 table. The process continues for the next point or 7 lbs of output from the combination and in this case C 56e is the lowest cost of the three and thus this particular point of information is stored in the T 56 table and continues until the total combinations are performed. The total output from the combinations can only be 90 lbs, i.e., M 5 and M 6 , or 40+50=90. Once all the points are determined the T 56 cost curve is completed. Then the T 56 cost curve is combined with the cost curve for boiler 4 resulting in the T 456 cost curve or T 456 solution table. This combination is then combined with boiler 3, . . . until finally a total combination of boilers 1-6 is performed, resulting in five solution tables T 123456 , T 23456 , T 3456 , T 456 , and T 56 . Once the total steam demand is known a fast table lookup is performed and the outputs of each individual boilers are determined from the solution tables and outputted (to the operator for a recommendation or automatically to the boilers, as discussed above).
In an alternative approach the optimal cost curve (or solution table for boilers 2 and 3 can be generated and an optimal solution, optimal cost curve for boilers 5 and 6 can be generated. Then the boiler 23 combination can be combined with boiler 1 and the boiler 56 combination can be combined with boiler 4 resulting in an T 123 table and an T 456 table, respectively. Finally the T 123 table and the T 456 table can be combined which results in a total solution of T 123456 solution table. This approach takes up less memory but requires slightly more processing time. The global tables referred to above would include various combinations eliminating first boiler 1, then boiler 12 . . . . The number of iterations for the method of the present invention as compared with classical methods which require solution of arrays is in the order of 1:10,000,000 times faster.
While there has been shown what is considered the preferred embodiment of the present invention, it will be manifest that many changes and modifications can be made therein without departing from the essential spirit and scope of the invention. It is intended, therefore, in the annexed claims to cover all such changes and modifications which fall within the true scope of the invention. | The method allocates a demanded amount of power to a plurality of power output apparatus, each power output apparatus having a cost curve associated therewith, such that each of the power output apparatus supplies a portion of the demanded power, and the total power outputted from the plurality of power output apparatus being optimally cost efficient. Data is entered for each of the power output apparatus into a controller. Solutions are generated for all possible output power demands using an optimization by parts technique within output power bounds of each of the power output apparatus. The solutions indicate the portion of power each power output apparatus is to supply to provide the total power demanded at the optimal cost efficient. The solutions are stored in tables within a storage unit of the controller. Upon receipt of a demand for power, a search is performed of the solution tables to obtain the amount of power each power output apparatus is to supply to meet the demand. Control signals are then outputted to each of the power output apparatus, the control signals being indicative of the amount of power to be supplied. | 8 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a liquid filter system, preferably an oil filter for an internal combustion engine, comprising a cup-shaped housing that is releasably connectable to a receiving head and a filter element disposed inside the housing.
[0002] Two types of fluid filters, particularly oil filters for internal combustion engines, are known in the art. On the one hand, so-called spin-on filters are used. A spin-on filter has a cup-shaped housing, a filter element non-releasably disposed therein, and a threaded end plate. The cup-shaped housing is made of metal, so that it can withstand the pressure pulsation occurring in the interior of the filter during operation of the internal combustion engine. The spin-on filter is screwed onto a receiving flange, or directly onto the engine block of the internal combustion engine, and during servicing is completely replaced with a new spin-on filter. This filter system has drawbacks, however, resulting from the material mix of the filter, because a mixture of plastics, paper, and metal must be disposed of, and separation of the various materials for disposal is problematic.
[0003] On the other hand, so-called oil modules are known in the art, in which a filter element is releasably disposed in a preferably cup-shaped housing and can likewise be screwed onto a receiving head disposed in the circuit by means of this housing. For servicing, only the metal-free filter cartridge needs to be replaced, whereas the cup-shaped housing is a lifetime component.
[0004] German Utility Model No. 200 04 31 U1 discloses a liquid filter with a bypass valve. A hollow cylindrical filter element is releasably disposed within a cup-shaped housing, and the cup-shaped housing is screwed into a connection head. A support tube, which receives the bypass valve, is disposed concentrically within the interior of the filter element. The drawback here lies in the changing of the filter element. There is a risk that the immediate surroundings of the oil filter element may be contaminated because the oil-soaked filter medium still contains a residual amount of oil, which may drip as the filter element is replaced. A further drawback is that the hands of the service personnel may become soiled by the direct contact with the oil-soaked filter element.
[0005] Another drawback is that it is not clear without closer inspection during installation of the outer housing whether a filter element is installed at all. This can be determined only by looking at the open underside of the housing, but in most cases this side has to be mounted face down, is inaccessible in an engine compartment, hidden, etc.
SUMMARY OF THE INVENTION
[0006] It is therefore an object of the invention to provide an improved liquid filter particularly suitable for filtering lubricating oil or fuel of an internal combustion engine.
[0007] Another object of the invention is to provide a filter system comprising a receiving head, a cup-shaped housing releasably attached to the receiving head and a filter element disposed within the housing in which the filter cartridge and the housing can be installed easily and in the correct position relative to each other.
[0008] A further object of the invention is to provide a liquid filter system in which it is clearly visible on the outer surface whether a filter element is installed in the housing.
[0009] A additional object of the invention is to provide a liquid filter system of the aforementioned type in which attachment of the releasable housing to the receiving head is prevented if a filter element is not properly installed in the housing.
[0010] These and other objects are achieved in accordance with the present invention by providing a liquid filter system comprising receiving head, a cup-shaped housing releasably connectable to the receiving head, and a filter element disposed inside the housing, wherein the housing is provided with a plurality of first interlocking elements that extend across at least a portion of the outer circumference of the housing or across a lower edge of the housing, each said interlocking element being interrupted by at least one axially extending recess or having a laterally adjoining axially extending recess, and wherein said filter element comprises a canister provided on an outer surface thereof or at a lower edge thereof with a plurality of second interlocking elements which are received in the axially extending recesses of the first interlocking elements when the filter element is installed in the housing.
[0011] The present invention thus relates to a liquid filter system in which:
the housing is provided with first interlocking elements that extend across at least a portion of the outer circumference and/or the bottom edge of the housing; the interlocking elements are each interrupted by at least one axially extending recess, or each have a laterally adjoining axially extending recess, and the filter element has a, preferably liquid-tight, canister which is provided on its exterior and/or its bottom edge with second interlocking elements, which as the filter element is inserted into the housing, are received in the axial recesses in the first interlocking elements.
[0015] With a liquid-tight canister, the filter element can be easily and cleanly removed from the housing in the form of a replaceable insert. A new filter element is positioned correctly, i.e., with respect to both the angular position of the two components in relation to each another and their axial position, because the second interlocking elements on the canister of the filter element mate or mesh with the recesses on the first interlocking elements of the housing.
[0016] The absence of a filter element on the inside would be visually detectable by an operator because in this case the recesses in the first interlocking element of the housing would not be filled in.
[0017] Because the first and second interlocking elements complement each other to form a uniform interlocking element, the filter element and the housing are simultaneously connected or latched to the receiving head of the liquid filter system.
[0018] In a preferred embodiment, the first and second interlocking elements complement each other to form a web with an inclined cam surface on the outer circumference of the housing. These webs can be inserted into arcuate recesses in the receiving head and then twisted relative to each other through a specific angle, so that the webs and the arc-shaped recesses produce a bayonet connection between the receiving head and the housing containing the filter element. The inclined cam surface causes axial locking when it slides under a corresponding projection on the receiving head. Thus, with a slight rotation, the housing, including the filter element, is clamped against the receiving head and sealed, so that the filter system is ready for use. At the same time, the inlet and outlet channels disposed on the receiving head are coupled to the corresponding flow passages in the filter element.
[0019] To simultaneously clamp and thereby seal the two parts, the recesses and the second interlocking elements are mutually congruent, so that on the outer circumference of the housing an interlocking element of a uniform appearance is formed, which can then be coupled to corresponding counterpart surfaces on the receiving head. In this embodiment, the outside diameter of the second interlocking elements corresponds to the outside diameter of the first interlocking elements, and the arc length of the second interlocking elements corresponds to the arc length of the axial recess in the first interlocking elements.
[0020] To further secure the filter system against leaks, particularly if the canister of the filter element breaks, at least one annular sealing element may be disposed between the canister and the housing. Any liquid escaping the filter element is then trapped in the gap between the inside of the cup-shaped housing and the canister. The annular sealing element may be a standard O-ring or an elastomer sealing collar that is formed onto the outer circumference of the filter element.
[0021] To interconnect the filter element and the housing in the correct position, the recesses in the first interlocking elements and the second interlocking elements engaging therein may be disposed in an unsymmetrical angular division, so that the user can combine the two parts only in the predefined position.
[0022] Unless the housing must have a specific angular position relative to the receiving head, the webs formed by the first and the second interlocking elements are disposed in a symmetrical angular division to facilitate mounting. This configuration may also be provided in combination with the asymmetrical arrangement of the first and second interlocking elements described above so that the filter element and the housing can then be positioned relative to each other only in a specific way, but the assembled filter element and housing can be fixed to the connection head in any angular position.
[0023] To facilitate removal of a filter element from the housing for disposal, the filter element may be provided with at least one fold-down handle element on the exposed end of the canister. Such a handle element is preferably formed by two semicircular partial handle elements made of synthetic resin material, which are flexibly interconnected by a film hinge along a diameter of the housing. This creates a centrally mountable disk-shaped body having large openings to enable connection with the inlet and outlet on the connection head on the one hand and can be easily gripped on the other. The two semicircles can be folded down on the foil hinge from their original position, perpendicularly to the longitudinal axis of the filter element.
[0024] The liquid filter system according to the invention is particularly suitable for a filter element comprising a filter insert member that is wound from a flat structure, i.e., one made of a pleated filter layer that is bonded to a cover layer on one side along its folded edges, as disclosed in principle in U.S. Pat. No. 6,004,462 (=DE 196 28 060). In contrast to conventional pleated filter insert members, the medium flows through not just primarily radially but also axially, so that the filter insert member as a whole is subject to large axial forces. Because the invention ensures a correct alignment of the filter element inside the housing, it is possible to provide support plates, etc. to absorb these axial forces on the pleated filter unit without unintentionally blocking the flow paths by incorrect alignment.
[0025] If the interlocking elements are to be coupled to the receiving head via a bayonet connection, it is particularly advantageous if at least one radially displaceable, flexibly supported detent pin is provided on the receiving head extending into the arcuate recesses in which the webs formed by the assembled first and second interlocking members are received. In this case, the webs should furthermore each have an inclined cam surface on at least one of their lateral edges for deflecting the detent pin element. If the housing with an installed filter element is inserted placed with its webs, which are uniformly made up of the assembled first and second interlocking elements, into the arcuate receiving grooves on the receiving head and is rotated through an angle relative to the center axis of the housing, the inclined cam surfaces on the interlocking elements push back the detent pin so that the housing can be turned until a tight connection is established between the housing and the receiving head. If, on the other hand, the user forgets to insert a filter element into the housing, this fact is not only visually detectable but a connection between the housing and the receiving head is actively prevented. In this case, the detent pin snaps into the recess that is located within, or next to, the first interlocking elements and is provided for receiving the second interlocking elements, so that the housing cannot be rotated all the way to its end position. The detent pin lies in the groove that extends axially to the lower edge of the housing, so that in this blocked position the housing can simply be axially removed again.
[0026] If axially acting spring elements are provided in addition between the end faces of the receiving head and the underside of the housing, the incorrectly mounted housing is rejected by the receiving head, so that in the blocked position the operator cannot leave the housing attached to the receiving head without a filter element.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] The invention will described in further detail hereinafter with reference to illustrative preferred embodiments shown in the accompanying drawing figures, in which:
[0028] FIG. 1 is a perspective view of a filter element according to the invention;
[0029] FIG. 2 is a bottom view of the housing and the filter element;
[0030] FIG. 3 is a perspective view of the housing and the filter element;
[0031] FIG. 4 is a perspective view of the housing;
[0032] FIG. 5 is a longitudinal section of the liquid filter system according to the invention;
[0033] FIG. 6 is a cross section of the liquid filter system taken along line VI-VI in FIG. 5 , and FIG. 7 is a longitudinal section of the housing and a second embodiment of a filter element according to the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0034] FIG. 4 shows a housing 11 for the filter system according to the invention, which is substantially pot-shaped or cup-shaped. A bottom edge 11 . 1 , shown pointing upwardly in FIG. 4 , has a plurality of axially extending recesses 43 around its circumference. In the illustrated embodiment, a total of six first interlocking elements 42 are arranged near the bottom edge of the housing 11 and distributed around its outer circumference. The recesses 43 each extend far enough in the axial direction to interrupt or split the first interlocking elements 42 . Thus, the first interlocking elements 42 are divided by the recesses 43 into partial areas 42 . 1 and 42 . 2 . An inclined ramp or cam surface 42 . 4 is formed on the partial area 42 . 1 .
[0035] FIG. 1 shows a bottom view of the filter element 19 with an annular closure face 26 . A central support tube 14 is disposed in the center, which also acts as an inlet to the filter element 19 . The liquid can flow out again through outlet openings 13 , which are arranged in the region between the support tube 14 and a collar 30 . The second interlocking elements 36 disposed around the outer circumference of the filter element are a significant aspect of the invention.
[0036] The interaction between the first and second interlocking elements 42 , 36 according to the invention can be seen from the perspective view of the housing 11 with a filter element 19 inserted therein as shown in FIG. 3 . The second interlocking elements 36 of the filter element 19 complement the first interlocking elements 42 , which are interrupted by the recesses 43 in the housing 11 , so that each set of first and second interlocking elements forms a uniform web on the outside of the housing 11 . This seamless integration of the second interlocking elements 36 into the gap in the first interlocking elements results in a flush outer surface 42 . 5 on the webs.
[0037] FIG. 2 shows a top view of the assembly of in FIG. 4 . This figure again shows how the second interlocking elements 36 mate precisely with the recesses 43 in the first interlocking elements 42 in both the circumferential and radial extent, resulting in a uniform web, which in the illustrated preferred embodiment is provided to form a bayonet connection with a receiving head.
[0038] The collar 30 furthermore accommodates a handle element, which is initially disk-shaped and formed from two semicircular partial handle elements 71 , 72 , which are interconnected by their straight bases along a film hinge 73 . The partial handle elements 71 , 72 may be folded down or folded up at the foil hinge 73 so that they protrude from the underside of housing 11 and filter element 19 and can be easily gripped to facilitate removal of the filter element from the housing.
[0039] FIG. 5 depicts a complete liquid filter system according to the invention in which housing 11 with inserted filter element 19 is attached to a receiving head 61 having arcuate grooves 62 along its inner circumference in order to produce a bayonet connection with the interlocking elements on the outside circumference of housing 11 . A flange housing 60 adjoining the receiving head 61 has integrated return and supply lines 63 , 64 , which lead to the return and inlet passages 13 and 14 of the filter element 19 .
[0040] The support tube 14 has a sealing ring along its inner circumference at the end face and is slipped onto a conical fitting 65 between the housing 11 and the receiving head 61 . At the end closure face 26 , the collar 30 is also sealingly connected to the inner circumference of a ring 66 , or an indentation in the receiving head 61 , via an interposed sealing ring, so that the return area is likewise sealed relative to the environment.
[0041] The filter element 19 is surrounded by a cylindrical canister 16 . The actual filter material, or the actual filter insert member, e.g., a wound compact filter insert made of pleated filter paper, is firmly connected to the canister 16 by a sealing compound 18 .
[0042] The canister 16 creates a hollow space 67 above the filter insert member. In this area the support tube 14 is provided with cutouts 68 . The liquid to be filtered is guided through the cutouts 68 into the hollow space 67 and then flows through the filter insert member 19 .
[0043] FIG. 6 is a section taken along line VI-VI in FIG. 5 . The first interlocking elements 42 of the housing are cut away in their first partial area 42 . 1 with the inclined cam surfaces 42 . 4 and lie within the arcuate receiving grooves 62 of the receiving head 61 . The receiving grooves 62 have slopes 62 . 1 to provide additional centering of the housing 11 and the filter element 19 relative to the receiving head 61 as the bayonet connection is locked.
[0044] A detent pin 51 extends into at least one of the receiving grooves 62 and is held in this position by a compression spring 50 . To create room for the detent pin 51 an additional small housing 38 may be provided on the outside of the receiving head 61 . The broken line 52 in FIG. 3 indicates the path of the detent pin 51 across the external face 42 . 5 of the assembled first and second interlocking elements 42 , 36 if a filter element 19 is properly installed in the housing 11 . The inclined cam surface 42 . 3 at the leading edge of the first interlocking element pushes the detent pin 51 radially outwardly so that the pin slides across the radially outer surface of the web formed by the assembled interlocking elements 42 and 36 .
[0045] In contrast, if no filter element 19 is installed in the housing 11 , the path of the detent pin 51 ends in the recess 43 within the first interlocking element 42 as indicated in FIG. 4 by the broken line 52 ′. The force of the spring 50 causes the detent pin 51 to snap into the recess 43 and thereby prevents further rotation of the housing 11 . In this way, the housing 11 is prevented from being assembled to the receiving head 61 if no filter element is installed in the housing.
[0046] FIG. 7 again shows the housing 11 . A second embodiment of a filter element 19 ′, in which the canister 16 ′ does not completely enclose the filter element 19 , but is configured simply as a ring in the end region, is inserted into this housing. The filter element 19 ′ is sealed relative to the housing 11 by an annular sealing element 15 ′. This partial canister 16 ′ reduces the amount of plastic to be disposed of and is suitable particularly if the medium to be filtered is relatively clean to handle, e.g., gasoline or water with suspended solids. In this case, the otherwise advantageous encapsulation of the filter element 19 in a liquid-tight canister depicted in FIGS. 1 to 6 may be omitted to save material.
[0047] The foregoing description and examples have been set forth merely to illustrate the invention and are not intended to be limiting. Since modifications of the described embodiments incorporating the spirit and substance of the invention may occur to persons skilled in the art, the invention should be construed broadly to include all variations within the scope of the appended claims and equivalents thereof. | An oil filter for an internal combustion engine with a cup-shaped housing that is releasably connectable to a receiving head. The housing has a first interlocking element that extends across at least a portion of the outer circumference of the housing and is interrupted by at least one axially extending recess. The filter element has a liquid-tight canister provided on its outer surface with second interlocking elements, which fit into the recesses of corresponding first interlocking elements when the filter element is installed in the housing. | 1 |
BACKGROUND OF THE INVENTION
The present invention relates to a new and improved construction of a shuttleless weaving machine, especially a ribbon loom, comprising at least one weft thread-or filling thread-insertion element and at least one to-and-fro driven knitting needle or equivalent structure movable back-and-forth along the selvage or edge of the woven cloth or ribbon opposite the filling thread-insertion element for the formation of a knitted edge by tying the inserted filling threads and/or auxiliary threads, and further comprises a deflection element associated with the knitting needle for the introduction or insertion of filling threads or auxiliary threads into the knitting region or zone of a hook of the knitting needle.
In the case of shuttleless ribbon looms it is already well known to those skilled in the art that the weft or filling thread loop inserted into the open shed by the filling thread-insertion element must be fixed at the opposite side of the insertion element.
During fixing of the inserted filling thread with the aid of a knitting needle there can be formed a knitted edge or selvage with or without the assistance of an auxiliary thread.
If there is dispensed with the use of an auxiliary thread, then, the filling threads are tied to one another with the aid of the knitting needle, and in each instance the filling thread which has been picked or inserted must be engaged by the knitting needle.
When using an auxiliary thread the momentarily inserted or shot-in filling thread either can be tied or secured by itself with the auxiliary thread or together therewith in one working step.
During typing of the filling thread alone to the auxiliary thread the knitting needle must engage the auxiliary thread and the filling thread should not be engaged by the knitting needle.
On the other hand, if the auxiliary thread and the filling thread are conjointly or collectively tied, then, the knitting needle must engage both the auxiliary thread and the filling thread.
Depending upon the tying operation either the filling or weft thread and/or the auxiliary thread must be brought into the operable zone or region of the knitting needle hook.
It is, for instance, known to the art from Swiss Patent 545,872 to employ an insertion lever for the insertion or introduction of the thread which is to be hooked into the knitting needle hook. This equipment is, however, associated with the drawback that the insertion lever only can be arranged at the outermost fabric edge or selvage and externally of the operable region of the reed, so that it is not engaged by the reed.
SUMMARY OF THE INVENTION
Hence, it is a primary object of the present invention to provide an improved apparatus of the previously mentioned character which is not associated with the aforementioned drawbacks and limitations of the prior art constructions.
A further object of the present invention aims at the provision of a new and improved construction of shuttleless weaving machine, especially a ribbon loom or the like, which is relatively simple in construction, extremely reliable in operation, not readily subject to breakdown or malfunction, requires a minimum of servicing and maintenance, and is not associated with the aforementioned limitations of the prior art looms.
Now in order to implement these and still further objects of the invention, which will become more readily apparent as the description proceeds, the weaving machine of the previously mentioned type is manifested by the features that the deflection element is driven back-and-forth or to-and-fro in synchronism with the associated knitting needle and by means of an actuation element driven in cycle with the operation of the machine can be brought, transversely with respect to its direction of movement, from a rest position into an operable position where the deflection element deflects or displaces filling threads or auxiliary threads, respectively, into the effective zone or knitting region of the knitting needle hook.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above, will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein throughout the various embodiments the same reference characters have been generally used for the same components and wherein:
FIG. 1 schematically illustrates a first exemplary embodiment of a ribbon loom comprising a deflection element acting upon the weft of filling threads; and
FIG. 2 illustrates a second exemplary embodiment of a ribbon loom comprising a deflection element acting upon the auxiliary threads.
DETAILED DESCRIPTION OF THE INVENTION
Describing now the drawings, it is to be understood that only enough of the construction of the weaving machine has been illustrated in order to enable those skilled in the art to readily understand the basic concepts of the present invention. With the exemplary embodiment of ribbon loom illustrated solely by way of example and not limitation in the drawings, the conventional components of the loom proper which are not necessary to the understanding of the basic concepts of the invention have been omitted to preserve clarity in illustration.
Turning attention therefore to FIG. 1, there is schematically illustrated therein by way of example a ribbon loom for the fabrication of a double shed fabric or cloth, wherein, for the formation of the knitted edge or selvage in each instance filling or weft threads are tied with filling threads. In this figure the woven ribbon or tape is designated by reference character 1 and the warp threads are designated by reference character 2. The ribbon 1 formed as a double shed fabric possesses two superimposed fabric portions 1a and 1b of different width. Furthermore, there are provided two filling thread-insertion elements or members 3 and 4, each of which have been illustrated engaging into a respective shed formed by the warp threads 2. Both of the weft or filling thread-insertion elements 3 and 4 are secured to a common shaft 5 and driven to oscillate back-and-forth or to-and-fro by means of a suitable drive 6 in the plane of the woven fabric, here the ribbon 1. The drive 6 is constructed, for instance, as a crank drive possessing a lever or link 8 eccentrically mounted on a rotatable disk or plate 7 and engaging with the filling thread-insertion element 4. The disk 7 is secured to a driven rotatable shaft 9 and is thus driven in the direction of the arrow A. Each filling thread-insertion element 3 and 4 possesses an eyelet or eye 3a and 4a, respectively, through which there is guided a filling or thread 10 and 11 respectively.
At the side of each fabric portion 1a and 1b which is opposite the filling thread-insertion element 3 and 4 there is arranged a knitting needle 12 and 13, respectively, or equivalent structure. Both knitting needles 12 and 13 are attached to an oscillating lever 14 which is moved to-and-fro by means of a rotatably driven control disk or cam 15 coacting with a roller or cam follower 16 or equivalent structure secured in any suitable fashion to the oscillating lever 14 or the like. By means of a tension spring 17 or equivalent structure the roller or cam follower 16 is continually biased or urged against the surface of the control disk or control cam 15. The knitting needles 12 and 13 carry out a to-and-fro or back-and-forth movement along the edges of both fabric portions 1a and 1b.
Adjacent the knitting needle 13 there is secured on the oscillating or rocker lever 14 a movable support means defining a deflection element or member 18. Cooperating with such deflection element 18 is an actuation lever or element 19 which is secured to a shaft 20 and can be moved up and down in the direction of the double-headed arrow B. In order to rotate the shaft 20 there is provided a revolving control cam or disk 21 which cooperates with a roller or cam follower 22 which is arranged at an arm 23 attached to the shaft 20. A tension spring 24 or the like engages the arm 23 in order to bias the roller 22 against the control cam 21.
During its downward movement the actuation lever 19 presses against the elastically or resiliently deflectable deflection element 18 and moves such from its rest position into its operative or knitting position. The deflection element 18 located in its so-called knitting position has been illustrated in broken or phantom lines and designated by reference character 18'. In the operative or knitting position (indicated by reference character 18') the deflection element 18 deflects or shifts the filling thread 11 into the operable region or knitting zone of the hook 13a of the knitting needle 13.
As soon as the actuation lever 19 again rocks or swings upwards the deflection element 18, owing to its resilient restoring characteristics automatically moves back into its rest position.
After the insertion of the filling or weft thread 11 the oscillating or rocker lever 14 and together therewith the knitting needle 13 and the deflection element 18 are moved towards the open shed. The actuation lever 19 is lowered and presses the deflection element 18 into its knitting position 18'. During the return movement of the filling thread-insertion element 4 out of the shed the filling thread 11 remains wrapped about the knitting needle 13. Now the actuation lever 19 is raised and the deflection element 18 resiliently springs back into its rest position. With the thereafter following retraction movement of the knitting needle 13 and the deflection element 18 the filling weft thread 11 is tied in a conventional manner with the previously inserted weft thread loop.
The formation of the knitted edge at the outermost ribbon edge or selvage occurs in a corresponding manner, and the inserted filling or weft thread 10 is directly engaged or seized by the knitting needle 12 without the aid of a deflection element or device.
With the exemplary embodiment of loom illustrated in FIG. 2 the formation of the knitted edge occurs with the aid of an auxiliary thread, and the filling or weft thread is tied together with such auxiliary thread or the weft thread and auxiliary thread are tied together in one working step or operation.
The ribbon loom or weaving machine illustrated in FIG. 2 essentially corresponds to the loom of FIG. 1. Hence, corresponding components have been conveniently designated by the same reference characters in both FIGS. 1 and 2.
The elastically or resiliently deflectable or displaceable deflection element 18 possesses an eyelet or eye 18a through which there is threaded or guided an auxiliary thread 25. At the outer ribbon or band edge of the fabric portion 1a there is guided an auxiliary thread 26 through an eyelet or eye 27a of a substantially L-shaped insertion lever 27. This insertion lever or lever member 27 carries a roller or cam follower 28 which bears upon a rotatably driven control cam or disk 29. In order to insure for continuous bearing contact of the roller 28 at the control cam or disk 29 there is provided a tension spring 30 or equivalent structure which engages with the insertion lever 27. By means of the control cam or disk 29 the insertion lever 27 is moved up and down in the direction of the double-headed arrow C.
The insertion lever 27, when in its upper terminal or end position, extends by means of the lever portion possessing the eyelet or eye 27a into the region or zone formed by the inserted filling thread 10, the filling thread-insertion element 3 and the ribbon edge or selvage. In this upper terminal position the auxiliary thread 26 is inserted into the hook 12a of the weaving needle 12, and there takes place the formation of a knitted edge or selvage by carrying out a tying operation in a conventional manner with the aid of auxiliary thread 26.
At the inner ribbon edge of the fabric portion 1b the knitted edge is formed as follows:
If the filling thread 11 is to be tied to the auxiliary thread 25, then after the insertion of the filling thread 11, the deflection element 18 and the knitting needle 13 are conjointly displaced towards the open shed, the knitting needle 13 moving therethrough below the filling or weft thread 11. As soon as the knitting needle 13 is located beneath the filling thread 11 the deflection element 18 is deflected downwardly with the aid of the actuation lever 19. Hence, with the knitting needle 13 downwardly inclined and a certain spacing between the needle end and the eyelet 18a of the deflection element 18 the auxiliary thread 25 wraps around the knitting needle 13. During further advancement of the knitting needle 13 the auxiliary thread 25 is secured between the tongue and hook of the knitting needle. The actuation lever 18 automatically returns back into its rest position. During the subsequent retraction of the knitting needle 13 and the deflection element 18 there occurs the desired tying of the filling thread 11 to the auxiliary thread 25. If, in the case of the ribbon loom illustrated in FIG. 2, the filling or weft thread 11 and the auxiliary thread 25 are to be tied together in one operation for forming the inner knitted edge or selvage, then during the forward displacement or advancement of the deflection element 18 and the knitting needle 13 the latter is pushed over the filling thread 11. By depressing the deflection element 18 by means of the actuation lever 19 the auxiliary thread 25 is inserted into the hook 13a of the weaving needle 13. As soon as the deflection element 18 is again located in its rest position, then, the deflection element 18 and the knitting needle 13 are again moved back, so that in known manner the auxiliary thread 25 and filling thread 11 are tied together.
With the illustrated exemplary embodiments, the deflection element, owing to its resilient-elastic properties, automatically returns or moves back into its rest position. However, it is also conceivable to use a deflection element which does not have any resilient or spring-like characteristics, in which case then there must be provided suitable means for returning the deflection element back into its rest position. For instance, the actuation lever also could be used for such retraction of the deflection element or member back into the rest position.
Due to the described construction of the deflection element coacting with an actuation lever it is possible to also arrange this deflection element at an inner ribbon edge without it being contacted by the reed. As mentioned, this is achieved in that the deflection element together with the knitting needle is moved out of the effective region or operable zone of the reed.
It is, of course, also possible to provide the disclosed deflection element together with the actuation lever at the outermost ribbon edge. In most instance it will be however, advantageous to use at the outermost ribbon edge a conventional thread insertion device, which, for instance, can possess a construction of the type shown in FIG. 2 or in Swiss Patent 545,872, the disclosure of which is incorporated herein by reference.
While there is shown and described present preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims. | A shuttleless weaving machine, especially a ribbon loom, comprising at least one filling thread-insertion element and at least one to-and-fro driven knitting needle moving along the selvage or cloth edge which is situated opposite the filling thread-insertion element for the formation of a knitted edge by tying the inserted filling threads and/or auxiliary threads. There is further provided a deflection element operatively associated with the knitting needle for the introduction of filling threads or auxiliary threads, respectively, into the knitting region or zone of a hook of the knitting needle. The deflection element is driven so as to move back-and-forth and by means of an actuation element driven in cycle with the machine can be brought, transversely to its direction of movement, from a rest position into a knitting position where the deflection element deflects filling thread or auxiliary thread, respectively, to the knitting region of the knitting needle hook. | 3 |
FIELD OF THE INVENTION
The present invention relates to positioning systems in general, and to methods and systems for positioning an item within a living tissue, in particular.
BACKGROUND OF THE INVENTION
Minimal Invasive Endoscopic Surgery (MIES) provides the means by which less invasive medical procedures can be employed cost-effectively for a huge segment of the patient population, covering the most important medical specialties and surgical interventions. While patients benefit from this innovative technique, much of the credit for its success must be given to physicians/endoscopists and to manufacturers who created the endoscopic video imaging systems and unique procedure-specific devices, which together made millions of procedures possible each year since the technique gained prominence in the late 1980's.
MIES reduces the cost of the overall procedure by reducing the number of days that a patient spends in a medical facility and by significantly reducing the trauma which is inflicted on the patient, which reduces the chance for complication during a procedure and afterwards.
Systems for determining the location of a medical device within a treated living tissue are known in the art. In general, these systems are divided into two major groups, which are visual systems, semi visual systems and non-visual positioning system.
A conventional visual system includes an optical imaging element such as a fiber optic based device. The imaging element is inserted into the body of the patient and assists the physician in locating any surgical tool therein. One such system is called an endoscope. A conventional endoscope includes a dilating catheter in which lighting means, visual image unit and a surgical tool, are inserted.
Semi-visual systems often include a real time imaging device such as an ultrasound mechanism, which is combined with the tip of the endoscope. An example for such a system is the EUB-525 ultrasound system with the 10R probe, manufactured and sold by Hitachi.
Non visual systems include additional means, which assist the user in determining the location of the medical device within the body of the patient. U.S. Pat. No. 5,729,129 to Acker is directed to a magnetic location system with feedback adjustment of magnetic field generator. It is noted that this system is subjected to metal object interference, which is produced by various metal objects, located in the vicinity of the system. Another disadvantage of this system is that the general method of operation of such a system includes three consecutive steps: transmitting an electromagnetic signal; detecting this signal and adjusting the electromagnetic signal according to the detected one. Hence the refresh rate of this system is significantly slow.
U.S. Pat. No. 5,840,025 to Ben-Haim, is directed to an Apparatus And Method for Treating Cardiac Arrhythmias. According to Ben-Haim, a catheter is inserted into the body of the patient and located in selected locations within the heart. The tip of the catheter includes a transmitting antenna, which transmits an electromagnetic signal. This signal is detected by external antennas and is then used to determine the location of the tip of the catheter. Finally, this information is super imposed on a pre-acquired image of the treated area.
U.S. Pat. No. 5,752,513 to Acker et al is directed to a Method And Apparatus for Determining the Position of an Object. The system uses an electromagnetic transmitter and receiver arrangement to determine the location and orientation of a medical device, which is inserted in the body of a patient. The location and orientation information is incorporated with a pre-acquired image of the treated area, using a plurality of markers, which have both visual as well as magnetic characteristics. It is noted that the accuracy of this apparatus significantly decreases in the presence of metal objects, which deform the magnetic fields.
A Bronchoscope is a specific type of an endoscope, which is directed for treating lungs. During a conventional lung treatment, the physician inserts the bronchoscope into the lung of the patient and operates the surgical tool (which can be a clamp, a brush, a laser device and the like) while viewing the inside volume of the lung, using the visual image unit.
It will be appreciated by those skilled in the art that the width of the bronchoscope is significant. Hence, a bronchoscope can not be used to treat places, where the access thereto is narrower than the diameter of the bronchoscope. In the case of lung treatment, the conventional method is to place the patient on an X-ray table system and place an X-ray video camera on top, which provides continuous images of the treated area and the surgical tool inserted therein. It will be appreciated by those skilled in the art that this method suffers several disadvantages. The imaging resolution is often not high enough and provides only vague indication of the location of the surgical too. Operating an X-ray table requires a medical staff of several people. X-ray based technology is known in the art as inflicting considerable hazards on the medical staff operating it.
Gastroscopy is also known in the art. One type of gastroscopes includes an ultrasound transceiver at the tip end, providing continuous semi-visual information, enabling the physician to operate a surgical tool using this information. It will be appreciated by those skilled in the art that operating an ultrasound-visualizing device requires a considerable training period, which conventionally is in the order of 18-24 months. Such a combined ultrasound gastroscopy system is the FG-34UX model, manufactured and soled by Pentax.
Another type of positioning system includes the UltraGuide 1000, which is a combined ultrasound and magnetic location system. This system includes an external ultrasound transducer and a magnetic field based location detection system, which is mounted on a firm surgical tool, such as a large needle. This ultrasound device enables the user to select an insertion point and angle that permit access, with a long needle, to a target within the body of the patient.
SUMMARY OF THE PRESENT INVENTION
It is an object of the present invention to provide a novel method and system for determining the location and orientation of objects, within a scanning volume, which overcomes the disadvantages of the prior art. It is another object of the present invention to provide a novel method and system for initiating and calibrating the location and orientation of a detector of the system, within the scanned volume.
It is a further object of the present invention to provide a novel method and system for obtaining an inner body three-dimensional image from a plurality of two dimensional images.
It is yet another object of the present invention to provide a novel method and system to operate within the body of the patient, wirelessly.
In accordance with the present invention, there is thus provided an apparatus for determining the position and orientation of a surgical tool relative to a reference frame, in association with an image. The apparatus includes a magnetic field transmitter, a detection probe, a signal generation module, connected to the magnetic field transmitter, a detection processor, connected to the detection probe and mounting means, for mounting onto the surgical tool.
The magnetic field transmitter, includes at least one magnetic field generating element. The detection probe includes at least one magnetic field detector
The combined number of the magnetic fields generators and the magnetic field detectors is at least four. The signal generation module determines a transmit signal and provides the transmit signal to the magnetic field transmitter. The detection processor receives a detected signal from the detection probe, determines the location and orientation of the detection probe from the detected signal and indicates the location of the surgical tool within the image. The detection probe can include any number of magnetic field detectors.
The signal generation module can include a digital to analog converter and a signal processor connected thereto. The signal processor determines a digital transmit signal. The digital to analog converter converts the digital signal to a respective analog signal and provides the analog signal to the magnetic field transmitter. The digital signal can include any number of transmission channels. Each of the channels can include any number of frequencies.
In accordance with one aspect of the invention, each of the channels includes a plurality of frequencies.
In accordance with another aspect of the invention, the apparatus can further include an ultra-sound interface, for connecting to an ultrasound system capturing ultrasound frames. The detection processor constructs the image from the ultrasound frames, with respect to the detected location and orientation of the surgical tool
It is noted that the detection probe can be wirelessly connected to the detection processor. The frequencies and for that matter the channels themselves, can either be transmitted in accordance with a predetermined non overlapping sequence or simultaneously
In accordance with another aspect of the invention, there is provided a medial device which includes a housing, a magnetic detection probe, a biometric unit and a controller, connected to the magnetic detection probe, to the biometric unit and to the storage unit. The controller receives magnetic field detection information from the magnetic detection probe. The controller operates the biometric unit in association with the magnetic field detection information. It is noted that the housing can be shaped like a capsule.
The medial device can further include a transmitter, which is connected to the controller, for transmitting the magnetic field detection information. The biometric unit includes at least one of the devices in the list consisting of an image detection unit, a substance releasing unit and a biometric sampling unit. The medial device can further include a storage unit for storing the magnetic field detection information, connected to the controller.
The biometric unit can include a biomedical sensor, wherein the biometric unit provides detected biometric information to the controller and wherein the controller produces a plurality of records. Each of the records can thus include a portion of the biometric information and a respective portion of the detected magnetic field information. The controller can store the records in the storage unit.
The medial device can further include a wireless transmitter, connected to the controller, wherein the controller provides the records to the wireless transmitter and wherein the transmitter transmits the records to an external receiver. It is noted that the magnetic fields, which are detected by the medical device are generated by an external transmitter. These electromagnetic fields can be generated in accordance with either a predetermined non overlapping sequence, semi overlapping sequence or simultaneously and continuously.
In accordance with another aspect of the invention, there is provided a method for calibrating a reference image onto a volume, from which the image is produced. The method includes the steps of determining a plurality of locations in the volume, the locations being visible, and present in the reference image, detecting a magnetic field reading in each of the locations, and calibrating the reference image with respect to the magnetic field readings, onto the volume. This method eliminates the need to place special markers, which can be located either in the image or by a detector.
The method can further include the steps of receiving additional magnetic field readings, each in an additional location within the volume, and determining the location and orientation of the additional location, within the reference frame.
In accordance with yet a further aspect of the invention, there is thus provided an Imaging system which includes an inner body ultrasound detector, and a location and orientation detector, firmly attached to the inner body ultrasound detector. The inner body ultrasound detector detects a plurality of two-dimensional images and the location and orientation detector detects the location and orientation of each of the two-dimensional images. The system can further include a three dimensional image generator, connected to the inner body ultrasound detector and to the location and orientation detector. The three dimensional image generator processes the two-dimensional images, each with its respecting location and orientation information, thereby producing a three dimensional image.
The imaging system can include a storage unit, connected between the three dimensional image generator the inner body ultrasound detector and the location and orientation detector, for intermediately storing the two-dimensional images, each with its respecting location and orientation information.
The imaging system can further include a combining processor, connected to the three dimensional generator and interfacing at least one additional location and orientation detector. The combining processor receives additional location and orientation information from the additional location and orientation detectors. The combining processor produces an indication of the additional location and orientation information onto the three-dimensional image. The inner body ultrasound detector can include either an angular ultrasound transceiver or a radial ultrasound transceiver.
The location and orientation detector can include at least one axial magnetic detector. Each of the location and orientation detectors can detect magnetic field in at least one axial magnetic direction. The location and orientation detector can detect magnetic field in at least one frequency in each of the axial magnetic directions. The location and orientation detector is generally mounted on the inner body ultrasound detector.
The inner body ultrasound detector can be mounted on a catheter. In this case the location and orientation detector can be mounted on the tip of the catheter, in the vicinity of the inner body ultrasound detector.
In accordance with yet another aspect of the invention, there is provided a method for producing a three dimensional image, which includes the step of detecting a plurality of two-dimensional ultrasound images, from the inner section of a scanned volume. The method can further include the steps of detecting the location and orientation of a selected vector in each of the two dimensional ultrasound images, and determining a three dimensional representation for each of the two-dimensional images, according to the location and orientation thereof.
The method can further include the step of producing a three-dimensional image from the three-dimensional representations.
The method can further include the step of receiving additional location and orientation information and producing an indication thereof onto the three-dimensional image.
The method can further include the step of producing a visible representation of the three-dimensional image and the indication.
The method can further include the step of inserting an ultrasound detector into the inner section of the scanned volume. According to one aspect of the invention, the two-dimensional ultrasound images can include angular two-dimensional ultrasound images.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be understood and appreciated more fully from the following detailed description taken in conjunction with the drawings in which:
FIG. 1A is a schematic illustration of a location and orientation determination system, constructed and operative in accordance with a preferred embodiment of the present invention;
FIG. 1B is an illustration in detail of the sensor of the system of FIG. 1A;
FIG. 1C is an illustration of a sensor, constructed and operative in accordance with a further preferred embodiment of the present invention;
FIG. 2A is an illustration of a patient and an invasive system, constructed and operative in accordance with another preferred embodiment of the invention;
FIG. 2B is an illustration of a 3D image, a positioning representation and the super imposing of both of them;
FIGS. 3A, 3 B and 3 C are illustrations of the location and orientation determination system of FIG. 1A, incorporated within a bronchoscope, constructed and operative in accordance with a further preferred embodiment of the present invention;
FIG. 4A is an illustration of a patient, a catheter and a location and orientation detection system, constructed and operative in accordance with another preferred embodiment of the present invention;
FIG. 4B is an illustration of the superimposing of the location information provided by the location and orientation detection system of FIG. 4A and a three dimensional image of a treated portion of the body of the patient;
FIG. 4C is an illustration in detail of the tip end of the catheter of FIG. 4A;
FIG. 5 is a schematic illustration of an inspection system, constructed and operative in accordance with a further preferred embodiment of the present invention
FIG. 6 is a schematic illustration in detail of the electromagnetic generator section of a positioning system, constructed and operative in accordance with another preferred embodiment of the present invention;
FIG. 7 is a schematic illustration of a method for generating a complicated magnetic field waveform, operative in accordance with a further preferred embodiment of the present invention;
FIG. 8 is a schematic illustration of a method for operating a system, operative in accordance with another preferred embodiment of the present invention;
FIG. 9 is a schematic illustration of a three dimensional imaging system, which combines an inner ultrasound transceiver and a location and orientation detector, constructed and operative in accordance with a further preferred embodiment of the present invention;
FIGS. 10A and 10B are illustrations in perspective of an inner body ultrasound assembly of FIG. 9, constructed and operative in accordance with another preferred embodiment of the present invention;
FIG. 10C is an illustration in perspective of a plurality of angular ultrasound slice images;
FIGS. 11A and 11B are illustration in perspective of an inner body ultrasound assembly, constructed and operative in accordance with a further preferred embodiment of the invention;
FIG. 12 is a schematic illustration of a method for operating a system, operative in accordance with another preferred embodiment of the invention;
FIG. 13 is a schematic illustration of a method for initially positioning a location and orientation detector onto a reference image, operative in accordance with a further preferred embodiment of the present invention; and
FIG. 14 is an illustration of two minimal invasive tools, constructed and operative in accordance with another preferred embodiment of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention overcomes the disadvantages of the prior art by providing a novel method and a novel system which provide accurate and harmless positioning of a medical device within a living tissue.
Reference is now made to FIG. 1A, which is a schematic illustration of a system, generally referenced 100 , constructed and operative in accordance with a preferred embodiment of the present invention.
System 100 includes a position & orientation processor 102 , a super imposing processor 104 , a sensor interface 106 , a main sensor 110 , an auxiliary sensor 112 , a 3D electromagnetic field generator 108 , an image interface 116 , a 3D image database 120 and a display unit 114 . It is noted that system 100 can include additional 3D electromagnetic field generators.
The position & orientation processor 102 is connected to the 3D electromagnetic field generator 108 , to the super imposing processor 104 and to the sensor interface 106 . The image interface is connected to the 3D-image database 120 and to the super imposing processor 104 . The super imposing processor 104 is further connected to the display unit 114 . The sensor interface is further connected to the main sensor 110 and to the auxiliary sensor 112 .
The 3D electromagnetic field generator 108 includes a plurality of electromagnetic generating elements such as coils, which produce a plurality of electromagnetic fields in a plurality of directions and in a plurality of magnitudes. It is noted that these fields can either be fixed or alternating. These fields are detected by each of the sensors 110 and 112 . The electromagnetic field detection results, provide an indication of the location and orientation of the main sensor 110 .
The main sensor 110 of system 110 is generally located on a probe or a medical tool, which is inserted within the inspected tissue. Auxiliary sensor 112 is generally located in the vicinity of the inspected tissue. It is noted that the use of such an auxiliary sensor enhances the performance of system 100 but is not essential. It is noted that more auxiliary sensors can be added to the system. For example, an auxiliary sensor can be attached to the body of the patient, providing reference to his movement.
The sensors 110 and 112 provide information related to detected electromagnetic fields, to the position and orientation processor 102 . From this information and with respect to the fields generated by the 3D electromagnetic field generator 108 , the position and orientation processor 102 determines the location and orientation of the sensor 110 and of auxiliary sensor 112 . The position and orientation processor 102 produces respective location and orientation data, and provides it to the super imposing processor 104 . It is noted that a system according to the present invention, can include a plurality of electromagnetic generators, such as the 3D electromagnetic field generator 108 .
The 3D-image database 120 includes a pre-detected image of the inspected tissue and provides it to the super imposing processor 104 . It is noted that the pre-detected image can be provided from any 3D image generating device, such as an X-ray detection system, a magnetic resonance imaging (MRI) system, an ultrasound imaging system and the like.
The 3D-image database 120 provides 3D image data to the super imposing processor 104 , via the image interface 116 . The super imposing processor 104 processes the location and orientation data, received from the location and orientation processor 102 , with the 3D image data, received from the 3D image database. The super imposing processor 104 thereby produces an image, which includes a representation of the pre-detected 3D image, and an indication of the position and orientation of the sensor 110 , thereon. The super imposing processor 104 provides this representation to the display unit 114 , which in turn produces a respective image.
Reference is further made to FIGS. 1B and 1C. FIG. 1B is an illustration of sensor 110 of system 100 of FIG. 1 A. FIG. 1C is an illustration of a sensor, generally referenced 170 , constructed and operative in accordance with a further preferred embodiment of the present invention.
Sensor 110 includes a core 150 and three coils 152 , 154 and 156 . It is noted that core 150 can be ferromagnetic. Each of the coils detects an electromagnetic field in a different direction. Hence, sensor 110 provides information with respect to three dimensions (x,y,z). It is noted that the core 150 can be replaced by other known means for amplifying the detected signal, such as using higher gain coils and the like. It is noted that any type of electromagnetic field sensors, such as Hall effect sensors, and the like, which is known in the art, is applicable for the present invention. Furthermore it is noted that the sensor can be used without a ferromagnetic core.
With reference to FIG. 1C, sensor 170 includes a core 172 and two coils 174 and 176 . It is noted that core 172 can be ferromagnetic. Each of these coils 174 and 176 detects electromagnetic field in a different direction. Hence, sensor 170 provides information with respect to two dimensions, for example (x,y).
A location and orientation detection system for helmets, which operates according to the same principle is disclosed in U.S. Pat. Nos. 5,646,524 and 5,646,525, which are hereby incorporated by reference. The present invention utilizes such a system to determine the location and the orientation of invasive medical devices within a living tissue.
In accordance with a further aspect of the invention, each of the magnetic fields is generated using a plurality of frequencies. This novel aspect of the invention overcomes several disadvantages of the prior art, such as increasing the metal effect and the like. By taking into account the field measurements of a plurality of detected electromagnetic fields, the system of the invention, eliminates the disturbing effects of metal objects which may disrupt these electromagnetic fields.
Reference is now made to FIG. 6, which is a schematic illustration in detail of the electromagnetic generator 108 section of a system 100 , constructed and operative in accordance with further preferred embodiment of the present invention.
Electromagnetic generator 108 includes a digital signal processor (DSP) 132 , a plurality of channel modules, generally referenced 131 , an analog to digital converter 138 , three amplifiers 140 A, 140 B and 140 N, three coils 142 A, 142 B and 142 N, three capacitors 144 A, 144 B and 144 N and a plurality of precise resistors 148 A, 148 B and 148 N. Coils 142 A, 142 B and 142 N have values L 1 , L 2 and L 3 , respectively. Capacitors 144 A, 144 B and 144 N have capacitance values of C 1 , C 2 and C 3 , respectively. Resistors 148 A, 148 B and 148 N have resistance values of R 1 , R 2 and R 3 respectively. It is noted that the system 108 uses capacitors 144 A, 144 B and 144 N so as to be operated in resonance modes. It is noted that system 108 can be operated in non-resonance modes, for addressing a wide band of transmission frequencies, when the capacitors 144 A, 144 B and 144 N are removed and the coils are directly connected to the resistors.
Each of the cannel modules 131 includes a look-up table module, generally referenced 130 , a digital to analog module, generally referenced 136 and an automatic gain control (AGC) module, generally referenced 134 . It is noted that each of the channel modules controls a magnetic generation unit, and hence a magnetic field generation channel.
DSP 132 and the DAC 136 are each connected to the look-up table module 130 and to the AGC module 134 . The AGC module is further connected to the positive input ports of amplifiers 140 A, 140 B and 140 N. Each of the coils 142 A, 142 B and 142 N is connected between an output of a respective one of the amplifiers 140 A 140 B and 140 N and a respective one of the capacitors 144 A, 144 B and 144 N. Each of the precise resistors 148 A, 148 B and 148 N is connected between the capacitors 144 A, 144 B and 144 N and the negative input of a respective amplifier 140 A, 140 B and 140 N. Coils 142 A, 142 B and 142 N are positioned in different directions, to each other. It is noted that the DSP 132 receives feedback from the coils 142 A 142 B and 142 C, using the precise resistors 148 A, 148 B and 148 N. The ADC converter 138 is connected to a plurality of voltage measurement units 150 A, 150 B and 150 N, each measuring the voltage across a selected one of the resistors 148 A, 148 B and 148 N. The ADC 138 is further connected to the DSP 132 .
Each of the power amplifiers 140 A, 140 B and 140 N drives a respective current I 1 , I 2 and I 3 through a respective coil 142 A, 142 B and 142 C, thereby generating three respective magnetic fields B 1 , B 2 and B 3 . Sensor 110 (FIG. 1B) simultaneously detects a magnetic signal which includes these three magnetic fields B 1 , B 2 and B 3 , which are translated to voltage in each of the coils 152 , 154 and 156 of sensor 110 . It is noted that the system 100 can include additional magnetic field generators and hence can generate additional magnetic fields. The produced voltage signals are:
V x ( t ) =X 1 ×sin(ω 1 t ) +X 2 ×sin(ω 2 t ) + . . . +X N ×sin(ω N t )
V y ( t ) =Y 1 ×sin(ω 1 t ) +Y 2 ×sin(ω 2 t ) + . . . +Y N ×sin(ω N t )
V z ( t ) =Z 1 ×sin(ω 1 t ) +Z 2 ×sin(ω 2 t ) + . . . +Z N ×sin(ω N t )
The detector voltage amplitude matrix (for a 3×3 example) is: Amp = [ X 1 X 2 X N Y 1 Y 2 Y N Z 1 Z 2 Z N ]
the present example, provides an explanation which addresses a three channel case. It is noted that the invention is not limited to the number of channels, and can be easily expanded as desired. Additional channels increase the level of accuracy of the detection of the location of the sensor. A plurality of measurements, produced from a plurality of transmitters, each at a different location, provide a lot of information, which can be used to eliminate distortions, interference and the like.
According to the present invention, this matrix is measured continuously at the detector end. At the same time, the currents I 1 , I 2 and I 3 , are measured at the transmitting end. Hence, since both the transmission and the reception processes are executed at the same time, then the system 100 can determine the location of the detector with respect to the transmitter at a fast refresh rate, which is in the order of 10 ms or less.
In accordance with a further aspect of the invention, the currents I 1 , I 2 and I N are measured using precise value resistors, which are connected in with each of the coils 142 A, 142 B and 142 N. Measuring the voltage across these resistors yields a precise determination of the currents therein. The measurements of the voltage values is provided in digital form from the ADC 138 to the DSP 132 .
In accordance with another aspect of the invention, a special hardware structure is used to improve the speed and quality of the sinusoidal waveform of the generated magnetic fields. The DSP 132 determines the signal, which is to be transmitted by each of the coils 142 A, 142 B and 142 N. Each of these signals includes a combination of a plurality of simple waveforms, such as sinusoids and the like. The DSP 132 can further determine a sequence in which each of the waveforms is to be transmitted. It is noted that according to the present invention, the signals can be transmitted simultaneously.
The DSP 132 stores the waveforms in the look-up table 130 . The look-up table 130 eliminates the need for the DSP 132 to compute waveforms during operation of the system. The waveforms are stored in a continuous wave format, where they can be retrieved directly from the look-up table and transmitted endlessly.
When the system is initiated, then the DSP 132 transmits a sequence of test signals and detects combines the selected numeric representations and produces a numeric representation, which is a summation thereof. At this point, the DSP 132 provides the summed numeric representation to the DAC 136 , via the look-up table 130 . The DAC 132 produces a respective analog signal for each of the coils 142 A, 142 B and 142 N and provides it to the respective amplifier 140 A, 140 B and 140 N. The DSP 132 detects signals, which are received on the transmitting coils, respective of cross talk and other interference. At this stage, the DSP 132 can recalculate the waveforms, thereby compensating for the detected interference and update the look-up table 130 , accordingly.
Reference is now made to FIG. 7, which is a schematic illustration of a method for generating a complicated magnetic field waveform, operative in accordance with another preferred embodiment of the present invention. In step 180 , a plurality of numeric representations, of simple signals are computed.
In step 181 , a plurality of complex waveforms, each including a plurality of selected simple signals is determined. Each of the waveforms, is basically a super-positioning of a plurality of such simple waveforms at selected frequencies. For example, such a complex waveform can include:
S complex ( t ) =A 1 ×sin(1000 π·t ) +A 2 ×sin(1100 π·t ) +A 3 ×sin(1500 π·t )
It is noted that a complex waveform signal can include as many simple signals as desired. In general, this depends on many factors such as the power of the determining DSP, the speed of the communication between the various components of the system, the accuracy specified for the system and the like. At this point the DSP 132 processes the wave forms, with respective parameters, such as amplitude, offset and the like thereby producing a numeric expression of the complex waveform. It is noted that the DSP 132 can further determine a sequence. for transmitting the waveforms (step 182 ).
In step 183 , the numeric representations of the waveforms are stored in the storage unit, which in the example of system 100 is the look-up table 130 .
In step 184 the waveforms are retrieved and transmitted according to the determined sequence. The numeric expression of the complex waveform is converted into an analog signal by the digital to analog converter 136 and transmitted using the transmission section.
In step 185 the DSP detects cross talk and general interference, which are received from the AGC unit 134 . Accordingly, the DSP 132 modifies the waveforms so as to compensate for the detected cross talk and updates the storage unit accordingly (step 186 ). The waveforms stored in the look-up table 130 can now be transmitted continuously. It is noted that only a drastic change in the electromagnetic environment requires repeating of this procedure.
Hence. the present invention eliminates the need to co-compute the numeric representation of each of complex waveforms, which include each of the magnetic field signals, thereby dramatically increasing the speed in which such signals are produced.
The magnetic fields B 1 , B 2 and B N , in each of the coils 142 A, 142 B and 142 C are dependant on the currents I 1 , I 2 and I N , flowing there through. In a physically ideal system there would be independence between I 1 , I 2 and I N . However, any multi dimensional magnetic field generator incorporates some cross talk between the field generating elements. The X direction field generating coil induces currents in the Y and Z direction field generating coils, the Y direction field generating coil induces currents in the X and Z direction field generating coils and the Z direction field generating coil induces currents in the X and Y direction field generating coils. The measured currents are: I x ( t ) = V 1 · sin ( ω 1 t ) R 1 ; I y ( t ) = V 2 · sin ( ω 2 t ) R 2 and I z ( t ) = V N · sin ( ω N t ) R N
The actual currents, as transformed to voltage across resistors R 1 , R 2 and R N are: I x ( t ) = V 1 · sin ( ω 1 t ) + B 1 · V 2 · sin ( ω 2 t ) + … + N 1 · V N · sin ( ω N t ) R 1 , I y ( t ) = A 2 V 1 · sin ( ω 1 t ) + V 2 · sin ( ω 2 t ) + … + N 2 · V N · sin ( ω N t ) R 2 , and I z ( t ) = A 3 V 1 · sin ( ω 1 t ) + B 3 V 2 · sin ( ω 2 t ) + … + V N · sin ( ω N t ) R N ,
where A 2 , A 3 , B 1 , B 3 , N 1 and N 2 are predetermined coefficients.
According to the present invention, system 100 measures the cross-talk components in each axis and provides a respective compensation. In accordance with a further aspect of the invention, there is provided a method for compensating for cross talk between cnannels. Reference is now made to FIG. 8, which is a schematic illustration of a method for operating system 100 , operative in accordance with a further preferred embodiment of the invention. At first, the DSP 132 (FIG. 6) determines a plurality of function current signals (step 190 ), one for each axis. These functions are provided as electrical currents to the coils, which in turn produce magnetic fields (step 191 ).
In step 192 , the system measures the voltage values across the resistors connected in series with each of the coils. It is noted that these are high precision resistors and thus the system 100 can determine an accurate current value, from each of them for a respective one of the axis (step 193 ).
In step 194 , the system 100 determines the induced currents in each of the coils, by subtracting the original function current from the determined current value. In step 195 the DSP 132 determines a compensation function for each of the determined magnetic fields, according to the determined induced currents and combines each of the compensation functions with the respective current function signals (step 196 ). Finally, the system 100 repeats from step 190
In accordance with another aspect of the present invention, multi-frequency signals are used so as to overcome metal distortions. Each of the coils receives a signal, which includes a different set of frequencies. The signal, which is provided to each of the coils, is of the form: F i ( t ) = ∑ i = 1 N A i · sin ( w i t )
where A is the amplitude vector for each of the frequencies.
The system of the present invention can be implemented in any invasive device, which is inserted within a living tissue. Reference is now made to FIGS. 2A and 2B. FIG. 2A is an illustration of a patient and an invasive system, generally referenced 200 , constructed and operative in accordance with another preferred embodiment of the invention. FIG. 2B is an illustration of a 3D image, a positioning representation and the super imposing of both of them.
System 200 includes a main unit 210 , an invasive device 202 and a display unit 206 . Invasive device 202 includes a 3D magnetic sensor 204 , which is located on its tip. It is noted that system 200 is generally similar to system 100 . The invasive device 202 can be selected from a plurality of invasive devices such as an endoscope, catheters, needles, surgery devices, and the like.
With further reference to FIG. 2B, the sensor 204 detects electromagnetic fields, which are generated within the main unit 210 , and produces a respective signal. The system 200 (FIG. 2A) analyses this information and produces a determination of the location and orientation of the sensor 204 (reference 222 ). It is noted that since the sensor 204 is firmly attached to the tip of invasive device 202 , then the determination of location and orientation also indicates the location and orientation of the tip of the invasive device 202 .
In the present example, the inspected living tissue is the head (reference 230 ) of a patient (reference 290 ). The system 200 combines a pre-scanned image (reference 220 ) of the inspected living tissue and the location and orientation of the sensor 204 (reference 222 ), thereby producing a superimposed image 224 . Superimposed image 224 provides visual information of the location and orientation of the tip 204 of invasive device 202 , within the inspected living tissue 204 .
According to this aspect of the invention the system 100 can be mounted on to a bronchoscope. Reference is now made to FIGS. 3A, 3 B and 3 C, which are illustrations of system 100 of FIG. 1A, incorporated within a bronchoscope, constructed and operative in accordance with a further preferred embodiment of the invention.
FIG. 3A shows a bronchoscope, referenced 260 , inserted into the lungs 280 of a patient. A typical bronchoscope includes three main devices, which are a lighting unit, a set of optic fibers for capturing the image at the tip of the bronchoscope and a surgical too. According to the present invention, a bronchoscope further, includes a sensor such as sensor 110 , attached to its tip. Reference is further made to FIG. 3C, which is an illustration in detail of the tip of the bronchoscope 260 , of FIG. 3 A.
Bronchoscope 260 includes an optic fiber 262 , a set of optic fibers 266 , a surgical tool 264 and sensor 110 of system 100 . Optic fiber 262 transfers light from an external source to the tip of the bronchoscope. The set of optic fibers 266 captures the image in the vicinity of the tip and optically conveys this image to an external optical assembly (not shown) for viewing by the physician. The surgical tool 264 , which in the present example is a remote controlled clamp, enables the operating physician to perform surgical actions. The sensor 110 , being firmly attached to the tip of surgical tool detects the electromagnetic fields in close vicinity of this tip and transfers this information to system 100 .
The system 100 analyzes this information and determines the location and orientation (reference 250 ) of the tip of the surgical tool 264 . The system 100 then superimposes the coordinates 250 of the tip of surgical tool 264 264 with a pre-detected image 252 of the treated area, which in the present example, is the lungs 280 of the patient. The outcome 254 is displayed on display unit 114 (FIG. 3 B).
It is noted that the diameter of the tip of the dilating catheter 260 is conventionally significantly larger than the diameter of the surgical tool 264 . Hence, when the surgical procedure requires accessing areas which are too narrow for the dilating catheter, then the physician can proceed with just the surgical tool, where the location and orientation of the tip of this tool are provided by system 100 264 .
According to another aspect of the present invention, the location and orientation detection system, can be combined with a catheter, thereby determining the position of its tip. Reference is now made to FIGS. 4A, 4 B and 4 C. FIG. 4A is an illustration of a patient, a catheter and a location and orientation detection system, constructed and operative in accordance with another preferred embodiment of the invention. FIG. 4B is an illustration of the superimposing of the location information 322 provided by the location and orientation detection system of FIG. 4A and a three dimensional image 320 of a treated portion of the body of the patient. FIG. 4C is an illustration in detail of the tip end of the catheter of FIG. 4 A.
Catheter 310 is a general dilation catheter, which is used to guide a specific device to the vicinity of the area to be treated. The physician operating the system inserts a mounting catheter 306 , which includes a balloon mechanism 312 . A sensor 304 is firmly attached to the end of the mounting catheter 306 .
The sensor 304 detects electromagnetic fields (produced by generator 302 ) in a plurality of directions and provides information to the processing unit 308 of system 300 . The processing unit 308 analyzes this information, thereby determining the location and orientation of the sensor 304 . The system 300 uses these coordinates to produces a superimposed image of the treated area (reference 324 ).
According to the present invention, the communication between the electromagnetic sensor and the analysis unit of the system can be in a wired or wireless manner. Reference is now made to FIG. 5, which is a schematic illustration of an inspection system, generally referenced 400 , constructed and operative in accordance with another preferred embodiment of the invention.
System 400 includes a base unit 402 and a remote unit 404 . The base unit 402 includes a receiver 412 , a three dimensional electromagnetic field generator 414 , a coordinate processor 410 , an imaging processor 418 , and imaging source 416 and a display unit 420 . The coordinate processor 410 is connected to the receiver 412 , the three-dimensionaL electromagnetic field generator 414 and the imaging processor 418 . The imaging processor 418 is further connected to the display unit 420 and to the imaging source 416 .
The remote unit 404 includes a storage unit 422 , a transmitter 424 , a processor 428 , a three-dimensional electromagnetic field sensor 430 and a biometric unit 426 . The processor 428 is connected to the storage unit 422 , the transmitter 424 , the three-dimensional electromagnetic field sensor 430 and the biometric unit 426 . It is noted that the base unit 402 can use any information received therein. with respect to the detected magnetic fields, so as to modify the electromagnetic fields, which are transmitted by generator 414 .
The biometric unit 426 is designed to perform an inner operation on the living tissue. It is noted that such a biometric unit can include an image detector such as a camera, a substance releasing unit for releasing materials at predetermined locations, according to the location and orientation of unit 404 , a sampling unit such an oxymeter. The biometric unit can further include a glucometer, a thermometer, an acidity detector and any other physiological probe which can detect predetermined properties of pre-specified tissues of the examined living tissue. According to another aspect of the present invention, biometric units of several types are included in unit 404 , such as a physiological probe and a video camera which detects the image of a specified organ of the examined patient.
The physiological probe provides information, with respect to the detected characteristics, to the processor 428 . It is noted that the processor can perform an interim analysis of this information, so as to determine if this physiological data is to be transmitted to the base unit 402 .
At the same time, the sensor 430 detects electromagnetic field properties in a plurality of directions and provides the detection results to the processor 428 . The electromagnetic fields are produced by the three-dimensional electromagnetic field generator 414 . It is noted that the system 400 can include a plurality of three-dimensional electromagnetic field generators, such as the one referenced 414 . The use of additional electromagnetic field generators enhances the location and orientation measurements accuracy.
The processor 428 packs the detection results with the physiological data and transmits it to the receiver 412 , using the transmitter 424 . It is noted that the processor 428 can also store selected portions of the data received from the physiological probe 426 and the sensor 430 , in the storage unit 422 .
The receiver 412 provides the received data to the coordinate processor 410 . The processor 410 extracts the data, which relates to the detected electromagnetic fields and determines the location and orientation of the sensor 430 at the time of detection
The processor 410 provides the coordinate location data to the imaging processor 418 , together with the physiological data. The imagine processor 418 uses this data together with a three dimensional image received from the imaging source 416 , to produce a superimposed image and displays it on the unit 420 .
Such a superimposed image can include the trail of acidity within the digestion system of the examined patient, where at each point of the journey of the remote unit, both location and acidity level are detected and recorded.
The remote unit 404 is basically designed to be inserted into the body and move about, with minor intervention from the physician. For example, the remote unit 404 can be designed as a capsuie which can be taken through the mouth, make its way through the digestion system of the patient, sampling various properties along the way, and transmit the findings along with the accurate location from which they were taken.
In accordance with a further aspect of the invention, the position and orientation device is combined with an inner body ultrasound transceiver, thereby providing a real-time three dimensional image generation system. Reference is now made to FIG. 9, which is a schematic illustration of a three dimensional imaging system, which combines an inner ultrasound transceiver and a location and orientation detector, generally referenced 500 , constructed and operative in accordance with another preferred embodiment of the invention.
System 500 includes an inner body ultrasound assembly 540 , a storage unit 532 , a three-dimensional image generator 530 , a combining processor 536 , a general location and orientation detector 534 and a display unit 536 . The inner body ultrasound assembly 540 includes an ultrasound detector 502 and a location and orientation detector 510 , which are firmly attached to each other. It is noted that detector 502 can be replaced with any type of ultrasound transceiver of sensor, such as an inner vascular ultrasound (IVUS) element, and the like. The inner body ultrasound assembly 540 is connected to the storage unit 532 . The three-dimensional image generator 530 is connected to the storage unit 532 and to the combining processor 536 . The combining processor 536 is further connected to the general location and orientation detector 534 and to the display unit 538 . It is noted that the storage unit 532 is redundant when the three-dimensional image generator 530 is powerful enough for real-time image processing. In this case, the inner body ultrasound assembly 540 is directly connected to the three-dimensional image generator 530 .
The inner body ultrasound assembly 540 detects a plurality of two dimensional ultrasound images, and a plurality of location and orientation readings of the ultrasound detector 502 , each associated with a selected one of the two dimensional ultrasound images. Each of the two dimensional ultrasound images presents a different slice of a scanned three-dimensional volume. Each such pair of a two-dimensional ultrasound image and a location and orientation reading of the ultrasound detector is stored, as a record, in storage unit 532 . It is noted that the location and orientation detector 510 can operate according to the electromagnetic methods, which are presented according to the present invention, as well as according to any other electromagnetic method which is known in the art, such as rotating field, simple magnetic feedback and the like.
The three-dimensional image generator 530 retrieves the records and produces a three dimensional representation of the scanned volume. This representation can be further combined with location and orientation data provided from another location and orientation detector which is associated with any surgical tool such as a camera, clamps, a laser device and the like. The final result, including a three dimensional representation of the scanned volume, combined with an indication of the location and orientation of the surgical tool. is displayed on display unit 538 .
Reference is now made to FIGS. 10A and 10B, which are illustrations in perspective of an inner body ultrasound assembly 540 , of FIG. 9, constructed and operative in accordance with another preferred embodiment of the invention. System 540 further includes a dilation catheter 508 , a mounting catheter 506 and a surgical tool 542 . The ultrasound transceiver 502 is fixed to the mounting catheter 506 , which is inserted in the dilation catheter 508 . The location and orientation detector 510 is attached to the rear side of the ultrasound transceiver 502 . The surgical tool 542 includes clamps, where the location and orientation detector 544 surrounds the tip of the guiding tube 546 thereof
The location and orientation detector 510 continuously detects the location and orientation of the ultrasound transceiver 502 . The ultrasound transceiver 502 continuously transmits and detects ultrasound waves, from its front end 504 , thereby generating an angular ultrasound slice image, generally referenced 512 A. The image 512 A is a two dimensional representation of the objects which are located in front of section 504 .
With reference to FIG. 10B, the user can direct the ultrasound transceiver 502 in various directions, for example by means of rotation, thereby producing additional angular ultrasound slice images such as the one denoted 512 B. Reference is now made to FIG. 10C, which is an illustration in perspective of a plurality of angular ultrasound slice images, generally referenced 512 . The angular ultrasound slice images 512 A (FIG. 10 A), 512 B (FIG. 10 B), 512 C and 512 D are two-dimensional representations of various sections of the scanned volume. These images are combined to a three dimensional image, by the three-dimensional image generator 530 .
It is noted that using system 500 , the physician can operate on the patient immediately after creating the image of the treated area and further update the image, at any desired moment, thereafter.
Reference is now made to FIGS. 11A and 11B, which are illustration in perspective of an inner body ultrasound assembly, generally referenced 550 , constructed and operative in accordance with another preferred embodiment of the invention. Inner body ultrasound assembly 550 includes a radial ultrasound transceiver 552 and a location and orientation detector 556 . The radial ultrasound transceiver 552 is mounted on a mounting catheter 554 , which is further inserted in a dilation catheter 558 . The location and orientation detector 556 is located at the tip of the mounting catheter 554 , near the base of the radial ultrasound transceiver 552 . As can be seen in FIG. 11A, the location and orientation detector 556 includes a single coil, which is twisted around the tip of the mounting catheter 554 . The inner body ultrasound assembly 550 can replace the inner body ultrasound assembly 540 of FIG. 9 . The operating user can move the inner body ultrasound assembly 550 back and forth (denoted by a bi-directional arrow) as well as in various directions as will be further illustrated in FIG. 11B, herein below.
The location and orientation detector 556 continuously detects the location and orientation of the tip of the mounting catheter 554 , and hence, the location and orientation of the base of the radial ultrasound transceiver 552 . The location and orientation detector 556 provides the detected information to the storage unit 532 (FIG. 9 ). The radial ultrasound transceiver 552 continuously detects a radial ultrasound slice image, generally referenced 570 . The radial ultrasound transceiver 552 provides the detected image information to the storage unit 532 .
The storage unit 532 includes a plurality of records, each including a two dimensional radial slice of the scanned volume and a location and orientation or a predetermined point with respect to that slice. Reference is now made to FIG. 11B, which is an illustration in perspective of a plurality of radial ultrasound slice images, generally referenced 570 . Radial angular ultrasound slice images 570 A, 570 B, 570 C, 570 D, 570 E and 570 F are two-dimensional representations of various sections of the scanned volume. These images are combined to a three dimensional image, by the three-dimensional image generator 530 .
Reference is now made to FIG. 12, which is a schematic illustration of a method for operating system 500 , operative in accordance with a further preferred embodiment of the invention. In step 580 , the ultrasound detector 502 with the location and orientation detector 510 are inserted into the body of the patient and located at the area to be inspected and treated. In step 582 the ultrasound detector 502 detects a plurality of two-dimensional images (references 512 in FIG. 9 C). In step 584 , the location and orientation detector 510 detects the location and orientation of each of the two-dimensional images.
In step 586 , records, which include image and location and orientation information, are stored. It is noted that this step is redundant, provided the three-dimensional image generator is powerful enough. In step 588 , the three image generator 530 processes the records thereby producing a three dimensional representation of the scanned volume. This image, produced from the inner part of the scanned volume can now be displayed. For example, an inner body ultrasound assembly using MPS sensor with an IVUS can be used to produce reconstructed three-dimensional images of blood vessels.
In step 590 , the system receives additional location and orientation information which are originated from a different location and orientation detector, associated with any of a plurality of surgical tools. Such a surgical tool can be selected from the list consisting of any type of operational catheter, a camera, a lighting device and the like. It is noted that the present invention is not limited to one additional location and orientation sensor, rather a plurality of such sensors can be incorporated in a single system, where each is indicated on the three dimensional image (step 592 ) and displayed thereafter (step 594 ).
In accordance with a further aspect of the invention, there is provided a method for positioning a location and orientation detector on a reference image, prior to maneuvering it inside the body of the patient.
Reference is now made to FIG. 13, which is a schematic illustration of a method for initially positioning a location and orientation detector onto a reference image, operative in accordance with a further preferred embodiment of the invention. The method of the present invention utilizes known locations on the treated area, which are visible thereon and also visible on the reference image, which is to be associated therewith. At first, a plurality of such locations is determined (step 600 ). With respect to FIG. 3B, the main junctions of the lung system are easily detected, so are specific bone areas such as the solar plexus, vocal cords. and the like
In step 602 , the location and orientation detector is places in each of these locations and a reading is taken accordingly (step 604 ). It is noted that two or three such locations are enough to position the detector within the reference image. Any more such locations can be used to improve the accuracy of the positioning process. Finally the reference image is oriented onto the treated area (step 606 ) and the location and orientation detector can be positioned within the reference image (step 608 ).
In accordance with a further aspect of the invention, the position and orientation system of the invention is incorporated in laparoscopy devices and procedure Reference is now made to FIG. 14, which is an illustration of two minimal invasive tools, generally referenced 630 and 640 , constructed and operative in accordance with another preferred embodiment of the invention.
Minimal invasive tool 630 is generally a guiding element, which is ended by a surgical tool, generally referenced 632 . The surgical tool 632 can be any known device which is used in the process of minimal invasive surgery, such as a marking device, devices used for performing biopsies, surgical devices, laser cutting, treating and tissue welding devices and the like.
Minimal invasive tool 640 is generally similar to tool 630 and includes a surgical tool 642 and a pair of position and orientation sensors 644 and 646 , where sensor 644 is directed in the axial direction of tool 640 and sensor 646 is directed perpendicular thereto.
The minimal invasive tools 630 and 640 are inserted into the body of the patient through minimal size holes, 638 and 648 , respectfully, in the skin layer 636 . The use of such techniques reduces the trauma caused to the treated area. Conventional laparoscopy often requires that a camera and illumination means be inserted into the treated volume, since a simple line of sight is not available to the physician. In accordance with this aspect of the invention, no camera or illumination device have to be inserted into the treated volume. The position and orientation of the surgical tools are determined by the system of the invention and are indicated on an image of the treated volume, for the physician to see.
It will be appreciated by persons skilled in the art that the present invention is not limited to what has been particularly shown and described hereinabove Rather the scope of the present invention is defined only by the claims, which follow. | Medial device comprising a housing, a magnetic detection probe, for detecting a plurality of magnetic fields, a biometric unit and a controller, connected to said magnetic detection probe, said biometric unit and said storage unit, wherein said controller receives magnetic field detection information from said magnetic detection probe, and wherein said controller operates said biometric unit in association with said magnetic field detection information. | 0 |
This application is a 371 of PCT/DK03/00790 filed on Nov. 19, 2003 and claims priority to foreign application Denmark PA 2002-01782 filed on Nov. 19, 2002.
TECHNICAL FIELD
The present invention relates to a biologically inhibiting material including an anode material and a cathode material, where the anode material and the cathode material both have a positive galvanic potential, and where the potential of the cathode material is more positive than the potential of the anode material. Due to this difference in the potentials, the biologically inhibiting material will act as a galvanic element in contact with an electrolyte. The invention also relates to a method of producing the material as well as to the use of the material for inhibiting live cells.
TECHNICAL BACKGROUND
Good hygiene is an essential factor in the food production field. Many resources are invested in cleaning and disinfecting the equipment to improve the shelf-life of the products. In addition, during recent years the attention has been focussed on the risk of contamination of food products with pathogenic bacteria. Accordingly, there is an increasing demand for improvements in the field of good hygiene not only with respect to the cleaning, but also in relation to the suitable design of the machines used for the production.
Since 1 Jan. 1995 the EU has prescribed that the machines for processing food products must be designed to support good hygiene and an efficient cleaning procedure which ensures an optimum food product safety. Accordingly, an obvious demand exists for systematically optimizing the hygienic design of machines for processing food products.
An optimum cleaning of a closed process equipment is obtained by ensuring that the cleaning fluids circulate at a sufficiently high flow rate providing turbulent flow throughout the entire process equipment. Dead areas involving a very low flow rate should therefore be avoided by suitable equipment design.
Despite the above efforts, it can be difficult to completely avoid areas in the process equipment in which small remnants of food products stick to the walls of the equipment or accumulate in small pockets and thereby provide growth conditions for unwanted and often pathogenic micro-organisms. As these micro-organisms grow very quickly in the food products being processed in the process equipment, such small residues can very quickly have a serious effect on both health and costs.
Presently, attempts are made to develop materials on which there will be a reduced tendency to form biofilm. Examples are materials having a reduced adhesion to protein and fat and micro-organisms. However, such a solution is unlikely to prevent food remnants and micro-organisms from accumulating in small pockets and cracks. Accordingly, a demand exists for a material with inherent antimicrobial properties.
U.S. Pat. No. 5,843,186 (Christ) discloses an intraocular plastic lens (IOL) with antibacterial activity based on an iontophoretic effect. At least a portion of the lens is made of an iontophoretic composite material including two components, such as silver and platinum, with different galvanic potentials dispersed in a conducting polymer matrix. The iontophoretic effect is obtained when the lens is implanted in an eye. Here saline body fluids penetrate into the polymer matrix and establish a galvanic element between the two embedded components, which causes the ions of one component to dissolve whereafter the ions can migrate out of the matrix and into the surrounding body fluid, where they exert an antibacterial effect. In order to protect the body against harm, the galvanic elements are per se isolated from direct body contact in the surrounding polymer matrix, strong electric field strengths optionally being generated adjacent said galvanic elements.
Due to the use of this known ocular implantate in contact with the eye the antibacterial effect thereof is adjusted to ensure that the body does not suffer any acute or accumulated harm. It is also important that an accumulation of antibacterial ions is avoided for a short or long period.
However, an antibacterial effect based on the iontophoretic principle as suggested by U.S. Pat. No. 5,843,186 (Christ) and adjusted to be used in an implantate is unlikely to suffice for such antimicrobial or other cytocidal uses where the desired effect must be significantly stronger than hitherto known. In addition, an intensification of the effect to release an increased amount of antimicrobial ions results in an increased amount of ion residues in the solution or in the killed micro-organism cells, which cannot be tolerated in many situations, such as in connection with processing of food products.
U.S. Pat. No. 4,886,505 (Haynes et al.) discloses an apparatus to be inserted in the body, such as a catheter. On the surfaces, this apparatus is coated with a first and a second metal in such a manner that a galvanic effect is provided when the apparatus is brought into contact with an electrolyte, such as a body fluid. It is suggested that the two metals are applied onto the surface of the catheter in form of very thin films of a thickness of approximately 5 to 500 nm, either one metal atop the other metal or in such a manner that portions are covered with one type of metal film while other portions are covered with the second type of metal film, a switch being coupled between said two types with the result that the galvanic effect can be switched on and off according to desire.
In one embodiment, the catheter is coated with two metal films, one over the other, and produces a galvanic effect resulting in relatively significant potential differences per distance, viz. high electric field strengths, in an area inaccessible to micro-organisms, i.e. the area at the contact surface between the two films. Thus the antimicrobial effect is based on metal ions being released in the contact layer despite the fact that they are attracted by the cathode material.
In another embodiment, approximately half the surface of the catheter is covered by one type of metal film while the remaining portion of said surface is covered by the second type of metal film apart from an intermediate non-covered portion where a switch is positioned. Here the galvanic effect is indeed active when in direct contact with the surrounding body fluids, but the relatively significant potential differences per distance, viz. the high electric field strengths, only apply to the interface area between the two metal films, whereas the potential difference per distance and consequently the electric field strength is significantly weaker in portions presenting a large distance to said interface area. According to the publication, the antimicrobial effect is obviously also based on released metal ions.
Accordingly, the principle suggested in U.S. Pat. No. 4,886,505 (Haynes et al.) cannot be used in situations where a strong galvanic effect with high electric field strengths across the entire surface is needed without involving a significant release of metal ions.
Therefore, a demand still exists for materials capable of efficiently inhibiting live cells across the entire surface of the material in such a manner that there are no areas or domains with an insufficient antimicrobial effect where unwanted micro-organisms can survive. Such materials are inter alia needed within the food industry where remaining live micro-organisms in the production equipment, during storage and during transport can cause serious problems such as rapid tainting of the product and disease-causing effects in the consumer. These problems are particularly serious when the processed food products are nutrient mediums for the micro-organisms in question and consequently can promote the growth of said micro-organisms. Such food products are for instance dairy products, meat and fish products, gravy, juice, lemonade, beer, wine or soft drinks.
BRIEF DESCRIPTION OF THE INVENTION
It turned out surprisingly that it is possible to obtain a particularly strong cell-inhibiting effect on a material which includes an anode material and a cathode material, said anode material and said cathode material forming a galvanic element in contact with an electrolyte, provided one or more surfaces of the material are designed so that any location on the surface is spaced a short distance from both the adjacent anode material and the adjacent cathode material.
Thus the invention relates to a biologically inhibiting material including an anode material and a cathode material, where both the anode material and the cathode material have a positive galvanic potential and where the potential of the cathode material is more positive than the potential of the anode material, said material being characterised in that it includes a surface with separated (discrete) areas of anode material and cathode material, where the distance between any point on the active surface and both the adjacent cathode material and the adjacent anode material does not exceed 200 μm.
The invention relates furthermore to a method of producing the biologically inhibiting material according to the invention, said method being characterised in that an incomplete layer of the second electrode material is applied onto a surface of the first electrode material by way of a conventional coating procedure in such a manner that the second electrode material is caused to partially cover the first electrode material or is integrated in a matrix of the first electrode material.
In addition, the invention relates to the use of the biologically inhibiting material for inhibiting or killing live cells.
The particular design of the surface of the material ensures that any point on the surface is positioned at a very short distance from the adjacent cathode and anode. As a result relatively strong potential differences are obtained per distance, viz. high electric field strengths. This is a clear improvement compared to the above embodiment described in U.S. Pat. No. 4,886,505 (Haynes et al.). In said embodiment the metal surfaces are divided into two halves. This means that it is only possible to obtain such high field strengths adjacent to the interface area in the immediate vicinity of both of the two different materials, whereas the electric field strength is significantly lower as the distance to the interface is increased. Correspondingly, the strong electric field strengths in the intraocular lens according to U.S. Pat. No. 5,843,186 (Christ) are generated inside the polymer matrix at a distance from the micro-organisms to be controlled.
An additional advantage of the biologically inhibiting material according to the invention is that the anode material—which can be made of silver—does not dissolve during the galvanic process and accordingly it does not release significant amounts of Ag + -ions to the electrolyte. In fact the concentration of Ag + -ions is very low and based on an equilibrium and no forced dissolution takes place. In this manner the inhibiting material can be used in the processing of products or materials where the presence of silver ions is undesirable.
The extent of the applicability of the invention appears from the following detailed description. It should, however, be understood that the detailed description and the specific examples are merely included to illustrate the preferred embodiments and that various alterations and modifications within the scope of protection will be obvious to persons skilled in the art on the basis of the detailed description.
DETAILED DESCRIPTION OF THE INVENTION
As mentioned above, the inhibiting material according to the invention has a surface with separated areas of the two electrode materials.
These areas are distributed on the active surface in such a manner that the distances between any point on the surface and the adjacent cathode material and between said point and the adjacent anode material do not exceed 200 μm. These distances are preferably shorter than 100 μm and typically considerably shorter.
A material meeting these requirements can be prepared starting with a material having a surface of one of the electrode materials followed by an incomplete coating procedure with the other electrode material. In this way an incomplete coverage with the second material is obtained.
A multitude of coating methods are available to the person skilled in the art for applying thin metal coatings onto a surface. This is also called a plating. It is well-known to the person skilled in the art to produce a metal coating by way of an appropriate choice of process parameters, such as processing time, concentration, temperature etc, where said metal coating completely covers the substrate surface in question in a desired layer thickness and without “skips” or “holes”, i.e. areas with none or only a partial covering of the coating.
Instead of following the above knowledge of the person skilled in the art, the process parameters can be chosen so that a coating having an incomplete coverage is obtained. Thus the coating process can be carried out with a reduced processing time, a lowered temperature, a reduced concentration of active substances, a reduced current density of the electrolytic processes etc. with the result that an incomplete coating with skips is obtained where the underlying material is uncovered or where the coating appears in form of separated (discrete) clusters distributed on the underlying material.
Thus, the active surface of the biologically inhibiting material can be composed of separated areas in form of clusters of a cathode material distributed across a continuous area of an anode material, or separated areas in form of skips where the cathode material is uncovered and distributed in a continuous area of an anode material.
It is also possible that the active surface of the biologically inhibiting material can be composed of separated areas in form of clusters of an anode material distributed across a continuous area of a cathode material, or separated areas in form of skips where the anode material is uncovered and distributed in a continuous area of a cathode material.
Theoretically speaking, the two electrode materials can be distributed in any pattern across the surface merely provided that the necessary short distance to both electrode materials applies from any point on the surface to ensure a sufficiently high electric field strength and consequently a sufficiently strong biological inhibition anywhere on or in the immediate vicinity of the surface.
The anode material and the cathode material both have positive galvanic potentials (relative to SHE), and the potential of the cathode material is more positive than the potential of the anode material. As a result, a galvanic element is formed by the contact of the inhibiting material with an electrolyte.
The galvanic potential of one of these materials M means the standard potential ε M of the reaction
M n+ ne − →M
The standard potential of both the anode material Ma and the cathode material Mk must be positive and meet the relation
ε Mk >ε Ma >0
where ε Mk represents the standard potential of the cathode material Mk, and ε Ma represents the standard potential of the anode material Ma.
The anode material Ma must have a positive standard potential, preferably a standard potential of at least 0.10 V relative to the standard hydrogen electrode (SHE), more preferred at least 0.30 V relative to SHE, yet more preferred at least 0.50 V relative to SHE, and particularly preferred at least 0.75 V relative to SHE. Examples of suitable anode materials are for instance Au and Ag, of which Ag is preferred.
The cathode material Mk must have a standard potential exceeding the potential of an anode material (in the actual case), preferably at least by 0.05 V, more preferred at least by 0.10 V, even more preferred at least by 0.25 V, and most preferred at least by 0.40 V.
Examples of suitable cathode materials combined with Ag as anode material are graphite, Au, Pd, Pt, Ru, Ir ad Rh, of which especially Pd is preferred. When the anode material is Au, it is possible to use Ru, Ir or oxides thereof as cathode material.
Further cathode materials, such as electroactive ceramics which appears electrochemically noble, are also contemplated by the present invention. An example is manganese dioxide which can be manufactured by an electrochermical process, where the material is deposited on the anode at a suitable anodic potential.
Both the anode materials and the cathode material are based on the relevant metals in the metallic form with oxidation step 0, the material according to the invention usually being produced by an application of the cathode material and/or the anode material onto a substrate by way of one or more conventional plating or deposition processes (including electroplating, CVD, PVD, thick film techniques and thermal spraying). However, the anode and/or the cathode material of the active material can be completely or partially converted into a metal compound where the metal has a positive oxidation step, for instance in form of oxide, salt or sulphide.
The conversion into metal with a positive oxidation step can take place during the production of the material as a result of the applied plating processes, by a subsequent treatment or during the application conditions. However, the form of the metal with the positive oxidation step is conditioned by the metal compound in question being sparingly soluble during the application conditions in such a manner that metal ions are not released in toxic amounts to the surrounding electrolyte.
Irrespective of whether it is a question of a metallic form or metal compounds, it is essential to the evaluation of the applicability of the electrode materials that a sufficient difference is ensured between the potentials of the forms in which the metals are present during the application conditions.
Detailed information about electrochemical potentials can be studied using E/pH diagrams based on relevant thermodynamic data from the literature.
The previously suggested antimicrobial materials based on a galvanic effect are designed to provide an iontophoretic effect where the anode material is a metal being converted into antimicrobial metal ions which are released to the surrounding electrolyte. However, the use of anode materials having a positive electrochemical potential implies that the concentration of released metal ions is low and that the cell-inhibiting effect is modest Such a modest effect can be sufficient for an implantate where the effect supports the immune system of the body. However, such a modest effect is not sufficient when used in connection with a preferred embodiment of the present invention, said embodiment dealing with a very efficient control of micro-organisms in connection with for instance food production, treatment of water, such as controlling Legionella in public baths and swimming pools, or protecting drinking water in for instance ice cube machines.
The inhibiting material according to the invention has a particular design ensuring a high electric field strength across the entire surface to be provided with a cell-inhibiting effect. In addition, a material having both a good conductivity and catalytic properties is chosen as the anode material.
A sample of the biologically inhibiting material according to the invention has been examined by means of a scanning technique involving a vibrating electrode, viz. a scanning vibrating electrode technique; SVET. The sample is immersed in a 10 mM solution of NaCl at room temperature for up to 24 hours, and local positive and negative currents were measured on the surface. The intensity of these currents remained at the same level during the entire examination which confirms that the biologically inhibiting material presents an electric/catalytic effect.
It turned out surprisingly that such a combination of a structure ensuring high field strengths and the electric and catalytic properties of the anode material provides a cell-inhibiting effect which is significantly stronger than the effect which can be ascribed to released anode metal ions in the liquid acting as an electrolyte.
Without committing ourselves to a specific theory it is assumed that a catalytic oxidation process takes place where small amounts of metal oxide ale converted into metal and oxygen affecting live cells. Thus, when the anode surface comes into contact with a cell which per se represents an oxidizable material and furthermore acts as an electrolyte, said cell is subjected to an oxidation, the reaction at the anode optionally being:
2Ma x O y →2 x Ma+ y O 2
It is assumed that oxygen in statu nascendi is formed at the anode surface when an oxidizable electrolyte, such as a live cell, comes into contact with the anode surface. The cathode has a more positive potential than the anode, and at the cathode the above reaction proceeds in the opposite direction which results in an oxidative regeneration of the surface:
2 x Ma+ y O 2 →2Ma x O y
The particular structure of the inhibiting material according to the invention implies that the electric field strength is sufficiently high everywhere on the cell-inhibiting surface. In addition to the potential difference between the cathode and the anode, the electric field strength is determined by the geometric conditions including the distance between the electrodes.
The structure is characterised by one electrode material being suitably distributed in small isolated areas either in form of microclusters on the surface of the second electrode material or in form of micro-skips in the surface of said second electrode material whereby the neighbouring microclusters or micro-skips are suitably spaced apart without a too long mutual distance.
The distance between these micro-areas should not exceed 400 μm in such a manner that the distance from any point on the active surface both to the adjacent cathode material and to the adjacent anode material does not exceed 200 μm. The distance between the micro-areas is preferably smaller than 150 μm, particularly preferred smaller than 75 μm.
The size of the individual micro-areas should not exceed 50 μm, preferably not 15 μm, particularly preferred not less than 10 μm.
The area ratio of the cathode areas to the anode areas on the active surface is not particularly critical and can for instance be in the range of 0.01:1 to 1:0.01, preferably in the range of 0.05:1 to 1:0.05, such as in the range of 0.15:1 to 1:0.15.
The biologically inhibiting material according to the invention has an inhibiting effect on live cells, including cells of both eucaryotic and procaryotic organisms. By the expression “biologically inhibiting effect” is here meant a reduction or retardation of the cell growth as well as a killing of cells including a disinfection or sterilization.
Thus, the biologically inhibiting material according to the invention can be used within the food industry, such as for sterilizing or retarding the growth of micro-organisms in liquid food products, such as milk products, ice cream, juice, lemonade, gravy, beer and soft drinks, as well as for controlling formation of biofilm on surfaces of products and of equipment at for instance dairies, slaughterhouses, within the fish industry, at the preparation of ready-made dishes, marmalade and jam.
The material according to the invention is furthermore applicable within the pharmaceutical industry for solving hygienic problems.
The material is also useful for limiting the growth of cells in water systems, such as for inhibition of Legionella in hot-water pipes, as well as for inhibition of bacterial growth in air-condition systems.
The active surface of the biologically inhibiting material according to the invention results from the second electrode material being applied onto a base of a first electrode material through an incomplete deposition process in such a manner that said second electrode material only partially covers the first electrode material in form of either microclusters or involving micro-skips leaving the first electrode material uncovered.
In principle, the inventive material can be made on the basis of a substrate of the first electrode material, but usually it is based on a substrate of metal, such as for instance stainless steel, polymer or ceramics provided with a coating of the electrode material. Such a coating can be applied by a conventional plating process, such as an electrolytic or autocatalytic, viz. chemical, plating, by way of vapour deposition or depositing through sputtering.
The second electrode material can be applied onto the first electrode material by an electrolytic or chemical deposition through a vapour deposition or depositing by way of sputtering to such a limited extent that the surface of the first electrode material is only partially covered by small clusters or in such a manner that holidays or openings still appear, viz. skips in the layer of the second electrode material.
The biologically inhibiting material according to the invention can also be based on ceramics or polymers, with a large active surface area coated with anode and cathode material, and which in use comes into contact with a thin liquid film in the same manner as in an ion exchanger. Filters or sieves are also possible where the surface of the filter or sieve wires are coated with the biologically inhibiting material. Furthermore, the biologically inhibiting material according to the invention can be in the form of particles coated with anode and cathode material. Such particles can for instance be used as an active filler in coating materials, such as paints.
As stated above the biologically inhibiting material according to the invention can be prepared by means of several per se conventional plating or deposition methods including chemical electrochemical methods, PVD (Physical vapour deposition) CVD (Chemical vapour deposition), thick film techniques and thermal spraying.
Chemical electrochemical methods: The silver coating (anode material) can be applied on electric conducting materials (metals or polymers) by an electroplating process or an electroless process (e.g. autocatalytic), where the anodic materials are deposited as first step followed by the cathodic material which shall be deposited as a non-coherent coating (separately) atop the anode material. The depositions of the cathodic material can be carried out by an ionexchange plating process based on metal ions or metal ion complexes, which has a higher electrochemical potential than the coherent coating (in this case silver). The chemical deposition of the cathodic material is diffusion controlled.
Alternative the process can be carried out in such way, that the cathode surfaces are integrated in the anode as particles or phases. Thus palladium can be dispersed in a coherent silver matrix. Such process can be carried out by alternating treatment of the surface with silver and palladium, deposited by chemical and electrochemical methods, as described above. Especially process techniques based upon coil coating and reel to reel plating can be usable techniques.
Alternating deposition in a one step process based on pulse plating techniques is a further possibility. Another method for integrating the cathode material in the anode material as described above is dispersion plating, where the particles of the cathode material is co-deposited in a matrix continuously under the electrolytic or the electroless deposition process.
PVD (Physical vapour deposition): Techniques such as PVD, where periodical sputtering of cathode and anode materials or electron-beam evaporation from at least two sources of materials (cathode and anode materials) is also considered as an attractive method for manufacturing of the coatings. Especially for coatings on ceramics and polymers with “short lifetime” for application (thickness in the range of 100 nm). This technique can be particular suitable for disposable goods.
CVD (Chemical vapour deposition): Process methods based on decomposition of metal containing gases, which decompose on the surface by thermal and/or plasma activation. Thus gases containing volatile Ag and a noble material may be deposited together or the one after the other.
Thick film techniques: Anodic and chatodic material are applied to the surface by a spray or paint process and later “cured” or sintered by heat treating. The methods also includes processes where thermal decomposition of metal compounds such as Ag 2 O or [Pt(NH 3 ) 4 ]Cl 2 is carried out.
Thermal Spraying of a suitable mix of cathode and anode material to the surface. Thermal spraying covers several processes such as plasma spraying, arc spraying, flame spraying etc.
The growth inhibitive effect of the biologically inhibiting material according to the invention has been demonstrated against Shewanella putrefaciens (fish putrefactive bacteria), Escherichia coli and Bacillus cereus.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of an embodiment of the biologically inhibiting material according to the invention,
FIG. 1A shows an enlarged detail of FIG. 1 ,
FIG. 2 is a comparing schematic view of the principle described in U.S. Pat. No. 4,886,505, and
FIG. 3 is a schematic view of an alternative embodiment of the biologically inhibiting material according to the invention.
FIG. 1 illustrates a wall of stainless steel 2 in an apparatus, such as for instance an apparatus for processing a dairy product, such as a pasteurizing apparatus, and this wall is on the inner side coated with a continuous layer of an anode material 4 of for instance silver. A plurality of clusters 6 of cathode material, such as palladium, is applied onto the anode material 4 . When the inner side is in contact with an electrolyte 8 , a potential difference Δp is generated between the potential p A of the anode material 4 and the potential p K of the cathode material 6 . A bacteria 10 coming close to the inhibiting material is subjected to a high electric field strength Ε=Δp B /L B , where Δp B is the potential difference across the length L B of the bacteria. When it is assumed that the presence of the bacteria does not change the field lines significantly, cf. the dotted lines, the path L B of the field line through the bacteria is of a considerable size, i.e. the ratio L B /L T is relatively high where L T corresponds to the total length of the field line in question, cf. FIG. 1A . A uniform field strength along each field line has the effect that the bacteria is subjected to a potential difference Δp B =Δp×(L B /L T ), i.e. a relatively high potential when the ratio L B /L T is high.
FIG. 2 shows for comparison a schematic view of the principle described in U.S. Pat. No. 4,886,505 (Haynes et al.), where an article 102 is coated on one half of the surface with an anode material 104 and on the other half of the surface with a cathode material 106 . The function of this principle is conditioned by an electric contact 116 between the anode material 104 and the cathode material 106 at their interface area 112 . A bacteria 110 in the interface area 112 between the anode material 104 and the cathode material 106 is subjected to a high potential difference Δp B similar to the potential difference associated with the inhibiting material according to the invention, the ratio L B /L T being high here as well. Compared thereto, a bacteria 114 positioned a distance from the interface area 112 is subjected to a significantly weaker potential difference Δp B as the ratio L B /L T is significantly lower.
Like in FIG. 1 , FIG. 3 illustrates a wall of stainless steel 202 in an apparatus coated on the inner side with a continuous layer of an anode material 204 of for instance silver. An incomplete coating of cathode material 206 of for instance palladium is applied onto the anode material 204 . This incomplete coating leaves openings, viz. skips 212 , where the anode material 204 is uncovered. A contact between the inner side and an electrolyte 208 generates a potential difference Δp between the potential p A of the anode material 204 and the potential p K of the cathode material 206 . A bacteria 210 adjacent the inhibiting material is subjected to a strong electric field strength in the same manner as explained in connection with FIG. 1 .
In a further alternative embodiment the inventive material may have the same design as shown in FIG. 1 but with the cathode material as the continuous layer 4 and the anode material spread as clusters 6 on the surface of the cathode material. In the same way a further embodiment may have the same design as shown in FIG. 3 but with the cathode material as the continuous layer 204 covered with an incomplete coating 206 of anode material.
EXAMPLE 1
Pretreatment
A plate of technical silver (99.75%) of 20×10×1 mm is degreased at room temperature (20 to 25° C.) through an electrolytic degreasing (cathodic) at 10 A/dm 2 for ten minutes and then rinsed in distilled water. Possible oxides and alkali residues are removed through pickling with dry acid and mechanical agitation for one minute followed by rinsing with distilled water, said dry acid being a solid commercial product based on sodium bifluoride.
Silver Plating
The pre-treated plate is strike silver plated (i.e. is given a short initial silver plating) in a bath containing 3.75 g/l of AgCN (80.5%) and 115 g/l of KCN with stainless steel electrodes at 1 A/dm 2 for approximately 60 seconds with mechanical agitation. After rinsing in distilled water, a technical silver plating is applied in a bath containing 45 g/l of AgCN (80.5%), 115 g/l of KCN and 15 g/l of K 2 CO 3 at 1 A/dm 2 for 20 minutes with mechanical agitation. The plate is rinsed in distilled water and dried in hot air. The thickness of the resulting silver layer is approximately 15 μm.
Stock Solution of Palladium Chloride
A Pd-stock solution of 0.5 g of palladium chloride and 4.0 g of NaCl per 1 of aqueous solution is produced. The solution is shaken and the solution is left over night so as to completely dissolve the solution containing Pd as Na 2 [PdCl 4 ].
Application of Incomplete Pd-Layer
The silver-plating is followed by a degreasing of the plate through an electrolytic cathodic degreasing in cyanide for 20 to 30 seconds, a rinsing, a pickling for 20 to 30 seconds with mechanical agitation and yet another rinsing.
Then the plate is processed by being immersed for 3 minutes in an aqueous solution containing 33% by volume of Pd-stock solution with mechanical agitation. The plate is rinsed in distilled water and dried in hot air. Such a processing results in a reduction of the PdCl 4 −− -ions into metallic palladium according to the reaction:
2Ag+PdCl 4 −− →2AgCl+Pd+2Cl −
EXAMPLE 2
A stainless steel plate of 20×10×1 mm of AISI 316 steel with 2 B finish is pre-treated in a conventional manner with Wood nickel strike (100 g/l NiCl 2 and 100 ml/l HCl 37%) and strike silver plated in a bath containing 3.75 g/l of AgCN (80.5%) and 115 g/l of KCN with stainless steel electrodes at 1 A/dm 2 for approximately 60 seconds with mechanical agitation. After rinsing in distilled water, a technical silver plating is applied in a bath containing 45 g/l of AgCN (80.5%), 115 g/l of KCN and 15 g/l of K 2 CO 3 at 1 A/dm 2 for 20 minutes with mechanical agitation. The plate is rinsed in distilled water and dried in hot air. The resulting layer of silver has a thickness of approximately 15 μm.
The silver-plating is followed by a degreasing of the surface through an electrolytic cathodic degreasing in cyanide for 20 to 30 seconds, a rinsing, a pickling for 20 to 30 seconds with mechanical agitation and yet another rinsing. Then the plate is immersed for 3 minutes in an aqueous solution containing 33% by volume of the Pd-stock solution of Example 1 with mechanical agitation. The plate is rinsed in distilled water and dried in hot air.
SEM/EDS-analysis (Scanning Electron Microscopy/Energy Dispersive X-ray Spectrometry) of the surface processed in this manner reveals that 15 to 25% of the surface area is covered by silver/silver chloride while the remaining surface area is covered by a thin layer of palladium of approximately 0.1 μm. The areas covered by silver/silver chloride present an extent of from 0.1 μm to 6 μm, and the distance between the individual areas of silver/silver chloride varies from 0.4 μm to 3 μm.
EXAMPLE 3
Method
Untreated stainless steel plates of 20×10×1 mm (control) were placed in one vessel, and silver plates coated with silver and palladium produced according to the invention as described in Example 1 were placed in a second vessel. Equal amounts of milk were added to the two vessels. The temperature was kept at 21° C., and the milk was circulated across the surfaces of the plates. Escherchia coli K12 was added to a cell level of the magnitude 10 4 /ml. Sample plates were removed immediately upon the addition of Escherichia coli and subsequently every hour for the first 6 hours as well as 24 hours after the start of the experiment. The formation of biofilm on the plates was examined with dyeing and confocal microscopy for protein and fat and with dyeing for live and dead bacteria.
Results
Confocal microscopy clearly demonstrated the presence of biofilm on the control plates where both proteins, fat and bacteria were detected on the surface. However, neither protein, fat nor bacteria were detectable on the plates according to the invention and thus no biofilm was recognizable on the plates according to the invention.
A cell-counting on liquid samples from the two vessels appears from the following table:
TABLE
Number of cells/ml
Vessel with silver and
Time (hours)
Vessel with untreated
palladium coated plates
after start
stainless steel plates (control)
(acc. to the invention)
0
32 × 10 4
33 × 10 4
1
29 × 10 4
34 × 10 4
2
36 × 10 4
26 × 10 4
3
34 × 10 4
27 × 10 4
4
49 × 10 4
39 × 10 4
5
69 × 10 4
56 × 10 4
6
73 × 10 4
71 × 10 4
24
10 × 10 8
79 × 10 4
It appears from the table that no bacterial growth was detected during the first six hours. After 24 hours, a clear bacterial growth was detected in the control vessel whereas no bacterial growth was detectable in the vessel with the plates according to the invention.
EXAMPLE 4
An incomplete Pd-layer is applied onto a silver plated stainless steel plate of 20×10×1 mm produced as described in Examples 1 and 2 in the same manner as described in Example 1, but with a solution containing 5% of Pd-stock solution and involving a processing time of 1 minute.
EXAMPLE 5
An incomplete Pd-layer is applied onto a silver plated stainless steel plate of 20×10×1 mm produced as described in Examples 1 and 2 in the same manner as described in Example 1, but with a solution containing 5% of Pd-stock solution and involving a processing time of 3 minutes.
EXAMPLE 6
An incomplete Pd-layer is applied onto a silver plated stainless steel plate of 20×10×1 mm produced as described in Examples 1 and 2 in the same manner as described in Example 1, but with a solution containing 33% of Pd-stock solution and involving a processing time of 1 minute.
The plates produced according to the Examples 3 to 6 were examined by an SEM/EDS-analysis This analysis revealed that an increased concentration of Pd-stock solution as well as a prolonged processing time result in an increased application of Pd. However, all plates still showed surface areas with silver/silver chloride alternating with areas of Pd, and a bacterial inhibiting effect was detected on all the plates.
EXAMPLE 7
A layer of silver and palladium is applied onto spiral wires of technical silver (99.75%) of a thickness of 0.5 mm in the same manner as described in Example 1. The spiral wires are suited for biological inhibition through immersion in biologically sensitive liquids.
EXAMPLE 8
A spiral wire produced according to Example 7 with an active surface of 160 cm 2 was immersed in a 3 l cleaned watering arrangement placed outdoors in a poultry keeping of 8 hens of the breed Buff Orpington. The reservoir of the watering arrangement was filled with 2 l of tap water. The water in the water reservoir kept fresh for several days, and no formation of biological slime was observed on the plastic surfaces apart from the external drinking bowl, where the water had left the reservoir with the spiral wire. However, the formation of slime in the drinking bowl was reduced compared to the usual formation of slime. After 3 days and nights, approximately 0.5 l of water was left, and this water was collected together with the dirt and gravel scraped into the drinking bowl by the hens. After filtration, both the filtrate and the solid gravel fraction were examined with respect to content of silver by way of atomic absorption (AAS). Both fractions disclosed a silver content significantly lower than 100 μg/l.
The above description of the invention reveals that it is obvious that it can be varied in many ways. Such variations are not to be considered a deviation from the scope of the invention and all such modifications which are obvious to persons skilled in the art are also to be considered comprised by the scope of the succeeding claims. | Method for inhibiting live cells including eukaryotic and prokaryotic cells on an item utilized outside the human or animal body. The method includes the step of providing on the item a biologically inhibiting material including an anode material and a cathode material. Both the anode material and the cathode material have a positive galvanic potential, and the potential of the cathode material is higher than the potential of the anode material. The anode material and the cathode material each include exposed active surfaces. The exposed active surfaces include at least one of a plurality of separated areas of anode material and a plurality of separated areas of cathode material. A distance between any point on the active surface and both the adjacent cathode material and the adjacent anode material does not exceed 200 μm for inhibiting live cells including eukaryotic and prokaryotic cells on the item utilized outside the human or animal body. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an apparatus for automatically mounting electronic parts on a printed circuit board.
2. Description of the Related Art
A known electronic-parts mounting apparatus includes an electronic-parts feeder, a mounting head, and a mounting portion. A printed circuit board is placed in position within the mounting portion. The mounting head carries electronic components (electronic parts) from the electronic-parts feeder to the mounting portion, and mounts the electronic components on the printed circuit board. The mounting portion is provided with an XY table for moving the printed circuit board in two perpendicular directions on a horizontal plane. The XY table is rotatable.
In the known electronic-parts mounting apparatus, the XY table is rotated from a normal position when the actual posture of an electronic component held by the mounting head differs from a desired posture, or when an electronic component is required to be obliquely mounted on the printed circuit board. Specifically, in the case where the actual posture of an electronic component held by the mounting head differs from a desired posture, the electronic component is carried to a place above the printed circuit board in the mounting portion while the actual posture thereof remains different from the desired posture. The XY table is rotated from its normal position to compensate for the error in the posture of the electronic component held by the mounting head. Then, the mounting head is lowered toward the printed circuit board, and the electronic component is mounted thereon by the mounting head.
The postural error compensation using rotation of the XY table causes a long mounting time to be spent per electronic component. The reason for the long mounting time is as follows. The XY table is large and heavy. Therefore, the time interval between the moment of start of rotation of the XY table and the moment of stop thereof is relatively long. After the stop of rotation of the XY table has been completed, the mounting head commences to be lowered toward the printed circuit board. Accordingly, the known electronic-parts mounting apparatus tends to be low in mounting speed or rate.
SUMMARY OF THE INVENTION
It is an object of this invention to provide an electronic-parts mounting apparatus having a high mounting speed or rate.
A first aspect of this invention provides an electronic-parts mounting apparatus comprising an electronic-parts feeder; a mounting head for carrying electronic parts from the electronic-parts feeder, the mounting head including a plurality of nozzles for holding the electronic parts respectively; an electronic-parts mounting portion for enabling the mounting head to mount the electronic parts on a circuit board; first means for rotating each of the nozzles; and second means for moving each of the nozzles upward and downward.
A second aspect of this invention is based on the first aspect thereof, and provides an electronic-parts mounting apparatus wherein the first means includes a pinion provided on an outer circumferential surface of each of the nozzles, and a rack meshing with the pinion.
A third aspect of this invention is based on the second aspect thereof, and provides an electronic-parts mounting apparatus wherein the rack includes a first rack plate, a second rack plate slidably superposed on the first rack plate, and means for urging the second rack plate relative to the first rack plate in a direction parallel to the first rack plate.
A fourth aspect of this invention is based on the third aspect thereof, and provides an electronic-parts mounting apparatus further comprising third means for urging each of the nozzles in a direction of rotation of the nozzle.
A fifth aspect of this invention is based on the second aspect thereof, and provides an electronic-parts mounting apparatus wherein positions of the nozzles correspond to integer multiples of a pitch of teeth of the rack respectively.
A sixth aspect of this invention is based on the first aspect thereof, and provides an electronic-parts mounting apparatus wherein each of the nozzles includes an outer cylinder, a holder, means for rotatably supporting the outer cylinder on the holder, an inner cylinder extending into the outer cylinder and being movable upward and downward relative to the outer cylinder, a pinion provided on the outer cylinder, and further comprising a rack meshing with the pinion, and means for supporting the rack slidably on the holder.
A seventh aspect of this invention is based on the sixth aspect thereof, and provides an electronic-parts mounting apparatus wherein each of the nozzles includes a coil spring provided between the outer cylinder and the holder.
An eighth aspect of this invention is based on the first aspect thereof, and provides an electronic-parts mounting apparatus wherein the second means includes a fluid-operated actuator having a piston in engagement with an upper end of each of the nozzles.
A ninth aspect of this invention is based on the eighth aspect thereof, and provides an electronic-parts mounting apparatus further comprising a limiting plate engageable with a lower end of the piston for determining a lower limit position of the piston, a first spring for urging the piston downward, and a second spring for urging the nozzle upward.
A tenth aspect of this invention provides an electronic-parts mounting apparatus comprising an electronic-parts feeder; a mounting head for carrying electronic parts from the electronic-parts feeder, the mounting head including a plurality of nozzles for holding the electronic parts respectively; an electronic-parts mounting portion for enabling the mounting head to mount the electronic parts on a circuit board; first means for rotating each of the nozzles; a fluid-operated actuator for moving each of the nozzles upward and downward, the fluid-operated actuator having a piston in engagement with an upper end of each of the nozzles; a limiting plate engageable with a lower end of the piston for determining a lower limit position of the piston; a first spring for urging the piston downward; a second spring for urging the nozzle upward; and second means for moving the limiting plate upward and downward.
An eleventh aspect of this invention provides an electronic-parts mounting apparatus comprising an electronic-parts feeder; a mounting head for carrying electronic parts from the electronic-parts feeder, the mounting head including a plurality of nozzles for holding the electronic parts respectively; an electronic-parts mounting portion for enabling the mounting head to mount the electronic parts on circuit board; first means for rotating each of the nozzles; a fluid-operated actuator for moving each of the nozzles upward and downward, the fluid-operated actuator having a piston in engagement with an upper end of each of the nozzles, a limiting plate engageable with a lower end of the piston for determining a lower limit position of the piston; a first spring for urging the piston downward; a second spring for urging the nozzle upward; second means for detecting heights of the electronic parts held by the nozzles; and third means for moving the limiting plate upward and downward in response to the heights detected by the second means.
A twelfth aspect of this invention is based on the eighth aspect thereof, and provides an electronic-parts mounting apparatus wherein the second means includes a bearing for rotatably connecting the piston and the upper end of each of the nozzles.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an electronic-parts mounting apparatus according to. first embodiment of this invention.
FIG. 2 is a top view of the electronic-parts mounting apparatus in FIG. 1 .
FIG. 3 is a front view of the electronic-parts mounting apparatus in FIG. 1 .
FIG. 4 is a perspective view of a mounting head in FIG. 1 with a portion broken away for the sake of clarity.
FIG. 5 is a front view of the mounting head in FIG. 4 .
FIG. 6 is a sectional view of a sucking nozzle in FIGS. 4 and 5.
FIG. 7 is a plan view of a rack and pinions in FIG. 4 .
FIG. 8 is a sectional view of the rack in FIG. 7 .
FIG. 9 is a top view of the rack in FIG. 7 .
FIG. 10 is a front view of the mounting head in FIG. 4 .
FIG. 11 is a sectional view of the mounting head in FIG. 10 .
FIG. 12 is a sectional view of the mounting head in FIG. 10 in which a nozzle assumes a higher position.
FIG. 13 is a sectional view of the mounting head in FIG. 10 in which the nozzle assumes a lower position.
FIG. 14 is a front view of a cam and an intermediate plate in the mounting head in FIG. 4 where the cam assumes a first limit position.
FIG. 15 is a front view of the cam and the intermediate plate in the mounting head in FIG. 4 where the cam assumes a second limit position.
FIG. 16 is a block diagram of an electric portion of the electronic-parts mounting apparatus in FIG. 1 .
FIG. 17 is a sectional view of a portion of a mounting head in an electronic-parts mounting apparatus according to second embodiment of this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
First Embodiment
With reference to FIGS. 1, 2 , and 3 , an electronic-parts mounting apparatus in a first embodiment of this invention includes a main body 1 being a metal frame. An electronic-parts mounting portion 2 is provided on a central part of the main body 1 . Electronic-parts feeders 3 and 4 are supported on the main body 1 . The electronic-parts feeders 3 and 4 extend at the left and the right of the electronic-parts mounting portion 2 respectively.
Mounting heads 5 and 6 are movably supported on the main body 1 . The mounting head 5 serves to carry electronic components (electronic parts) from the electronic-parts feeder 3 to the electronic-parts mounting portion 2 . The mounting head 6 serves to carry electronic components (electronic parts) from the electronic-parts feeder 4 to the electronic-parts mounting portion 2 . The electronic-parts mounting portion 2 is provided with a Y table 7 . The Y table 7 can move relative to the main body 1 in a horizontal direction, that is, a Y direction. A printed circuit board is placed on the Y table 7 .
The electronic-parts feeder 3 includes taping reels 8 from which electronic components (electronic parts) are fed to the mounting head 5 . The electronic-parts feeder 4 includes cassettes 9 from which electronic components (electronic parts) are fed to the mounting head 6 .
The mounting heads 5 and 6 have similar structures. Therefore, only the mounting head 5 will be explained in detail. As shown in FIGS. 4 and 5, the mounting head 5 includes ten sucking nozzles 10 arranged in a line. Also, the mounting head 5 includes a motor 11 for circumferentially rotating the sucking nozzles 10 . Furthermore, the mounting head 5 includes a motor 12 for controlling the lower limit of vertical displacements of the sucking nozzles 10 .
As shown in FIG. 6, each sucking nozzle 10 includes an outer cylinder (an outer sleeve) 13 and an inner cylinder (an inner sleeve) 14 . The inner cylinder 14 coaxially extends into the outer cylinder 13 via an upper end thereof. The outer cylinder 13 and the inner cylinder 14 are connected via a suitable coupling such as a pin-slit coupling or a key coupling which allows the inner cylinder 14 to circumferentially rotate together with the outer cylinder 13 , and to axially slide relative to the outer cylinder 13 . The outer cylinder 13 is rotatably supported on a holder 15 by upper and lower bearings 16 . The outer cylinder 13 is allowed to rotate in a circumferential direction. An upper end of the outer cylinder 13 is formed with a pinion 17 . The pinion 17 meshes with a rack 18 . The rack 18 is slidably supported by the holder 15 .
As shown in FIGS. 7, 8 , and 9 , the rack 18 includes upper and lower plates 19 and 20 both formed with teeth. The upper plate 19 is superposed on the lower plate 20 . The lower plate 20 can move relative to the holder 15 in a horizontal direction. The upper plate 19 is thinner than the lower plate 20 . The upper plate 19 can slide horizontally relative to the lower plate 20 .
As best shown in FIGS. 7 and 8, the upper plate 19 has holes 21 through which pins 22 extend respectively. The pins 22 are fixed to the lower plate 20 . The inside dimensions of the holes 21 are set greater than the outside dimensions of the pins 22 to allow leftward and rightward horizontal slide of the upper plate 19 relative to the lower plate 20 .
As best shown in FIG. 8, an arm 23 is fixed to one end of the lower plate 19 . One end of a spring 24 engages the arm 23 while the other end of the spring 24 abuts against one end of the upper plate 19 . The spring 24 urges the upper plate 19 rightward as viewed in FIGS. 7, 8 , and 9 .
As shown in FIGS. 4, 7 , and 8 , a pinion 25 meshes with the teeth of the upper plate 19 and also the teeth of the lower plate 20 . As best shown in FIG. 7, the spring 24 presses a tooth 27 of the upper plate 19 against the left side of a tooth 26 of the pinion 25 , thereby pressing the right side of the tooth 26 of the pinion 25 against a tooth 28 of the lower plate 20 . Therefore, the tooth 26 of the pinion 25 is firmly held between the tooth 27 of the upper plate 19 and the tooth 28 of the lower plate 20 . Thus, the mesh between the rack 18 (including the upper plate 19 and the lower plate 20 ) and the pinion 25 is free from backlash.
The pinion 25 is mounted on an output shaft of the motor 11 . The pinion 25 rotates in accordance with rotation of the output shaft of the motor 11 . As previously indicated, the pinion 25 meshes with the rack 18 . The rack 18 moves rightward and leftward in accordance with rotation of the pinion 25 . Accordingly, the rack 18 is moved horizontally by the motor 11 .
With reference back to FIG. 6, a helical spring (a coil spring) 29 extends around the outer cylinder 13 of the sucking nozzle 10 . One end of the spring 29 is fixed to the holder 15 while the other end thereof is attached to the outer cylinder 13 . As previously indicated, the outer cylinder 13 is formed with the pinion 17 which meshes with the rack 18 . As shown in FIGS. 6 and 7, the spring 29 urges the outer cylinder 13 circumferentially relative to the holder 15 so that a side of a tooth 30 of the pinion 17 is pressed against a tooth 28 of the rack 18 . Thus, the mesh between the rack 18 and the pinion 17 is free from backlash.
The pinion 17 rotates as the rack 18 moves horizontally. Accordingly, the outer cylinder 13 rotates in accordance with horizontal movement of the rack 18 . Since the rack 18 can be moved horizontally by the motor 1 , the outer cylinder 13 can be rotated by the motor 11 . A working portion (a lower portion) of the sucking nozzle 10 is connected by a suitable coupling such as a pin-slit coupling or a key coupling to the outer cylinder 13 so that the working portion of the sucking nozzle 10 will rotate circumferentially together with the outer cylinder 13 while being able to move vertically relative to the outer cylinder 13 . The working portion of the sucking nozzle 10 operates to suck and hold an electronic component. The electronic component held by the working portion of the sucking nozzle 10 can be rotated by the motor 11 .
The ten sucking nozzles 10 are arranged at equal intervals chosen so that the pinions 17 on the sucking nozzles 10 will be equal to each other in teeth phase (angular teeth position) with respect to the teeth of the rack 18 . For example, the positions of the sucking nozzles 10 correspond to integer multiples of the pitch of the teeth of the rack 18 respectively. Thus, the angular positions of the ten sucking nozzles 10 are equal to each other. The angular positions of the sucking nozzles 10 vary equally (or in synchronization) in accordance with horizontal movement of the rack 18 , that is, in accordance with rotation of the pinion 25 .
As shown in FIG. 6, the inner cylinder 14 extends into the outer cylinder 13 via an upper end of the outer cylinder 13 . The inner cylinder 14 can slide axially relative to the outer cylinder 13 . In other words, the inner cylinder 14 can move upward and downward relative to the outer cylinder 13 . The working portion (the lower portion) of the sucking nozzle 10 is connected to or integral with the inner cylinder 14 so that the working portion of the sucking nozzle 10 can move and rotate together with the inner cylinder 14 .
One of the ten sucking nozzles 10 will be further explained. As shown in FIGS. 10 and 11, an upper end of the inner cylinder 14 contacts a large-diameter lower end 32 of an actuator piston 31 . The actuator piston 31 slidably extends into an actuator cylinder 33 . The actuator piston 31 can move axially relative to the actuator cylinder 33 . In other words, the actuator piston 31 can move upward and downward relative to the actuator cylinder 33 . A spring 34 is provided between an upper end of the outer cylinder 13 and a flange on the inner cylinder 14 . The spring 34 urges the inner cylinder 14 upward relative to the outer cylinder 13 . A spring 35 disposed in the actuator cylinder 33 extends between an upper wall of the actuator cylinder 33 and an upper end of the actuator piston 31 . The spring 35 urges the actuator piston 31 downward relative to the actuator cylinder 33 . The springs 34 and 35 bring the upper end of the inner cylinder 14 and the large-diameter lower end 32 of the actuator piston 31 into contact with each other.
Working fluid such as air can be supplied to and drawn from a working chamber within the actuator cylinder 33 which extends above the actuator piston 31 . As the working fluid is supplied to the working chamber within the actuator cylinder 33 , the actuator piston 31 is moved downward. As the working fluid is drawn from the working chamber within the actuator cylinder 33 , the actuator piston 31 is moved upward.
With reference to FIGS. 4 and 11, the large-diameter lower end 32 of the actuator piston 31 can meet a limiting plate 36 . The limiting plate 36 has ten semicircular recesses 37 which correspond to the ten sucking nozzles 10 respectively. The inner cylinder 14 movably extends through the corresponding recess 37 in the limiting plate 36 . As the working fluid is supplied to the working chamber within the actuator cylinder 33 , the actuator piston 31 is moved downward until the large-diameter lower end 32 thereof meets the limiting plate 36 . In other words, downward movement of the actuator piston 31 is stopped by the limiting plate 36 . Thus, the limiting plate 36 determines the lower limit position of the actuator piston 31 . Also, the limiting plate 36 determines the lower limit position of the working portion of the sucking nozzle 10 . In the case where the large-diameter lower end 32 of the actuator piston 31 reaches the limiting plate 36 , the piston 32 remains in its lower limit position even if the working fluid is further supplied to the working chamber within the actuator cylinder 33 . As will be made clear later, the lower limit position of the piston 32 is variable or movable.
The limiting plate 36 can move upward and downward. In the case where the working fluid is supplied to the working chamber within the actuator cylinder 33 so that the large-diameter lower end 32 of the actuator piston 31 is in contact with the limiting plate 36 , as the limiting plate 36 moves upward and downward, the actuator piston 31 and the inner cylinder 14 move upward and downward while the large-diameter lower end 32 of the actuator piston 31 remains in contact with the limiting plate 36 and also the upper end of the inner cylinder 14 (see FIGS. 12 and 13 ). Thus, in this case, the inner cylinder 14 moves upward and downward in accordance with the movement of the limiting plate 36 . The working portion of the sucking nozzle 10 is connected to the inner cylinder 14 so as to move upward and downward in accordance with the movement of the inner cylinder 14 . The downward movement of the working portion of the sucking nozzle 10 is used in access to an electronic component 38 as follows. After the working portion of the sucking nozzle 10 reaches the electronic component 38 according to the downward movement thereof, a lower end of the sucking nozzle 10 sucks and picks up the electronic component 38 . Then, the working portion of the sucking nozzle 10 moves upward while holding the electronic component 38 (see FIGS. 12 and 13 ). During the downward movement of the working portion of the sucking nozzle 10 in accordance with the downward movement of the limiting plate 36 , the large-diameter lower end 32 of the actuator piston 31 remains in contact with the limiting plate 36 and also the upper end of the inner cylinder 14 so that unwanted vibration or unwanted sound is prevented from occurring.
As shown in FIGS. 4, 14 , and 15 , the limiting plate 36 is fixed to an intermediate plate 39 on which two rollers 40 are rotatably mounted. The two rollers 40 are vertically spaced from each other by a predetermined interval. An effective portion of a rotatable cam 41 is sandwiched between the rollers 40 . The cam 41 is connected to an output shaft of the motor 12 so that the cam 41 can be rotated by the motor 12 . The cam 41 is designed so that rotation of the cam 41 will move the intermediate plate 39 upward and downward. The limiting plate 36 moves upward and downward together with the intermediate plate 39 . Thus, the limiting plate 36 is moved upward and downward by the motor 12 .
The operation of the mounting head 6 will be further explained. The mounting head 6 is placed above the electronic-parts feeder 4 . In the mounting head 6 , the limiting plate 36 is moved downward by the motor 12 . The working portion (the lower portion) of the sucking nozzle 10 is moved downward to access an electronic component 38 in the corresponding cassette 9 of the electronic-parts feeder 4 in accordance with the movement of the limiting plate 36 . Then, the lower end of the sucking nozzle 10 sucks an electronic component 38 from the corresponding cassette 9 (see FIGS. 11 and 13 ). Subsequently, the cam 41 is rotated by the motor 12 from the position shown in FIG. 15 to the position shown in FIG. 14 so that the working portion of the sucking nozzle 10 moves upward while the lower end of the sucking nozzle 10 continues to hold the electronic component 38 . In this way, the sucking nozzle 10 picks up the electronic component 38 . Then, the mounting head 6 is moved (leftward as viewed in FIG. 1) by a suitable drive mechanism to the electronic-parts mounting portion 2 along a carry path.
When the mounting head 6 is moved along the carry path, an image sensor or a camera 42 located below the carry path takes an image of the electronic component 38 held by the sucking nozzle 10 . As shown in FIG. 16, the image sensor 42 is electrically connected to a controller 44 including a CPU (central processing unit). When the mounting head 6 is moved along the carry path, a height sensor 43 located near the carry path detects the height of the electronic component 38 held by the sucking nozzle 10 . As shown in FIG. 16, the height sensor 43 is electrically connected to the controller 44 . In addition, the motors 11 and 12 are electrically connected to the controller 44 . Furthermore, a memory 45 is electrically connected to the controller 44 . The memory 45 stores data representing a desired posture of an electronic component held by each sucking nozzle 10 . The desired posture of the electronic component includes a desired tilt or inclination of the electronic component, and a desired angle thereof. The controller 44 drives the motors 11 and 12 in response to output signals of the image sensor 42 and the height sensor 43 and output data from the memory 45 according to a program stored in a ROM within the CPU. The program is designed to implement the following processes.
The controller 44 calculates the actual posture of the electronic component 38 held by the sucking nozzle 10 in response to the output signal of the image sensor 42 . The controller 44 collates the calculated actual posture with the desired posture represented by the output data from the memory 45 , and thereby calculates a postural error of the electronic component 38 held by the sucking nozzle 10 . The calculated postural error includes a calculated angular error. The controller 44 drives the motor 11 in response to the calculated angular error of the electronic component 38 held by the sucking nozzle 10 . As the motor 11 is driven, the outer cylinder 13 is rotated and hence the electronic component 38 held by the sucking nozzle 10 is also rotated. The rotation of the electronic component 38 corrects the angular error thereof. Accordingly, the actual posture of the electronic component 38 held by the sucking nozzle 10 is corrected into agreement with the desired posture thereof.
The mounting head 6 carries electronic components to the electronic-parts mounting portion 2 , and then mounts them on a printed circuit board placed on the Y table 7 . Since angular errors of the electronic components are corrected as indicated above, they can be accurately mounted on the printed circuit board.
When the mounting head 6 carries the electronic component 38 toward the electronic-parts mounting portion 2 , the controller 44 derives the height of the electronic component 38 held by the sucking nozzle 10 from the output signal of the height sensor 43 . The controller 44 drives the motor 12 in response to the derived height of the electronic component 38 . As the motor 12 is driven, the limiting plate 36 is moved vertically. The vertical movement of the limiting plate 36 is designed so as to prevent the sucking nozzle 10 from excessively pressing the electronic component 38 against the printed circuit board during the electronic-parts mounting process. It should be noted that the limiting plate 36 determines the lower limit position of the working portion of the sucking nozzle 10 .
The memory 45 may store data representing the height of electronic components. The controller 44 may drive the motor 12 in response to the height data fed from the memory 45 .
Second Embodiment
FIG. 17 shows a second embodiment of this invention which is similar to the first embodiment thereof except for the following design change. A large-diameter lower end 32 of each actuator piston 31 is provided with a bearing 46 via which an upper end of an inner cylinder 14 is associated or connected with the actuator piston 31 . The bearing 46 allows circumferential rotation of the inner cylinder 14 relative to the actuator piston 31 . Therefore, when the inner cylinder 14 rotates, the bearing 46 prevents rotation of the actuator piston 31 which might damage a combination of the actuator piston 31 and an actuator cylinder 33 . | An electronic-parts mounting apparatus includes an electronic-parts feeder. A mounting head operates for carrying electronic parts from the electronic-parts feeder. The mounting head includes a plurality of nozzles for holding the electronic parts respectively. An electronic-parts mounting portion operates for enabling the mounting head to mount the electronic parts on a circuit board. A first mechanism operates for rotating each of the nozzles. A second mechanism operates for moving each of the nozzles upward and downward. The first mechanism may include a pinion provided on an outer circumferential surface of each of the nozzles, and a rack meshing with the pinion. | 8 |
BACKGROUND OF THE INVENTION
This invention relates to an improved railcar transport.
In some instances it is desirable to move railcars over the road to railcar repair facilities or to move railcars about railcar repair facilities or wherever desired without having large amounts of space devoted to trackage and switching facilities.
In order to transport railcars over the road and about various facilities, it is desirable to utilize a transport trailer capable of hauling a wide variety of railcars thereon without modification.
One such prior art railcar transport trailer comprises a trailer for use with a suitable truck tractor towing means. The trailer comprises an elongated rectangular frame having a pair of rails located inboard of the longitudinal side frame members of the frame on the frame cross members, having a railcar ramp secured to one end thereof and having a power winch mounted on the other end thereof to pull railcars thereon. The trailer also includes a rail alignment means on one end of the railcar ramp comprising a hydraulic cylinder mounted on a bracket secured on one side of the railcar ramp having the piston rod thereof secured to one of the rails with motion being transmitted to the other rail by means of a linkage. The railcar ramp is raised and lowered by means of a pair of hydraulic cylinders each having one end thereof secured to a vertically upward extending beam from the rear of the railcar trailer and the other end secured by means of a linkage to the railcar ramp near the point of attachment of the ramp to the rectangular frame, thereby having the hydraulic cylinders mounted above the pivot point of the ramp where it is secured to the elongated trailer frame. The trailer further includes rigidly mounted wheels and axles thereon with no provision for any type of suspension means, thereby causing the trailer to be suitable only for use at very low speeds on smooth surface.
STATEMENT OF THE INVENTION
In contrast to the prior art, the present invention is directed to a railcar transport suitable for use with a truck tractor towing means comprising a trailer having an elongated rectangular frame having the rails thereon located on the longitudinal side frame members, having a railcar ramp secured to one end thereof, having a power winch mounted on the other end thereof to pull railcars thereon, having rail alignment means on one end of the railcar ramp mounted between the rails thereon, and having railcar ramp articulation means which are mounted either at the ramp pivot point or therebelow. The rail alignment means on one end of the railcar ramp comprises a hydraulic cylinder mounted between the rails on the ramp having one end thereof engaging one of the rails which the rails are linked together by a linkage. The railcar transport further includes suspension means connecting the wheels and axles to the trailer's rectangular frame, thereby allowing the transport to be used at high speeds and on rough surfaces.
By placing the rails on the longitudinal side frame members of the elongated rectangular frame of the railcar transport, it is not necessary to utilize heavy cross members on the elongated rectangular framework for rail support thereby increasing the load carrying capacity of the railcar transport.
Also, by articulating the railcar ramp utilizing a power means mounted at either the ramp pivot point or therebelow, the railcar ramp may be moved through a greater angle or the end thereof elevated to a higher position and the rails on the railcar ramp and elongated rectangular framework are not obstructed by members extending thereabove.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing invention and its advantages will be more fully understood from the following description of the invention taken in conjunction with the drawings wherein:
FIG. 1 is a side view of a portion of the front portion of the railcar transport.
FIG. 1a is a side view of a portion of the rear portion of the railcar transport.
FIG. 2 is a top view of a portion of the front portion of the railcar transport.
FIG. 2a is a top view of a portion of the rear portion of the railcar transport.
FIG. 3 is a cross-sectional view taken along line 3--3 of FIG. 2.
FIG. 4 is a cross-sectional view taken along line 4--4 of FIG. 2a.
FIG. 5 is a cross-sectional view taken along line 5--5 of FIG. 2a.
FIG. 6 is a view taken along line 6--6 of FIG. 2a.
FIG. 7 is a cross-sectional view taken along line 7--7 of FIG. 1a.
FIG. 8 is a top view of an alternate ramp pivoting means for the railcar transport.
FIG. 9 is a top view of an alternate ramp pivoting means for the railcar transport.
DESCRIPTION OF THE INVENTION
Referring to FIG. 1 and 1a, the railcar transport 10 of the present invention is shown.
The railcar transport 10 comprises an elongated rectangular frame 12 and a railcar ramp 14 pivotally secured to the frame 12.
The elongated rectangular frame 12 comprises a pair of longitudinal side frame members 16 having a pair of rails 18 mounted thereon being secured thereto by any suitable means, such as by clamping, a plurality of cross members 20 (see FIG. 2) secured to the longitudinal side frame members 16 by any suitable means, such as welding, extensible trailer stand 2, power means 24 located on one end of the frame 12, kingpin means 26 and multiaxle trailer suspension means 28 having wheels 30 thereon (shown in phantom). The multiaxle trailer suspension means 28 may be of any suitable type having any number of axles thereon, such as a Model TR-8750 or TR-8900 available from Neway Division, Lear Siegler, Inc., Muskegon, Michigan.
The power means 24 comprises an engine 32, winch 34 and hydraulic pump and tank 36. The winch 34 may be of any suitable type, such as either a gear driven type or hydraulically driven type. The power means 24 is contained on raised support 38 which serves as an operator platform having ladder 40 leading thereto and safety rail 42 therearound.
The railcar ramp 14 comprises a pair of longitudinal members 44 having a pair of rails 18' mounted thereon by any suitable means, such as by clamping, and interconnecting plates 46. The railcar ramp 14 is pivotally secured to one end of the elongated rectangular frame 12 by hinge means 48. The hinge means 48 comprises a first portion 50 secured to the one end of the elongated rectangular frame 12, a second portion 52 secured to one end of the railcar ramp 14 and pin means 54 pivotally securing the first portion 50 to the second portion 52. Mounted below the plane of the pin means 54 located on each side of the elongated rectangular frame 12 are hydraulic cylinder means 56 which are utilized to pivot the railcar ramp 14 relative to the elongated rectangular frame 12. Each hydraulic cylinder means 56 comprises a hydraulic cylinder 58 having one end thereof secured to the elongated rectangular frame 12 and piston rod 60 having one end thereof secured to the railcar ramp 14. The hydraulic cylinder means 56 are supplied pressurized hydraulic fluid from hydraulic pump and tank 36 of the power means 24 through suitable fluid lines (not shown). It should be noted that by mounting the hydraulic cylinder means 56 below the plane of the pin means 54 of the hinge means 48, a one-way acting hydraulic cylinder means may be utilized, if desired, and the railcar ramp has no obstructions thereabove.
Not shown in FIG. 1 or 1a located forward of the hinge means 48 and hydraulic cylinder means 56 and aft of multiaxle trailer suspension means 28 is an operator's stand where the various hydraulic controls are located to operate the various hydraulic components of the railcar transport 10.
Referring to FIGS. 2 and 2a, the cross members 20 securing the longitudinal side frame members 16 are shown. Shown in phantom on one side of the railcar transport is an operator's stand 58. Also shown in phantom, located between the rails 18 near one end of the elongated rectangular frame 12, are hydraulic chocks 60 which are utilized to engage the wheels of a railcar being transported on the railcar transport 10 to prevent the railcar from moving about the railcar transport 10. The hydraulic chocks 60 may utilize any suitable hydraulic actuating means, such as a hydraulic cylinder which may be supplied pressurized hydraulic fluid from the hydraulic pump and tank 36 of the power means, such as a block secured to the end of the rod of a hydraulic cylinder, 24 and may utilize any suitable means to engage the wheels of a railcar being transported on the rail car transport 10.
Located on one end of the railcar ramp 14 is rail alignment means 62 which is utilized to align rails 18' of the railcar transport 10 with the rails of a railroad track in order to facilitate the transfer of a railcar to the transport 10. The rail alignment means 62 comprises support means 64 secured to the railcar ramp 14 intermediate the rails 18' thereon, double acting hydraulic cylinder means 66 having one end of the hydraulic cylinder 68 thereof secured to the support means 64 and one end of the piston rod 70 secured to one of the pair of rails 18' of the railcar ramp 14 and rail connection means 72 interconnecting the pair of rails 18' such that any movement of one of the rails 18' is transferred to the other. The hydraulic cylinder means 66 is supplied pressurized hydraulic fluid from the hydraulic pump and tank 36 of the power means 24.
Referring to FIG. 3, the elongated rectangular frame 12 is shown in cross section. The longitudinal side frame members 16 comprise elongated I-beam shaped members having flanges 70 and interconnecting web 72. The longitudinal side frame members 16 are interconnected by means of cross members 20.
Referring to FIG. 4, the rails 18 are shown in cross section along with member 20'. For clarity, the portion of the underlying structure of the elongated frame 12 has been deleted.
Referring to FIG. 5, the construction of the railcar ramp 14 is shown having the rail alignment means 62 deleted for clarity. The rails 18' are located above longitudinal member 44 which are interconnected by plates 46.
Referring to FIG. 6, the construction of the railcar ramp 14 is further shown. The railcar ramp 14 includes a grating 46' which is installed on the top of a portion of the plate 46 interconnecting the longitudinal members 44.
Referring to FIG. 7, the construction of the elongated rectangular frame 12 is shown. Shown in phantom is the outline of the operator's stand 80 which is installed on one side of the elongated rectangular framework 12. The railcar transport 10 further includes suitable lighting and reflector means 90 mounted thereon.
Referring to FIG. 8, an alternative means of moving the railcar ramp 14 relative to the elongated rectangular framework 12 is shown. If it is desired to rotate the railcar ramp 14 about pin means 54 into a vertical or any intermediate position, rather than utilizing hydraulic cylinder means 56, a low speed, high torque hydraulic motor means 100 is utilized. The low speed, high torque hydraulic motor means 100 is mounted having the output shaft (not shown) thereof secured by means of a spline (not shown) to the pin means 54 which is in turn secured to the second portion 52 of hinge means 48 by means of a spline (not shown) while the mounting flange 104 of housing 102 thereof is secured to the first portion 50 of the hinge means 48. The low speed, high torque hydraulic motor means 100 is supplied pressurized hydraulic fluid from hydraulic pump and tank 36 of the power means 24. Any suitable low speed, high torque hydraulic motor means 100 may be used, such as a ROTO-VERSAL® hydraulic drive available from Gearmatic, a division of Paccar of Canada, Surrey, B.C., Canada.
Referring to FIG. 9, another alternative means of moving the railcar ramp 14 relative to the elongated rectangular framework 12 is shown. If it is desired to rotate the railcar ramp 14 about pin means 54 into a vertical or intermediate position, rather than utilizing either hydraulic cylinder means 56 or dual low speed, high torque hydraulic motor means 100, a single high torque hydraulic motor means 200 is utilized. A hydraulic motor 200 is mounted on elongated rectangular frame 12 having the output shaft thereof connected by means of a sprocket 204, chain 206 and sprocket 208 to the pin means 54. The sprocket 208 is secured to the pin means 54 by any suitable means with the ends of pin means 54 being secured to the second portions 52 of the hinge means 48 such that upon rotation of the output shaft 202 of the hydraulic motor 200, the pin means 54 rotates therewith thereby causing the railcar ramp 14 to rotate with respect to the elongated rectangular frame 12. The hydraulic motor means 200 is supplied pressurized hydraulic fluid from hydraulic pump and tank 36 of the power means 24. Any suitable high torque hydraulic motor means 200 may be used, such as a CHAR-LYNN® 10,000 series hydraulic motor available from Eaton Corporation, Fluid Power Operations, Minneapolis Division, Eden Prairie, Minnesota.
From the foregoing, it can be easily seen that the railcar transport 10 of the present invention offers several advantages over the prior art. | A railcar transport for use with a truck tractor towing means comprising a trailer having an elongated rectangular frame having the rails thereon located on the longitudinal side frame members, having a railcar ramp secured to one end thereof, having a power winch mounted on the other end thereof to pull railcars thereon, having a rail alignment mechanism on one end the trailcar ramp mounted between the rails thereon, and having railcar ramp articulation means which are mounted either at the ramp pivot point or therebelow. | 1 |
RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Application No. 61/244,341, Attorney Docket Number SSP09-1012PSP, entitled “STACKING CONCENTRIC MULTI PORT GAS-EXHAUST NOZZLE” by inventors Steve Poppe, Yan Rozenzon, and Peijun Ding, filed 21 Sep. 2009.
BACKGROUND
[0002] 1. Field
[0003] This disclosure is generally related to deposition systems. More specifically, this disclosure is related to a stackable multi-port gas nozzle used in a deposition reactor.
[0004] 2. Related Art
[0005] The negative environmental impact caused by the use of fossil fuels and their rising cost have resulted in a dire need for cleaner, cheaper alternative energy sources. Among different forms of alternative energy sources, solar power has been favored for its cleanness and wide availability.
[0006] A solar cell converts light into electricity using the photoelectric effect. There are several basic solar cell structures, including a single p-n junction, p-i-n/n-i-p, and multi-junction. A typical single p-n junction structure includes a p-type doped layer and an n-type doped layer of similar material. A heterojunction structure includes at least two layers of materials of different bandgaps. A p-i-n/n-i-p structure includes a p-type doped layer, an n-type doped layer, and an optional intrinsic (undoped) semiconductor layer (the i-layer) sandwiched between the p-layer and the n-layer. A multi junction structure includes multiple semiconductor layers of different bandgaps stacked on top of one another.
[0007] In a solar cell, light is absorbed near the p-n junction generating carriers. The carriers diffuse into the p-n junction and are separated by the built-in electric field, thus producing an electrical current across the device and external circuitry. An important metric in determining a solar cell's quality is its energy-conversion efficiency, which is defined as the ratio between power converted (from absorbed light to electrical energy) and power collected when the solar cell is connected to an electrical circuit.
[0008] Materials that can be used to construct solar cells include amorphous silicon (a-Si), polycrystalline silicon (poly-Si), crystalline silicon (c-Si), cadmium telluride (CdTe), etc. FIG. 1 illustrates an exemplary crystalline-silicon thin-film solar cell. Solar cell 100 includes a low-grade crystalline-Si substrate 102 , a p-type doped single-crystal Si layer 104 , an n + silicon emitter layer 106 , front electrodes 108 , and an Al back electrode 110 . Arrows in FIG. 1 indicate incident sunlight.
[0009] Based on industrial surveys, c-Si wafer-based solar cells dominate nearly 90% of the market. However, the cost of producing c-Si wafer-based solar cells is high, and the waste of Si material during the ingot-cutting process and the wafer-polishing process has caused a bottleneck in the supply of crystalline-Si wafers. Due to the soaring price and the supply shortage of Si material, there has been a great interest in alternative ways to manufacture solar cells. Recently, photovoltaic thin-film technology has been drawing vast interest because it can significantly reduce the amount of material used, thus lowering the cost of solar cells. Among various competing technologies, single-crystal Si thin-film solar cells have drawn great interest for their low cost and high efficiency.
[0010] Single-crystal Si thin-film solar cells can be created using conventional semiconductor epitaxy technologies which not only reduce manufacturing costs but also enable flexible doping levels in the emitter, absorber and back surface field of the solar cell, thus enhancing its efficiency. Single-crystal Si thin-film solar cells with an efficiency as high as 17% have been demonstrated in research labs (see M. Reutuer et al., “17% Efficient 50 μm Thick Solar Cells,” Technical Digest, 17 th International Photovoltaic Science and Engineering Conference, Fukuoka, Japan, p. 424).
[0011] A high-quality single-crystal Si thin film can be produced using Si epitaxy, which has been widely used in the semiconductor industry to create a high-quality single-crystal Si layer for CMOS integrated circuits, power devices and high-voltage discrete devices. Among possible Si epitaxial deposition techniques, trichlorosilane (TCS) based chemical vapor deposition (CVD) can provide a deposition rate of up to 10 μm/min. Therefore, it is possible to achieve a high-throughput and low-cost epitaxial process for solar cell application.
[0012] However, there is a lack of suitable Si epitaxy tools that can meet the demand for high throughput and low deposition cost for Si film layers with thicknesses up to several tens of microns, as required by the solar cell industry. Existing Si epitaxy tools, such as AMC7810™ and Centura 5200™ by Applied Materials, Inc., of Santa Clara, Calif., US; MT7700™ by Moore Epitaxial, Inc., of Tracy, Calif., US; PE2061™ by LPE Epitaxial Technology of Italy; and Epsilon 3200™ by ASM International of the Netherlands, are optimized for the needs of semiconductor device manufacturing. Although these epitaxial tools can deliver Si films with the highest quality, these tools are not compatible, in terms of throughput and gas conversion efficiency, with the economics of the solar cell industry.
[0013] FIG. 2 presents a diagram illustrating the structure of an existing barrel epitaxial reactor (prior art), such as that used for the batch processing of multiple wafers. Barrel reactor 200 includes a reaction chamber 202 , which has a gas inlet 204 at the top and a vent 206 at the bottom. A vertically positioned susceptor 208 holds a number of wafers, such as wafer 210 . Radio frequency (RF) heating coils 212 radiate heat onto the susceptor and wafers. Although barrel reactor 200 can batch process multiple wafers, the number of wafers it can process is limited by the architect of the system, the size of the chamber, and the design of the susceptor. Once built, it is difficult to modify the reactor or the susceptor to accommodate more wafers. In addition, the susceptor needs to be rotated during deposition in order to achieve a better uniformity. Because in barrel reactor 200 the process gas is delivered from gas inlet 204 to inner chamber walls and wafers with bottom exhaust, deposition can occur on the inner chamber walls, thus reducing radiant heating to wafers and requiring frequent cleaning cycles of quartz chambers. These limitations make it difficult to achieve a scalable high throughput system.
[0014] U.S. Pat. No. 6,399,510 proposed a reaction chamber that provides a bi-directional process gas flow to increase uniformity without the need for rotating susceptors. However, it does not solve the issues of low throughput, low reaction gas conversion rate, low power utilization efficiency, minimal Si deposition on the quartz chamber, and processing scalability. In addition, using the same gas lines for gas inlet and outlet increases the risk of contamination and re-deposition.
SUMMARY
[0015] One embodiment of the present invention provides a reactor for material deposition. The reactor includes a chamber and at least one gas nozzle. The chamber includes a pair of susceptors situated inside the chamber. Each susceptor has a front side and a back side, and the front side mounts a number of substrates. The susceptors are positioned vertically in such a way that the front sides of the susceptors face each other, and the vertical edges of the susceptors are in contact with each other, thereby forming a substantially enclosed narrow channel between the substrates mounted on different susceptors. The gas nozzle includes a gas-inlet component situated in the center of the gas nozzle and a detachable gas-outlet component stacked around the gas-inlet component. The gas-inlet component includes at least one opening coupled to the chamber, and is configured to inject precursor gases into the chamber. The detachable gas-outlet component includes at least one opening coupled to the chamber, and is configured to output exhaust gases from the chamber.
[0016] In a variation on the embodiment, the susceptors are formed using SiC-coated graphite or monolithic SiC.
[0017] In a variation on the embodiment, the cross section of the susceptors is U-shaped, and the wafer-holding sides of the susceptors are the inner surfaces of the “U.”
[0018] In a variation on the embodiment, the chamber is made of a material that comprises quartz.
[0019] In a variation on the embodiment, the gas nozzle further includes a second detachable gas-inlet component stacked around the detachable gas-outlet component. The second detachable gas-inlet component includes at least one opening coupled to the chamber, and the second detachable gas-inlet component is configured to inject purge gas into the chamber, thereby reducing deposition on walls of the chamber.
[0020] In a further variation, the second detachable gas-inlet component is configured to inject the purge gas into a space between the walls of the chamber and the back-side surfaces of the susceptors.
[0021] In a further variation on the embodiment, the purge gas flows between the inner walls of the second detachable gas-inlet component and the outer walls of the detachable gas-outlet component.
[0022] In a variation on the embodiment, the gas-inlet component is configured to inject precursor gas into the enclosed narrow channel.
[0023] In a variation on the embodiment, the exhaust gas flows between the inner walls of the detachable gas-outlet component and the outer walls of the gas-inlet component.
[0024] In a variation on the embodiment, at least one component of the gas nozzle is made of a material that comprises quartz.
BRIEF DESCRIPTION OF THE FIGURES
[0025] FIG. 1 presents a diagram illustrating the structure of an exemplary crystalline-Si thin-film solar cell.
[0026] FIG. 2 presents a diagram illustrating an existing barrel reactor (prior art).
[0027] FIG. 3A presents a diagram illustrating the front side of a susceptor in accordance with an embodiment of the present invention.
[0028] FIG. 3B presents a diagram illustrating the back side of a susceptor in accordance with an embodiment of the present invention.
[0029] FIG. 3C demonstrates the side view of a pair of susceptors in accordance with an embodiment of the present invention.
[0030] FIG. 3D presents a diagram illustrating the top view of a pair of susceptors in accordance with an embodiment of the present invention.
[0031] FIG. 4A presents the cross-sectional view of the stackable multi-port nozzle in the vertical direction in accordance with an embodiment of the present invention.
[0032] FIG. 4B presents the cross-sectional view of a nozzle in the horizontal direction in accordance with an embodiment of the present invention.
[0033] FIG. 4C presents a three-dimensional view of a stackable multi-port nozzle in accordance with an embodiment of the present invention.
[0034] In the figures, like reference numerals refer to the same figure elements.
DETAILED DESCRIPTION
[0035] The following description is presented to enable any person skilled in the art to make and use the embodiments, 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 disclosure. Thus, the present invention is not limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein.
Overview
[0036] Embodiments of the present invention provide a stackable multi-port gas nozzle, which can be used in a material deposition reactor. The gas nozzle includes a number of stackable components; each can be used as a port for gas delivery or exhaust. A gas-inlet port delivers precursor gas to an inner channel formed by two U-shaped susceptors with wafers facing each other. A gas-outlet port outputs exhaust from the reactor chamber. In addition, a third gas-inlet port delivers a purge gas between the chamber walls and the back side of the susceptors, significantly reducing deposition on the chamber wall.
Susceptors
[0037] FIG. 3A presents a diagram illustrating the front side of a susceptor in accordance with an embodiment of the present invention. During deposition, a susceptor 302 is placed vertically inside the reactor chamber. Note that, to avoid heat absorption by chamber walls, the reactor chamber is formed using a material that is transparent to radiant heat. In one embodiment, the reactor chamber is formed using quartz. By contrast, susceptor 302 is formed using a material that is opaque and absorbs radiant heat energy, such as SiC-coated graphite and monolithic SiC. In one embodiment, susceptor 302 is formed using SiC-coated graphite. As a result, most of the radiant heat from lamp-heating units located outside the reactor chamber is absorbed by susceptor 302 .
[0038] The front side of susceptor 302 includes a set of pockets, such as pocket 304 , for supporting substrates to be deposited. The shape of the bottom of the pockets is carefully designed to ensure a good thermal contact between the susceptor and the substrates. In one embodiment, the bottom of pocket 304 has a contour shape. Depending on the size of susceptor 302 , various numbers of substrates can fit onto susceptor 302 . In one embodiment, susceptor 302 includes 12 pockets for supporting 12 125×125 mm 2 substrates. FIG. 3B presents a diagram illustrating the back side of a susceptor in accordance with an embodiment.
[0039] FIG. 3C demonstrates the side view of a pair of susceptors in accordance with an embodiment of the present invention. In FIG. 3C , a pair of susceptors, susceptor 306 and susceptor 308 , are placed vertically inside the reaction chamber. A narrow channel 310 is formed between susceptors 306 and 308 . FIG. 3D presents a diagram illustrating the top view of a pair of susceptors in accordance with an embodiment of the present invention. FIG. 3D illustrates that the cross sections of susceptors 306 and 308 are U-shaped. The vertical edges of susceptors 306 and 308 are in contact with each other forming an enclosed narrow channel 310 . The wafers mounted on susceptors 306 and 308 , such as wafers 312 and 314 , are facing inward to narrow channel 310 . As a result, during deposition, the precursor gases, such as TCS, can be contained within narrow channel 310 . Other examples of precursor gases include, but are not limited to: SiH 4 , SiH 2 Cl 2 , and SiCl 4 . In addition to the “U” shape, the cross sections of susceptors 306 and 308 can form other shapes, include but are not limited to: half circle, half eclipse, and other regular or irregular shapes. Note that the front sides (i.e., the wafer-holding sides) of susceptors 306 and 308 are facing each other. Thus, the deposition substrates, such as substrates 312 and 314 , have their deposition surfaces surrounding channel 310 , which contains the precursor gases and keeps them from depositing material on the inner walls of the reactor chamber. Such a configuration can increase the TCS gas utilization rate significantly, because the probability for the TCS gas to successfully deposit Si on substrate surfaces is now much higher. The increased deposition probability results from the precursor gases being surrounded by deposition surfaces, as well as the reduced deposition on the inner walls of the reactor chamber.
Nozzle
[0040] In a solar cell, film uniformity greatly impacts the solar cell's efficiency. In a traditional epitaxial system, it has been difficult to achieve good deposition uniformity and a high reaction-gas-utilization rate at the same time. Substrate rotation can be used to improve uniformity. However, it becomes increasingly difficult to rotate substrates in a large batch reactor. To achieve better deposition uniformity, in one embodiment, precursor gases, such as TCS and H 2 , are injected into the channel formed by the two susceptors from the top and bottom of the reactor chamber, alternately. To do so, two nozzles are installed, one on the top of the reactor chamber and one on the bottom. Similarly to the reactor chamber, the nozzles are made of material that is resistant to radiant heat. In one embodiment, the nozzles, or at least portions of the nozzles, are formed using quartz.
[0041] Each nozzle includes a gas-inlet port for injecting precursor gas. In addition, each nozzle also includes a gas-outlet port for exhaust. To simplify the design and fabrication of the nozzle, the gas-inlet and gas-outlet ports are made of detachable components. In one embodiment, they can be stacked together with the gas-inlet port located inside of the gas-outlet port. Note that the gas-inlet port for the precursor and the gas-outlet port for the exhaust are both coupled to the channel formed by the two susceptors.
[0042] In addition to a gas-inlet port for precursor gas and a gas-outlet port for exhaust, each nozzle also includes a third port which delivers a purge gas between the chamber walls and the back side of the susceptors. The existence of the purge gas can significantly reduce deposition on the chamber walls. This purge-gas-inlet port is also made of a detachable component and can be stacked outside of the gas-outlet port for exhaust.
[0043] FIG. 4A presents the cross-sectional view of the stackable multi-port nozzle in the vertical direction in accordance with an embodiment of the present invention. A gas nozzle 400 includes three detachable components, including precursor-gas-inlet component 402 , exhaust component 404 , and purge-gas-inlet component 406 . Precursor-gas-inlet component 402 is located at the center of nozzle 400 , and includes an opening 408 at the bottom coupled to the narrow channel formed by the pair of susceptors to allow the precursor gas to enter the narrow channel during deposition. Exhaust component 404 can be stacked around the precursor-gas-inlet component 402 . In one embodiment, the inner walls of exhaust component 404 and the outer walls of precursor-gas-inlet component 402 form an enclosed space to allow the flow of the exhaust. In a further embodiment, exhaust component 404 includes a number of openings, such as openings 410 and 412 , at the bottom to allow the exhaust to exit the reactor chamber. During deposition, the openings on exhaust component 404 , such as openings 410 and 412 , remain closed when opening 408 is open. However, when opening 408 is closed, openings 410 and 412 will open to allow exhaust gas to exit the reactor chamber. During deposition, precursor-gas-inlet component 402 and exhaust component 404 alternately turn on, and together with another nozzle similar to nozzle 400 located on the opposite side of the reactor chamber, the precursor gas can be injected into the narrow channel within the reactor chamber from two directions alternately to ensure a uniform deposition on the wafers surrounding the narrow channel. In FIG. 4A , the flow direction of the precursor gas is illustrated by an arrow 418 , and the flow direction of the exhaust gas is illustrated by arrows 420 and 422 .
[0044] Purge-gas-inlet component 406 is stacked around exhaust component 404 . In one embodiment, the inner walls of purge-gas-inlet component 406 and the outer walls of exhaust component 404 form an enclosed space to allow the flow of the purge gas. In a further embodiment, purge-gas-inlet component 406 includes a number of openings, such as openings 414 and 416 , at the bottom. These openings are coupled to the space between the back sides of the susceptors and the walls of the reactor chamber. As a result, the purge gas, such as H 2 , can flow between the back sides of the susceptors and the chamber walls, thus preventing unwanted deposition on the chamber walls. In FIG. 4A , arrows 424 and 426 illustrate the flow direction of the purge gas.
[0045] FIG. 4B presents the cross-sectional view of a nozzle in the horizontal direction in accordance with an embodiment of the present invention. From FIG. 4B , one can see that opening 408 for the precursor-gas-inlet component is located at the center of nozzle 400 . During operation, precursor gas can be injected into the reactor chamber via opening 408 . By carefully aligning opening 408 with the narrow channel formed by the susceptors, the system contains the precursor gas within the narrow channel, thus improving the utilization of the precursor gas. In addition, the containment of the precursor gas within the narrow channel also prevents the deposition on the chamber walls. Note that the shape of opening 408 is not limited to the one illustrated in FIG. 4B .
[0046] FIG. 4B also illustrates that openings for the exhaust component, such as openings 410 and 412 , are located surrounding opening 408 . These openings and opening 408 open alternately to allow the exhaust gas to exit the reactor chamber. Note that the number of openings included in the exhaust component can be more or fewer than in the example shown in FIG. 4B . In addition, the shapes of the openings included in the exhaust component are not limited to the ones shown in FIG. 4B .
[0047] In FIG. 4B , openings for the purge-gas-inlet component, such as openings 414 and 416 , are located surrounding openings for the exhaust component. These openings allows the purge gas, such as H 2 , to be injected between the back side of the susceptor and the chamber walls, thus reducing unwanted deposition on the chamber walls. The gas pressure between the back sides of the susceptors and the chamber walls can be kept equal or more than the gas pressure inside the narrow channel formed by the susceptors, thus preventing the precursor gas contained in the narrow channel to leak into the space next to the chamber wall. Note that the number of openings included in the purge-gas-inlet component can be more or fewer than the example shown in FIG. 4B . In addition, the shapes of the openings included in the purge-gas-inlet component are not limited to the ones shown in FIG. 4B .
[0048] FIG. 4C presents a three-dimensional view of a stackable multi-port nozzle in accordance with an embodiment of the present invention.
[0049] Having stackable components makes the manufacture and the maintenance of the nozzle much easier. Each component can be manufactured separately, which significantly lowers the cost. In addition, if one component breaks down, the system operator only needs to replace the faulty component instead of replacing the whole nozzle, which is much more expensive.
[0050] Note that, although this disclosure gives an example of a nozzle with three stackable components, other configurations with fewer or more stackable components are also possible. Also note that, although in the example shown in FIGS. 4A-4C the stackable components are concentric to each other, the relative configurations of the stackable components are not limited to concentric. For example, it is possible for one or more stable components to be off center from each other as long as the components provide appropriate channels for the flow of gases. In addition to placing such stackable nozzles on the top and bottom of the reactor chamber, it is also possible to place fewer or more such nozzles at other locations surrounding the reactor chamber.
[0051] The foregoing descriptions of various embodiments have been presented only for purposes of illustration and description. They are not intended to be exhaustive or to limit the present invention to the forms disclosed. Accordingly, many modifications and variations will be apparent to practitioners skilled in the art. Additionally, the above disclosure is not intended to limit the present invention. | One embodiment provides a reactor for material deposition. The reactor includes a chamber and at least one gas nozzle. The chamber includes a pair of susceptors, each having a front side and a back side. The front side mounts a number of substrates. The susceptors are positioned vertically so that the front sides of the susceptors face each other, and the vertical edges of the susceptors are in contact with each other, thereby forming a substantially enclosed narrow channel between the substrates mounted on different susceptors. The gas nozzle includes a gas-inlet component situated in the center and a detachable gas-outlet component stacked around the gas-inlet component. The gas-inlet component includes at least one opening coupled to the chamber, and is configured to inject precursor gases into the chamber. The detachable gas-outlet component includes at least one opening coupled to the chamber, and is configured to output exhaust gases from the chamber. | 2 |
TECHNICAL FIELD
This is a continuation-in-part of U.S. Ser. No. 899,128 filed Apr. 24, 1978, abandoned.
The invention relates to improved methods for staining papers suitable for use as wrappers for smoking articles wherein alkali humates are utilized. The humates are rendered insoluble on the paper using solutions of magnesium sulfate.
BACKGROUND OF THE PRIOR ART
The use of humic acid and fractions thereof as dyes is well known. ("Recent Progress in the Chemistry of Natural and Synthetic Coloring Matters," T. S. Gore et al. eds., Academic Press, N.Y. 1962, pps. 99-112.) Recently, a variety of cigarettes manufactured with brown paper wrappers have enjoyed increased popularity among smokers, and some of these cigarettes are fabricated using brown wrappers stained with humic acid. Processes for staining cigarette paper brown have included the use of dyes such as synthetic azo dyes, dyes produced from walnut shells, caramel, tannic acid and the like. However, the aforementioned stains or dyes are undesirable for a variety of reasons. First, the azo dyes, which contain large amounts of nitrogen, may produce undesirable pyrolysis products and, therefore, could be unsuitable for use in smoking articles. Secondly, the amount of caramel required to produce the desired intensity of brown color considerably inhibits the burn rate of the paper. The use of such stains as tannic acid may provide the desired brown color; however, treatment of this type simultaneously reduces the porosity of the paper thereby also reducing the rate of combustion. In addition, adverse affects on the gas phase composition are also noted (see Austrian Pat. No. 175,148).
By definition, humic acids are allomelanins found in soil, peat, and low-rank coal. They are generally alkali soluble and precipitated in the presence of acids. From a chemical standpoint, humic acids generally consist of a mixture of complex macromolecules characterized as having polymeric phenolic structures with the ability to chelate with metals. In addition, humic acids have a strong base-binding power, and this ion-exchange capability can be used advantageously in their use as dyes. There are many variations of humic acid depending upon differences in the plant remains from which they originate as well as the soil, climate, microflora, drainage, etc.
Humic acids, by nature, are intensely chocolate brown in color; and because of their natural origin, they are particularly preferred over synthetic dyes as staining pigments for producing brown wrappers or papers for smoking products. Generally, an alkaline solution is prepared by mixing the powdery humic acid with an alkali metal hydroxide, i.e., sodium hydroxide, to form a soluble humate salt. This solution is used to impregnate the paper on one or both sides, and this is followed by a fixing step, generally with salts such as aluminum, calcium, iron, chromium and the like. In essence, sodium ions are partially exchanged for the other metal ions added in the fixing process, thus leaving a water insoluble humate salt on the paper.
henning in Allgemeine Papier-Rundschau, No. 31:1027 (21 August 1967) describes methods for staining paper, and especially paper suitable for cigarette wrappers, with Sap Brown (also termed "nut stain" or humates) at about neutral pH. The Sap Brown may be rendered insoluble on the paper by fixing with aluminum or iron sulfate. We have found that certain disadvantages are encountered when utilizing the foregoing method of Henning. For instance, when aluminum sulfate is employed as the fixing agent, an undesirable white masking of the rich brown color is observed. When iron sulfate is used as the fixing agent, and the paper is ultimately used for smoking products, a brown ash forms on smoking. It is generally recognized that a grey to white ash is more preferable, particularly from an appearance standpoint.
German Pat. No. 957,361 discloses dyeing methods for yellow straw with an alkali humate solution. The humate is fixed on the straw by means of iron or chromium salts such as, for example, FeSO 4 .7H 2 O or [CrCl 2 (H 2 O) 4 ]Cl-2(H 2 O). Iron is unsuitable for the aformentioned reasons. The use of chromium salts in smoking products would be undersirable because of their well established toxicity. See, for example Dangerous Properties of Industrial Materials, N. Irving Sax, Fourth Edition, 1975 pages 558-9.
Others have suggested that various cations are useful for precipitating humates, and they include lead, copper, calcium, potassium, and the like. However, none have suggested that the cations mentioned would be suitable for use as a fixing agent when staining paper for ultimate use in smoking articles. Moreover, no suggestion has been made to indicate that a particular cation, magnesium when used as a fixing agent, might be preferable for use in smoking articles due to improved smoking characteristics, improved appearance, or lowered gas phase constituents on smoking.
Austrian Pat. No. 175148 to Ringer discloses the use of various acids in combination with cigarette paper to effect a denicotinization of the smoke. The porosity of the paper is decreased by Ringer's method, and the addition of salts, such as magnesium sulfate, apparently reduced the porosity to an even greater extent thereby resulting in a more significant reduction of nicotine in the smoke.
We have observed that a post-treatment of humate stained paper with magnesium sulfate has little effect on nicotine delivery or reduced porosity. These observations will be described in detail hereinbelow.
Analytical studies using humic acid-treated brown wrappers have indicated in some instances a tendency toward increased gas phase constituents. Various attempts have been made to reduce constituents, such as carbon monoxide, by using more efficient filter elements, by increasing the degree of ventilation in filters, or by increasing the porosity of the paper or wrapper, etc. However, none of these methods has proven to be entirely satisfactory.
BRIEF SUMMARY OF THE INVENTION
This invention concerns the improvement of humic acid-treated paper or sheet material in which tobacco or any other smoking product is rolled for the fabrication of cigarettes, cigars, or the like.
The invention relates specifically to a process for treating humic acid-dyed brown paper suitable for use as wrappers for smoking articles wherein some of the products of pyrolysis are substantially reduced. In studies with cigarettes made with commercially available humic acid-stained papers, it was observed that on pyrolysis the burning papers produced more carbon monoxide than conventional white cigarette wrappers. In an effort to identify the cause, experiments were designed to study a number of parameters related to dyeing with humic acid. The concentration and composition of humic acid was varied as well as the pH of the staining solution; and in addition, a variety of cations (fixing agents) that render the humic acid insoluble and colorfast on the paper, were utilized in an attempt to reduce gas phase delivery. From the results obtained, a total system has been developed for coating cigarette wrappers having reduced gas phase constituents on smoking and this system will be described in detail hereinbelow.
Thus, it is an object of this invention to provide a method for producing a humic acid-coated paper or smoking wrapper whereby smoking articles produced from said paper can be materially improved.
It is a further object of this invention to provide methods and means that individually operate to provide a more desirable brown paper or wrapper from the standpoint of gas phase delivery whereby such gas phase constituents, such as carbon monoxide, are substantially reduced.
It is yet a further object of this invention to provide a method for fixing humates on paper whereby a desirable color intensity is obtained with a concomitant reduction in gas phase constituents such as carbon monoxide.
Other objects and advantages will be discussed and described in detail hereinbelow.
DETAILED DESCRIPTION OF THE INVENTION
In the practice of the present invention, commercially available humic acid is suspended in water with stirring. The mixture is then centrifuged to recover the insoluble humic acid, and the acid-soluble materials are discarded. Experimentation indicates that the acid-soluble fraction is undesirable in that at certain concentrations there is a tendency towards gel formation, and, in addition, this fraction does not appreciably improve color depth or intensity of the final staining solution.
The acid-insoluble humic acid fraction is generally dried, weighed, and then suspended in water. The pH of the suspension is adjusted with a base such as sodium, potassium, or ammonium hydroxide, with sodium hydroxide being preferred. The final pH of the staining solution should be between about 7 and 8 for optimum results. There appears to be a tendency towards increased carbon monoxide delivery as the pH of the staining solution is increased over about a pH of 8. Stabilization of the pH of the solution may require about 8 to about 20 hours with continual stirring.
Just prior to the actual staining or dyeing of the paper, the alkaline humate solution may be centrifuged to remove any remaining insoluble materials. The insoluble materials are dried and weighed. The staining solution containing the alkali humate is adjusted by the addition of water to give a final concentration of about 12 to 16% humate and preferably about 14% humate by weight.
The actual staining process may be carried out utilizing a conventional size press wherein standard bobbins of cigarette paper are passed through a staining bath containing the alkali humte at a predetermined speed to insure that the desired amount of staining solution is retained on the paper. The paper may be stained on one or both sides depending on the desired effect to be achieved.
In an alternate approach, sodium humate is added to a slurry of purified cellulose pulp, and the slurry is used as a furnish in a conventional papermaking machine to produce a brown paper suitable for use in the fabrication of smolking products.
In a preferred embodiment of the present invention, the alkali humate is fixed on the paper by treatment with a dilute solution of magnesium sulfate. This salt post-treatment is preferably carried out after the paper has been stained and dried by conventional methods. although calcium salts are well known fixing agents for alkali humates, we have found magnesium sulfate unexpectedly superior for use as a fixing agent when preparing paper for ultimate use in smoking articles. Magnesium sulfate at a concentration of about 1 to 3%, and preferably about 2% by weight, provided consistently lower carbon monoxide delivery when compared to calcium chloride or magnesium acetate. Tests were conducted using aluminum sulfate as a fixing agent; and although carbon monoxide deliveries were acceptable, it was noted that at even the lowest concentration possible for fixing the alkali humate, the aluminum salt caused an unacceptable white film on the paper, thereby masking the rich brown color of the humate stained paper.
Following the fixing step, the paper may be washed with water to remove excess magnesium sulfate or alkali sulfate salts, i.e., sodium sulfate, which is formed during fixing. If a post-washing step is employed, it is necessary to use a more concentrated solution of magnesium sulfate for fixing, for example, a 3 to 5% solution of magnesium sulfate would be acceptable. This washing step is preferably carried out using a conventional size press as previously described. The insoluble magnesium humate remains on the paper and, after drying, is color fast and provides an acceptable paper for use in smoking articles. An acceptably intense brown color is obtained using the salt post-treatment of the present invention while maintaining a lowered carbon monoxide delivery.
The following examples are illustrative but are not intended to be limitive thereof.
EXAMPLE 1
Studies were conducted to compare different salts for use in fixing sodium humate stained papers. Conventional white cigarette paper was stained with a sodium humate solution having a pH of 12.7. The stained paper was dried and separate pieces were treated with one of the following solutions: 5.0% calcium chloride, 4.9% magnesium acetate, or 5.5% magnesium sulfate. Increased concentrations of fixing solutions were used to assure that some of the sodium ions would be displaced or exchanged by either magnesium or calcium ions. The humate-stained papers were fixed by immersion in the fixing solution using a conventional size press.
Following the fixing step with the above-named solutions, the stained and fixed papers were dried. Cigarettes containing a typical blend of tobacco were fabricated at 85 mm lengths. All of the cigarettes had conventional cellulose acetate filters attached thereto.
The cigarettes were smoked under controlled laboratory conditions and the gas phase that passed through the filters was trapped and analyzed for carbon monoxide using known infrared spectroscopy techniques. Nicotine delivery was measured using standard methods well known in the art. Cigarettes fabricated from paper that had not been treated by fixing with a calcium or magnesium salt served as controls. The results are tabulated in Table 1 below.
Table 1______________________________________SALT POST TREATMENT Nic- CO/cigt otine/cigtSalt CO/Puff P.C..sup.+ (mg) (mg)______________________________________ Control 3.37 9.0 30.3 1.36*85 mm 5.0% CaCl.sub.2 3.09 9.3 28.8 1.36cigarettes 4.9% MgAc 3.44 9.0 31.0 1.41 5.5% MgSO.sub.4 2.64 9.3 24.6 1.34______________________________________ *Stained with Na Humate Ph 12.7 .sup.+ Puff count
The data indicate that the papers treated with 5.5% magnesium sulfate resulted in reduced carbon monoxide delivery when compared to the untreated control and the other salts shown above.
EXAMPLE 2
Cigarette Paper was stained with sodium humate having a pH of 10.0. The paper was dried and fixed with one of the following solutions: 5% CaCl 2 , 5.5% MgSO 4 , and 10% HCl. Cigarettes were fabricated as in Example 1 and smoked under controlled laboratory conditions. The gas phase was trapped and analyzed according to the method previously disclosed. The total particulate matter and nicotine were trapped on cambridge filter pads and measured using standard procedures. The porosity of the control and treated papers were determined using a modified Greiner Water Porosity Device. The porosity of the paper was determined by the length of time necessary to draw 50 ml of air through a 0.786 inch area. The air flow was induced by a falling water column, and the time for 50 ml of air to pass through the sample area was measured by the time required for the water level to pass between two electrodes, the equivalent of 50 ml. The determinations were made under carefully controlled laboratory conditions at about 24° C. and 60 % r/h. The results are tabulated in Table 2.
Table 2______________________________________SALT POST-TREATMENT85 mm CigarettesNa Humate, pH 10 CO/cigt. Nicotine PorositySalt PC* (mg) mg/cigt (sec)______________________________________control--no salt 8.5 20.5 1.35 27.05% CaCl.sub.2 9.8 25.0 1.44 20.05.5% MgSO.sub.4 8.5 20.4 1.33 21.010% HC1 10.0 32.0 1.50 21.0______________________________________ *PC = puff count
Although the salts shown above are acceptable in rendering the sodium humate insoluble, use of magnesium sulfate as the fixing agent results in a more acceptable carbon monoxide delivery rate.
EXAMPLE 3
The sodium salt of sap brown, obtained from Abbey Chemical Company, was dissolved in water to give a final concentration of 20% by weight. Conventional white cigarette paper was stained with the sap brown solution and dried. Separate pieces of the dried paper were fixed using either a 5% solution of calcium chloride or a 5.5% solution of magnesium sulfate.
Cigarettes (85 mm) were fabricated using the prepared papers. Control cigarettes were prepared using stained but unfixed paper. Cellulose acetate filters were attached and the cigarettes were smoked and the gas phase analyzed as in Example 1. The nicotine delivery and porosity were determined as described in Example 2.
Table 3______________________________________ CO/cigt. Nicotine TPM PorosityPaper CO/Puff (mg) (mg) (mg) (sec)______________________________________Control 3.35 26.8 1.21 27.5 23CaCl.sub.2 --fixed 3.37 23.6 1.21 26.7 21MgSO.sub.4 --fixed 2.43 21.9 1.22 25.8 27______________________________________
EXAMPLE 4
Technical grade humic acid (Aldridge Chemical Company) was washed extensively with tap water until the supernatant liquid became clear. Approximately 4% of the acid soluble material was removed. The humic acid was then treated with 1% by weight sodium hydroxide. The pH of the mixture was 5.0. Extensive washing resulted in a 20% weight loss, which represented additional acid soluble materials.
The washed humic acid weighing 350 g was then treated with 21 g sodium hydroxide in three steps. At each step, the solution having a pH of 7-8 was centrifuged, and the supernatant liquid was decanted, dried at 50° C., and weighed. The separated sodium humate was combined with an additional wash of the insoluble residue and dried to yield about 160 g. This represented approximately 32% of the starting material.
The dried sodium humate was dissolved in water to give a final concentration of 15% (W/V). Following centrifugation to remove insolubles, the humate solution was 13.7% (W/V). The solution was coated on conventional cigarette paper by means of a size press. The paper was dried and post treated with a 2% (W/V) solution of magnesium sulfate. Unstained white cigarette paper was also treated in a similar manner with 2% magnesium sulfate.
Cigarettes, (120 mm) fabricated using a conventional blend of tobaccos, were wrapped with the treated papers. Cellulose acetate filters were attached to the cigarettes. Cigarette A was wrapped with untreated white paper; Cigarette B was unstained paper treated with magnesium sulfate; Cigarette C was stained with humic acid; and Cigarette D was stained with humic acid and post-treated with magnesium sulfate.
The cigarettes were smoked under controlled laboratory conditions and analyzed as described in Examples 1 and 2. The results are as follows.
Table 4______________________________________ CO/cigt. CO/ Nicotine Porosity PC* (mg) Puff mg/cigt (sec)______________________________________Cigarette Acontrol 11.9 13.5 1.13 0.86 14.0Cigarette Bcontrol + MgSO.sub.4 11.8 14.6 1.24 1.01 14.0Cigarette Chumate stained 13.4 24.4 1.82 1.26 16.0Cigarette Dhumate + MgSO.sub.4 13.6 22.6 1.66 1.27 14.0______________________________________ *PC = puff count | Humic acid-dyed paper suitable for use as wrappers for smoking articles is post treated with magnesium sulfate to fix or render the humic acid insoluble. Paper treated in this manner provides a product of acceptable brown color. Smoking articles wrapped in the treated paper evolve a reduced amount of carbon monoxide on smoking under normal conditions in comparison to currently available brown papers stained with humic acid. | 8 |
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